Spontaneously organizing metal connectors as supramolecular structure directors of two- and three-dimensional organometallic assemblies

The supramolecular interplay of Me(3)Sn(+) and M(CN)(2n)](n-) ions (n=3 and 4) with either 4,4'-bipyridine (bpy), trans-bis(4-pyridyl)ethene (bpe) or 4cyanopyridine (cpy) in the presence of H(2)O has been investigated for the first time. Crystal structures of the six novel assemblies: (Me(3)Sn)(4)Mo(IV)(CN)(8).2 H(2)O.bpy] (8) and (Me(3)Sn)(4)Mo(IV)(CN)(8).2 H(2)O.bpe] (8 a; isostructural), (Me(3)Sn)(3)Fe(III)(CN)(6).4 H(2)O.bpy] (9), (Me(3)Sn)(3)Co(III)(CN)(6).3 H(2)O.3/2 bpy] (10), (Me(3)Sn)(4)Fe(II)(CN)(6).H(2)O.3/2 bpy] (11), and (Me(3)Sn)(4)Ru(II)(CN)(6).2 H(2)O.3/2 cpy] (12) are presented. H(2)O molecules are usually coordinated to tin atoms and involved in two significant O-H.N hydrogen bonds, wherein the nitrogen atoms belong either to bpy (bpe, cpy) molecules or to M-coordinated cyanide ligands. Extended supramolecular assemblies such as -CN-->Sn(Me(3))<--O(H.)H.N(L)N.HO(H.)-->Sn(Me(3))<--NC- (L=bpy, bpe or cpy) function as efficient metal connectors (or spacers) in the structures of all six compounds. Only in the three-dimensional framework of 11, one third of all bpy molecules is involved in coordinative N-->Sn bonds. The supramolecular architecture of 9 involves virtually non-anchored (to cyanide N atoms), Me(3)Sn(+) units with a strictly planar SnC(3) skeleton, and two zeolitic H(2)O molecules. Pyrazine (pyz) is surprisingly reluctant to afford assemblies similar to 8-12, however, the genuine host-guest systems (Me(3)Sn)(4)Mo(CN)(8).0.5pyz] and (Me(3)Sn)(4)Mo(CN)(8).pym] (pym=pyrimidine) could be isolated and also structurally characterized.