Solvothermal Syntheses of (H_2en)_2Sn_2S_6·en and[(H_2hmda)_3(Hhmda)_2](Sn_2S_6)_2Using SnCl_4 and S_8 as Starting Materials

1 INTRODUCTION Since Bedard et al. reported microporous tin(IV) sulfides synthesized by hydrothermal method in the presence of organic amine in 19891, 2], a number of thiostannates have been synthesized using hydro- or solvothermal techniques with organic amines as tem- plates. The structures of the resulting tin(IV) sulfi- des are related to the types of organic amines. Two- dimensional polyanions of the types of Sn3S7]2- and Sn4S9]2-, which are denoted as SnS-1 and SnS-3, respe…

Solvothermal Syntheses of (H_2en)_2Sn_2S_6·en and[(H_2hmda)_3(Hhmda)_2](Sn_2S_6)_2Using SnCl_4 and S_8 as Starting Materials

Three thiostannates (H2en)2Sn2S6?en 1, (Hen)4Sn2S6 2 (en = ethylenediamine, a known compound) and (H2hmda)3(Hhmda)2](Sn2S6)2 3 (hmda = hexamethylenediamine) were prepared using SnCl4?5H2O and S8 as starting materials in alkylenediamine solutions under mild solvothermal conditions. Compound 1 crystallizes in the triclinic system, space group P1 with a = 8.7491(17), b = 10.704(2), c = 12.2031(19) ?, α = 74.888(13), β = 72.998(12), γ = 89.032(15)°, V = 1052.9(3) ?3, Mr = 614.08, Z = 2, Dc = 1.937 g/cm3, μ = 2.966 mm-1, F(000) = 604, S = 1.211, R = 0.0579 and wR = 0.0770 for 3999 observed reflections with I > 2σ(I); while 3 crystallizes in the triclinic system, space group P1 with a = 9.8075(13), b = 10.8266(16), c = 14.303(2) ?, α = 88.611(10), β = 81.030(9), γ = 74.609(9)°, V = 1446.1(4) ?3, Mr = 1448.78, Z = 1, Dc = 1.664 g/cm3, μ = 2.173 mm?1, F(000) = 730, S = 1.173, R = 0.0457 and wR = 0.0667 for 5738 observed reflections with I > 2σ(I). The compounds are composed of dimeric Sn2S6]4– anions and proto- nated alkylenediamine cations.