II complex with a Schiff base ligand formed in situ from cysteamine (2-aminoethanethiol) and o-vanillin is reported as well results of its antibacterial activity screening.The crystal structure of a trinuclear Ni 3(C10H11NO2S)3]·C3H7NO, with a Schiff base ligand formed in situ from 2-aminoethanethiol and o-vanillin crystallizes in the orthorhombic space group Pbca. Its asymmetric unit consists of one neutral Ni3L3 molecule and one DMF solvent molecule. The solid-state organization of the complex can be described as an insertion of the solvent molecules within the crystallographically independent trinuclear NiII species. Several C—H⋯π edge-to-face interactions and π–π stacking interactions link the components in the crystal. A first example of a short intermolecular C—H⋯Ni contact is found. Antibacterial in vitro screening revealed that the title compound has antibacterial activity, the best effect being against Acinetobacter baumannii.The title trinuclear nickel(II) complex, [Ni The deviation of the NiII atom from the NOS2 mean plane is 0.0927 (14) Å. Thus, the molecule has a ‘crown’ or bowl shape with the Ni3S3 unit as its base in a distorted chair conformation. The torsion angles [between 78.49 (5) and 84.79 (5)°] deviate significantly from the ideal chair conformation for c-hexane which has torsion angles of 60°. For the Ni2 atom in this core, one additional short contact should be noted, C27—H27C⋯Ni with an H⋯Ni distance of 2.58 Å. Thus, with this additional contact, the coordination geometry of the Ni2 atom is square pyramidal with heteroatom—Ni2—H27C bond angles in the range 78.0-95.1°.The coordination geometry around each Niet al., 2001et al., 1988Unlike in closely related compounds, the solvent molecule is not encapsulated. The distances observed between the Ni atoms are within Ni1⋯Ni2 3.5706 (4) and 3.6656 (5) Å. The intramolecular Ni—S distances with the dianionic Schiff base ligand  are in the range 2.1888 (12)–2.2036 (13) Å. They are slightly shorter than analogous ones with the bridging sulfur atom  of the neighboring ligand [2.2171 (12)–2.2262 (13) Å]. These data are comparable with those previously reported for related structures  of 3.722 (6) Å for connect the neighboring units . Several C—H⋯O and C—H⋯π edge-to-face interactions iminomethyl]phenolato}trinickel and tris(μ2-2-(2-naphthylmethoxy)-6-[{(2-sulfidoethyl)imino]methyl}phenolato)trinickel(II) dichloromethane solvate, tris(μ2-2-(benzyloxy)-6-{[(2-sulfidoethyl)imino]methyl}phenolato)trinickel(II) dichloromethane solvate, tris(μ2-2-ethoxy-6-[{(2-sulfidoethyl)imino]methyl}phenolato)trinickel(II) C60-fullerene dichloromethane solvate, tris(μ2-2-ethoxy-6-{[(2-sulfidoethyl)imino]methyl}phenolato)trinickel(II) dichloromethane solvate  in ethanol (5 ml) was added to the filtrate and stirred on air magnetically for 2 h. Nickel acetate tetrahydrate  in ethanol (6 ml) was added to the yellowish solution of the Schiff base formed in situ, and the resulting deep-brown solution was stirred magnetically and heated at 340–347 K for 1.5 h resulting in a dark-colored precipitate. The product was isolated by filtration, washed with dry ii=PrOH and finally dried in vacuo. Crystals suitable for crystallographic study were grown from a saturated solution in DMF (deep-brown solution). The crystals were filtered off, washed with dry i-PrOH and finally dried at room temperature (yield: 47%).A solution of KOH  in a minimum amount of methanol (2–3 ml) was added to a solution of 2-aminoethanethiol hydrochloride  in methanol (5 ml) and stirred in an ice bath for 10 min. The white precipitate of solid KCl was removed by filtration and −1 indicating the formation of a Schiff base (–H—C=N–)  (as well in CH3 groups of the solvent molecule) and aromatic –C=C– stretching vibrations. Other strong bands at 1228 and 1244 cm−1 are due to the phenolic CO stretching  proton signal. The O—CH3 protons peaks only appear at 3.92 ppm. The multiplets of the aromatic protons appear in the range 6.39–6.79 ppm with different multiplicity and coupling constants. The strong singlet at 3.39 ppm could be assigned to the aliphatic –CH2–CH2– protons according to its integral intensity. Signals from the DMF methyl protons appear at 2.94 and 2.78 ppm. Analysis calculated for for C33H40N4Ni3O7S3 (877.00): C, 45.20; H, 4.60; N, 6.39; found: C, 45.5; H, 4.77; N, 6.25.The IR spectrum of the title compound (as KBr pellets) is consistent with the above structural data. It displays the characteristic peak at 1610 cmUiso(H) = 1.2–1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 2in vitro screening of all test compounds was carried out against reference strains of bacteria  and clinical strains . The broth microdilution method was used according to the European Committee on Antimicrobial Susceptibility Testing (EUCAST). The results obtained indicate that the synthesized compound possesses a broad spectrum of activity against the tested microorganisms and shows relatively better activity against Gram-negative than Gram-positive bacteria. The title complex showed activity with lowest minimum inhibitory concentrations (MIC) values 312.5 µg ml−1 against Gram-negative bacteria E. coli, K. pneumoniae and P. aeruginosa. The highest activity was against clinical strain A. baumannii - MIC = 156.2 µg ml−1. The poorest activity of the complex was against clinical strain Staphylococcus aureus (MRSA). It is well known that A. baumannii is one of the most important nosocomial pathogens because of its longevity in the hospital environment and ability to resist various antimicrobial agents, such as resistance to broad-spectrum β-lactam antibiotics by β-lactamases production  I. DOI: 10.1107/S2056989019004730/ex2019Isup2.hklStructure factors: contains datablock(s) I. DOI: 1865532CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title diepoxyphenalene derivative, two dihydrofuran and two tetrahydrofuran rings, as well as one cyclohexane ring, are fused together with two methyl carboxylate groups in positions 2- and 3-. In the crystal, two pairs of C—H⋯O hydrogen bonds link the molecules to form inversion dimers, enclosing two  17H18O6, comprises a fused cyclic system containing four five-membered rings (two dihydrofuran and two tetrahydrofuran) and one six-membered ring (cyclohexane). The five-membered dihydrofuran and tetrahydrofuran rings adopt envelope conformations, and the six-membered cyclohexane ring adopts a distorted chair conformation. Two methyl carboxylate groups occupy adjacent positions (2- and 3-) on a tetrahydrofuran ring. In the crystal, two pairs of C—H⋯O hydrogen bonds link the molecules to form inversion dimers, enclosing two R22(6) ring motifs, that stack along the a-axis direction and are arranged in layers parallel to the bc plane.The title diepoxyphenalene derivative, C Reactions totally depending on thermodynamic and kinetic control are infrequently found in the field of organic synthesis, at the same time such transformations are very perspective and attractive from a practical point of view since they allow the direction of the reaction to be changed radically by varying only one of the reaction parameters .et al., 2010et al., 2000et al., 1998et al., 1996et al., 2014et al., 1996et al., 2010et al., 2010et al., 1978The first example of kinetic/thermodynamic control in the course of the Diels–Alder reaction was reported in 1948  into the ‘domino-adduct’ (2)  cycloaddition in an intermediate, leading to the formation of the thermodynamically controlled ’domino-adduct’ (2) in an almost quantitative yield.The present paper describes the uncommon thermal rearrangement of the ‘ al. 2018 and Bori al. 2018; for ref al. 2018, Lautens al. 2018 and Domi al. 2000]. The tr2) is illustrated in Fig. 1Q(2) = 0.5230 (18) Å and φ(2) = 178.1 (2)° for ring A, Q(2) = 0.5492 (17) Å and φ(2) = 182.3 (2)° for B, Q(2) = 0.5230 (18) Å and φ(2) = 1.0 (2)° for C, and Q(2) = 0.5303 (17) Å and φ(2) = 358.9 (2)° for D. The puckering parameters of the six-membered cyclohexane ring (C1/C2/C10–C13) are QT = 0.518 (2) Å, θ = 6.9 (2)° and φ = 178.2 (18)°. In positions 2- and 3-, i.e. on atoms C8 and C9 . The contribution from the O⋯H/H⋯O contacts, corresponding to C—H⋯O interactions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bonding interaction  and O⋯O . The large number of H⋯H and O⋯H/H⋯O interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing  and (2), viz. 2-benzyl-6a,9b-bis(trifluoromethyl)-2,3,6a,9b-tetrahydro-1H,6H,7H-3a,6:7,9a-diepoxybenzo[de]isoquinoline -2--2,3-dihydro-1H,6H,7H-3a,6:7,9a-diepoxybenzo[de]isoquinoline-3a1,6a-dicarboxylate . C—H⋯π interactions are also observed, together with intramolecular F⋯F contacts. The asymmetric unit of HENLEU contains two independent molecules. In the crystal, molecules are linked by C—H⋯O and C—H⋯F hydrogen bonds, forming columns along [010]. Likewise, C—H⋯π interactions and F⋯F intramolecular contacts are also present. In the crystal structure of LIRKAB, intermolecular C—H⋯O interactions involving the O atoms of the carbonyl groups, the oxygen bridgehead atoms and the methoxy O atoms, as well as C—H⋯F hydrogen bonds, define the crystal packing. These packing features lead to the formation of a supramolecular three-dimensional structure. C—H⋯π and π–π interactions are not observed, but H⋯H interactions dominate in the packing. This situation is similar to that in the crystal of the title compound.2) is illustrated in the Scheme. Compound (1)  was dissolved in dry o-Me2C6H4 (15 ml) and then heated under reflux for 4 h at ∼413 K (thin-layer chromatography monitoring). The reaction mixture was cooled and the solvent removed under reduced pressure. The residue was purified by recrystallization from an EtOAc/hexane mixture (1:1 v/v) to give compound (2) as large colourless prismatic crystals . 1H NMR : δ 6.43 , 6.27 , 5.09 , 4.88 , 3.78 , 3.73 , 2.23–2.17 , 2.00–1.88  1.71–1.68 . 13C NMR : δ 164.7 (CO2Me), 162.6 (CO2Me), 150.6 (C-3), 143.8 (C-2), 140.8 (C-7), 138.5 (C-8), 89.3 (C-3a), 85.8 (C-6a), 81.3 (C-1), 80.5 (C-9), 52.2 (C-9a), 52.0 (2 × CO2Me), 49.8 (C-9b), 26.7 (C-9), 25.0 (C-6), 17.2 (C-5). IR νmax/cm−1 (KBr): 1709, 1628, 1284, 1261. HRMS (ESI–TOF): calculated for C17H18O6 [M + H]+ 318.1103; found 318.1125.The synthesis of the title compound (Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989019003499/rz5253sup1.cifCrystal structure: contains datablock(s) 2, Global. DOI: 1902671CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, one molecule interacts with six neighbouring molecules  17H14O, which is used as a sensitiser for thermal paper, has a twisted conformation with a dihedral angle of 48.71 (12)° between the phenyl ring and the naphthyl ring system. In the crystal, one molecule interacts with six neighbouring molecules via intermolecular C—H⋯π interactions to form a herringbone molecular arrangement.The title compound [systematic name: 2-(benzyloxy)naphthalene], C Herein, we report the crystal structure of 1 as fundamental data for the investigation of its influence on the solid-state physicochemical properties of the thermosensitive layer of the thermal paper.Thermal printing is a rapid and inexpensive printing technology widely used in commercial applications such as receipts, faxes and tickets  and the phenyl ring (C12–C17) is 48.71 (12)°. The related torsion angles for this dihedral angle are −44.9 (3)° (O1—C11—C12—C17), 178.7 (2)° (C1—O1—C11—C12) and −5.6 (3)° (C6—C1—O1—C11).The title compound Fig. 1 is a simvia intermolecular C—H⋯π interactions  = 1.2Ueq(C).The crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989019000690/is5508sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019000690/is5508Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019000690/is5508Isup3.cmlSupporting information