Two new layered bimetallic sulfides: Solvothermal synthesis, crystal structure, optical and magnetic properties

Two new bimetallic sulfides, (Haep)2·Ga2Sb2S7 (1) and Mn2(phen)Sb2S5 (2), have been synthesized under solvothermal conditions, where aep = 1-(2-aminoethyl)piperazine and phen = 1,10-phenanthroline. The structure of 1 consists of GaS4 tetrahedra and SbS3 trigonal pyramids and has a layered structure with 8-membered-ring windows. Interestingly, the interlayer organic cations form helices through extensive hydrogen bonds. Compound 2 has a neutral layered structure containing infinite Mn–S sheets. The organic species are attached directly to Mn atoms within the layers by covalent bonds and protrude into the interlayer region. Both compounds 1 and 2 exhibit intense photoluminescence upon photoexcitation at 360 nm. Magnetic susceptibility measurements demonstrate the existence of antiferromagnetic interactions in compound 2. Crystal data: 1, orthorhombic, P212121 (No. 19), a = 9.9274(2) Å, b = 12.9201(3) Å, c = 21.2254(4) Å, V = 2722.43(10) Å3, Z = 4; 2, monoclinic, P21/c (No. 14), a = 12.6385(3) Å, b = 12.3998(3) Å, c = 12.3670(3) Å, β = 111.8240(10)°, V = 1799.19(7) Å3, Z = 4.