Linear chain thiocyanate complexes of M(NCS)(2)(OCMe2)(2) (M = Fe, Mn, Cr) composition have been prepared and structurally, chemically, and magnetically characterized. Fe(NCS)(2)(OCMe2)(2) exhibits metamagnetic-like behavior, and orders as an antiferromagnet at 6 K. The Mn and Cr compounds are antiferromagnets with T-c of 30 and 50 K, respectively, with J/K-B = -3.5 (-2.4 cm(-1)) and -9.9 K (-6.9 cm(-1)), respectively, when fit to one-dimensional (1-D) Fisher chain model (H = -2JS(i).S-j). Co(NCS)(2) was prepared by a new synthetic route, and powder diffraction was used to determine its structure to be a two-dimensional (2-D) layer with mu(N,S,S)-NCS motif, and it is an antiferromagnet (T-c = 22 K; theta = -33 K for T > 25 K). M(NCS)(2)(OCMe2)(2) (M = Fe, Mn) and Co(NCS)2 react with (NBu4)(TCNE) in dichloromethane to form M(TCNE)[C-4(CN)(8)](1/2), and in acetone to form M[C-4(CN)(8)(OCMe2)(2) (M = Fe, Mn, Co). These materials possess mu(4)-[C-4(CN)(8)](2-) that form 2-D layered structural motifs, which exhibit weak antiferromagnetic coupling. Co(TCNE)[C-4(CN)(8)](1/2) behaves as a paramagnet with strong antiferromagnetic coupling (theta = -50 K).