The fused oxazine ring adopts an approximately half-chair conformation. The two benzoxazine rings are oriented anti to one another around the central C—C bond. The dominant intermolecular interaction in the crystal structure is a C—H⋯F hydrogen bond between the F atoms and the axial H atoms of the OCH2N methylene group in the oxazine rings of neighbouring molecules. C—H⋯π contacts further stabilize the crystal packing.The title fluorinated bisbenzoxazine, C Bond lengths in the benzoxazine moiety in (I)et al., 2012abThe molecular structure of the title compound is illustrated in Fig. 1Q = 0.4913 (15) Å, and θ = 52.03 (17)° and φ = 98.3 (2)°, with C2 and N1 displaced from the mean plane by −0.299 (2) and 0.331 (1) Å, respectively. The C1—C1A bond is in an axial position with a C5—N1—C1—C1A torsion angle of 75.45 (18)°. The two benzoxazine rings are oriented anti to one another about the central C1—C1A bond, with an N1—C1—C1A—N1A torsion angle of 180.0 (2)°.The fused six-membered heterocyclic rings exist in an approximately half-chair conformation, characterized by a puckering amplitude A⋯F1 hydrogen bonds  and 3.577 (2) Å and with C—H⋯Cg angles of 126 and 129°, respectively.The packing of title compound is dominated by C2—H2s Table 1, that cos Table 1, as indiH-1,3-benzoxazine)   monohydrate  bis set to 1.2Ueq of the parent atom.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016015243/sj5506sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016015243/sj5506Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016015243/sj5506Isup3.cmlSupporting information file. DOI: 1507056CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The structure of the title squarate salt is reported. Classical N—H⋯O and O—H⋯O hydrogen bonds combine with weak C—O⋯π(ring) and π–π contacts to stabilize the crystal packing. 6H10N22+·2C4HO4−, comprises two hydrogen squarate  anions and a 2-(azaniumylmethyl)pyridinium dication. The squaric acid molecules each donate an H atom to the N atoms of the pyridine ring and the aminomethyl units of a 2-(aminomethyl)pyridine molecule, forming the 1:2 salt. The Hsq− anions are linked by strong O—H⋯O hydrogen bonds and an N—H⋯O hydrogen bond links the 2-(azaniumylmethyl)pyridinium cation to one of the squaric acid anions. The crystal structure features additional N—H⋯O and O—H⋯O hydrogen bonds, π–π stacking and unusual weak C—O⋯π(ring) interactions.The asymmetric unit of the title compound, C It can be found in three forms: uncharged H2sq, the Hsq− monoanion and the sq2− dianion. The mono- and dianions are often produced following deprotonation by amines  electron donors of one or two lone pairs of electrons. Recently, we reported the synthesis and characterization of the same organoammonium squarate as the title compound but as a hydrate in the triclinic space group PP21/c.Hydrogen bonding is the most common way of generating supramolecular organic systems in crystal engineering and molecular recognition. Hydrogen-bonded systems generated from organic cations and anions are of special interest as they would be expected to form stronger hydrogen bonds than those in neutral molecules  Å] hydrogen bond  pyridine forms a salt with two squaric acid molecules and each molecule of the acid loses one proton. One of these is transferred to the N atom of the pyridine ring, generating the 4-(aminomethyl)morpholinium mono-cation. The other from the second acid molecule is engaged in the formation of a homo-conjugated hydrogen squarate anion nd Fig. 1. The elend Fig. 1. ConsideCg1, Cg2 and Cg3. The dihedral angles between the mean plane of ring 1 and those of rings 2 and 3 are 18.818 (8) and 31.564 (6)°, respectively. The dihedral angle between the two squarate anions is 29.19 (1)°. The angles between the C—C bonds in the Hsq− anions are close to 90°, with the oxygen atoms directed almost along the diagonals.N1/C1–C5, C7–C10 and C11–C14 are defined as rings 1, 2 and 3, respectively, with centroids − ion has one C—O bond (C11—O5) at 1.3023 (17) Å, which is significantly longer than a normal single C—O bond. This most likely reflects the involvement in the negative charge-assisted hydrogen bonding mentioned earlier. At 1.3000 (15) Å, the C10—O4 bond is similarly extended. The remaining C—O bonds in both rings display a similar pattern with one obvious C=O double bond in each ring  and the others of intermediate length in the range 1.2356 (16) to 1.2658 (15) Å, indicating some delocalization occurring in both rings.The C—C distances in the planar squarate ring systems reflect partial double-bond character for C9—C10, C7—C10, C11—C12 and C11—C14 with distances of 1.4291 (17), 1.4357 (16), 1.4139 (17) and 1.4465 (18) Å, respectively. In contrast C7—C8, C8—C9, C12—C13 and C13—C14 display more single-bond character with distances of 1.4886 (17), 1.4929 (17), 1.4802 (18) and 1.5141 (17) Å, respectively. The HsqA⋯O3 [2.4583 (14) Å] related to the proton-sharing interaction discussed earlier. This pair of anions is further linked to the 2-(azaniumylmethyl)pyridinium dication by an N1—H1A⋯O1 hydrogen bond, Fig. 1A⋯O3, N2—H2B⋯O2i and N2—H2B⋯O5i hydrogen bonds form rings with an C⋯O6i and N2—H2B⋯O5i hydrogen bonds combine to form C⋯O6i, and N2—H2A⋯O8ii and homonuclear O4—H4A⋯O6iii and O5—H5A⋯O3 hydrogen bonds generate a larger Cg2ii, C7—O1⋯Cg3iv and C13—O7⋯Cg2v interactions reinforced by π–π stacking interactions. These latter contacts  also contribute to the stabilization of the crystal packing  and 2-(aminomethyl)pyridine  were dissolved in water (25 cm3) to obtain a mixture in the molar ratio 2:1 and the solution was heated to 323 K in a temperature-controlled bath and stirred for one h. The reaction mixture was then slowly cooled to room temperature. The crystals formed were filtered and washed with 10 cm3 of methanol, and dried in air.All chemical reagents were analytical grade commercial products. The solvent was purified by conventional methods. Squaric acid (HUiso(H) = 1.2Ueq(C). The NH3 group (N—H = 0.89 Å) was also allowed to ride in the refinement with Uiso(H) = 1.5Ueq(N). The O-bound H atoms and N1-bound H atom were located in a difference-Fourier map and refined with Uiso(H) = 1.2Ueq(O) and Uiso(H) = 1.5Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017004376/sj5524sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017004376/sj5524Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017004376/sj5524Isup3.cmlSupporting information file. DOI: 1538918CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The macrocyclic title compound crystallizes as a dihydrate with a 12-membered inner ring system. Hydrogen bonds involving the lattice water molecules link the components into a three-dimensional network system. 21H40N4·2H2O, has been determined from synchrotron X-ray radiation data. The asymmetric unit comprises one 12-membered macropolycycle and two lattice water molecules. The macropolycycle contains two cyclohexane rings and one 1,3-diazacyclohexane ring, all in chair conformations. The C—N and C—C bond lengths are in the ranges 1.4526 (16)–1.4786 (17) and 1.517 (2)–1.5414 (17) Å, respectively. One intramolecular N—H⋯N hydrogen bond helps to stabilize the molecular conformation while medium-strength intermolecular N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds involving the lattice water molecules connect the components into a three-dimensional network.The structure of the title compound, C The two methyl substituents of the C10 and C20 atoms are on the same side with respect to the macrocyclic plane of the four N atoms –1.4786 (17) Å and 1.517 (2)–1.5414 (17) Å for the C—N and C—C bonds, respectively. The N1—C20 distance is the longest C—N distance, presumably as a consequence of the methyl group on the C20 atom and the N⋯H—O hydrogen bond involving N1. The bond angles within the six-membered 1,3-diazacyclohexane ring, N2—C7—N3, C7—N2—C8, and C7—N3—C10, are 109.89 (10), 109.60 (10), and 108.08 (9)°, respectively. All other C—N, C—C, and C—H bond lengths and corresponding angles are in the normal range for such compounds  unit, viz. the crystal structure of [Cr(L2)(H2O)](ClO4)2·3H2O docosane (L1) was synthesized according to a literature protocol  in H2O (40 mL) was rapidly added 37% formaldehyde  at room temperature. The reaction mixture was refluxed for 3 h. After cooling, the resultant white solid was filtered, washed with water, and dried. The crude product of L2·2H2O, (I)2O (1:2 v/v) solution to give colourless crystals suitable for X-ray analysis.Commercially available (Sigma–Aldrich) 1,2-cyclohexanediamine was used as provided. All other chemicals were reagent grade and used without further purification. The starting material, 3,14-dimethyl-2,6,13,17-tetraazatricyclo(16.4.0Uiso(H) values of 1.5 and 1.2 Ueq of the parent atoms, respectively. N- and O-bound H atoms were assigned based on a difference Fourier map, and were refined with distance restraints of 0.91 (4) and 0.88 (2) Å (using DFIX and DANG commands), respectively, and with Uiso(H) values of 1.2Ueq of the parent atoms.Crystal data, data collection, and structure refinement details are summarized in Table 210.1107/S2056989017002444/wm5364sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017002444/wm5364Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017002444/wm5364Isup3.cmlSupporting information file. DOI: 1532347CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N6-benzoyladenine (BA) and one molecule of 4-hydroxybenzoic acid (HBA). The N6-benzoyladenine (BA) has an N(7)—H tautomeric form with non-protonated N-1 and N-3 atoms. This tautomeric form is stabilized by a typical intramolecular N—H⋯O hydrogen bond on the Hoogsteen face of the purine ring. The primary robust via N—H⋯O and O—H⋯N hydrogen bonds.The asymmetric unit of the title co-crystal contains one molecule of  12H9N5O·C7H6O3, contains one molecule of N6-benzoyladenine (BA) and one molecule of 4-hydroxybenzoic acid (HBA). The N6-benzoyladenine (BA) has an N(7)—H tautomeric form with nonprotonated N-1 and N-3 atoms. This tautomeric form is stabilized by a typical intramolecular N—H⋯O hydrogen bond between the carbonyl (C=O) group and the N(7)—H hydrogen on the Hoogsteen face of the purine ring, forming a graph-set S(7) ring motif. The primary robust R22(8) ring motif is formed in the Watson–Crick face via N—H⋯O and O—H⋯N hydrogen bonds . Weak interactions, such as, C—H⋯π and π–π are also observed in this crystal structure.The asymmetric unit of the title co-crystal, C N6-derivatives have plant hormone (kinetin) (Tr). They also offer a variety of hydrogen-bonding donor and acceptor sites  molecule and one 4-hydroxybenzoic acid (HBA) molecule —H tautomeric form with non-protonated N1, N3 and N9 atoms. In the crystal structures of N6-benzoyladenine  and N6-benzoyl adenine-dl-tartaric acid (1:1)    ring motif in the Hoogsteen face. In contrast, it may be noted that in the crystal structure of N6-benzyladenine, (where no intramolecular hydrogen bond is present) the N6-substituent is syn to N1 and distal to N7 and the adenine moiety exists in the N(9)—H tautomeric form le Fig. 1. The bond Table 1 with an via N—H⋯O and O—H⋯N hydrogen bonds involving the carboxyl group of HBA. The N7 atom is a bifurcated donor and the carbonyl oxygen atom acts as a double acceptor for the N—H⋯O hydrogen bonds. Inversion-related BA molecules form dimers through an array of hydrogen bonds, generating ring motifs, and these dimers are doubly bridged by inversion-related HBA molecules  supramolecular ring is formed along the c-axis direction. A weak C8—H8⋯π interaction is also present. Further consolidation of the structure is provided by homo and hetero π–π stacking interactions   and N6-benzoyladenine–dl-tartaric acid (1:1)    and 4-hydroxybenzoic acid (35 mg) in an equimolar ratio in a total volume of 30 mL. The mixture was warmed over a water bath for 30 min, filtered, and left aside for a few days. Colourless plate-shaped crystals were collected from the mother solution following slow cooling at room temperature.The title co-crystal was prepared by mixing a hot ethanol solution of Uiso(H) = kUeq, where k = 1.5 for hydroxy and 1.2 for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989017002171/hg5481sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017002171/hg5481Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017002171/hg5481Isup3.cmlSupporting information file. DOI: 1531929CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title zwitterion exists in the iminium/phenoxide form. The molecule is twisted around the N—C(benzene) bond with the C=N—C—C torsion angle being 39.42 (8)°. In the crystal, a zigzag supramolecular chain is sustained by charge-assisted hydroxy-O—H⋯O(phenoxide) hydrogen bonding. 