Three new compounds (enH)(6+n)Cu(40)Sn(15)S(60) (1), (enH)(3)Cu(7)Sn(4)S(12) (2), and (trenH(3))Cu(7)Sn(4)S(12) (tren = tris(2-aminoethyl)amine) (3) containing Cu(8)S(12) and Cu(7)SnS(12) clusters have been prepared from direct solvothermal reaction of the elements in amine solvents. In 1, the cubic close-packed arrangement of Cu(8)S(12) clusters, interconnected by capping SnS(4) tetrahedra and CuS(3) triangles, form two interpenetrating channel networks that are presumably filled with disordered solvent molecules. Structures 2 and 3 contain well-ordered, protonated amine molecules and Cu(7)SnS(12) clusters. The clusters are connected by SnS(4) tetrahedra to form a three-dimensional structure with ReO(3) topology. (119)Sn Mössbauer measurement is consistent with Sn(IV) atoms linking, and Sn(II) atoms within, the mixed-metal Cu(7)SnS(12) clusters.

The crystal growth and kinetics of the formation of [Co(C 6 H 18 N 4 )][Sb 2 S 4 ] were investigated under solvothermal conditions with combined in situ EDXRD (energy dispersive X-ray diffraction) and in situ EXAFS (extended X-ray absorption fine structure) at different temperatures. In the overwhelming number of reactions all product reflections occur simultaneously in the EDXRD spectra. A detailed analysis of the extent of reaction R vs time clearly shows that the mechanism changes during the reaction. Such a change occurs at different temperatures after different reaction times. At the early stages the reactions are controlled by diffusion, and later the reaction exponents m suggest a more complex behavior. At the end of the formation of [Co(C 6 H 18 N 4 )][Sb 2 S 4 ] a second phase is formed which does not contain Co. The results of the in situ experiments suggest that [Co(C 6 H 18 N 4 )][Sb 2 S 4 ] is not only a metastable phase but rather that the second product crystallizes because the Co 2+ concentration in solution is too low for further formation of [Co(C 6 H 18 N 4 )][Sb 2 S 4 ]. In the minor cases of the solvothermal reaction a very different growth was observed. At the beginning only one intense reflection occurs in the spectra and after a distinct time all other reflections start to grow simultaneously. This strange behavior indicates that disordered layers are formed at the beginning which start to arrange at later stages, yielding the threedimensional long-range order. The in situ EXAFS experiments performed at the Sb K-edge demonstrate that, independent of the reaction time, the Sb/S ratio, and the amine applied, only the two species SbS 3 and SbS 4 are present in solution.

Six new thioantimonates(III) with the [Sb 4 S 7 ] 2Ϫ anion were obtained under solvothermal conditions with in-situ formed transition metal complexes as structure directors. In the two isostructural compounds [Fe(dien) 2 ]Sb 4 S 7 · H 2 O (1) and [Co(dien) 2 ]Sb 4 S 7 · 0.5 H 2 O (2) (dien ϭ diethylenetriamine; space group: P2 1 /c) the layered [Sb 4 S 7 ] 2Ϫ anion is characterized by Sb 8 S 8 rings with a diameter of about 9.6 · 7.6 Å . The cation complexes are located above and below the pores of the rings. Despite the larger size of the cation complex the network topology of the third thioantimonate [Ni(dien)(tren)]Sb 4 S 7 (3) (tren ϭ tris(2-aminoethyl-)amine; space group: P2 1 /n) is similar to that of the first two compounds. In the isostructural thioantimonates [M(trien)]Sb 4 S 7 (M ϭ Zn (4); M ϭ Mn (5); trien ϭ triethylenetetramine; space group: P1) the M 2ϩ ions are fivefold coordinated by four N atoms of the amine 1687 molecule and by one S atom of the thioantimonate anion forming a MN 4 S trigonal bipyramid. Sb 8 S 16 building blocks are the central structural motifs of the anion. Two of the terminal S atoms at the periphery of the Sb 8 S 16 units are bound to M 2ϩ ions and the four remaining terminal S atoms connect adjacent Sb 8 S 16 groups into the final [Sb 4 S 7 ] 2Ϫ chain. [Ni(tren)]Sb 4 S 7 (6) (space group: P1) contains a one-dimensional anionic chain. The Ni 2ϩ ion has two bonds to the [Sb 4 S 7 ] 2Ϫ anion which is a unique feature in the thioantimonate(III) chemistry. The NiN 4 S 2 octahedron is severly distorted with one very long Ni-S bond of 2.782(2) Å . In all compounds several short S···H distances indicate hydrogen bonding interactions.

The two new thiostannate compounds (trenH) 2 Sn 3 S 7 (1) and {[Mn(tren)] 2 Sn 2 S 6 } (2) (tren = tris-2-aminoethylamine) were obtained under solvothermal conditions. Compound 1 crystallizes in the hexagonal space group P6 3 /mmc with a = 13.2642(19), c = 19.078(3) Å, V = 2906.9(7) Å 3 . The layered [Sn 3 S 7 ] 2− anion is constructed by Sn 3 S 4 semi-cubes sharing common edges. The layers are characterized by large hexagonal pores with dimensions of about 11 × 11 Å 2 . Compound 2 crystallizes in the triclinic space group P1 with lattice parameters a = 7.6485(7), b = 8.1062 (7), c = 12.1805(11) Å, α = 97.367(11), β = 103.995(11), γ = 108.762(10) • , V = 676.17(10) Å 3 . The [Sn 2 S 6 ] 4− anion is composed of two edge-sharing SnS 4 tetrahedra and joins two Mn 2+ -centered complexes by Mn-S bond formation. The Mn 2+ cation is in a trigonal-bipyramidal environment of four N atoms of the tren ligand and one S atom of the thiostannate anion. Both compounds are semiconductors with a band gap of 2.96 eV for 1 and of 2.75 eV for 2.

The structures of the new thioantimonates (III) (monoclinic, space group P21/c, Z = 4), (VI) (monoclinic, P21/n, Z = 4), and (VIII) (triclinic, P1, Z = 2) are determined by single crystal XRD. Compounds (III) consists of anioniclayers characterized by Sb8S8 rings. The [M 1 (dien)2] 2+ units are located above and below the pores of the rings. Despite the larger size of the cation complex the network topology of (VI) is similar to that of the (III). The transition metals in the thioantimonates (VIII) are fivefold coordinated by four N atoms of the amine molecule and one S atom of the thioantimonate anion forming a MN4S trigonal bipyramid. Sb8S16 building blocks are the central structural motifs of the anion. Several short S···H distances in all compounds indicate hydrogen bonding interactions. -(LUEHMANN, H.; REJAI, Z.; MOELLER, K.; LEISNER, P.; ORDOLFF, M.-E.; NAETHER, C.; BENSCH