An ionic compound containing molecular iodine (ipq)(4)(Cu2I6)center dot 2I(2): Synthesis and theoretical investigation

作者:Li Hao Hong; Chen Zhi Rong*; Liu Yuan; Liu Ji Bo; Guo Liang Qia; Li Jun Qian
来源:Journal of Molecular Structure, 2009, 934(1-3): 112-116.
DOI:10.1016/j.molstruc.2009.06.026

摘要

Dark-red block-shaped crystals of the ionic compound (ipq)(4)[(Cu2I6)center dot 2I(2)] (1) (ipq( ) = N-(isopentyl)-quinolinium) were obtained by the reaction of ibq.l, Cul with 12 in polar solvent DMF. Compound I crystallizes in triclinic system [space group P (1) over bar Z = 2, a = 10.4236(8) angstrom, b = 12.1950(9) angstrom, c = 15.6214(10) angstrom, alpha = 95.879(2)degrees, beta = 102.174(2)degrees, and gamma = 113.757(2)degrees]. As indicated by structural analysis, 1 is constituted by ipq( ) cations, [Cu2I6](4-) anions and molecular iodine [d(1-1) = 2.8499(5) angstrom]. In 1, dinner Cu2I64- anion is composed by two edge-sharing CuI4 tetrahedra. Cu2I64- anions interact with I-2 via strong I center dot center dot center dot I interaction to give [(Cu2I6)center dot 2I(2)](4-) clusters. Furthermore, electrostatic interactions between organic cations and inorganic clusters could be observed and contribute to the crystal packing. Finally, quantum chemistry calculation with DFT method was carried out to reveal the electronic structure of 1.