Cs(ATZ)的制备、晶体结构与热力学性质

以5-氨基四唑(ATZ)和氢氧化铯溶液为原料, 制备了配合物Cs(ATZ)并培养出单晶, 结构由X-ray单晶衍射测定. 晶体属正交晶系, 空间群Pnma, 晶体学参数: a＝0.8114(4) nm, b＝0.6907(4) nm, c＝0.9122(5) nm, V＝0.5113(5) nm³, D_c＝2.819 g/cm³, Z＝4, F(000)＝392, m＝7.112 mm^－1, R＝0.0485. 其中Cs^＋与9个氮原子配位, 分子间通过氢键、金属离子与N原子的桥连接及分子间作用力, 形成三维结构, 增加了晶体结构的稳定性. 同时, 用红外、拉曼光谱对配合物进行了表征. 根据测得的ATZ及Cs(ATZ)在氢氧化铯溶液中的反应焓和溶解焓, 算得配合物Cs(ATZ)标准摩尔生成焓为 (－430.56±0.43) kJ•mol^－1.

Preparation, Crystal Structure and Thermodynamic Properties of Cs(ATZ)

Complex Cs(ATZ) was prepared by mixing aqueous solution of CsOH and 5-aminotetrazole (ATZ). The crystal structure of Cs(ATZ) was determined by X-ray diffraction analysis. The crystal is orthorhombic with space group Pnma and unit-cell parameters of a＝0.8114(4) nm, b＝0.6907(4) nm, c＝0.9122(5) nm, V＝0.5113(5) nm³, D_c＝2.819 g/cm³, Z＝4, F(000)＝392, μ＝7.112 mm^－1, R＝0.0485. Cs^＋ is 9-coordinated with N atoms. 3-D framework structure was formed by hydrogen bonds, bridging between metal cations with N atoms and intermolecular forces. Cs(ATZ) was also characterized by IR and Raman spectroscopy. From measurements of the reaction enthalpy and solution enthalpy of ATZ and Cs(ATZ) in CsOH aqueous solution, the standard enthalpy of formation of the complex was calculated as (－430.56±0.43) kJ•mol^－1.