Novel Examples of High-Dimensional Mixed-Valence Copper Cyanide Complexes

The first examples of high-dimensional mixed-valence homometallic cyano-bridged copper complexes were
synthesized and characterized:  net-structured [Cu(CN)4{Cu(cyclam)}1.5]2n(H2O)5n (1), ladder-type double-chain-structured [Cu(CN)2{Cu(CN)2Cu(cyclam)}]n(H2O)n (2), layer-structured [{Cu(CN)2}2Cu(cycalm)]n (3), and hydrogen-bond-based 2-D [Cu(CN)3Cu(cyclam)]n(CH3OH)n (4) (cyclam = 1,4,8,11-tetraazacyclotetradecane). 1 crystallizes
in triclinic space group P1̄ with a = 8.3589(11) Å, b = 13.478(2) Å, c = 14.828(2) Å, α = 66.895(2)°, β =
77.916(3)°, γ = 85.939(3)°, and Z = 1; 2 crystallizes in triclinic space group P1̄ with a = 8.2305(12) Å, b =
9.8861(15) Å, c = 13.219(2) Å, α = 84.863(3)°, β = 75.744(3)°, γ = 89.818(3)°, and Z = 2; 3 crystallizes in
monoclinic space group P21/c with a = 6.830(2) Å, b = 8.482(2) Å, c = 17.306(4) Å, β = 98.144(4)°, and Z =
2; 4 crystallizes in triclinic space group P1̄ with a = 9.470(1) Å, b = 10.034(1) Å, c = 12.064(1) Å, α = 67.325(2),
β = 75.593(2), γ = 70.672(2), and Z = 2. The coordination sphere of CuI sites in the complexes shows diverse
structures:  tetrahedral [CuC4] for 1, tetrahedral [CuC3N] and triangular [CuC2N] for 2, triangular [CuC2N] for 3, and
triangular [CuC3] for 4. In particular, 1 constitutes the first example of a structurally characterized system containing
a bridging tetrahedral [Cu(CN)4]3- unit. The diverse structural nature of these complexes is governed by the capping
amines and the content of water in the reaction media. The magnetic interactions are negligible in these mixed-valence complexes.

首例高维混合价同金属氰桥铜配合物得以合成并进行了表征：网络结构的[Cu(CN)4{[Cu(cyclam)]1.5]}2n(H2O)5n (1)、梯形双链结构的[Cu(CN)2{[Cu(CN)2Cu(cyclam)]]}n(H2O)n (2)、层状结构的[{Cu(CN)2}2Cu(cycalm)]n (3)以及基于氢键的二维[Cu(CN)3Cu(cyclam)]n(CH3OH)n (4)（cyclam 为 1,4,8,11-四氮杂环十四烷）。其中，1 晶体以三斜晶系 P1̄ 空间群结晶，其晶胞参数为 a = 8.3589(11) Å, b = 13.478(2) Å, c = 14.828(2) Å, α = 66.895(2)°, β = 77.916(3)°, γ = 85.939(3)°, 且 Z = 1；2 晶体以三斜晶系 P1̄ 空间群结晶，其晶胞参数为 a = 8.2305(12) Å, b = 9.8861(15) Å, c = 13.219(2) Å, α = 84.863(3)°, β = 75.744(3)°, γ = 89.818(3)°, 且 Z = 2；3 晶体以单斜晶系 P21/c 空间群结晶，其晶胞参数为 a = 6.830(2) Å, b = 8.482(2) Å, c = 17.306(4) Å, β = 98.144(4)°, 且 Z = 2；4 晶体以三斜晶系 P1̄ 空间群结晶，其晶胞参数为 a = 9.470(1) Å, b = 10.034(1) Å, c = 12.064(1) Å, α = 67.325(2), β = 75.593(2), γ = 70.672(2), 且 Z = 2。这些配合物中 CuI 位点的配位球表现出多样的结构：1 的配位结构为四面体 [CuC4]，2 的配位结构为四面体 [CuC3N] 和三角形 [CuC2N]，3 的配位结构为三角形 [CuC2N]，4 的配位结构为三角形 [CuC3]。特别是，1 构成了第一个结构表征含有桥连四面体 [Cu(CN)4]3- 单元的系统。这些配合物的多样结构性质受反应介质中封端胺的类别及水含量所支配。在这些混合价态配合物中，磁相互作用可以忽略不计。