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In the title compound, C19H13N5·C4H8O2·2H2O, the mol­ecular skeleton of the 2,6-bis­(benzimidazol-2-yl)pyridine (bbip) mol­ecule is essentially planar (r.m.s. deviation = 0.023 Å). An extensive three-dimensional network of inter­molecular N—H...O, O—H...O and O—H...N hydrogen bonds consolidates the crystal packing, which also exhibits π–π inter­actions between the five- and six-membered rings from neighbouring bbip mol­ecules.

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In the title compound, C14H11N3OS·C2H5OH, the dihedral angle between the pyridine N—Cfused—Cfused—C(thio­phene) plane and the plane of the thio­phene ring is 81.9 (3)°, indicating that they are close to perpendicular. The dihedral angle between this pyridine plane and the benzene ring is 1.3 (3)°. The thio­phene ring is disordered over two coplanar orientations with an occupancy ratio of 0.692 (7):0.308 (7), while the ethanol solvent mol­ecule is also disordered over two sets of site in a 0.66 (4):0.34 (4) ratio. In the crystal, chains are formed along the b axis by N—H...O and O—H...N inter­actions with adjacent chains being connected through C—H...N and C—H...S inter­actions.

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The asymmetric unit of the title hydrated co-crystal, 2C19H13N5·C6H10O4·4H2O, consists of one 2,6-bis­(1H-benzimidazol-2-yl)pyridine mol­ecule, half of an adipic acid mol­ecule (bis­ected by an inversion center) and two water solvates. In the crystal, N—H...O, O—H...O and O—H...N hydrogen bonds and π–π inter­actions [centroid–centroid distances = 3.769 (2) and 3.731 (2) Å] form a three-dimensional supra­molecular structure.
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