Synthesis and Crystal Structure of Me 3 NHCu 2 (SCN) 3 , Me 2 C=NMe 2 Cu 2 (SCN) 3 , and Me 2 C=NMe 2 Ag 2 (SCN) 3 . Three‐dimensional Networks of Thiocyanatometallates(I)

Attempts to build up polyanionic networks on the basis of thiocyanatometallates of Cu I and Ag I led to the synthesis of three new tris(thiocyanato)dimetallates(I) A[M 2 (SCN) 3 ] with M = Cu, Ag and A = Me 3 NH and A = [Me 2 CNMe 2 ]. The crystal structures show distorted tetrahedral [M(SCN) 3 (NCS)] and [M(SCN) 2 (NCS) 2 ] building groups interlinked by SCN bridges. The resulting 3‐dimensional frame works accommodate the counter cations in spacious voids. Me 3 NHCu 2 (SCN) 3 ( 1 ) was synthesized by reaction of CuSCN with (CH 3 ) 3 NHCl in the presence of an excess of KSCN in acetone. 1 crystallizes in the monoclinic space group P2 1 /c with a = 578.4(1), b = 3025.1(5), c = 754.7(3) pm; β = 112.53°; Z = 4. The reaction of CuSCN or AgSCN with (CH 3 ) 2 NH 2 Cl and KSCN in acetone resulted in the formation of [Me 2 CNMe 2 ]Cu 2 (SCN) 3 ( 2 ) and [Me 2 CNMe 2 ]Ag 2 (SCN) 3 ( 3 ). Compound 2 crystallizes in the orthorhombic space group P2 1 2 1 2 1 with a = 720.6(1), b = 1161.5(1), c = 1655.0(2) pm; Z = 4. The isotypical structure of 3 exhibits somewhat larger unit cell dimensions; a = 743.4(1), b = 1222.5(1), c = 1683.9(2) pm.