Chemistry and Physics Faculty Articles

Title

Coordination Chemistry of New Sulfur-Containing Ligands. 22. Synthesis and Structure of bis(pyridine)bis(pyrrole-N-carbothioato)nickel(II), Ni(SOCNC4H4)2(C5H5N)2. Evidence for New Resonance Forms in Monothiocarbamates

Document Type

Article

Publication Date

6-1982

Publication Title

Inorganic Chemistry

ISSN

0020-1669

Volume

21

Issue/No.

6

First Page

2365

Last Page

2368

Abstract

This bis(pyridine) adduct of the Ni(II) complex of pyrrole-N-carbothioate, Ni(ptc)2(py)2 has been synthesized by the addition of pyridine to a THF solution of Ni2(ptc)4·3THF. The crystal and molecular structure of the title compound has been solved by a single-crystal X-ray diffraction study at room temperature. The compound crystallizes in the centrosymmetric monoclinic space group P21/c with a = 11.423 (5) Å, b = 9.415 (4) Å, c = 21.651 (11) Å, β = 112.92 (3)°, V = 2145 (2) Å, and dcbod (dcalcd) = 1.46 (1.45) g/cm3 for a mol wt = 469.2 and Z = 4. Diffraction data were collected with a Syntex P1 diffractometer using Mo Kα radiation (λ = 0.71069 Å). The nickel atom was located from a Patterson synthesis, and all other nonhydrogen atoms were located via difference Fourier techniques. Hydrogens were placed in calculated positions whenever necessary. Least-squares refinement resulted in RF = 6.9% and “goodness-of-fit” = 1.28 for all 1469 reflections having I ≥ 3σ(I) with 5° < 2θ < 42°. The molecules are well separated and monomeric. The coordination geometry about the Ni atom is best described as a distorted octahedron. The arrangement of the nitrogen, sulfur, and oxygen donor atoms is discussed in terms of the trans influence. In addition, bond distances and angles indicate little or no contribution from the resonance form usually associated with monothiocarbamates. Comparisons between this new (aromatic) monothiocarbamate and dialkylmonothiocarbamates are made.

Comments

©1982 American Chemical Society

DOI

10.1021/ic00136a049

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