X is said to be End-completely-regular  if its endomorphism monoid End(X) is completely regular . In this paper, we will show that if X[Y] is End-completely-regular , then both X and Y are End-completely-regular . We give several approaches to construct new End-completely-regular graphs by means of the lexicographic products of two graphs with certain conditions. In particular, we determine the End-completely-regular and End-inverse lexicographic products of bipartite graphs.A graph  Endomorphism monoids of graphs are generalizations of automorphism groups of graphs. In recent years, much attention has been paid to endomorphism monoids of graphs and many interesting results concerning graphs and their endomorphism monoids have been obtained. The aim of this research is to develop further relationship between graph theory and algebraic theory of semigroups and to apply the theory of semigroups to graph theory. The bipartite graph is a class of famous graphs. Their endomorphism monoids are studied by several authors. In , the conX considered in this paper are undirected finite simple graphs. The vertex set of X is denoted by V(X) and the edge set of X is denoted by E(X). If two vertices x1 and x2 are adjacent in X, the edge connecting x1 and x2 is denoted by {x1, x2} and we write {x1, x2} ∈ E(X). A subgraph H is called an induced subgraph of X if for any a, b ∈ V(H), {a, b} ∈ E(H) if and only if {a, b} ∈ E(X). A graph X is called bipartite if X has no odd cycle. It is known that if a graph X is a bipartite graph, then its vertex set can be partitioned into two disjoint nonempty subsets such that no edge joins two vertices in the same set.The graphs X and Y be two graphs. The join of X and Y, denoted by X + Y, is a graph such that V(X + Y) = V(X) ∪ V(Y) and E(X + Y) = E(X) ∪ E(Y)∪{{x1, x2} | x1 ∈ V(X), x2 ∈ V(Y)}. The lexicographic product of X and Y, denoted by X[Y], is a graph with vertex set V(X[Y]) = V(X) × V(Y), and with edge set E(X[Y]) = {{, }∣{x, x1} ∈ E(X), or x = x1 and {y, y1} ∈ E(Y)}. Denote Yx = { | y ∈ V(Y)} for any x ∈ V(X).Let X and Y be graphs. A mapping f from V(X) to V(Y) is called a homomorphism (from X to Y) if {x1, x2} ∈ E(X) implies that {f(x1), f(x2)} ∈ E(Y). A homomorphism f is called an isomorphism if f is bijective and f−1 is a homomorphism. A homomorphism  f from X to itself is called an endomorphism  of X (see ρf the equivalence class containing a ∈ V(X) with respect to ρf.Aa of a semigroup S is called regular if there exists x ∈ S such that axa = a. An element a of a semigroup S is called completely regular if a = axa and xa = ax hold for some x ∈ S. A semigroup S is called regular  if all its elements are regular . An inverse semigroup is a regular semigroup in which the idempotents commute. A graph X is said to be End-regular  if its endomorphism monoid End(X) is regular . Clearly, End-completely-regular graphs as well as End-inverse graphs are End-regular.An element For undefined notation and terminology in this paper, the reader is referred to –14. We lX[Y] is End-regular, then both X and Y are End-regular.If G be a graph and let f ∈ End(G). Then f is completely regular if and only if f|If ∈ Aut(If).Let X be a bipartite graph. Then X is End-completely-regular if and only if X is one of K1, K2, P2, 2K1, 2K2, and K1 ⋃ K2.Let X and Y be two bipartite graphs. Then X + Y is End-completely-regular if and only if one of them is End-completely-regular and the other is K1 or K2.Let G be a graph and f ∈ End(G). Then f is completely regular if and only if there exists g ∈ Idpt(G) such that ρg = ρf and Ig = If.Let X be a bipartite graph. Then X is End-inverse if and only if X = K1 or X = K2.Let X and Y be two graphs. Then End(X[Y]) = End(X)[End(Y)] if and only if for any f ∈ End(X[Y]) and x ∈ V(X), there exists x′ ∈ V(X) such that f(Yx)⊆Yx′.Let X[Y] is End-completely-regular, then both X and Y are End-completely-regular.In this section, we will characterize the End-completely-regular and End-inverse lexicographic products of two graphs. We first show that if X and Y be two graphs. If X[Y] is End-completely-regular, then both X and Y are End-completely-regular.Let X is End-completely-regular, it is only necessary to verify that f|If is an automorphism of If for each f ∈ End(X). Define a mapping F from V(X[Y]) to itself byF ∈ End(X[Y]). Since X[Y] is End-completely-regular, by F|IF is an automorphism of IF. It is easy to see that IF = If[Y]. For any distinct x1, x2 ∈ V(If) and y ∈ V(Y), F) = (f(x1), y) and F) = (f(x2), y) hold. Since F|IF is an automorphism of IF, (f(x1), y)≠(f(x2), y). Hence f(x1) ≠ f(x2) and so f|If is an automorphism of If.By g ∈ End(Y). Define a mapping G from V(X[Y]) to itself byG ∈ End(X[Y]). Since X[Y] is End-completely-regular, by G|IG is an automorphism of IG. It is easy to see that IG = X[Ig]. For any x ∈ V(X) and y1, y2 ∈ V(Ig), G) = ) and G) = ). Since G|IG is an automorphism of IG, )≠), we get that g(y1) ≠ g(y2) and so g|Ig is an automorphism of Ig, as required.Let X and Y being End-completely-regular does not yield that X[Y] is End-completely-regular.The following example shows that X and Y be two graphs with V(X) = {x1, x2}, V(Y) = {y1, y2}, E(X) = {{x1, x2}}, and E(Y) = ϕ. By X and Y are End-completely-regular. It is easy to see that X[Y]≅C4. Also by Let X[Y] to be End-completely-regular. To this aim, we need the following result due to Fan ) = End(X)[End(Y)], where End(X)[End(Y)] is the wreath product of the monoids End(X) and End(Y).Let X and Y be two K3-free connected graphs such that girth(X) or girth(Y) is odd. In  is End-regular. Here we prove that if X is an End-completely-regular graph and Y is an unretractive graph, then X[Y] is End-completely-regular.Let  odd. In , Fan proX and Y be two K3-free connected graphs with girth(X) or girth(Y) being odd, and assume thatX  is End-completely-regular,Y is unretractive.Then X[Y] is End-completely-regular.Let X and Y be two graphs satisfying the assumptions. To show that X[Y] is End-completely-regular, we prove that for any F ∈ End(X[Y]), there exists an idempotent endomorphism G ∈ End(X[Y]) such that ρF = ρG and IF = IG.Let F ∈ End(X)[End(Y)]. Since End(X[Y]) = End(X)[End(Y)], F =  for some s ∈ End(X) and f ∈ End(Y)V(X). Thus, for any u ∈ V(X), there exists fu = f(u) ∈ End(Y). Let X and Y be K3-free connected graphs with girth(X) or girth(Y) being odd. By u ∈ V(X), F(Yu)⊆Yv for some v ∈ V(X). Note that Y is unretractive. Then F(Yu) = Yv. Since X is End-completely-regular and s ∈ End(X), by t ∈ Idpt(X) such that ρt = ρs and It = Is. Clearly, Is is an induced subgraph of X. Hence IF = Is[Y] is an induced subgraph of X[Y].Let X is End-completely-regular, s|Is is an automorphism of Is. Thus for any u ∈ Is, there exists only one vertex u1 ∈ Is such that s(u1) = u. Then F(Yu1) = Yu. Now for any  ∈ IF, there exists only one vertex  ∈ IF such that F) = . Define a mapping G from V(X[Y]) to itself in the following way. If  ∈ V(IF), then G) = ; if  ∉ V(IF), then F) =  for some  ∈ V(IF). Now let G) = , where  is the only vertex in V(IF) such that F) = . Then it is easy to see that G is well-defined. Let  ∈ V(X[Y]). If  ∈ V(IF), then x ∈ Is. Thus t(x) = x. Hence G) =  ∈ Yt(x). If  ∉ V(IF), then t(x) = u1. Hence G) =  ∈ Yt(x). Therefore, G) ∈ Yt(x) for any  ∈ V(X[Y]).Since x1, y1),  ∈ V(X[Y]) be such that {, } ∈ E(X[Y]). If ,  ∈ V(IF), then {G), G)} = {, } ∈ E(X[Y]). If  ∈ V(IF) and  ∉ V(IF), then x1 ≠ x2 and {x1, x2} ∈ E(X). Thus G) ∈ Yt(x1) and G) ∈ Yt(x2). Since t ∈ Idpt(X) and {x1, x2} ∈ E(X), {t(x1), t(x2)} ∈ E(X). Hence {G), G)} ∈ E(X[Y]). If  ∉ V(IF) and  ∉ V(IF), there are two cases.Let . Then G) ∈ Yt(x1) and G) ∈ Yt(x2). Since t ∈ Idpt(X) and {x1, x2} ∈ E(X), {t(x1), t(x2)} ∈ E(X). Hence we have {G), G)} ∈ E(X[Y]).Case 2. Assume that x1 = x2 and {y1, y2} ∈ E(Y). Then we have ,  ∈ Yx1 and G), G) ∈ Yt(x1). Since G|Yx1 is an isomorphism from Yx1 to Yt(x1), {G), G)} ∈ E(X[Y]). Therefore, G ∈ End(X[Y]).x, y) ∈ V(IF), then G2) = G) = . If  ∉ V(IF), then G) ∈ V(IF). Thus G2) = G)) = G). Hence G ∈ Idpt(X[Y]). Clearly, IG = IF.If ]ρF = {, ,…, } for some , ,…,  ∈ V(X[Y]). In fact, it is easy to prove that ρF⊆ρG⊆ρF. Let ρF. Then, by the definition of G, we have G) = G) =  for some  ∈ V(IF) with F) = F = F). So ρG and thus ρF⊆ρG⊆ρF. Hence ρF = ρG.Suppose [ such that If = R. Let g ∈ End(R[Y]). Since R[Y] is not End-completely-regular, there exists g ∈ End(R[Y]) such that g is not completely regular. By g|Ig is not an automorphism of Ig. Thus there exist x1, x2 ∈ Ig with x1 ≠ x2 such that g(x1) = g(x2). Define a mapping F from V(X[Y]) to itself byF ∈ End(X[Y]) and IF = R[Y]. Now it is easy to see that gF ∈ End(X[Y]) and IgF = Ig. It follows from (gF)(x1) = (gF)(x2) that (gF)|IgF is not an automorphism of IgF. Hence X[Y] is not End-completely-regular.Let X and Y be two graphs. If at least one of X and Y is not End-completely-regular, then X ∪ Y is not End-completely-regular (where X ∪ Y is the disjoint union of X and Y).Let X is not End-completely-regular. By f ∈ End(X) such that f|If is not an automorphism of If. Define a mapping F from V(X ∪ Y) to itself byF ∈ End(X ∪ Y). Now it is easy to see that IF = If ∪ Y and F(x) = f(x) for any x ∈ V(X). Since f|If is not an automorphism of If, F|IF is not an automorphism of IF. Hence X ∪ Y is not End-completely-regular.Without loss of generality, we may suppose that X and Y be two bipartite graphs. Then X[Y] is End-completely-regular if and only ifX = K1 and Y is End-completely-regular orX is End-completely-regular and Y = K1 or K2.Let Sufficiency. Since K1[Y] = Y and X[K1] = X, we have immediately that K1[Y](X[K1]) is End-completely-regular if and only if Y(X) is End-completely-regular. If X = Y = K2, then X[Y] = K4. Thus End(X[Y]) is a group. Since any group is a completely regular semigroup, X[Y] is End-completely-regular. If X = 2K1 and Y = K2, then X[Y] = 2K2. By X[Y] is End-completely-regular for the following cases (see ases see .Case 1. X = P2 and Y = K2. Let f ∈ End(X[Y]). If [x1]ρf = {x1}, then [x2]ρf = {x2}. Otherwise, f(x2) = f(z1) or f(x2) = f(z2). Without loss of generality, we can suppose f(x2) = f(z1). Since z1 is adjacent to every vertex of {z2, y1, y2} and {x1, x2} ∈ E(X[Y]), f(z1) is adjacent to every vertex of {f(z2), f(y1), f(y2), f(x1)}. Note that there is no vertex in X[Y] adjacent to 4 vertices. This is a contradiction. Hence f ∈ Aut(X[Y]) and so f is completely regular. If [x1]ρf ≠ {x1}, then f(x1) = f(z1) or f(x1) = f(z2). Without loss of generality, we can suppose f(x1) = f(z1). Then f(x2) = f(z2). Otherwise, a similar argument as above will show that f(x1) is adjacent to every vertex of {f(x2), f(y1), f(y2), f(z2)}, which yield a contradiction. Thus If≅K4. Since any endomorphism f maps a clique to a clique of the same size, f(If) = If. By f is completely regular. Hence P2[K2] is End-completely-regular.Case 2. X = K1 ∪ K2 and Y = K2. Let f ∈ End(X[Y]). If [c1]ρf = {c1}, then [c2]ρf = {c2}. Otherwise, f(c2)∈{f(a1), f(a2), f(b1), f(b2)}. Without loss of generality, we can suppose f(c2) = f(a1). Since any endomorphism f maps a clique to a clique of the same size and there is only one clique of size 4 in X[Y], {f(a1), f(a2), f(b1), f(b2)} = {a1, a2, b1, b2}. Note that {c1, c2} ∈ E(X[Y]). Then {f(c1), f(c2)} = {f(c1), f(a1)}∈ E(X[Y]). Thus f(c1)∈{f(a1), f(a2), f(b1), f(b2)}, which is a contradiction. Clearly, [x]ρf = {x} for any x ∈ {a1, a2, b1, b2}. Hence f ∈ Aut(X[Y]) and so f is completely regular. If [c1]ρf ≠ {c1}, then f(c1) = f(t) for some t ∈ {a1, a2, b1, b2}. Without loss of generality, we can suppose f(c1) = f(a1). Then f(c2)∈{f(a2), f(b1), f(b2)}. Thus If≅K4. Hence f(If) = If and f is completely regular. Consequently, (K1 ∪ K2)[K2] is End-completely-regular.Case 3. X = 2K2 and Y = K2. Let f ∈ End(X[Y]). If [x]ρf = {x} for any x ∈ V(X[Y]), then f ∈ Aut(X[Y]) and so f is completely regular. If f(x) = f(y) for some x, y ∈ V(X[Y]) with x ≠ y, without loss of generality, we can suppose f(a1) = f(c1). Since