A new copper-antimony sulfide, [C 4 H 12 N 2 ] 0.5 [CuSb 6 S 10 ], has been hydrothermally synthesized from binary metal sulfides in the presence of triethylenetetramine and characterized by single-crystal X-ray diffraction, thermogravimetry, elemental analysis, and SQUID magnetometry. The product (M r ) 1158.72) crystallizes in the monoclinic space group P2 1 /n with a ) 11.2578(4) Å, b ) 12.5259(5) Å, c ) 13.9390(7) Å, β ) 102.445(3)°, and V ) 1919.4 Å 3 . The structure consists of cyclic Sb 3 S 6 3units in a boatlike conformation, linked by Sb-S bonds to form a complex Sb 6 S 12 6building block. Sb-S bonds serve to link Sb 6 S 12 6units to four others in a herringbone array, forming a sheet of stoichiometry Sb 6 S 10 2-, containing 24-membered rings of alternating Sb and S atoms. Pairs of edge-sharing CuS 4 distorted tetrahedra form pillars which link Sb 6 S 10 2layers together. The interlayer space contains piperazine cations, formed by cyclization of the triethylenetetramine during synthesis. Bondvalence sums are consistent with the presence of antimony(III) and copper(I), requiring complete protonation of the amine.

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