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Single crystals of the mixed-valent compounds Hg 7 Se 3 O 13 H 2  ( I ) and Hg 8 Se 4 O 17 H 2  ( II ) were grown under hydrothermal conditions. The crystal structures were solved and refined from single crystal X-ray data collected at room temperature ( I :  R 3,  Z  = 3,  a  = 5.9239(3),  c  = 37.096(3) Å, 1465 structure factors, 60 parameters,  R [ F  2  &gt; 2 σ ( F  2 )] = 0.0383,  wR ( F  2  all) = 0.0970, Goof = 1.047;  II :  P 31 c, Z  = 2,  a  = 5.8908(6),  c  = 31.048(3) Å, 1889 structure factors, 69 parameters,  R [ F  2  &gt; 2 σ ( F  2 )] = 0.0662,  wR ( F  2  all) = 0.1626, Goof = 1.088). Both compounds show a multifarious crystal chemistry and contain triangular Hg 3  4+  cluster cations, Hg 2  2+  dumbbells, Hg 2+  cations, HgO 2  2–  mercurate groups, and trigonal-pyramidal SeO 3  2–  as well as tetrahedral SeO 4  2–  anions and water molecules as simple building units. The description in terms of crystal chemistry leads to the more detailed formulae (Hg IV/3  3 ) (Hg I  2 )(Hg II )(Hg II O 2 )(Se IV O 3 ) 2 (Se VI O 4 )(H 2 O) for  I  and (Hg IV/3  3 )(Hg I  2 )(Hg II ) 2 (Hg II O 2 )(Se IV O 3 ) 2 (Se VI O 4 ) 2 (H 2 O) for  II , respectively. Characteristic features of the closely related structures are building blocks formed by parallel layers of Hg 3  4+  triangles, layers of disordered Hg 2  2+  dumbbells, layers of SeO 4  2–  and HgO 2  2–  groups, and layers of SeO 3  2–  groups which are all stacked along [001]. The layers are linked into a complex three-dimensional framework  via  common O atoms and H 2 O molecules. In comparison with Hg 7 Se 3 O 13 H 2 , the structure of Hg 8 Se 4 O 17 H 2  contains an additional and disordered HgSeO 4  layer which leads to a significant distortion of parts of the resulting structure.

zeitschrift für kristallographie - crystalline materials

The crystal structures of Hg 7 Se 3 O 13 H 2  and Hg 8 Se 4 O 17 H 2  — two mixed-valent mercury oxoselenium compounds with a multifarious crystal chemistry