17H13NO2 (systematic name: 1-{(1E)-[(4-hydroxyphenyl)iminiumyl]methyl}naphthalen-2-olate), features an intramolecular charge-assisted N+—H⋯O− hydrogen bond. A twist in the molecule is evident around the N—C(hydroxybenzene) bond [C—N—C—C torsion angle = 39.42 (8)°] and is reflected in the dihedral angle of 39.42 (8)° formed between the aromatic regions of the molecule. In the crystal, zigzag supramolecular chains along the a axis are formed by charge-assisted hydroxy-O—H⋯O(phenoxide) hydrogen bonding. These are connected into a layer in the ab plane by charge-assisted hydroxybenzene-C—H⋯O(phenoxide) interactions and π–π contacts [inter-centroid distance between naphthyl-C6 rings = 3.4905 (12) Å]. Layers stack along the c axis with no specific interactions between them. The Hirshfeld surface analysis points to the significance C⋯H contacts between layers.The title zwitterion, C The dihedral angle between the two aromatic regions is 39.42 (8)°. The coplanar relationship between the imine and naphthyl residues is stabilized by an intramolecular charge-assisted N+—H⋯O− hydrogen bond, Table 1The molecular structure of (I)a axis mediated by hydroxy-O—H⋯O(phenoxide) charge-assisted hydrogen bonding, Fig. 2a and Table 1ab plane by charge-assisted hydroxybenzene-C—H⋯O(phenoxide) interactions, Table 1i = 3.4905 (12) Å and angle of inclination = 2.68 (8)° , Fig. 2b. Layers stack along the c axis with no directional interactions between them, Fig. 2c.The most prominent feature of the molecular packing is the formation of a zigzag (glide symmetry) supramolecular chain along the et al., 2017dnorm, Fig. 3The Hirshfeld surface was calculated for (I)a, and those delineated into H⋯H, C⋯H/H⋯C, O⋯H/H⋯O and C⋯C contacts  and -(C12–C17) rings through the arrow-shaped distribution with the green points spread about de = di = 1.8 Å. The small contributions from other interatomic contacts summarized in Table 3The overall two-dimensional fingerprint plot, Fig. 6et al., 2016i.e. (I)·0.5EtOH  and 1.2943 (19) Å. By contrast to (I)viz. a P21/c form with Z′ = 2 ° for the C2/c form. Finally, a deprotonated form of (I)et al., 2007The most closely related structure to (I)v/v) by slow evaporation.4-Hydroxyaniline  was added to a solution of 2-hydroxy-1-napthaldehyde  in ethanol (25 ml). The resulting mixture was refluxed at 333 K and stirred for 2.5 h. The reaction mixture was cooled to room temperature and the resulting orange precipitate was filtered off and washed with cold ethanol to obtain the pure product in 65% yield. Crystals of (I)Uiso(H) values set at 1.2Ueq(C). The O- and N-bound H atoms were located in a difference Fourier map, but were refined with distance restraints of O—H = 0.82±0.01 Å and N—H = 0.86±0.01 Å, and with Uiso(H) values set at 1.5Ueq(O) and 1.2Ueq(N), respectively. To confirm the positions of the acidic-H atoms, a separate refinement was conducted whereby no distance restraints were applied resulting in O—H and N—H bond lengths of 0.93 (2) and 1.00 (3) Å, respectively.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S205698901701458X/ex2001sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901701458X/ex2001Isup2.hklStructure factors: contains datablock(s) I. DOI: 1429885CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II centre via the thiolate S and imine N atoms in each of the two independent molecules comprising the asymmetric unit, leading to N2S2 donor sets and distorted tetrahedal geometries. The crystal features zigzag chains of molecules sustained by N—H⋯N and amine-N—H⋯S hydrogen bonds.The title thiosemicarbazonate complex has the ligands coordinating the Zn II complex, [Zn(C18H18N3S)2], (I), features two independent but chemically equivalent molecules in the asymmetric unit. In each, the thiosemicarbazonate monoanion coordinates the ZnII atom via the thiolate-S and imine-N atoms, with the resulting N2S2 donor set defining a distorted tetrahedral geometry. The five-membered ZnSCN2 chelate rings adopt distinct conformations in each independent molecule, i.e. one ring is almost planar while the other is twisted about the Zn—S bond. In the crystal, the two molecules comprising the asymmetric unit are linked by amine-N—H⋯N(imine) and amine-N—H⋯S(thiolate) hydrogen bonds via an eight-membered heterosynthon, {⋯HNCN⋯HNCS}. The dimeric aggregates are further consolidated by benzene-C—H⋯S(thiolate) interactions and are linked into a zigzag supramolecular chain along the c axis via amine-N—H⋯S(thiolate) hydrogen bonds. The chains are connected into a three-dimensional architecture via phenyl-C—H⋯π(phenyl) and π–π interactions, the latter occurring between chelate and phenyl rings [inter-centroid separation = 3.6873 (11) Å]. The analysis of the Hirshfeld surfaces calculated for (I) emphasizes the different interactions formed by the independent molecules in the crystal and the impact of the π–π interactions between chelate and phenyl rings.The title Zn The similarity in bond lengths extends to the angles subtended at the ZnII atoms which, for the Zn1-containing molecule range from 87.00 (5)° for S2—Zn1—N6, to 134.00 (5)° for S2—Zn1—N3, i.e. a range of 47°; the acute angle is associated with the chelate angle. A slightly narrower range is noted for the Zn2-containing molecule, i.e. 85.99 (5)° for S3—Zn2—N9, to 131.29 (5)° for S3—Zn2—N12, i.e. about 45°. The assignment of four-coordinate geometries can be quantified by the values of τ4, which range from 1.00 for an ideal tetrahedron to 0.00 for perfect square-planar geometry E, as are the conformations about the ethylene bonds, Table 1Two independent molecules comprise the asymmetric unit of (I)II atoms to form five-membered ZnSCN2 rings. The chelate rings adopt different conformations in each independent molecule. For the Zn1-containing molecule, the Zn1/S1/C1/N2/N3 ring is almost planar (r.m.s. deviation = 0.005 Å) but the Zn1/S2/C19/N5/N6 ring is twisted about the Zn1—S2 bond. A similar situation pertains to the Zn2-containing molecule where there is a small twist about the Zn2—S3 bond in the Zn2/S3/C37/N8/N9 ring and the Zn2/S4/C55/N11/N12 ring is planar to within an r.m.s. deviation of 0.008 Å. To a first approximation, for each thiosemicarbazone ligand, all atoms but the terminal ethyl and central phenyl rings lie in a plane. This is quantified in the dihedral angle between each five-membered chelate ring and the central and terminal rings of the prop-2-en-1-ylidene substituent, as summarized in Table 2The thiosemicarbazone ligands chelate the ZnCrystal Explorer a and Table 4c axis via additional amine-N—H⋯S(thiolate) hydrogen-bonds, Fig. 3b. Chains are connected via π–π interactions occurring between Zn2-containing molecules, involving chelate rings, comprising the Zn2/S4/C55/N11/N12 atoms and phenyl (C61–C66) rings. Precedents for chelate/arene ring interactions have been established in the literature  involving residues of the Zn1-containing molecule exclusively, Table 4c.The most prominent feature of the molecular packing is the formation of an eight-membered heterosynthon, {⋯HNCN⋯HNCS}, mediated by amine-N—H⋯N(imine) and amine-N—H⋯S(thiolate) hydrogen-bonds which occur between the two molecules comprising the asymmetric unit, Fig. 3et al., 2016dnorm in Fig. 4a and e, the bright-red spots near the amine-H1N, H7N, H10N, imime-N2 and thiolate-S2 and S3 atoms indicate their participation in N—H⋯N and N—H⋯S bonds between the two independent molecules. In the views of the Hirshfeld surfaces mapped over electrostatic potential for the Zn1-molecule in Fig. 4b and c, and for the Zn2-molecule in Fig. 4f and g, the hydrogen-bond donors and acceptors are represented by blue and red regions, respectively. Greater insight into intermolecular interactions in the crystal can be obtained by modifying the mapping range for dnorm, as shown in Fig. 4d and h, which reveals additional characteristic spots on the surface. A pair of red spots near amine-HN4 and near phenyl-C7 and C8 in Fig. 4d indicate the presence of short inter-atomic C⋯H/H⋯C contacts in the crystal, see Table 5a and e, respectively. The immediate environments about the Zn1- and Zn2-molecules within shape-index-mapped Hirshfeld surfaces highlighting hydrogen-bonding and C—H⋯π interactions are illustrated in Fig. 5a and 5b while the C—H⋯π and their reciprocal, i.e. π⋯H—C, contacts involving phenyl-C8 and C32 atoms as donors and phenyl (C31–C36 and C13–C18) rings as acceptors are shown in Fig. 5c.The Hirshfeld surface calculations of (I)i.e. (I)a. In addition, the fingerprint plots delineated into H⋯H, S⋯H/H⋯S, N⋯H/H⋯N, C⋯H/H⋯C,C⋯N/N⋯C and C⋯C contacts  rings of Zn2-molecules is evident from the presence of short inter-atomic Zn⋯C/C⋯Zn contacts, Table 5c, these contacts are reflected by a pair of points with an S-shaped distribution at around de + di ∼1.9 to 2.1 Å. This π–π stacking is also apparent from the small but effective contributions from Zn⋯C/C⋯Zn and C⋯N/N⋯C contacts to the Hirshfeld surface of the Zn2-molecule, Table 6The presence of a short inter-atomic C⋯S contact between the thiolate-S3 and phenyl-C66 atoms is evident from the typical H-shaped plot in Fig. 7et al., 2016i.e. of general formula Zn[SC(NHR)=NN=CR′R′′]2 reflecting the interest in this class of compound. All of the structures resemble the molecular geometry described above for (I)i.e. R′ = R′′ = Me for the R = Ph compound thiosemicarbazide , was used without further purification and was dissolved in heated absolute ethanol (50 ml). Zn(CH3COO)2·2H2O  was dissolved separately in heated absolute ethanol (30 ml) and then added into an ethanolic N-ethyl-N-thiosemicarbazide solution. The mixture was heated and stirred for about 10 mins, followed by stirring for 1 h at room temperature. The obtained yellow precipitate was filtered, washed with cold ethanol and dried in vacuo. Single crystals were grown at room temperature from the slow evaporation of a solution of dimethylformamide and acetonitrile (1:1 v/v 20 ml).Analytical grade reagents were used as procured without further purification. Equimolar quantities of 4-ethyl-3-thiosemicarbazide  and 1,3-diphenylprop-2-en-1-one  were dissolved in heated absolute ethanol (30 ml) separately and the mixtures were mixed with stirring. About five drops of concentrated hydrochloric acid were added to the mixture to catalyse the reaction. The reaction mixture was kept under heating and stirring for about 10 mins, followed by stirring for 1 h at room temperature. The resulting yellow precipitate was filtered off, washed with chilled absolute ethanol and dried Uiso(H) set to 1.2–1.5Ueq(C). The nitrogen-bound H atoms were located in a difference-Fourier map but were refined with a distance restraint of N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table 710.1107/S2056989017008064/hb7684sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017008064/hb7684Isup2.hklStructure factors: contains datablock(s) I. DOI: 1553218CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure of the centrosymmetric title compound features short N—H⋯π interactions. 