file. DOI: 1890872CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The two benzene rings are twisted by angles of 79.14 (7) and 19.02 (14)° in the two independent molecules. In the crystal, amide–amide interactions link the molecules into chains running along  17H16N4O6, contains two independent molecules (A and B). The two benzene rings are twisted by an angle of 79.14 (7)° in molecule A, whereas, in molecule B, they are inclined by 19.02 (14)°. The conformations of the molecules are stabilized by intramolecular N—H⋯O hydrogen bonds between the amide nitrogen atom and the O atom of the ortho-nitro substituent on the phenyl ring, enclosing an S(6) ring motif. In the amide and aliphatic segments, all the N—H, C=O and C—H bonds are anti to each other. In the crystal, the A and B molecules are linked by intermolecular amide-to-amide N—H⋯O hydrogen bonds, resulting in chains running along the b-axis direction. The intermolecular interactions were analysed using Hirshfeld surface analysis. The two-dimensional fingerprint plots of the intermolecular contacts indicate that the major contributions are from H⋯H and O⋯H interactions.The asymmetric unit of the title compound, C There has been a study on the influence of the length of the connecting chain on the antimalarial activity of bisquinolines  and −161.9 (3)° for C2—C1—N1—C7 and C19—C18—N5—C24, respectively. In the other half, they are syn to the ortho-substituent as shown by the torsion angles of 48.6 (4) and −50.6 (4)° for C13—C12—N2—C11 and C30—C29—N6—C28, respectively. The O1—C7, O2—C11, O7—C24 and O8—C28 bond lengths are 1.213 (3), 1.224 (3), 1.218 (3) and 1.218 (3) Å, respectively, which indicate that the molecules exist in their keto forms in the solid state. In molecule A, the bis-amide group forms dihedral angles of 24.79 (12) and 55.04 (7)° with the phenyl rings C1–C6 and C12–C17, respectively. In molecule B, the plane of the amide group forms dihedral angles of 34.24 (13) and 24.27 (12)° with the C18–C23 and C29–C34 phenyl rings, respectively, while the two benzene rings form a dihedral angle of 79.14 (7) and 19.02 (14)° in molecules A and B, respectively. The planes of molecules A and B are almost coplanar with each other, as is evident from the dihedral angle of only 3.15 (17)° between phenyl rings C1–C6 and C18–C23.The asymmetric unit of the title compound (I)ortho-substituted nitro groups attached to the C1/C6 and C18/C23 phenyl rings form short intramolecular contacts, each of 2.01 (3) Å, with the nearest amide N atom, forming an N—H⋯O contact resulting in an S(6) hydrogen bonding motif.The O atoms of the b-axis direction. The oxygen atom of the amide C=O group in molecule B forms a bifurcated hydrogen bond with the N—H group of the amide unit and the C—H group of the aliphatic chain of an adjacent molecule. The C3—H3 unit of the C1–C6 ring of molecule A forms a short intermolecular contact with the oxygen atom O5 belonging to the nitro group of the C12–C17 phenyl ring of another A molecule at position −x, 1 − y, −z. C—H groups of the C12–C17 and C29–C34 phenyl rings form hydrogen bonds with the O atoms of the nitro groups of the C12/C17 and C29/C34 phenyl rings at −x, −y + 2, −z + 1 and −x + 1, −y + 1, −z + 1, respectively. A packing diagram of the title compound is shown in Fig. 3In the crystal, the molecules are linked by N—H⋯O and C—H⋯O hydrogen bonds Table 1. An inteCrystalExplorer , with de + di ∼ 2.4 Å . H⋯H contacts represent the next largest contribution to the Hirshfeld surfaces (29.2%) and show a distinct pattern with a minimum value of de = di ∼ 1.2 Å . O⋯C/C⋯O and N⋯H/H⋯N interactions cover only 5.4%  and 3.4%  of the surface, respectively. Two triangles featuring the C⋯C contacts contribute 3.2% to the Hirshfeld surfaces, with a minimum (de + di) distance of 3.5 Å .In the two-dimensional fingerprint plot Fig. 6, di is  Å Fig. 6b. H⋯H c Å Fig. 6c. O⋯C/C4% Fig. 6d and 3.4% Fig. 6e of the Å Fig. 6f.et al., 2010bcN,N′-bis(phenyl)suberamide . The purity of the compound was checked by TLC and it was characterized by IR spectroscopy. The characteristic absorptions were observed at 3334.9, 1693.5 and 1330.9 cm−1 for N—H, C=O and C—N, respectively. 1H NMR : 1.93 to 2.00 , 2.48 , 7.95  , 7.28–7.33 , 7.63–7.70 , 7.82  , 10.24 . 13C NMR : 20.40, 35.19, 124.38, 124.65, 124.68, 131.71, 133.75, 141.36 and 170.82. Rod-shaped yellow single crystals of the title compound were obtained by slow evaporation of a DMF solution at room temperature.A mixture of glutaric acid (0.2 mol) and thionyl chloride (1.0 mol) was heated for half an hour at 363 K. Then 2-nitroaniline (0.4 mol) was added dropwise under stirring. The resultant mixture was stirred for 3 h and left standing for 12 h for the completion of the reaction. The product was added to crushed ice. The white precipitate obtained was washed thoroughly with water and then with saturated sodium bicarbonate solution and again with water. It was washed first with 2 Uiso(H) = 1.2Ueq(C). The H atoms of the NH groups were located in a difference map and later restrained to a distance of N—H = 0.86 (2) Å. They were refined with Uiso(H) = 1.2 Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989018013075/zl2738sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018013075/zl2738Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018013075/zl2738Isup3.cmlSupporting information file. DOI: 1578746CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The asymmetric unit of the title 1:2 co-crystal has a half molecule of twofold symmetric dithiodibenzoic acid and a full molecule of benzoic acid. These are connected into three-molecule aggregates via hydroxy-O—H⋯O(hydroxy) hydrogen bonds. 14H10O4S2·2C7H6O2, comprises half a molecule of dithiodibenzoic acid [systematic name: 2-[(2-carboxyphenyl)disulfanyl]benzoic acid, DTBA], as the molecule is located about a twofold axis of symmetry, and a molecule of benzoic acid (BA). The DTBA molecule is twisted about the disulfide bond [the C—S—S—C torsion angle is −83.19 (8)°] resulting in a near perpendicular relationship between the benzene rings [dihedral angle = 71.19 (4)°]. The carboxylic acid group is almost co-planar with the benzene ring to which it is bonded [dihedral angle = 4.82 (12)°]. A similar near co-planar relationship pertains for the BA molecule [dihedral angle = 3.65 (15)°]. Three-molecule aggregates are formed in the crystal whereby two BA molecules are connected to a DTBA molecule via hydroxy-O—H⋯O(hydroxy) hydrogen bonds and eight-membered {⋯HOC=O}2 synthons. These are connected into a supramolecular layer in the ab plane through C—H⋯O interactions. The interactions between layers to consolidate the three-dimensional architecture are π–π stacking interactions between DTBA and BA rings [inter-centroid separation = 3.8093 (10) Å] and parallel DTBA-hydroxy-O⋯π(BA) contacts [O⋯ring centroid separation = 3.9049 (14) Å]. The importance of the specified interactions as well as other weaker contacts, e.g. π–π and C—H⋯S, are indicated in the analysis of the calculated Hirshfeld surface and interaction energies.The asymmetric unit of the title 1:2 co-crystal, C Such oxidation of the original 2-thiobenzoic acid to DTBA is well known in co-crystallization studies i—C3i torsion angle being −83.19 (8)°; symmetry operation (i): 1 − x, y, z. This almost orthogonal disposition is also seen in the dihedral angle between the benzene rings of 71.19 (4)°. The presence of a carboxylic acid group is readily confirmed by the disparity in the C1—O1, O2 bond lengths, i.e. 1.317 (2) and 1.229 (2) Å, respectively. This group is practically co-planar with the benzene ring to which it is bonded, as seen in the dihedral angle of 4.82 (12)°. This co-planar arrangement allows for a significant intramolecular S←O interaction, i.e. S1⋯O2 = 2.6712 (12) Å, as the carbonyl-O2 atom is orientated towards a disulfide-S1 atom  and 1.233 (2) Å, respectively. As for the DTBA molecule, the carboxylic acid group is close to co-planar with the benzene ring to which it is bound, forming a dihedral angle of 3.65 (15)°.PLATON . The resultant three-molecule aggregates are connected through DTBA-C—H⋯O3(hydroxyl-BA) and BA-C—H⋯O1(hydroxyl-DTBA) interactions, to form non-symmetric, ten-membered {O⋯HCCC}2 homo-synthons leading to supramolecular layers in the ab plane, Fig. 2b). Owing to the nearly right-angle relationship between the rings in the DTBA molecule, and the co-planarity between the carboxylic acid groups and the respective rings they are connected to, the layers also have a similar topology. Adjacent layers inter-digitate with other layers, on both sides, i.e. approximately orthogonally, as highlighted in Fig. 2c). As illustrated in Fig. 2d), the connections between layers are of two types and include π–π stacking interactions between DTBA and BA rings with the inter-centroid (C2–C7)⋯(C9–C14)iv separation being 3.8093 (10) Å, an angle of inclination of 8.36 (8)° and an off-set of 1.40 Å for symmetry operation (iv): 1 − x, 1 − y, 1 − z. The second interaction is a weak, parallel DTBA-hydroxy-O1⋯π(C9–C14)ii contact with a O1⋯ring centroid(C9–C14)v separation of 3.9049 (14) Å and angle at O1 = 60.96 (9)° for symmetry operation (v): x, y, 1 − z.The geometric parameters characterizing the interatomic contacts, as identified in dnorm) as well as calculation of the interaction energies using CrystalExplorer  and external (de) distances to the nearest nucleus dnorm mapping of the three-molecule aggregate is shown in Fig. 3−1, Table 2−1. The short π–π interaction involving the DTBA and BA benzene rings, mentioned in Supramolecular features, has an interaction energy of −21.7 kJ mol−1, i.e. more stable than the C—H⋯O interactions. The energy calculation reveals that such an interaction is mainly dispersive in nature, cf Table 2a) and (b), and the molecular dimer sustained by π–π contacts in Fig. 4c).The v separation of 4.4323 (10) Å, an angle of inclination of 8.36 (8)° and an off-set of 2.74 Å for symmetry operation (v): x, y, 1 − z. In addition, a BA-benzene-C6—H⋯S contact (2.94 Å) is noted, Table 2Other important but less significant contacts are noted through the Hirshfeld surface analysis such as a longer π–π interaction between DTBA and BA rings with an inter-centroid (C2–C7)⋯(C9–C14)di and de contact distances at the interval of 0.01 Å , O⋯H/H⋯O , S⋯H/H⋯S  and other contacts (8.0%). Among these contacts, only the O⋯H/ H⋯O, C⋯C and S⋯H/ H⋯S contacts are shorter than the respective sums of the van der Waals radii to result in meaningful interactions in the crystal, i.e. O⋯H, C⋯C and S⋯H = ∼1.72, ∼3.4 and ∼3.0 Å, respectively.A quantitative analysis of the Hirshfeld surfaces was performed through the generation of two-dimensional fingerprint plots by combining the di + de distances except for the O⋯H/H⋯O interactions. Thus, overall (I)i.e. 12.8 versus 12.3%. The apparent disparity arises as a result of the larger surface area to volume ratio for the DTBA molecule as compared to the DTBA+BA aggregate when it is considered as a single entity, hence leading to greater exposure of the O⋯H/H⋯O contacts in DTBA within its surrounding interacting environment. A smaller disparity is evident for the -S⋯H-/-H⋯S- contacts, in that the former constitutes about 6.3% in (I)A close inspection on the corresponding decomposed fingerprint plots of the individual DTBA and BA molecules reveals similar compositions as well as a)–(c), the crystal is significantly governed by electrostatic force owing to the strong O—H⋯O interactions that result in an alternate V-shape energy topology across the b-axis direction. A relatively less significant, but essential dispersion contribution is also observed and arises from the π–π interactions spanning all benzene rings. Overall, it can be concluded that these interacting forces directed the assembly of the molecules in (I)In order to study the overall topology of the energy distributions in the crystal of (I)Structural commentary, the DTBA molecule is twisted about the central disulfide bond, having a C—S—S—C torsion angle of −83.19 (8)°. A survey of the literature indicates that this is a common feature of such molecules. A search of the Cambridge Structural Database ethene  solution of the ground mixture. M.p. 384.2–385.6 K. IR (cm−1): 3070 ν(C—H), 1677 ν(C=O), 1584 ν(C=C), 1415 δ(C—H), 706 δ(C=C), 684 δ(OCO).All chemicals were of reagent grade and used as received without purification. 