b1, b2, c1, c2 is a clique of size 4 in X[Y], f(b1), f(b2), f(c1), f(c2) is also a clique of size 4 in X[Y]. Note that a2, d1, d2 are adjacent to a1. Then f(a2), f(d1), f(d2) are adjacent to f(a1) = f(c1). Thus f(a2), f(d1), f(d2)∈{f(b1), f(b2), f(c2)} and If≅K4. Hence f(If) = If and f is completely regular. Consequently, (2K2)[K2] is End-completely-regular. Necessity. We only need to show that X[Y] is not End-completely-regular in the following cases.Case 1  (X = K2). Then X[Y] = Y + Y. By K2[Y] is not End-completely-regular for the corresponding Y.Case 2  (X = P2). Then K2 is a retract of X. Since K2[Y] is not End-completely-regular for Y = P2, 2K1, 2K2, K1 ∪ K2, by P2[Y] is not End-completely-regular for the corresponding Y.Case 3  (X = 2K1). Then X[Y] = 2Y. If Y is bipartite, then X[Y] is also bipartite. By K1)[Y] is not End-completely-regular for the corresponding Y.Case 4  (X = 2K2). Then X[Y] = 2(Y + Y). Since Y + Y is not End-completely-regular for Y = P2, 2K1, 2K2, K1 ∪ K2, by K2)[Y] is not End-completely-regular for the corresponding Y.Case 5  (X = K1 ∪ K2). Then X[Y] = Y ∪ (Y + Y). Since Y + Y is not End-completely-regular for Y = P2, 2K1, 2K2, K1 ∪ K2, by K1 ∪ K2)[Y] is not End-completely-regular for the corresponding Y.X and Y under which X[Y] is End-inverse.Next we start to seek the conditions for a lexicographic product of bipartite graphs X and Y be two graphs. If X[Y] is End-inverse, then both X and Y are End-inverse.Let X[Y] is End-inverse, X[Y] is End-regular. By X and Y are End-regular. To show that X is End-inverse, we only need to prove that the idempotents of End(X) commute.Since f1 and f2 be two idempotents in End(X). Define two mappings g1 and g2 from V(X[Y]) to itself byg1 and g2 are two idempotents of End(X[Y]) and so g1g2 = g2g1, since X[Y] is End-inverse. For any  ∈ V(X[Y]), we havef1f2 = f2f1. Hence X is End-inverse.Let f3 and f4 be two idempotents in End(Y). Define two mappings g3 and g4 from V(X[Y]) to itself byg3 and g4 are two idempotents of End(X[Y]) and so g3g4 = g4g3, since X[Y] is End-inverse. For any  ∈ V(X[Y]), we havef3f4 = f4f3. Hence Y is End-inverse, as required.Similarly, let The next theorem characterizes the End-inverse lexicographic products of bipartite graphs.X and Y be two bipartite graphs. Then X[Y] is End-inverse if and only if X[Y] is one of K1[K1], K1[K2], K2[K1], and K2[K2].Let Necessity. This follows directly from Sufficiency. It is easy to see that K1[K1] = K1, K1[K2] = K2[K1] = K2, and K2[K2] = K4 are End-inverse, since they are unretractive.


The aromatic rings attached to the SO 14H13NO5S, was synthesized via a nucleophilic substitution reaction between 3,5-dimethylphenol and 2-nitrobenzenesulfonyl chloride. The aromatic rings attached to the SO3 group are oriented in a gauche fashion around the ester S—O bond, with a C—S—O—C torsion angle of 84.68 (11)°. The molecules form centrosymmetric dimers via π–π stacking interactions between 3,5-dimethylphenyl groups (centroid–centroid distance = 3.709 Å). An intermolecular S=O⋯N interaction between the sulfonyl and nitro groups, with an O⋯N distance of 2.9840 (18) Å, organizes the dimers into columns extending along [011]. These columns are further assembled into (111) layers through C—H⋯O interactions.The title compound, C Owing to steric hindrance between the ortho substituents of the benzene ring, the nitro group is twisted relative to the benzene best plane by 39.91 (2)°, so that the shortest contact of 2.7941 (16) Å between the O atoms of these groups is close to the sum of the van der Waals radii.In the title molecule Fig. 2, the O1=via intermolecular π–π stacking interactions between the relatively electron-rich C7–C12 benzene rings  layers. The geometry of these interactions is given in Table 1o-nitroarylsulfonyl moiety bonded to an aromatic ring through an ester linkage. These are CSD refcodes FEMQUK –103.43 (13)°. In each of these structures there are either intra- or intermolecular S=O⋯N interactions between the sulfonate and o-nitro groups.The Cambridge Structural Database  portion-wise. The mixture was stirred at 273 K for 30 mins and then at room temperature for 24 h. The product precipitated from the reaction mixture after sitting at 277 K for two weeks. The product was redissolved in dichloromethane, and the solvent was allowed to evaporate slowly to give large block-shaped crystals that were suitable for analysis by X-ray diffraction (m.p. 374–378 K).3,5-Dimethylphenol  was dissolved in chilled dichloromethane (25 ml). This was followed by the addition of pyridine . The resulting solution was cooled in an ice bath under an NUiso(H) = 1.2Ueq(C) for CH groups and 1.5Ueq(C) for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015015078/gk2639sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015015078/gk2639Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015015078/gk2639Isup3.cmlSupporting information file. DOI: 1418463CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure of a binuclear monocarboxylato dirhenium(III) complex with a fulvalene derivative is reported. This compound represents a radical cation salt containing a cluster unit with rhenium–rhenium quadruple bond. 10H8S8)[Re2Br6(CH3COO)]·0.5C2H3Cl3, contains one bis(ethylenedithio)tetrathiafulvalene (ET) radical cation, one μ2-acetato-bis[tribromidorhenate(III)] anion and a 1,1,2-trichloroethane molecule with half-occupancy disordered about a twofold rotation axis. The tetrathiafulvalene fragment adopts an almost planar configuration typical of the ET radical cation. The C atoms of both ethylenedithio fragments in the cation are disordered over two orientations with occupancy factors 0.65:0.35 and 0.77:0.23. In the anion, six Br atoms and a μ2-acetate ligand form a strongly distorted cubic O2Br6 coordination polyhedron around the Re2 dinuclear centre. In the crystal, centrosymmetrically related ET cations and Re2O2Br6 anions are linked into dimers by π–π stacking interactions [centroid-to-centroid distance = 3.826 (8) Å] and by pairs of additional Re⋯Br contacts [3.131 (3) Å], respectively. The dimers are further packed into a three-dimensional network by non-directional interionic electrostatic forces and by C—H⋯Br and C—H⋯S hydrogen bonds. The disordered 1,1,2-trichloroethane molecules occupy solvent-accessible channels along the b axis.The asymmetric unit of the title salt, (C Neither acetic acid nor acetate was used in the synthesis of this radical cation salt. Evidently, the acetate ligand arose by hydrolysis of CH3CN ] anions and 1,1,2-trichloroethane molecules in the stoichiometric molar ratio of 1:1:0.5. The solvent molecule is disordered over two orientations of equal occupancy about a twofold rotation axis intersecting the mid-point of the C—C ethane bond. The tetrathiafulvalene fragment adopts an almost planar configuration (r.m.s. deviation = 0.033 Å) that is typical for ET radical cations. The dihedral angle between the five-membered rings is 0.3 (6)°. The carbon atoms of both ethylenedithio fragments (C4/C5 and C9/C10) are disordered over two sets of sites with occupancy ratios of 0.65:0.35 and 0.77:0.23, respectively.The title compound Fig. 1 consistsIII atom is coordinated by three Br atoms forming ReBr3 units which are linked by a Re—Re multiple bond [2.2174 (10) Å] and a bridging μ2-acetate ligand, forming a strongly distorted cubic O2Br6 coordination polyhedron around the Re2 core. The length of the Re—Re bond is very close to the mean value of 2.222 Å for quadruple bonds –2.2731 (9) Å for compounds with no bridging ligands and in the range 2.2168 (8)–2.2532 (2) Å for compounds with O,O-bridging ligands  Å]. Cationic and anionic dimers are packed into a three-dimensional network by non-directional intermolecular electrostatic forces and by C—H⋯Br and C—H⋯S hydrogen bonds -hexachloridodirhenate anion exhibiting the same structure of the title compound  anion  in a two-electrode U-shaped glass cell with platinum electrodes. The initial current intensity of 0.1 µA was increased by 0.05 µA per day to a final value of 0.45 µA. A mixture of 1,1,2-trichloroethane/acetonitrile (12:1 v/v) was used as solvent. [(C4H9)4N]2[Re2Br8] (0.008 mol l−1) was used as electrolyte. After a period of 6–7 weeks, black shiny plate-shaped crystals of the title salt suitable for X-ray analysis were formed.The synthesis of the radical cation title salt was performed by galvanostatic anodic oxidation of ET (0.002 mol lUiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. The 1,1,2-trichloroethane molecule is disordered over two sets of sites about a twofold rotation axis with equal occupancy. The C4–C5 and C9–C10 groups of the ET cations are disordered over two orientations with occupancy factors of 0.65/0.35 and 0.77/0.23, respectively. These occupancies were initially obtained as free variables by the full-matrix refinement, and were then fixed in the final refinement cycles. The C—C and C—Cl bond lengths in the solvent molecule were constrained to be 1.52 (1) and 1.80 (1) Å, respectively, and the C—Cl bonds of the solvent molecule were restrained to have the same lengths to within 0.01 Å. The C—S and C—C bonds of the disordered fragments of the ET cation were also restrained to have the same lengths to within 0.005 Å. The atoms of each disordered fragment, including the solvent molecule, were restrained to have approximately the same displacement parameters to within 0.02–0.04 Å2. DELU restraints to within 0.01 Å2 were applied to atoms C4B, C5B, C9B, C10B, C1S and Cl2S. In addition, all non-hydrogen atoms of the solvent molecule were restrained to be approximately isotropic to within 0.03–0.06 Å2. Several outlier reflections (67) that were believed to be affected by the contribution of several unresolved minor twin domains were omitted from the final cycles of refinement, reducing the R factor from 0.061 to 0.052. Attempts to refine the structure using a two-component twin model were unsuccessful. Moreover, the crystals of the title compound are stable but show a strong tendency to splicing. The poor quality of the available crystal may account for the rather low bond precision of the C—C bonds and the presence of several large residual density peaks.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016006058/rz5188sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016006058/rz5188Isup2.hklStructure factors: contains datablock(s) I. DOI: 1473493CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


