Synthesis and structure of a complex of copper(I) with l-cysteine and chloride ions containing Cu12S6 nanoclusters.

Daut Islamov,Siegfried Schindler,Nikita Serov,Valery Shtyrlin,Amir Gizatullin,Alexander Klimovitskii,Jonathan Becker

doi:10.1107/s2056989021002012

Abstract

The title hydrated copper(I)-l-cysteine-chloride complex has a polymeric structure of composition {[Cu16(CysH2)6Cl16]·xH2O} n [CysH2 = HO2CCH(NH3 +)CH2S- or C3H7NO2S], namely, poly[[tetra-μ3-chlorido-deca-μ2-chlorido-di-chlorido-hexa-kis-(μ4-l-cysteinato)hexa-deca-copper] polyhydrate]. The copper atoms are linked by thiol-ate groups to form Cu12S6 nanoclusters that take the form of a tetra-kis cubocta-hedron, made up of a Cu12 cubo-octa-hedral subunit that is augmented by six sulfur atoms that are located symmetrically atop of each of the Cu4 square units of the Cu12 cubo-octa-hedron. The six S atoms thus form an octa-hedral subunit themselves. The exterior of the Cu12S6 sphere is decorated by chloride ions and trichlorocuprate units. Three chloride ions are coordinated in an irregular fashion to trigonal Cu3 subunits of the nanocluster, and four trigonal CuCl3 units are bonded via each of their chloride ions to a copper ion on the Cu12S6 sphere. The trigonal CuCl3 units are linked via Cu2Cl2 bridges covalently connected to equivalent units in neighboring nanoclusters. Four such connections are arranged in a tetra-hedral fashion, thus creating an infinite diamond-like net of Cu12S6Cl4(CuCl3)4 nanoclusters. The network thus formed results in large channels occupied by solvent mol-ecules that are mostly too ill-defined to model. The content of the voids, believed to be water mol-ecules, was accounted for via reverse Fourier-transform methods using the SQUEEZE algorithm [Spek (2015 ▸). Acta Cryst. C71, 9-18]. The protonated amino groups of the cysteine ligands are directed away from the sphere, forming N-H⋯Cl hydrogen bonds with chloride-ion acceptors of their cluster. The protonated carb-oxy groups point outwards and presumably form O-H⋯O hydrogen bonds with the unresolved water mol-ecules of the solvent channels. Disorder is observed in one of the two crystallographically unique [Cu16(CysH2)6Cl16] segments for three of the six cysteine anions.

Highlights

The title hydrated copper(I)–l-cysteine–chloride complex has a polymeric structure of composition {[Cu16(CysH2)6Cl16]ÁxH2O}n [CysH2 = HO2CCH(NH3+)CH2SÀ or C3H7NO2S], namely, poly[[tetra-3-chlorido-deca2-chlorido-dichloridohexakis(4-l-cysteinato)hexadecacopper] polyhydrate]
The copper atoms are linked by thiolate groups to form Cu12S6 nanoclusters that take the form of a tetrakis cuboctahedron, made up of a Cu12 cubooctahedral subunit that is augmented by six sulfur atoms that are located symmetrically atop of each of the Cu4 square units of the Cu12 cubo-octahedron
The copper atoms are linked by thiolate groups to form Cu12S6 copper thiolate nanoclusters (‘atlas spheres’), which have the form of a tetrakis cuboctahedron, made up of a Cu12 cubo-octahedral subunit that is augmented by six sulfur atoms that are located symmetrically atop of each of the Cu4 square units of the Cu12 cubo-octahedron

Summary

Supramolecular features

The ‘atlas spheres’ are linked to form a threedimensional framework with the Cu2Cl2 linkages forming a tetrahedral environment in each of the clusters (Fig. 3). It is not possible to give an exact description of the topology (O’Keeffe et al, 2008) These bridges are based on the 3-Cl atoms described above, with the exception of Cl15 and eight copper atoms in a distorted tetrahedral environment (four such atoms per cage); ,. Symmetry codes: (i) Àx þ 12; y þ 12; Àz þ 1; (ii) Àx þ 12; y À 12; Àz þ 1; (iii) Àx þ 12; y þ 12; Àz; (iv) Àx þ 12; y À 12; Àz; (v) Àx þ 1; y; Àz

Database survey

Findings

Refinement