Synthesis and Crystal Structure of Me3NHCu2(SCN)3, Me2C=NMe2Cu2(SCN)3, and Me2C=NMe2Ag2(SCN)3. Three-dimensional Networks of Thiocyanatometallates(I)

✍ Scribed by Roland Hehl; Gerhard Thiele

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: German
• Weight: 172 KB
• Volume: 626
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/1521-3749(200010)626:10<2167::aid-zaac2167>3.0.co;2-7

✦ Synopsis

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; b = 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 CN-Me 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.