One O atom from the adjacent hydroxyimino-tosylhydrazone ligand bridges the CuII cation, forming the centrosymmetric dimeric complex. The cation is in an overall distorted N2O3 square-pyramidal coordination environment. The methylbenzene ring is twisted with respect to the hydrazine fragment, with a dihedral angle of 89.54 (9)° between the planes. An intramolecular C—H⋯O hydrogen bond occurs. In the crystal, molecules are linked by weak C—H⋯O and C—H⋯S interactions. Weak π–π stacking is also observed between parallel benzene rings of adjacent molecules, the centroid–centroid distance being 3.9592 (17) Å.In the title compound, [Cu DOI: 10.1107/S1600536814016651/xu5805Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814016651/xu5805fig1.tifx y z . DOI: x + 1,-y + 1,-z + 1The molecular structure of the title compound with labeling and displacement ellipsoids drawn at the 40% probability level showing the dimeric structure. Symmetry code: (i)-Click here for additional data file.10.1107/S1600536814016651/xu5805fig2.tifb . DOI: b-axis showing the column of the aromatic rings with very weak π–π interactions.Molecules of the title compound arranged along 1014769CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II ions through eight- and 12-membered rings, respectively, forming polymeric chains running along the a-axis direction.The asymmetric unit of the title zinc(II) coordination polymer contains two 4-nitrobenzoate (NB) anions and two nicotinamide (NA) ligands. Only one of the two NB anions and one of the two NA ligands bridge adjacent Zn 7H4NO4)2(C6H6N2O)2]n, contains two 4-nitrobenzoate (NB) anions and two nicotinamide (NA) ligands. The ZnII atom has a slightly distorted octahedral coordination sphere. In the equatorial plane, it is coordinated by three carboxylate O atoms of the NB anions and one O atom of one of the two NA ligands. The axial positions are occupied by the pyridine N atoms of the two NA ligands. In the two NB anions, the carboxylate groups are twisted away from the attached benzene rings by 13.8 (2) and 13.4 (2)°, while the benzene rings are oriented at a dihedral angle of 11.5 (2)°. The dihedral angle between the NA rings is 10.3 (1)°. Only one of the two NB anions and one of the two NA ligands bridge adjacent ZnII ions through eight- and twelve-membered rings, respectively, forming polymeric chains running along the a-axis direction. In the crystal, N—H ⋯ O hydrogen bonds link adjacent chains, enclosing R(16), R22(20) and R66(16) ring motifs, forming layers parallel to (01-1). The layers are linked via a number of C—H⋯O hydrogen bonds, forming a three-dimensional network.The asymmetric unit of the title coordination polymer, [Zn(C N,N-diethylnicotinamide (DENA) is an important respiratory stimulant  is one form of niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels , 5.855 (4), 4.480 (3) Å and 4.67 (6), 3.668 (4), 4.256 (4) Å, respectively ; see Fig. 3The asymmetric unit of the title polymeric compound contains two 4-nitrobenzoate (NB) anions and two nicotinamide (NA) ligands; the NB anions act as monodentate ligands Fig. 1. Only onon Fig. 2. In the II cation form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two pyridine N atoms (N3 and N5) of the two NA ligands in the axial positions  of the three NB anions and one O atom (O10) of one of the two NA ligands in the equatorial plane around the Zns Table 1.carboxylate and Zn—N distances are 2.147 (2) Å and 2.285 (3) Å, respectively, while Zn1—O10 distance is 2.280 (2) Å. The Zn1 atom lies 1.4330 (4) Å and 0.1897 (4) Å above the planar (O1/O2/C1) and (O5/O6/C8) carboxylate groups, respectively. The average O—Zn—O and O—Zn—N bond angles are 89.93 (10) and 89.99 (10)°, respectively.The near equality of the C1—O1 [1.247 (4) Å], C1—O2 [1.261 (4) Å], C8—O5 [1.248 (4) Å] and C8—O6 [1.255 (4) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The average Zn—OA (C2—C7) and B (C9—C14)] are 13.8 (2) and 13.4 (2)°, respectively, while the benzene rings are oriented at a dihedral angle of 11.5 (2)°. The dihedral angle between the nicotinamide rings [C (N3/C15—C19) and D (N5/C21—C25)] is 10.3 (1)°, and they are oriented with respect to benzene rings A and B at dihedral angles of A/C = 17.3 (1), A/D = 7.7 (1), B/C = 28.8 (1) and B/D = 18.9 (1)°.The dihedral angles between the planar carboxylate groups [(O1/O2/C1) and (O5/O6/C8)] and the adjacent benzene rings [c (c = carboxylate) and N—H⋯On (n = nicotinamide) hydrogen bonds (Table 2R(16), et al., 1995n⋯Oc and intermolecular C—Hn⋯Onb (nb = nitrobenzoate) and C—Hn⋯On hydrogen bonds  Fig. 4. Weak ins Table 1 link the4·H2O  in H2O (25 ml) and nicotinamide  in H2O (25 ml) with sodium 4-nitrobenzoate  in H2O (150 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving yellow block-like crystals.The title compound was prepared by the reaction of ZnSOUiso(H) = 1.2Ueq. The highest residual electron density and the deepest hole were found 0.29 Å and 0.48 Å from atoms N6 and Zn1, respectively.The experimental details including the crystal data, data collection and refinement are summarized in Table 310.1107/S2056989015006490/su5099sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015006490/su5099Isup2.hklStructure factors: contains datablock(s) I. DOI: 1057121CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


H,3H,5H)-trione, which crystallized with two molecules in its asymmetric unit along with two solvent water molecules. A hydrogen-bonded sheet is formed by a combination of N—H⋯O and Owater—H⋯O hydrogen bonds, which are further interconnected by C—H⋯πaryl interactions, leading to a three-dimensional supramolecular architecture.Reaction of 4-methyl benzyl chloride with barbituric acid gave 5,5-bis(4-methylbenzyl)pyrimidine-2,4,6, with similar conformations and two independent water molecules. In the crystal, N—H⋯O and Owater—H⋯O hydrogen bonds link all moieties into two crystallographically independent kinds of sheets parallel to the ac plane. These independent sheets, each containing either A or B molecules, are further alternately stacked along the b axis and interconnected via C—H⋯πaryl interactions.The asymmetric unit of the title compound, C In B, the corresponding angles are 50.44 (18), 69.90 (19) and 59.8 (2)°, respectively. In the related compound 5,5-dibenzylbarbituric acid monohydrate (II) via strong N2—HN2⋯O4 (A) and N3—HN3⋯O7 (B) hydrogen bonds C(6). Six chains pass through the unit cell. These chains are linked via water molecules through N1—H1⋯O1 and O1—H1B⋯O5 (for A) and N4—HN4⋯O2 and O2—H2A⋯O8 (for B) hydrogen bonds (Table 1D(2). In addition, the symmetry-dependent parallel chains are interconnected via bridging water molecules through O—H⋯O3 and O1—HIB⋯O5 (for A) and O2—H2B⋯O6 and O2—H2A⋯O8 (for B) hydrogen bonds  crystallizes in the monoclinic space group P21/n. Secondly, (I)There are several interesting differences between the two chemically closely related structures (I)To an ice-cooled stirring solution of acetonitrile (5 ml), 4-methyl benzyl chloride , 1,8-diazabicycloundec-7-ene (DBU)  and barbituric acid  were added. The reaction mixture was stirred to the room temperature and then refluxed for 8 h. Thin-layer chromatography showed the absence of any starting material. The reaction mixture was cooled and poured into ice-cold water. The solid obtained was extracted with ethyl acetate and the organic layer was washed with saturated ammonium chloride solution and dried over anhydrous sodium sulphate. The solvent was removed under reduced pressure to give the title compound as a white solid .Colourless prisms of the title compound suitable for diffraction studies were grown from an ethyl acetate–petroleum ether solvent system in the ratio 2.5:7.5, by the solvent evaporation technique.Ueq(C) for methyl H atoms and = 1.2Ueq for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901402619X/cv5478sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901402619X/cv5478Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901402619X/cv5478Isup3.cmlSupporting information file. DOI: 1036677CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds link the molecular components, enclosing In the title salt, [Zn(C 8H4NO2)(C6H6N2O)(H2O)3](C8H4NO2), contains one complex cation and one 4-cyanobenzoate (CNB) counter-anion. The ZnII atom in the cation is coordinated by one 4-cyanobenzoate ligand, one nicotinamide (NA) ligand and three water molecules, the CNB anion thereby coordinating in a bidentate O,O′-mode through the carboxylate group. The latter, together with one water O atom and the N atom of the NA ligand, form a distorted square-planar arrangement, while the considerably distorted octahedral coordination sphere of the ZnII atom is completed by the two O atoms of additional water molecules in the axial positions. The dihedral angles between the planar carboxylate groups and the adjacent benzene rings in the two anions are 10.25 (10) and 5.89 (14)°. Intermolecular O—H⋯O hydrogen bonds link two of the coordinating water molecules to two free CNB anions. In the crystal, further hydrogen-bonding interactions are present, namely N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds that link the molecular components, enclosing R22(12), R33(8) and R33(9) ring motifs and forming layers parallel to (001). π–π contacts between benzene rings [centroid-to-centroid distances = 3.791 (1) and 3.882 (1) Å] may further stabilize the crystal structure.The asymmetric unit of the title salt, [Zn(C N,N-diethylnicotinamide (DENA), an important respiratory stimulant , one form of niacin (C6H6ON2)(H2O)3](C8H4O2N), is composed of one complex cation and one 4-cyanobenzoate (CNB) counter-anion. The ZnII atom is coordinated by one 4-cyanobenzoate (CNB) anion, one nicotinamide (NA) ligand and three water molecules, the CNB anion and NA ligand coordinating in bidentate and monodentate modes, respectively  in the axial positions  around the Zn1 atom show a distorted square-planar arrangement, while the considerably distorted octahedral coordination environment of Zns Table 1.9H10NO2)(C6H6N2O)·2H2O] (C6H6N2O)]·H2O 2(C6H6N2O)]  Å], C1—O2 [1.2591 (19) Å] and C15—O7 [1.266 (2) Å], C15—O8 [1.237 (2) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The average Zn—O bond lengths are 2.19 (11) Å for benzoate oxygen atoms and 2.10 (9) Å for water oxygen atoms; the Zn—N bond length is 2.0545 (12) Å, close to the values in related structures. The Zn1 atom lies 0.0093 (2) Å above the planar (O1/O2/C1) carboxylate group, with a bite angle of 59.48 (4)°. Corresponding O—Zn—O angles are 60.03 (6)° in [Zn(CA (C2–C7) and C (C16–C21)] are 10.25 (10) and 5.89 (14)°, respectively, while the benzene rings and benzene and pyridine [B (N2/C9—13)] rings are oriented at dihedral angles of A/C = 77.84 (6), A/B = 8.97 (5) and B/C = 71.43 (5)°.The dihedral angles between the planar carboxylate groups [(O1/O2/C1) and (O7/O8/C15)] and the adjacent benzene rings , may further stabilize the structure, with centroid-to-centroid distances of 3.791 (1) Å and 3.882 (1) Å, respectively.In the crystal, N—H⋯Os Table 2 link the4·7H2O  in H2O (30 ml) and nicotinamide  in H2O (50 ml) with sodium 4-cyanobenzoate  in H2O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving colourless single crystals.The title compound was prepared by the reaction of ZnSO2 group) and H41, H42, H51, H52, H61 and H62 (as part of the water molecules) were located in a difference Fourier map and were refined freely. The aromatic C-bound H atoms were positioned geometrically with C—H = 0.93 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).The experimental details including the crystal data, data collection and refinement are summarized in Table 310.1107/S2056989015009743/wm5158sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015009743/wm5158Isup2.hklStructure factors: contains datablock(s) I. DOI: 1401948CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports6: Article number: 2019910.1038/srep20199; published online: 02012016; updated: 04202016.This Article contains typographical errors in in the Methods section.Kα radiation was used with the X-ray source that was run at 14.5 kV. The energy analyzer operated at a constant pass energy of 50 eV. Since the XPS detectable depth for Fe 2p and Pt 4f electrons are only 5.19 nm and 4.17 nm43, the NiTi(Nb)-SMA/L10-FePt(3 nm)/Ta(5 nm) samples with different elastic strain treatments were designed for the XPS tests.”“Mg should read:Kα radiation was used with the X-ray source that was run at 14.5 kV. The energy analyzer operated at a constant pass energy of 50 eV. Since the XPS detectable depth for Fe 2p and Pt 4f electrons are only 3.9 nm and 3.2 nm43, the NiTi(Nb)-SMA/L10-FePt(3 nm)/Ta(5 nm) samples with different elastic strain treatments were designed for the XPS tests.”“Al


The supramolecular interactions between cations and anions lead to a two-dimensional network structure parallel to (001).The complex cation of the title salt, (C9H6NO3S)2. In its crystal structure, the complex cation [Cd(TEA)2]2+ and two independent NBTA− units with essentially similar geometries and conformations are present. In the complex cation, each TEA molecule behaves as an N,O,O′,O′′-tetradentate ligand, giving rise to an eight-coordinate CdII ion with a bicapped trigonal–prismatic configuration. All ethanol groups of each TEA molecule form three five-membered chelate rings around the CdII ion. The Cd—O and Cd—N distances are in the ranges 2.392 (2)–2.478 (2) and 2.465 (2)–2.475 (3) Å, respectively. O—H⋯O hydrogen bonds between the TEA hydroxy groups and carboxylate O atoms connect cationic and anionic moieties into chains parallel to [110]. Each NBTA− anion is additionally linked to a symmetry-related anion through π–π stacking interactions between the benzene and thiazoline rings [minimum centroid-to-centroid separation = 3.604 (2) Å]. Together with additional C—H⋯O interactions, these establish a double-layer polymeric network parallel to (001).The reaction of 2-acetic acid (NBTA) and triethanolamine (TEA) with Cd(CH The N—Cd—O bond angles range from 68.58 (8) to 122.59 (10)° and the O—Cd—O angles are in an interval of 72.54 (9) to 162.13 (11)°. Both thiazoline rings (C1/C6/N1/C7/S1 and C1A/C6A/N1A/C7A/S1A) and bicyclic benzothiazole units (N1/S1/C1–C7 and (N1A/S1A/C1A–C7A) are close to planar, the largest deviations from the least-squares planes being 0.002 (2), 0.004 (2) and 0.008 (3), 0.005 (3) Å, respectively. The dihedral angles between the plane of the carboxylate group and the attached benzothiazole ring system are 77.895 (3) and 71.408 (3)° in the two anions.The structure of the molecular entities of (I)− anions into a chain structure extending parallel to [110], whereby each cation is surrounded by four NBTA− anions. The H atoms of all hydroxyl groups of the TEA ligands form a hydrogen bond with a carboxylate O atom of the NBTA− ions. In addition, there is weak hydrogen bond between one –CH2 group and the O1 atom of the NBTA anion, with a C⋯O distance of 3.282 (6)Å  and thiazoline rings (centroid Cg2) of adjacent inversion-related molecules [Cg1⋯Cg2  = 3.604 (2) Å] Å Table 1. The abofs Fig. 2. The NBTÅ] Fig. 3. Togethes-, d-, p-, and f-block elements have been reported. Structures containing the [Cd(TEA)2]2+ cation are deposited in the CSD with reference codes EYIPAD, MEVQIN and YOVBIU.A survey of the Cambridge Structural Database 2  was slowly added an ethanolic solution (5 ml) containing TEA (132 µl) and NBT  under constant stirring. A bright-yellow crystalline product was obtained at room temperature by solvent evaporation after four weeks. Yield: 75%; calculated for C30H42CdN4O12S2: C, 43.56; H, 5.12; N, 6.77, found: C, 43.61; H, 5.15; N, 6.69To an aqueous solution (2.5 ml) of Cd(CHUiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016004515/wm5280sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016004515/wm5280Isup2.hklStructure factors: contains datablock(s) I. DOI: 1468939CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The corresponding coordination polyhedron is a distorted trigonal bipyramid, with Cd—Cl distances in the range 2.4829 (4)–2.6402 (4) Å. The bipyramids are condensed into a polyanionic zigzag chain extending parallel to [101]. The tetramethylguanidinium cations are situated between the polyanionic chains and are linked to them through N—H⋯Cl hydrogen bonds, forming a layered network parallel to (010).In the structure of the title salt, {(C Several cationic complexes of Pd, Ga and Pt have been reported with tetramethylguanidine acting as a ligand  x, y, 1 − z] are in axial positions with a Cl3—Cd1—Cl4i angle of 166.347 (10)°. The equatorial Cd—Cl bond lengths range from 2.4829 (4) Å to 2.5829 (4) Å while the axial bond lengths Cd1—Cl3 and Cd1—Cl4i are 2.5854 (4) Å and 2.6403 (4) Å, respectively. The CdCl4 moieties of the asymmetric unit are related by an inversion center, generating an extended zigzag chain of edge-sharing trigonal bipyramids running parallel to [101]. These 1∞[CdCl4/2Cl1/1]− chains are formed by the bridging atoms Cl2, Cl3, Cl4 and Cl4i with a Cd—Cd—Cd angle of 137.893 (6)°. The corrugation of the chains results in rather short Cd⋯Cd distances of 3.8720 (3) and 3.8026 (3) Å. The same kind of zigzag chain is found, for example, in the [CdCl3]− salt obtained with benzyltriethylammonium as counter-cation ° in the structure of the benzyltriethylammonium compound compared with 129.859 (2)° for the present structure. The tetramethylguanidinium cation has the central atom C1 in an almost trigonal–planar configuration. The three N—C—N angles range from 119.26 (14) to 121.14 (14)° and the r.m.s deviation from the least-squares plane calculated with atoms C1, N1, N2 and N3 is only 0.005 Å. The corresponding C—N bond lengths of 1.330 (2), 1.3360 (19), and 1.3441 (19) Å indicate a partial double-bond character. Hence the positive charge may be considered as delocalized in the CN3 plane 1∞[CdCl4/2Cl1/1]− chains are interconnected through N—H⋯·Cl hydrogen bonds by pairs of tetramethylguanidinium cations linked to symmetry-related Cl1 atoms  = 1.5Ueq(C). H atoms bonded to the N atoms were located from a Fourier difference map and were refined freely.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015020836/wm5207sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015020836/wm5207Isup2.hklStructure factors: contains datablock(s) I. DOI: 1434977CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, molecules are linked via pairs of O—H⋯O hydrogen bonds, involving the boronic acid OH groups, forming inversion dimers. The dimers are linked via O—H⋯O hydrogen bonds, involving a boronic acid OH group and the carbonyl O atom, forming undulating sheets parallel to (10-2). Within the sheets there are also C—H⋯O hydrogen bonds present, also involving the carbonyl O atom. The sheets are linked via C—H⋯π and offset face-to-face π-interactions between inversion-related molecules , forming a three-dimensional structure.In the title compound, C The unit cell consists of four molecular units which form π-aggregated pairs in a head-to-tail fashion and are stabilized through offset face-to-face π-interactions ; see Fig. 4A of the boronic acid is in an inversion-related hydrogen-bonded network with the oxygen O2 of the boronic acid at a distance of 2.762 (1) Å, forming a head-to-head hydrogen-bonded network with adjacent molecules (2-methylimidazolyl)boronate monohydrate, tris(4-(dimethylamino)pyridinium) bis(4-(dimethylamino)pyridine) tris(4-carboxybenzeneboronate) trihydrate and 4-acetylpyridine oxime 4-carboxybenzeneboronate dihydrate which presented out-of-plane tilt angles of ca 10.45–27.74° and O—B—O bond angles of ca 114.23–124.94°  bis(4-carboxylatophenylboronic acid) tetrahydrate, where M is nickel, manganese or cobalt. These structures where similar to the title compound and exhibited similar characteristics for the O—B—O bond angle and the out-of-plane tilt of the carboxyl acid group compared to the title compound. The carboxylic group deviated from the plane with an angle of ca 3.40–4.53° and the O—B—O bond angles were in the range of ca 121.43–122.18°  4-(dihydroxyboryl)benzoic acid monohydrate exhibited a tilt angle of ca 2.14° for the carboxylic group and an O—B—O bond angle of ca 126.53° . The compound was then crystallized from a solution of 1% MeOH in CH2Cl2 layered with hexane to give a single crystal suitable for X-ray diffraction.The compound was purchased from Alfa Aesar and was purified with silica gel column chromatography using CHUiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Uiso(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015015923/su5188sup1.cifCrystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S2056989015015923/su5188Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015015923/su5188Isup3.cmlSupporting information file. DOI: 1416885CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The grid layers are held together by hydrogen bonds between the organic guest molecules and the host framework and gives rise to a three-dimensional supramolecular architecture.{[Fe(H 2Fe(CN)4(H2O)2]·2C12H10N2}n, the asymmetric unit contains one FeII cation, two water molecules, two dicyanidoargentate(I) anions and two uncoordinating 1,2-bis(pyridin-2-yl)ethylene  molecules. Each FeII atom is six-coordinated in a nearly regular octahedral geometry by four N atoms from dicyanidoargentate(I) bridges and two coordinating water molecules. The FeII atoms are bridged by dicyanidoargentate(I) units to give a two-dimensional layer with square-grid spaces. The intergrid spaces with interlayer distance of 6.550 (2) Å are occupied by 2,2′-bpe guest molecules which form O—H⋯N hydrogen bonds to the host layers. This leads to an extended three-dimensional supramolecular architecture. The structure of the title compound is compared with some related compounds containing dicyanidoargentate(I) ligands and N-donor organic co-ligands.In the title compound, {[Ag These structural properties lead to potential interesting applications in the filed of magnetism, sensing, porous materials and catalysis 4(H2O)2]·2C12H10N2}n, (I)One-, two- and three-dimensional frameworks containing dicyanidoargentate(I) and N-donor linkers such as pyrazine, 4,4′-bpy and 4,4′-bpe  ligands have been studied  ligands, two water molecules and two uncoordinating 2,2′-bpe molecules  ligands and two water molecules.The asymmetric unit consists of one Fees Fig. 1. Ag1 andÅ2 Fig. 2. The FeIW⋯N5 = 2.07 Å and O2–H4W⋯N6 = 2.09 Å) , while the other two arrange themselves across the host layer to form also hydrogen bonds (O1—H1W⋯N7 = 2.14 Å and O2—H3W⋯N8 = 2.15 Å)  to the host layers. These hydrogen bonds generate an extended three-dimensional supramolecular framework.Four independent 2,2′-bpe molecules are located between adjacent grid layers of which two are parallel (blue) to the grid layers and two non-parallel (red) Fig. 3. The intÅ) Fig. 4a, whileÅ) Fig. 4b to the4[Ag(CN)2]2]n (imH = imidazole), a one-dimensional chain via bridging dicyanidoargentate(I) is found, while all imidazole molecules act as a terminal ligand 2]2]n (3-Fpy = 3-fluoropyridine) consists of four cyanide moieties occupying the equatorial positions generating a square grid-type structure similar to that of the title compound, while the axial positions are occupied by two terminal 3-Fpy ligands instead of two water molecules in (I)et al., 20072]2].pz}n (pz = pyrazine), [Mn2[Ag(CN)2]2]n, [Fe2[Ag(CN)2]2]n and [Fe(bpe)2[Ag(CN)2]2]n 2]  was added dropwise to an MeOH–H2O mixed solution  of (NH4)2[Fe(SO4)2]·6H2O  and 2,2′-bpe  at room temperature. After filtration and slow evaporation for 1 d, yellow crystals were obtained.An aqueous solution (5 ml) of K[Ag(CN)isoU(H) = 1.2eqU(C). Water H atoms were located in difference Fourier maps and refined isotropically.Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S1600536814016250/vn2085sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814016250/vn2085Isup2.hklStructure factors: contains datablock(s) I. DOI: 1013775CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In this manuscript the molecular and supramolecular structure of 2′,3,6′-trichlorobiphenyl-2-ylboronic acid tetrahydrofuran monosolvate is presented 12H8BCl3O2·C4H8O, crystallizes as a tetrahydrofuran monosolvate. The boronic acid group adopts a syn–anti conformation and is significantly twisted along the carbon–boron bond by 69.2 (1)°, due to considerable steric hindrance from the 2′,6′-dichlorophenyl group that is located ortho to the boronic acid substituent. The phenyl rings of the biphenyl are almost perpendicular to one another, with a dihedral angle of 87.9 (1)° between them. In the crystal, adjacent molecules are linked via O—H⋯O interactions to form centrosymmetric dimers with R22(8) motifs, which have recently been shown to be energetically very favourable. The hydroxy groups are in an anti conformation and are also engaged in hydrogen-bonding interactions with the O atom of the tetrahydrofuran solvent molecule. Cl⋯Cl halogen-bonding interactions [Cl⋯Cl = 3.464 (1) Å] link neigbouring dimers into chains running along [010]. Further aggregation occurs due to an additional Cl⋯Cl halogen bond [Cl⋯Cl = 3.387 (1) Å].The title compound, C In the structure of the related (2-biphenylyl)boronic acid °], whereas in (2-biphenylyl)boronic acid they are rotated by only 48.4 or 45.4° for the two unique molecules in the asymmetric unit.The B—C [1.5907 (16) Å] and B—O  bonds in the title compound (I)on Fig. 1. The boranti-oriented OH group is engaged in an intermolecular O—H⋯O hydrogen bond  Å; the sum of the van der Waals radii for Cl is 3.50 Å]. In terms of geometry of this contact, it can be classified as a type I halogen bond ,  Å] .In the crystal, centrosymmetric O—H⋯O hydrogen-bonded dimers are formed. The d Table 1 with thend Fig. 2a,  A solution of 2-iodo-2′,3,6′-trichlorobiphenyl  in THF (50 mL) was added to a stirred solution of n-BuLi (10 mmol) in THF (30 mL) at 195 K. The resulting colorless solution was stirred for 1 h to give a colorless precipitate. The electrophile, B(OMe)3  was then added to the stirred mixture to give a colorless solution which was stirred for 1 h and then hydrolyzed with H2O (100 mL). Dilute aq. H2SO4 was added until the pH was slightly acidic. Et2O (50 mL) was next added and the mixture stirred for 10 min. The organic phase was separated and the aqueous phase was extracted with Et2O (20 mL). The combined organic solutions were dried over MgSO4 and evaporated to give a colorless precipitate, yield 2.0 g (66%). 