8H8N2, is generated by a crystallographic center of symmetry. In the crystal, short N—H⋯π [H⋯π = 2.499 (19) Å] interactions link the molecules into a herringbone structure.The complete molecule of the title compound, C The double bonds C1=C2 and C3=C4 in (I)versus the double-bond length in pyrrole of 1.357 Å. The shortening of the C2—C3 bond and the lengthening of the adjacent C=C double bonds in (I)The complete molecule of (I)1 screw axis is 2.499 (19) Å Å Table 1. A surveet al., 2015et al., 1997There are very few examples of similar compounds available in the literature. Most bipyrroles have carbonyl groups as substituents on the pyrrole ring in which the N—H group forms hydrogen bonds with the oxygen atom of the carbonyl (Okawara 230 µl (3.3 mmol) of pyrrole was added to dichloromethane (10 ml), degassed and cooled to 195 K. Trimethylsilyl bromide  and phenyl iodine trifluoracetic acid  were added quickly to the cooled reaction. The mixture was stirred for 1 h then extracted with a saturated sodium bicarbonate solution and purified by column chromatography with a pentane/ethyl acetate (1:1) solution. Colourless blocks of (I)Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017013433/hb7692sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017013433/hb7692Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017013433/hb7692sup3.pdfSurvey of the Cambridge Database NH-pi bond lengths. DOI: 1575394CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound has a ‘banana’ shape, with the dihedral angle formed by the outer rings being 8.30 (7)°. In the crystal, the three-dimensional architecture features nitrobenzene-C—H⋯O(carbonyl), pyrrole-C—H⋯O(nitro), π(pyrrole)—π(nitrobenzene) and nitro-O⋯π(pyrrole) interactions. 12H12N2O4, the dihydropyrrole ring is almost planar (r.m.s. deviation = 0.0049 Å) and is nearly coplanar with the adjacent C2O2 residue [dihedral angle = 4.56 (9)°], which links to the 4-nitrobenzene substituent [dihedral angle = 4.58 (8)°]. The molecule is concave, with the outer rings lying to the same side of the central C2O2 residue and being inclined to each other [dihedral angle = 8.30 (7)°]. In the crystal, supramolecular layers parallel to (10-5) are sustained by nitrobenzene-C—H⋯O(carbonyl) and pyrrole-C—H⋯O(nitro) interactions. The layers are connected into a three-dimensional architecture by π(pyrrole)–π(nitrobenzene) stacking [inter-centroid separation = 3.7414 (10) Å] and nitro-O⋯π(pyrrole) interactions.In the title compound, C The planarity extends to the 4-nitrobenzene ring, with the dihedral angle between the C2O2 and C6 planes being 4.58 (8)°. However, the molecule is not planar but rather is curved as the outer rings lie to the same side of the central C2O2 residue; the dihedral angle = 8.30 (7)°. To a first approximation, the nitro group is co-planar with the benzene ring to which is connected, as seen in the value of the O4—N2—C10—C9 torsion angle of 173.50 (15)°.The molecular structure of (I)3OCO}2 synthons. The dimeric aggregates are connected into a supramolecular layer via pyrrole-C4—H⋯O3(nitro) interactions. The layers lie parallel to –π(C7–C12)i stacking interactions occur between pyrrole and nitrobenzene rings: inter-centroid separation = 3.7414 (10) Å and angle of inclination = 7.99 (9)° for symmetry code: (i): x, −y, z. The other interactions between layers are of the type nitro-O4⋯π, Table 1et al., 2008b.The molecular packing of (I)et al., 2017The Hirshfeld surface calculations for (I)dnorm in Fig. 3B and ester-C5 atoms, respectively, Fig. 4a. The other short interatomic C⋯H/H⋯C contacts between the nitrobenzene-H11 and pyrrole-C2 and C3 atoms  contacts is highlighted in Fig. 4b, showing the Hirshfeld surface mapped over the electrostatic potential.In addition to the bright-red spots on the Hirshfeld surface mapped over s Table 2 are intret al., 2007a–d, respectively, and the percentage contribution from the identified interatomic contacts to the Hirshfeld surface are summarized in Table 3i.e. 39.0%, contribution from H⋯H contacts to the overall surface is due to the involvement of many hydrogen atoms in directional intermolecular interactions, e.g. C—H⋯O, π (Tables 1b). Conversely, the relatively significant contribution of 33.8% from O⋯H/H⋯O contacts to the Hirshfeld surface is consistent with this observation. The fingerprint plot delineated into O⋯H/H⋯O contacts  features a pair of green aligned points within the pair of spikes with their tips at de + di ∼2.3 Å superimposed upon a distribution blue points characterizing intermolecular C—H⋯O interactions. The short interatomic C⋯H/H⋯C contacts in the inter- and intra-layer regions are represented by the two pairs of short forceps-like spikes at de + di ∼2.8 and 2.9 Å, respectively, in Fig. 5d. The small but discernible contributions from interatomic C⋯C and C⋯N/N⋯C contacts 2 Dihydropyrrole rings as found in (I)M solution, 10.56 mmol) in dry toluene was then added. The bath was removed and the solution stirred for 2 h at room temperature. Subsequently, the flask was immersed for 20 min in an oil bath preheated to 393–403 K with a reflux condenser. The solution was concentrated in a rotary evaporator and the residue was purified by flash column chromatography on silica gel, using a mixture of EtOAc/n-hexane (1:4) as the eluent. The yield of (I)2Cl2 solution.A solution of (4-nitrophenyl)methyl 2-hydroxypyrrolidine-1-carboxylate  in toluene (100 ml) was cooled to 273 K in an ice/water bath. Under an atmosphere of nitrogen, 2,4-lutidine  was added to this solution. The solution was stirred for 15 min at 273 K. A trifluoroacetic anhydride (TFAA) solution : δ 8.21 , 7.54 , 6.80 and 6.68 , 5.35 , 5.03 , 3.71 , 2.46 . 13C NMR : δ = 152.3 (CO2R), 151.5 (CO2R), 147.8 (C4′), 144.9 (C1′), 129.8 (C2), 129.2 (C2), 128.4 (C2′ and C6′), 128.3 (C2′ and C6′), 123.9 (C3′ and C5′), 109.4 (C3), 65.8 (CH2), 65.6 (CH2), 45.8 (C5), 45.4 (C5), 30.1 (C4), 29.0 (C4). ESI–MS (m/z) calculated for C12H12N2O4 248.07971, found 248.07876.Spectroscopic characterization. Uiso(H) set to 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989018002451/hb7736sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018002451/hb7736Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018002451/hb7736Isup3.cmlSupporting information file. DOI: 1823263CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, the 1:2 co-crystalline adducts are linked by π–π stacking interactions. 3,8]undecano (TATU) with 4-chloro-3,5-dimethylphenol led to the formation of the title co-crystal, C7H14N4·2C8H9ClO. The asymmetric unit contains one aminal cage molecule and two phenol molecules linked via two O—H⋯N hydrogen bonds. In the aminal cage, the N–CH2–CH2–N unit is slightly distorted from a syn periplanar geometry. Aromatic π–π stacking between the benzene rings from two different neighbouring phenol molecules [centroid–centroid distance = 4.0570 (11) Å] consolidates the crystal packing.Solvent-free treatment of 1,3,6,8-tetraazatricyclo[4.3.1.1 NitrogCg8⋯Cg9i = 4.0570 (11); symmetry code: (i) x, y, Cgz; 8 and Cg9 are the centroids of the C11–16 and C21–C26 rings, respectively] and the benzene ring planes are inclined to one another by 0.58 (9)°. These additional contacts link the three-membered co-crystal units into chains approximately parallel to undecane hydroquinone   and 4-chloro-3,5-dimethylphenol  was ground using a mortar and pestle at room temperature for 15 min. Completion of the reaction was monitored by TLC. The mixture was recrystallized from n-hexane solution to obtain colourless crystals suitable for X-ray analysis, m.p. = 375–376 K. (yield: 63%).A mixture of 1,3,6,8-tetraazatricyclo[4.3.1.1Uiso(H) set to 1.2Ueq of the parent atom. The hydroxyl H atoms were refined freely.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016016650/sj5512sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016016650/sj5512Isup2.hklStructure factors: contains datablock(s) I. DOI: 1510356CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II cation is five-coordinated in a distorted trigonal–bipyramidal geometry. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (58.4%), H⋯C/C⋯H (20.3%) and H⋯O/O⋯H (18.3%) interactions.In the title Zn complex, the Zn 10H11O2)2(C6H6N2O)2(H2O)], contains one half of the complex molecule, and the ZnII cation and the water O atom lie on a twofold rotation axis. The ZnII cation is coordinated by two carboxylate O atoms of the two symmetry-related 2,4,6-trimethylbenzoate (TMB) anions and by the water O atom at distances of 2.0311 (16) and 2.076 (2) Å to form a slightly distorted trigonal–planar arrangement, while the distorted trigonal–bipyramidal coordination sphere is completed by the two pyridine N atoms of the two symmetry-related monodentate nicotinamide (NA) ligands at distances of 2.2066 (19) Å in the axial positions. In the crystal, molecules are linked via intermolecular N—H⋯O and O—H⋯O hydrogen bonds with R22(12), R33(10) and R33(16) ring motifs, forming a double-column structure running along the c-axis direction. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (58.4%), H⋯C/C⋯H (20.3%) and H⋯O/O⋯H (18.3%) interactions.The asymmetric unit of the title complex, [Zn(C A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels 2(C6H6N2O)2]  ·H2O     (I)The transition metal complexes with ligands of biochemical interest as imidazole and some II cation (site symmetry 2), one 2,4,6-trimethylbenzoate (TMB) anion and one nicotinamide (NA) molecule together with one water molecule (point group symmetry 2), all ligands coordinating in a monodentate manner  1 − x, y, z] of the two symmetry-related monodentate TMB anions and the coordinating water O atom (O4) are at distances of 2.0311 (16) and 2.076 (2) Å, respectively, around the Zn1 atom and form a slightly distorted triangular planar arrangement. The sum of the bond angles O2—Zn1—O2i [95.38 (9)°], O2—Zn1—O4 [132.31 (5)°] and O2—Zn1—O4i [132.31 (5)°] in the basal plane around ZnII cation is 360°. This confirms the presence of the ZnII cation with very slight deviation from the basal plane. The slightly distorted trigonal–bipyramidal coordination sphere is completed by the two pyridine N atoms (N1 and N1i) of the two symmetry-related monodentate NA ligands at distances of 2.2066 (19) Å in the axial positions. The index of trigonality τ  and C1—O2 [1.259 (3) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements rather than localized single and double bonds. The O2—C1—O1 bond angle [121.8 (2)°] seems to be slightly decreased than that present in a free acid [122.2°], in which the O2—C1—O1 bond angle may be compared with the corresponding values of 123.5 (2) and 120.4 (2)° in (II), 125.2 (5)° in (III), 119.2 (3) and 123.8 (2)° in (IV), 123.6 (3) and 119.4 (3)° in (V), 124.4 (2)° in (VI) and 124.3 (2)° in (VII), where the benzoate ions coordinate to