Syntheses and coordination isomerism of heteroleptic divalent-metal (M = Co, Zn) carbazate complexes

Krishnan Srinivasan, Ayyasamy Kathiresan, William T. A. Harrison, Subbaiah Govindarajan*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

21 Citations (Scopus)

Abstract

Three heteroleptic divalent-metal alkyl-carbazate-thiocyanate complexes, [M(NCS)2(NH2NHCOOR)2] [M = Co and R = CH2CH3 (1); M = Co and R = CH3 (2); M = Zn and R = CH3 (3)], have been prepared and characterized, and their crystal structures determined. In 1, Co(II) adopts a fairly regular centrosymmetric trans-CoO2N4 octahedral geometry arising from its coordination by two N,O-bidentate ethylcarbazate ligands and two trans N-bonded thiocyanates. In isostructural 2 and 3, the metals adopt distorted cis-MO2N4 octahedral geometries arising from two N,O-bidentate methylcarbazate ligands with cis N-bonded thiocyanates. The crystal structures feature N-HO and N-HS interactions. Thermal analysis data show that these compounds begin to decompose at temperatures between 130 and 160 °C. Crystal data: 1, CoC8H16N6O4S2, Mr = 383.32, P21/n (No. 14), a = 5.2599(3) Å, b = 7.4209(4) Å, c = 20.1948(12) Å, β = 94.070(1)°, V = 786.28(8) Å3, Z = 2, R(F) = 0.028, wR(F2) = 0.073; 2, CoC6H12N6O4S2, Mr = 355.27, P21/n (No. 14), a = 7.8663(3) Å, b = 10.5804(3) Å, c = 17.6313(5) Å, β = 102.019(10)°, V = 1435.26(8) Å3, Z = 4, R(F) = 0.036, wR(F2) = 0.097; 3, ZnC6H12N6O4S2, Mr = 361.71, P21/n (No. 14), a = 7.8883(2) Å, b = 10.5756(3) Å, c = 17.5827(5) Å, β = 101.676(1)°, V = 1436.46(7) Å3, Z = 4, R(F) = 0.031, wR(F2) = 0.084.

Original languageEnglish
Pages (from-to)3324-3334
Number of pages11
JournalJournal of Coordination Chemistry
Volume67
Issue number20
Early online date9 Oct 2014
DOIs
Publication statusPublished - Oct 2014

Keywords

  • Bidentate ligand
  • Coordination isomerism
  • Crystal structure
  • Thiocyanate anion

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