Layered solids based on second-sphere coordination interactions: synthesis, spectroscopic characterization, crystal structure and packing of two copper(II) naphthalene-2-sulfonates

• DOI: 10.1016/j.molstruc.2004.12.038
• Publication Date: 2005-02-11T14:15:45Z
• Authors: Raj Pal Sharma; Rajni Sharma; Ritu Bala; Urszula Rychlewska; Beata Warżajtis
• Keywords: Triclinic crystal system; Monoclinic crystal system; Ethylene diamine

Abstract [Cu(H 2 O) 6 ](C 10 H 7 SO 3 ) 2 1 was obtained from reaction of CuCO 3 ·Cu(OH) 2 and naphthalene-2-sulphonic acid in aqueous medium in 1:4 molar ratio. It crystallizes in the monoclinic space group P 2 1 / n with a =7.0582(3) A, b =6.2666(3) A, and c =27.1420(10) A, β =92.678(4)°, Z =2. The structure was determined from 1986 observed reflections and refined to R =0.033. When ethylenediamine was added to hexaaquacopper(II) naphthalene-2-sulfonate dissolved in water, [Cu(en) 2 (H 2 O) 2 ](C 10 H 7 SO 3 ) 2 2 was obtained which crystallizes in the triclinic space group P 1 ¯ with a =7.1491(5) A, b =7.1949(5) A, and c =14.6500(10) A, α =99.025(6)°, β =98.976(6)°, and γ =104.262(6)°, Z =1. The structure was determined from 2296 observed reflections and refined to R =0.0313. X-ray structure determination of 1 revealed an ionic structure consisting of [Cu(H 2 O) 6 ] +2 and two naphthalene-2-sulfonate anions while that of 2 contains [Cu(en) 2 (H 2 O) 2 ] 2+ cation and two naphthalene-2-sulfonate anions. Characteristic for the studied crystals is the alternated-layer arrangement of complex cations and naphthalene-2-sulfonate anions, linked together via hydrogen bonding, and the presence of a particularly robust R 2 2 ( 8 ) hydrogen-bonding motif that joins the complex cation with two oxygen atoms of the same sulfonate group. Elemental analyses, IR, UV/vis spectroscopic studies are consistent with the structures revealed by X-ray structure determination.