1H NMR : δ = 8.00 , 7.51 , 7.39 , 7.05 ;13C{1H} NMR : δ = 141.49, 139.62, 139 (br), 136.17, 134.84, 130.49, 129.99, 128.24, 128.14, 127.53.Crystals suitable for X-ray diffraction analysis were grown by slow evaporation of a THF solution.Uiso(phenyl H) = 1.2Ueq(C). The positions of the OH hydrogen atoms were first found in a difference map. Then their bond lengths were restrained in the last least-squares cycles, with an O—H distance of 0.85 Å and their coordinates refined with Uiso(hydroxyl H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901502054X/sj5482sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901502054X/sj5482Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901502054X/sj5482Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S205698901502054X/sj5482Isup4.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S205698901502054X/sj5482Isup5.cmlSupporting information file. DOI: 1434205CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Eight O—H⋯O hydrogen bonds [d(O⋯H) < 2.00 Å], form a two-dimensional network parallel to the ab plane.In the crystal structure of the title compound, [Fe(dmbpy)(H 12H12N2)(H2O)4]SO4, the central FeII ion is coordinated by two N atoms from the 5,5′-dimethyl-2,2′-bipyridine ligand and four water O atoms in a distorted octahedral geometry. The Fe—O coordination bond lengths vary from 2.080 (3) to 2.110 (3) Å, while the two Fe—N coordination bonds have practically identical lengths [2.175 (3) and 2.177 (3) Å]. The chelating N—Fe—N angle of 75.6 (1)° shows the largest deviation from an ideal octahedral geometry; the other coordination angles deviate from ideal values by 0.1 (1) to 9.1 (1)°. O—H⋯O hydrogen bonding between the four aqua ligands of the cationic complex and four O-atom acceptors of the anion leads to the formation of layers parallel to the ab plane. Neighbouring layers further interact by means of C—H⋯O and π–π interactions involving the laterally positioned bipyridine rings. The perpendicular distance between π–π interacting rings is 3.365 (2) Å, with a centroid–centroid distance of 3.702 (3) Å.In the title compound, [Fe(C The FeII atom is in a distorted octahedral coordination environment and the equatorial plane of the octahedron is formed by a pair of nitrogen donors from the 5,5′-dimethyl-2,2′-bipyridyl ligand and two molecules of water, while the axial sites are occupied by two other water molecules. The equatorial donor atoms are nearly coplanar (r.m.s. deviation = 0.0062 Å), while the deviation of the Fe atom from the least-squares plane is somewhat larger [0.021 (2) Å]. The bipyridine chelating angle N1—Fe—N2 of 75.6 (1)° shows the most significant deviation from an ideal octahedral geometry. The other angular distortions from an ideal octahedral geometry are in the range 0.1 (1) to 9.1 (1)°. The S—O bond lengths [1.466 (3)–1.480 (3) Å] and O—S—O angles [108.8 (2)–109.9 (2)°] indicate a nearly ideal tetrahedral geometry for the anion.A molecular view of complex (I)2O)4]2+ cations engages all four coordinating water molecules in hydrogen bonding to four [SO4]2− anions . The anions surrounding the cationic unit are positioned at similar Fe⋯S distance of 4]2− anions appears surrounded with four cationic units, where its four O atoms engage as acceptors in bifurcated O—H⋯O hydrogen bonds towards neighbouring cations . Such a mutual arrangement leads to the formation of a two-dimensional hydrogen-bonded network parallel to the ab plane . Laterally arranged aromatic rings of the 5,5′-dimethyl-2,2′-bipyridine ligand in neighbouring layers interact by means of weak C—H⋯O and π–π interactions, forming the three-dimensional crystal packing  in water–ethanol . The mixture was transferred to a Teflon-lined autoclave and heated at 410 K for 3 d. The autoclave was then allowed to cool to ambient temperature. Red crystals of (I)The title compound, (I)Uiso(H) values were equal to 1.2 and 1.5 times Ueq of the corresponding C(sp2) and C(sp3) atoms. The H atoms of the four water molecules were initially located in a difference Fourier map. During the refinement, these H atoms were allowed to ride on their parent O atoms and also to rotate about the corresponding Fe—O bonds. The Uiso(H) values were set equal to 1.2 times Ueq of the parent O atom. The reflections (100) and (002) were excluded from the refinement because they were nearly completely obscured by the beamstop.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814024982/vn2087sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814024982/vn2087Isup2.hklStructure factors: contains datablock(s) I. DOI: 1034106CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The core is decorated by four triphenylphosphine ligands bonded to the AgI cations. Ag⋯Ag distances as short as 3.133 (9) Å suggest the presence of argentophilic (d10⋯d10) interactions.In the title compound a distorted Ag 6H5)3P]Ag}4{NCO}4], a distorted Ag4N4-heterocubane core is set up by four AgI ions being coordinated by the N atoms of the cyanato anions in a μ3-bridging mode. In addition, a triphenylphosphine ligand is datively bonded to each of the AgI ions. Intramolecular Ag⋯Ag distances as short as 3.133 (9) Å suggest the presence of argentophilic (d10⋯d10) interactions. Five moderate-to-weak C—H⋯O hydrogen-bonding interactions are observed in the crystal structure, spanning a three-dimensional network. A region of electron density was treated with the SQUEEZE procedure in PLATON  following unsuccessful attempts to model it as being part of disordered tetrahydrofuran solvent molecules. The given chemical formula and other crystal data do not take into account these solvent molecules.In the title compound, [{[(C The characterization of the crystals obtained by X-ray diffraction, NMR and IR spectroscopy is in accordance with the formation of the title compound, [{((C6H5)3P)Ag}4{NCO}4], (I)To get access to a large range of metal allophanates 3 moieties. However, the respective components of both disordered Ag(PPh3) units share one phenyl ring (C41–C46 and C59–C64). The Ag4N4-heterocubane is distorted which is reflected by the variation of the Ag—N distances in the range 2.273 (13)–2.605 (12) Å. Likewise, the Ag—N—Ag [78.7 (3) – 98.5 (3)°] and N—Ag—N [80.9 (3) – 98.5 (3)°] angles significantly deviate from 90°. The Ag2N2-faces of the Ag4N4-core are not planar [r.m.s. deviations in the range 0.0293  to 0.1947 Å ], however, the opposing least-squares planes are almost parallel [angles between planes: 0.40 (3) and 3.2 (3)°]. Opposing planes are twisted by some degrees relative to each other, which is reflected by the Ag—N—Ag—N and N—Ag—N—Ag torsion angles ranging from 2.8 (3)–19.4 (3)°. As a result of the distortion of the Ag4N4-core, the Ag⋯Ag and N⋯N separations differ significantly. The shortest distances are observed between Ag1 and Ag2 as well as Ag3/Ag3′ and Ag4/Ag4′ (Table 1I(PPh3) fragment. The scattering contributions of two severely disordered THF solvent molecules were treated with the SQUEEZE procedure in PLATON ·0.25THF. This discrepancy may be due to a facile evaporation of the co-crystallized solvent under reduced pressure.The title compound consists of a Agde Fig. 1. Each Ag′ Table 1. Conside′ Table 1 a weak a′ Table 1. The Ag—Five moderate-to-weak C—H⋯O hydrogen bonds  in the CSD database μ3-κN coordination of the cyanate anions towards AgI has been described for five compounds only  in anhydrous ethanol (40 ml), was added at 273 K ethyl allophanate . The reaction was heated to reflux overnight. The colourless precipitate formed was filtered off, washed thrice with ethanol (each 20 ml) and dried under vacuum (yield: 850 mg). The resulting solid material (407 mg) was dissolved in water (20 ml) and was added dropwise to a solution of silver nitrate  in water (15 ml). The suspension obtained was stirred at ambient temperature overnight. Filtration afforded a colourless solid, which was washed with cold water (20 ml) and dried under vacuum (yield: 250 mg). A suspension of this solid (120 mg) in anhydrous THF (20 ml) was treated with PPh3  at 273 K. After stirring overnight at this temperature, the reaction mixture was filtered through a pad of celite. Removal of all volatiles under reduced pressure afforded a pale purple solid . Colourless crystals of (I)To a solution of sodium ethanolate in ethanol, generated 1H NMR : δ = 7.40–7.28 . 13C{1H} NMR : δ = 134.0 , 132.1 , 130.4 , 129.1 . The resonance signal of the cyanate carbon atom is not observed under the measurement conditions applied. 31P{1H} NMR : δ = 9.0 (s). IR : ν = 3449 (w), 3356 (w), 2170 , 1603 (w), 1429 (w), 1388 (w), 1300 (m), 1206 (m), 638 (m).M.p. 458 K (decomp.). viz. (240), (Uiso(H) = 1.2Ueq(C) and a C—H distance of 0.93 Å. Atoms Ag3 and Ag4 and two of the four P atoms of the PPh3 moieties with attached phenyl rings are disordered over two sets of sites, with occupancy ratios of 0.54 (4):0.46 (4) and 0.55 (2):0.45 (2), respectively. A phenyl ring of another PPh3 moiety is likewise disordered over two sets of sites in a 0.67 (5):0.33 (5) ratio. The disordered phenyl rings were treated by rigid-group refinements. If necessary, the respective C—P distances were restrained to 1.85 (2) Å. Anisotropic displacement parameters of all atoms were restrained using enhanced rigid-bond restraints  I, New_Global_Publ_Block. DOI: 10.1107/S2056989015017636/wm5201Isup2.hklStructure factors: contains datablock(s) I. DOI: 1426238CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Fdd2 space group. Instead, there are two molecules in the asymmetric unit, and both of them display a pseudo-trans conformation.The title compound was obtained in crystalline form after preparative HPLC. Conformation of the proposed molecular structure was obtained by single-crystal X-ray analysis at 173 K. The molecules do not take advantage of the twofold axis provided as an available symmetry option by the  14H16N2S3, crystallized with two independent molecules [(1a) and (1b)] in the asymmetric unit. Both molecules display a pseudo-trans conformation. The two consecutive S—S bond lengths of the trisulfane unit of molecule (1a) are 2.06 (3) and 2.08 (3) Å, and 2.08 (3) and 2.07 (2) Å for molecule (1b). Torsion angles about each of the two S—S bonds are 86.6 (2) and 87.0 (2)° for (1a), and −84.6 (2) and −85.9 (2)° for (1b). The core atoms, viz. the N—S—S—S—N moiety, of the two molecules superimpose well if one is inverted on the other, but the phenyl groups do not. Thus, the two units are essentially conformational enantiomers. In molecule (1a), the two phenyl rings are inclined to one another by 86.7 (3)°, and in molecule (1b), by 81.1 (3)°. In the crystal, molecules are linked via C—H⋯π interactions, forming sheets lying parallel