2-Thiobenzoic acid  was mixed with benzoic acid  and ground for 15 minutes in the presence of a few drops of methanol. The procedure was repeated three times. Colourless blocks were obtained by carefully layering toluene (1 ml) on an Uiso(H) set to 1.2Ueq(C). The oxygen-bound H atoms were located from difference-Fourier maps and refined without constraint.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989018017097/hb7790sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018017097/hb7790Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018017097/hb7790Isup3.cmlSupporting information file. DOI: 1882556CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Z′ = 1 is reported and compared with first polymorph with Z′ = 2.A second polymorph of 3-methoxybenzoic acid with  8H8O3, is described in the centrosymmetric monoclinic space group P21/c with Z′ = 1 as compared to the first polymorph, which crystallizes with two conformers (Z′ = 2) in the asymmetric unit in the same space group. In the crystal of the second polymorph, inversion dimers linked by O—H⋯O hydrogen bonds occur and these are linked into zigzag chains, propagating along the b-axis direction by C—H⋯O links. The crystal structure also features a weak π–π interaction, with a centroid-to-centroid distance of 3.8018 (6) Å. The second polymorph of the title compound is less stable than the reported first polymorph, as indicated by its smaller calculated lattice energy.A new polymorphic form of the title compound, C Polymorph Iα crystallizes in the monoclinic space group P21/n with a = 13.8034 (17) Å, b = 5.0275 (5) Å, c = 21.446 (3) Å and β = 99.320 (13)° , which are connected into a homodimer through strong O—H⋯O hydrogen bonds. As described below, these two conformers (A and B) differ in the orientation of the methoxy group and its relative position from the —OH group. DFT calculations suggest that the A conformer of Iα is more energetically stable than the B conformer . The molecule is almost planar with a maximum deviation of 0.107 (1) Å at atom O1. The molecules of Iβ adopt a similar conformation (overlay r.m.s.d. = 0.052 Å) as compared to the conformer A of Iα  of Iβ is close to coplanar with the attached phenyl ring (C1–C6) as indicated by the dihedral angle of 5.6 (7)°. The C8—O3—C3—C2 torsion angle of Iβ is −176.63 (7)° as compared to −176.75 (11) and −1.4 (2)° for conformers A and B, respectively, of Iα.The asymmetric unit of Iβ Fig. 1 consistsb-axis direction. The [010] chains are stacked along the a axis into corrugated sheets parallel to the ab plane via weak π–π interactions with a centroid-to-centroid distance of 3.8018 (6) Å  and slippage of 1.676 Å.In the crystal of Iβ, two inversion-related molecules are joined into a homodimer with an ds Fig. 2. The homdnorm and the two-dimensional fingerprint plots for Iβ were generated using CrystalExplorer17.5 . The H⋯H contact is the most populated contact and contributes 42.3% of the total intermolecular contacts, followed by H⋯O/O⋯H (32.9%), H⋯C/C⋯H (11.4%) and C⋯C (8.1%) contacts .The Hirshfeld surfaces mapped with normalized contact distance rm Fig. 3 correspots Fig. 4. The tipPIXEL software  is larger than that of Iβ (98.5 kJ mol−1) and this comparison is in agreement with the report of Pereira Silva et al. , see: Parvez 1987 and Ette al. 1988. For the al. 1988, Colapie al. 1988, Fausto  al. 1997 and Hath al. 2011. For the al. 2014 and Pere al. 2015.Single crystals of Iβ were obtained from an unsuccessful attempt of co-crystallization between 3-methoxybenzoic acid and hexamethylenetetramine. Colourless plate-like crystals were obtained from slow evaporation of a methanolic mixture of 3-methoxybenzoic acid and hexamethylenetetramine in equimolar ratio at room temperature.O2 = 1.01 (2) Å]. The remaining H atoms were positioned geometrically [C—H = 0.95 and 0.98 Å] and refined using a riding model with Uiso(H) = 1.2 or 1.5Ueq(C). A rotating group model (AFIX 137) was applied to the methyl group.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989018016900/hb7789sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018016900/hb7789Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018016900/hb7789sup3.docxHirshfeld shape-index and curvedness Figures. DOI: Click here for additional data file.10.1107/S2056989018016900/hb7789Isup4.cmlSupporting information file. DOI: 1448794CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


C5H7N2+·C6H7O7− (I) and 3C5H7N2+·C6H5O73− (II). Salt I is formed by the protonation of the pyridine N atom and deprotonation of the central carboxylic group of the acid, while in II all three carboxylic groups of the acid are deprotonated and the charges are compensated for by three 2-aminopyridinium cations.2-Aminopyridine and citric acid mixed in 1:1 and 3:1 ratios in ethanol yielded crystals of two 2-aminopyridine citric acid salts,  viz. C5H7N2+·C6H7O7− (I) (systematic name: 2-aminopyridin-1-ium 3-carboxy-2-carboxymethyl-2-hydroxypropanoate), and 3C5H7N2+·C6H5O73− (II) . The supramolecular synthons present are analysed and their effect upon the crystal packing is presented in the context of crystal engineering. Salt I is formed by the protonation of the pyridine N atom and deprotonation of the central carboxylic group of citric acid, while in II all three carboxylic groups of the acid are deprotonated and the charges are compensated for by three 2-aminopyridinium cations. In both structures, a complex supramolecular three-dimensional architecture is formed. In I, the supramolecular aggregation results from Namino—H⋯Oacid, Oacid⋯H—Oacid, Oalcohol—H⋯Oacid, Namino—H⋯Oalcohol, Npy—H⋯Oalcohol and Car—H⋯Oacid interactions. The molecular conformation of the citrate ion (CA3−) in II is stabilized by an intramolecular Oalcohol—H⋯Oacid hydrogen bond that encloses an S(6) ring motif. The complex three-dimensional structure of II features Namino—H⋯Oacid, Npy—H⋯Oacid and several Car—H⋯Oacid hydrogen bonds. In the crystal of I, the common charge-assisted 2-aminopyridinium–carboxylate heterosynthon exhibited in many 2-aminopyridinium carboxylates is not observed, instead chains of N—H⋯O hydrogen bonds and hetero O—H⋯O dimers are formed. In the crystal of II, the 2-aminopyridinium–carboxylate heterosynthon is sustained, while hetero O—H⋯O dimers are not observed. The crystal structures of both salts display a variety of hydrogen bonds as almost all of the hydrogen-bond donors and acceptors present are involved in hydrogen bonding.2-Aminopyridine and citric acid mixed in 1:1 and 3:1 ratios in ethanol yielded crystals of two 2-aminopyridinium citrate salts,  Organic crystals, especially salts, are now considered as potential materials for optical applications because of their flexibility in molecular design , whose structure is illustrated in Fig. 1I have different conformations. In one of them (C5/O4/O5) the O—H and C=O bonds are in a syn conformation while in the other (C3/O2/O3), they have an anti conformation  hydrogen bonds [acid(t1) = C3/O2/O3], viz. N2—H2D⋯O2 , 4.762 and 6.396 . Thus, an equimolar mixing of citric acid and 2-aminopyridine resulted in the formation of salt on Fig. 1. In the 2 Table 1.II, illustrated in Fig. 23− [(C5H5O7)3−], and three 2-AMP+ cations , wherein the pyridine N atom of each 2-AMP unit is protonated and all three carboxylic groups of the acid are deprotonated. This is supported by the observation that the C—O bonds of all the three carboxylic groups have similar bond lengths, in the range 1.231 (2)–1.266 (2) Å, which is an indication of the partial double-bond character of all of the C—O bonds resulting from deprotonation. The molecular conformation of the CA3− anion is stabilized by an intramolecular Oalcohol—H⋯Oacid(t1) hydrogen bond, namely O1—H1O⋯O3, that closes an S(6) ring motif  hydrogen bond, namely N1—H1B⋯O6. The second cation, 2-AMP2, interacts with the CA3− anion via a charge-assisted 2-aminopyridinium-carboxylate amino—H⋯Oacid(t1) (N3—H3A⋯O3) and Npy—H⋯Oacid(t1) (N4—H4⋯O2) hydrogen bonds. The third cation, 2-AMP3, interacts with the anion via a discrete Namino—H⋯Oacid(c) hydrogen bond, namely N6—H6B⋯O7.In the asymmetric unit of salt I are given in Table 1I, the cations and anions of adjacent units are interconnected by a Car—H⋯Oacid(t1) interactions, viz. C9—H9⋯O3, while adjacent anions related by b-glide symmetry form chains running along the b-axis direction, consisting of an acid(c)⋯H—Oacid(t1) and Oalcohol—H⋯Oacid(c) hydrogen bonds, namely O3—H3⋯O7i and O1—H1⋯O6i; see Fig. 3+ and CA− ions further aggregate to form sheets parallel to the ac plane —H⋯Oacid(c) hydrogen bonds, namely O4—H4⋯O6iii, running along the a-axis direction and linking the twofold-symmetry-related CA− anions (Table 1+ ions via Namino—H⋯Oacid(t1)=C hydrogen bonds, namely N2—H2D⋯O2, and an amino—H⋯Oalcohol and Npy—H⋯Oalcohol hydrogen bonds, N2—H2C⋯O1ii and N1—H1A⋯O1ii, respectively, is formed  hydrogen bond. The CA3− anion and the first 2-AMP+ cation (2-AMP1) form sheets lying parallel to the (101) plane . The sheet consists of alternating CA3− and 2-AMP+ ions, forming chains via C11—H11⋯O2iii interactions, with adjacent anti-parallel chains linked by C10—H10⋯O2ii, N1—H1A⋯O7i, N1—H1B⋯O6, N2—H2⋯O7i and N2—H2⋯O1i hydrogen bonds (Table 2+ ions (2-AMP2) propagate alternately along the a-axis direction to form ribbons  consisting of alternating A⋯O3 and N4—H4⋯O2 hydrogen bonds (Table 2B⋯O4 and C13—H13⋯O6 hydrogen bonds (Table 2+ ions (2-AMP3) are interlinked to the adjacent citrate ions, forming ribbons of alternating i and N6—H6A⋯O5i hydrogen bonds . Adjacent ribbons are further interconnected by N6—H6B⋯O7 hydrogen bonds to form corrugated sheets parallel to the ab plane (Table 2b). Overall a complex supramolecular three-dimensional structure is formed.In the crystal of s Table 2. Howeverne Fig. 5a and 5bs Table 2. On the ns Fig. 6a consiss Table 2 and (11)s Table 2. Finallys Table 2, and . The most common hydrogen bonds observed in these hydrated salts are Namine—H⋯Ocitric, Namine—H⋯Owater and Owater—H⋯Ocitric, forming different supramolecular architectures. In the absence of a water molecule, the most common hydrogen bonds are Namine—H⋯Ocitric and Ocitric—H⋯Ocitric. However, the nature of these supramolecular synthons varies from one structure to another, depending on the nature of the organic cations.A survey of the Cambridge Structural Database . Single crystals of salt II were obtained from a similar procedure; an ethanolic solution (15 ml) of citric acid  was mixed with an ethanolic solution (15 ml) of 2-aminopyridine .A solution of citric acid  in ethanol (15 ml) was added to an ethanolic solution (15 ml) of 2-aminopyridine . The resulting solution was heated and the hot solution was filtered. Slow evaporation of the solution resulted in the formation of colourless prismatic crystals of salt I, the OH H atom (H1) was positioned geometrically and refined as riding: O—H = 0.82 Å with Uiso(H) = 1.5Ueq(O). In salt II, the OH H atom (H1O) was located in a difference-Fourier map and freely refined. In both salts, the other H atoms were positioned geometrically and refined as