Unactivated copper metal powder and zinc oxide readily react with ethylenediamine (en) in nonaqueous [methanol, dimethylformamide (dmf), dimethyl sulfoxide (dmso), acetonitrile] solutions of ammonium salts under ambient conditions producing, in high yields, a series of heterobimetallic complexes of general formula [Cu(en) 2 ZnX 4 ]·(Solv), where X = Cl, Br, NCS, CH 3 COO (OAc); Solv = dmf, dmso, CH 3 CN, H 2 O. The single-crystal X-ray analysis of the complexes reveals chain structures, which are based on the completion of the octahedral coordination of Cu II by two bridging X atoms from ZnX 4 2− . The ZnX 4 2− is shown to be a distorted tetrahed-
A novel heterometallic 1D coordination polymer [{Ni(en)2}2(micro-NCS)4Cd(NCS)2](n) x nCH3CN (en = ethylenediamine) has been prepared using the self-assembly process in a one-pot reaction of cadmium oxide, nickel and ammonium thiocyanates with an acetonitrile solution of ethylenediamine. The complex consists of an uncommon cis-Cd(SCN)4(NCS)2(4-) fragment and a rare combination of cis-Ni(en)2(2+) and trans-Ni(en)2(2+) building blocks linked by micro(1,3)-NCS bridges into a double-stranded zigzag chain structure. Each chain is comprised of [Ni2Cd2(micro-NCS-N,S)4)] macrocycles with chair-like and rectangular-like shapes arrayed alternately. The shortest intrachain CdCd separations are 9.535(1) and 10.868(2) A, while the nearest NiNi distances are 5.418(1) and 6.612(2) A. A network of weak N-HS hydrogen bonds, involving the terminal NCS ligands and NH2-groups of en, links the infinite chains and results in the formation of an extended supramolecular three-dimensional framework. Variable-temperature (1.8-300 K) magnetic susceptibilities show a slight change of the micro(B) value at low temperature, indicative of weak antiferromagnetic interactions (J = 1.55 cm-1) between magnetic canters. High-field, high-frequency (100-400 GHz) EPR spectra were simulated using S = 1 ground state for separate Ni2+ ions with the spin Hamiltonian parameters g = 2.165, D = 0.45 cm-1 and E = 0.03 cm(-1). According to DFT calculations, the D and E parameters are -0.35 cm(-1) and 0.049 cm-1 for the cis arrangement of Ni2+ and 0.58 cm(-1) and 0.012 cm(-1) for trans.
Synthesis, Zinc, Nickel(II), Triethylenediamine, X-RayThe peculiarities of the formation of zinc and nickel(II) complexes by interaction of metal powder or metal oxide with ammonium salts (halides, nitrate, thiocyanate) were investigated in non-aqueous solutions (methanol, acetonitrile, N,N-dimethylformamide=DMF, dimethylsulfoxide=DMSO) in presence of l,4-diazabicyclo[2.2.2]octane. The stoichiometry of the com plexes was found to depend on the initial reagent ratio Ni/ZnOiNfLX and Ni/ZnO:Ten. The compounds of compositions Z n(H Ten)(H 20)(N 03)3 and Ni(HTen)(Ten)Cb were character ized by X-ray crystallography. Both complexes contain five-coordinate metal atoms. The zinc compound possesses monomeric molecular structure whilst the nickel complex is polymeric.
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