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Three heterometallic Cu/Cd complexes [Cu(en) 2 CdBr 4 ]·dmso (1), [Cu(en) 2 CdI 4 ]·dmf (2) and [{Cu(en) 2 } 3 Cd(NCS) 6 ](NCS) 2  (3) have been synthesized by means of an open-air reaction of unactivated copper powder, cadmium oxide, NH 4 X (X = Br, I, NCS) and ethylenediamine in non-aqueous solvents, like dmso, dmf and CH 3 OH. The selection of a counter-anion in the initial ammonium salt provides a facile approach to the controlled assembly of one- or two-dimensional extended networks. Crystallographic investigations reveal that 1 and 2 possess 1D structures via semi-coordination (Cu 2+  . . .X) and hydrogen bonds (NH 2  . . . O Solv ) forming chains with a zigzag arrangement of copper and cadmium atoms. In complex 3 the cadmium atom of each Cd(NCS) 6  4−  anionic block forms bridges with Cu(II) ions via the sulfur atoms of thiocyanate groups to give 2D polymeric sheets, featuring two different ring sizes, one a 32-membered ring [Cu 4 Cd 4 (μ−SCN−S,N) 8 ] and the other a 16- membered ring [Cu 2 Cd 2 (μ−SCN−S,N) 4 ]. It is noteworthy, that 3 shows a quite rare Cd(NCS) 6  4−  fragment with N-bonded thiocyanate groups.

zeitschrift für naturforschung b

New One- and Two-Dimensional Heterometallic Cu/Cd Halogeno or Thiocyanato Bridged Coordination Polymers Synthesized Directly from Elemental Copper and Cadmium Oxide in the Presence of Ethylenediamine