Thiourea N- and S-derivatives as ligands: Synthesis and crystal structure of 4CuCl center dot All-NHCSNH2 and [(All-NH)(2)C-SC2H5]Cu2ClxBr3-x (x=0.765, All is allyl)

Crystals of the compounds 4CuCl . 6CH(2)=CH-CH2-NHCSNH2 (I) and [(CH2=CH-CH 2-NH)(2)CSC2H5]Cu2ClxBr3-x (x = 0.765) (II) were synthesized by the ac elec trochemical method, and their crystal structures were determined (CuKalpha and MoKalpha radiation, 2575 and 1090 unique reflections with F greater tha n or equal to 4 sigma (F), R = 0.050 and 0.028 for I and II, respectively). Complex I crystallizes in space group C2/c, a = 17.230(7) Angstrom, b = 12 .258(5) Angstrom, c = 42.95(2) Angstrom, beta = 97.48(4)degrees, V= 8994(7) Angstrom (3), Z = 8. The structure of pi -complex II is described by space group P2(1)/n, a = 10.633(5) Angstrom, b = 9.280(5) Angstrom, c = 16.024(4) Angstrom, gamma = 102.16(3)degrees V=1546(1) Angstrom (3), Z = 4. Complex I is built from isolated units of the aforementioned composition; every all ylthiourea molecule coordinates two metal atoms through the sulfur atom. Th e distorted tetrahedral surrounding of every Cu(I) atom involves three 8 at oms and one Cl atom. The N,N'- diallyl-S-ethylisotiouronium cation coordina tes two copper atoms through the C=C bonds, 1.32(1) and 1.35(1)Angstrom, un iting the cuprohalide chains in layers. The structure of complex II is very close to the structure of the previously studied pi -complex of diallylamm onium [H+L]Cu2Cl3.