the metal atoms only monodentately in (III), (VI) and (VII), and both monodentately and bidentately in (II), (IV) and (V). The Zn1 atom lies 0.0817 (1) Å above of the planar (O1/O2/C1) carboxylate group. In the TMB anion, the carboxylate group is twisted away from the attached benzene C2–C7 ring by 61.32 (14)°, while the benzene ring and the pyridine N1/C11–C15 ring are oriented at a dihedral angle of 81.90 (8)°.2 group links to the non-coordinating carboxylate and NA oxygen atoms via intermolecular N—H⋯O hydrogen bonds, and the water molecule links to the NA oxygen atoms via intermolecular O—H⋯O hydrogen bonds , the 18.3% contribution to the HS arises from the intermolecular O—H⋯O hydrogen bonding and is viewed as pair of spikes with the tip at de + di ∼1.9 Å. The short H⋯O/O⋯H contacts are masked by strong O—H⋯O hydrogen bonding in this plot. The H⋯N/N⋯H contacts in the structure with 1.9% contribution to the HS has a symmetrical distribution of points with the tips at de + di ∼2.8 Å arising from the short interatomic H⋯N/N⋯H contact . The HSs mapped over shape-index, curvedness and those with the function dnorm plotted onto the surface are shown for the H⋯H, H⋯C/C⋯H, H⋯O/O⋯H and H⋯N/N⋯H interactions are shown in Figs. s1–s3 in the Supporting Information.A Hirshfeld surface (HS) analysis  in H2O (50 ml) and nicotinamide  in H2O (25 ml) with sodium 2,4,6-trimethylbenzoate  in H2O (150 ml) at room temperature. The mixture was set aside to crystallize at ambient temperature for ten weeks, giving colourless single crystals . FT–IR: 3396, 3111, 2953, 2919, 2740, 2321, 1947, 1693, 1665, 1621, 1601, 1584, 1445, 1397, 1199, 1113, 1047, 860, 839, 797, 731, 647, 614, 545, 559 cm−1.The title compound was prepared by the reaction of ZnSO2 group were also located in a difference Fourier map and the positions were refined with Uiso(H) = 1.5Ueq(N). The C-bound H atoms were positioned geometrically with C—H = 0.93 and 0.96 Å for aromatic and methyl H-atoms, respectively, and refined as riding with Uiso(H) = k × Ueq(C), where k = 1.5 for methyl H-atoms and k = 1.2 for aromatic H-atoms.The experimental details including the crystal data, data collection and refinement are summarized in Table 210.1107/S2056989017011690/is5478sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017011690/is5478Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017011690/is5478sup3.pdfHirsfeld surface plotted over shape-index. DOI: 10.1107/S2056989017011690/is5478sup4.pdfHirshfeld surface plotted over curvedness. DOI: 10.1107/S2056989017011690/is5478sup5.pdfHirshfeld surfaces plotted over dnorm. DOI: 1567723CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the isomeric title compounds, N—H⋯O and C—H⋯O hydrogen bond, and C—H⋯π and π–π interactions build different supramolecular architectures. 14H13Cl2NO2S, namely 3,5-dichloro-N--benzenesulfonamide (I), 3,5-dichloro-N-benzenesulfonamide (II) and 3,5-dichloro-N-benzenesulfonamide (III) are described. The molecules of all the three compounds are U-shaped with the two aromatic rings inclined at 41.3 (6)° in (I), 42.1 (2)° in (II) and 54.4 (3)° in (III). The molecular conformation of (II) is stabilized by intramolecular C—H⋯O hydrogen bonds and C—H⋯π interactions. The crystal structure of (I) features N—H⋯O hydrogen-bonded R22(8) loops interconnected via C(7) chains of C—H⋯O interactions, forming a three-dimensional architecture. The structure also features π–π interactions [Cg⋯Cg = 3.6970 (14) Å]. In (II), N—H⋯O hydrogen-bonded R22(8) loops are interconnected via π–π interactions [intercentroid distance = 3.606 (3) Å] to form a one-dimensional architecture running parallel to the a axis. In (III), adjacent C(4) chains of N—H⋯O hydrogen-bonded molecules running parallel to [010] are connected via C—H⋯π interactions, forming sheets parallel to the ab plane. Neighbouring sheets are linked via offset π–π interactions [intercentroid distance = 3.8303 (16) Å] to form a three-dimensional architecture.The crystal structures of three isomeric compounds of formula C The structure also features π–π interactions involving the benzenesulfonyl ring and the aniline ring as illustrated in Fig. 4Cg1⋯Cg2iii = 3.6970 (14) Å; Cg1 and Cg2 are the centroids of the C1–C6 and C7–C12 rings, respectively; symmetry code: (iii) x, −y, z].The crystal structure of (I)ps Fig. 4. The (8)i hydrogen-bonded via π–π interactions involving inversion-related benzenesulfonyl rings, forming a one-dimensional architecture running parallel to the a axis, as shown in Fig. 5Cg1⋯Cg1ii = 3.606 (3) Å; Cg1 is the centroid of the C1–C6 ring; symmetry code: (ii) 2 − x, 1 − y, −z].In (II)ps Fig. 5 are connvia N1—H1⋯O1i hydrogen bonds  chains running parallel to [010]. Adjacent chains are connected by C14—H14B⋯π interactions involving the aniline ring, forming two-dimensional sheets parallel to the ab plane. Neighbouring sheets are further linked via offset π–π interactions involving inversion-related benzenesulfonyl rings, forming a three dimensional architecture as as illustrated in Fig. 7Cg1⋯Cg1i = 3.8303 (16) Å, interplanar distance = 3.3874 (11) Å, slippage 1.788 (3) Å; Cg1 is the centroid of the C1–C6 ring; symmetry code: (iii) 1 − x, −y, −z].In the crystal structure of (III)ds Fig. 6 to form N-(substitutedphenyl)-benzenesulfonamides, namely 3,5-dichloro-N-(4-methylphenyl)benzenesulfonamide [Shakuntala, Naveen et al., 2017N-benzenesulfonamide [Shakuntala, Lokanath et al., 2017via N—H⋯O and C—H⋯O hydrogen bonds and C—H⋯π interactions, whereas in (V) the three-dimensional supramolecular architecture is built through N—H⋯O and C—H⋯O hydrogen bonds, Cl⋯Cl contacts and π–π interactions.Two 3,5-dichloro-et al., 2015The title compounds were prepared according to a literature method (Rodrigues Uiso(H) = 1.2 or 1.5Ueq(C). A rotating model was applied to the methyl groups. To improve considerably the values of R1, wR2, and S (goodness-of-fit), a low-angle reflection partially obscured by the beam-stop (100) was omitted from the final refinement of (III)Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989017005230/rz5211sup1.cifCrystal structure: contains datablock(s) I, II, III, shelx. DOI: 10.1107/S2056989017005230/rz5211Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017005230/rz5211IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989017005230/rz5211IIIsup4.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S2056989017005230/rz5211Isup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017005230/rz5211IIsup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017005230/rz5211IIIsup7.cmlSupporting information file. DOI: 1542706, 1542704, 1542705CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


C(6) helical chain running along the [100] direction.In the two independent molecules in the asymmetric unit of the title compound, the cyclohexane rings adopt a chair conformation, while the oxane rings are also puckered. In the crystal, O—H⋯ O hydrogen bonds connect adjacent molecules, forming a  20H34O2, contains two crystallographically independent molecules (1 and 2) with similar conformations. In both molecules, the cyclohexane rings adopt a chair conformation, while the oxane rings are also puckered. In the crystal, O—H⋯O hydrogen bonds connect adjacent molecules, forming C(6) helical chains located around a 21 screw axis and running along the crystallographic a axis. The packing of these chains is governed only by van der Waals interactions. Semi-empirical PM3 quantum chemical calculations are in a satisfactory agreement with the structural results of the X-ray structure analysis. The absolute structure was indeterminate in the present experiment.The asymmetric unit of the title compound, C Sideritis genus belonging to the Lamiaceae family is represented by more than 150 species in the world  Å, θ = 0.0 (3), φ = 270 (81)° and QT = 0.584 (3) Å, θ = 4.4 (3), φ = 59 (4)°, respectively. The oxane ring (O2/C11/C12/C15–C17) is also puckered, with puckering parameters QT = 0.551 (3) Å, θ = 12.1 (3) and φ = 133.5 (16)°. The equivalent rings in molecule 2  have as puckering parameters QT = 0.534 (3) Å, θ = 1.9 (3), φ = 296 (11)°, QT = 0.583 (3) Å, θ = 5.0 (3), φ = 72 (3)° and QT = 0.554 (3) Å, θ = 11.9 (3), φ = 127.2 (15)°, respectively. Bond lengths and angles are within normal range, comparable with each other and with those reported for similar structures in the literature  helical chains located around a 21 screw axis running along the crystallographic a axis  is a semi-empirical method for the quantum calculation of the molecular electronic structure in computational chemistry. It is based on the neglect of differential diatomic overlap integral approximation. The semi-empirical PM3 parameterization used in the MOPAC program is widely used to derive charges, dipole moments and bond lengths. The computed quantum chemical descriptors include bond lengths, bond angles, torsion angles, atom charges, HOMO and LUMO energy levels, dipole moment, polarizability, etc. In the present case, the geometry of the molecule of the title compound was calculated with a semi-empirical PM3 method , with the sole exception of the angles in the methoxy groups. This may be ascribed to the steric interactions between adjacent molecules in the crystal structure.−1 flow rate. 16 fractions, each of which was 150 mL, were collected. Similar fractions were combined according to the TLC profile. Further purification was carried out with silica gel column chromatography to isolate the title compound. Colourless prisms were recrystallized from ethanol solution.The aerial part of the plant material (5 g) was extracted with ethyl acetate (3 × 20 mL). After removal of the solvent by rotary evaporator, the extract was subjected to column chromatography (2.5 × 70 cm); sephadex LH-20 (50 g) was used as a stationary phase and methanol was used as a mobile phase with a 0.25 ml minUiso fixed at 1.5 times Ueq(O). H atoms bound to carbon were positioned geometrically and allowed to ride on their parent atoms with Uiso = 1.2Ueq(C)  and with Uiso = 1.5Ueq(C) (C—H = 0.96 Å) for methyl H atoms. The absolute structure was indeterminate in the present experiment.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016013864/bg2593sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016013864/bg2593Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016013864/bg2593sup3.pdfSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016013864/bg2593sup4.tifSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016013864/bg2593Isup5.cmlSupporting information file. DOI: 1501445CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecular and crystal structure of the title imidazole derivative is reported. The structure features an extensive O—H⋯N, C—H⋯O/N and C—H⋯π(ring) hydrogen-bonding network. 