Archive / Volume LXXVIII 2025

Alona LUBA-ONUFRIICHUK, Oleksii PAVLYUK

Ivan Franko National University of Lviv, Kyryla і Mefodiya Str., 6, 79005 Lviv, Ukraine
e-mail: alona.luba@lnu.edu.ua

DOI:

COMPLEXATION OF CU(I) HALIDES WITH N-ALLYLTHIOMORPHOLINE DERIVATIVES: SYNTHESIS AND CRYSTAL STRUCTURES OF [C₄H₈NS(C₃3H5)2CuBr2] AND C4H8NS(C3H5)2I

Two new compounds based on N,N′-diallylthiomorpholinium derivatives were synthesized using alternating current electrochemical synthesis and structurally characterized by single-crystal X-ray diffraction. The Cu(I) complex [C₄H₈NS(C₃H₅)₂CuBr₂] (1) was obtained from an ethanol solution of CuBr₂ and the organic bromide salt C₄H₈NS(C₃H₅)₂Br: space group P21/c, Z = 4, a = 8,1635(4), b = 13,3270(6), c = 13,1121(7) Å, β = 104,310(5)°, V = 1382,27(12) Å3, calc. = 1,959 г/см3, (MoK) = 7,48 mm−1, max. = 28,9, 20071 measured, 3169 used reflections, R(F2) = 0,025, S = 1,02. The crystal structure reveals that the copper(I) center is tetrahedrally coordinated by one sulfur atom from the heterocyclic ligand and three bromide ions, forming a distorted [CuSBr₃] polyhedron (τ₄ = 0.87). Bridging bromide atoms link two such units into a dimeric {Cu₂L₂Br₄} motif, stabilized by weak intermolecular C–H···Br hydrogen bonds. Notably, the allyl groups of the organic cation remain uncoordinated. In contrast, electrochemical synthesis from an acetonitrile solution of C₄H₈NS(C₃H₅)₂Br and iodine yields the iodide salt C₄H₈NS(C₃H₅)₂I (2), which does not form a Cu(I) complex: space group P21/c, Z = 4, a = 10,1197(6), b = 8,7394(6), c = 14,5837(9) Å, β = 102,702(6), V = 1258,22(14) Å3, calc. = 1,643 г/см3, (MoK) = 2,67 mm−1, max. = 29,0, 6518 measured, 2777 used reflections, R(F2) = 0,033, S = 1,05. Its crystal structure shows partial disorder of one allyl group over two positions with comparable occupancy, and the lattice is stabilized only by weak C–H···I interactions. These results highlight the different coordination behavior of bromide and iodide anions in the presence of soft sulfur-donor ligands, and emphasize the structural impact of halide identity on Cu(I) complex formation with N-allyl-substituted heterocycles.

Keywords: Cu(I) complexes, N-allyl derivatives, thiomorpholine, crystal structure, electrochemical synthesis, halide ligands.

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