HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés. 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...

The two new one-dimensional polymeric compounds [Ce(C 4 N 3 H 13 ) 2 (μ 3 -SbS 4 )] n (1) and [La(C 4 N 3 H 13 ) 2 (μ 4 -Sb 2 S 5 )(μ 3 -SO 4 )] n (2) were synthesized under solvothermal conditions. In the first compound, the unique Ce 3+ cation is surrounded by six nitrogen atoms of the amine ligands and by three sulfur atoms of the thioantimonate(V) anion. The CeN 6 S 3 polyhedron may be described as a distorted tricapped trigonal prism. The prisms are interconnected by [SbS 4 ] 3anions, which act in a μ 3 -binding mode yielding a chain running along [100]. An extended hydrogen-bonding network leads to the formation

Four compounds of composition [dienH 2 ][Co(dien) 2 ][Ge 2 S 6 ] (dien = diethylenetriamine) were obtained under solvothermal conditions changing the reaction time and educt ratio in the reaction slurries. In three compounds the [Co(dien) 2 ] 2+ complexes adopt the s-fac and in one the u-fac configuration. The main differences between the samples are found in the number and type of protonated dien molecules. In one distinct cation of compound 1 as well as in compound 2 the terminal N atoms are protonated, whereas in the second cation of 1 as well as in 3 and 4, one terminal and the central N atom are protonated. Therefore, the compounds with different protonated cations are tautomers, whereas compounds 3 and 4 represent polymorphic modifications. The occurrence of tautomerism and polymorphism for compounds with identical chemical composition is unprecedented in the chemistry of thiometallates and was never reported until now. In the crystal structure of all compounds the (dienH 2) 2+ cations and the [Ge 2 S 6 ] 4− anions are linked by intermolecular N-H⋯S hydrogen bonding into different supramolecular networks.

Cobalt I 7200The Effect of Temperature onto the Crystal Structure of Thioantimonates: Solvothermal Syntheses and Crystal Structures of [Co(dien) 2 ][Co(tren)SbS 4 ] 2 ·0.5H 2 O and {[Co(tren)]2[CoSb2S6]}·H2O. -The two new compounds (IV) and (V) are characterized by powder XRD. (IV) crystallizes in the monoclinic space group C2/c with Z = 4. Its structure contains isolated [Co(dien)2] 2+ and [Co(tren)SbS4]complexes. (V) crystallizes in the monoclinic space group P21/c with Z = 4. It contains a central [CoSb 2 S 6 ] 4core acting as a bidentate ligand to two independent [Co(tren)] 2+ complexes. The [CoSb2S6] core is composed of two [SbS3] pyramids and a [CoS4] tetrahedron sharing two edges with the [SbS3] units. -(LICHTE, J.; LUEHMANN, H.; NAETHER, C.; BENSCH

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