Alkylation of a bioinspired high spin Ni(II)N₃S₂ complex with bifunctional reagents

Crystal structures of two S-alkylated complexes generated from the reaction of iodoacetamide and iodoethanol with an air and moisture sensitive high spin Ni(II) pentacoordinate triaminodithiolate complex, 1 are determined by X-ray structure analysis. Crystals of complex 2, [NiC₁₆H₃₁N₅O₂S₂]I₂, are triclinic, sp. gr. $P\overline{1}$, Z = 2. Crystals of complex 3, [NiC₁₆H₂₈N₃O₂S₂]I₂, are monoclinic, sp. gr. P2₁/c, Z = 4. Structures of complexes 2 and 3 are very similar: one of the S-acetamide (2) or S-ethanol (3) groups coordinates to the Ni center through the oxygen atom forming N₃S₂O hexacoordination; the other group remains unbound to the Ni and left dangling. Crystal packing shows that complexes 2 and 3 interact with the iodide counterions, and that only complex 2 interact with neighboring molecules; some of these close intermolecular contacts include H-bonding interactions.