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Synthesis of 1D {Cu<sub>6</sub>(μ<sub>3</sub>-SC<sub>3</sub>H<sub>6</sub>N<sub>2</sub>)<sub>4</sub>(μ-SC<sub>3</sub>H<sub>6</sub>N<sub>2</sub>)<sub>2</sub>(μ-I)<sub>2</sub>I<sub>4</sub>}<i><sub>n</sub></i> and 3D {Cu<sub>2</sub>(μ-SC<sub>3</sub>H<sub>6</sub>N<sub>2</sub>)<sub>2</sub>(μ-SCN)<sub>2</

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The reaction of copper(I) iodide with 1, 3-imidazolidine-2-thione (SC3H6N2) in a 1:2 molar ratio (M/L) has formed unusual 1D polymers, {Cu6(μ3-SC3H6N2)4(μ-SC3H6N2)2(μ-I)2I4}n (1) and {Cu6(μ3-SC3H6N2)2(μ-SC3H6N2)4(μ-I)4I2}n (1a). A similar reaction with copper(I) bromide has formed a polymer {Cu6(μ3-SC3H6N2)2(μ-SC3H6N2)4(μ-Br)4Br2}n (3a), similar to 1a, along with a dimer, {Cu2(μ-SC3H6N2)2(η1-SC3H6N2)2Br2} (3). Copper(I) chloride behaved differently, and only an unsymmetrical dimer, {Cu2(μ-SC3H6N2)(η1-SC3H6N2)3Cl2} (4), was formed. Finally, reactions of copper(I) thiocyanate in 1:1 or 1:2 molar ratios yielded a 3D polymer, {Cu2(μ-SC3H6N2)2(μ-SCN)2}n (2). Crystal data: 1, C9H18Cu3I3N6S3, triclinic, P1̄, a = 9.6646(11) Å, b = 10.5520(13) Å, c = 12.6177(15) Å, α = 107.239(2)°, β = 99.844(2)°, γ = 113.682(2)°, V = 1061.8(2) Å3, Z = 2, R = 0.0333; 2, C4H6CuN3S2, monoclinic, P21/c, a = 7.864(3) Å, b = 14.328(6) Å, c = 6.737(2) Å, β = 100.07(3)°, V = 747.4(5), Z = 4, R = 0.0363; 3, C12H24Br2Cu2N8S4, monoclinic, C2/c, a = 19.420(7) Å, b = 7.686(3) Å, c = 16.706(6) Å, β = 115.844(6)°, V = 2244.1(14) Å3, Z = 4, R = 0.0228; 4, C12H24Cl2Cu2N8S4, monoclinic, P21/c, a = 7.4500(6) Å, b = 18.4965(15) Å, c = 16.2131(14) Å, β = 95.036(2)°, V = 2225.5(3) Å3, Z = 4, R = 0.0392. The 3D polymer 2 exhibits 20-membered metallacyclic rings in its structure, while synthesis of linear polymers, 1 and 1a, represents an unusual example of I (1a)−S (1) bond isomerism.

创建时间:
2006-11-13
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