riding: N—H = 0.86 Å, C—H = 0.93–0.97 Å with Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989018009787/su5449sup1.cifCrystal structure: contains datablock(s) I, II, Global. DOI: 10.1107/S2056989018009787/su5449Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018009787/su5449IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989018009787/su5449Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018009787/su5449IIsup5.cmlSupporting information file. DOI: 1854628, 1854627CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Deletional hereditary persistence of fetal hemoglobin (HPFH)/δβ‐thalassemia and δ‐thalassemia are rare inherited disorders which may complicate the diagnosis of β‐thalassemia. The aim of this study was to reveal the frequency of these two disorders in Southwestern China.2 levels were confirmed by δ‐globin gene sequencing. Furthermore, the pathogenicity and construction of a selected δ‐globin mutation were analyzed.A total of 33,596 subjects were enrolled for deletional HPFH/δβ‐thalassemia, and positive individuals with high fetal hemoglobin (Hb F) level were diagnosed by multiplex ligation‐dependent probe amplification (MLPA). A total of 17,834 subjects were analyzed for mutations in the δ‐globin gene. Positive samples with low Hb A2 ≤2.0%) were characterized by molecular analysis. δ‐Globin gene mutation was found at a frequency of 0.49% in Yunnan. The pathogenicity and construction for a selected δ‐globin mutation was predicted.A total of 92 suspected cases with Hb F ≥5.0% were further characterized by MLPA. Eight different deletional HPFH/δβ‐thalassemia were observed at a frequency of 0.024%. In addition, 195 cases suspected to have a δ‐globin gene mutation (Hb AScreening of these two disorders was analyzed in Southwestern China, which could define the molecular basis of these conditions in this population. Fetal hemoglobin (Hb F) is a minor hemoglobin that is composed of two α‐ and two γ‐globin chains (α2γ2). Hereditary persistence of fetal hemoglobin  is caused by mutations in the promoter of the γ‐globin gene  . As summarized in Globin Gene Server home page (http://globin.cse.psu.edu/hbvar/menu.html), more than 50 deletional HPFH/δβ‐thalassemias and 130 mutations in the δ‐globin gene have been reported to date. However, few reports on deletional HPFH/δβ‐thalassemia and mutations in the δ‐globin gene in Chinese population have been investigated at the molecular level. The aim of this study was to determine the frequency of deletional HPFH/δβ‐thalassemia mutations and δ‐globin gene mutations in Yunnan population. Furthermore, we characterized a rare δ‐globin gene mutation using a comprehensive clinical and structure‐function analysis. These findings are important for accurate thalassemia prenatal diagnosis, as well as for providing molecular insights into new mutations in δ‐globin gene.Both deletional HPFH/δβ‐thalassemia and δ‐thalassemia mutations are related to different ethnic backgrounds  and (b) low levels of Hb A2 associated with a visible second Hb A2 fraction . Internal quality control of the hemoglobin analysis was performed using the control materials provided by the manufacturer. A total of 33,596 subjects  were screened for deletional HPFH/δβ‐thalassemia using capillary electrophoresis from July 2014 to September 2016. Individuals showing Hb F ≥5.0% were considered to be carriers of deletional HPFH/δβ‐thalassemia 0 thalassemia and Southeast Asia HPFH (SEA‐HPFH) deletion were identified by Gap‐PCR  was performed using multiplex ligation‐dependent probe amplification (MLPA) following the manufacturer's instructions . Two commonest deletional HPFH, Chinese 2.43.7 (NC_000016.9:g.223300_227103del), ‐α4.2 (NC_000016.9:g.219817_(223755_224074)del), ‐‐SEA (NC_000016.9:g.215400_234700del), αCSα , αWSα , and αQSα .Two fragments of the δ‐globin gene (NG_000007.3) were amplified using the following primers: δ1‐F 5′CTGAGTCAAGACACACATGACAG3′, δ1‐R 5′ TGGTATGCATAATTTGAGTTGTTG3′; δ2‐F 5′ AATATCCTGTCTTTCTCTCCCAAC3′, δ2‐R 5′ TAATTTCTGCTCTTTGGAGGTAG3′   and SIFT (http://sift.jcvi.org)   were determined for the normal and mutant δ‐globin variant (monomer) using the Isoelectric Point Calculator (IPC) /δβ‐thalassemia, 165 positive samples were selected (Hb F ≥5.0%). Eight cases of deletional HPFH/δβ‐thalassemia were found by MLPA Figure , with a 0 deletion). Two unrelated individuals (case 3 and case 4) showed a similar (δβ)0‐deletion. A Gγ(Aγδβ)0‐deletion was found in case 5. Two unrelated individuals (cases 6 and case 7) had a Gγ(Aγδβ)0 deletion, and this was confirmed as Chinese Gγ(Aγδβ)0 thalassemia by Gap‐PCR. Furthermore, case 7 was a compound heterozygous for Chinese Gγ(Aγδβ)0 and IVS‐I‐1 (G > T) (HBB:c.92 + 1G>T). Case 8 showed a “discontinuous” (εγδβ)0 deletion, where the size of the deletion ranged from OR51M1‐1 probe to hemoglobin subunit beta (HBB)‐up probe; however, among this deletion region, the hemoglobin subunit gamma (HBG)2–3 and HBG1‐up probes detected a fragment. Therefore, this deletion was considered to be a “discontinuous” (εγδβ)0 deletion, and its sequence was further confirmed by targeted next‐generation sequencing  or a second Hb A2 fraction, and were selected for further molecular diagnosis. Seven types of δ‐globin mutations were found in 87 δ‐thalassemia patients  mutation had Hb A2 values below 1.6% (Hb A2 ≤ 1.6%). One sample was a compound heterozygote for −77 (T > C) and ‐α3.7 with Hb A2 value of 1.4% .The number of subjects for each Hb A3.312/L, Hb 13.8g/dl, MCV 91.0fl, MCH 30.3pg, RDW‐CV 13.1%, and MCHC 333g/L. The predicted pIs of the wild type and mutant type were 7.42 and 6.87 respectively  mutation was selected for further bioinformatics analysis. The proband was a 31‐year‐old Chinese woman. Her hematological characteristics were as follows: RBC 4.5×10y Figure a. The Lyy Figure b. Polyphy Figure c. Howevey Figure d.2O atoms  and B cell CLL/lymphoma 11A (BCL11A) can modulate fetal‐to‐adult globin switching. Mutations in KLF1 can result in significantly boosted Hb F levels in normal individuals 0‐deletion, one case of Gγ(Aγδβ)0‐deletion, two cases of Chinese Gγ(Aγδβ)0 deletion, and one case of (εγδβ)0‐deletion were identified. All eight samples had typical β‐thalassemia phenotypes with hypochromic and microcytic erythrocytes due to deletions in the β‐globin gene or promoter. Case 7 was a compound heterozygote for the Chinese Gγ(Aγδβ)0 deletion and IVS‐I‐1 (G > T). As a result, this patient had typical β‐thalassemia intermedia symptoms with increased Hb F levels  should be regarded as the frequency of deletional HPFH/δβ‐thalassemia but not β‐globin cluster deletions. Some β‐globin cluster deletions, such as the 118 kb Filipino deletion with a normal Hb F 1.7% cannot be screened by capillary electrophoresis . The individuals who have δ‐globin gene mutations do not usually have clinical phenotypes because of the physiologically lower expression levels of the δ‐globin gene  Lys > Asn, HBB:c.198G > T]. A previous study also had shown that those heterozygous for Hb J Sicilia had no clinically significant problems (Ricco et al., 2 with a slight subunit modification (Sen et al., 2 structure obviously and p.K65N mutation in δ‐globin gene should be benign.The 3D models evaluated by SWISS‐MODEL and PyMol showed that the K65 was located in a helix near the periphery of the protein. Based on the results from SWISS‐MODEL and PyMol, we observed that K65 was not positioned in a complex or important interaction network. Therefore, the substitution of the Lys residue should not significantly disrupt the structure and function of Hb AIn conclusion, this is the first report on the frequency and spectrum of deletional HPFH/δβ‐thalassemia and mutations in the δ‐globin gene in a Southwestern Chinese population. Bioinformatic analysis of a rare mutation characterized the potential changes at the protein‐level. Our study will provide a guideline for genetic counseling and prenatal diagnosis.The author reports no conflict of interest in this work. Click here for additional data file. Click here for additional data file. Click here for additional data file. Click here for additional data file.


The dihydrobenzodiazole moiety is not quite planar while the whole molecule adopts a U-shaped conformation in which there is a close approach of the two benzyl groups. Chains of alternating molecules and lattice water extending along the normal to (301) are formed by O—H⋯O and O—H⋯N hydrogen bonds. 24H21N5O·H2O, the dihydrobenzodiazole moiety is not quite planar, while the whole molecule adopts a U-shaped conformation in which there is a close approach of the two benzyl groups. In the crystal, chains of alternating molecules and lattice water extending along [201] are formed by O—HUncoordW⋯ODhyr and O—HUncoordW⋯NTrz  hydrogen bonds. The chains are connected into layers parallel to (010) by C—HTrz⋯OUncoordW hydrogen bonds with the dihydrobenzodiazole units in adjacent layers intercalating to form head-to-tail π-stacking [centroid-to-centroid distance = 3.5694 (11) Å] interactions between them, which generates the overall three-dimensional structure. Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H⋯H (52.1%), H⋯C/C⋯H (23.8%) and O⋯H/H⋯O (11.2%) interactions. Hydrogen-bonding and van der Waals interactions are the dominant interactions in the crystal packing. Density functional theory (DFT) optimized structures at the B3LYP/ 6–311 G level are compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.In the title molecule, C The benzene ring D (C12–C17) is inclined to the triazole ring C by 78.91 (11)° while the latter ring is inclined to the B ring by 64.70 (11)°. The dihedral angle between the mean planes of the B and E (C19–C24) rings is 87.67 (8)°.The title molecule, (I) C Fig. 1. The diUncoordW⋯ODhyr and O—HUncoordW⋯NTrz  hydrogen bonds (Table 1Trz⋯OUncoordW hydrogen bonds (Table 1Cg2⋯Cg1i = 3.5694 (11) Å where Cg1 and Cg2 are the centroids of the A and B rings, respectively; symmetry code: (i) −x + 1, −y + 1, −z + 2; dihedral angle = 2.50 (10)°] leads to the final three-dimensional structure  analysis , Fig. 6c,, Fig. 6d, have a symmetrical distribution with the edges at de + di = 1.85 Å. The H⋯N/N⋯N contacts, contributing 7.4% to the overall crystal packing, are shown in Fig. 6e as widely scattered points with the tips at de + di = 2.56 Å. The C⋯C contacts, Fig. 6f, have an arrow-shaped distribution of points with the tip at de = di = 1.77 Å. Finally, the C⋯N/N⋯C interactions (2.2%) are reflected in Fig. 6g as tiny characteristic wings with the tips at de + di = 3.44 Å.The overall two-dimensional fingerprint plot, Fig. 6n Table 2 is H⋯H, c,Table 2 with tridnorm plotted onto the surface are shown for the H⋯H, H⋯C/C⋯H, H⋯O/O⋯H and H⋯N/N⋯H interactions in Fig. 7a–d, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing  using standard B3LYP functional and 6–311 G basis-set calculations , hardness (η), potential (μ), electrophilicity (ω) and softness (σ) are recorded in Table 4H-1,2,3-triazol-4-yl)methyl]-2,3-dihydro-1H-1,3-benzodiazol-2-one hydrate ring. The energy band gap [ΔE = ELUMO - EHOMO] of the molecule is 5.3468 eV, and the frontier molecular orbital energies, EHOMO and ELUMO are −6.1633 and −0.8166 eV, respectively.The optimized structure of the title compound, (I)To a mixture of 3-methyl-1-(prop-2-ynyl)-3,4-dihydroquinoxalin-2(1H)-one (0.65 mmol) in ethanol (20 ml) was added 1-(azidomethyl)benzene (1.04 mmol). The mixture was stirred under reflux for 24 h. After completion of the reaction (monitored by TLC), the solution was concentrated and the residue obtained was purified by column chromatography on silica gel by using as eluent a mixture (hexane/ethyl acetate: 9/1). The isolated solid product was recrystallized from ethanol to afford yellow crystals (yield: in 19%).Uiso(H) = 1.2Ueq(C).The experimental details including the crystal data, data collection and refinement are summarized in Table 510.1107/S2056989019016876/lh5940sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019016876/lh5940Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019016876/lh5940Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019016876/lh5940Isup4.cmlSupporting information file. DOI: 1972575CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


