Novel Copper(I)‐Thioantimonates(III): Solvothermal Synthesis, Crystal Structures, Thermal Stability and Magnetic Properties of (C 2 N 2 H 10 ) 0.5 Cu 2 SbS 3 , (C 3 N 2 H 12 ) 0.5 Cu 2 SbS 3 , and (C 4 N 2 H 14 ) 0.5 Cu 2 SbS 3

The novel copper(I)‐thioantimonates(III) (enH 2 2+ ) 0.5 Cu 2 SbS 3 ( I ) (en = ethylendiamine), (1, 3‐DAPH 2 2+ ) 0.5 Cu 2 SbS 3 ( II ) (1, 3‐DAP = 1, 3 diaminopropane) and (1, 4‐DABH 2 2+ ) 0.5 Cu 2 SbS 3 ( III ) (1, 4‐DAB = 1, 4‐diaminobutane) were synthesized under solvothermal conditions reacting Sb 2 S 3 , CuCl 2 ·2H 2 O, S with the amines. The compounds crystallize in the monoclinic space group P2 1 /n. The primary building units are a SbS 3 trigonal pyramid and two distorted CuS 3 units. In the structures the SbS 3 pyramid is connected to six CuS 3 moieties and every S atom has bonds to one Sb atom and to two Cu atoms. Further interconnection leads to the formation of ten‐membered (10 MR) Cu 3 Sb 2 S 5 and six‐membered (6 MR) Cu 2 SbS 3 rings. Every 10 MR is condensed to four 10 MR and four 6 MR to form a single layer within the (010) plane. Two such single layers are connected to a double layer thus forming the final [Cu 2 SbS 3 ] — layered anion. The [CuSbS 3 ] — protonated amines are located between the layers and the interlayer spacing depends on the size and orientation of these amines. Between the Sb atom and one Cu atom a remarkable short distance of about 2.7Å is observed. At elevated temperatures the compounds decompose into CuSbS 2 and Cu 3 SbS 4 suggesting a complex redox reaction. Diamagnetic susceptibilities indicate the copper(I) in the metal sulfide frameworks. All three compounds are semiconductors with intermediate band gaps of about 2 eV.