In the crystal of (I), pairs of [Fe(CN)4]− units  are linked together through π–π stacking between the pyridyl rings of the 2,2′-bipy ligands to form a graphite-like structure parallel to the ab plane. The three independent water molecules are hydrogen-bonded alternately with each other, forming a ladder chain structure with R44(8) and R66(12) graph-set ring motifs, while the disordered [N(CH3)4]+ cations lie above and below the water chains, and the packing is stabilized by weak C—H⋯O hydrogen bonds. The water chains are further linked with adjacent sheets into a three-dimensional network via O—H⋯O hydrogen bonds involving the lattice water molecules and the N atoms of terminal cyanide groups of the [Fe(CN)4]− building blocks, forming an R44(12) ring motif. Compound (II) features a two-dimensional {[Fe(CN)4Cd(en)2]}n layer structure (en is ethylenediamine) extending parallel to (010) and constructed from {[Fe(CN)4Cd(en)]}n chains interlinked by bridging en ligands at the Cd atoms. Classical O—H⋯N and N—H⋯O hydrogen bonds involving the lattice water molecule and N atoms of terminal cyanide groups and the N—H groups of the en ligands are observed within the layers. The layers are further connected via π–π stacking interactions between adjacent pyridine rings of the 2,2′-bipy ligands, completing a three-dimensional supramolecular structure.The crystal structures of the building block tetramethylammonium (2,2′-bipyridine-κ M(CN)6]n− (n = 2–4), have been used extensively as building blocks for the design and construction of a large number of high-dimensional cyanide-bridged bimetallic coordination polymers because of their ability to act as multidentate ligands to link numerous metal atoms through all six cyanide groups 6]3– with octahedrally coordinated transition metal ions  such as 2,2′-bipyridine  or 1,10-phenanthroline  in cyanide-containing building blocks of general formula [M(L)(CN)4]n−  instead of [M(CN)6]n− has been a recent development in the field of low-dimensionality cyanide-bridged bimetallic coordination compounds 4][Fe(CN)4(C10H8N2)]·3H2O (I)4)(C10H8N2)(C2H8N2)2]·H2O (II)As part of our search for novel cyanide-bridged bimetallic coordination polymers, we herein describe the synthesis and crystal structure of [N4]+ and three water molecules, as displayed in Fig. 1III ion is coordinated by two nitrogen atoms from one 2,2′-bipy ligand and four cyanide carbon atoms in a distorted octahedral geometry. This distortion around the metal atom is defined by the sum of the octahedral angular deviations from 90° (Σ), in which the trigonal distortion angle = 0 for a perfect octahedron °. The three trans angles  are bent slightly from the ideal value of 180°. The iron atom and terminal cyanido groups, viz. [Fe1—C3≡N3 = 178.7 (3) and Fe1—C4≡N4 = 179.8 (4)°] are almost linear compared to the iron atom and the corresponding equatorial cyano groups [viz. Fe1—C1—N1 = 175.8 (4) and Fe1—C2—N2 = 176.6 (4)°]. This difference is probably caused by hydrogen bonding (see below). The Fe—C bond lengths range from 1.917 (4) to 1.969 (4) Å, whereas the Fe—N bond lengths are 1.981 (3) and 1.985 (3) Å. The whole molecule of 2,2′-bipy ligand is planar with an r.m.s. deviation of 0.016 Å; the dihedral angle between the two pyridyl rings is 1.57 (18)°. Bond lengths and angles within the [Fe(CN)4]− anion in (I)4]·H2O (CN)4]·H2O (CN)4]·CH3CN  consists of one [Fe(CN)III precursor was reduced to FeII under the crystallization conditions. The asymmetric unit contains half each of an [Fe(CN)4]− anion and a [Cd(en)2]2+ cation, with the molecules lying across twofold rotation axes, Fig. 2II ion is a distorted octahedron with a Σ of 28.90°. The Fe—C—N angles for both bridging [Fe1—C1—N1 = 178.15 (14)°] and terminal [Fe1—C2—N2 = 176.85 (16)°] cyanide groups deviate slightly from strict linearity. The Fe—Ccyanide bond lengths at 1.8950 (16) and 1.9363 (17) Å are slightly shorter than the Fe—N2,2′-bipy bond length, 1.9976 (14) Å. The CdII ion is six-coordinated by two N atoms from two cyanide groups, two N atoms from a chelating en ligand and two N atoms from two different bridging en ligands in a highly distorted octahedral geometry with a Σ of 108.08°. The Cd—N bond lengths and the N—Cd—N bond angles in (II)4N)[{Fe(CN)6}3{Cd(en)}4] 2] }3]·4H2O ]2+cations, forming a chain of [Fe(CN)4Cd(en)] units running parallel to the a axis. Along the b axis, adjacent chains are then interconnected through the N atoms of the bridging en ligands at the Cd atoms into a two-dimensional layer of [Fe(CN)4Cd(en)2], as shown in Fig. 32}2{Cd(en)}2] units with an Fe⋯Cd distance through the cyanide bridge and a Cd⋯Cd distance through the en bridge of 5.1292 (7) and 7.6692 (12) Å, respectively. The M⋯M distances across the cyclic windows vary from 5.5614 (10) to 14.0061 (10) Å.Compound (II)4]− molecules are linked together through the parallel pyridyl rings of the 2,2′-bipy ligands to generate a graphite-like layers parallel to the ab plane. Within the sheets, the neighbouring pyridyl moieties related by an inversion centre are in a head-to-head arrangement with centroid (Cg) to centroid distances of 4.005 (3) Å [interplanar angle = 0.0 (4)°] and 3.903 (3) Å [interplanar angle = 0.0 (3)°] for rings A⋯Ai and B⋯Bii , respectively. The FeIII⋯FeIII separations along the π–π stacking of parallel rings A⋯Ai and rings B⋯Bii are 8.2821 (12) and 8.4572 (13) Å, respectively. The adjacent pyridyl rings A and Biii  related by translation parallel to the a axis are arranged alternately in a head-to-tail manner with a Cg⋯Cg distance of 3.865 (2) Å [interplanar angle = 1.51 (12)°] and an FeIII⋯FeIII separation of 6.8690 (9) Å.The three-dimensional supramolecular structure in (I)2O)4 and hexameric (H2O)6 subunits into (H2O)10 units [the dihedral angle between the best plane of the (H2O)4 and (H2O)6 subunits is 55.2 (2)°]; neighbouring units are further joined together, giving rise to ladder-like water chains running parallel to the a axis. As can be seen from Fig. 5i, O2, and O2i (for symmetry code see Table 12O)4 3(DMF)4(H2O)2]·4DMF·4H2O i, O1ii, O2, O2iii, O3, and O3iii ]+ cations lie above and below the water chains and take part in the formation of weak C—H⋯O hydrogen bonds with the water molecule.The hexameric water unit has crystallographically imposed inversion symmetry. The six water molecules O1via π–π stacking between adjacent pyridyl rings with Cg⋯Cg distances of 4.2925 (18) [interplanar angle = 1.55 (18)°] and 4.0642 (18) Å [interplanar angle = 0.0 (3)°] for rings C⋯Civ and C⋯Cv , respectively, Fig. 6For (II)3)4[Fe(CN)4]·3H2O (I)4[Fe(CN)4]·H2O . Analysis calculated for C18H26FeN7O: C, 48.66; H, 5.90; N, 22.07%. Found: C, 48.66; H, 5.90; N, 22.07%.The building block N(CH3)2·4H2O  and ethylenediamine  were dissolved in distilled H2O (4 ml), and this was pipetted into one side of an H-tube. N(CH3)4[Fe(CN)4]·3H2O  was dissolved in distilled H2O (4 ml), and this was pipetted into the other side arm of the H-tube. The H-tube (15 ml capacity) was then carefully filled with distilled H2O. Slow diffusion in the dark for three weeks yielded dark-yellow plate-shaped crystals of (II)18H26CdFeN10O: C, 38.15; H, 4.62; N, 24.72%. Found: C, 38.18; H, 4.60; N, 24.68%.For the synthesis of (II)Uiso(H) = 1.5Ueq(C) for methyl groups and 1.2Ueq otherwise. For (I)Uiso(H) = 1.5Ueq(O). For (II)Uiso(H) = 1.5Ueq(O). The tetrametylammonium cation in (I)A, C17A and C18A, and 0.560 (6) for atoms C16B, C17B, and C18B. Anisotropic displacement parameters of all atoms were restrained using enhanced rigid-bond restraints  I, II. DOI: 10.1107/S2056989016006848/bg2584Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016006848/bg2584IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1476008, 1476007CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structures of two bromo–hydroxy–benzoic acid derivatives, namely, methyl 4-bromo-2-(methoxymethoxy)benzoate, (I), and 4-bromo-3-(methoxymethoxy)benzoic acid, (II), are compared. Compound (II) crystallizes with two independent molecules in the asymmetric unit. In the crystal structures of both compounds, two-dimensional architectures are formed principally by C—H⋯O hydrogen bonds, and by Br⋯O interactions in (I) and by π–π interactions in (II). 10H11BrO4, (I), and C9H9BrO4, (II), are derivatives of bromo–hydroxy–benzoic acids. Compound (II) crystallizes with two independent molecules (A and B) in the asymmetric unit. In both (I) and (II), the O—CH2—O—CH3 side chain is not in its fully extended conformation; the O—C—O—C torsion angle is 67.3 (3) ° in (I), and −65.8 (3) and −74.1 (3)° in molecules A and B, respectively, in compound (II). In the crystal of (I), molecules are linked by C—H⋯O hydrogen bonds, forming C(5) chains along [010]. The chains are linked by short Br⋯O contacts [3.047 (2) Å], forming sheets parallel to the bc plane. The sheets are linked via C—H⋯π interactions, forming a three-dimensional architecture. In the crystal of (II), molecules A and B are linked to form R22(8) dimers via two strong O—H⋯O hydrogen bonds. These dimers are linked into ⋯A–B⋯A–B⋯A–B⋯ [C22(15)] chains along [011] by C—H⋯O hydrogen bonds. The chains are linked by slipped parallel π–π interactions [inter-centroid distances = 3.6787 (18) and 3.8431 (17) Å], leading to the formation of slabs parallel to the bc plane.The title compounds, C The dihedral angle between the benzene ring and the ester segment (O1/C7/O2/C8) is 14.5 (2)°, while the plane through atoms C10/O4/C9 of the methoxymethoxy side chain is inclined to the benzene ring by 82.5 (3)°.The molecular structure of compound (I)A and B) in the asymmetric unit. The conformations of the two molecules differ in the torsion angles of the –O–CH2–O–CH3 side chains and the orientation of the –COO– group with respect to the benzene ring, as shown in the AutoMolFit diagram °, and torsion angle O3B—C8B—O4B–-C9B in molecule B is −74.1 (3)°. The dihedral angle between the benzene ring and the plane through atoms C8A/O4A/C9A of the methoxymethoxy side chain in molecule A is 79.2 (3)°, while the corresponding dihedral angle in molecule B, between the benzene ring and plane C9B/O4B/O8B is 67.1 (3)°. This is less than in compound (I)A and 9.1 (4)° in B; also less than observed in compound (I)viz. 14.5 (2)°.The molecular structure of compound (II)am Fig. 3. The –O–A⋯O1 hydrogen bonds (Table 1C(5) chains along the b axis. Adjacent chains are linked by short Br1⋯O4i contacts  leading to the formation of sheets parallel to plane (100). The sheets are linked by C5—H5⋯π interactions (centroid of the benzene ring C1–C6) along the a-axis direction, forming a three-dimensional structure s Table 1, forminge Table 1.A and B are linked via two strong O—H⋯O hydrogen bonds, namely, O2A–-H2A⋯O1B and O2B–-H2B⋯O1A, forming dimers with an B—H8B2⋯·O3A hydrogen bonds  Å; Cg2 is the centroid of ring C1B–C6B; inter-planar distance = 3.3691 (12) Å; slippage = 1.477 Å; symmetry code (ii): −x, −y + 2, −z + 1], and between A and B molecules , thus forming slabs lying parallel to the bc plane f Table 2. Adjacens Table 2, formingne Fig. 7.Synthesis of methyl 4-bromo-2-(methoxymethoxy) benzoate (I)N,N-diisopropylethylamine  (DIPEA), followed by chloromethyl methyl ether  (MOM-Cl), at 273 K and the reaction mixture was stirred at room temperature overnight. The reaction mixture was then diluted with water (50 ml) and the organic layer was extracted with ethyl acetate (2 × 50 ml). The combined organic layers were washed successively with water, brine, dried over anhydrous magnesium sulfate (MgSO4), filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate:hexane (1:9) as eluent to afford (I)1H NMR : δ = 3.39 , 3.79 , 5.29  7.29 , 7.44 , 7.60 .To a stirred solution of methyl 4-bromo-2-hydroxy-benzoate  in dichloromethane (15 ml) (DCM) was added Synthesis of 4-bromo-3-(methoxymethoxy)benzoic acid (II)N hydrochloric acid. The precipitated solid was filtered, dried under vacuum to afford (II)1H NMR : δ = 3.39 , 5.28 , 7.26 , 7.40 , 7.59 , 12.90 .A mixture of methyl 4-bromo-3-(methoxymethoxy) benzoate , 10% aqueous potassium hydroxide , tetrahydrofuran (5 ml) and methanol (20 ml) was stirred at room temperature for 2 h. The mixture was then concentrated to remove organic solvents and the aqueous layer was acidified with 6 Single crystals of compounds (I)Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. In the final cycles of refinement reflection (0 0 2) in (I)F2obs and F2calc, considerably improving the values of R1, wR2, and GOF.