III complex compound with pentetic acid is reported. The complex molecule is a zwitterion and the GaIII centre is bound in a slightly distorted octahedral coordination sphere by two amine N atoms, three carboxylate O atoms and one water O atom.The structure of a Ga III complex compound with pentetic acid, [Ga(C14H20N3O10)(H2O)]·3H2O, the GaIII centre is bound in a slightly distorted octahedral coordination sphere by two amine N atoms, three carboxylate O atoms and one water O atom. The complex molecule exists as a zwitterion. In the crystal, the complexes are linked to each other via O—H⋯O and C—H⋯O hydrogen bonds, forming layers parallel to (001). Three uncoordinating water molecules link the complex layers via O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, forming a three-dimensional network.In the title Ga A complex is easily formed between gallium and DTPA and it has a stability constant of 1023.32, which makes the complex stable against exchange with transferrin  Å]. The C—O bond lengths coordinating to the GaIII atom vary little, with the shortest and longest bonds differing by only 0.019 Å . The three trans angles, N1—Ga1—O1W, O1—Ga1—O5 and O3—Ga1—N2, are 174.57 (16), 174.05 (12) and 164.97 (13)°, respectively. The O—Ga—O, O—Ga—N and N—Ga—N bite angles in the chelate rings deviate somewhat from 90°, ranging from 81.75 (12) to 95.91 (12)°.The complex molecule (abbreviated as Ga-DTPA) is a zwitterion and has a slightly distorted octahedral coordination geometry with one water and one amine in the axial positions, and three carboxylate groups and one amine in the equatorial positions. The complex consists of three five-membered Ga/N/C/C/O chelate rings and one five-membered Ga/N/C/C/N chelate ring. The Ga—N bonds [Ga1—N1 = 2.081 (4) Å and Ga1—N2 = 2.156 (3) Å] are significantly longer than the Ga—O bonds [Ga1—O1 = 1.933 (3) Å, Ga1—O3 = 1.925 (3) Å, Ga1—O5 = 1.964 (3) Å and Ga1—O1a and b axes provided in Figs. 2via O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, forming a three-dimensional network.Packing depictions viewed along the et al., 2016In our survey of the Cambridge Structural Database  in acetate buffer (2 mL) adjusted to pH = 4.2 was heated with stirring for dissolution. Gallium nitrate (39.9 mg) was then added to the DTPA solution and the mixture was stirred for at least 10 min at 353 K. The solution was concentrated under ambient pressure at room temperature. When almost all of the solvent had evaporated, methanol was added dropwise to precipitate Ga-DTPA. The precipitate was collected on a 0.22 µm polyamide filter and dried at room temperature. The obtained Ga-DTPA (1.30 mg) was re-dissolved in ultra-pure water (1 mL) and single crystals suitable for X-ray diffraction were obtained after four weeks by slow diffusion of tetrahydrofuran into the aqueous solution, as illustrated in Fig. 4Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989018009428/is5497sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018009428/is5497Isup2.hklStructure factors: contains datablock(s) I. DOI: 1852608CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


T was isolated from laboratory tap water during a water quality assessment in University of Malaya, Malaysia. The strain was a Gram‐negative, rod‐shaped, nonmotile, and aerobic bacterium. Complete genome of P08T comprised of a 2,820,660 bp chromosome with a G + C content of 36.43%. Both 16S rRNA phylogeny and phylogenetic tree inferred from the core gene matrix demonstrated that P08T formed a hitherto unknown subline within the family Neisseriaceae. Ortho average nucleotide identity (OrthoANI) values and the percentage of conserved proteins (POCP) calculated from complete genome sequence indicated low relatedness between P08T and its phylogenetic neighbors. Respiratory quinone analysis revealed Q‐8 as the only detectable quinone. The predominant cellular fatty acids were identified as C14:0, iso‐C15:0, and summed feature 3 (C16:1ω7c/C16:1ω6c). The polar lipids consisted of uncharacterized aminolipid, phosphatidylglycerol, and phosphatidylethanolamine. All aspects of phenotypic and phylogenetic data suggested that strain P08T represents a novel genus within family Neisseriaceae, for which the name Aquella gen. nov. is proposed. The type species of the genus is Aquella oligotrophica sp. nov., and the type strain is P08T (=LMG 29629T =DSM 100970T).A bacterial strain designated as P08 After 3 days of incubation on R2A agar (BD Difco) at 37°C, bacteria isolation and purification were performed. The purified strain was routinely cultivated in R2A liquid medium, unless specified. Cells were preserved in 20% (v/v) glycerol at −80°C. The strain P08T has been deposited in the German Collection of Microorganisms and Cell Cultures  and the Belgium Coordinated Collections of Microorganisms .Strain P082.2T was extracted using the MasterPureTM DNA purification kit  following the manufacturer's protocol. Extracted genomic DNA was sheared and constructed into a template library according to the “Guidelines for Preparing 20 kb SMRTbell™ Templates.” Genome sequencing was performed in 1 SMRT cell using the PacBio RS II single‐molecule real‐time (SMRT) sequencing technology . The reads were de novo assembled using the hierarchical genome assembly process (HGAP) algorithm version 2  version 2.10   analysis, the homologous clusters were determined using panX pan‐genome pipeline  , Luria‐Bertani agar (Merck), Pseudomonas agar (BD Difco), MacConkey agar (Merck), R2A agar (BD Difco), and trypticase soy agar (Merck), and the ability to grow in this media was recorded after incubation of 3 days at 37 °C. Oxidase and catalase activities were examined with solutions of oxidase reagent (bioMérieux) and 3% (v/v) hydrogen peroxide, respectively. The morphology of bacterial cells was observed using tabletop scanning electron microscopy . Cellular motility was tested by the hanging drop method , 0.1 M NaHCO3/0.1 M Na2CO3 (pH 9.0–10.0), and 0.05 M Na2HPO4/0.1 M NaOH. Growth on medium added with sodium chloride (NaCl) was determined in R2A medium supplemented with 0, 0.5, 1%–6%  (w/v) NaCl after 14 days of incubation at 37 °C. Growth under anaerobic condition was determined by incubating strain P08T on R2A agar in the Oxoid AnaeroGen system.Growth of strain P08T was tested on R2A agar supplemented with casein , starch , cellulose , urease, Tweens 20, 40, 60, and 80 for hydrolysis activities, respectively  on R2A agar (BD Difco) plates. The disks (Oxoid) contained the following antibiotics: ampicillin (10 μg), ampicillin/sulbactam (20 μg), chloramphenicol (30 μg), gentamicin (10 μg), kanamycin (30 μg), nalidixic acid (30 μg), rifampicin (5 μg), penicillin G (10 μg), streptomycin (10 μg), sulfamethoxazole (23.75 μg) plus trimethoprim (1.25 μg), and tetracycline (30 μg). The effect of antibiotics on cell growth was assessed after incubation for 2 days at 37°C. The diameter of the antibiotic disks was 6 mm. The strain was considered susceptible when the diameter of the inhibition zone was>13 mm, intermediate at 10–12 mm, and resistant at <10 mm as described by Nokhal and Schlegel , and lesser to all validly described type strains, for instance Neisseria iguana NVSL 85737T (89.4%), Neisseria flavescens ATCC 13120T (89.3%), Paludibacterium paludis KBP‐21T (89.3%), Uruburuella testudines 07_OD624T (89.3%), and Morococcus cerebrosus CIP 81.93T (89.3%) based on EzBioCloud similarity‐based search  phylogenetic tree based on 16S rRNA gene sequences. Strain P08T formed a branch clearly separated from the remaining genera from Neisseriaceae. As indicated in Figure T appeared to be more closely related to Neisseriaceae, compared to the type species of genus Prolinoborus, which have a questionable taxonomic status in Neisseriaceae  and JGI portal . Out of a total of 2,625 genes in the genome, 2,564 protein‐coding gene, 12 rRNAs, and 46 tRNAs were predicted from the chromosome by PGAP analysis  designation  algorithm version 2 . Intriguingly, strain P08T has the lowest G + C content among these genomes. The range of G + C contents ranged widely from the lowest 36.43% in strain P08T to the highest 68.30% in genome of Crenobacter luteus CN10 , iso‐C15:0 (36.2%), C16:0 (9.9%), summed feature 3 (C16:1ω7c/C16:1ω6c) (16.4%), and summed feature 8 (C18:1ω7c) (6.8%). Strain P08T exhibited a polar lipid profile consisting of uncharacterized aminolipid, phosphatidylglycerol, and phosphatidylethanolamine  value suggested by Ludwig et al.  .14:0, iso‐C15:0, and summed feature 3 (C16:1ω7c/C16:1ω6c). The main polar lipids consist of uncharacterized aminolipid, phosphatidylglycerol, and phosphatidylethanolamine. The G + C content of the DNA of the type strain of the type species is 36.43 mol%. Based on 16S rRNA sequence analyses, P08T belongs to the Betaproteobacteria. The type species is Aquella oligotrophica P08T.Cells are Gram‐negative, aerobic, nonmotile, rod‐shaped. Cells are oxidase and catalase negative. Q‐8 is the only quinone type. Major fatty acids (>10%) are C4.2Aquella oligotrophica .D‐galactopyranoside, 2‐nitrophenyl‐β‐D‐galactopyranoside, and sodium pyruvate. Negative reactions toward potassium nitrate, L‐tryptophane, D‐glucose, L‐arginine, urea, esculin, ferric citrate, gelatin (bovine origin), D‐glucose, L‐arabinose, D‐mannose, D‐mannitol, N‐acetyl‐glucosamine, D‐maltose, potassium gluconate, capric acid, malic acid, trisodium citrate, phenylacetic acid, L‐lysine, L‐ornithine, sodium thiosulfate, inositol, D‐sorbitol, L‐rhamnose, D‐sucrose, D‐melibiose, and amygdalin. Based on testing with API ZYM kit, C4 esterase, C8 esterase lipase, leucine arylamidase, acid phosphatase, naphthol‐AS‐BI‐phosphohydrolase, β‐galactosidase, and N‐acetyl‐β‐glucosaminidase activities are detected but negative for activities of C14 lipase, valine arylamidase, trypsin, α‐chymotrypsin, β‐glucuronidase, α‐glucosidase, β‐glucosidase, α‐mannosidase, and α‐fucosidase. Weak enzymatic activities of alkaline phosphatase, cystine arylamidase, and α‐galactosidase are detected. The major fatty acids (> 5%) are C14:0, iso‐C15:0, C16:0, summed feature 3 (C16:1ω7c/C16:1ω6c), and summed feature 8 (C18:1ω7c). The following compounds are utilized as sole carbon sources in the GEN III microplate: D‐galactose, D‐glucuronic acid, D‐mannose, glucuronamide, glycyl‐L‐proline, inosine, L‐alanine, L‐arginine, L‐aspartic acid, L‐glutamic acid, L‐serine, methyl pyruvate, N‐acetyl‐D‐glucosamine, α‐D‐glucose, and β‐hydroxy‐D,L‐butyric acid. All other substrates in the GEN III microplate are not utilized. Sensitive to ampicillin/sulbactam (20 μg), chloramphenicol (30 μg), nalidixic acid (30 μg), rifampicin (5 μg), sulfamethoxazole (23.75 μg) plus trimethoprim (1.25 μg), and tetracycline (30 μg).Exhibits the following properties in addition to those given in the genus description. Cell sizes range from 0.7–1.4 μm in length and 0.3–0.5 μm in width  was isolated from laboratory tap water collected at University of Malaya, Malaysia.The type strain The authors declare no conflict of interest.KGC supervised the project. LSL carried out the experiments. WSST and LSL wrote the manuscript with support from KGC, KOC, AP, KMG, KWH, and WFY. WSST and LSL analyzed the data.None required. Click here for additional data file.


