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Crystal Structure of the Mixed‐Valent Basic Mercury Nitrate Hg I 2 (NO 3 ) 2 ·Hg II (OH)(NO 3 )·Hg II (NO 3 ) 2 ·4Hg II O [= Hg 8 O 4 (OH)(NO 3 ) 5 ]
Author(s) -
Weil Matthias
Publication year - 2005
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200400562
Subject(s) - monoclinic crystal system , chemistry , mercury (programming language) , crystallography , nitrate , crystal structure , stoichiometry , oxygen , inorganic chemistry , analytical chemistry (journal) , organic chemistry , computer science , programming language , chromatography
Light‐yellow single crystals of the mixed‐valent mercury‐rich basic nitrate Hg 8 O 4 (OH)(NO 3 ) 5 were obtained as a by‐product at 85 °C from a melt consisting of stoichiometric amounts of (Hg I 2 )(NO 3 ) 2 ·2H 2 O and Hg II (OH)(NO 3 ). The title compound, represented by the more detailed formula Hg I 2 (NO 3 ) 2 ·Hg II (OH)(NO 3 )·Hg II (NO 3 ) 2 ·4Hg II O, exhibits a new structure type (monoclinic, C 2/ c , Z = 4, a = 6.7708(7), b = 11.6692(11), c = 24.492(2) Å, β = 96.851(2)°, 2920 structure factors, 178 parameters, R 1[ F 2 > 2 σ ( F 2 )] = 0.0316) and is made up of almost linear [O‐Hg II ‐O] and [O‐Hg I ‐Hg I ‐O] building blocks with typical Hg II ‐O distances around 2.06Å and a Hg I ‐O distance of 2.13Å. The Hg 2 2+ dumbbell exhibits a characteristic Hg‐Hg distance of 2.5079(7) Å. The different types of mercury‐oxygen units form a complex three‐dimensional network exhibiting large cavities which are occupied by the nitrate groups. The NO 3 − anions show only weak interactions between the nitrate oxygen atoms and the mercury atoms which are at distances > 2.6Å from one another. One of the three crystallographically independent nitrate groups is disordered.