to (010).The title compound, C The molecules do not take advantage of the twofold axis provided as an available symmetry option by the Fdd2 space group. Instead, there are two molecules, (1a) and (1b), in the asymmetric unit . All bond distances and angles in both molecules are within expected ranges. Selected geometric parameters for compound (1) are given in Table 11a) are 2.064 (3) and 2.078 (3) Å, and for molecule (1b) are 2.076 (3) and 2.067 (2) Å. These values are similar to the value of 2.07 Å reported for the S—S bond length in elemental sulfur (S8). Torsion angles about each of the two S—S bonds (comprising the trisulfane) are, respectively, 86.6 (2) and 87.0 (2)° for (1a), and −84.6 (2) and −85.9 (2)° for (1b). The core atoms, viz. the N—S—S—S—N moiety, of the two units superimpose well if one is inverted on the other, but the phenyl groups do not. Thus, the two units are essentially conformational enantiomers. Moreover, with respect to the four measured torsion angles, which range in absolute value from 84.6 (2) to 87.0 (2)°, these are slightly smaller than the theoretical optimum of 90.0° . The theoretically possible pseudo-cis  conformation , molecules are linked via C—H⋯π interactions, forming sheets lying parallel to (010) trisulfane, (2) amino]trisulfane, (3) , compounds (2) and (3) each have a unique conformation in the unit cell (Z′ = 1). Selected geometric parameters of (1) and the comparison compounds, (2) and (3), are given in Table 1ca 2.07 Å, the corresponding value is longer (2.09 Å) in (3) and shorter (2.04 Å) in (2). The absolute value of the average torsion angle of the title compound (1) is ca 86.0°, while the corresponding value is larger (93.2 and −89.5°) and closer to the theoretical optimum in (2), and significantly larger (109.7 and 95.9°) in (3).A search of the Cambridge Structural Database trisulfan, (2) amino]trisulfan, (3) , was synthesized and obtained in crystalline form after preparative HPLC, as described by Schroll & Barany (198637) in that publication.The title compound, (rany 1986: compounUiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989015011342/su5144sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989015011342/su5144Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015011342/su5144Isup3.cmlSupporting information file. DOI: 1406065CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystals of both compounds, molecules are linked  13H8ClN3O6, (I), and C13H9N3O6, (II), differ in the orientation of the two aromatic rings. In (I), they are essentially coplanar, making a dihedral angle of 8.2 (1)°, while in (II), they are inclined to one another by 76.2 (1)°. The two nitro groups are essentially coplanar with the attached benzene rings, as indicated by the dihedral angles of 1.4 (2) and 2.3 (2)° in (I), and 4.96 (18) and 5.4 (2)° in (II). The carbamate group is twisted slightly from the attached benzene ring, with a C—N—C—O torsion angle of −170.17 (15)° for (I) and 168.91 (13)° for (II). In the crystals of of both compounds, molecules are linked via N—H⋯O hydrogen bonds, forming chains propagating along [010]. In (I), C—H⋯O hydrogen bonds also link molecules within the chains. The crystal packing in (I) also features a very weak π–π interaction [centroid–centroid distance = 3.7519 (9) Å].The title compounds, C Within via N—H⋯O hydrogen bonds, this time involving the carbonyl O atom O5, forming chains propagating along the b axis; see Table 2In the crystal of (II)N-phenylcarbamate gave 16 hits for similar compounds, including two orthorhombic poylmorphs of phenyl N-phenylcarbamate itself ° in (I)A search of the Cambridge Structural Database  dissolved in 100 ml of dry THF, and to it was added the calculated amount (with 5% excess) of 4-chlorophenylchloroformate for compound (I)Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989015010245/su5141sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989015010245/su5141Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010245/su5141IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989015010245/su5141Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015010245/su5141IIsup5.cmlSupporting information file. DOI: 1403525, 1403524CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal of the former, molecules are linked  25H29BrN5O7, (I) dioxola-1-benzenacyclononaphane], and C24H29N5O7S, (II) thiazola-6-triazola-3-furodioxola-1-benzenacyclononaphane], the triazole rings adopt almost planar conformations. In (I), the fused pyrrolidine rings adopt envelope conformations with the C atoms opposite the fused N—C bond as the flap in each ring, and their mean planes are inclined to one another by 52.8 (3)°. In (II), the pyrrolidine and thiazole rings are both twisted on the fused N—C bond, and their mean planes are inclined to one another by 70.8 (2)°. In both (I) and (II), the furan ring adopts an envelope conformation with the adjacent C atom of the macrocycle as the flap. In the crystal of (I), molecules are linked via C—H⋯N and C—H⋯O hydrogen bonds, forming sheets parallel to (10-1), while in (II), molecules are linked via C—H⋯N and C—H⋯O hydrogen bonds, forming helical chains propagating along [010], which are linked via C—H⋯S hydrogen bonds, forming slabs parallel to (001).In the title compounds, C In compound (I)D = N1/C11–C13/C7 and E = N1/C8–C11) and the furan ring (B = O3/C15/C19/C20/C14) have envelope conformations with the maximum deviations from the respective mean planes of 0.465 (5) Å for atom C13, 0.490 (7) Å for C9 and 0.500 (4) Å for C14. The dioxalane ring (C = O4/C15/C19/O5/C16) has a twisted conformation on bond O5—C15. The mean planes of rings B and C are inclined to one another by 70.0 (3)°, and the mean planes of rings D and E are inclined to one another by 52.8 (3)°. The molecular structures of compounds (I) and (II) are illustrated in Figs. 1D) and thiazole rings (E = N1/C8/S9/C10/C11) have twist conformations on bond N1—C11. The furan and dioxolane rings (B and C) adopt envelope conformations with maximum deviations from the mean planes of 0.631 (3) Å for atom C14 and 0.319 (4) Å for C16. The mean planes of rings B and C are inclined to one another by 68.5 (2)° and the mean planes of rings D and E are inclined to one another by 70.8 (2)°. This latter dihedral angle is much larger than that in compound (I)cf. 52.8 (3)°.In compound (II)A) makes dihedral angles of 74.0 (3), 65.8 (3) and 65.8 (3)° with the mean planes of rings B and D and the benzene ring (C1–C6), respectively. The corresponding dihedral angles in compound (II)A/B and A/D; 74.0 (3) and 65.8 (3), respectively, for (IIn compound (I)via C—H⋯N and C—H⋯O hydrogen bonds, forming sheets parallel to ; Table 2In the crystal of (I)Compound (I): A solution of 5-bromo-2--2,2-dimethyl-5-[(Z)-2-nitrovinyl]tetrahydrofurodioxol-6-yl}oxy)methyl]-1H-1,2,3-triazol-1-yl}ethoxy)benzaldehyde (1 mmol) and proline (1.5 mmol) was refluxed in dry acetonitrile (50 ml) under a nitrogen atmosphere for 9 h. After completion of the reaction, as indicated by TLC, the acetonitrile was evaporated under reduced pressure. The crude product was purified by column chromatography using hexane/EtOAc (3:7) as eluent (yield 75%). After purification the compound was recrystallized in CHCl3 by slow evaporation yielding colourless block-like crystals.Compound (II): A solution of 5-bromo-2--2,2-dimethyl-5-[(Z)-2-nitrovinyl]tetrahydrofurodioxol-6-yl}oxy)methyl]-1H-1,2,3-triazol-1-yl}ethoxy)benzaldehyde (1 mmol) and thiazolidine-4-carboxylic acid (1.5 m mol) was refluxed in dry acetonitrile (50 ml) under a nitrogen atmosphere for 9 h. After completion of reaction, as indicated by TLC,the acetonitrile was evaporated under reduced pressure. The crude product was purified by column chromatography using hexane/EtOAc (4:6) as eluent (yield 75%). After purification the compound was recrystallized in CHCl3 by slow evaporation yielding colourless block-like crystals.Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. Compound (I) was refined using the instructions TWIN/BASF  global, I, II. DOI: 10.1107/S205698901501141X/su5103Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S205698901501141X/su5103IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1023614, 1023839CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II atom is located on an inversion centre and is coordinated by two 4-cyanobenzoate (CNB) anions, two nicotinamide (NA) ligands and two water molecules. The four O atoms in the equatorial plane form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination sphere is completed by the two N atoms of the NA ligands in the axial positions.In the title complex, the Co 8H4NO2)2(C6H6N2O)2(H2O)2], the CoII atom is located on an inversion centre and is coordinated by two 4-cyanobenzoate (CNB) anions, two nicotinamide (NA) ligands and two water molecules. The four O atoms in the equatorial plane form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination sphere is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxylate group and the adjacent benzene ring is 22.11 (15)°, while the pyridine and benzene rings are oriented at a dihedral angle of 89.98 (5)°. In the crystal, intermolecular N—H⋯O and O—H⋯O hydrogen bonds link the molecules, enclosing R22(8) and R44(8) ring motifs, forming layers parallel to (100). The layers are linked via C—H⋯O and C—H⋯N hydrogen bonds, resulting in a three-dimensional network. A weak C—H⋯π interaction is also observed.In the title complex, [Co(C N,N-diethylnicotinamide (DENA) is an important respiratory stimulant  is one form of niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels bis(nicotinamide-κN1)cobalt(II), [Co(C8H4O2N)2(C6H6N2O)2(H2O)2], and report herein its crystal structure.The structure–function–coordination relationships of the arylcarboxylate ion in ZnII atom is located on an inversion centre and is coordinated by two 4-cyanobenzoate (CNB) anions, two nicotinamide (NA) ligands and two water molecules, with all ligands coordinating in a monodentate manner  and the two symmetry-related water O atoms (O4 and O4i) form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination sphere is completed by the two symmetry-related N atoms (N2 and N2i) of the two NA ligands in the axial positions   Å] and C1—O2 [1.256 (2) Å], bond lengths of the carboxylate group indicate delocalized bonding arrangements, rather than localized single and double bonds. The Co—O bond lengths are 2.0835 (12) Å (for benzoate oxygen atoms) and 2.1350 (13) Å (for water oxygen atoms), and the Co—N bond length is 2.1390 (15) Å, close to standard values. The Co1 atom lies 0.3921 (1) Å above the planar (O1/O2/C1) carboxylate group. The O—Co—O and O—Co—N bond angles deviate only slightly from ideal values, with average values of 90 (3)° and 90 (2)°, respectively.A (C2–C7)] is 22.11 (15)°, while the benzene and pyridine [B (N2/C9–C13)] rings are oriented at a dihedral angle of 89.98 (5)°.The dihedral angle between the planar carboxylate group (O1/O2/C1) and the adjacent benzene ring [c (c = carboxylate), N—H⋯On (n = nicotinamide), O—Hw⋯Oc (w = water) and O—Hw⋯On hydrogen bonds  and C—Hn⋯Ncnb hydrogen bonds  in H2O (50 ml) and nicotinamide  in H2O (50 ml) with sodium 4-cyanobenzoate  in H2O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving pink-coloured single crystals.The title compound was prepared by the reaction of CoSO2) and H41 and H42 (for H2O) were located in a difference Fourier map and were refined freely. The aromatic C-bound H atoms were positioned geometrically with C—H = 0.93 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). The highest electron density and the deepest hole were found 0.80 Å and 0.83 Å, respectively, from Co1.The experimental details including the crystal data, data collection and refinement are summarized in Table 210.1107/S2056989015008270/wm5151sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015008270/wm5151Isup2.hklStructure factors: contains datablock(s) I. DOI: 1061935CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


