Thiourea N- and S-Derivatives as Ligands: Synthesis and Crystal Structure of 4CuCl · 6All–NHCSNH2 and [(All–NH)2C–SC2H5]Cu2ClxBr3 – x (x = 0.765, All is Allyl)
Crystals of the compounds 4CuCl · 6CH2=CH–CH2–NHCSNH2 (I) and [(CH2=CH–CH2–NH)2C–SC2H5]Cu2ClxBr3 – x (x = 0.765) (II) were synthesized by the ac electrochemical method, and their crystal structures were determined (CuKα and MoKα radiation, 2575 and 1090 unique reflections with F ≥ 4σ(F), R = 0.050 and 0.028 for I and II, respectively). Complex I crystallizes in space group C2/c, a = 17.230(7) Å, b = 12.258(5) Å, c = 42.95(2) Å, β = 97.48(4)°, V = 8994(7) Å3, Z = 8. The structure of π-complex II is described by space group P21/n, a = 10.633(5) Å, b = 9.280(5) Å, c = 16.024(4) Å, γ = 102.16(3)°, V = 1546(1) Å3, Z = 4. Complex I is built from isolated units of the aforementioned composition; every allylthiourea molecule coordinates two metal atoms through the sulfur atom. The distorted tetrahedral surrounding of every Cu(I) atom involves three S atoms and one Cl atom. The N,N"-diallyl-S-ethylisotiouronium cation coordinates two copper atoms through the C=C bonds, 1.32(1) and 1.35(1)Å, uniting the cuprohalide chains in layers. The structure of complex II is very close to the structure of the previously studied π-complex of diallylammonium [H+L]Cu2Cl3.
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- 1.Filinchuk, Ya.E., Oliinik, V.V., and Schollmeier, D., Koord. Khim., 1999, vol. 25, no. 3, p. 226.Google Scholar
- 2.Oliinik, V.V., Goreshnik, E.A., Schollmeier, D., and Mys'kiv, M.G., Koord. Khim., 1997, vol. 23, no. 7, p. 548.Google Scholar
- 3.Filinchuk, Ya.E., Schollmeier, D., Oliinik, V.V., et al., Koord. Khim., 1996, vol. 22, no. 11, p. 870.Google Scholar
- 4.Spofford, W.A. and Amma, E.L., Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem., 1970, vol. 26, no. 10, p. 1474.Google Scholar
- 5.Okaya, Y. and Knobler, C.B., Acta Crystallogr., 1964, vol. 17, no. 7, p. 928.Google Scholar
- 6.Oliinik, V.V., Schollmeier, D., Filinchuk, Ya.E., and Mys'kiv, M.G., Koord. Khim., 1998, vol. 24, no. 1, p. 52.Google Scholar
- 7.Weygand, C. and Hilgetag, G., Organische-chemische Experimentierkunst, Leipzig: J. A. Barth, 1970, 4th ed. Translated under the title Metody eksperimenta v organicheskoi khimii, Moscow: Khimiya, 1968.Google Scholar
- 8.Aksel'rud, L.G., Grin', Yu.N., Zavalii, P.Yu., et al., Paket programm dlya strukturnogo analiza kristallov CSD. Obshchee opisanie (Program Package for Structural Analysis of CSD Crystals. General Account), Lvov: Lvov. Gos. Univ., 1990.Google Scholar
- 9.Sheldrick, G.M., SHELXL97: Program for the Refinement of Crystal Structures, Germany: Univ. of Göttingen, 1997.Google Scholar
- 10.Pakawatchai, C., Thanyasirikul, Y., Saepae, T., et al., Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 1998, vol. 54, no. 12, p. 1750.Google Scholar
- 11.Filinchuk, Ya.E. and Mys'kiv, M.G., Koord. Khim., 1999, vol. 25, no. 5, p. 376.Google Scholar
- 12.Oliinik, V.V., Glovyak, T., and Mys'kiv, M.G., Koord. Khim., 1999, vol. 25, no. 10, p. 790.Google Scholar