SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF COPPER(II) COMPOUNDS CONTAINING NITROGEN SULFUR DONOR LIGANDS - THE CRYSTAL AND MOLECULAR-STRUCTURE OF AQUA[1,7-BIS(N-METHYLBENZIMIDAZOL-2'-YL)-2,6-DITHIAHEPTANE]COPPER(II) PERCHLORATE
SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF COPPER(II) COMPOUNDS CONTAINING NITROGEN SULFUR DONOR LIGANDS - THE CRYSTAL AND MOLECULAR-STRUCTURE OF AQUA[1,7-BIS(N-METHYLBENZIMIDAZOL-2'-YL)-2,6-DITHIAHEPTANE]COPPER(II) PERCHLORATE
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DOI：
10.1039/dt9840001349
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发表时间：
1984-01-01
期刊：
影响因子：
--
通讯作者：
VERSCHOOR, GC
中科院分区：
文献类型：
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作者：
ADDISON, AW;RAO, TN;VERSCHOOR, GC
线性四齿N2 S2供体配体1，7-双（N-甲基苯并咪唑-2“-基）-2，6-二硫杂庚烷（bmdhp）形成单水合物和二水合物1：1 Cu（II）络合物，其对自还原的稳定性显著高于非甲基化类似物。深绿色的高氯酸盐一水合物结晶为单核水配合物[Cu（bmdhp）（OH 2）] [ClO 4]2，单斜空间群P21/n，Z = 4，a = 18.459（3），B = 10.362（2），c = 16.365（3）。和β= 117.14（1）°。通过标准Patterson、傅立叶和最小二乘技术解析和精制该结构，对于I > 2 β的3343个独立反射，R = 0.047和R“= 0.075。（一）.该化合物由[Cu（bmdhp）（OH 2]2+离子和ClO 4-反离子组成。Cu周围的配位是三角双锥和正方锥之间的中间配位，Cu-N距离为1.950（4）和1.997（4）埃，Cu-O（水）2.225（4）埃，和Cu-S 2.328（1）和2.337（1）。在固态下，高氯酸二水合物的配位球可能是高氯酸一水合物的拓扑异构体。一个新的角结构参数τ，定义并提出作为三角性指数，作为5坐标中心分子的一般描述符。根据这一判据，[Cu（bmhp）（OH_2）]~（2+）在固态时的不规则配位几何构型被描述为沿着从四方锥到三角双锥的畸变路径占沿着48%.在络合物的电子光谱中，归属于S（硫醚）→。Cu的电荷转移带与无色配合物Zn（bmdhp）（OH）（ClO 4）的电荷转移带进行比较。ESR和配位场谱表明，Cu（II）化合物在给体溶剂中呈四方晶系结构。
The linear quadridentate N2S2 donor ligand 1,7-bis(N-methylbenzimidazol-2''-yl)-2,6-dithiaheptane (bmdhp) forms mono- and di-hydrate 1:1 Cu (II) complexes which are significantly more stable toward autoreduction than those of the non-methylated analog. The deep green monohydrate of the perchlorate salt crystallizes as the mononuclear aqua-complex, [Cu(bmdhp) (OH2)] [CIO4]2, in the monoclinic space group P21/n, with Z = 4, a = 18.459 (3), b = 10.362(2), c = 16.365(3) .ANG., and .beta. = 117.14(1).degree.. The structure was solved and refined by standard Patterson, Fourier and least-squares techniques to R = 0.047 and R'' = 0.075 for 3343 independent reflections with I > 2.beta.(1). The compound consists of [Cu(bmdhp) (OH2]2+ ions and ClO4- counter ions. The co-ordination around Cu is intermediate between trigonal bipyramidal and square pyramidal with Cu-N distances of 1.950(4) and 1.997(4) .ANG., Cu-O (water) 2.225(4) .ANG., and Cu-S 2.328(1) and 2.337(1) .ANG.. In the solid state, the perchlorate dihydrate''s co-ordination sphere may be a toposisomer of the monohydrate''s. A new angular structural parameter, .tau., is defined and proposed as an index of trigonality, as a general descriptor of 5 co-ordinate centric molecules. By this criterion, the irregular co-ordination geometry of [Cu(bmhp) (OH2)]2+ in the solid state is described as being 48% along the pathway of distortion from square pyramidal toward trigonal bipyramidal. In the electronic spectrum of the complex, assignment is made of the S(thioether) .fwdarw. Cu charge-transfer bands by comparison with those of the colorless complex Zn (bmdhp) (OH) (CIO4). ESR and ligand-field spectra show that the Cu (II) compounds adopt a tetragonal structure in donor solvents.