III complex with a Schiff base ligand formed in situ from cysteamine (2-aminoethanethiol) and 5-bromosalicylaldehyde is reported.The crystal structure of novel binuclear Co III complex, [Co2(C9H8BrNOS)2(C18H16Br2N2O2S2)]·C3H7NO, with a Schiff base ligand formed in situ from cysteamine (2-aminoethanethiol) and 5-bromosalicylaldehyde crystallizes in the space group P21. It was found that during the synthesis the ligand undergoes spontaneous oxidation, forming the new ligand H2L′ having an S—S bond. Thus, the asymmetric unit consists of one Co2(L)2(L′) molecule and one DMF solvent molecule. Each CoIII ion has a slightly distorted octahedral S2N2O2 coordination geometry. In the crystal, the components are linked into a three-dimensional network by several S⋯ Br, C⋯ Br, C—H⋯Br, short S⋯C  contacts as well by weak C—H⋯O hydrogen bonds. The crystal studied was refined as an inversion twin.The title binuclear Co The synthesis, crystal structure and spectroscopic characterization are described herein.Schiff bases represent one of the most widely used organic compounds. The ability to construct novel ligand systems by means of condensation of a variety of readily available aldehydes and amine makes them and their metal complexes ideal candidates for the construction of novel polynuclear compounds as well for investigation of a large range of properties ° between the mean planes of atoms O3/N3/C19/C24/C25 and O4/N4/C28/C33/C34 around Co1, and 64.78 (2)° between the mean planes of atoms O2/N2/C15/C10/C16 and O1/N1/C1/C6/C7 around Co2. During the synthesis, the ligand is partially oxidized with the formation of a –(CH2)2–S–S–(CH2)2– bridge. Thus, in contrast to a closely related complex  Å. The Co—S distances in the title complex are in the range 2.207 (3)–2.289 (3) Å, which is generally comparable to the range 2.23–2.26 Å observed for other thioether–CoIII complexes published earlier  [3.596 (2) Å] and S⋯ Br [3.364 (2) Å] contacts, which connect neighboring structural units into chains along [001]  are essentially shorter than the sum of the van der Waals radii for the atoms involved [S4⋯C16 = 3.198 (8) Å] ethanethiolato]-N-(3-thiapent-5-enyl)salicylaldiminato-N,O)dicobalt(III) acetonitrile solvate and [1,8-bis-3,6-dithiaoctane)cobalt(III) perchlorate with a disulfide moiety . Analysis calculated for C39H39Br4Co2N5O5S4 (M = 1223.49): C,38.28; N, 5.72; H, 3.21%. Found: C, 38.31; N, 5.79; H, 3.28%. The compound is sparingly soluble in CH3CN and good in DMSO, DMF.A solution of KOH  in a minimum amount of methanol was added to a solution of 2-aminoethanthiol hydrochloride  in methanol (5 ml) and stirred in an ice bath for 10 min. The white precipitate of solid KCl was removed by filtration and 5-bromosalicylaldehyde  in dimethylformamide (10 ml) were added to the filtrate and stirred on air magnetically for 40 min. Cobalt acetate  was added to the yellowish solution of the Schiff base formed −1 range shows the characteristic azomethine group (–H—C=N) peak at 1616 cm−1, indicating the formation of the Schiff base. There are no bands assignable to υ(O—H), indicating the loss of the phenolic hydrogen of the free ligand. In addition, all the characteristic functional group peaks are present in the spectrum. Thus, signals in the 3000–3100 cm−1 and 1600–1400 cm−1 regions were assigned to the aromatic C—H and C—C stretches, and weak bands at 544 cm−1 and 684 cm−1 to the S—S and C—S stretches, respectively. The very strong bands at 1454 cm−1 can be attributed to overlapped C—H bending (scissoring) (in the CH3 groups of the solvent molecule) and aromatic –C=C stretching vibrations. Another strong band at 1310 cm−1 can be assigned to C—O vibrations.The IR spectrum of the title complex in the 4000–400 cm1H NMR spectra, obtained in DMSO-d6 at room temperature using TMS as the internal standard. It revealed an azomethine proton singlet at 8.099 ppm as well the increase in spectroscopic complexity in both the aromatic and aliphatic regions. 1H NMR, DMSO-d6, δ in ppm: –CH=N, 8.099 (s); aromatic protons (C6H3): 7.94–6.52; aliphatic protons (–SCH2CH2N=): 4.44 (m); solvent CH3: 2.96 (s), 2.8 (s). Unfortunately, it could not provide any indication of the dinuclear binding mode, which was revealed only by the X-ray structure determination.The structural assignment of the title compound was supplemented by its Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atom. The crystal studied was refined as an inversion twin with the ratio of the twin components refining to 0.436 (12):0.564 (12).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989019007217/lh5903sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019007217/lh5903Isup2.hklStructure factors: contains datablock(s) I. DOI: 1916953CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound is built up from the benzodiazepine ring system linked to the pyridyl and pendant dihydropyran rings. In the crystal, N—H⋯O and C—H⋯O hydrogen bonds link the molecules into a three-dimensional network. A weak C—H ⋯ π interaction is also observed. 17H18N2O3, is constructed from a benzodiazepine ring system linked to a pendant dihydropyran ring, where the benzene and pendant dihydropyran rings are oriented at a dihedral angle of 15.14 (4)°. Intramolecular N—HDiazp⋯ODhydp and C—HDiazp⋯ODhydp (Diazp = diazepine and Dhydp = dihydropyran) hydrogen bonds link the seven-membered diazepine ring to the pendant dihydropyran ring, enclosing S(6) ring motifs. In the crystal, N—HDiazp⋯ODhydp hydrogen bonds link the molecules into infinite chains along [10via C—HBnz⋯ODhydp, C—HDhydp⋯ODhydp and C—HMth⋯ODhydp (Bnz = benzene and Mth = methyl) hydrogen bonds, forming a three-dimensional network. The observed weak C—HDiazp ⋯ π interaction may further stabilize the structure. Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (51.1%), H⋯C/C⋯H (25.3%) and H⋯O/O⋯H (20.3%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing.The title compound, C Many members of this family are widely used as anticonvulsant, anti-anxiety, anti-seizure, analgesic, sedative, antidepressive and hypnotic or anti-inflammatory agents   Å (for atom C10), and is oriented at a dihedral angle of 15.14 (4)° with respect to the benzene (B: C4–C9) ring. A puckering analysis of the seven-membered diazepine ring (A: N1/N2/C1–C4/C9) gave the parameters QT = 0.6874 (14), q2 = 0.5903 (14), q3 = 0.3523 (14) Å, φ2 = 352.88 (14), φ3 = 245.8 (2)°. In ring A, the N1—C1—C2 [117.10 (2)°], C1—C2—C3 [114.17 (11)°], C3—N2—C4 [128.91 (11)°], N2—C4—C9 [127.38 (12)°], C4—C9—N1 [126.21 (12)°] and C9—N1—C1 [130.71 (12)°] bond angles are enlarged, while the C2—C3—N2 [108.97 (11)°] bond angle is narrowed, when compared with the corresponding values in the seven-membered diazepine ring in the closely related compound, 3,4-dihydro-2--4-(4-pyridin-4-yl)-1,5-benzo- diazepine, (II), where the pendant dihydropyran ring is not planar The title compound, (I)4) Fig. 1. Ring C Diazp⋯ODhydp and C—HDiazp⋯ODhydp (Diazp = diazepine and Dhydp = dihydropyran) hydrogen bonds  ring motifs s Table 1 link thefs Fig. 1.Diazp⋯ODhydp hydrogen bonds  hydrogen bonds  analysis  and H⋯N/N⋯H  contacts in the structure contribute only 1.6 and 1.1%, respectively, to the HS. The Hirshfeld surface representations with the function dnorm plotted onto the surface are shown for the H⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions in Fig. 7a–c, respectively.The overall two-dimensional fingerprint plot, Fig. 6s Table 2. In the s Table 2. There is Table 1 as well s Table 1 and is s⋯O Fig. 6e and H⋯⋯H Fig. 6f contacet al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing  in ethanol (40 ml) was refluxed for 1 h. After cooling to room temperature, the colourless intermediate solid compound, a mono-Schiff base, was obtained in 70% yield. The intermediate  was refluxed in acetone (10 ml) for 1h. After cooling, the crystals formed were filtered and dried (yield: 65%).A solution of dehydroacetic acid  and Uiso(H) = kUeq, where k = 1.5 for methyl H atoms and 1.2 for the other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989019000689/lh5890sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019000689/lh5890Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019000689/lh5890Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019000689/lh5890Isup4.cmlSupporting information file. DOI: 1890950CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structures of two new forms of cobalt–pyridine–sulfate complexes are presented. The feature infinite chains of metal–pyridine units connected by bridging sulfate anions, which are distinct from the only previously reported structure of a cobalt–pyridine–sulfate compound. catena-poly[[tetrakis(pyridine-κN)cobalt(II)]-μ-sulfato-κ2O:O′], [Co(SO4)(C5H5N)4]n, (1), and catena-poly[[tetrakis(pyridine-κN)cobalt(II)]-μ-sulfato-κ3O:O′,O′′-[bis(pyridine-κN)cobalt(II)]-μ-sulfato-κ3O,O′:O′′]n, [Co2(SO4)2(C5H5N)6]n, (2), are reported. Compound (1) displays a polymeric structure, with infinite chains of CoII cations adopting octahedral N4O2 coordination environments that involve four pyridine ligands and two bridging sulfate ions. Compound (2) is also polymeric with infinite chains of CoII cations. The first Co center has an octahedral N4O2 coordination environment that involves four pyridine ligands and two bridging sulfate ligands. The second Co center has an octahedral N2O4 coordination environment that involves two pyridine ligands and two bridging sulfate ions that chelate the Co atom. The structure of (2) was refined as a two-component inversion twin.The solid-state structures of two cobalt–pyridine–sulfate compounds, namely  When grown out, the cobalt ion shows an octahedral coordination environment . The equatorial positions of the octahedron are occupied by four pyridine ligands in a square-planar arrangement. The CoN4 unit exhibits planarity enforced by symmetry, with cis N—Co—N angles of 86.45 (6) and 93.55 (6)°. To complete the octahedron, the axial positions are occupied by two sulfate ions, with an inversion enforced O—Co—O angle of 180° and cis O—Co—N angles of 88.87 (6) and 91.67 (6)°. The pyridine rings are rotated from the CoN4 plane by dihedral angles of 47.30 (10) and 78.33 (9)°. The 78.33 (9)° angles are constrained by two C—H⋯O interactions between the ortho hydrogen atoms and the two trans sulfates  consists of two cobalt atoms, six coordinated pyridines and two sulfate anions . There are two crystallographically unique cobalt atoms, with Co1  displaying an octahedral N4O2 coordination environment and Co2  exhibiting an octahedral N2O4 coordination geometry.The asymmetric unit of the purple crystals of  to 93.18 (12)°, and the trans O—Co—O angle is 173.43 (12)°. The planes of the four pyridine rings are rotated from the equatorial CoN4 plane by dihedral angles of 58.6 (2), 64.6 (2), 65.6 (2), and 73.1 (2)°. Two of the rings show one C—H⋯O interaction with an ortho hydrogen atom, one ring shows two C—H⋯O interactions with two ortho hydrogen atoms, and the fourth ring shows no C—H⋯O interactions °. The two sulfate ligands exhibit O—Co—O bite angles of 65.90 (10) and 66.37 (10)°. The other cis O—Co—O angles are 86.87 (11), 98.98 (11), and 102.84 (11)°, and the six cis N—Co—O angles range from 92.49 (12) to 98.33 (13)°. Each pyridine ring is involved in ortho C—H⋯O interactions  are linked together into infinite chains along the [001] direction through sulfate anions with O—S—O bridges . Between each successive tetrapyridine cobalt unit, there are parallel slipped π–π interactions .The Cos Figs. 3a, 4 ▸aII atoms in compound (2) are linked together into infinite chains along the [111] direction through the sulfate anions . The chain alternates between tetrapyridine cobalt units and dipyridine cobalt units. No π–π interactions are observed in the crystal.The Cos Figs. 3b, 4 ▸b3(SO4)3(C5H5N)11)]n, which was grown at a lower concentration of cobalt. This structure shows two successive octahedral cobalt atoms with N4O2 coordination, where each atom is coordinated to four pyridines and two bridging