硼氢二茂铁季铵盐的结构化学研究——Ⅰ、十硼十氢双(二茂铁甲基三甲基)铵晶体结构

本文报告了(C_5H_5FeC_5H_4CH_2N(CH_3)_3)_2B_(10)H_(10)晶体的结构。该晶体属三斜晶系、空间群为P_1~-。晶胞参数为:a=10.043(2),b=10.513(7),C=15.094(10),a=85.01(6),β=97.58(3),Υ=94.87(3)°,V=1625.7~3,Z=2。晶体在室温下用CAD-4四圆衍射仪收集衍射强度数据(MoKa),用重原子法解出铁原子坐标,综合应用E图、Fourief合成和差Fourier合成解出其他非氢原子坐标,按SDP加氢程序等求解阳离子中40个氢原子位置。各原子坐标及热振动参数经全矩阵最小二乘方修正,对于2258个独立衍射点(I≥3σI)],偏离因子R=0.043。 结构分析表明,B_(10)H_(10)~(2+)阴离子和C_5H_5FeC_5H_4CH_2N(CH_3)_3~+阳离子分别按畸变的八面体和畸变的三角形配位。两个二茂铁季铵阳离子中,两对戊二稀环平面间距为3.271(5)。阳离子中主要键长平均值为:Fe-C=2.026,C—C(环)=1.401,C—N=1.503。B_(10)H_(10)~(2+)阴离子为四方(三角)十六面体笼状结构,主要键长平均值为:B—B(顶点到正方形平面原子)1.706A,B—B(其它原子间)=1.830。

Structural Chemistry Studies on Boron Hydrogen Ferrocence Quaternary Ammonium SaltⅠ.The Crystal Structure of [C_5H_6FeC_5H_4CH_2N(CH_3)_3]_2B_(10)H_(10)

The Crystal [C5H5FeC5H4CH2N(CH3)3] 2B10H10 is triclinic belonging to the space group P . There are two molecules of [C5H5FeC5H4CH2N(CH3)3] 2-B10H10 in a unit cell with the following cell dimensions: a = 10.043 (2) , b = 10.513(7), c = 15.094(10)A,α = 85.01°(6), β = 97.58°(3),γ =94.87°(3),V = 1625.7(± 2.6)A3.The positions of the two Fe atoms, have been determined by using the three- dimentional Patterson functions. In addition, Fourier syntheses and direct methods have beed used to determine the positions of all C, N, and H atoms, with the exception of H atoms in the boron cage. The structure has been refined by full-matrix least-squares procedure to R = 0.043 for 2258 [I≥ 3σ(I)] independent reflections.[C5H5FeC5H4CH2N(CH3)3]2B10H10 is an ionic compound.The anious B10-H10- and cations C5H5FeC5H4CH2N(CH3)+ are of the distorted octahedral co -ordination and of the distorted trihedral co-ordination respectively.In the two ferrocence quaternary ammonium cations, the cyclopentadienyl rings are plane regular pentagonal, and the distance between the planes is 3.271(5) A with a complete eclipse structure. The average bond lengths are as follows. Fe- C = 2.026(4)A, C-C(ring) = 1.401(8)A, C-N = 1.503(8)A. The anion B10-H10= is a tetragonal hexadecahedron with its average bond length B-B (from the vertex to the atoms at the square plane) -1.706(4) A and B-B (between the other B atoms) = 1.830(5)A.