Synthesis and Crystal Structure of Me3NHCu2(SCN)3, Me2C=NMe2Cu2(SCN)3, and Me2C=NMe2Ag2(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[M₂(SCN)₃] with M = Cu, Ag and A = Me₃NH and A = [Me₂CNMe₂]. 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. Me₃NHCu₂(SCN)₃ ( 1 ) was synthesized by reaction of CuSCN with (CH₃)₃NHCl in the presence of an excess of KSCN in acetone. 1 crystallizes in the monoclinic space group P2₁/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 (CH₃)₂NH₂Cl and KSCN in acetone resulted in the formation of [Me₂CNMe₂]Cu₂(SCN)₃ ( 2 ) and [Me₂CNMe₂]Ag₂(SCN)₃ ( 3 ). Compound 2 crystallizes in the orthorhombic space group P2₁2₁2₁ 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.