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The crystal structure of the title compound, C7H5F5NO+·Cl, consists of two-dimensional networks of hydrogen-bonded primary NH3+ cations and chloride anions with the penta­fluoro­benzyl moieties located on one side of the layer. To maximize the Coulombic interactions, the Cl anions approach the NH3+ groups of the neighbouring network along the O—N bond direction [O—N...Cl = 174.3 (2)°]. The N...Cl distance between the ions belonging to two adjacent networks is 3.066 (2) Å and is shorter than the N...Cl distances in the N+—H...Cl hydrogen bonds [3.099 (3)–3.133 (3) Å].

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A new polymorph of 1H-benzotriazole, C6H5N3, with a melting point of 372 K and a crystal density of 1.33 Mg m−3, has been obtained by recrystallization from acetone. The triclinic unit cell contains ten mol­ecules joined by N—H...N hydrogen bonds into a discrete large supramolecular macrocycle.

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A second ortho­rhom­bic polymorph (β) of 1H-benzimidazole, C7H6N2, metastable at room temperature, has been obtained. It has a melting point of 431 K and a crystal density of 1.27 Mg m−3. At room temperature, the crystals transform into the well known ortho­rhom­bic α form, with a melting point of 445 K. In both polymorphs, benzimidazole mol­ecules are connected into polymeric chains via N—H...N hydrogen bonds. However, the mode of aromatic ring inter­actions differs significantly in the two crystalline forms. In the α form, the mol­ecules show edge-to-face inter­actions, whereas in the new β form, a sandwich–herringbone arrangement of the aromatic mol­ecules is observed.

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1H-Benzimidazole-2-carboxylic acid crystallizes as the mono­hydrate, C8H6N2O2·H2O, and the organic mol­ecule exists in a zwitterionic form, viz. 1H-benzimidazolium-2-carboxyl­ate. Hydrogen bonds connect the mol­ecules of acid and water into a two-dimensional network.
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