24H21N3O3, crystallizes with two unique but closely r.m.s. overlay fit = 0.215 Å) comparable molecules (1 and 2) in the asymmetric unit of the triclinic unit cell. In molecule 1, the dihedral angles between the central imidazlole ring and the benzene-ring substituents are 42.51 (9), 45.41 (9) and 56.92 (8)°, respectively. Comparable data for molecule 2 are 39.36 (10), 34.45 (11) and 60.34 (8)°, respectively. The rings at the 2-positions carry p-nitro substituents that subtend dihedral angles of 12.9 (4)° in molecule 1 and 11.7 (4)° in molecule 2 to their respective benzene ring planes. The imidazole rings also have propan-2-ol substituents on the 1-N atoms, which adopt extended conformations for the N—C—C—C chains. In the crystal, classical O—H⋯N hydrogen bonds combine with C—H⋯O, C—H⋯N and C—H⋯π(ring) hydrogen bonds and stack the molecules along the a-axis direction.The title compound, C The benzene rings are inclined to the imidazole ring plane at angles of 42.51 (9) and 39.36 (10)° for C121–C126 and C221–C226, 45.41 (9) and 34.45 (11)° for C141–C146 and C241–C246 and 56.92 (8) and 60.34 (8) for C151–C156 and C251–C256, values that further attest to the close similarities between the structures of the two unique molecules. Bond lengths and angles in the two molecules are also similar and compare well with those found in comparable molecules with isopropanol substituents at the 1-position  chains along the b-axis direction, Fig. 3c, in this case head-to-head, due to C153—H153⋯Cg5 and C255—H255⋯Cg1 contacts  combined with C152—H152⋯O212, C153—H153⋯N21 and C256—H256⋯O112 hydrogen bonds, Fig. 4via C243—H243⋯O23 hydrogen bonds, forming C(13) chains along a, Fig. 5a. Overall, these numerous contacts generate layers of molecules of (I)a-axis direction, Fig. 6In the crystal, classical O112—H11et al., 20162 substituent on N1 are reasonably common with 43 entries. However, restricting the search to compounds with isopropanol substituents on N1 reduces the hits to three reports of our work to produce compounds with 4-benzoic acid . All other atoms were refined using a riding model with d(C—H) = 0.95 Å for aromatic, 1.00 Å for methine and 0.98 Å for CH2 atoms, all with Uiso(H) = 1.2Ueq(C). For methyl H atoms d(C—H) = 0.98 Å and Uiso(H) = 1.5Ueq(C). One low angle reflection with Fo << Fc that may have been affected by the beamstop was omitted from the final refinement cycles.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017011057/hg5491sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017011057/hg5491Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017011057/hg5491Isup3.cmlSupporting information file. DOI: 1565059CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


I atom in the title compound is two-coordinate, being bound to two pyridine N atoms from two N-(pyridin-3-ylmethyl)pyridin-3-amine ligands in a slightly distorted linear fashion. Each AgI ion bridges the dipyridyl-type ligands to form polymeric zigzag chains. The chains are connected via Ag⋯Ag and π–π interactions, forming a corrugated layer parallel to ]PF6·2CH3CN or {[AgL]·PF6·2CH3CN}n, L = N-(pyridin-3-ylmethyl)pyridin-3-amine, comprises one AgI atom, one L ligand, two acetonitrile solvent molecules and one PF6− anion disordered over two orientations in a 0.567 (11):0.433 (11) ratio. Each AgI atom is coordinated by two pyridine N atoms from two L ligands in a slightly distorted linear coordination geometry [N—Ag—N = 170.55 (8)°]. Each L ligand bridges two AgI ions, resulting in the formation of a zigzag chain propagating along the [101] direction. In the crystal, Ag⋯Ag contacts [3.3023 (5) Å] and intermolecular π–π stacking interactions [centroid-to-centroid distance = 3.5922 (15) Å] between the pyridine rings link these chains into a corrugated layer parallel to the  Å] between the layer and the intercalated guests and between the intercalated guests, forming a three-dimensional supramolecular network.The asymmetric unit in the title compound, [Ag(C The silver(I) atom is coordinated by two pyridine N atoms (N1 and N2) from two symmetry-related L ligands, leading to the formation of an infinite zigzag chain propagating along the [101] direction. Thus, the AgI atom is two-coordinated in a slightly distorted linear coordination geometry . All other H atoms were positioned geometrically and refined as riding: C—H = 0.95 Å for Csp2—H, 0.99 Å for methylene C—H and 0.98 Å for methyl C—H with Uiso(H) = 1.5Ueq (C-methyl) and 1.2Ueq(C) for other C-bound H atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989017013421/su5393sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989017013421/su5393Isup2.hklStructure factors: contains datablock(s) I. DOI: 1575393CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The dithiocarbamate ligand coordinates to the metal atom in an asymmetric mode with the resulting C2S4 donor set defining a skew trapezoidal bipyramidal geometry; the n-butyl groups are disposed to lie over the longer Sn—S bonds. Supramolecular chains aligned along the a-axis direction and sustained by methylene-C—H⋯S(weakly coordinating) interactions feature in the molecular packing. A Hirshfeld surface analysis reveals the dominance of H⋯H contacts in the crystal.The complete molecule of the title compound, [Sn(C R2Sn(S2CNRR′)2 is diverse with coordination geometries ranging from five, as in trigonal bipyramid (t-Bu)2Sn(S2CNMe2)2 2 Me]2, with a dithiocarbamate ligand with dissimilar substituents, was found to be octahedral but, Ph2Sn[S2CN(CH2CH2OMe)2]2, with the dithiocarbamate ligand having similar substituents, was skew trapezoidal bipyramidal Me]2, (I)via an analysis of the Hirshfeld surface.The structural chemistry of molecules with the general formula n-butyl groups lying on the plane, Fig. 1i.e. the difference between the Sn—Slong and Sn—Sshort distances, being ca 0.39 Å, Table 1n-butyl groups. The four S atoms are co-planar and define a skewed trapezoidal plane, and the α-C atoms are disposed over the weaker Sn—S bonds so that the C2S4 donor set defines a skew trapezoidal bipyramidal geometry.The asymmetric unit of (I)a-axis direction, Fig. 2a and Table 2b. In order to ascertain more information of the nature of interactions between molecules, the molecular packing and its Hirshfeld surface was analysed, as discussed in Hirshfeld surface analysis.The only notable contacts identified in the molecular packing are methylene-C—H⋯S(weakly coordinating) interactions that assemble molecules into linear supramolecular chains propagating along the et al., 2016dnorm, in the range −0.298 to +1.346 au, in Fig. 3C and H13B of the disordered methyl groups, i.e. deviating from mirror symmetry, indicate their participation in specific intermolecular H⋯H interactions. In the crystal, these lead to a supramolecular chain along the c axis. The presence of this dihydrogen interaction, resulting from disparate charges on respective hydrogen atoms, can also be viewed by the different curvatures and electrostatic potentials around these atoms on the Hirshfeld surface mapped over the electrostatic potential in the range −0.082 to +0.163 au, Fig. 4dnorm, highlighting the intermolecular C—H⋯S and H⋯H interactions.The Hirshfeld surface analysis for (I)a, and those delineated  region, Fig. 6a and b, show the dominance of these interactions in the molecular packing. The peak in the plot corresponding to a second short interatomic H⋯H contact, i.e. between methyl-H2B and methylene-H10A, Table 4B⋯H13B interaction. The dihydrogen H⋯H bonding also results in short interatomic C⋯H/H⋯C contacts, Table 4de + di ∼ 2.8 Å in the delineated fingerprint plot, Fig. 6c; the other interatomic short C⋯H/H⋯C contact is merged within the plot. The presence of the weak C—H⋯S interactions, Table 2d, and is evident as a pair of broad peaks at de + di ∼ 2.9 Å. The fingerprint plots delineated into O⋯H/H⋯O and N⋯H/H⋯N contacts, Fig. 6e and f, contribute in a minor fashion to the Hirshfeld surface and their characteristic points are longer than their respective van der Waals separations, i.e. longer than 2.72 and 2.75 Å, respectively, and hence it is likely they do not make any significant contribution to the molecular packing.In the fingerprint plot delineated into H⋯H contacts, Fig. 6b) that that H atoms adopt positions as far apart from each other as possible rather than participate in ‘non-bonded steric repulsion’ et al., 2016n-Bu2Sn(S2CNRR’)2. One structure, i.e. R = R′ = i-Pr , seven, i.e. R = Me, R′ = n-Bu Me2 piperazine 2.The interest in organotin dithiocarbamates is reflected in the relatively large number of crystal structures available in the crystallographic literature (Groom n-Bu2Sn(S2CNRR′)2 is that they all conform to the same structural motif as adopted for (I)short bond lengths in these structures span a relatively narrow range of 2.51 to 2.55 Å and cluster around 2.53 Å. As might be anticipated, a wider range is exhibited by the Sn—Slong bonds, i.e. 2.83 to 3.08 Å and these cluster around 2.96 Å. Given the range of Sn—Sshort bond lengths is 0.04 Å and that for Sn—Slong is 0.25 Å, the observation that differences between the average values of Sn—Sshort and Sn—Slong span a range of 0.43 Å indicates no specific correlations exist between Sn—Sshort and Sn—Slong bond lengths. The Sshort—Sn—Sshort, Slong—Sn—Slong and C—Sn—C angles cluster around 83, 147 and 136°, respectively. However, these angles span ranges of 8° (range: 80 to 88°), 10° (140 to 151°) and 18° (127 to 145°), respectively. The disparity in the S—Sn—S angles is as expected from the adopted coordination geometry. While, generally, the Slong—Sn—Slong angles are wider than the C—Sn—C angles, there are three exceptional structures, namely R = R′ = Et 2 structural motif does not translate to the diphenyl analogues, i.e. Ph2Sn(S2CNRR′)2. Of the 19 structures conforming to this general formula, seven resemble the skew trapezoidal bipyramidal motif with the majority, i.e. twelve, having a cis-disposition of the tin-bound phenyl substituents. In this context, it is noteworthy that all structures of the general formula Sn(S2CNRR′)2X2, where X = halide, are invariably cis-S4X2 octahedral 2 compounds.The homogeneity in the ca 277 K) for 30 min. 25% Ammonia solution (ca 2 ml) was added to make the solution basic. Then, a cold ethanol solution of carbon disulfide (10 mmol) was added to the solution followed by stirring for about 2 h. Next, di-n-butyltin(IV) dichloride (5 mmol), dissolved in ethanol (30 ml), was added to the solution which was further stirred for 2 h. The precipitate that formed was filtered and then washed three times with cold ethanol to remove any impurities. The precipitate was then dried in a dessicator. The compound was crystallized in a mixture of chloroform and ethanol (1:2 v/v) at room temperature to give colourless slabs. Yield: 66%, m.p. 333–336 K. Analysis. Found C, 40.3; H, 7.3; N, 5.0; S, 22.8. C18H38N2O2S4Sn requires: C, 38.5; H, 6.8; N, 5.0; S, 23.7. IR (cm−1): 1490 ν(C—N), 991 ν(C—S), 553 ν(Sn—C), 420 ν(Sn—S). 1H NMR (CDCl3): 7.40–7.74 , 4.07 , 3.71 , 3.46 , 3.40 , 2.04 , 1.92 , 1.44 , 0.98 . 13C{1H} NMR (CDCl3): δ 201.2 (S2C), 70.1 (OCH2), 59.1 (NCH2), 56.6 (OCH3), 44.5 (NCH3), 34.3 (SnCH2), 28.6 (SnCH2CH2), 26.5 (CH2CH3), 13.9 (CH2CH3). 119Sn{1H} NMR (CDCl3): 338.6.