Tetrakis(tert-butyl isocyanide)copper(I) chloride monohydrate

Abstract

The title compound, [Cu(C5H9N)4]Cl·H2O, was obtained from the reaction of copper(II) chloride hydrate with KCN in the presence of two equivalents of tert‐butyl­isocyanide. The reaction proceeds via the reduction of copper and the formation of (CN)2. The compound shows a tetra­hedrally surrounded CuI centre, with the CuI ion and the water O atom being situated on crystallographic twofold axes. The crystal structure contains infinite chains of alternating solvent mol­ecules and Cl− anions, with additional weak C—H⋯Cl or C—H⋯O inter­actions with the [Cu(CNtBu)4] cations.

Structural and spectroscopic studies of some copper(i) halide tert-butyl isocyanide adducts

“…8 Following the methodology of ref. 3, we have isolated, and structurally characterized all adducts of the form CuX : CNR (1 : 4) (X = Cl, Br, I; R = t-Bu), establishing that these are indeed of the form [CuL 4 ]X, the halide remaining uncoordinated; contemporaneously with this work, an independent study of the chloride has appeared, 9 interestingly of a different but related solvated form. A 1 : 2 adduct has also been obtained and structurally characterized for X = Cl; 1 : 1.5 adducts have been isolated and spectroscopically characterized for X = Br, I, while a crystallographically characterized 1 : 1 adduct is reported for X = CN.…”

“…The recent report of ref. 9 describes a monohydrate, the structure being fully ordered, in orthorhombic space group Pcca, a = 22.3933 (9), b = 5.6174(2), c = 22.3033(8) A ˚, V = 2806 A ˚3 at 183 K, the copper, chlorine and water molecule oxygen atoms being located on crystallographic 2-axes, the chloride ions and water molecules linked by hydrogen-bonding in a chain parallel to the short crystallographic axis (Fig. 1(b)).…”

“…(The IUCr archive records (but not the CCDC entry or the Acta Crystallogr. report 9 ) that the tert-butyl groups were modelled as rotationally disordered, major component occupancies 0.61, 0.55.) The present structure is obviously derivative, the water molecule/chloride chain of the monohydrate being expanded into the disordered solvent/anion sheet of the present structure, with a considerable increase in cell volume and decrease in symmetry to that of the sub-group.…”

“…The hydrated 1 : 4 chloride (see ref. 9) was obtained in a similar way but with addition of water (0.5 ml) prior to the final recrystallization.…”