Synthesis, X-ray structural and spectroscopic study of [bis(1,10-phenanthrolinium)](1+) {3,3′-commo-bis-[η5-1,2-dicarba-(3)-nickel(III)-closo-dodecaborate]}(1-), [H(1,10-C12H8N2)2]+{NiIII[η5-(3)-1,2-B9C2H11]2}−

Abstract

A new compound comprising a Ni(III) di-carbollide cluster anion [H(Phen)2][Ni(B9C2H11)2], Phen = 1,10-phenanthroline, has been prepared and structurally characterized. Crystal data: C28H39B18N6Ni, M = 684.92, monoclinic, space group P21/n; unit cell parameters: a = 19.337(3) A, b = 6.9968(8) A, c = 25.630(4) A; β = 101.69(1)°; V = 3395.8(9) A3, Z = 4, d calc = 1.340 g/cm3, T = 293 K, F(000) = 1412, μ = 0.602 mm−1. The structure was solved by the direct and Fourier methods and refined in the full-matrix anisotropic approximation (isotropic for hydrogen atoms) to final agreement factors R 1 = 0.0372, wR 2 = 0.0887 for 4136 I hkl ⩾ 2σI from 5445 measured I hkl (an Enraf-Nonius CAD-4 diffractometer, λMoK α , graphite monochromator, ω-scanning). The structure is built from [H(Phen)2]+ cations and [Ni(C2B9H11)2]− anions. The anions have a usual for commo-metal carboranes sandwich structure consisting of two icosahedra {NiC2B9} sharing a common Ni vertex. EPR technique shows that nickel ion has the electron state 3d 7 with S = 1/2. The angular dependence of single-crystal EPR spectra was used to calculate g-factors (g 1 = 2.0803, g 2 = 2.0229 and g 3 = 1.9810) and to assign principal values of the g-tensor to the directions in the crystal structure, in accord with which g 1 is directed along the Cb-Ni-Cb axis, while the direction and the value of g 2 is determined by a distortion introduced by the cation. The compound has been characterized by IR and Raman spectroscopy.