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989016003777/su5284sup1.cifCrystal structure: contains datablock(s) I, II, Global. DOI: Click here for additional data file.10.1107/S2056989016003777/su5284Isup2.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016003777/su5284IIsup3.cmlSupporting information file. DOI: 1457944, 1457943CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The triflate ligand was found to be disordered over two sets of sites, with a site-occupancy ratio of 0.622 (16):0.378 (16). Weak intermolecular C—H⋯O and C—H⋯F hydrogen-bonding interactions generate a two-dimensional supramolecular structure lying parallel to (100). This is only the second crystal structure reported of a mononuclear bis(acetylacetonato)iron(III) complex.The mononuclear title complex, [Fe(CF The dinuclear alkoxides, [Fe(acac)2(μ-OR)] are also known iron(III) complex, [Fe(acac)2(OTf)(THF)], the title compound (I)Because of its ease-of-handling, relative stability and good solubility in most organic solvents, tris(acetylacetonato)iron(III) [Fe(acac)3+ atom in an slightly distorted octahedral FeO6 environment. The coordination sphere of the metal comprises four oxygen atoms from two κ2-acac ligands [Fe—Oacac range = 1.9517 (11)–1.9762 (11) Å], one oxygen atom of a THF solvate molecule [Fe1—O8 = 2.0781 (11) Å] and one oxygen atom of a disordered triflate anion [Fe1—O5 = 2.063 (4) Å or Fe1—O5B = 2.066 (6) Å] (Table 1cis angles range from 84.63 (5)° to 98.09 (5)° and the trans angles range from 172.60 (5)° to 174.9 (6)°.The molecular structure of the mononuclear complex (I)] Table 1. The disa,b). A series of Cmethyl—H⋯Oacac, Cmethyl—H⋯Otriflate, Cmethyl—H⋯Ftriflate, CTHF—H⋯Otriflate, and CTHF—H⋯Ftriflate interactions make up the layers, the details of these interactions are presented in Table 2c,d.There are no significant supramolecular features to discuss in the extended structure of (I)2Cl] acac range of 1.945–2.062 Å.Only one other mononuclear bis(acetylacetonato)iron(III) complex has been characterized crystallographically, [Fe(acac)2(C6H5)(OTf)] (THF)] -triflate complex, [Os(acac)3]  in dry THF (5 mL). The resulting purple–red solution was stirred at room temperature for 1 h. The reaction mixture was then concentrated under vacuum to a volume of approximately 2 mL, and 20 mL of pentane was added. A dark purple–red microcrystalline solid precipitated. The mixture was filtered through a glass-frit and the microcrystalline solid was dried under vacuum . Crystals suitable for X-ray diffraction were grown by slow diffusion of pentane into a THF solution of the purple–red solid. CH analysis calculated for C15H22F3FeO8S (MW: 475.235): C 37.91%; H 4.67%. Found: C 37.69%; H, 4.45%.Triflic acid  was added to a solution of . Remaining H atoms were also included as riding idealized contributors .Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989015016849/zs2341sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015016849/zs2341Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015016849/zs2341Isup3.tifSupporting information file. DOI: 1423096CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports6: Article number: 2427810.1038/srep24278; published online: 04072016; updated: 06102016.This Article contains an error in Figure S3; where the labels ‘0 °C’ and ‘25 °C’ are inverted. The correct Figure S3 appears below as


In the crystal, molecules are linked  12H13N2+·Cl−, the chloride salt of 1,1′-diphenylhydrazine, the phenyl rings are inclined to one another by 78.63 (17)°. The N—+NH3 bond lengths is 1.445 (3) Å, and the N—Cphenyl bond lengths are 1.435 (3) and 1.447 (4) Å. In the crystal, molecules are linked via N—H⋯Cl hydrogen bonds, forming chains along [10-1], which enclose two adjacent R42(6) ring motifs. The chains are reinforced by C—H⋯Cl hydrogen bonds.In the title compound, C It has been used as a starting reagent for the preparation of Schiff bases as fluorescent sensors for fluoride . The latter compound is one of a series that has been used to prepare bis(imino)pyridyl iron and cobalt complexes to study the effect of nitrogen substituents on ethylene oligomerization and polymerization via N—H⋯Cl hydrogen bonds, forming chains along . There are no π–π interactions present in the crystal structures of any of the three compounds.In the crystal of compound (II), molecules are linked by N—H⋯N, N—H⋯O and O—H⋯N hydrogen bonds, forming two-dimensional networks parallel to (001). These sheets are linked N,N-diphenylhydrazone) by a condensation reaction involving 1,1′-diphenylhydrazinium hydrochloride and 2,6-diacetylpyridine in methanol.Brown block-like crystals of the title compound were obtained during an attempt to prepare the ligand 2,6-diacetylpyridine bis(Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S1600536814022879/lh5735sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814022879/lh5735Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814022879/lh5735Isup3.cmlSupporting information file. DOI: 1029761CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


However, the crystal structure exhibits pseudosymmetry as the two independent molecules are related by an approximate but non-crystallographic inversion located close to  in the selected asymmetric unit, and the structure exhibits partial inversion twinning. The approximate inversion relationship between the two molecules in the selected asymmetric unit is clearly shown by comparison of the relevant torsion angle in the two molecules; the corresponding torsion angles have similar, although not identical magnitudes but with opposite signs. The mean planes of the quinoline rings in the two independent molecules are almost parallel, with a dihedral angle of only 0.16 (3)° between them, and the mutual orientation of these rings permits significant π–π stacking interactions between them [centroid–centroid distances = 3.7579 (15) and 3.7923 (15) Å]. In addition, the bimolecular aggregates which are related by translation along [010] are linked by a further π–π stacking interaction [centroid–centroid distance = 3.7898 (15) Å], so forming a π-stacked chain running parallel to [010]. However, there are no C—H⋯N hydrogen bonds in the structure nor, despite the number of independent aromatic rings, are there any C—H⋯π hydrogen bonds; hence there are no direction-specific interactions between adjacent π-stacked chains.The title compound, C Åb = 7.1401 (3) Åc = 13.0804 (5) ÅV = 2532.47 (17) Å3Z = 8Kα radiationMo −1μ = 0.30 mmT = 173 K0.48 × 0.32 × 0.22 mmAgilent Eos Gemini diffractometerCrysAlis RED; Agilent, 2012Tmin = 0.808, Tmax = 0.936Absorption correction: multi-scan (29727 measured reflections5975 independent reflectionsI > 2σ(I)5204 reflections with Rint = 0.037R[F2 > 2σ(F2)] = 0.040wR(F2) = 0.097S = 1.085975 reflections331 parameters1 restraintH-atom parameters constrainedmax = 0.25 e Å−3Δρmin = −0.22 e Å−3Δρx determined using 1610 quotients [(I+)−(I−)]/[(I+)+(I−)] CrysAlis PRO  global, I. DOI: 10.1107/S205698901500804X/hg5440Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901500804X/hg5440Isup3.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S205698901500804X/hg5440fig1.tif. DOI: The two independent molecules in the title compound showing the atom-labelling scheme. Displacement ellipsoids are shown at the 30% probability level.Click here for additional data file.10.1107/S205698901500804X/hg5440fig2.tif. DOI: The two molecules in the selected asymmetric unit, viewed normal to the planes of the quinolone units, showing the ring overlap which leads to a π..π sktacking interaction. For the sake of clarity, the H atoms have been omitted.Click here for additional data file.10.1107/S205698901500804X/hg5440fig3.tif. DOI: A stereoview of part of the crystal structure of the title compound showing the formation of a π-stacked chain parallel to [010]. For the sake of clarity, the H atoms have been omitted.1061227CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The bond lengths and angles of the cyclopentadienyl and phosphane ligands are very similar to that of the unsolvated complex [Taqui Khan et al.  and 1.156 (3) Å and has an N—N—Ru angle of 119.20 (15)°, indicating a greater contribution of the canonical form Ru—N=N(+)=N(-) for the bonding situation. An intramolecular C—H⋯N hydrogen-bonding interaction between one ortho H atom of a phosphane ligand and the N atom coordinating to the metal is observed. A similar intermolecular interaction is observed between a meta H atom of a phosphane ligand and the terminal azide N atom of a neighbouring complex. Finally, two C—H⋯N interactions exists between the H atoms of the dichloromethane solvent molecule and the terminal N atom of two azide anions. The solvent molecule is located about a twofold rotation axis and shows disorder of the Cl atoms with an occupancy ratio of 0.62 (3):0.38 (3).The title solvated complex, [Ru(η al. 1994. Acta Cr For oth al. 1999; Govinda al. 2005. For met al. 2005; Seok &  al. 2005. Non-cla al. 2005 of respe al. 2002.5H5)(N3)(C18H15P)2]·0.5CH2Cl2[Ru Åb = 12.4559 (3) Åc = 28.6781 (6) Åβ = 94.213 (2)°V = 7189.7 (3) Å3Z = 8Kα radiationMo −1μ = 0.63 mmT = 293 K0.72 × 0.51 × 0.20 mmAgilent Xcalibur Atlas Gemini diffractometerCrysAlis PRO 6038 reflections with Rint = 0.032R[F2 > 2σ(F2)] = 0.027wR(F2) = 0.065S = 1.067106 reflections449 parametersH-atom parameters constrainedmax = 0.33 e Å−3Δρmin = −0.49 e Å−3ΔρCrysAlis PRO  I, New_Global_Publ_Block. DOI: 10.1107/S1600536814019187/wm5050Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814019187/wm5050fig1.tif. DOI: Molecular structure of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Only the major component of the disordered dichloromethane solvate is shown. Hydrogen atoms of the metal complex have been removed for clarity.Click here for additional data file.10.1107/S1600536814019187/wm5050fig2.tif. DOI: View of the molecular arrangement in the title structure viewed along [010]. Hydrogen bonds are denoted by dashed lines.1021189CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II atom with a distorted octahedral coordination environment defined by six N atoms from three bidentate phenanthroline ligands. The non-coordinating N,N′-diglycine ligand links the cationic building blocks via C—H⋯O contacts and through lone-pair⋯π interactions. Further observed non-covalent interactions contribute to the consolidation of the supramolecular network.The complex cation of the title compound includes one Co 12H8N2)3]2(NO3)4·C12H12N2O6·8H2O, contains a CoII atom with a distorted octahedral coordination environment defined by six N atoms from three bidentate 1,10-phenanthroline ligands. The asymmetric unit of the title compound is completed by one-half of the N,N′-diglycine solvent molecule, which is located on a centre of inversion, by two nitrate counter-anions and four solvent water molecules. Two [Co(C12H8N2)3]2+ cations are connected through C—H⋯O contacts and through lone-pair⋯π interactions involving the non-coordinating N,N′-diglycine and phenanthroline molecules. The different aromatic ring systems are involved in π–π stacking and C—H⋯π interactions, with centroid-to-centroid distances in the range 3.7094 (8)–3.9973 (9) Å. The