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2005
Structure
D 2000
06- 008
X-Ray and Transmission Electron Microscopy Investigations of the New Solids
In5S5Cl, In5Se 5Cl, In 5S5Br, and In5Se5Br. — The title compounds are prepared by
solid state reaction of In, S or Se, and InX3 (X: Cl, Br) at 773 K (evacuated quartz tube,
7 d). In5S5Cl and In5Se5Cl crystallize in the monoclinic space group P21/m with Z = 2
while In5S5Br and In5Se 5Br have an orthorhombic structure, space group Pmn2 1, Z = 2.
The four compounds represent new mixed valence solids with indium in three different
oxidation states: In+, In3+ and In 2+, where the latter appears as covalently bonded dumbbells (In2)4+. Ignoring the distribution of the halogen atoms, the anionic partial structure
is very similar in both structure types. The main difference is an exchange of In+ by
(In2)4+ and vice versa on selected positions. This is possible due to the nearly identical
coordination of both ions (tri-capped trigonal prisms). In contrast to the perfectly
ordered crystals of the bromides, the chlorides exhibit a variety of nanoscaled crystal
defects, i.e. twinning, polylamellar intergrowth of polymorphs and lamellar intergrowth of structurally related compounds as demonstrated in In5S5Cl/In6S7. The occurrence of these defects is discussed using an appropriate structure model. —
(DEISEROTH*, H.-J.; REINER, C.; XHAXHIU, K.; SCHLOSSER, M.; KIENLE, L.;
Z. Anorg. Allg. Chem. 630 (2004) 13-14, 2319-2328; Fachbereich 8, Anorg. Chem.,
Univ.-GH Siegen, D-57068 Siegen, Germany; Eng.) — Schramke
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