An Antimony Sulfide with Copper Pillars:  [C₄H₁₂N₂]_0.5[CuSb₆S₁₀]

Abstract

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.

Facile surfactant-thermal syntheses and characterization of quaternary copper thioantimonates(III) ACu 2 SbS 3 (A = K, Rb, Cs)

“…Therefore, the integration of Cu(I) ions is beneficial to generate new multinary thioantimonates(III) with novel crystal structures and integrated physical properties. Representative examples of copper-containing thioantimonates(III) are [C 4 N 2 H 12 ] 0.5 [CuSb 6 S 10 ] [21], RCu 2 SbS 3 (R ¼ amine) [22,23] [25], and [Ni(dien) 2 ][CuSb 3 S 6 ] (dien ¼ diethylenetriamine) [25], in which organic cations or transition-metal complexes served as the templates. When the organic cations or transition-metal complexes were replaced by alkali or alkaline earth metal ions, six quaternary AeCueSbeS (A ¼ alkali or alkaline earth metals) thioantimonates(III) were obtained [26e29].…”

Copper‐Rich Framework Selenoarsenates Based on Icosahedral Cu8Se13 Clusters

“…[10][11][12][13][14][15][16] In contrast, transition metal M I (M = Cu, Ag) cations have diverse coordination modes (2,3,4) with chalcogen Q 2-(Q = S, Se) anions, and flexible linkages between M I Q x polyhedra. Generally, M I exists in the form of isolated M + or dimeric M 2 2+ to bridge main group thio-anionic building units, [17][18][19][20][21] or partially substitute the cation sites of supertetrahedral building units in low M I -containing 3D frame-1 ties. The icosahedral Cu 8 Se 13 clusters represent the first icosahedral Cu-Se unit found in 3D framework chalcogenides, and contain an unusual μ 8 -cubic bridging Se 2-ion at the core site.…”

Solvothermal synthesis and crystal structure of Sb(III) and Sb(V) thioantimonates: [Mn(en)3]2Sb2S5 and [Ni(en)3(Hen)]SbS4

“…In recent years, a large number of thioantimonates(III) with organic cations [1][2][3][4], transition metal complex cations [5][6][7][8][9][10][11][12][13][14][15][16][17][18] and other cations [19,20] serving as counterions to Sb x III S y nÀ anions, have been synthesized under hydro-or solvo-thermal conditions. The rich structural diversity of thioantimonates(III) results from variable coordination behaviors of Sb(III) atom caused by the stereochemically active lone pair [21].…”