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Colourless columnar crystals of Ph4PCu(SCN)2 (1) were obtained by reaction of CuSCN with Ph4PSCN in acetone. 1 crystallises in the orthorhombic space group P212121 with a = 746.50(10); b = 1623.8(3); c = 1999.4(4) pm; Z = 4; V = 2423.6(7) · 106 pm3. Colourless lamella shaped crystals of (PPN)Cu(SCN)2 (2) were formed by reactions of (PPN)CuCl2 with KSCN in ethanol. 2 crystallises in the triclinic space group P1 with a = 1101.3(2); b = 1141.6(2); c = 1522.9(3) pm; alpha = 74.75(3); beta = 80.50(3); gamma = 70.74(3); Z = 2; V = 1737.4(6) · 106 pm3. In both compounds the anions consist of approximately planar groups with Cu atoms co-ordinated by two N and one S atom. In each case one SCN is a N-bound terminal group while the second SCN forms a 1,3-mu bridge between two Cu centres. In 1 the planar CuN2S units are connected to polymer anions with chain structure, whereas 2 contains dimeric anions [SCNCu(SCN)2CuNCS].
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Reference：
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”