Crystal structure determination, and dft calculations of DICHLOROBIS(DIMETHYLSULFOXIDE-O)COPPER(II)
H. Chebbi1,2, M. Chebbi2, A. Guesmi2, Y. Arfaoui2
1University of Monastir, Tunisia
2University of Tunis El Manar, 2092, Tunisia
Keywords: crystal structure, DFT calculation, FT-IR, UV-visible spectroscopy
Abstract
The crystal structure of dichlorobis(dimethylsulfoxide-O)copper(II), [CuCl2(DMSO)2] (I), previously determined by Willett and Chang, is reinvestigated. It crystallizes in the orthorhombic system with the space group Pnma (N°62), Z = 4, and unit cell parameters a = 8.053(1) Å, b = 11.642(5) Å, c = 11.347(3) Å. Our structure determination is of a significantly higher precision in terms of bond lengths, angles, and R factors (e.g., Cu1-O1 = 1.9737(24) Å, O1-Cu1-O1i = 173.08(13)° (symmetry code: i x , 1/2- y , z ) and R ( F 2) = 0.046 compared to 1.955(4) Å, 173.0(3)° and R ( F ) = 0.075). In contrast to the previous investigation, all H atoms are placed at calculated positions. In the title molecule, the CuII atom is five coordinated in a distorted square pyramidal geometry. Thus, as reported previously, it can be shown that the crystal structure consists of [CuCl2(DMSO)2] molecules which, by virtue of long Cu-Cl interactions, are tied together to form chains parallel to the [100] direction. The density functional theory (DFT) optimized structure at the B3LYP/6-311++G(2 d ,2 p ) level is compared with the experimentally determined molecular structure. The HOMO-LUMO energy gap and other related molecular properties are also calculated. Comprehensive experimental and theoretical structural studies on the studied complex are carried out by FT-IR and UV-visible spectroscopies.
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