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 thiocyanatometall ates of Cu-I and Ag-I led to the synthesis of three new tris(thiocyanato)di metallates(I) A[M-2(SCN)(3)] with M=Cu, Ag and A=Me3NH and A=[Me2CMe2]. 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-di mensional frame works accommodate the counter cations in spacious voids. Me3NHCu2(SCN)(3) (1) was synthesized by reaction of CuSCN with (CH3)(3)NHCl in the presence of an excess of KSCN in acetone. 1 crystallizes in the mon oclinic space group P2(1)/c with a = 578.4(1), b = 3025.1(5), c = 754.7(3) pm; beta = 112.53 degrees; Z=4. The reaction of CuSCN or AgSCN with (CH3)(2 )NH2Cl and KSCN in acetone resulted in the formation of [Me2CNMe2]Cu-2(SCN) (3) (2) and [Me2CNMe2]Ag-2(SCN)(3) (3). Compound 2 crystallizes in the orth orhombic space group P2(1)2(1)2(1) With a=720.6(1), b=1161.5(1), c=1655.0(2 ) pm; 2=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.