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The bis{(μ2-chloro)[2-(imidazol-4-yl)ethyl][(1-methylimidazol-2-yl)methyl]amine}dicopper(II) bis[tetrachloro-cuprate (II)] complex [Cu2(HISMIMA)2Cl2]2(CuCl4)2 (HISMIMA:[(2-(imidazol-4-yl)ethyl)(1-methylimidazol-2-yl)methyl)amine]) was obtained by serendipity during the reaction of the mononuclear [Cu(HISMIMA)Cl2] complex and gaseous nitric oxide in methanolic solution. The title complex unit cell has the composition: an anion complex {[Cu2(HISMIMA)2Cl2][CuCl4]2}2- (1) and a cation complex [Cu2(HISMIMA)2Cl2]2+ (2). Cation 2 displays a crystallographic centrosymmetric Cu2Cl2 core with each CuII atom coordinated to the tripodal ligand in a square pyramidal geometry (Addison parameter τ=0.07). In 1, a distorted octahedral geometry is observed, in which the CuII ions are coordinated in a way similar to that in 2 but with an additional interaction with the [CuCl4]2- ions. Cyclic voltammetric experiments reveal that the title complex does not dissociate in acetonitrile solution and has E1/2=-0.24 V vs NHE (ΔEp=0.19 V, ipa/ipc=0.75) for the CuIICuII to CuICuI process at the Cu(μ-Cl)2Cu core. [Copyright &y& Elsevier]

Abstract: Pure N,N′-di(methoxycarbonylsulfenyl)urea, [CH3OC(O)SNH]2CO, is quantitatively prepared by the hydrolysis reaction of CH3OC(O)SNCO and characterized by 1H NMR, GC–MS and FTIR spectroscopy techniques. Structural and conformational properties are analyzed using a combined approach with data obtained from X-ray diffraction, vibrational spectra and theoretical calculation methods. The IR and Raman spectra for normal and deuterated species are reported. The crystal structure of [CH3OC(O)SNH]2CO was determined by X-ray diffraction methods. The substance crystallizes in the orthorhombic P21212 space group with a =9.524(2), b =12.003(1), c =4.481(1)Å, and Z =2 moieties in the unit cell. The molecule is sited on a twofold crystallographic axis (C 2) parallel to c and shows the anti–anti conformation (S–N single bonds antiperiplanar with respect to the opposite C–N single bonds in sulfenyl-ureasic group). Neighboring molecules are arranged in a chain motif that extends along the C 2-axis and is held by bifurcated NH⋯O⋯HN intermolecular bonds. A local planar symmetry is observed in the crystal for the central –SN(H)C(O)N(H)S– skeleton. Experimental and calculated data allow to trace this structural feature to the occurrence of N–H⋯On bonding interactions. Calculated vibrational and structural properties are in good agreement with the experimentally determined features. [Copyright &y& Elsevier]