crystal structure is stabilized by further anion⋯π interactions and C—H⋯O contacts, as well as O—H⋯O and N—H⋯O hydrogen bonds between water molecules, the non-coordinating nitrate anions, N,N′-diglycine and phenanthroline molecules. These non-covalent interactions give rise to a three-dimensional supramolecular network.The complex cation of the title compound, [Co(C Application fields for these materials are in catalysis, in gas storage diglycine as metal-linking ligand, zigzag chains are formed, constructing interpenetrating networks (see Database survey). In our synthetic approach, we offer such systems another electron-deficient bidentate aromatic ring system like phenanthroline or bipyridine in order to block parts of the coordination sphere of the metal atoms so that these zigzag chains are truncated or not formed at all. Thus, an alternative route for the resultant system lies in the use of the offered π-interaction possibilities as well as in stacking interactions as a new linking mode. Recently, we have described the interactions of a cobalt(III) bipyridine complex with supramolecular synthons diglycine. The chosen ligand N,N′-diglycine is a relatively rigid molecule with one sp3-hybridized methylene carbon atom that allows the acid moiety to rotate. Moreover, this ligand simultaneously possesses several coordination sites through the carboxylic group and the oxygen atom of the amide group. These functional groups can also be involved in hydrogen bonding and D—H⋯π interactions.In previously synthesized transition metal complexes with N,N′-diglycine solvent molecule linking two tris(phenanthroline)cobalt(II) cationic building blocks via the mentioned non-classical interactions.In the present contribution we have determined the structure of a novel cobalt(II) coordination polymer with a non-coordinating II complex cation in which three bidentate phenanthroline ligands define a distorted octahedral coordination sphere. Distances and angles of this rather common cationic species, [Co(C12H8N2)3]2+, are well within expected ranges and are comparable to those found in the literature diglycine molecule. The asymmetric unit is completed by two non-coordinating nitrate counter-anions and four solvent water molecules. The N,N′-diglycine molecule links two complex triscobalt(II) cations via lone-pair⋯π interactions involving the carboxylic acid function and the phenanthroline aromatic system as well as C—H⋯O contacts between the oxygen atom of the amide group and one phenanthroline ligand. Moreover, π–π stacking interactions between different aromatic ring systems and C—H⋯π as well as O—H⋯O and N—H⋯O hydrogen bonding are observed and consolidate an extensive three-dimensional supramolecular network.The molecular entities Fig. 1 of the tvia O—H⋯O, C—H⋯O and partly via N—H⋯O hydrogen bonds with water, phenanthroline and N,N′-diglycine molecules diglycine solvent molecules stack these components along the c axis  Å and between Cg7⋯Cg7 is 3.9973 (9) Å ⋯Cg8 of 3.037 (1) Å, where Cg8 is the centroid defined by the ring atoms N5/C25–C28/C36. Moreover, a relatively short N—H⋯π distance of 4.08 (6) Å is observed diglycine solvent and the Cg2 centroid of a phenanthroline ligand are associated with a distance of 3.400 (5) Å. Similar distances of 3.461 (5) Å prevail between the O10 atom of a water molecule and the Cg3 centroid of a phenanthroline ligand, where Cg2 and Cg3 are the centroids defined by the ring atoms N1/C1–C4/C12 and C4–C7/C11/C12, respectively. The values are similar to those found in the literature  Å that is comparable to previously reported structures diglycine resulted in six metal-organic compounds diglycine and shows a number of non-classical interactions diglycine, was prepared by the method of Cleaver & Pratt (1955v/v) mixture of water and methanol (50 ml) and refluxed for 30 minutes. The mixture was allowed to cool to room temperature, and a previously prepared aqueous solution of cobalt nitrate (1 mmol) was slowly added under continuous stirring. Deep dark-orange block-shaped crystals of the title compound were obtained by slow evaporation at room temperature.The starting material, ratt 1955. Cesium Uiso(H) = 1.2 Ueq(C) and C—H(aromatic) = 0.94 Å and C—H(methylene) = 0.98 Å using a riding model. The water H atoms were located in a different Fourier map and were refined with O—H distances restrained to 0.82–0.87 Å and with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015013006/wm5178sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015013006/wm5178Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015013006/wm5178Isup4.cdxSupporting information file. DOI: 1410901CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


I with the pyridylimidazol ligand 4--1H-imidazol-2-yl)pyridine, afforded a nitrate-free one-dimensional looped-chain polymeric structure. The AgI cation adopts a highly distorted tetrahedral geometry coordinated by two pyridine N atoms and two imidazole N atoms from four individual ligands.The reaction of Ag 29H25N3)2]NO3·CH3OH·H2O}n, the AgI cation is four-coordinated by two pyridine N atoms and two imidazole N atoms from four individual 4--1H-imidazol-2-yl)pyridine (i-pro-pyim) ligands. This gives rise to a highly distorted tetrahedral geometry with bond angles falling in the range 100.33 (19)–122.76 (19)°. Two crystallographically independent i-pro-pyim ligands (A and B) adopt very similar conformations to one another, such that the dihedral angles between the pyridyl and imidazolyl rings in the two ligands are 40.7 (3) and 42.2 (3)°, respectively. Each i-pro-pyim ligand binds two symmetry-related Ag+ cations, leading to the formation of 14-membered cyclic dimers, in which the AgI atoms are separated by 6.963 (2) Å for the Ag–A2–Ag dimer and 7.020 (2) Å for Ag–B2–Ag. These cyclic dimers are alternately connected to each other by sharing AgI atoms, resulting in the formation of a looped-chain structure extending along the [100] direction. Moreover, adjacent looped chains are connected by intermolecular π–π interactions [centroid-to-centroid distance = 3.689 (4) Å], giving rise to the formation of a two-dimensional supramolecular network propagating parallel to (110). Several intermolecular C—H⋯O and O—H⋯O hydrogen bonds further contribute to the stabilization of the crystal structure.In the title compound, {[Ag(C The coordination polymer is obtained by addition of the ligand to AgNO3 in methanol/acetonitrile. The title nitrate salt is closely related to the perchlorate salt  because of their high efficiency and long-term stability , one nitrate anion, one methanol solvent molecule, and two water solvent molecules, each with an occupancy factor of 0.5, in the asymmetric unit. As shown in Fig. 1I atom is coordinated by two pyridine N atoms and two imidazole N atoms from four individual i-pro-pyim ligands, giving rise to a highly distorted tetrahedral geometry with bond angles falling in the range of 100.33 (19)–122.76 (19)°  and 42.2 (3)°, respectively. Moreover, there are intramolecular π–π interactions between the pyridyl and phenyl rings of both ligand types, N3,C4–C8 and C21–C26 [centroid-to-centroid distance = 3.760 (4) Å] for A and N6,C33–C37 and C51–C56 [centroid-to-centroid distance = 3.716 (4) Å] for B.In the title compound there are two crystallographically independent ligands, A ligands link two AgI atoms, resulting in the formation of a 14-membered cyclic dimer with an Ag⋯Ag distance of 6.963 (2) Å and a π–π interaction [centroid-to-centroid distance = 3.890 (4) Å] between N3-containing pyridine rings  Å and a π–π interaction [centroid-to-centroid distance = 3.922 (4) Å] between N6-containing pyridine rings. The two cyclic dimers are connected alternately by sharing AgI atoms, leading to the formation of a looped-chain structure extending along the a axis  −x + 2, −y, −z + 1], resulting in the formation of a two-dimensional supramolecular network propagating parallel to (110)  Å] between the C50–C55 and C500) Fig. 3. No nota0) Fig. 3.i-pro-pyim ligand was synthesized according to literature procedures  and allowing the solution to evaporate slowly at room temperature.The W and O2W) were refined with site-occupancy factors of 0.5, and their H atoms were not included in the model. All H atoms except those of the water molecules were positioned geometrically and refined using a riding model, with d(C—H) = 0.95 Å for Csp2—H, 1.00 Å for methine, C—H, 0.98 Å for methyl, and O—H 0.84 Å for hydroxyl H atoms. For all H atoms, Uiso(H) = 1.2–1.5Ueq of the parent atom.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S205698901600949X/sj5501sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901600949X/sj5501Isup2.hklStructure factors: contains datablock(s) I. DOI: 1484735CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title salt, crystalline water molecules serve as donors for the weak intermolecular O—H⋯O and O—H⋯Br hydrogen bonds which link adjacent polymeric chains. 2(C5H9NO2)]·H2O}n, the CdII ion is coordinated by four bromido ligands and two carboxylate oxygen atoms of two symmetry-related proline ligands, which exist in a zwitterionic form, in a distorted octahedral geometry. There is an intramolecular N—H⋯O hydrogen bond between the amino group and the carboxylate fragment. Each coordinating ligand bridges two CdII atoms, thus forming polymeric chains running along the c-axis direction. The water molecules of crystallization serve as donors for the weak intermolecular O—H⋯O and O—H⋯Br hydrogen bonds that link adjacent polymeric chains, thus forming a three-dimensional structure. N—H⋯O and N—H⋯Br hydrogen bonds also occur.In the title coordination polymer, {[CdBr It is known that the chiral amino acids and their complexes are potential materials for NLO applications –2.7737 (12) Å] and two carboxylate oxygen atoms [Cd—O = 2.312 (8) and 2.318 (8) Å] of two proline ligands in a slightly distorted octahedral geometry. The title complex is extended as a polymeric chain which runs parallel to the c axis. Within one chain, adjacent CdII ions are separated by 3.727 (1) Å. The closest Cd⋯Cd distance between neighbouring polymeric chains is 8.579 (2) Å. The five endocyclic torsion angles of the pyrrolidine ring of the proline residue are N1—C2—C3—C4 = 31.8 (13)°, C2—C3—C4—C5 = −39.1 (15)°, C3—C4—C5—N1 = 29.9 (14)°, C2—N1—C5—C4 = −9.7 (12)° and C5—N1—C2—C3 = −13.1 (11)°. The pyrrolidine ring exhibits twisted conformation on the C3—C4 bond with a pseudo-rotation angle Δ = 249.3 (12)° and a maximum torsion angle ϕm = 38.5 (8)° et al., 1983A⋯O2 hydrogen bond between the amino group and the carboxylate fragment.In (I)The crystal structure of (I)viz. catena-[dichlorido-(4-hydroxy-l-proline)cadmium] (μ2-l-proline)cadmium monohydrate] manganese(II) monohydrate], has been structurally determined three times and has similar cell parameters and the same space group as the title compound  and cadmium bromide tetrahydrate (Loba) in an equimolar ratio were dissolved in double-distilled water. The obtained solution of the homogeneous mixture was evaporated at room temperature to afford the white crystalline title compound, which was then recrystallized by slow evaporation from an aqueous solution.To prepare the title compound, et al., 1983W⋯H2W distances of the water molecules were restrained to 0.85 (2) and 1.38 (2) Å, respectively, using the DFIX option and included in the structure-factor calculations with Uiso(H1W/H2W) = 1.1Ueq(O1W). The remaining hydrogen atoms were placed in geometrically idealized positions (C—H = 0.97–0.98 Å and N—H = 0.89 Å) with Uiso(H) = 1.2Ueq(C/N) and were constrained to ride on their parent atoms. Reflections 110 and 020 were partially obscured by the beam stop and were omitted.