Two novel trinuclear Cu II complexes have been synthesised from the nucleophilic addition derivatives of the small cyano anion, dicyanonitrosomethanide (dcnm). The reaction of Cu II with the water adduct ligand, carbamoylcyanonitro-somethanide (ccnm) and teaH 3 (triethanolamine) in a basic MeOH/MeCN solution results in the formation of [Cu 3 (acnm) 2 (teaH 2) 2 ]Á2MeOH (1) (acnm ¼ amidocarbonyl(cyano)nitrosomethanide and teaH 2 À ¼ singly deprotonated triethanolamine). The reaction of Cu II with dicyanonitrosomethanide (dcnm) and m-xylenediamine in a basic MeOH/ MeCN solution results in the formation of [Cu 3 (cimm) 2 (a3acnm) 2 ]Á6MeCN (2) (cimm ¼ cyano(imido(methoxy)methyl) nitrosomethanide and a3acnm ¼ {amino(3-aminomethylphenyl)methylimino}methyl(cyanonitrosomethanide)). Both complexes display linear trinuclear Cu II metallic cores. Solid state DC magnetic susceptibility studies were performed on 1 and 2. Compound 1 revealed very strong antiferromagnetic interactions between central and terminal Cu atoms, while compound 2 displayed ferromagnetic interactions because of the orthogonal relationship of the terminal Cuðd x 2 Ày 2Þ and the central Cuðd x 2 Ày 2Þ 'magnetic' orbitals, which contrasts with these orbitals being coplanar in 1 thus providing strong superexchange pathways involving Cu-N-O-Cu moieties.