The preparation, i.r. and electronic spectra, and magnetic properties of M(ROH)2(NCS)2(R = Me or Et; M = Mn, Co, or Ni), M(NCS)2(M = Mn, Co, Ni, Zn, or Cd), and Co(NCS)2,½H2O are reported. The alcohol complexes have pseudo-octahedtal co-ordination with bridging thiocyanate groups. For M(NCS)2(M = Mn, Fe, or Ni) and Co(NCS)2,½H2O the results indicate a tetragonal N2S4 co-ordination sphere with triply ligating thiocyanate ions; anhydrous cobalt thiocyanate however has a different structure. The magnetic properties of Mn(NCS)2 and Co(NCS)2,½H2O indicate negative magnetic coupling through the thiocyanate bridges but in Ni(NCS)2 the positive coupling through the sulphur bridges overrides this effect.