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015001176/cv5483sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015001176/cv5483Isup2.hklStructure factors: contains datablock(s) I. DOI: 1044327CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The Stevens classification of levels of measurement involves four types of scale: “Nominal”, “Ordinal”, “Interval” and “Ratio”. This classification has been used widely in medical fields and has accomplished an important role in composition and interpretation of scale. With this classification, levels of measurements appear organized and validated. However, a group theory-like systematization beckons as an alternative because of its logical consistency and unexceptional applicability in the natural sciences but which may offer great advantages in clinical medicine. According to this viewpoint, the Stevens classification is reformulated within an abstract algebra-like scheme; ‘Abelian modulo additive group’ for “Ordinal scale” accompanied with ‘zero’, ‘Abelian additive group’ for “Interval scale”, and ‘field’ for “Ratio scale”. Furthermore, a vector-like display arranges a mixture of schemes describing the assessment of patient states. With this vector-like notation, data-mining and data-set combination is possible on a higher abstract structure level based upon a hierarchical-cluster form. Using simple examples, we show that operations acting on the corresponding mixed schemes of this display allow for a sophisticated means of classifying, updating, monitoring, and prognosis, where better data mining/data usage and efficacy is expected. In 1946, S. S. Stevens devised his classification of “levels of measurement” ,3.Thus, in the following, we re-interpret Stevens classification, and endeavour to give it meaning in some abstract algebra-like modelling. There, the most preferred construct is a vector-like structure of various sets of scores based on individual scales and operators that permit changes of score within the set. Additionally, classical datasets that are classified in terms of the Stevens scales of measurement can be mined and combined on a higher abstract structure level based upon a hierarchical-cluster form. To explore this possibility, we provide simple examples to help readers understand this modelling tool.Stevens classified the scales of measurement into four scale types ; І) “NomFor І), the “Nominal scale”, there seems to be little room where group theoretical operations apply because within that scale only a labelling scheme is permissible. Although some non-cyclic group might be definable, it seems that little meaning can be attached to operations for this sort of scale.N = {0, 1, 2, 3,…, N – 2, N – 1}, where modulo N addition is postulated. With this assumption, given two elements ‘Xj’ and ‘Xk’  corresponding for example to the severity of a clinical symptom and/or finding, then composition (denoted by ‘*’) is taken to be modulo N addition; ‘Xj*X(j→k) = Xk’ (with X(j→k) ∈ ZN). Here ‘X(j→k)’ is an operator that produces the change in score, ‘Xj → Xk’  = Xj-1*Xk = Xk – Xj’). Then, all scores ‘Xj’s and operators ‘X(j→k)’ are composable within a single Abelian modulo additive group ‘ZN’, where ‘Xj*Xk = Xk*Xj’ holds, at least, in terms of operation ‘*’. Thus a patient’s state corresponding to a certain illness or disease can be changed through the application of a single operation determined by the two elements belonging to ‘ZN’ , the combination of all scores being ‘0’ and represented by the identity element for group Y = {ZN×n, *}. Here, Y is the n-fold Cartesian product of ‘ZN’ (n: the number of components) that comprises all possible assessments related to each state of a given disease, for instance, ‘hypertension’, ‘hyperglycaemia’, ‘diabetes mellitus’, ‘acute pancreatitis’, ‘systemic lupus erythematosus’, and ‘cerebral artery stroke’. If in addition composition is given by modulo ‘N’ arithmetic, prime numbers  are preferable , cj = Xj - [Xj], ‘0 ≤ cj < 1’; ‘[X]’ is the floor function meaning the highest integer below ‘X’). Similarly, - (v) can be redefined using the unit length ‘1’ as an interval scale,0’ (=0) that satisfies ‘Xj ◦X0 = X0 ◦Xj (=Xj + X0 = Xj + 0) = Xj’. Additionally, the inverse element is ‘Xj-1 = -Xj’ satisfying ‘Xj-1◦Xj = Xj ◦Xj-1 = Xj + Xj-1 = Xj - Xj = X0 (=0)’.There exists an identity element ‘Xj’s, i.e., U ≡ {Xj | Xj ∈ R}. Because ‘Xj , Xk, Xj ∈ set U, the closure law holds. Therefore, this operation defines a group U = {Xj, ◦}  (mEq/l), sodium: [Na+] (mEq/l), calcium: [Ca++] (mg/dl), chloride: [Cl-] (mEq/l) and bicarbonate: [HCO3-] (mEq/l)’. Also, there are clinical scales whose ranges are the open interval like ‘-∞ < X < +∞’ ; ‘Anion gap [AG] = [Na+] - ([Cl-] + [HCO3-]) (reference range for blood tests: 12 ± 2 mEq/l)’ and ‘Base excess [BE] (reference range for blood tests: 0 ± 2 mmol/l)’. However, both can be treated using the notion of ‘field’ because those values are real numbers where all four arithmetic operations are included, with the exception of division by zero. Thus, the above clinical values could be definable over a ‘field’. In this regard, we assume a rule that each unit like ‘mEq/l’ accompanies the value automatically with the results of operations regardless of types of operation among the four arithmetic operations (Note that there are cases when units vanish as when ratios are taken ‘mEq/mEq (unitless)’ or displayed in reciprocal form like ‘l/mEq’). Examples for ‘[WBC] (/mm3)’, ‘[Na+] (mEq/l)’ are presented in Appendix C.Nevertheless, other clinical scales range over a semi-open continuous interval like ‘0 ≤ X < +∞’ , such as ‘blood concentration of white blood cells: [WBC] (/mmj # Xk = Xl (∈V), where ordinal arithmetic calculations are performed excluding of course division by zero.In this case, we consider a set V and assume that ‘#’ means one of ‘addition, subtraction, multiplication, and division’ collectively; thus, ‘Xj + Xk = Xk + Xj, and associative: (Xj + Xk) + Xl = Xj + (Xk + Xl). As for multiplication, set V meets the conditions of a ‘monoid’  (/mm3)”, field V2 ≡ {X2j | X2j ∈ R (mEq/l)} and V2 = {X2j, #} for “administration of a certain drug like lithium carbonate: [Li+] (mEq/l)”, field V3 ≡ {X3j | X3j ∈ R (mEq/l)} and V3 = {X3j, #} for “sodium: [Na+] (mEq/l)”, field V4 ≡ {X4j, #} for calcium: [Ca++] (mg/dl), field V5 for chloride: [Cl-] (mEq/l), field V6 for ‘Anion gap [AG] (mEq/l)’, field V7 for ‘Base excess [BE] (mmol/l)’,…, VN,…, . For each, an independent abstract algebraic treatment is possible as for ordinal abstract algebra.Furthermore, different fields based on different sets of clinical values can be described as follows: field Vj’, j = 1, 2, 3,…: number of sessions), where the mixed expression and its totality of operations that could be performed belong to a single set R. Because of the possible variety of operation rules, the genuine use of this set may be unwieldy at this stage.By making use of all types of scales of measurement, we propose a vector-like expression of a patient’s state  | clock time for the onset of sleep (/24 hrs) | blood concentration of white blood cell [WBC] (/mm3) | blood concentration of [Na+] (mEq/l)| a certain value ],Rj’ changes to ‘Rj+1’ effected by operator ‘R(j→j+1)’; we denote by ‘◊’ the binary composition composed of the product of compositions for each component. Three possible states are:Next, suppose the patient’s state ‘R(1)1’,‘X(2)1’, and ‘X(3)1’, modulo 7 arithmetic (addition) is used. For the 2nd components, ‘X(1)2, X(2)2, X(3)2’, operations of Abelian addition are used. For the 3rd component, ‘X(1)3, X(2)3, X(3)3’, 4th ‘X(1)4, X(2)4, X(3)4’, the four arithmetic operators (those operations denoted by ‘#’) are required, and for the 5th, ‘X(1)5, X(2)5, X(3)5’, a certain operational unit is postulated. In the following examples, only addition/subtraction is presented; naturally, multiplication/division is also considered permissible.For the 1st component, ‘X(1→ 2) = [X(1→ 2)1(mod 7) | X(1→ 2)2(/24 hrs)| X(1→ 2)3(/mm3)| X(1→ 2)4(mEq/l)|X(1→ 2)5(…)], and R(2→ 3) = [X(2→ 3)1(mod 7) | X(2→ 3)2(/24 hrs)| X(2→ 3)3(/mm3)| X(2→ 3)4(mEq/l)|X(2→ 3)5(…)]With related operators R(1→2)’ and ‘R(2→3)’ from the three states given above are as follows:Then, using results in Appendix D, ‘RThus, we confirm the relationDetails are illustrated in Appendix E.0) = [0 (mod 7)| 0 (/24 hrs)| 0 (/mm3)| 0 (mEq/l) | X0 (…)]’ such that ‘Rj◊E = E◊Rj = Rj’. Additionally, there exists an inverse for any ‘Rj’, ‘Rj- 1 = [X(j)1- 1(mod 7) | X(j)2- 1(/24 hrs)| X(j)3- 1(/mm3)| X(j)4- 1(mEq/l)|X(j)5- 1(…)] = [7–X(j)1(mod 7) | 24 - X(j)2(/24 hrs)| - X(j)3(/mm3)| - X(j)4(mEq/l)|X(j)5- 1(…)]’ that satisfies ‘Rj-1◊Rj = Rj◊Rj-1 = E’. However, commutativity, ‘Rj◊Rk = Rk◊Rj’ and associativity, ‘(Rj◊Rk)◊Rl = Rj◊(Rk◊Rl)’ are not satisfied. Here, we assume that operators acting on ‘Rj’s should be performed from left to right, that is, from R1 to Rm . They should not be applied between ‘Rj’s. For any assortment of ‘Rj’s with scales of measurement among types I)–IV), a single set R = {Rj| X(j)1 × X(j)2 × X(j)3 × X(j)4 × X(j)5} (‘×’ means products among groups and fields) using a vector-like notation for the scoring of patient states can be structured where all possible assessments and/or clinical findings of the patient and treatment are included. The general form is the n-fold product; set R = {Rj| X(j)1 × X(j)2 × X(j)3 × X(j)4 × …×X(j)(n-2) × X(j)(n-1) × X(j)n} .Note that, in general, there exists an identity ‘E  each with four component (‘n = 5’) and arrows (only symbols) that indicate the possible changes among the ‘Rj’s, as displayed in Figure j’s, are not combined directly with each other in the sense of operations. Then, the arrows could be re-displayed according to our concepts as operators ‘R(j→k) that can be regarded as elements ‘Rj’ belonging to a set R as in Figure j’s are merely a collection of values and the arrows in Figure j’s and ‘R(j→k)’s are elements of a single set R subject to axioms of an abstract algebra as indicated using composition symbol ‘◊’ in Figure j to Rk’ can be traced at each session. Displayed in this way, Figure As for the possible application to better data mining or data usage from the viewpoint of our reinterpretation, we provide a simple example that may help readers to follow an outline of the argument. Consider an example of 17 states “R1’ there are four outcomes ‘R6’, ‘R9’, ‘R16’, and ‘R17’ containing nodes at ‘R2’ ‘R4’ ‘R10’ ‘R12’ and ‘R13’. By making use of our previous examples ‘R1 - R3’, the next simplest examples with ‘n (component number) = 5’ can be confirmed easily:Here, consider the scenario of Figure Following these results, the next relations, according to the tree in Figure The operator expressions are evaluated in Appendix F.Similarly, the next sequences are definable in principle,a to Rb (=Ra◊R(a→b) = Rb)’ and ‘Ra to Rc (=Ra◊R(a→c) = Rc)’ as ‘Ra[(◊R(a→b))(◊R(a→c))]’ ; here ‘…’ meaning simple juxtaposition. All paths belonging to the operational tree of Figure In general, we denote a node divergence ‘R6, R9, R16, and R17’ and divergence point ‘R4’ a notation ‘(=R6), (=R9), (=R16) and (=R17)’ might be considered. Hence,To display for easy recognition, for example, end states like ‘R(3 → 4)[(◊R(4 → 5) ◊ R(5 → 6))(◊R(4 → 8) ◊ R(8 → 9) ◊ R(9 → 10))(◊R(4 → 15) ◊ R(15 → 16)) …] from the left-hand side by ‘R3’. The subsequent result can be expressed in accordance with the single scheme presented in Figure Moreover, composition with an operator as in operating on ‘R → 4, ‘2Rj1 = 21Rj2 ∪ 22Rj2’ = [X(j)3 (/mm3) | X(j)4 (mEq/l)|X(j)5 (…)], whereas at the third level, ‘22Rj2 = 221Rj3 ∪ 222Rj3’ = [X(j)4 (mEq/l)|X(j)5 (…)], 221Rj3 = [X(j)4 (mEq/l)], 222Rj3 = [X(j)5 (…)] 1, X(j)2, X(j)3, X(j)4, X(j)5} = [X(j)1 (mod 7) | X(j)2 (/24 hrs) | X(j)3 (/mm3) | X(j)4 (mEq/l) | X(j)5 (…)]. A hierarchy has additional levels as necessary to reach single units at its base ’ and ‘R1 = [X(1)1| X(1)2 |…| X(1)b]’, ‘{Rk, R1} =Rj [X(j)1| X(j)2 |…| X(j)a | X(j)a+1| X(j)a+2 |…| X(j)a+b] ’ . In this way, classical datasets that are classified in the Stevens scales of measurement could be mined and combined on a higher abstract structure level. To help better understand the concept, a sequence of schemes illustrating the principles of our model is presented in Figure Additionally, we can include data mining in a more symbolic/abstract way as follows. For an arbitrary j , a hierarchical-cluster-like expression can be defined . For ins X(j)2 /2 hrs], ‘2Subject to future improvements, we envisage that this compact description is versatile to provide better data mining/data usage than from existing methods, although a final version is far from complete at this early stage.11’ arises as a natural modular scale. In contrast, similar approaches might be difficult for a “visual analogue scale”  changes in the following manner: ‘5000 (/mm1 = 145 (mEq/l)’ changes into ‘[Na]2 = 128 (mEq/l)’, because ‘[Na]1 # [Na](1→2) = [Na]2’, the operator for addition is obtain from ‘[Na](1→2) = [Na]2 - [Na]1 = 128 - 145 = - 17 (mEq/l)’. Collectively, the operator for division is ‘[Na](1→2) = [Na]2/[Na]1 = 128/145 (mEq/l)’.For an another example, if ‘[Na](1→2) = R2 - R1R3) | 128 (mEq/l) | X(2)5 (…)] - [2 (mod 7) | 21 (/24 hrs) | 5000 (/mm3) | 145 (mEq/l) | X(1)5 (…)],= [5 (mod 7) | 19.5 (/24 hrs) | 18000 (/mm3) | 128 - 145 (mEq/l) | X(1→2)5 (…)],= [5 - 2 (mod 7) | 19.5 - 21 (/24 hrs) | 18000 - 5000 (/mm3) | - 17 (mEq/l) | X(1→2)5 (…)].= [3 (mod 7) | - 1.5 (/24 hrs) | 13000 (/mm(2→3) = R3 - R2R3) | 158 (mEq/l)] | X(3)5 (…)] - [5 (mod 7) | 19.5 (/24 hrs) | 18000 (/mm3) | 128 (mEq/l) | X(2)5 (…)],= [3 (mod 7) | 22 (/24 hrs) | 7000 (/mm3) | 158 - 128 (mEq/l) | X(2→3)5 (…)],= [3 - 5 (mod 7) | 22 - 19.5 (/24 hrs) | 7000 - 18000 (/mm3) | 30 (mEq/l) | X(2→3)5 (…)],= [- 2 (mod 7) | 2.5 (/24 hrs) | - 11000 (/mm3) | 30 (mEq/l) | X(2→3)5 (…)].= [5 (mod 7) | 2.5 (/24 hrs) | - 11000 (/mm1◊R(1→2)◊R(2→3) = [2 (mod 7) | 21 (/24 hrs) | 5000 (/mm3) | 145 (mEq/l) | X(1)5 (…)]◊[3 (mod 7) | - 1.5 (/24 hrs) | 13000 (/mm3) | - 17 (mEq/l) | X(1→2)5 (…)]◊[5 (mod 7) | 2.5 (/24 hrs) | - 11000 (/mm3) | 30 (mEq/l) | X(2→3)5 (…)],R3) | 145 - 17 +30 (mEq/l) | X(3)5 (…)],= [2 + 3 + 5 (mod 7) | 21 - 1.5 + 2.5 (/24 hrs) | 5000 + 13000 - 11000 (/mm3) | 158 (mEq/l) | X(3)5 (…)],= [10 (mod 7) | 22 (/24 hrs) | 7000 (/mm3) | 158 (mEq/l) | X(3)5 (…)].= [3 (mod 7) | 22 (/24 hrs) | 7000  = R10 - R2 = [0 - 5 (mod 7) | 17 - 19.5 (/24 hrs) | 9000 - 18000 (/mm3) | 130 - 128 (mEq/l) | X(2→10)5 (…)] = [- 5 (mod 7) | - 2.5 (/24 hrs) | - 9000 (/mm3) | 2 (mEq/l) | X(2→10)5 (…)],R(10→11) = R11 - R10 = [6 - 0 (mod 7) | 20 - 17 (/24 hrs) | 20000 - 9000 (/mm3) | 149 - 130 (mEq/l) | X(10→11)5 (…)] = [6 (mod 7) | 3 (/24 hrs) | 11000 (/mm3) | 19 (mEq/l) | X(10→11)5 (…)],R(11→12) = R12 - R11 = [4 - 6 (mod 7) | 23 - 20 (/24 hrs) | 6000 - 20000 (/mm3) | 140 - 149 (mEq/l) | X(11→12)5 (…)] = [- 2 (mod 7) | 3 (/24 hrs) | - 14000 (/mm3) | - 9 (mEq/l) | X(11→12)5 (…)],R(10→13) = R13 - R10 = [1 - 0 (mod 7) | 18 - 17 (/24 hrs) | 5000 - 9000 (/mm3) | 135 - 130 (mEq/l) | X(10→13)5 (…)] = [1 (mod 7) | 1 (/24 hrs) | - 4000 (/mm3) | 5 (mEq/l) | X(10→13)5 (…)],R(13→17) = R17 - R13 = [2 - 1 (mod 7) | 23.5 - 18 (/24 hrs) | 3000 - 5000 (/mm3) | 150 - 135 (mEq/l) | X(13→17)5 (…)] = [1 (mod 7) | 5.5 (/24 hrs) | - 2000 (/mm3) | 15 (mEq/l) | X(13→17)5 (…)].RThe authors declare that they have no competing interests.JS conceived the main concept of this article and wrote the manuscript. SM revised the manuscript. JI gave advice on the potential validity from the viewpoint of clinical research and treatment. Additionally, all authors read and approved the final manuscript.


The aromatic substituents on the sulfonate group are oriented gauche to one another with a C—O—S—C torsion angle of −62.0 (3)°. The supramolecular features that contribute to the crystal lattice are offset π-π and multiple C—H⋯O interactions.The title compound, C 13H10N2O7S, was synthesized via a nucleophilic substitution reaction between 2,4-dinitrophenol and p-toluenesulfonyl chloride. This crystal structure is a polymorph of CSD entry WUVYUH . The aromatic substituents on the sulfonate group are oriented gauche to one another with a C—O—S—C torsion angle of −62.0 (3)°. The supramolecular features that contribute to the crystal stability are offset π–π [centroid–centroid distance = 3.729 (2) Å] and multiple C—H⋯O interactions.The title compound, C Analogous to the carbonyl group, nucleophilic substitution reactions of sulfonyl derivatives have also been reported  reactions similar to those reported by others . The bond angle between the S=O groups (O1—S1—O2) is 121.20 (17)°, while that of the aromatic substituents (O3—S1—C5) is 103.27 (15)°. The two aromatic rings are in a gauche orientation about the O3—S1 bond with a torsion angle (C8—O3—S1—C5) of −62.0 (3)°.The central sulfur atom (S1) is tetrahedral with S=O bond lengths of 1.415 (3) and 1.414 (3) Å, and an S—O bond length of 1.634 (3) Å Fig. 2a. The bet al., 2003ab). While the bond lengths of the two polymorphs agree within 0.01 Å of each other, there are some differences between bond angles. The aromatic rings in WUVYUH are in an anti orientation along the S—O bond, with a torsion angle of 141.02 (9)°. The bond angle between the S=O groups (O1—S1—O2) is 119.80 (6)°, while that of the aromatic substituents (O3—S1—C5) is 98.17 (5)°.For comparison, the polymorph WUVYUH  = 3.379 (4) Å, and O7(nitro)⋯S1v(sulfonic ester) = 3.877 (3) Å. The relatively short intermolecular distance between N2 and O17 suggests the presence of favorable N⋯O interactions in the crystal  is in proximity to the sulfonic ester of the C2–C7et al., 2008ortho-substituent is a nitro group and the para-position bears a second tosylate group. The remaining entries have various electron-rich groups in the ortho-position including methoxy .The CSD contains three additional structures where the position p-toluenesulfonyl chloride (5 mmol) and pyridine (3 mmol) in 10 mL of dichloromethane for 30 minutes at room temperature. The reaction was heated to 353 K for 30 minutes in a microwave reactor, then cooled to room temperature and stirred overnight in a fume hood. The reaction mixture was transferred to a scintillation vial where the pale yellow product crystallized upon standing after several days and was filtered from the mother liquor (m.p. 393.4–394.7 K).The title compound was prepared by stirring 2,4-dinitrophenol (5 mmol), Uiso(H) = 1.2Ueq(C) for CH groups and Uiso(H) = 1.5 Ueq(C) for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015015650/pk2562sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015015650/pk2562Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015015650/pk2562Isup3.cmlSupporting information file. DOI: 1419864CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N-tosylacrylamide compounds, (I) and (II), the conformation about the C=C bond is E. In (I), the furan, phenyl and 4-methylbenzene rings are inclined to the acrylamide mean plane [–NH—C(= O)—C=C–] by 26.47 (11), 69.01 (8) and 82.49 (9)°, respectively. In (II), the phenyl, and 3-methyl and 4-methylbenzene rings are inclined to the acrylamide mean plane by 11.61 (10), 78.44 (10) and 78.24 (10)°, respectively. In the crystals of both compounds, molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers with In the title  N-tosylacrylamide compounds, C20H17NO4S, (I), and C23H21NO3S, (II), the conformation about the C=C bond is E. The acrylamide groups, [–NH—C(=O)—C=C–], are almost planar, with the N—C—C=C torsion angle being −170.18 (14)° in (I) and −168.01 (17)° in (II). In (I), the furan, phenyl and 4-methylbenzene rings are inclined to the acrylamide mean plane by 26.47 (11), 69.01 (8) and 82.49 (9)°, respectively. In (II), the phenyl, 3-methylbenzene and 4-methylbenzene rings are inclined to the acrylamide mean plane by 11.61 (10), 78.44 (10) and 78.24 (10)°, respectively. There is an intramolecular C—H⋯π interaction present in compound (II). In the crystals of both compounds, molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R22(8) ring motif. In (I), the dimers are reinforced by C—H⋯O hydrogen bonds and linked by C—H⋯π interactions, forming chains along [011]. In the crystal of (II), the dimers are linked via C—H⋯O hydrogen bonds, forming chains along [100]. The chains are further linked by C—H⋯π interactions, forming layers parallel to (010).In the title  There is also a C—H⋯π interaction present, linking the chains to form layers lying parallel to (010).In the crystal of both compounds, molecules are linked by pairs of N—H⋯O hydrogen bonds Tables 1 and 2 ▸,et al., 2016N-(phenylsulfonyl)acrylamide yielded five hits. Four of these compounds involve the 4-methylbenzenesulfonyl group and one compound involves a phenylsulfonyl group. This later compound, 2-(4-chlorophenyl)-3-(2-furyl)-N-(phenylsulfonyl)acrylamide : 4-methylbenzenesulfonyl azide (4.5 mmol), CuI , Et4NI , ethynylbenzene (4.5 mmol), and furan-2-carbaldehyde (3 mmol) were suspended in CH2Cl2 (5 ml) in a 10 mL Schlenk tube under nitrogen at rt. LiOH  was then added, and the resulting solution was stirred at this temperature. Upon full consumption of furan-2-carbaldehyde, the reaction was quenched by saturated aqueous NH4Cl (5 ml) and extracted with CH2Cl2 (10 ml × 3). The combined organic layers were dried over anhydrous Na2SO4 and concentrated in vacuo. The crude residue was purified by column chromatography on silica gel (n-hexane/EtOAc 5:1 v/v) to afford compound (I)n-hexane/EtOAc and after slow evaporation over several days, colourless crystals suitable for analysis by X-ray diffraction were formed.Compound (II): 4-methylbenzenesulfonyl azide (4.5 mmol), CuI , Et4NI , 1-ethynyl-3-methylbenzene (4.5 mmol), and benzaldehyde (3 mmol) were suspended in CH2Cl2 (5 ml) in a 10 mL Schlenk tube under nitrogen at rt. LiOH  was then added, and the resulting solution was stirred at this temperature. Upon full consumption of benzaldehyde, the reaction was quenched by saturated aqueous NH4Cl (5 ml) and extracted with CH2Cl2 (3 × 10 ml). The combined organic layers were dried over anhydrous Na2SO4 and concentrated in vacuo. The crude residue was purified by column chromatography on silica gel (n-hexane/EtOAc 5:1 v/v) to afford compound (II)n-hexane/EtOAc and after slow evaporation over several days, colourless block-like crystals were obtained.Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989016007611/su5296sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: Click here for additional data file.10.1107/S2056989016007611/su5296Isup2.