III ion in the title compound shows a slightly distorted FeCl2N2O2 octahedral coordination geometry. In the crystal, two complex molecules are linked by duplex O—H⋯O hydrogen bonds. Additional hydrogen-bonding interactions lead to the formation of undulating sheets parallel to (010).The Fe 10H15N2O2)Cl2]·2H2O, the FeIII ion is coordinated by two N and two O atoms of the tetradentate 2-{(2-hydroxyethyl)(pyridin-2-ylmethyl)amino}ethanolate ligand and by two chloride anions, resulting in a distorted octahedral coordination sphere. The average Fe—X (X = ligand N and O atoms) and Fe—Cl bond lengths are 2.10 and 2.32 Å, respectively. In the crystal, duplex O—H⋯O hydrogen bonds between the hydroxyl and ethoxy groups of two neighbouring complexes give rise to a dimeric unit. The dimers are connected to the lattice water molecules  through O—H⋯Cl hydrogen bonds, forming undulating sheets parallel to (010). Weak C—H⋯Cl hydrogen bonds are also observed.In the title compound, [Fe(C The chloride anions are trans to the deprotonated ethoxy O atom and the N atom of the pyridine group of the Hpmide ligand, respectively, and coordinate in cis position to each other. The average Fe—XHpmide  bond length is 2.10 Å and the Fe—Cl bond lengths are 2.2773 (5)  and 2.3581 (7)  Å. Both the average Fe—N (2.182 Å) and Fe—O (2.010 Å) distances in (I)2O2-chelated high-spin FeIII complexes The hydroxyl substituent of the Hpmide ligand forms a strong hydrogen bond with the O atom of the deprotonated ethoxy group of a neighbouring molecule. These duplex interactions lead to a dinuclear dimeric unit. The dimers are linked through O—H⋯Cl interactions to the lattice water molecules, that are likewise connected to each other through O—H⋯O hydrogen bonds. All these hydrogen-bonding interactions  was added dropwise a MeOH solution (3 ml) of H2pmide . The colour became yellow, and then the solution was stirred for 30 min at room temperature. Yellow crystals of (I)10H15Cl2FeN2O2: C 37.30, H 4.70, N 8.70%; found: C 37.19, H 4.58, N 8.78%.The HUiso(H) values of 1.2Ueq(C) of the parent atoms. One lattice water molecule (OW1) was found to be equally disordered over two positions. The H atoms of this disordered water molecule (H1W1 and H1W2) were located from difference Fourier maps and refined with restraints and a fixed O—H distances of 0.84 Å, with Uiso(H) values of 1.2Ueq(O). Moreover, the second water molecule (O2W) was modelled without hydrogen atoms because difference Fourier maps did not suggest suitable H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814022089/wm5071sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814022089/wm5071Isup2.hklStructure factors: contains datablock(s) I. DOI: 1027864CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Supramolecular chains about a 4 10H7N3O4S, the dihedral angle between the terminal five-membered rings is 27.4 (2)°, with these lying to the same side of the plane through the central CN2C(=O) atoms (r.m.s. deviation = 0.0403 Å), leading to a curved molecule. The conformation about the C=N imine bond [1.281 (5) Å] is E, and the carbonyl O and amide H atoms are anti. In the crystal, N—H⋯O hydrogen bonds lead to supramolecular chains, generated by a 41 screw-axis along the c direction. A three-dimensional architecture is consolidated by thienyl-C—H⋯O(nitro) and furanyl-C—H⋯O(nitro) interactions, as well as π–π interactions between the thienyl and furanyl rings [inter-centroid distance = 3.515 (2) Å]. These, and other, weak intermolecular interactions, e.g. nitro-N—O⋯π(thienyl), have been investigated by Hirshfeld surface analysis, which confirms the dominance of the conventional N—H⋯O hydrogen bonding to the overall molecular packing.In the title carbohydrazide, C The thienyl ring is also planar within experimental error [r.m.s. deviation = 0.005 Å] and orientated so that the sulfur atom is syn to the carbonyl-O1 atom. Overall, the molecule is curved with the rings lying to the same side of the plane through the bridging CN2C(=O) atoms, r.m.s. deviation = 0.0403 Å, with twists noted in both the S1—C1—C5—O1 and N2—C6—C7—O2 torsion angles of −9.8 (5) and 5.4 (6)°, respectively; the dihedral angle between the five-membered rings is 27.4 (2)°.In (I)anti relationship between the carbonyl-O and amide-H atoms enables the formation of directional N—H⋯O hydrogen bonds leading to supramolecular chains, generated by a 41 screw-axis propagating along the c-axis direction, Fig. 2a and Table 1y, x, −z. A view of the unit-cell contents is shown in Fig. 2b.The Crystal Explorer 3.1 Cg = 3.506 (4) Å, O4⋯Cg = 3.639 (4) Å and N3—O4⋯Cg = 74.0 (2)°] is also evident from the light-blue and red regions corresponding to their respective potentials on the Hirshfeld surface mapped over electrostatic potential in Fig. 4The presence of a short intermolecular C⋯C contact between thienyl-C2 and furanyl-C10 atoms, Table 2a and those delineated into O⋯H/H⋯O, H⋯H, N⋯H/H⋯N, C⋯H/H⋯C, C⋯C, C⋯O/O⋯C and S⋯H/H⋯S contacts  distances greater than their van der Waals separations with the comparatively low contribution, i.e. 13.6%, due to the relatively low hydrogen-atom content in the molecule. The absence of characteristic wings in the fingerprint plot delineated into C⋯H/H⋯C and the low contribution to the Hirshfeld surface, Fig. 6e and Table 3de + di ∼2.9 Å belong to short interatomic C⋯H contacts, Table 2de + di ∼2.7 Å in the fingerprint plot corresponding to N⋯H/H⋯N contacts, Fig. 6e, with a 7.5% contribution to the Hirshfeld surface is the result of short interatomic N⋯H/H⋯N contacts, Table 2de = di ∼1.7 Å, Fig. 6f. The presence of π–π stacking interactions between the symmetry-related thienyl and furanyl rings is also indicated by the appearance of red and blue triangle pairs on the Hirshfeld surface mapped with the shape-index property identified with arrows in the images of Fig. 7h, they do not have a significant influence on the molecular packing as they are separated at distances greater than the sum of their van der Waals radii.The overall two-dimensional fingerprint plot is shown in Fig. 6et al., 2014i.e. 0.99, corresponding to the C⋯O/O⋯C contacts. The high propensity to form π–π stacking interactions between the thienyl and furanyl rings is reflected from the high enrichment ratio 2.66 for C⋯C contacts. The ER value of 1.26 resulting from 6.75% of the surface occupied by nitrogen atoms and a 7.5% contribution to the Hirshfeld surface from N⋯H/H⋯N contacts is due to the presence of short N⋯H contacts in the structure, Table 2The final analysis based on the Hirshfeld surfaces is an evaluation of enrichment ratios (ER) methylene]thiophene-2-carbohydrazide +;  = 1.2Ueq(C). The N-bound H atom was located from a difference map and refined with (N—H = 0.88±0.01 Å), and with Uiso(H) = 1.2Ueq(C). The slightly elongated displacement ellipsoid for the C2 atom in the thienyl ring is likely due to unresolved disorder in the ring where the second, co-planar orientation related by 180° to that modelled is present. However, this was not modelled as the maximum residual electron density peak was only 0.46 e Å−3, 0.61 Å from the C2 atom. It is also noted that the relevant S—C and C—C bond lengths show the expected values.Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989016009968/hb7593sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016009968/hb7593Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016009968/hb7593Isup3.cmlSupporting information file. DOI: 1486459CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure consists of hydrogen-bonded planar arrays held by X—H⋯O  and X—O⋯π(ring)  interactions, leaving interstitial columnar voids.A dinuclear Cd 3-carboxy-6-methylpyridine-2-carboxylate complex is reported, in which the anionic ligand displays an unusual μ 3N,O2:O2;κ3O2:N,O2-bis[(nitrato-κO)cadmium] methanol monosolvate, [Cd2(C8H6NO4)2(NO3)2(C10H8N2)2]·CH3OH, was isolated as colourless crystals from the reaction of Cd(NO3)2·4H2O, 6-methylpyridine-2,3-dicarboxylic acid (mepydcH2) and 2,2′-bipyridine in methanol. The asymmetric unit consists of a CdII cation bound to a μ-κ3N,O2:O2-mepydcH− anion, an N,N′-bidentate 2,2′-bipyridine group and an O-monodentate nitrate anion, and is completed with a methanol solvent molecule at half-occupancy. The Cd complex unit is linked to its centrosymmetric image through a bridging mepydcH− carboxylate O atom to complete the dinuclear complex molecule. Despite a significant variation in the coordination angles, indicating a considerable departure from octahedral coordination geometry about the CdII atom, the Cd—O and Cd—N distances in this complex are surprisingly similar. The crystal structure consists of O—H⋯O hydrogen-bonded chains parallel to a, further bound by C—H⋯O contacts along b to form planar two-dimensional arrays parallel to (001). The juxtaposed planes form interstitial columnar voids that are filled by the methanol solvent molecules. These in turn interact with the complex molecules to further stabilize the structure. A search in the literature showed that complexes with the mepydcH− ligand are rare and complexes reported previously with this ligand do not adopt the μ-κ3 coordination mode found in the title compound.The centrosymmetric dinuclear complex bis(μ-3-carboxy-6-methylpyridine-2-carboxylato)-κ The two deprotonated forms pydcH− and 2−pydc have been shown to adopt a wide range of coordination modes through their carboxylate oxygen and pyridyl nitrogen atoms , only a single structure was found involving the monoanionic mepydcH− ligand similar to that reported here  complexes [M(bpee)2(mepydcH)2] ethylene) with octahedral geometry around MII. Both mepydcH− fragments act in a simple κ22N,O-chelating mode binding to a single nucleus while the two N-bound bpee ligands are trans-monodentate. The formation of these mononuclear complexes is unusual considering the obvious bridging potential of the bpee ligands. Mixed-ligand complexes based on non-methylated 2,3-pyridinedicarboxylate and 4,4′-bipyridine-like ligands usually generate stable polymeric structures with the exo-bidentate ligands adopting a bridging role 2(mepydcH)2(NO3)2]·MeOH (I)2- coordination behaviour and the fact that the ligand is only singly deprotonated has no counterpart in complexes of the non-methylated ligands and makes this a genuinely novel structure. The closest relatives with 2,2′-bipyridine as the auxiliary ligand are found with di-anionic 2−pydc ligands, but these are either mononuclear  chelates through the pyridine N and carboxylate O atoms. A chelating 2,2′-bipyridine that binds through both nitrogen atoms and a unidentate nitrate anion complete the coordination sphere; the asymmetric unit also contains a non-coordinating half-occupancy methanol solvate. This five coordinate CdII unit, in turn, binds to its centrosymmetric image through the carboxylate oxygen atom of the mepydcH− ligand, forming a pair of Cd–O–Cd bridges. As a result, a dimeric unit forms  distances are reasonable, spanning the range 2.304 (2)–2.332 (3) Å. However, the coordination angles vary widely ; the result is a rather distorted octahedral geometry around Cd1. Selected geometric parameters are shown in Table 1The complex consists of a Cdms Fig. 1 with eacviz., hydrogen bonds  Contacts #1  when a lone pair provided by a carbonyl oxygen points toward the centroid of an aromatic ring  Strong intermolecular O—H⋯O contacts #2  C—H⋯O interactions #3, #4 and #5  . These planes juxtapose along [001] with rather weak direct interactions. In the process, however, significant columnar voids parallel to the chains are formed  in which the partial occupancy methanol solvate molecules reside. These are not free, but enter instead into a number of weak C—H⋯O, O—H⋯O and C—H⋯π interactions  Fig. 3a. ThesemepydcH2, 2.2′-bipyridine and (I)Resolutions Pro software, using