Redetermination of the lanthanum iron sulfide La52Fe12S90.
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Biomedical subjects
Publications and source records attributed to Michael Ruck.
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The compounds Ce53Fe12S90X3 (X = Cl, Br, I), which represent the first examples of rare-earth transition-metal sulfide halides, were prepared using the reactive-flux method, through reaction of Ce2S3, FeS, or Fe and S in a CeX3 flux at 1320 K. Their structures were determined by single-crystal X-ray diffraction. The compounds are isostructural, crystallizing in the trigonal space group Rm with Z = 1 [Ce53Fe12S90Cl3, a = 13.9094(9) A, c = 21.604(2) A, V = 3619.7(4) A3; Ce(53)Fe(12)S(90)Br(3), a = 13.916(1) A, c = 21.824(2) A, V = 3660.0(5) A3; Ce53Fe12S90I3, a = 13.863(3) A, c = 21.944(6) A, V = 3652(2) A3]. The structure adopted is a stuffed variant of the La52Fe12S90 structure type. Fe2S9 dimers of face-sharing octahedra are linked by face- and vertex-sharing capped CeS6 trigonal prisms, forming a three-dimensional framework containing cuboctahedral cavities of two sizes. The smaller cavities accommodate alternative sites for disordered cerium atoms. The larger cavities, which remain empty in the parent structure, are filled by halogen atoms in Ce53Fe12S90X3. Alternatively, the structure can be described as a 9-fold superstructure of the Mn5Si3 structure type (P6(3)/mcm), with a = a' and c = 3c'. Temperature-dependent magnetic susceptibility measurements suggest that Ce53Fe12S90I3 may order antiferromagnetically at low temperatures.
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The silver bismuth tridecasulfide Ag3.5Bi7.5S13 crystallizes in the monoclinic space group C2/m. Its structure is built up of two alternating kinds of layered modules parallel to (001). In the module denoted A, octahedra around the metal positions (M = Ag/Bi, M2 and an S atom on 2/m, other atoms on m) alternate with paired monocapped trigonal prisms around Bi. The NaCl-type module B is composed of parallel eight-membered chains of edge-sharing octahedra running diagonally across it. Ag3.5Bi7.5S13 is the member with N = 8 of the pavonite homologous series (N)P of ternary compounds with the general formula [Bi2S3]2.[AgBiS2]((N-1)/2).
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Subvalent compounds, that is, metal-rich substances in which the average oxidation state of the cation is smaller than would be expected from the (8-N) rule, have proved to be a rich source of unexpected structural and physical features. The extraordinary structural chemistry generally observed in subvalent compounds is a consequence of the low and often non-integer oxidation states of the metal atoms coupled with the low concentration of valence electrons. Both factors can lead to a wide-range of bonding types within the same compound. A characteristic of these compounds is the interplay between "metallic" regions, with delocalized electrons and mainly nonpolar bonds between the metal atoms, and "saltlike" regions, which are characterized by strong localization of the electrons and heteropolar exchange between the metal and nonmetal atoms. The volumes of the different structural regions as well as the extent to which they interpenetrate can vary from compound to compound. The ternary subhalides of bismuth belong to a new class of substances which cover the whole spectrum from partially oxidized "porous" metals, through one- and two-dimensional metals, up to semiconducting ionic or molecular cluster compounds. These subvalent compounds with their unusually high chemical stabilities provide excellent vehicles for further research and their potential is described in the following article.