Комплексы меди [CuBr2(DMSO-O)3] и [Cu(DMSO-O)4SF6]. Синтез и строение

Abstract

The dissolution of copper (II) bromide and copper (II) fluoride in the presence of hydrofluoric acid in dimethyl sulfoxide, followed by slow evaporation of the solvent, have synthesized copper complexes [CuBr 2 (DMSO- O ) 3 ] ( 1 ) and [Cu(DMSO- O ) 4 SF 6 ] ( 2 ). They have been structurally characterized. The X-ray diffraction pattern has been obtained at 293 K on an automatic diffractometer D8 Quest Bruker (Mo K α -radiation, λ = 0.71073 Å, graphite monochromator) of crystals 1 [C 6 H 18 O 3 S 3 Br 2 Cu, M 457,74, the monoclinic syngony, the symmetry group P 2 1 /c; cell parameters: a 8.812(6), b 15.335(11), c 12.272(8) Å, α = 90.00 degrees, β = 105.82(3) degrees, γ = 90,00 degrees; V = 1595.5(19)Å 3 ; the crystal size is 0.59 × 0.32 × 0,24 mm; intervals of reflection indexes are –13 ≤ h ≤ 11, –23 ≤ k ≤ 23, –18 ≤ l ≤ 18; total reflections 45529; independent reflections 5832; R int 0.0971; GOOF 1.001; R 1 = 0.0497, wR 2 = 0.1073; residual electron density 0.77/–1.36 e/Å 3 ] and 2 [C 8 H 24 O 4 F 6 S 5 Cu, M 522.11, the triclinic syngony, the symmetry group P –1; cell parameters: a 10.325(18), b 10.428(18), c 10.60(2) Å, α = 77.93(11) degrees, β = 89.49(9) degrees, γ = 68.12(6) degrees; V = 1033(3) Å 3 ; the crystal size is 0.47×0.16×0.13 mm; intervals of reflection indexes are –11 ≤ h ≤ 11, –12 ≤ k ≤ 12, –12 ≤ l ≤ 12; total reflections 9324; independent reflections 3307; R int 0.0709; GOOF 1.029; R 1 = 0.0555, wR 2 = 0.1309; residual electron density 0.64/–0.82 e/Å 3 ], the copper atoms have a distorted square-pyramidal coordination (the trans -OCuO and trans -OCuBr angles are 165.68(11)° and 143.37(10)° ( 1 ); trans -OCuO are 163.8(2), 169.0(2)° ( 2 ); the Cu-Br and Cu-O bond lengths are 2.4681(14) Å and 2.5922(14) Å ( 1 ), 1.944(3)–2.054(3) Å ( 1 ) and 1.940(6)–1.956(5) Å ( 2 ) respectively). Fragment SF 6 in 2 (the FSF trans -angles 178.8(2)–179.7(3)°, cis -angles 88.7(2)–91.0(3)°) linked to the central copper atom (the Cu–F bond length 2.208(6) Å). The structural organization of crystals 1 and 2 is controlled by intermolecular bonds O (DMSO) ∙∙∙H–С (DMSO) (2,57 Å) and Cu–Br∙∙∙H–C (DMSO) (2.89–3.04 Å) ( 1 ), S–F∙∙∙H–C (DMSO) (2.32–2.60 Å) ( 2 ). Complete tables of coordinates of atoms, bond lengths and valence angles for structures 1 and 2 are deposited at the Cambridge Structural Data Bank (no. 1883471, 1898916; deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk).