Thiourea N- and S-Derivatives as Ligands: Synthesis and Crystal Structure of 4CuCl · 6All–NHCSNH2 and [(All–NH)2C–SC2H5]Cu2ClxBr3x (x = 0.765, All is Allyl)

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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 (Cu Kα and Mo Kα 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 P21n, 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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