sulfates. The third cobalt atom in the chain shows N3O3 coordination where three pyridines are bound and there are two sulfates bound, one of which is chelating to the cobalt  and (2). In compound (1), every cobalt atom possesses an octahedral N4O2 coordination. This complex is isostructural with the structure observed for the iron and nickel pyridine–sulfate complexes , the cobalt atoms alternate between N4O2 coordination and N2O4 coordination. This tetrapyridine/bipyridine alternation is similar to what is observed in the zinc–pyridine–sulfate structure, which alternates between octahedral and tetrahedral zinc centers. In the case of cobalt, the bis(pyridine) cobalt center is still octahedral because the two coordinated sulfates both chelate to the cobalt. The end result is an infinite chain of octahedral cobalt atoms, which is true in compound (1) and the previously reported cobalt–pyridine–sulfate complex. The methanesulfato complexes of cobalt (II) have also been reported as octahedral tetrakis(pyridine), [Co(SO3CH3)2(py)4], and octahedral bis(pyridine), [Co(SO3CH3)2(py)2], compounds, consistent with the two independent cobalt centers observed in (2) , 40 mg of cobalt sulfate heptahydrate (J. T. Baker) was dissolved in pyridine  and distilled water (100 µL) in a 20 mL vial. The vial was heated to 338 K for 48 h, after which single crystals suitable for X-ray diffraction studies were isolated from the reaction mixture.For compound (2), 48 mg of cobalt sulfate heptahydrate (J. T. Baker) was dissolved in pyridine  and distilled water (30 µL) in a 20 mL vial. The vial was heated to 358 K for 48 h, after which single crystals suitable for X-ray diffraction studies were isolated from the reaction mixture.For compound (SHELXL) by full-matrix least squares on F2. Hydrogen atoms were placed in calculated positions and then refined with a riding model with C—H bond lengths of 0.95 Å and with isotropic displacement parameters set to 1.20 Ueq of the parent C atom. The structre of (2) was refined as a two-component inversion twin, BASF = 0.165 (13).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S205698901901538X/sj5586sup1.cifCrystal structure: contains datablock(s) 1, 2, I. DOI: 10.1107/S205698901901538X/sj55861sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S205698901901538X/sj55862sup3.hklStructure factors: contains datablock(s) 2. DOI: 1965662, 1965663, 1965662, 1965663CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The structures of the two isomeric hydrogen-bonded 1:1 co-crystals of 3-chloro-2-nitrobenzoic acid with 5-nitroquinoline and 6-nitroquinoline, and the 1:1 salt of 3-chloro-2-nitrobenzoic acid with 8-hydroxyqunoline have been determined at 190 K. In each crystal, the acid and base molecules are linked by a short O—H⋯N or N—H⋯O hydrogen bond. 7H4ClNO4·C9H6N2O2, the acid and base molecules are held together by O—H⋯N and C—H⋯O hydrogen bonds. In compound (III), C9H8NO+·C7H3ClNO4−, an acid–base interaction involving H-atom transfer occurs and the H atom is located at the N site of the base molecule. In the crystal of (I), the hydrogen-bonded acid–base units are linked by C—H⋯O hydrogen bonds, forming a tape structure along the b-axis direction. Adjacent tapes, which are related by a twofold rotation axis, are linked by a third C—H⋯O hydrogen bond, forming wide ribbons parallel to the (via π–π interactions between the quinoline ring systems [centroid–centroid distances = 3.4935 (5)–3.7721 (6) Å], forming layers parallel to the ab plane. In the crystal of (II), the hydrogen-bonded acid–base units are also linked into a tape structure along the b-axis direction via C—H⋯O hydrogen bonds. Inversion-related tapes are linked by further C—H⋯O hydrogen bonds to form wide ribbons parallel to the –3.9247 (9) Å], and the molecular chains are linked into layers parallel to the ab plane through these interactions.The structures of three compounds of 3-chloro-2-nitrobenzoic acid with 5-nitroquinoline, (I), 6-nitroquinoline, (II), and 8-hydroxyquinoline, (III), have been determined at 190 K. In each of the two isomeric compounds, (I) and (II), C The ΔpThe molecular structure of (I)The molecular structure of (II)+—H⋯O− hydrogen bond (Table 3The molecular structure of (III)d Table 3. In the i and C14—H14⋯O5i; symmetry codes as in Table 1b-axis direction. Adjacent tapes, which are related by a twofold rotation axis, are linked by a third C—H⋯O hydrogen bond (C13—H13⋯O6ii), forming wide ribbons parallel to the  −x + 1, y, −z + 2].In the crystal of (I)ne Fig. 4. These rne Fig. 5. The cenb-axis direction via C—H⋯O hydrogen bonds  via weak π–π interactions  −x, −y + 2, −z; (v) x − 1, y + 1, z; (vi) −x + 1, −y + 1, −z + 1]. A pair of short O⋯N contacts  between the nitro groups of the base molecule are alsso observed.In the crystal of (II)ne Fig. 6. The acins Fig. 7, so formvia N—H⋯O and O—H⋯O hydrogen bonds  Å]; Cg1 and Cg3 are, respectively, the centroids of the C1–C6 ring of the anion and the C11–C16 ring of the cation. In addition to the π–π interaction (Cg1⋯Cg3i), other π–π interactions are observed; the centroid–centroid distances are 3.5469 (6), 3.8550 (6) and 3.5133 (6) Å, respectively, for Cg1⋯Cg2iii, Cg1⋯Cg3iii and Cg1⋯Cg4iii, where Cg2 and Cg4 are the centroids of the N2/C8–C11/C16 and N2/C8–C16 rings of the cation, respectively  is observed between the layers.In the crystal of compound (III)on Fig. 8. In the ns Fig. 9, and theet al., 2016et al., 2002et al., 2018et al. , 2.561 (1), 2.540 (2)–2.571 (2), 2.573 (1) and 2.613 (3) Å, respectively. Furthermore, in the short hydrogen bonds of AJIWOG, CALJUW and NOVLAN, the H atom is disordered over two positions. On the other hand, the compounds (I)Ka values of 0.98, 1.42 and 3.02, respectively, show longer O⋯N distances of 2.673 (1), 2.631 (1) and 2.636 (1) Å, which suggests that the ΔpKa value is not an effective measure of hydrogen-bond strength in the 3-chloro-2-nitrobenzoic acid–organic base system.A search of the Cambridge Structural Database , in which the O⋯N distance of the N—H⋯O hydrogen bond is 2.644 (3) Å.A search for organic co-crystals/salts of 5-nitroquinoline showed six structures. Limiting the search to benzoic acid derivatives gave two hits, namely, 3-aminobenzoic acid–5-nitroquinoline (1/1) –(III), were obtained by slow evaporation from acetonitrile solutions of 3-chloro-2-nitrobenzoic acid with quinoline derivatives in a 1:1 molar ratio at room temperature [100 ml acetonitrile solution of 3-chloro-2-nitrobenzoic acid (0.39 g) and 5-nitroquinoline (0.34 g) for (I)O = 0.872 (19) Å in (III)Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989019012799/lh5922sup1.cifCrystal structure: contains datablock(s) global, I, II, III. DOI: 10.1107/S2056989019012799/lh5922Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019012799/lh5922IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989019012799/lh5922IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 1953605, 1953604, 1953603CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The dimeric molecules of the complexes crystallize together with water and methanol molecules, with which they form a variety of weak and medium-strength hydrogen bonds.Oxalate-bridged, centrosymmetric binuclear complexes of gadolinium(III) and dysprosium(III) with hexadentate bbpen Ln(bbpen)Cl]  and potassium oxalate monohydrate in water/methanol produced the solvated centrosymmetric isostructural binuclear bis{dilanthanide(III)}–methanol–water (1/4/4) complexes, [Ln2(C28H28N4O2)2(C2O4)]·4CH3OH·4H2O, with lanthanide(III) = gadolinium(III) (Ln = Gd) and dysprosium(III) (Ln = Dy), in high yields (ca 70%) directly from the reaction mixtures. In both complexes, the lanthanide ion is eight-coordinate and adopts a distorted square-antiprismatic coordination environment. The triclinic (PPLATON . These two new compounds are of interest with respect to magnetic properties.The reaction between mononuclear [Spek 2015. Acta Cr The lanthanide cations assume square-antiprismatic coordination environments while the d-block metal is octahedrally coordinated 2]+ complex had previously been employed to produce binuclear [Dy2(μ-ox)(HBpz3)4]·2CH3CN·CH2Cl2, this time with oxalate (ox2–) as the bridging ligand. Direct current (DC) magnetic susceptibility measurements performed with this dimeric compound revealed the presence of an intramolecular ferromagnetic interaction between the DyIII cations 3{Ln(bbpen)}3] -N,N′-bis(pyridin-2-ylmethyl)ethylenediamine) via modular synthesis employing [Ln(bbpen)Cl] (LnIII = Gd or Dy) and K3[M(ox)3] (MIII = Cr or Co) as building blocks in a 3:1 proportion. The syntheses with gadolinium(III) and chromium(III) produced colourless crystals of the binuclear complex [{Gd(bbpen)}2(μ-ox)]·4CH3OH·4H2O, as revealed by single crystal X-ray diffraction analysis. The formation of this dimer is explained by dissociation of [Cr(ox)3]3– into {Cr(ox)2(OH2)2}− and ox2– in aqueous solution +. Structural elucidation of this otherwise unexpected product prompted us to try and perform its targeted preparation with both gadolinium(III) and dysprosium(III) in good yields.In our research group, we first attempted to prepare heterometallic complexes of general formula [Ln(bbpen)}2(μ-ox)] products [Ln = Gd (1) or Dy (2)], prepared from the direct reaction between [Ln(bbpen)Cl] and K2C2O4·H2O in water/methanol media.In this paper we report the rational synthesis and the crystal and molecular structures of the two binuclear and solvated [{1 and 2 are isostructural and crystallize in the PLn2(μ-ox)(bbpen)2] molecules  or dysprosium(III) (2) are eight-coordinate; the [Ln(bbpen)]+ units are connected to one another by oxalate bridging in the usual bis(bidentate) coordination mode. The ox2– ligand lies about an inversion centre. The coordination sphere of the lanthanide(III) ion is formed by an N4O2 donor set from the bbpen2– ligand and two oxygen atoms from the bridging oxalate. In 1 and 2 each metal cation has a distorted square-antiprismatic coordination environment  and 2.24 Å (2). The non-bonding Dy⋯Dy distance in 2, 6.1488 (17) Å, is close to the analogous distance of 6.14 Å in [Dy2(μ-ox)(HBpz3)4]·2CH3CN·CH2Cl2  −x, 1 − y, 1 − z] are also similar to those reported for the dysprosium(III)–hydrotris(pirazolylborate) dimer mentioned above. The slightly decreased crystal volume of the Dy compound [1626.3 (7) Å3] compared with that of the Gd compound [1633.7 (3) Å3] is a perfect match with the smaller effective ionic radius of eight-coordinate DyIIIversus GdIII  product 2 gives rise to very similar results.Compounds es Fig. 1 in whichnt Fig. 2, as indiIn both structures, the hydrogen atoms from the crystallizing solvents (water and methanol) participate in an extensive three-dimensional hydrogen-bonding network that may be described as medium-strength intermolecular interactions Tables 1 and 2 ▸.1 and 2. As seen in Fig. 3W—H⋯O2iii ‘bridge’, as well as a symmetry-related chain on both sides of the plane formed by the metal and oxalate ions. The water molecules in these chains also connect one dimer to another through weak C1—H1B⋯O1Wii interactions  molecules, half of which refine well and are depicted in Fig. 3ns Fig. 4 and 2 ▸.PLATON  for O⋯O30. On the other hand, any possible interaction involving the phenolate oxygen atoms would be very weak, with the shortest O⋯O contact with the disordered solvents being longer than 4.0 Å.The other half of the solvent molecules in the unit cell, the electron densities of which have been removed with the SQUEEZE routine in 2– and related ligands appear in the literature  complexes with bbpen al. 2005, and by  al. 2000.LnCl3·6H2O (LnIII = Gd or Dy) and K2C2O4·H2O were purchased from Aldrich and used without purification. N,N′-Bis(2-hydroxybenzyl)-N,N′-bis(pyridin-2-ylmethyl)ethylenediamine (H2bbpen) Cl] precursors, with Ln = Gd or Dy ]·4CH3OHSynthesis of [{Gd(bbpen)}·2O (compound 1)4H2C2O4·H2O in 1.0 ml of water was slowly added to a methanol solution of 61.1 mg (0.0947 mmol) of [Gd(bbpen)Cl]. The colourless reaction mixture was stirred at room temperature