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016007611/su5296IIsup3.cmlSupporting information file. DOI: 1478730, 1478729CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, supramolecular chains are formed  13H10N2O2 , features an almost planar (r.m.s. deviation = 0.0095 Å) central C3O2 core consolidated by an intramolecular hydroxy-O—H⋯O(carbonyl) hydrogen bond. Twists are evident in the molecule, as seen in the dihedral angles between the central core and the 2- and pyridin-3-yl rings of 8.91 (7) and 15.88 (6)°, respectively. The conformation about the C=C bond [1.3931 (17) Å] is Z, and the N atoms lie to the same side of the molecule. In the molecular packing, supramolecular chains along the a axis are mediated by π(pyridin-2-yl)–π(pyridin-3-yl) interactions [inter-centroid distance = 3.7662 (9) Å]. The observation that chains pack with no directional interactions between them is consistent with the calculated electrostatic potential, which indicates that repulsive interactions dominate.The title compound, C III and GaIII octahedral building blocks for network structures linked by AgI ions -2,4-pentanedione as well as the mixed-MOF with AgNO3 in a two-dimensional honeycomb structure while at higher AgI concentrations, a one-dimensional ladder motif was formed versus hydroxy-O atoms is not readily confirmed by a great disparity in the C1—O1 [1.2871 (14) Å] and C3—O2 [1.3041 (14) Å] bond lengths. The assignment was based on an unrestrained refinement of the H1O atom which resulted in a O2—H1O bond length of 1.090 (18) Å. More certainty is associated with the assignment of the nitrogen atoms in the pyridyl rings. Thus, the short C5—N1 and C4—N1 [1.3325 (17) and 1.3484 (15) Å] and C10—N2 and C11—N2 [1.3371 (17) and 1.3397 (18) Å] bond lengths cf. the C—C bonds in the rings confirm their assignment. The central C3O2 residual in (I)syn arrangement of the oxygen atoms enables the formation of an intramolecular hydroxy-O—H⋯O(carbonyl) hydrogen bond, Table 1Z, and, to a first approximation, the N1 and N2 atoms lie to the same side of the molecule.In (I)Cg(N1-pyridinyl)⋯Cg(N2-pyridinyl) = 3.7662 (9) Å, angle of inclination = 7.45 (6)° for symmetry operation 1 + x, y, z]. The result is the formation of a linear supramolecular chain, Fig. 2a. The chains pack with no directional interactions between them in accord with the distance criteria in PLATON , is viewed as bright-red spots near these atoms on the Hirshfeld surface mapped over dnorm, Fig. 4From the Hirshfeld surface mapped over electrostatic potential, Fig. 3gs Fig. 2a, is via, and those delineated into H⋯H, C⋯C, O⋯H/H⋯O, C⋯H/H⋯C and N⋯H/H⋯N contacts are illustrated in Fig. 5b–f, respectively; their relative contributions to the surface are quantified in Table 2et al., 2007b, with a single peak at  less than the van der Waals separation corresponding to a short H13⋯H13 contact of 2.33 Å . The short interatomic C5⋯C10 contact and π–π stacking interactions appear as an arrow-like distribution of points with the tip at de + di ∼ 3.3 Å . The presence of π–π stacking interactions between the pyridyl rings is also apparent from the appearance of red and blue triangle pairs on the Hirshfeld surface mapped with shape-index property identified with arrows in the image of Fig. 6The overall 2D fingerprint plot, Fig. 5 Å Fig. 5c. The pd–f. However, the points are distributed at  distances greater than their respective van der Waals separations. This is consistent with the repulsion between the atoms having electrostatic negative potential dominating the molecular packing, hence the lack of specific intermolecular interactions between supramolecular chains.The two-dimensional fingerprint plots delineated into O⋯H/H⋯O, C⋯H/H⋯C and N⋯H/H⋯N interactions exhibit their usual characteristic features in their respective plots; Fig. 4et al., 2016et al.  solution afforded colourless crystals. Yield: 4.03 g (70.7%). M.p: 377–378 K. IR (KBr pellet) νmax/cm−1: 3121 (m), 3053 (m), 2922 (m), 2853 (m), 1611 (s), 1595 (s), 1539 (m), 1458 (m), 1418 (m), 1221 (m), 1188 (m), 1146 (m), 1115 (m), 1067 (m), 1018 (m), 989 (m), 926 (m), 775 (s), 739 (m), 679 (s), 611 (m). Analysis calculated for C13H10N2O2: C, 69.03; H, 4.42; N, 12.19. Found: C, 68.73; H, 4.54; N, 12.16. MS: m/z 226. 1H NMR  δ 9.22 , 8.82 , 8.44 , 8.17 , 8.09 , 7.70 , 7.63 .2-Acetylpyridine  was added to a suspension of NaH  in anhydrous THF (10 ml) at room temperature with stirring. Ethyl nicotinate  in anhydrous THF (10ml) was added dropwise to the mixture over 3 min. The yellow mixture was refluxed under a nitrogen atmosphere for 1.3 h and then quenched with ice–water (50 ml). Glacial acetic acid was added to adjust the pH to 6–7. The resulting yellow precipitate was collected by filtration, washed with cold water and dried under vacuum. Recrystallization from dichloromethane–hexane (1:1 Uiso(H) set to 1.2Ueq(C). The hydroxy-H atom was located in a difference map and refined with O—H = 0.82±0.01Å, and with Uiso(H) set to 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S205698901600832X/hb7587sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901600832X/hb7587Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901600832X/hb7587Isup3.cmlSupporting information file. DOI: 1481225CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


A and B) in the asymmetric unit. In the crystal, individual molecules are linked by pairs of O—H⋯O hydrogen bonds, forming A–A and B–B inversion dimers with The title compound, crystallized with two conformationally similar molecules  in the asymmetric unit. The two molecules have the same conformation; the molecular overlap gives weighted and unit-weight r.m.s. fits of 0.047 and 0.043 Å, respectively. The conformation of the N-(hydroxethyl)formamide chains are very similar, as indicated by the C—N(H)—C=O and C—N(H)—C—O(H) torsion angles, which are, respectively, −1.8 (3) and −91.5 (2)° for molecule A, and −2.1 (3) and −95.7 (2)° for molecule B. In the crystal, individual molecules are linked by pairs of O—H⋯O hydrogen bonds, forming A–A and B–B inversion dimers with R22(12) ring motifs. The dimers are linked via N—H⋯O hydrogen bonds, forming alternating layers of A and B molecules parallel to the bc plane. Within the layers of B molecules, there are weak C—H⋯Cl hydrogen bonds present.The title compound, C This has led to the use of formamides as key intermediates in numerous organic synthetic endeavours (Kobayashi A and B) in the asymmetric unit. The arbitrarily chosen chirality of atoms C2 in molecule A and C5 in molecule B is the same. The backbones of the two molecules  have almost identical conformations with weighted and unit-weight r.m.s. overlay fits of 0.047 and 0.043 Å, respectively, for the six atoms in each molecule formamide, yielded 25 hits. The majority concern metal complexes of the ligand N-(hydroxymethyl)nicotinamide. Only one compound, N,N′-diformamide formamide chain as indicated by the C—N(H)—C—O(H) and C—N(H)—C=O torsion angles: 1.6 (2) and −99.09 (14)° for the above mentioned compound compared to −1.8 (3) and −91.5 (2)° for molecule A and −2.1 (3) and −95.7 (2)° for molecule B of the title compound formamide was dissolved in hot ethanol, followed by treatment with charcoal. The filtered solution was left to crystallize by slow evaporation, forming colourless block-like crystals (m.p. 393 K).The title compound can be synthesized following a literature procedure  I. DOI: 10.1107/S2056989015020459/hg5462Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015020459/hg5462Isup3.cmlSupporting information file. DOI: 1009715CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The two aromatic rings present in the molecule are almost coplanar, forming a dihedral angle of 1.4 (2)°. The five-membered ring involving the metal atom is puckered, with an amplitude Q = 0.358 (2) Å and ϕ = 204.1 (6)°. In the crystal, pairs of inversion-related molecules are linked by O—H⋯N hydrogen bonds. An O—H⋯O hydrogen bond connects the water ligand to the dimethylformamide solvent molecule. The crystal packing also features π–π [centroid–centroid distance of 3.688 (2) Å] and C—H⋯O interactions.The title compound, [Mo(C The complex adopts a distorted octahedral geometry around the Mo atom  Å] is close to the reported C—O single bond length  and −1.4 (4)°, respectively]. This configuration is similar to that of the metal-free ligand Å and ϕ = 204.1 (6)°.The ligand adopts D⋯A distances 2.891 (4) and 2.701 (4) Å respectively, and a non-classical C—H⋯O interaction with a D⋯A distance of 3.421 (5) Å. These interactions connect pairs of molecules along with the solvent dimethylformamide. The complex molecule is stacked along the b axis through two different types of O—H⋯π interaction  with a centroid-centroid distance of 3.688 (2) Å  for 3 h. The brown precipitate obtained was filtered, washed with methanol, dried and recrystallized from dimethylformamide . FT–IR  νmax: 3400, 3194, 1657, 1546, 1345, 937, 810.The complex was synthesized by refluxing a methanolic solution of benzoyl hydrazone  and MoClUiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl C). The O—H distances were restrained with 1,2 and 1,3 distance restraints of 0.86 (1) and 1.36 (2) Å. Reflections (0 0 2), (1 0 1) and  I. DOI: 10.1107/S2056989015009639/pk2550Isup2.hklStructure factors: contains datablock(s) I. DOI: 1401828CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Weak C—H⋯Cl and C—H⋯S hydrogen-bonding interactions consolidate the packing of the structure.The title cobalt(II) complex consists of a CoCl 3CS)2C=NC  N}2CoCl2], consists of a CoII atom coordinated in a distorted tetrahedral manner by two Cl− ligands and the terminal N atoms of two dimethyl N-cyanodithioiminocarbonate ligands. The two organic ligands are almost coplanar, with a dihedral angle of 5.99 (6)° between their least-squares planes. The crystal packing features pairs of inversion-related complexes that are held together through C—H⋯Cl and C—H⋯S interactions and π–π stacking [centroid-to-centroid distance = 3.515 (su?) Å]. Additional C—H⋯Cl and C—H⋯S interactions, as well as Cl⋯S contacts < 3.6 Å, consolidate the crystal packing.The structure of the mononuclear title complex, [{(H N-cyanodithioiminocarbonate with its two N and two S atoms has four possible coordination sites and hence should present a high coordination ability. The behaviour of N and S atoms according to Pearson’s concept as hard and soft donors, respectively, may allow coordination to both hard and soft Lewis acids. Despite this coordination property, the ligand has scarcely been studied. Only one crystalline compound with dimethyl N-cyanodithioiminocarbonate as a ligand has been reported previously  chloride hexahydrate and dimethyl N-cyanodithioiminocarbonate which has yielded the title complex, [{(H3CS)2C=NC  N}2CoCl2].Dimethyl II atom coordinated in a distorted tetrahedral manner by two Cl− ligands and the cyanide N atoms of two dimethyl N-cyanodithioiminocarbonate ligands °]. The CoII atom lies 0.437 (2) and 0.557 (2) Å from the mean planes of the two ligands.The structure of the title complex consists of a Cods Fig. 1. Co—Cl ads Fig. 1. The Cl—t Table 1. Despite3C—S groups of the adjacent molecule, presumably reducing steric interactions. Apart from C—H⋯Cl and C—H⋯S interactions (Table 2(su?) Å prevails within a pair of complex molecules. In the crystal, these pairs are arranged parallel to (110)  Fig. 2. Additio0) Fig. 2.2·6H2O  in acetonitrile (30 ml) and dimethyl N-cyanodithioiminocarbonate  in acetonitrile (20 ml) at room temperature. The resulting blue solution was stirred for about 2 h. Blue crystals suitable for single-crystal X-ray diffraction were obtained after six days of slow solvent evaporation at room temperature (300 K).All chemicals were purchased from Aldrich (Germany) and were used as received. The title compound was prepared by mixing of CoClν(C N) 2224 cm−1, ν(C=N) 1458 cm−1, ν(CS2) + rocking CH3 1024 and 962 cm−1. Melting point 398 K. Elemental analyses of C8H12Cl2CoN4S4: calculated (found): C 22.75 (21.91), H 2.86 (3.43), N 13.27 (12.63), S 30.37 (29.40).Infra-red bands: Uiso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989015023439/wm5249sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015023439/wm5249Isup2.hklStructure factors: contains datablock(s) I. DOI: 1440755CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II complex, the MnII atom is coordinated by two 4-nitrobenzoate (NB) anions, two nicotinamide (NA) ligands and two water molecules; the NB and NA ligands act as monodentate ligands. The resulting MnN2O4 coordination polyhedron is a distorted octahedron.In the title centrosymmetric Mn 7H4NO4)2(C6H6N2O)2(H2O)2], contains one MnII atom, one 4-nitrobenzoate (NB) anion, one nicotinamide (NA) ligand and one water molecule; NA and NB each act as a monodentate ligand. The MnII atom, lying on an inversion centre, is coordinated by four O atoms and two pyridine N atoms in a distorted octahedral geometry. The water molecules are hydrogen bonded to the carboxylate O atoms. The dihedral angle between