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IntroductionIn the past few years we and other groups demonstrated that a large variety of amines are suitable structure directing molecules for the preparation of thioantimonates under solvothermal conditions . A challenge in the field of thioantimonate chemistry is the integration of transition metal ions into the thioantimonate networks. Using mono-, bi-or tridentate amine molecules like methylamine, ethylenediamine or diethylenetriamine (dien) mainly transition metal complexes are formed which are separated from the anionic network [25][26][27][28][29][30][31][32][33][34][35][36][37][38]
Results and DiscussionThe two new compounds were obtained in a mixture of dien and tren applying the ratio dien:tren = 2.4:0.6 mL in 1 mL water. Phase pure [Co(dien) 2 ][Co(tren)SbS 4 ] 2 ⋅0.5 H 2 O is formed exclusively at 110 °C whereas mixtures of both compounds were observed at 120 and 130 °C. A series of experiments was performed at 120 and 130 °C varying the reaction time between 3 and 6 d. But in all products a mixture of the two title compounds was obtained. Variation of the ratio of the amines (T = 120 and 130 °C, dien:tren = 2.7:0.3, 2.6:0.4 and 2.5:0.5 with 1 mL H 2 O) and also the absolute amount of the amine in 1 mL water (dien:tren: 1.3:0. 3-anion (Fig. 1). Like in the pseudo-polymorph the Co(1)-N bond in trans position to the Co(1)-S(1) bond is longer (2.247(3) Å) than the remaining Co(1)-N bonds (2.072(3) -2.083(2) Å; Table 1). Such an elongation of a bond can be explained with the so-called trans-effect. The Co(1)-S(1) bond at 2.3701(8) Å is in the range of data published in literature [54,55]. The angles around the Co(1) 2+ cation suggest an appreciable distortion ( Table 2). The Sb-S bond lengths and S-Sb-S angles are typical for a moderately distorted [Sb(V)S 4 ] 3-tetrahedron. The arrangement of the cations and anions in the unit cell is very similar to that observed for the pseudo-polymorphic compound. The shortest O⋅⋅⋅O, O⋅⋅⋅S and O⋅⋅⋅N separations are 3.054, 3.471 and 3.722 Å respectively which are all significantly longer than in [Co(dien) 2 ][Co(tren)SbS 4 ] 2 ⋅4H 2 O and too long for significant H-bonding interactions. Nevertheless, the S atoms join neighbored cations and anions to form layers in he (001) plane (see Table 3). (Fig. 3). Alternatively one may describe the structure as two independent [Co(tren)SbS 3 ] -complexes which are connected by a Co 2+ cation. The Co(1) 2+ and Co(3) 2+ cations are each coordinated by four N atoms of the tren ligand and b...