三(3,5-二甲基吡唑)氢合硼酸钾及双[三(3,5-二甲基吡唑)]氢合硼酸根合铜(II)的合成和晶体结构

为研究吡唑硼类配体的配位行为, 合成了三(3,5-二甲基吡唑氢合硼酸钾KHB(C~5H~7N~2)~3], 简称(KL)和双三(3,5-二甲基吡唑)氢合硼酸根]合铜(II){CuHB(C~5H~7N~2)~3]~2}, 简称(CuL~2), 并测定了它们的晶体结构。化合物KL属空间群P2~1/n。a=1.0527(8), b=0.9464(3), c=1.7730(9)nm, β=94.51(5)°,Z=4, D~c=1.268g.cm~-~3, R=0.079。化合物CuL~2属空间群PI, a=0.8768(1),b=1.0170(2), c=1.0859(1)nm, α=62.45(1),β=83.78(1), γ=78.52(1)°, Z=2,D~c=1.298 g.cm~-~3, R=0.062。晶体结构测定结果表明: 化合物KL由钾离子和配体负离子组成, K~+与配体L中的B原子相距0.3634nm, 在配体负离子中B原子与三个吡唑环的N原子及H原子形成四面体构型。化合物CuL~2由孤立分子组成, 铜离子处于分子的对称中心且与两个配体分子中的六个N原子形成六配位的八面体构型, 并表现出明显的Jahn-Teller效应。

Synthesis and crystal structures of [Hydridotris (3,5-dimethylpyrazol-1-yl)borato]K and bis-[hydridotris (3,5-dimethylpyrazol-1-yl)borato] Cu(II)

To study the coordination action of pyrazolylborato ligands, KBHR3 (R = 3,5-dimethylpyrazol-1-yl) and Cu(BHR3)2 were prepared, and their crystal structures were determine by x-ray anal. The crystallog. data are as follows: KBHR3, monoclinic, space group P21/n, and R = 0.079; Cu(BHR3)2 triclinic, space group P1, Z = 2, and R = 0.062. The distance between atom K(1) and B(1) is 0.3634 nm. Atom B(1) in BHR3- is tetrahedrally coordinated by one H atom and three N atoms from three pyrazole rings. The bond distances B(1)-N(12), B(1)-N(22) and B(1)-N(32) are 0.1587, 0.1586 and 0.1509 nm, resp. In Cu(BHR3)2, the Cu atom is located about a crystallog. center of symmetry and coordinated octahedrally by six N atoms which are from two BHR3- ligands. The bond distances Cu(1)-N(11), Cu(1)-N(21) and Cu(1)-N(31) are 0.2153, 0.2344 and 0.2035 nm, resp. An obvious Jahn-Teller effect is displayed.