(2-Methoxyethyl)methylamine (10 mmol) dissolved in ethanol (30 ml) was stirred in an ice bath (Uiso(H) set to 1.2–1.5Ueq(C). The molecule has crystallographic mirror symmetry with the Sn atom and n-butyl-C atoms lying on the plane. The terminal CH2CH3 residue of each n-butyl group is statistically disordered across this plane. Owing to poor agreement, three reflections, i.e. (172), (124) and (155), were omitted from the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989017001098/hb7654sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017001098/hb7654Isup2.hklStructure factors: contains datablock(s) I. DOI: 1528948CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, the complex molecules interact with the caffeine molecules through O—H⋯N, O—H⋯O, C–H⋯S hydrogen bonds and π–π interactions.In the structure of the title compound, , [Co(NCS)2(H2O)4]·2C8H10N4O2·4H2O, the cobalt(II) cation lies on an inversion centre and is coordinated in a slightly distorted octahedral geometry by the oxygen atoms of four water molecules and two N atoms of two trans-arranged thiocyanate anions. In the crystal, the complex molecules interact with the caffeine molecules through O—H⋯N, O—H⋯O and C—H⋯S hydrogen bonds and π–π interactions [centroid-to-centroid distance = 3.4715 (5) Å], forming layers parallel to the ab plane, which are further connected into a three-dimensional network by O—H⋯O and O—H⋯S hydrogen bonds involving the non-coordinating water molecules.In the structure of the title compound [systematic name: tetraaquabis(thiocyanato-κ The cobalt(II) cation lies on an inversion centre and displays a trans-arranged octahedral coordination geometry provided by the N atoms of two thiocyanate anions and four O atoms of coordinating water molecules. The Co1—N15 [2.0981 (8) Å] and Co1—O18 [2.0981 (7) Å] bond lengths are equal within standard uncertainties and significantly longer than the Co1–O19 bond length [2.0732 (7) Å], and therefore the CoN2O4 octahedron is slightly axially compressed. This structural feature is typical for related compounds  Å; Cg is the centroid of the N3/N7/C4/C6/C8/C9 ring; symmetry code: (i) 1 − x, 2 − y, 1 − z; Fig. 2In the crystal, each complex molecule interacts with four neighboring caffeine molecules through classical O—H⋯N and O—H⋯O hydrogen bonds Table 1 involvin2·6H2O  in 5 ml of water and caffeine  in 10 ml of ethanol was added to a solution of potassium thiocyanate  in 5 ml of water. Single crystals of the title compound suitable for X-ray analysis were grown after several months by slow evaporation of the solvent at room temperature.In a glass tube, a solution of CoClUiso(H) set at 1.2–1.5 times of the Ueq of the parent atom, after which the positions were refined with riding constraints  global, I. DOI: 10.1107/S2056989017008180/rz5216Isup2.hklStructure factors: contains datablock(s) I. DOI: 1553654CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In this study, we investigated the proliferation and activation of lung γδ T cell subsets, specifically the IL-17 and IFNγ production by them following Cm lung infection. Our results found that five γδ T cell subsets, Vγ1+ T, Vγ2+ T, Vγ4+ T, Vγ5+ T, and Vγ6+ T, expressed in lungs of naïve mice, while Cm lung infection mainly induced the proliferation and activation of Vγ4+ T cells at day 3 p.i., following Vγ1+ T cells at day 7 p.i. Cytokine detection showed that Cm lung infection induced IFNγ secretion firstly by Vγ4+ T cells at very early stage (day 3) and changed to Vγ1+ T cells at midstage (day 7). Furthermore, Vγ4+ T cell is the main γδ T cell subset that secretes IL-17 at the very early stage of Cm lung infection and Vγ1+ T cell did not secrete IL-17 during the infection. These findings provide in vivo evidence that Vγ4+T cells are the major IL-17 and IFNγ-producing γδ T cell subsets at the early period of Cm lung infection.Our previous studies showed that  C. pneumoniae causes respiratory diseases like bronchitis, sinusitis, and pneumonia, whereas C. trachomatis is a major cause of ocular and sexually transmitted diseases  and 2 mg/ml collagenase type XI ) for 60 min at 37°C and added 2 mM EDTA 5 min before incubation finished. Then the cell population was purified by mixing with 35% Percoll (Sigma-Aldrich) and centrifuged for 20 min at 750 g, followed by lysis of erythrocytes with ammonium chloride-potassium (ACK) lysis buffer . The cells were washed twice using RPMI 1640 with 2% fetal calf serum and resuspended in complete RPMI 1640 medium (containing 10% FBS) for further experiment.Lung mononuclear cells were prepared as described previously . Brieflyγ transcripts, total RNA was extracted from frozen lung tissues using Trizol agent (Invitrogen) according to the manufacturer's instruction. The isolated total RNA was reversely transcribed into cDNA (TaKaRa). Special primers for Vγ1, Vγ2, Vγ4, Vγ5, Vγ6, and Vγ7 were used to amplify cDNA. And β-actin, a housekeeping gene, was used as a control. The primers used in the PCR analysis were as follows: Vγ1 (320 bp), forward: 5′-ACACAGCTATACATTGGTAC-3′, reverse: 5′-CTTATGGAGATTTGTTTCAGC-3′; Vγ2 (270 bp), forward: 5′-CGGCAAAAAACAAATCAACAG-3′, reverse: 5′-CTTATGGAGATTTGTTTCAGC-3′; Vγ4 (310 bp), forward: 5′-TGTCCTTGCAACCCCTACCC-3′, reverse: 5′-CTTATGGAGATTTGTTTCAGC-3′; Vγ5 (300 bp), forward: 5′-TGTGCACTGGTACCAACTGA-3′, reverse: 5′-CTTATGGAGATTTGTTTCAGC-3′; Vγ6 (300 bp), forward: 5′-TGTGCACTGGTACCAACTGA-3′, reverse: 5′-CTTATGGAGATTTGTTTCAGC-3′; Vγ7 (380 bp), forward: 5′-AAGCTAGAGGGGTCCTCTGC-3′, reverse: 5′-CTTATGGAGATTTGTTTCAGC-3′; β-actin (582 bp), forward: 5′-CTTATGGAGATTTGTTTCAGC-3′, reverse: 5′-ATGAGGTAGTCMGTCAGGT-3′. The products were electrophoresed in 1% agarose gel containing Gel-Red (0.01%). The bands were visualized and photographed by automatic gel imaging system and were analyzed for density on Image J software.To analyze the expressions of TCR Vγδ, anti-CD69, anti-TCRVγ1, anti-TCRVγ4, and isotype control Abs for 30 min on ice for surface marker analysis. For intracellular cytokine analysis, single cell suspensions were stimulated with PMA (50 ng/ml)/ionomycin (1 μg/ml) (Sigma) for 6 hours at 37°C in the presence of 20 mg/ml brefeldin A (Sigma). After the stimulation, cells were washed with FACS buffer twice and incubated with Fc receptor (FcR) block antibodies  for 15 min on ice to block nonspecific staining. Surface markers  were stained first. The cells were then fixed with 4% w/v paraformaldehyde in PBS and permeabilized with permeabilization buffer , subsequently stained with anti-IFNγ, IL-17, or corresponding isotype control Abs (eBioscience). The raw data were collected using FACS CantoII flow cytometer (BD Biosciences) and were analyzed using Flowjo 6.0 software.Lung mononuclear cells were aseptically prepared from mice at different time points postinfection and incubated with anti-CD3, anti-TCRt-test were used to determine statistical significance among groups. IFUs of Cm were converted to logarithmic values and analyzed using ANOVA. The value of p < 0.05 was considered as a statistically significant difference.One-way analysis of variance (ANOVA) and unpaired γδ T cells are the vital components of the innate immune system and play important roles in the early responses to pathogens. Our previous studies have shown that γδ T cells are the major producer of IL-17A in the very early stages of infection and depletion of γδ T cells by administration of mAb (GL3) against TCRγδ i.n. exists more body weight loss following Cm lung infection. The results here keep consistent with our previous studies that the percentage and absolute number of lung γδ T cells significantly increased at day 3 postinfection (p.i.) and reached to the highest level at day 7 p.i. Even though the percentage of γδ T cells reduced to baseline levels, the absolute number of γδ T cells still kept in a relatively higher level . All these results implicated that γδ T cells contribute to the IFNγ and IL-17 production and reduce morbidity during Cm infection, but its role in bacterial clearance is rather limited. Figures . CD69 wa Figures . TCRδ−/−o 6 p.i. ; howeverfference . Furtherγδ T cells are heterogeneous population that can be subdivided based on the expression of specific Vγ and Vδ TCR chains. Although we already demonstrated the importance of γδ T cell in the early protection against Cm lung infection, this did not prove that γδ T cell subpopulation actually contributes to the γδ T cell-mediated early protection. To investigate this, we first analyzed the γδ T cell subsets in lungs of naive mice. Our results by using RT-PCR detection showed that there are more than five subpopulations, Vγ1+ T, Vγ2+ T, Vγ4+ T, Vγ5+ T, and Vγ6+ T but not Vγ7+ T cells; in lungs of naive mice, the expression intensity of mRNA is Vγ2 > Vγ4 > Vγ1 > Vγ6 > Vγ5  while Vγ1 T cells at midstage p.i. (day 7)  against TCRγδ i.n. exists more body weight loss following Cm lung infection, which suggested that γδ T cells played a protective role in mice Chlamydia lung infection [δ−/− mice in this paper. It is worth mentioning that γδ T cell is the highest producer of IL-17A but the protection conferred by IL-17A is mainly mediated by Th17 cells following Cm infection. Therefore, the protective role of early production of IL-17 and IFNγ by Vγ4+ T and Vγ1+ T cells is not essential but supplementary in clearance of Chlamydia. In our present study using Cm infection model, it was found that Vγ4+ T cells were the major source of IL-17 in the early stage, and Vγ1+ T cells did not secrete IL-17. Similarly, Listeria monocytogenes also induces γδ T cells, especially Vγ4+ T and Vγ6+ T cells, and secretes IL-17 in infected liver, but more than 60 percent of the IL-17 are produced by Vγ6+ T cell, which have fast kinetic response characteristics [γ1+ γδ T-cell reactivity which dominantly produces IL-17. Furthermore, with anti-CD3 antibody and virus-LPS stimulation in vitro, Vγ1+ T cells dramatically produced IL-17, while only IL-10+ Vγ4+ T cells existed [γδ T cell in varieties of pathogen infections are not always the same pattern, while these data suggest increased numbers of γδ T cells with cytokine-producing potential during immune response; any role for γδ T cell-derived cytokines in various model remains to be defined.The effector functions of le genes . IL-17-pfections , 36, 37.nfection . These reristics . However existed . Unlike γ4-γδ T cell subsets which is not identified during Cm infection. Interestingly, in our model, Vγ6+ cells also present to proliferate following the Cm infection at the middle stage, which might be an important IL-17-producing cell after the early infection stage. IL-17+ Vγ6+ T cells promote cancer cell growth by mobilizing peritoneal macrophages in the mice model of ovarian cancer [Listeria monocytogenes, more than 60 percent of the IL-17 are produced by Vγ6+ T cell in infected liver, which have fast kinetic response characteristics [γ6+ T cell because it is reported that Vγ6+ cells are the major γδ T cell population in reproductive tract but not in lungs [γ and IL-17 may be partially secreted by Vγ6+ T cells apart from Vγ1+ T and Vγ4+ T cells during Cm infection.Notably, there are still a small number of IL-17-producing-Vn cancer . In Listeristics . In thisin lungs . But it γ1+ T and Vγ4+ T cells are the major proliferative cell subsets of γδ T cell during Cm lung infection in mice. Moreover, Vγ4+ T cells are the major IL-17 and IFNγ-producing γδ T cell subsets at the early period of Cm lung infection. The findings in the present study provide new insights into the mechanisms bridging innate and adaptive immunity during lung chlamydial infections, which may have implications in developing effective chlamydial vaccines and in the understanding of host defense mechanisms in other lung infections.In conclusion, our data show that V


