摘要：

The structure of an organic disulfide complex of Ni(II), chloro[bis[2-[(2-pyridylmethyl)imino]phenyl] disulfide]nickel(II) perchlorate, alternatively named chloro[α,α′-[dithiobis(o-phenylenenitrilo)]di-2-picoline] nickel(II) perchlorate or [Ni(py-CH=N-ph-S-S-ph-N=CH-py)Cl](ClO4) where py is α-substituted C5H4N and ph is ortho-substituted C6H4, has been determined by single-crystal X-ray diffraction techniques using a small crystal and a scintillation counter. After near-full-matrix least-squares refinement using anisotropic temperature factors only for atoms heavier than carbon, the conventional R index converged at 0.058. The brown monoclinic needles form in the space group P21/c with a = 16.249 (33) , b = 9.558 (11) , c = 16.685 (13) , β = 100.34 (12)°, and Z = 4. The organic disulfide coordinates to Ni(II) at five of its six octahedral sites, with the sixth site being occupied by a chloride ion. One sulfur atom of the disulfide group is coordinated to Ni(II) at a distance of 2.470 (5) . Half of the ligand is nearly planar, retaining its conjugation; the other half is twisted 92 (1)° about its ph-N bond, destroying the conjugation through that bond and causing it to lengthen from 1.430 (14) to 1.49 (2) . The S-S bond (2.089 (8) ), the CSSC torsion angle (55.4 (10)°), and the C-S bonds (1.76 (2) ) have been altered significantly due to intraligand electronic factors and to the stereochemical requirements of the coordination environment about the Ni(II) ion (the near-right "octahedral" angles range from 76.2 (5) to 101.9 (4)°). A structural trans effect involving the nickel(II)-imine nitrogen bonds has been observed; the bond trans to chloride is longer (2.07 (2) A") than that trans to a pyridyl nitrogen (2.02 (2) A"). Preliminary Weissenberg photographs indicate that the corresponding tetrafluoroborate salt is isostructural.

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