for ca 5 min, and was then cooled down to 277 K to give block-shaped colourless crystals after four days. These were isolated by filtration, washed with diethyl ether and dried. Total yield: 49.0 mg (68.6%) based on the [{Gd(bbpen)}2(μ–ox)]·4CH3OH·4H2O formulation, compound 1. FTIR : 3362, 3198 ; 1655 ; 1590, 1568 , 1290 , 762 and 768 . Product 1 is soluble in acetonitrile, 1,2-dimethoxyethane (dme), dichloromethane and tetrahydrofuran. Elemental analysis: calculated for 1 (C62H80Gd2N8O16) C 49.39, H 5.35, N 7.43%. Found: C 48.56, H 5.49, N 7.45%.A solution of 8.11 mg (0.0440 mmol) of K2(μ–ox)]·4CH3OHSynthesis of ·4CH3OH·4H2O formulation, compound 2. FTIR : 3363, 3198 , 1590 ; 1570 (m), 1481 (s), 1459 ; 1290 , 762 and 768 . The product solubility is similar to that described for 1. Elemental analysis: calculated for 2 (C62H80Dy2N8O16) C 49.04, H 5.31, N 7.38%. Found: C 49.02, H 5.71, N 7.56%.A mixture of 61.0 mg (0.0938 mmol) of [Dy(bbpen)Cl] in 9.0 ml of methanol and 8.90 mg (0.0483 mmol) of K1 and 2 showed high susceptibility to the loss of the crystallization solvent molecules once removed from the mother liquor. Hydrogen atoms in 1 and 2 were included in idealized positions with methyl, methylene and aromatic C—H distances set at 0.98, 0.99 and 0.95 Å, respectively, and O—H at 0.84 Å and refined as riding with Uiso(H) = 1.2–1.5Ueq. Hydrogen atoms on the water molecules were located in difference-Fourier maps and were refined with distance restraints .Crystal data, data collection and structure refinement details for the two structures are summarized in Table 3PLATON  1, 2. DOI: 10.1107/S2056989019002998/wm54891sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989019002998/wm54892sup3.hklStructure factors: contains datablock(s) 2. DOI: 1899963, 1899964CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N-oxide and solvent molecules are reported. The pyridine N--oxide, 2-methylpyridine N-oxide, 3-methylpyridine N-oxide, and 4-methylpyridine N-oxide complexes all form similar structures with slight differences owing to the substituent group effects.The synthesis and crystal structures of four dimeric complexes composed of manganese(II) dibromide, a pyridine  N-oxides, viz. pyridine N-oxide (PNO), 2-methylpyridine N-oxide (2MePNO), 3-methylpyridine N-oxide (3MePNO), and 4-methylpyridine N-oxide (4MePNO). The compounds are bis(μ-pyridine N-oxide)bis[aquadibromido(pyridine N-oxide)manganese(II)], [Mn2Br4(C5H5NO)4(H2O)2] (I), bis(μ-2-methylpyridine N-oxide)bis[diaquadibromidomanganese(II)]–2-methylpyridine N-oxide (1/2), [Mn2Br4(C6H7NO)2(H2O)4]·2C6H7NO (II), bis(μ-3-methylpyridine N-oxide)bis[aquadibromido(3-methylpyridine N-oxide)manganese(II)], [Mn2Br4(C6H7NO)4(H2O)2] (III), and bis(μ-4-methylpyridine N-oxide)bis[dibromidomethanol(4-methylpyridine N-oxide)manganese(II)], [Mn2Br4(C6H7NO)4(CH3OH)2] (IV). All the compounds have one unique MnII atom and form a dimeric complex that contains two MnII atoms related by a crystallographic inversion center. Pseudo-octahedral six-coordinate manganese(II) centers are found in all four compounds. All four compounds form dimers of Mn atoms bridged by the oxygen atom of the PNO ligand. Compounds I, II and III exhibit a bound water of solvation, whereas compound IV contains a bound methanol molecule of solvation. Compounds I, III and IV exhibit the same arrangement of molecules around each manganese atom, ligated by two bromide ions, oxygen atoms of two PNO ligands and one solvent molecule, whereas in compound II each manganese atom is ligated by two bromide ions, one O atom of a PNO ligand and two water molecules with a second PNO molecule interacting with the complex via hydrogen bonding through the bound water molecules. All of the compounds form extended hydrogen-bonding networks, and compounds I, II, and IV exhibit offset π-stacking between PNO ligands of neighboring dimers.Four manganese(II) bromide coordination complexes have been prepared with four pyridine  N-oxides have interesting binding modes that facilitate the growth of unique coordination structures. Their utility to facilitate organic oxotransfer reactions has been well documented over the years  and manganese(II) metal ions with a single bifunctional ligand containing an acetate and N-oxide moiety  dimeric complexes, using pyridine N-oxide (PNO) and its mono-methyl-substituted forms, 2-methylpyridine N-oxide (2MePNO), 3-methylpyridine N-oxide (3MePNO), and 4-methylpyridine N-oxide (4MePNO). This was done to study the impact of substitution of the pyridine on the two- and three-dimensional solid-state structures, and to compare them to previous structures in which the bromide ions are replaced with chloride ions.Herein, we report the synthesis and solid-state structures of four pyridine General structural detailsN-oxide complexes form dimers consisting of two MnII atoms related by an inversion center; the dimer contains a six-coordinate metal center at each MnII ion with four donor oxygen atoms and two bromides. The Mn1⋯Mn1′ dimer is bound trans by two μ2-1,1-PNO ligands, and the octahedral environment is completed by a water molecule of hydration or a solvent molecule, non-bridging PNO ligands, and bromide ions. The dimer is constructed from symmetry-related atoms and molecules using a crystallographic inversion center of the space group (PP21/n). The molecular structures of compounds I, II, III and IV are given in Figs. 1The pyridine Specific structural detailsI  and 2.235 (2) Å for Mn1—O1 and Mn1—O1i, respectively, which is unremarkable for compounds of MnII and pyridine N-oxide  Å. The octahedral geometry around the Mn atoms is significantly distorted with the O1—Mn1—O1i bond angle measuring 69.66 (9)°; the other bond angles are within ca 9° of 90°. These bond angles and bond lengths are similar to those for other MnII halide PNO structures  Å .Compound I Fig. 1 crystallII  and 2.321 (2) Å for Mn1—O1 and Mn1—O1i, respectively. The two bound water molecules have Mn—O bond lengths of 2.237 (3) and 2.157 (3) Å for Mn1—O3 and Mn1—O4, respectively, and are similar to those reported previously  Å. Once again the octahedral geometry around the Mn atoms is significantly distorted with the O1—Mn1—O1i bond angle measuring 74.40 (9)°. The other bond angles are within ca 11° of 90°. The dimer forms an intramolecular hydrogen bond between O3 and Br1i with a hydrogen-bond distance of 2.44 (2) Å . In the asymmetric unit there is a second PNO molecule interacting with the complex via hydrogen bonding through the bound water molecules  and 2.219 (3) Å for Mn1—O2 and Mn1—O2i, respectively. The non-bridging Mn1—O1 bond is 2.129 (3) Å, and the bound water Mn1—O3 bond distance is 2.245 (3) Å. The bound bromide ions have bond distances of Mn1—Br1 = 2.7237 (7) Å and Mn1—Br2 = 2.5687 (7) Å; again the difference in Mn—Br bond distances can be attributed to the hydrogen-bonding interactions that exist with Br1 but not with Br2 (Table 3i distance is 3.6497 (13) Å. The octahedral geometry around the Mn atoms is significantly distorted with the O2—Mn1—O2i bond angle measuring 69.05 (11)° the other bond angles are within ca 11° of 90°. The dimer forms an intramolecular hydrogen bond between O3 and Br1ii with a hydrogen-bond distance of 2.55 (2) Å .Compound II Fig. 3 crystall2 Table 3. The Mn1IV  and 2.230 (3) Å for Mn1—O2 and Mn1—O2i, respectively. The non-bridging Mn1—O1 bond is 2.116 (3) Å, and the bound methanol Mn1—O3 bond distance is 2.225 (3) Å. The bound bromide ions have bond distances of Mn1—Br1 = 2.7181 (7) Å and Mn1—Br2 2.5806 (7) Å, again the difference in Mn—Br bond distance can be attributed to the hydrogen-bonding interactions (Table 4i distance is 3.61254 (12) Å. The octahedral geometry around the Mn atoms is significantly distorted with the O2—Mn1—O2i bond angle measuring 70.77 (11)° the other bond angles are within 13° of 90°. The dimer forms an intramolecular hydrogen bond between O3 and Br1i with a hydrogen-bond distance of 2.41 (2) Å .Compound IV Fig. 4 crystalls Table 4. The Mn1I, the dimers are linked by Owater—H⋯Br hydrogen bonds, forming chains parallel to the [100] direction; see Table 1ac plane  Å and O4⋯O2ii = 2.721 (4) Å (Table 2B⋯Br1i with a distance of 2.44 (2) Å , with an inter-centroid distance of the stacked aromatic rings of 3.516 (4) Å, so forming layers parallel to the ac plane  Å, with a significant centroid shift of 3.221 (9) Å preventing π-stacking. Neighboring dimers are linked by O—H⋯Br hydrogen-bonds forming chains parallel to the a axis. There are two observed interactions, O3—H3A⋯Br1i with a distance of 2.60 (2) Å and O3—H3B⋯Br1ii with a distance of 2.55 (2) Å . Five of these structures contain derivatives of pyridine N-oxides and one of them is a 4,4′-dipyridal N,N′-dioxide (H2O)]n, [MnCl2(2MPNO)(H2O)]n, and [MnCl2(3MPNO)(H2O)2]2 2(H2O)6I2]I2  bromide tetrahydrate  was dissolved in a minimal amount (20 ml) of methanol. Two molar equivalents of pyridine N-oxide  were also dissolved in methanol. The solutions were mixed and stirred for 10 min and the solvent was allowed to evaporate to produce X-ray quality crystals . Selected IR bands  3470 , 1471 (s), 1216 (s), 833 (s) 773 (m), 669 (m), 558 (m). Analysis calculated for C20H24N4Mn2Br4O6: C, 28.40; H, 2.86; N, 6.62%. Found: C, 28.13; H, 2.86; N, 6.50%.Compound II: Manganese(II) bromide tetrahydrate  was dissolved in a minimal amount (20 ml) of methanol. Two molar equivalents of 2-methylpyridine N-oxide  were also dissolved in methanol. The solutions were mixed and stirred for 10 min and the solvent was allowed to evaporate to produce X-ray quality crystals . Selected IR bands  3349 , 1600 (m), 1461 (s), 1195 (s) 842 (m), 772 (s), 557 (m). Analysis calculated for C24H36N4Mn2Br4O8: C, 30.73; H, 3.87; N, 5.97%. Found: C, 30.30; H, 3.62; N, 6.17%.Compound III: Manganese(II) bromide tetrahydrate  was dissolved in a minimal amount (20 ml) of methanol. Two molar equivalents of 3-methylpyridine N-oxide  were also dissolved in methanol. The solutions were mixed and stirred for 10 min and the solvent was allowed to evaporate to produce a powder . X-ray quality crystals were grown by recrystallizing a second time by slow evaporation from methanol. Selected IR bands  3373 , 1631 (s), 1492 (m), 1260 (m), 1163(s), 943 (m), 802 (m).Compound IV: Manganese(II) bromide tetrahydrate  was dissolved in a minimal amount (20 ml) of methanol. Two molar equivalents of 4-methylpyridine N-oxide  were also dissolved in methanol. The solutions were mixed and stirred for 10 min and the solvent was allowed to evaporate to produce a powder . X-ray quality crystals were grown by recrystallizing a second time from methanol with a slower evaporation rate. Selected IR bands  3227 , 3004 (m), 1670 (m), 1494(s), 1213 (s), 852(s), 763(s).I and II have been reported analytically pure, whereas III and IV were not isolated analytically pure. The FT–IR spectra of the four N-oxide complexes all exhibit broad absorbances in the 3500–3100 cm−1 region characteristic of the ν(O—H) of the coordinated water or methanol molecules. In addition, the ν(N—O) stretching frequency that is due to the N-oxide pyridyl moiety is observed in the region between 1260 and 1195 cm−1, as noted previously  Å and refined with Uiso(H) = 1.5Ueq(O). In compound IV, the hydroxyl H atom was located in a difference-Fourier map and refined with O—H distance restrained to 0.85 (1) Å and with Uiso(H) = 1.5Ueq(O). All carbon-bound H atoms were positioned geometrically and refined as riding: C—H = 0.95–0.98 Å with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989019010557/su5505sup1.cifCrystal structure: contains datablock(s) Global, II, III, IV, I. DOI: 10.1107/S2056989019010557/su5505Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019010557/su5505IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989019010557/su5505IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 10.1107/S2056989019010557/su5505IVsup5.hklStructure factors: contains datablock(s) IV. DOI: 1942967, 1942966, 1942965, 1942964CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: