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2005
Structure
D 2000
21- 008
Hydrothermal Single-Crystal Growth in the Systems Ag/Hg/X/O (X: Vv, Asv):
Crystal Structures of (Ag3Hg)VO4, (Ag2Hg2)3(VO4)4, and (Ag2Hg 2)2(HgO2)(AsO4)2
with the Unusual Tetrahedral Cluster Cations (Ag3Hg)3+ and (Ag2Hg 2)4+ and Crystal Structure of AgHgVO4. — Single crystals of (Ag3Hg)VO4 (I), (Ag2Hg2)3(VO4)4
(II), AgHgVO4 (III), and (Ag2Hg 2)2(HgO2)(AsO4)2 (IV) are grown under hydrothermal
conditions (250 C, 5 d) from mixtures of Hg, AgNO3, and NH4VO3 or Na2HAsO 4,
respectively. All crystal structures are determined by single crystal XRD. (I) crystallizes in the tillmannsite structure (tetragonal, space group I4, Z = 2), whereas (II)
(tetragonal, I42d, Z = 4), (III) (monoclinic, C2, Z = 4), and (IV) (trigonal, P31c, Z = 2)
adopt new structure types. The most striking structural features of (I), (II), and (IV) are
the formation of tetrahedral cluster cations (Ag3Hg)3+ and (Ag2Hg2)4+ , resp., built of statistically distributed Ag and Hg atoms with a metal—metal distance of about 2.72 Å.
The electronic structure of these clusters can formally be considered as two-electron-four-center bonding. — (WEIL*, M.; TILLMANNS, E.; PUSHCHAROVSKY,
D. Y.; Inorg. Chem. 44 (2005) 5, 1443-1451; Inst. Chem. Technol. Anal., Univ.
Technol., A-1060 Wien, Austria; Eng.) — Schramke
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