Cis versus trans arrangement of dithiocarbazate ligands in bis-chelated Ni and Cu complexes

Abstract

The structures are described of two bis-chelated metal complexes of nickel(II) and copper(II) with S-n-hexyl 3-(1-phenylethylidene)dithiocarbazate Schiff bases in a cis configuration, namely, bis[S-n-hexyl 3-(1-phenylethylidene)dithiocarbazato-κ2 N 3,S]nickel(II), [Ni(C15H21N2S2)2], and bis[S-n-hexyl 3-(1-phenylethylidene)dithiocarbazato-κ2 N 3,S]copper(II), [Cu(C15H21N2S2)2]. In both complexes, the metals have distorted square-planar geometries. A search in the Cambridge Structural Database [Groom et al. (2016). Acta Cryst. B72, 171–179] for bis-chelated nickel(II) and copper(II) complexes with similar Schiff bases retrieved 55 and 36 hits for the two metals, respectively. An analysis of the geometrical parameters of complexes showing cis and trans configurations is reported and the values compared with those for the complexes described in this work.

Crystal structure of S-n-octyl 3-(1-phenylethylidene)dithiocarbazate and of its bis-chelated nickel(II) complex

“…Correspondingly the N2-C9 bond of 1.340 (4) A ˚in HL shortens to essentially double bonds of 1.293 (3) and 1.290 (2) A ˚in the complex, while the N1-N2 bond length of 1.377 (4) A ˚is slightly elongated in the complex [to 1.414 (2) and 1.417 (2) A ˚, see the supporting information]. These parameters agree with those in previously reported Ni II complexes with similar ligands (Begum et al, 2016(Begum et al, , 2017(Begum et al, , 2020(Begum et al, , 2023Howlader et al, 2015;Islam et al, 2014;Khan et al, 2023;Zangrando et al, 2015). Upon coordination the ligand L undergoes a rotation of ca.…”

“…An analysis of dithiocarbazate ligands in bis-chelated Ni and Cu complexes of cis and trans arrangement was reported by us earlier (Begum et al, 2020). Among the Ni II complexes with dithiocarbazate Schiff base N,S-ligands having long alkyl chains, the cis configuration was observed in derivatives with a phenylethylidene fragment bound at N1 (Zangrando et al, 2015;Begum et al, 2020), as in the present complex.…”

“…Numerous Ni II complexes with dithiocarbazate ligands have been reported from these laboratories (Begum et al, 2016(Begum et al, , 2017(Begum et al, , 2020(Begum et al, , 2023Howlader et al, 2015;Islam et al, 2014;Khan et al, 2023;Zangrando et al, 2015; CSD refcodes = JUYCAJ, WEGKEB, TILVUJ, PICMOH, LUBYAK, MIXRAO, MIMKIG and LUBNON, respectively).…”

Crystal structure of bis{S-octyl-3-[(thiophen-2-yl)methylidene]dithiocarbazato-κ2 N 3,S}nickel(II)

“…For comparison, Ni II complexes with comparable ligands bearing long alkyl chains have been reported from these laboratories (Begum et al, 2016(Begum et al, , 2017(Begum et al, , 2018(Begum et al, , 2020(Begum et al, , 2023; CSD refcodes = JUYCAJ, WEGKEB, BIQTIH, TILVUJ and PICMOH, respectively).…”

“…These values agree with those reported in previous papers (Begum et al, 2016;Islam et al, 2014;Howlader et al, 2015) for related compounds. It is worth mentioning that nickel(II) and copper(II) complexes with dithiocarbazate ligands have been reported to crystallize in both cis and trans configurations, although the latter is slightly more frequent (Begum et al, 2020).…”