The two new compounds [Me 2 Sn(CH 2 ) 3 SnMe 2 1.5 Co(CN) 6 ], 1, and [Me 2 Sn(CH 2 ) 3 SnMe 2 2 Mo(CN) 8 ], 2, have been prepared and compared with their notional ‘parent’ systems [(R 3 Sn) 3 Co(CN) 6 ] (R = Me, Et, n Bu) and solvent-free [(Me 3 Sn) 4 M(CN) 8 ] (M = Mo, W) respectively. Results of extensive spectroscopic (i.e. IR/Raman as well as multinuclear CP MAS NMR) studies and of X-ray powder diffractometry suggest that the crystal structures of 1 and 2 involve three-dimensional networks notably different from those of their ‘parent’ systems. The probably regular, pairwise linkage of two CNSnMe 2 CH 2 ligand fragments by a third CH 2 group even appears to ‘improve’ the local symmetry of the respective M(CN) k building block (k = 6 or 8) and simplifies the corresponding asymmetric units.