Novel anionic water-containing inorganic fragment in [4-NH 2PyH] 8[Bi 2Cl 11] [Bi 2Cl 9(H 2O) 2]: Structural characterization, thermal, dielectric and vibrational properties

• Published in: Polyhedron 2010-05, Vol.29 (8), p.2014-2022
• Main Authors: Kulicka, B., Lis, T., Kinzhybalo, V., Jakubas, R., Piecha, A.
• Format: Article
• Language: English
• Subjects: Halogenobismuthates(III); Infrared; Phase transition; X-ray diffraction
• ISSN: 0277-5387
• DOI: 10.1016/j.poly.2010.03.017

The view of the independent part of the title compound crystal structure at 100 K. The probability of thermal ellipsoids is 50%. The numbering is shown for the independent part of the structure. A novel compound, [4-NH 2PyH] 8[Bi 2Cl 11][Bi 2Cl 9(H 2O) 2] (abbreviated as 4APCB), was synthesized and structurally characterized at 100, 150 and 301 K. 4APCB crystallizes in a triclinic centrosymmetric space group, P 1 ¯ . The anionic framework is built up of two types of inorganic fragments, namely [ Bi 2 Cl 11 ] 5 - and [ Bi 2 Cl 9 ( H 2 O ) 2 ] 3 - , and 4-aminopyridinium- cations stacked between inorganic chains via π– π interactions. The latter type of anionic fragment was found for the first time in halobismuthate(III) solid complexes. Based on the results of differential scanning calorimetry (DSC), dilatometric and dielectric studies, 4APCB was found to undergo irreversible phase transition at ca. 342 K, accompanied by a partial decomposition of the compound (loss of water molecules). This chemical transformation is well reflected in the infrared spectrum of 4APCB.