the carboxylate group and the adjacent benzene ring is 24.4 (3)°, while the benzene and pyridine rings are oriented at a dihedral angle of 86.63 (11)°. In the crystal, O—H⋯O and N—H⋯O hydrogen bonds link the molecules, forming a layer parallel to the ab plane. The layers are further linked via weak C—H⋯O hydrogen bonds, a π–π stacking interaction [centroid–centroid distance = 3.868 (2) Å] and a weak C—H⋯π interaction, resulting in a three-dimensional network.The asymmetric unit of the title compound, [Mn(C A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. The NA ring is the reactive part of nicotinamide adenine dinucleotide (NAD) and its phosphate (NADP), which are the major electron carriers in many biological oxidation–reduction reactions manganese bis(4-nitrobenzoato)manganese  of the two symmetry-related monodentate NB anions and the two symmetry-related water O atoms (O6 and O6iii) around the MnII atom form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination sphere is completed by the two pyridine N atoms (N2 and N2iii) of the two symmetry-related monodentate NA ligands in the axial positions  in the carboxylate group indicates delocalized bonds rather than localized single and double bonds. The Mn—O bond lengths [2.156 (2) and 2.115 (2) Å] and the Mn—N bond length [2.134 (3) Å] are close to the standard values. Atom Mn1 lies 0.4172 (1) Å above the O1/O2/C1 plane of the carboxylate group. The O—Mn—O and O—Mn—N bond angles deviate slightly from the ideal value of 90°. The dihedral angle between the carboxylate group (O1/O2/C1) and the adjacent benzene (C2–C7) ring is 24.4 (3)°, while the benzene ring and the pyridine (N2/C8–C12) ring are oriented at a dihedral angle of 86.63 (11)°.na⋯Ona (na = nicotinamide), N—Hna⋯Oc (c = carboxylate group) and O—Hw⋯Ona (w = water) hydrogen bonds  Å; symmetry code: (ix) 1 − x, −y, 1 − z, where Cg1 is the centroid of the C2–C7 ring].In the crystal, intermolecular N—Hs Table 1 link thene Fig. 2. In the n Table 1 and a π–4·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 colourless single crystals.The title compound was prepared by the reaction of MnSOA and H3B of the NH2 group were located in a difference Fourier map, and their coordinates were refined with distance restraints of O—H = 0.85 (2) Å and N—H = 0.86 (2) Å, and with Uiso(H) = 1.5Ueq. The C-bound H atoms were positioned geometrically with C—H = 0.93 Å and were 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 210.1107/S2056989016005612/is5449sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016005612/is5449Isup2.hklStructure factors: contains datablock(s) I. DOI: 1472331CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


III atom in the title molecule adopts a distorted octahedral coordination sphere, being C,N-chelated by two 2-(pyridin-2-yl)phenyl ligands and N,O-chelated by one ancillary 2-[(phenylimino)methyl]phenolate ligand. The crystal packing is stabilized by intermolecular C—H⋯π interactions and π–π interactions.The Ir 11H8N)2(C13H10NO)]·CH2Cl2, the IrIII ion is six-coordinated by two C,N-bidentate 2-(pyridin-2-yl)phenyl ligands and one N,O-bidentate 2-[(phenylimino)methyl]phenolate anion, giving rise to a distorted octahedral environment. The C,N-bidentate ligands, in which the C and N atoms are statistically disordered over two sites and therefore both pairs of C and N atoms are trans and cis relative to each other, are almost perpendicular to each other [the dihedral angle between the least-square planes is 87.00 (4)°]. An intramolecular C—H⋯O hydrogen bond, as well as intermolecular C—H⋯π interactions and π–π interactions, contribute to the stabilization of the molecular and crystal structure.In the title compound, [Ir(C III complexes are of great interest due to their excellent phosphorescent properties and electroluminescence applications. In particular, heteroleptic IrIII complexes with imine-based ancillary ligands exhibit aggregation-induced phosphorescent emission (AIPE), resulting in enhanced phosphorescence phenomena in the solid state 2(C13H10NO)]·CH2Cl2, a heteroleptic IrIII complex with an ancillary salicylimine ligand.Cyclometallated IrIII ion, two 2-(pyridin-2-yl)phenyl ligands, and one 2-[(phenylimino)methyl]phenolate anion. The IrIII ion adopts a distorted octahedral coordination geometry, being N,O-chelated by the 2-[(phenylimino)methyl]phenolate ligand and C,N-chelated by two 2-(pyridin-2-yl)phenyl ligands, in which the C and N atoms are equally disordered over two sites and therefore both pairs of C and N atoms are trans and cis relative to each other. The equatorial plane is formed by N1/O1/N2/C12 atoms, the mean deviation from the least-squares plane being 0.002 Å. The IrIII ion is displaced by 0.0481 (9) Å from the equatorial plane towards the axial imino N3 atom. The C,N-bidentate ligands are nearly perpendicular to each other, with a dihedral angle between the least-squares planes of 87.00 (4)°. Within the C,N-bidentate ligands, the dihedral angles between the aromatic rings are 3.70 (10) (between rings C1–C6 and N1/C7–C11) and 7.67 (16)° (between rings C12–C17 and N2/C18–C22). As shown in Table 1III compounds, e.g. {(E)-2-[methyl]phenolato-κ2N,O}bisiridium(III) -2-[methyl]phenolato-κ2N,O}bisiridium(III) -2-[(phenylimino)methyl]phenolato-κ2N,O}bisiridium(III)  Å and Cg3⋯Cg4 = 3.8873 (17) Å; Cg1, Cg3 and Cg4 are the centroids of the N1/C7–C11, C12–C17 and C30–C35 rings, respectively; symmetry code: (ii) −x + 1, −y + 2, −z + 1] contribute to the stabilization of the crystal structure  = 1.2Ueq of the parent atom.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989016008100/wm5290sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989016008100/wm5290Isup2.hklStructure factors: contains datablock(s) I. DOI: 1480710CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II cation while a water molecule further coordinates to the CuII cation to complete the elongated distorted octahedral coordination geometry.In a hydrated copper(II) complex, 2-amino-7-methyl-4-oxidopteridine-6-carboxylate and 1,10-phenanthroline ligands chelate the Cu 8H5N5O3)(C12H8N2)(H2O)]·3H2O, the CuII cation is O,N,O′-chelated by the 2-amino-7-methyl-4-oxidopteridine-6-carboxylate anion and N,N′-chelated by the 1,10-phenanthroline (phen) ligand. A water molecule further coordinates to the CuII cation to complete the elongated distorted octahedral coordination geometry. In the molecule, the pteridine ring system is essentially planar [maximum deviation = 0.055 (4) Å], and its mean plane is nearly perpendicular to the phen ring system [dihedral angle = 85.97 (3)°]. In the crystal, N—H⋯O, O—H⋯N and O—H⋯·O hydrogen bonds, as well as weak C—H⋯O hydrogen bonds and C—H⋯π interactions, link the complex molecules and lattice water molecules into a three-dimensional supramolecular architecture. Extensive π–π stacking between nearly parallel aromatic rings of adjacent molecules are also observed, the centroid-to-centroid distances being 3.352 (2), 3.546 (3), 3.706 (3) and 3.744 (3) Å.In the title compound, [Cu(C Location of the pyrazine ring N atom (N6) in the equatorial plane is in agreement with earlier observations on related copper and cobalt complexes  Å] may be elucidated in the light of Joule’s hypothesis  complexes chelated by the pterin-6-carboxylate anion have been reported by Kohzuma  al. 1989 and Funa al. 1999. In both8H7N5O3·1.5H2O) was obtained by a published procedure  containing Cu(NO3)2·3H2O , 1,10-phenanthroline monohydrate  and pterin  dissolved in NaOH  for 60 h at 310–312 K under subdued light; additional NaOH solution was added for adjusting the initial pH at 10.5. Within a short while the initial bright-green solution turned hazy blue due to the presence of a fine white precipitate which gradually disappeared substantially. The final blue solution was slightly hazy. Upon storage under aerobic conditions for one week the clear blue solution yielded green crystals, suitable for X-ray structure determination. Analysis calculated for C20H21CuN7O7: C 44.90, H 3.93, N 18.33%; found: C 44.38, H 4.06, N 17.65%. ESIMS data: the molecular ion peak [M + 2H]+ appeared at 536.4 (relative abundance = 41.2%); the [M − 4H2O − 3H]+ peak was observed at 459.2 (relative abundance = 100%), indicating stability of the desolvated ternary species arising from the title complex.Method B. Using NaBH4 reduction in equimolar proportion of the original complex (obtained by Method A) and subsequent aerial reoxidation of the reduced complex to the present crystals merits attention due to the involvement of intricate redox chemistry. The NaBH4 treatment  to be Na2[Cu2I(L′)2(phen)(H2O)4]·2H2O, where L′ is the 7,8-dihydro form of the present pterin ligand anion (C8H5N5O3) .Method B, represent better accuracy [R = 0.057 and wR(F2)= 0.135] as compared to the other one [R = 0.113 and wR(F2) = 0.279].Although the title compound could be obtained by two alternative methods, the present structural data obtained using the crystals from E°′ value of −0.68 V; now using an E°′ value of −0.80 V for NaBH4 in neutral medium  for the FeIII–tetrahydrobiopterin reduction in phenylalanine hydroxylase ; using an E°′ value of 0.70 V for the O2/H2O2 couple, an Ecell value of 1.37 V is obtained, indicating facile aerial oxidation. Now using an E°′ value of 0.19 V for the chelated pterin ligand  = 1.2–1.5Ueq.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S1600536814022302/xu5822sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814022302/xu5822Isup2.hklStructure factors: contains datablock(s) I. DOI: 1028413CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The highlighted ruthenium complex forms discrete dimers by π–π stacking interactions and hydrogen bonds. This combination of interactions results in an unusual nearly face-to-face π–π stacking mode. 14H16N4)(C16H8N4)](PF6)2·1.422CH3CN, discrete dimers of complex cations, [Ru(L–N4H2)tape]2+ are formed {L–N4H2 = 2,11-diaza[3.3]pyridinophane; tape = 1,6,7,12-tetraazaperylene}, held together by π–π stacking interactions via the tape ligand moieties with a centroid–centroid distance of 3.49 (2) Å, assisted by hydrogen bonds between the non-coordinating tape ligand α,α′-diimine unit and the amine proton of a 2,11-diaza[3.3]-pyridinophane ligand of the opposite complex cation. The combination of these interactions leads to an unusual nearly face-to-face π–π stacking mode. Additional weak C—H⋯N, C—H⋯F, N—H⋯F and P—F⋯π-ring  (with F⋯centroid distances of 2.925–3.984 Å) interactions are found, leading to a three-dimensional architecture. The RuII atom is coordinated in a distorted octahedral geometry, particularly manifested by the Namine—Ru—Namine angle of 153.79 (10)°. The counter-charge is provided by two hexafluoridophosphate anions and the asymmetric unit is completed by acetonitrile solvent molecules of crystallization. Disorder was observed for both the hexafluoridophosphate anions as well as the acetonitrile solvate molecules, with occupancies for the major moieties of 0.801 (6) for one of the PF6 anions, and a shared occupancy of 0.9215 (17) for the second PF6 anion and a partially occupied acetonitrile molecule. A second CH3CN molecule is fully occupied, but 1:1 disordered across a crystallographic inversion center.In the title compound, [Ru(C The microwave-assisted synthesis of the precursor [Ru(L–N4Me2)]2+, starting from [Ru(DMSO)4Cl2] and L–N4Me2, in an ethanolic solution finished within 30 min. It is not only fast, but also reproducible with only few byproducts, and hence requires no labor-intensive workup. Moreover, using the C2v symmetric macrocycle rather than bipyridine-type ligands avoids the formation of mono- and dinuclear complexes with multiple stereoisomeric forms -pyridinophane (L–N4H2) as a new ligand for RuII. Herein, we present the structure of the complex [Ru(L–N4H2)tape](PF6)2, , obtained