C(4) along [100] and and There are two molecules in the asymmetric unit of the title compound, one of them being disordered over the methyl group. The molecules are linked by weak H⋯S interactions into chains with graph-set motifs  13H17N3S, one of them being disordered over the methyl group [site-occupancy ratio = 0.705 (5):0.295 (5)]. The maximum r.m.s. deviations from the mean plane of the non-H atoms for the tetralone fragments amount to 0.4572 (17) and 0.4558 (15) Å. The N—N—C—N fragments are not planar and torsion angles are −9.4 (2) and 8.3 (2)°. In the crystal, the molecules are linked by weak N—H⋯S interactions into chains along [100] with graph-set motif C(4) and connected by weak N—H⋯S and C—H⋯S interactions, forming R21(10) rings. The Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are the H⋯H (64.20%), H⋯S (12.60%) and H⋯C (12.00%) interactions. The crystal packing resembles a herringbone arrangement when viewed along [001].There are two crystallographically independent molecules in the asymmetric unit of the title compound, C In the 1940s it was reported that in in vitro assays, the thiosemicarbazone turned out to be very effective against tuberculosis. In contrast, the related oxygen-containing semicarbazones did not shown biological activity in the same assays, so that the sulfur atom in the molecular structure is essential for Mycobacterium tuberculosis growth inhibition, a true milestone in the thiosemicarbazone pharmacological research :0.295 (5) with ed Fig. 1.For the first molecule, the C1/C2/C5/C10 atoms are essentially planar and atoms C3 and C4 deviate by 0.564 (2) and −0.142 (2) Å, respectively, from this plane. For the second, the C14/C15/C18/C23 atoms are essentially planar while atoms C16 and C17 deviate from the plane by −0.534 (2) and 0.201 (2) Å, respectively.In addition, the N1—N2—C11—N3 and N4—N5—C24—N6 torsion angles are 9.4 (2)° and 8.3 (2)°. The dihedral angle between the tetralone fragments of the two molecules within the asymmetric unit is 85.51 (02)°.i interactions into chains along [100]. The S1–C11–N3–H12 and S2–C24–N6–H29 fragments are the subunits of the periodic arrangement, with graph-set motif C(4). In addition, the molecules are linked by C9—H10⋯S2 and C22—H27⋯S1i interactions building rings with graph-set motif D—H⋯S interactions  and di (x axis) values are the closest external and internal distances (in Å) from given points on the Hirshfeld surface contacts hydrazinecarbothioamide, the molecules are linked into chains by N—H⋯S hydrogen bonds (H⋯S distances = 2.45 and 2.71 Å) and the H⋯S contribution for the cohesion of the structure amounts to 19.20% . This kind of arrangement, the one-dimensional hydrogen-bonded polymer, is possible due to the unsubstituted amine, which increases the possibilities for intermolecular hydrogen bonding hydrazinecarbothioamide, one H atom of the amine group is substituted by one methyl group. The N—H⋯S hydrogen bonds are weaker in comparison with the first structure (H⋯S distances = 3.03 and 3.29 Å), the H⋯S contribution for the cohesion of the structure amounts to 15.80% and the dimensionality of the structure is preserved with molecules linked into chains . The disorder over the molecules in the asymmetric unit was not considered and the calculations were performed using atoms of the major occupancy component hydrazinecarbothioamide, the molecules are also linked by N—H⋯S hydrogen bonds, but not into hydrogen-bonded polymers (H⋯S distance = 2.70 Å). The phenyl rings linked to the amino groups change the molecular arrangement due to steric effects: the molecules build dimers and the H⋯S contribution to the crystal packing amounts to 13.00%  . Thus, there is a relationship between the molecular assembly, the geometry of the H⋯S interactions and their contribution to the crystal structures  and two positions will be possible for the terminal CH3–group. The C25 and C26 atoms were fixed with restraints (SADI command) and had to be split over two positions. The occupancy factor for C25A and C26A is 0.705 (5) and for C25B and C26B it is 0.295 (5). H atoms were located in difference maps but were positioned with idealized geometry and were refined with isotropic displacement parameters using a riding model (HFIX command) with Uiso(H) = 1.2Ueq(secondary C atoms) , Uiso(H) = 1.5 Ueq (C—H = 0.98 Å) and Uiso(H) = 1.2 Ueq(N) (N—H = 0.88 Å). Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017001311/lh5835sup1.cifCrystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S2056989017001311/lh5835Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017001311/lh5835Isup3.cmlSupporting information file. DOI: 1529622CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


By contrast, analogous syntheses from o‐xylene and m‐xylene as the solvent yield the solvent‐free coordination polymer [Ag4(O2CCF3)4(phen)2] (2). Toluene, p‐xylene and benzene have been successfully used in mixed‐arene syntheses to template the formation of coordination polymers 1⋅phen⋅arene, which incorporate o‐ or m‐xylene. The selectivity of 1⋅phen⋅arene for the arene guests was determined, through pairwise competition experiments, to be p‐xylene>toluene≈benzene>o‐xylene>m‐xylene. The largest selectivity coefficient was determined as 14.2 for p‐xylene:m‐xylene and the smallest was 1.0 for toluene:benzene.The coordination polymers [Ag Materials that are porous on the molecular scale have been in use for many years in applications involving molecular separation. Fixed‐pore materials, exemplified by zeolites and related inorganic porous materials,4{O2C(CF2)2CF3}4(phen)2(arene)n]⋅m (arene) (phen=phenazine) and examined the role of these guests in templating solid‐state transformations.o‐xylene, m‐xylene and p‐xylene by the coordination polymer [Ag4(O2CCF3)4(phen)3] (1) during its self‐assembly from the solution phase. This results in the crystalline materials [Ag4(O2CCF3)4(phen)3]⋅phen⋅arene (1⋅phen⋅arene), in which the arenes act as co‐guests alongside non‐coordinated phenazine. Specifically, we are able to establish the selectivity of the coordination polymer for each of the five arenes by determination of the pairwise selectivity coefficients, and are able to determine the potential of this material in separation of structurally similar arenes by recycling of the encapsulation process.We have developed a class of 1D coordination polymers based on silver(I) perfluoroalkylcarboxylate dimer units linked through diimine ligands, such as substituted pyrazine or phenazine  is important commercially due to the large scale on which such compounds are synthesised for use as precursors in the chemical industry, combined with the non‐regiospecific manner in which alkylarenes, such as xylenes, are synthesised. Their similarity in physical properties  makes conventional methods of separation, such as distillation, a difficult and not very cost‐effective approach.p‐xylene or benzene resulted in exclusive formation of the corresponding arene‐guest‐containing 1D coordination polymer [Ag4(O2CCF3)4(phen)3]⋅phen⋅arene (1⋅phen⋅arene). Phase purity was confirmed by elemental analysis and Pawley fitting of the corresponding X‐ray powder patterns. Crystal structures of [Ag4(O2CCF3)4(phen)3]⋅phen⋅2 (toluene) (1⋅phen⋅tol), [Ag4(O2CCF3)4(phen)3]⋅phen⋅2 (p‐xylene) (1⋅phen⋅pxyl) and [Ag4(O2CCF3)4(phen)3]⋅phen⋅2 C6H6 (1⋅phen⋅benz) were determined by single‐crystal X‐ray diffraction 4(L)3]  described in our previous work.1⋅phen⋅arene material additional non‐coordinated phenazine molecules are included as guests, situated between each of the doubly‐bridging phenazine linkers in a π‐stacked manner. Two equivalents of the arene used as solvent are also present as guests per repeat unit of the polymer. These molecules  are π‐stacked on both sides of the electron‐deficient central ring of the singly‐bridging phenazine ligands. The arenes are crystallographically ordered and each arene molecule is related to another by a centre of symmetry located in the centre of those phenazine ligands  trifluoroacetate in methanol onto a solution of phenazine dissolved in either toluene, o‐ and m‐xylene, however, did not yield the analogous 1D coordination polymer. Rather, these syntheses led exclusively to the 2D coordination polymer [Ag4(O2CCF3)4(phen)2] (2), which excludes the xylene guests. This more densely‐packed phase is propagated in one dimension by an extended arrangement of silver perfluoroacetate units that employ both the anti and syn lone pairs on the carboxylate oxygen in coordination to AgI centres,Analogous syntheses conducted using p‐xylene and benzene) were included in the self‐assembly of 1⋅phen⋅arene, the selectivity of this inclusion process was examined by means of pairwise competition experiments between the three arenes. This was achieved by conducting the assembly of 1⋅phen⋅arene in the presence of a 1:1 mixture (by volume) of two of the three possible pairs of arenes. Pawley fitting of X‐ray powder diffraction confirmed the formation of 1⋅phen⋅arene, along with a very small amount of 2.6]DMSO, and studying the resulting solution by 1H NMR spectroscopy and gas chromatography (GC). These data and their analyses are presented in full in the Supporting Information. Pairwise selectivity constants, KA:B were determined from the corresponding inclusion experiments ⋅phen⋅2 (toluene) (1⋅phen⋅tol)⋅phen⋅2 (p‐xylene) (1⋅phen⋅pxyl)⋅phen⋅2 C6H6 (1⋅phen⋅benz)⋅phen⋅2 {(toluene)0.73⋅(p‐xylene)0.27} (1⋅phen⋅ tol⋅pxyl)⋅phen⋅2 {(toluene)0.49⋅(p‐xylene)0.51} (1⋅phen⋅ tol⋅pxyl)⋅phen⋅2 {(toluene)0.38⋅(p‐xylene)0.62} (1⋅phen⋅ tol⋅pxyl)⋅phen⋅2 {(toluene)0.30⋅(p‐xylene)0.70} (1⋅phen⋅ tol⋅pxyl)⋅phen⋅2 {(toluene)0.14⋅(p‐xylene)0.86} (1⋅phen⋅ tol⋅pxyl)⋅phen⋅2 {(toluene)0.46⋅(C6H6)0.54} (1⋅phen⋅tol⋅ benz)⋅phen⋅2 {(p‐xylene)0.58⋅(C6H6)0.42} (1⋅phen⋅ pxyl⋅benz)⋅phen⋅2 {(C6H6)0.81⋅(o‐xylene)0.19} (1⋅phen⋅ C6H6⋅oxyl)[Ag: A 0.05 m solution of AgO2CCF3  in methanol (8 mL) was layered on to a 0.05 m solution of phenazine  in 1:1 (v/v) benzene:o‐xylene (8 mL). Yield 40 % .4(O2CCF3)4(phen)3]⋅phen⋅2 {(C6H6)0.91⋅(m‐xylene)0.09} (1⋅phen⋅C6H6⋅mxyl)[Ag: A 0.05 m solution of AgO2CCF3  in methanol (8 mL) was layered on to a 0.05 m solution of phenazine  in 1:1 (v/v) benzene:m‐xylene (8 mL) . Yield 40 % .4(O2CCF3)4(phen)3]⋅phen⋅2 {(toluene)0.84⋅(o‐xylene)0.16} (1⋅phen⋅ tol⋅oxyl)[Ag: A 0.05 m solution of AgO2CCF3  in methanol (8 mL) was layered on to a 0.05 m solution of phenazine  in 1:1 (v/v) toluene:o‐xylene (8 mL). Yield 33 % .4(O2CCF3)4(phen)3]⋅phen⋅2 {(toluene)0.91⋅(m‐xylene)0.09} (1⋅phen⋅tol⋅mxyl)[Ag: A 0.05 m solution of AgO2CCF3  in methanol (8 mL) was layered on to a 0.05 m solution of phenazine  in 1:1 (v/v) toluene:m‐xylene (8 mL). Yield 32 % .4(O2CCF3)4(phen)3]⋅phen⋅2 {(p‐xylene)0.90⋅(o‐xylene)0.10} (1⋅phen⋅pxyl⋅oxyl)[Ag: A 0.05 m solution of AgO2CCF3  in methanol (8 mL) was layered on to a 0.05 m solution of phenazine  in 1:1 (v/v) p‐xylene:o‐xylene (8 mL). Yield 42 % .4(O2CCF3)4(phen)3]⋅phen⋅2 {(p‐xylene)0.96⋅(m‐xylene)0.04} (1⋅phen⋅pxyl⋅mxyl)[Ag: A 0.05 m solution of AgO2CCF3  in methanol (8 mL) was layered on to a 0.05 m solution of phenazine  in 1:1 (v/v) p‐xylene:m‐xylene (8 mL). Yield 45 % .2(O2CCF3)2(phen)] (2)DMSO, then filtered through cotton wool. 1H NMR spectra were measured on a Bruker AV 400 MHz spectrometer. The NMR spectra can be found in the Supporting Information, Section 4. The NMR spectra were analysed using the Bruker TOPSPIN 3.1 programme. Methyl peaks for mixed xylene systems, which did not show complete baseline separation, were deconvoluted using the mixed‐line descriptor (mixed Lawrencian & Gaussian) deconvolution function in TOPSPIN.Gas chromatography: The solutions used for 1H NMR were transferred to glass vials using crimped caps, and then analysed using a PerkinElmer Autosystem GC with an AlltechTM HeliflexTM AT‐1 capillary column (L×I.D. 30 m×0.32 mm×df 5.00 μm), heating from 40 to 200 °C at 10 °C min−1. Expected guest retention times were found to be 9.9 min (benzene), 12.7 min (toluene), 15.1 min (p‐xylene), 15.2 min (m‐xylene‐indistinguishable from p‐xylene) and 15.7 min (o‐xylene). Relative content of guests was determined by direct comparison of chromatogram peak areas. The gas chromatograms can be found in the Supporting Information.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file.


