Lewis-base adducts of Group 1B metal(I) compounds. Part 17. Synthesis and crystal structures of adducts of copper(I) cyanide with nitrogen bases
Lewis-base adducts of Group 1B metal(I) compounds. Part 17. Synthesis and crystal structures of adducts of copper(I) cyanide with nitrogen bases
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DOI：
10.1039/dt9850000839
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发表时间：
1985
期刊：
影响因子：
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通讯作者：
J. C. Dyason;P. Healy;L. M. Engelhardt;C. Pakawatchai;V. Patrick;Allan H. White
中科院分区：
文献类型：
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作者：
J. C. Dyason;P. Healy;L. M. Engelhardt;C. Pakawatchai;V. Patrick;Allan H. White
用氰化铜重结晶法合成了[Cu（CN）Ln][L =二乙胺，（1），三乙胺，（2），4-甲基吡啶，（3），1，10-邻菲咯啉，（4）]型化合物，用单晶X射线衍射法测定了它们的晶体结构; n= 1，除了在n= 1.5的情况（3）之外。晶体为单斜晶系，空间群为P21/n，a= 15.108（7），B= 7.321（5），c= 13.699（6）A，β= 103.00（4）°，Z= 8;对于（2），晶体为正交晶系，空间群为Pnma，a= 9.501（4），B= 8.921（4），c= 11.279（5）A，Z= 4; R= 0.039，No= 369。晶体属单斜晶系，空间群Cc，a= 9.587（3），B= 16.326（4），c= 14.022（4）A，β= 109.38（2）°，Z= 4; R= 0.031，No= 1070。对于（4），晶体为三方晶系，空间群P31，a= 9.175（5），c= 11.753（8），Z= 3; R= 0.041，No= 812。所有的配合物都是一维聚合物，在（2）中除了取代基烷基之外，完全位于镜像平面内。（1）和（2）中的铜原子是由C、N（氰化物）和N（碱）配位的三角平面，（3）中的两个铜原子之一也是如此;（3）中的另一个铜原子是不寻常的，是由C、N（氰化物）和两个N（碱）配位的四配位假四面体。在（4）中发现了类似的铜环境。
Compounds of the type [Cu(CN)Ln][L = diethylamine, (1), triethylamine, (2), 4-methylpyridine, (3), or 1,10-phenanthroline, (4)] have been synthesized by recrystallization of copper(I) cyanide from (or with) the parent base and their crystal structures have been determined by single-crystal X-ray diffraction methods; n= 1 except in the case of (3) where n= 1.5. Crystals of (1) are monoclinic, space group P21/n, with a= 15.108(7), b= 7.321(5), c= 13.699(6)A, β= 103.00(4)°, and Z= 8; R was 0.044 for No= 871 independent ‘observed’ reflections. For (2), crystals are orthorhombic, space group Pnma, with a= 9.501(4), b= 8.921(4), c= 11.279(5)A, and Z= 4; R= 0.039, No= 369. For (3), crystals are monoclinic, space group Cc, with a= 9.587(3), b= 16.326(4), c= 14.022(4)A, β= 109.38(2)°, and Z= 4; R= 0.031, No= 1 070. For (4), crystals are trigonal, space group P31, with a= 9.175(5), c= 11.753(8)A, and Z= 3; R= 0.041, No= 812. All complexes are one-dimensional polymers, that in (2) being disposed completely in a mirror plane except for the substituent alkyl groups. Copper atoms in (1) and (2) are trigonally planar co-ordinated by C,N(cyanide) and N(base), as is one of the two copper atoms in (3); the other copper atom in (3) is unusual, being four-co-ordinated pseudo-tetrahedrally by C,N(cyanide) and two N(base). A similar copper environment is found in (4).