Crystal and Molecular Structure of Pyridine and 3-methylpyridine Adducts of [N,N-bis[(5-chloro-2-hydroxyphenyl)phenylmethylene]-4-thiaheptane-1,7-diaminato] Cobalt(II) and -nickel(II)
Abstract
Complexes of N,N-bis[(5-chloro-2-hydroxyphenyl)phenylmethylene]-4-thiaheptane-1,7-diamine (cbpSH2) and 3-methylpyridine (mpy) or pyridine (py) with cobalt(II) and nickel(II), [Co(cbpS)mpy], [Ni(cbpS)mpy], and [Ni(cbpS)py], have been synthesized and studied by single-crystal x-ray diffraction. In each case the metal complexes were found to consist of distorted octahedra, with the pentadentate ligand forming a square pyramid about the metal atom, having approximately linear N-M-N′ and O-M-O′ arrangements. The Lewis base mpy or py occupies the sixth octahedral position, opposite the sulfur atom. The metal-thioether bond is of special interest, and in each case this is found to be a normal metal-sulfur bond (Ni, 2.484 (1) Å; Co, 2.537 (1) Å). Although the formation of this bond, especially in the cobalt(II) complex, is unexpected from earlier literature data, it is proposed that such bonds are not the exception but the rule. Each of the three complexes contains a small amount of solvent included in the crystal lattice and the solvent molecules could not be fully located due to extreme positional disorder. No unsolvated complexes were obtained in crystalline form. Crystal data for [Co(cbpS)mpy]: space group P21/c, Z = 4, a = 16.456 (7) Å, b = 14.74 (1) Å, c = 16.56 (1) Å, β = 112.79 (5)°, V = 3704 Å3, R = 3.7%, 2825 reflections. Crystal data for [Ni(cbpS)mpy]: space group P21/c, Z = 4, a = 16.450 (6) Å, b = 14.674 (1) Å, c = 16.59 (1) Å, β = 112.56 (3)°, V = 3698 Å3, R = 3.7%, 2103 reflections. Crystal data for [Ni(cbpS)py]: space group P21/c, Z = 4, a = 18.002 (9) Å, b = 15.691 (4) Å, c = 16.401 (9) Å, β = 116.07 (4)°, V = 4164 Å3, R = 4.6%, 4466 reflections.
Recommended Citation
E. M. Boge et al., "Crystal and Molecular Structure of Pyridine and 3-methylpyridine Adducts of [N,N-bis[(5-chloro-2-hydroxyphenyl)phenylmethylene]-4-thiaheptane-1,7-diaminato] Cobalt(II) and -nickel(II)," Inorganic Chemistry, American Chemical Society (ACS), Jan 1977.
The definitive version is available at https://doi.org/10.1021/ic50168a049
Department(s)
Chemistry
International Standard Serial Number (ISSN)
0020-1669
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 1977 American Chemical Society (ACS), All rights reserved.
Publication Date
01 Jan 1977