In their respective crystals, hydrogen bonding leads to dimeric aggregates in the former (O—H⋯S) and supramolecular chains in the latter .Highly-distorted five-coordinate NS 5H10NS2)2(C5H5NO)], (I), and [Zn(C4H8NOS2)2(C5H5NO)], (II), are NS4 donor sets derived from N-bound hydroxypyridyl ligands and asymmetrically chelating dithiocarbamate ligands. The resulting coordination geometries are highly distorted, being intermediate between square pyramidal and trigonal bipyramidal for both independent molecules comprising the asymmetric unit of (I), and significantly closer towards square pyramidal in (II). The key feature of the molecular packing in (I) is the formation of centrosymmetric, dimeric aggregates sustained by pairs of hydroxy-O—H⋯S(dithiocarbamate) hydrogen bonds. The aggregates are connected into a three-dimensional architecture by methylene-C—H⋯O(hydroxy) and methyl-C—H⋯π(chelate) interactions. With greater hydrogen-bonding potential, supramolecular chains along the c axis are formed in the crystal of (II), sustained by hydroxy-O—H⋯O(hydroxy) hydrogen bonds, with ethylhydroxy and pyridylhydroxy groups as the donors, along with ethylhydroxy-O—H⋯S(dithiocarbamate) hydrogen bonds. Chains are connected into layers in the ac plane by methylene-C—H⋯π(chelate) interactions and these stack along the b axis, with no directional interactions between them. An analysis of the Hirshfeld surfaces clearly distinguished the independent molecules of (I) and reveals the importance of the C—H⋯π(chelate) interactions in the packing of both (I) and (II).The common feature of the molecular structures of the title compounds, [Zn(C Zn(S2CNEt2)2]2(bpe)·bpe 2]2(bpe)}n, for R = Et and n-Bu 2]2(bpe) S2CN(+)RR′, with two formally negatively charged sulfur atoms, which makes dithiocarbamate a very effective chelating agent, thereby decreasing the Lewis acidity of the zinc atom.The structures of binary zinc bis(dithiocarbamates) are always zero-dimensional (i.e using dithiocarbamate anions of the type −S2CN(R)CH2CH2OH. This influence is seen in the recent report of the structures of Zn[S2CN(R)CH2CH2OH]2 for R = i-Pr and CH2CH2OH 2 CH2CH2OH]2, in the case when R = CH2CH2OH, isolated as a 1:1 hydrate, leads to supramolecular ladders and these extend in two dimensions via water-O—H⋯S(dithiocarbamate) hydrogen bonds. When R = i-Pr, layers are sustained by hydroxy-O—H⋯S hydrogen bonds 2 has been complexed with 3-hydroxypyridine (pyOH) to yield two 1:1 complexes. Quite different aggregation patterns are observed when R = R′ = Et (I)R = i-Pr and R′ = CH2CH2OH (II)An approach to increase the supramolecular aggregation in the crystal structures of zinc dithiocarbamates has been to introduce hydrogen bonding functionality into the ligands, 2CNEt2)2(pyOH) comprise the asymmetric unit of (I)a, the ZnII atom is chelated by two dithiocarbamate ligands and one nitrogen atom derived from the monodentate pyOH ligand. The S1-dithiocarbamate ligand chelates the zinc atom forming quite different Zn—S bond lengths compared with the S3-dithiocarbamate ligand. This is quantified in the values of Δ(Zn—S), being the difference between the Zn—Slong and Zn—Sshort bond lengths, Table 1i.e. 0.43 and 0.15 Å, respectively. The Zn1—N3 bond length is significantly shorter than the Zn—S bonds. The NS4 coordination geometry is highly distorted as seen in the value of τ of 0.48  and, especially, the Sl—Zn—Sl (l = long) bond angles, Table 1b, is quite similar to that just described for the Zn1 atom. The values of Δ(Zn—S) of 0.21 and 0.25 Å are intermediate to those for the Zn1-molecule. Even so, the differences in the Zn—S bond lengths in both molecules are not that great with this observation reflected in the closeness of the C—S bond lengths, Table 1cf. the Zn1-molecule.Two independent molecules of Zn(S2CN(Me)CH2CH2OH]2(pyOH), is shown in Fig. 2The molecular structure of (II)Overlay diagrams of the three molecules in (I)via a 14-membered {⋯HOC2NZnS}2 synthon, Fig. 4a and Table 2x, y, z. The aggregates are further stabilized by pyOH-C—H⋯π interactions where the π-system is a chelate ring. Such C—H⋯π(chelate) interactions are increasingly being recognized as being important in the supramolecular chemistry of metal 1,1-dithiolates  but with methyl-H atoms as the donors, Fig. 4b. The connections between layers along the c direction are of the type methylene-C—H⋯O(hydroxy), Fig. 4c.The key feature of the molecular packing of (I)a, these hydrogen bonds lead to a centrosymmetric 22-membered {⋯SZnSCNC2OH⋯OH}2 synthon. On either side of these synthons, the pyOH hydroxy group hydrogen bonds to the O2-hydroxy atom and through symmetry, a centrosymmetric 24-membered {⋯OC2NCSZnNC2OH}2 synthon is formed, highlighted as ‘2’ in Fig. 5a. Alternating synthons generate a supramolecular chain aligned along the c axis. Methylene-C—H⋯π(chelate) interactions link molecules into dimeric units, Fig. 5b. The combination of the aforementioned interactions lead to supramolecular layers that stack along the b axis with no directional interactions between them, Fig. 5c.The addition of greater hydrogen-bonding potential in (II)et al., 2016dnorm in the range −0.2 to + 1.3 au for the Zn1- and Zn2-containing molecules of (I)O and -H2O, and dithiocarbamate-S2 and S8 atoms represent the donors and acceptors of the O—H⋯S hydrogen bonds; these are viewed as blue and red regions on the Hirshfeld surfaces mapped over electrostatic potential (mapped over the range −0.07 to +0.10 au), Fig. 7b and 6c are due to comparatively weaker intermolecular C—H⋯O interactions. The intra-dimer π–π stacking interaction between the pyOH rings, Fig. 4a, is evident through the appearance of faint-red spots near the arene-C13 and C26 atoms of the rings, Fig. 6a and 6b, forming a close interatomic C⋯C contact, Table 4a–c, characterize the influence of the C—H⋯π(chelate) interactions; in Fig. 7The Hirshfeld surface analysis for (I)dnorm, Fig. 9a and 9b, and result in the blue and red regions corresponding to positive and negative potential on the Hirshfeld surface mapped over electrostatic potential (mapped over the range −0.12 to +0.18 au), Fig. 9c. The faint-red spots near the S4, C8, C9 and H2B atoms in Fig. 9a and 9b indicate their involvement in short interatomic S⋯S, C⋯C and C⋯H/H⋯C contacts, Table 4a illustrates the immediate environment about a reference molecule within Hirshfeld surfaces mapped over electrostatic potential and highlights the O—H⋯O hydrogen bonds. The C—H⋯π(chelate) and its reciprocal contact, i.e. π—H⋯C, and short interatomic S⋯S, C⋯C and C⋯H/H⋯C contacts, with labels 3–6, are shown in Fig. 10b.The presence of peripheral hydroxy groups participating in the O—H⋯O hydrogen bonds in the structure of (II)a. The respective plots delineated into H⋯H, O⋯H/H⋯O, S⋯H/H⋯S, C⋯H/H⋯C, C⋯C and S⋯S contacts The overall two-dimensional fingerprint plot for individual Zn1- and Zn2-containing molecules, overall (I)b, show different distributions of points in the individual plots for Zn1- and Zn2-molecules. This, as well as their different percentage contributions to the Hirshfeld surface, Table 5de, di) distances shorter than their van der Waals separations, corresponding to short interatomic H⋯H contacts, Table 4The fingerprint plots delineated into H⋯H contacts for (I)c, also exhibit slightly different profiles for the independent molecules. The respective peaks at de + di ∼ 2.7 Å and ∼ 2.6 Å correspond to donors (upper region) and the acceptors (lower region) for the Zn1-molecule, whereas these appear as a pair of peaks at the same de + di ∼ 2.6 Å distance for the Zn2-molecule. This is likely due to the interacting oxygen and hydrogen atoms for the Zn1-molecule being at their van der Waals separation in the donor region, i.e. at 2.72 Å, while in the acceptor region the peak corresponds to a short interatomic O⋯H contact, Table 4de + di ∼ 2.6 Å.The fingerprint plots delineated into O⋯H/H⋯O contacts, Fig. 11de + di distances in the fingerprint plots delineated into S⋯H/H⋯S contacts, Fig. 11d, for the Zn1- and Zn2-molecules result from different hydroxy-O—H⋯S(dithiocarbamate) hydrogen bonds. The tips at de + di ∼ 2.4 Å in the donor region of the plot for the Zn1-molecule and in the acceptor region for the Zn2-molecule are due to the formation of O—H⋯S hydrogen bonds between the hydroxy-O1 and dithiocarbamate-S8 atoms; the other hydrogen bond, involving the O2 and S2 atoms, gives rise to tips at de + di ∼ 2.3 Å in the respective donor and acceptor regions of the plots, Fig. 11d. The plot for the overall structure results from the superimposition of individual plots and shows the symmetric distribution of points as a pair of long spikes having tips at de + di ∼ 2.3 Å. The short interatomic S⋯H/H⋯S contacts in the crystal of (I)de + di ∼ 3.0 Å in the respective plots.The pair of spikes with their tips at different e, have the same shape with tips at de + di ∼ 2.7 Å which are due to the short interatomic C⋯H/H⋯C contacts, Table 4i.e. 1.8%, but recognizable contribution to the Hirshfeld surface and appear as an arrow-like distribution of points around de = di = 1.8 Å in Fig. 11f. As indicated in Fig. 11g, S⋯S contacts do not figure prominently in the molecular packing of (I)Almost the same percentage contribution from C⋯H/H⋯C contacts to the overall surface is made by the Zn1- and Zn2-molecules, Table 5b, a pair of very thin spikes having their tips at de + di ∼ 2.3 Å indicate the presence of short interatomic H⋯H contacts between hydroxy-H1O and -H2O atoms, Table 4O and H3O atoms, Table 4cf. (I)de + di ∼ 1.8 Å, Fig. 11c. The tips corresponding to the O1⋯H6A contact, Table 4The corresponding two-dimensional fingerprint plots for (II)i.e. 22.2 and 22.7%, respectively, reflect the O—H⋯S hydrogen bonds and additional S⋯H contacts resulting in tips at de + di ∼ 2.9 Å in Fig. 11d and Table 4de + di ∼ 2.6 Å in the plot, Fig. 11e, results from the C—H⋯π(chelate) and short interatomic C⋯H/H⋯C contacts, Table 4f, as the pair of tips at de + di ∼1.7 Å. Finally, a cone-shaped distribution of points with a 3.8% contribution to the surface from S⋯S contacts having a vertex at de = di ∼ 1.7 Å in the fingerprint plot, Fig. 11g, results from short interatomic contacts between S4 atoms, Table 4The S⋯H/H⋯S contacts with the nearly same contribution to the surface of (II)Chemical context, the presence of hydroxyethyl groups in zinc dithiocarbamates leads to a higher degree of recognizable supramolecular aggregation owing to hydrogen bonding, usually of the type hydroxy-O—H⋯O(hydroxy) but, sometimes also of the type hydroxy-O—H⋯S(dithiocarbamate) 2]2}2, the usual dimeric motif is evident but these self-assemble via strong hydrogen bonding into three-dimensional architectures in both of the polymorphs characterized thus far, with the difference between the structures being the topology of supramolecular layers, i.e. flattened CH2CH2OH]2}2, the reduced hydrogen bonding leads to supramolecular chains CH2CH2OH)2]2}2L, where L is (3-pyridyl)CH2N(H)C(=O)C(=O)N(H)CH2(3-pyridyl). However, hydrogen bonding of the type hydroxy-O—H⋯O(hydroxy) links the molecules into inter-woven double chains 2, N,N′-bis(pyridin-3-ylmethyl)ethanedithiodiamide : ν(C=N) 1482 ; ν(C—S) 987 (s). 1H NMR : δ 9.91 , 8.20–8.00 , 7.30–7.10 , 3.82 ; 1.22 .Synthesis of (I)2N(Me)CH2CH2OH]2 and 3-hydroxy pyridine were dissolved in a MeOH/EtOH (1:1 v/v) solution. Solvent diffusion of hexane into this solution led to the formation of colourless crystals. FT–IR (cm−1): ν(C=N) 1480 (s); ν(C—S) 1002 (s). 1H NMR : δ 9.91 , 8.20–8.00 , 7.30–7.10 , 4.91 ; 3.90 ; 3.70 ; 3.41 .Synthesis of (II)Uiso(H) set to 1.2–1.5Ueq(C). The oxygen-bound H-atoms were located in difference Fourier maps but were refined with a distance restraint of O—H = 0.84±0.01 Å, and with Uiso(H) set to 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 610.1107/S205698901601728X/hb7628sup1.cifCrystal structure: contains datablock(s) . DOI: 10.1107/S205698901601728X/hb7628Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S205698901601728X/hb7628IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1511865, 1511864CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: