Diaquatetrakis(tert-butyl isocyanide)cobalt(II) bis(perchlorate): an example of cobalt(II) coordinated by only four alkyl isocyanide ligands

Acta Crystallogr C. 2009 Aug;65(Pt 8):m302-4. doi: 10.1107/S0108270109024500. Epub 2009 Jul 11.

Abstract

The title compound, [Co(C5H9N)4(H2O)2](ClO4)2, crystallizes in the monoclinic space group C2/m. The cation has space-group-imposed 2/m symmetry, while the perchlorate ion is disordered about a mirror plane. The two slightly non-equivalent Co-C bonds [1.900 (3) and 1.911 (3) A] form a rectangular plane, with a C-Co-C bond angle of 86.83 (11) degrees, and the linear O-Co-O C2 axis is perpendicular to this plane. The C[triple-bond]N bond lengths are 1.141 (4) A and the Co-C[triple-bond]N and C[triple-bond]N-C angles average 175.5 (4) degrees. The perchlorate counter-ions are hydrogen bonded to the water molecules. The title compound is the first example of four alkyl isocyanide ligands coordinating Co(II) upon initial reaction of Co(ClO4)(2).6H2O/EtOH with alkyl isocyanide. In all other known examples, five alkyl isocyanide molecules are coordinated, as in [(RNC)5Co-Co(CNR)5](ClO4)4 (R = Me, Et, CHMe2, CH2Ph, C4H9-n or C6H11) or [Co(CNC8H17-t)5](ClO4)2. This complex, therefore, is unique and somewhat unexpected.