[Cr(bipy)(C2O4)2]−—a versatile building block for the design of heteropolymetallic systems 2. Syntheses and crystal structures of and (AgCr(bipy)(μ-C2O4)2(H2O)2)2 and magnetic properties of the copper(II) derivative
Inorganica Chimica Acta(1996)
Abstract
Abstract The compounds CuCr 2 ( bipy ) 2 (μ- C 2 O 4 ) 2 ( H 2 O ) 2 ·1 1 2 H 2 O (1) and (AgCr(bipy)(μ-C2O4)2(H2O)2)2 (2) have been obtained by self-assembling [Cr(bipy)(C2O4)2]− building blocks with Cu(II) and Ag(I) ions, respectively. The molecular and crystal structures of the two compounds were determined. Crystal 1 is monoclinic, C2/c, a = 20.379(14), b = 11.037(4), c = 17.480(7) A , β = 124.83(3)° , Z = 4 and R = 0.0369. Its structure consists of discrete linear {CrCuCr} trinuclear species with the copper atom lying on an inversion center. The copper atom exhibits [4 + 2] axially elongated octahedral geometry, the apical positions being occupied by two oxalato oxygen atoms. The CuO bond distances are 1.953(4) (H2O), 1.998(3) and 2.357(3) A, the CrO bonds vary from 1.945(3) to 1.982(3) A, and the CrN bonds are 2.031(4) and 2.054(3) A. The Cr…Cu distances are 5.288 A. Crystal 2 is monoclinic, P21/c, a = 14.639(16), b = 15.553(10), c = 16.899(12) A , β = 114.70(4)°, Z = 4 and R = 0.0629 , and contains discrete tetranuclear cycles formed by two chromium and two silver atoms bridged by the oxalato groups. The silver atoms are penta-coordinated, exhibiting distorted trigonal bipyramidal geometries. The AgO bond distances vary from 2.350(8) to 2.548(7) A, while the CrO bonds are in the range 1.942(7) to 1.982(6) A. The magnetic susceptibility data of 1 reveal an irregular spin state structure with S = 5/2 ground state and an antiferromagnetic interaction between the central copper(II) and the chromium(III) atoms (J = −18.8 cm−1.
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Key words
heteropolymetallic systems,crystal structures,copperii,magnetic properties
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