Investigation of the structure and phase transitions of the polymeric inorganic-organic hybrids: [M(Im)4V2O6]∞; M = Mn, Co, Ni, Im = imidazole

• Published in: Acta crystallographica. Section B, Structural science Vol. 67; no. 1; pp. 41 - 52
• Main Authors: Chainok, Kittipong, Haller, Kenneth J., Rae, A. David, Willis, Anthony C., Williams, Ian D.
• Format: Journal Article
• Language: English
• Published: 5 Abbey Square, Chester, Cheshire CH1 2HU, England International Union of Crystallography 01.02.2011; Blackwell Publishing Ltd
• Subjects: Chemical compounds; Crystal structure; Crystallography; Crystals; Hybrids; Hydrogen; hydrogen bonding; inorganic-organic hybrid; Low temperature; order-disorder phase transition; Phase transitions; Polymers; temperature dependence; twinning; Vanadium; X-ray diffraction
• ISSN: 0108-7681; 2052-5192; 1600-5740; 2052-5206
• DOI: 10.1107/S0108768110042941

The polymeric isomorphous hybrid inorganic–organic vanadium oxide compounds [M(Im)4V2O6]∞, M = Mn, Co, Ni, Im = imidazole, were investigated at various temperatures between 100 and 295 K by single‐crystal X‐ray diffraction. The crystals all contain two‐dimensional polymeric sheets packed perpendicular to c* and are 1:1 disordered in the space group P42/n (Z = 8) at 295 K. The disordered phase is reversibly transformed to an I41/a ordered phase (Z = 32) below 281 K for the Mn compound and below 175 K for the Co compound. Within a localized region of the I41/a phase eight imidazoles are in close proximity and seven of these are hydrogen bonded to framework O atoms. The hydrogen‐bond connectivity of six of these ligands is unchanged by the phase transition that allows an inversion of the local geometry using an inversion operator that is a symmetry element of P42/n, but not I41/a. The Mn structure has a well defined phase transition but the Co structure shows a large hysteresis and it was necessary to include stacking faults in the modelling of the Co structure at low temperatures. The Ni structure was shown to be partially twinned, but ordered in the space group P2/n (Z = 8) at 100 K, with two different localized regions each containing four pairs of inversion‐related imidazoles, hydrogen bonding to framework O atoms involving eight imidazoles in one region and six imidazoles in the other. Models for the phase transition mechanisms are considered.