a Diamond ATR accessory. The FT–IR spectrum of (I)−1 range, and confirms the structural data indicating the presence of the coordinating nitrate and mepydcH− anions. Bands due to the unidentate NO3− group were found at 1478 and 1298 cm−1 and appear due to the νasym(ONO) and νsym(ONO) vibrations, with a shoulder at 1010 cm−1 due to the ν(NO) stretching modes of nitrate groups −1, ν(OH) stretching for a hydrogen-bonded system  stretch. The deprotonated carboxylate (COO−) is characterized by the asymmetric and symmetric stretching modes νas at 1593 cm−1 and νs at 1322 cm−1. This confirms the unidentate coordination of the carboxylate O atom, with the difference between these frequencies being > 200 cm−1(Δ = νas − νs = 271 cm−1)  of almost equal intensity due to the ν(C=C) + ν(C=N) vibrations from the coordinating 2,2′-bipyridine ligand ·4H2O  and mepydcH2  in MeOH (4.0 mL). The mixture was stirred to dissolve the 2,2′-bipyridine and was then allowed to stand undisturbed at room temperature in an uncovered 10 mL beaker. Colourless single crystals of compound (I)Solid 2,2′-bipyridine  was added to a solution prepared by disolving Cd = 1.2Ueq(C); C—Hmethyl: 0.97 Å, Ueq(H) = 1.5Ueq(C). The O—H hydrogen atom was refined with a restrained O—H distance [0.85 (1)Å], and with U(H) = 1.2Ueq(O). The methanol solvate was refined at half occupancy.Relevant crystallographic data for (I)10.1107/S2056989015012384/sj5468sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015012384/sj5468Isup2.hklStructure factors: contains datablock(s) I. DOI: 1409269CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound is an example of a ‘false conglomerate’ with two molecules of opposite handedness in the asymmetric unit. Each molecule exists as a zwitterion, with proton transfer from the amino acid carboxylic acid group to the amine group. In the crystal, the components are linked by N—H⋯O and O—H⋯O hydrogen bonds, generating (100) sheets. 6H9NO4·H2O [systematic name: -rel-α-amino-2-carboxycyclopropaneacetic acid monohydrate], crystallizes with two organic molecules and two water molecules in the asymmetric unit. The space group is P21 and the organic molecules are enantiomers, thus this is an example of a ‘false conglomerate’ with two molecules of opposite handedness in the asymmetric unit (r.m.s. overlay fit = 0.056 Å for one molecule and its inverted partner). Each molecule exists as a zwitterion, with proton transfer from the amino acid carboxylic acid group to the amine group. In the crystal, the components are linked by N—H⋯O and O—H⋯O hydrogen bonds, generating (100) sheets. Conformationally restricted glutamate analogs are of interest due to their selective activation of different glutamate receptors, and the naturally occurring (+)-CCG-III is an inhibitor of glutamate uptake and the key geometrical parameters are discussed.The title compound, C CCG-I, CCG-III and CCG-IV glycines IV Fig. 1 are natuII Fig. 1 have beeThe racemic title compound Fig. 2 crystallX = −4.3° and O3A—C6A—C2A—X = −11.1°  indicate that the carboxylic acid attached to the cyclpropane ring adopts a bisected conformation ; C2A—C3A = 1.516 (2) Å] and are longer than the cyclopropane bonds distal to the C2 carboxylic acid . These distances and torsion angles are consistent with other cyclopropane carboxylic acids , between the α- and γ-carboxylate carbon atoms (2d), and their sum (1d + 2d). The classifications ‘folded’, ‘semi-folded’, ‘semi-extended’, and ‘extended’ are defined by (1d + d2) ≤ 7.5 Å, 7.5 Å ≤ (1d + d2) ≤ 8.0 Å, 8.0 Å ≤ (1d + d2) ≤ 8.5 Å, and (1d + d2) ≥ 8.5 Å, respectively , 8.24 and 8.30 Å, respectively. From these values, these conformers of CCG-III can be considered to be in the ‘semi-extended’ class.Conformationally restricted glutamic acid analogs can be classified into one of four categories, which are characterized by the distances between the nitrogen atom of the amino group and the γ-carboxylate carbon atom ; Table 1The racemic title compound was prepared according to the literature procedure  I, New_Global_Publ_Block. DOI: 10.1107/S2056989015011500/hb7407Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015011500/hb7407Isup3.cmlSupporting information file. DOI: 1406594CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


III iridabenzenes that contain an open coordination site.Treatment of an iridabenzene with either bromine or iodine generates high-oxidation-state Ir 3)2], with either bromine or iodine produced dibromido(triphenylphosphine)iridium(III), [IrBr2{—C(Ph)=C(Ph)—CH=CH—CH=}(PPh3)], (I), and diiodido(triphenylphosphane)iridium(III), [IrI2{—C(Ph)=C(Ph)—CH=CH—CH=}(PPh3)], (II), respectively, which are two rare examples of 16-electron metallabenzenes. Structural elucidation of (I) and (II) reveals that these isotypic iridabenzenes are unusual, not only in their electron count, but also in their coordination sphere of the IrIII atom where they contain an apparent open coordination site. The crystal structures of (I) and (II) confirm that the molecules are complexes containing five-coordinated IrIII with only one triphenylphosphine group bound to the iridium atom, unambiguously proving that the molecules are indeed 16-electron, high-oxidation-state iridabenzenes. The coordination geometry of the IrIII atom in both structures can be best described as a distorted square pyramid with the P, two Br (or I) and one C atom in the basal plane and another C atom in the apical position.Treatment of carbonylbis(triphenylphosphane)iridium, [IrCO(—C(Ph)=C(Ph)—CH=CH—CH=)(PPh The molecular structures of (I)III is five-coordinated in these complexes with only one triphenylphosphine group bound to the iridium atom, unambiguously proving that the molecules are indeed 16-electron, high-oxidation-state iridabenzenes. The coordination geometry of the IrIII atom in both structures can be best described as a distorted square pyramid with the P1, Br1(I1), Br2(I2) and C1 atoms in the basal plane and the C5 atom in the apical position. The Br1(I1), Br2(I2), P1, C1 fragments are planar within 0.17 Å (Br) and 0.21 Å (I)I iridabenzenes (2.01–2.05 Å), reflecting the higher IrIII oxidation state et al., 2007cf, Br1(I1)—Ir—C5, 110.5 (2) [113.6 (4)°]}. This site is typically occupied by CO in all of our previous iridabenzene studies, such as (III)  in (I)ca 3.18 Å. This H29A atom is on the opposite side from the C5 atom (the C5—Ir1⋯H29A angle is 147°). If present, the Ir—H distance would be around 1.5–1.6 Å. In such a case, the distance between this H atom and the H29A atom from the phenyl ring should be 1.6–1.7 Å. This distance is too short as a typical H⋯H contact is 2.4 Å. It follows then that if one H atom does not fit, H2 will not either. The displacement parameters of most C atoms in the phenyl rings are elongated perpendicular to the average plane of the Ph rings showing their flexibility or statistical disorder.Additionally, the iridabenzene ring in both structures significantly deviates from planarity (Zhu I) Fig. 3. The steX  interactions with C⋯X distances in the ranges of 3.533 (7)– 3.717 (5) and 3.699 (17)–3.707 (12) Å, respectively, for Br and I (Tables 1Compounds (I) Tables 1 and 2 ▸.et al., 1999Reaction of iridabenzene (Gilbertson Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989015018952/wm5215sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989015018952/wm5215Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018952/wm5215IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1430096, 1430095CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


III(C48H36N4O2)(H2O)2][K(C12H24O6)(H2O)2](SO3CF3)2·2C12H24O6, the FeIII atom is situated on an inversion centre and is octahedrally coordinated by four pyrrole N atoms of the deprotenated 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinate ligand and two water molecules. The average equatorial Fe—N(pyrrole) bond length [2.043 (6) Å] is consistent with a high-spin (S = 5/2) iron(III) metalloporphyrin derivative. The K+ cation, which also lies on an inversion centre, is chelated by the six O atoms of one 18-crown-6 molecule and is additionally coordinated by two water molecules in a distorted hexagonal–bipyramidal geometry. In the crystal, the cations, anions and one non-coordinating 18-crown-6 molecule are linked by classical O—H⋯O hydrogen bonds and non-conventional C—H⋯O hydrogen bonds, leading to a one-dimensional supramolecular architecture along [10-1]. The crystal packing is further stabilized by weak C—H⋯π interactions involving pyrrole and phenyl rings of the porphyrins, as well as weak C—H⋯F contacts involving the (SO3CF3)− counter-ion and the 18-crown-6 molecules.In the title compound, [Fe DOI: 10.1107/S2056989015021039/im2471Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015021039/im2471fig1.tifORTEP III 2 2 + 2 2 + 3 3 − x y z . DOI: ORTEP view of the [FeIII(TMPP)(H2O)2]+ and [K(18-crown-6)(H2O)2]+ cations, the (SO3CF3)− anion and the 18-crown-6 molecule. Displacement ellipsoids are drawn at 50% probability level. H atoms have been omitted for clarity. .An Click here for additional data file.10.1107/S2056989015021039/im2471fig2.tifb Cg . DOI: b axis. The O—H⋯O classic H bonds are drawn as dashed light blue lines, the C—H⋯O contacts as dashed dark red lines while the C—H⋯Cg intermolecular interactions are shown as dashed green lines.A drawing showing the one-dimensional supramolecular structure of the title compound viewed down the 976053CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Two novel G3P[4] rotavirus strains were detected from children with acute diarrhea in Sendai, Japan, identified as a G3–P[4]–I2–R2–C2–M2–A2–N2–T2–E2–H2 genotype constellation by whole-genome sequence analysis. The VP7 gene of the two strains displayed the highest nucleotide sequence identity (91 %) and showed a close genetic relationship  to an equine rotavirus reported in India. The other gene segments were related to human group A rotaviruses. This report suggests a possible reassortment event between human and equine rotaviruses.The online version of this article (doi:10.1007/s11262-014-1135-z) contains supplementary material, which is available to authorized users. Rotaviruses are a leading cause of acute diarrhea in young children and cause approximately 453,000 deaths per year worldwide . In JapaReoviridae, genus Rotavirus. Its double-stranded RNA genome consists of 11 gene segments that encode six structural viral proteins  and six non-structural proteins (NSP1–6). The genes of the two antigenically distinct outer capsid proteins, VP7 (G type) and VP4 (P type), are used for genotyping [x–P[x]–Ix–Rx–Cx–Mx–Ax–Nx–Tx–Ex–Hx (where “x” depicts the number of the genotype) for symbolizing the VP7–VP4–VP6–VP1–VP2–VP3–NSP1–NSP2–NSP3–NSP4–NSP5 genes  followed by G3P[8], G9P[8], and G2P[4] . Rotavir°C for 5 min, and cooled on ice. Then 2 μl of 5× first strand buffer (F.C: 1×), 0.5 μl of 0.1 M DTT (F.C: 5 mM), 0.25 μl of 40U/μl RNaseOUT (F.C: 1U/μl), and 0.25 μl of 200 U/μl superscript III RT (F.C: 5 U/μl) were added into the mixture. The reverse transcription step was carried out at 25 °C for 10 min, 50 °C for 50 min, followed by heating at 70 °C for 15 min to inactivate the enzyme, and cooling at 4 °C immediately. For screening of RVA, real-time PCR was performed , and 0.5 μl of 300 ng/μl random hexamer primers  (F.C: 15 ng/μl) and 0.5 μl of 10 mM dNTP (F.C: 0.5 mM), heated at 98 erformed  and for erformed . Nucleothttp://rotac.regatools.be/)  . Interestingly, two samples were of the G3P[4] genotype. One of the samples (S13–30) was collected from a 4-year-old boy in the last week of February 2013 and the other (S13–45) was collected from a 1-year-old infant girl in the middle of March 2013. Both children did not receive rotavirus vaccines.In Table Phylogenetic trees of all 11 segments were constructed based on complete nucleotide sequences of each gene  Below is the link to the electronic supplementary material.