as its acetonitrile solvate.Heteroaromatic ligands with more than three fused rings are commonly called large-surface ligands. Such ligands have attracted attention due to their use as connecting building blocks for supramolecular assemblies. If large-surface ligands feature more than one ligand donor site, connection between neighboring complexes can be realized through normal metal coordination (Ishow 4H2)tape]2+ in [Ru(C14H16N4)(C16H8N4](PF6)2·1.422CH3CN. The Ru—N bond lengths formed by the tape ligand (Table 14Me2)tape]2+ °] from the idealized value of 180° is slightly larger than for analogous ruthenium L–N4Me2 complexes 2+, the dimers are also connected through bifurcated hydrogen bonds between one of the two L–N4H2 ligand amine protons and both nitrogen atoms of the non-coordinating tape ligand α,α′-diimine unit of the second complex cation of the dimer. In the crystal structure, these additional hydrogen bonds result in a short Ru⋯Ru distance of 8.8306 (2) Å, a tape ligand centroid–centroid distance of 3.49 (2) Å and an angle of 13.7 (1.4)° between the ring normal and the centroid-to-centroid vector. Therefore, the π–π stacking motif can be described as parallel-displaced, but near to face-to-face -pyridinophane, see Brietzke, Mickler, Kelling, Schilde et al. tape](PF6)2 was synthesized as reported for [Ru(L–N4Me2)tape](PF6)2  instead of L–N4Me2. A yield of 44%  was obtained; m.p. > 573 K. 1H NMR = (MeCN–d3): δ = 8.69 , 8.56 , 8.01 , 7.77 , 7.72 , 7.65 , 5.6 , 4.83 , 4.47  p.p.m. 13C NMR = (MeCN-d3): δ = 160.0 (C2 + C6), 152.4 (Ce), 150.28 (Cd), 150.24 (Ca), 145.7 (Cf), 138.9 (C4), 136.7 (Cb′), 123.5 (Cb), 122.7 (C3 + C5), 122.0 (Cc), 119.3 (Ce′), 64.8 (CH2) p.p.m. ESI=-MS: calculated for [M–PF6]+ 743.0809; found 743.0778.The syntheses of the ligands L–N4H2)tape](PF6)2. The solution was filled into a test tube, which was placed into a diethyl ether-containing bottle. Dark-green crystals began to form at ambient temperature within a few days.Crystals suitable for X-ray structure analysis were obtained by vapor diffusion of diethyl ether into a saturated acetonitrile solution of [Ru(L–N6 anions were refined as disordered over one major and one minor moiety each. The geometry of the minor moieties were each restrained to be similar to that of the major moieties (within an estimated standard deviation of 0.02 Å). The minor moieties were subjected to a rigid bond restraint , and the anisotropic displacement parameters of the major and minor phosphorus atoms were each constrained to be identical. Associated with the major moiety of the PF6 anion of P1 is an acetonitrile molecule that is absent for the minor moiety. Subject to the restraints and constraints used, the occupancy ratios refined to 0.9215 (17) to 0.0785 (17) for the PF6 units of P1A and P1B, and to 0.801 (6) and 0.199 (6) for those of P2A and P2B.Disorder was observed for both the hexafluoridophosphate anions as well as the acetonitrile solvate molecules. Both PFUij components to their neighbors closer than 2 Å, including those of symmetry-related atoms .A second acetonitrile molecule is disordered across a crystallographic inversion center, with substantial overlap for the two carbon atoms of symmetry-related molecules. The geometry of the molecule was restrained to be similar to that of the first acetonitrile molecule, and the ADPs of its C and N atoms were restrained to be have similar 3), 0.99 (CH2), 0.95 (Carom), N—H = 1.0 Å, and with Uiso(H) = 1.2Ueq(C) with the exception of methyl hydrogen atoms, which were refined with Uiso(H) = 1.5Ueq(C).All hydrogen atoms connected to C and N atoms were placed in their expected calculated positions and refined as riding with C—H = 0.98  global, I. DOI: 10.1107/S1600536814021060/zl2602Isup2.hklStructure factors: contains datablock(s) I. DOI: 1025408CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Water molecules play an important role in the structure connectivity.In a novel one-dimensional hybrid compound, the inorganic part contains zigzag chains formed by corner-sharing [SbCl catena-poly[[[bis [tetraachloridoantimonate(III)]-μ-chlorido-[tetrachloridoantimonate(III)]-μ-chlorido]] monohydrate], {(C6H14N2)2[Sb2Cl10]·H2O}n, is self-assembled into alternating organic and inorganic layers parallel to the bc plane. The anionic inorganic layer consists of infinite zigzag chains of corner-sharing [SbCl6]3− octahedra running along the b axis. The organic part is made up of 1,4-diazoniabicyclo[2.2.2]octane dications (dabcoH22+). The water molecules in the structure connect inorganic and organic layers. Hydrogen-bonding interactions between the ammonium groups, water molecules and Cl atoms ensure the structure cohesion.The hybrid title compound,  Ra)n+MbX3b+na}  are able to combine desirable characteristics from both types of constituents into a molecular scale composite. These hybrids have been extensively studied for their excitonic and magneto-optical properties. In recent years, a significant number of organic–inorganic hybrid materials based on antimony–halide units have been studied. Six-coordinate antimony halides can arrange themselves in three-, two- or one-dimensional networks through sharing halides in the SbX6 octahedra, separated by organic cations 2[Sb2Cl10]·H2O, (I)2)2+ dications, a corner sharing bi-octahedron decachloridodiantimonate(III) anion and one crystallization water molecule. The cations are labeled Cat1 (containing atoms N1 and N2) and Cat2 (containing N3 and N4) and the atomic numbering scheme is shown in Fig. 1The asymmetric unit of the new chloridoantimonate(III) compound, 2)2+ cations located in the holes around the corner-sharing octahedra. The layers are stacked along the a axis and water molecules connect the organic and inorganic components ts Fig. 2.6]3− and [Sb2Cl6]3−) joined by the Cl2 ion. Both octahedra are severely distorted with Sb—Cl bond lengths lying in the range of 2.5233 (18)–3.073 (2) Å for the bridging ones and 2.4277 (15)–2.8233 (17) Å for the terminal ones. The two bridging halides (Cl2 and Cl4) connecting the central octahedron to its neighbours are related cis, leading to zigzag chain of corner-sharing [SbCl6]3− octahedra running along the b axis is Fig. 3.P63/m) 2+ cations exhibit deviations from ideal Dh3 symmetry. The observed lowering symmetry  is probably due to the distortion of the (dabcoH2)2+ cation and can be related to the complex hydrogen-bond network linking the molecular components .It is worth noting that at room temperature the DABCO molecule crystallizes in the hexagonal system (Pna21). These are two indispensable conditions making this phase a potential promising candidate for non-linear optical (NLO) behaviour as is the case for the well-known KTiOPO4 (KTP) and equivalent efficient NLO materials.The studied compound crystals are transparent and the structure is noncentrosymmetric (2)2+ cations and two water molecules via hydrogen bonds  −x + 1, −y + 1, −z − x + y − z − via Cl1⋯H2iii—N2iii, Cl3⋯H2iii—N2iii and Cat2 by Cl3⋯H4ii—N4ii 3− octahedra via O—H13A⋯Cl5 and O—H13B⋯Cl9iii ·2H2O containing isolated [Sb2Cl10]4− double octahedra, (dabcoH2)2+ cations and water molecules 2NH(CH2)2NH3]2+, see: Bujack & Angel  and DABCO (0.5 mmol) was dissolved in a hydrochloric aqueous solution and stirred for several minutes at 353 K. Colourless crystals suitable for X-ray diffraction analysis were obtained by slow evaporation at room temperature after two weeks.A mixture of SbClSHELXL  I, New_Global_Publ_Block. DOI: 10.1107/S2056989015007379/vn2091Isup2.hklStructure factors: contains datablock(s) I. DOI: 943047CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal structure of 2,2′′-bis-1,1′:4′,1′′-terphenyl as the tris(triethylamine) solvate, the diol host molecule possesses a ‘folded’ molecular conformation with inversion symmetry. Two of the three solvent molecules form O—H⋯N hydrogen bonds and the third one forms C—H⋯N hydrogen bonds with the host compound. 44H26Cl4O2·3C6H15N, the asymmetric part of the unit cell comprises two halves of the diol molecules, 2,2′′-bis-1,1′:4′,1′′-terphenyl, and three molecules of triethylamine, i. e. the diol molecules are located on crystallographic symmetry centres. Two of the solvent molecules are disordered over two positions [occupancy ratios of 0.567 (3):0.433 (3) and 0.503 (3):0.497 (3)]. In the diol molecules, the outer rings of the 1,1′:4′,1′′-terphenyl elements are twisted with reference to their central arene ring and the mean planes of the fluorenyl moieties are inclined with respect to the terphenyl ring to which they are connected, the latter making dihedral angles of 82.05 (8) and 82.28 (8)°. The presence of two 9-fluoren-9-ol units attached at positions 2 and 2′′ of the terphenyl moiety induces a ‘folded’ geometry which is stabilized by intramolecular C—H⋯O hydrogen bonds and π–π stacking interactions, the latter formed between the fluorenyl units and the central ring of the terphenyl unit [centroid–centroid distances = 3.559 (1) and 3.562 (1) Å]. The crystal is composed of 1:2 complex units, in which the solvent molecules are associated with the diol molecules via O—H⋯N hydrogen bonds, while the remaining solvent molecule is linked to the host by a C—H⋯N hydrogen bond. The given pattern of intermolecular interactions results in formation of chain structures extending along [010].In the title solvate, C Moreover, the location of the central ring of the terphenyl unit between the fluorenyl units [ring centroid distances = 3.559 (1) and 3.562 (1) Å] indicate the presence of π–π stacking interactions  with respect to the inner ring (A or A′)  Fig. 2 of the td(H⋯N) 1.91–1.95 Å] (Table 1via C—H⋯O hydrogen bonding , giving an overall chain structure extending along [010] -1,1′:2′,1′′:4′′,1′′′:2′′′,1′′′’-quinquephenyl  bis(diethylamine) clathrate  bis(propan-1-ol) clathrate  bis(butan-1-ol) clathrate  bis(ethanol) clathrate  bis(propan-1-ol) clathrate  bis(diethylamine) clathrate  bis(butan-1-ol) clathrate  to a cold solution (195 K) of 2,2′′-diiodo-1,1′:4′,1′′-terphenyl  in 20 ml of dry THF. After 45 min of stirring, 4,4′-dichlorobenzophenone , dissolved in 4 ml benzene and 15 ml THF, was added. The colourless reaction mixture was warmed to room temperature and stirred for 4 h. The solution was extracted twice with diethyl ether. The combined organic extracts were washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. Colourless crystals were isolated by recrystallization from hexane (yield: 7.0%). M.p. 543–546 K; ESI–MS [M + H]−m/z 731.3. IR (KBr) ν (cm−1) 3547, 3056, 3025, 1913, 1641, 1591, 1575, 1489, 1331, 1182, 1157, 1097, 1014, 919, 903, 840, 761. 1H NMR : δ = 2.84 , 6.75 , 7.09 , 7.11 , 7.22 , 7.26 , 7.32 . 13C NMR : δ = 82.68 (C-OH), 126.89, 127.43, 128.10, 129.11, 129.33, 129.83, 133.40, 140.24, 141.01, 144.06, 145.58 (Ar-C). EA calculated for C44H30O2Cl4: C 72.1, H 4.1%; found: C 72.2, H 4.4%. Crystals of (IIa) suitable for X-ray diffraction were obtained from a solution of (II) in triethylamine upon slow evaporation of the solvent at room temperature.The unsolvated compound (II) was prepared by addition of a solution of Uiso(H) = 1.2Ueq(C) for aromatic and methylene, with C—H = 0.98 and O—H = 0.84 Å and Uiso(H) = 1.5Ueq(C) for methyl and hydroxy groups, respectively. Two molecules of triethylamine are each disordered over two positions with occupancy ratios of 0.567 (3):0.433 (3) and 0.503 (3):0.497 (3). They were modelled with restrained bond lengths based on average values of 1.47 (1) Å for N—C and 1.53 (1) Å for C—C bonds.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015018824/zs2345sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015018824/zs2345Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015018824/zs2345Isup3.cmlSupporting information file. DOI: 1430018CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: