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Anhydrous Nitrates and Nitrosonium Nitratometallates of Manganese and Cobalt, M(NO 3 ) 2 , NO[Mn(NO 3 ) 3 ], and (NO) 2 [Co(NO 3 ) 4 ]: Synthesis and Crystal Structure
Author(s) -
Tikhomirov Grigorii A.,
Znamenkov Konstantin O.,
Morozov Igor V.,
Kemnitz Erhard,
Troyanov Sergei I.
Publication year - 2002
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 - 10.1002/1521-3749(200201)628:1<269::aid-zaac269>3.0.co;2-p
Subject(s) - crystal structure , orthorhombic crystal system , manganese , monoclinic crystal system , octahedron , crystallography , chemistry , cobalt , hydrate , anhydrous , metal , inorganic chemistry , organic chemistry
Crystalline NO[Mn(NO 3 ) 3 ] ( I ) and (NO) 2 [Co(NO 3 ) 4 ] ( II ) were synthesized by reaction of the corresponding metal and a liquid N 2 O 4 /ethylacetate mixture. I is orthorhombic, Pca 2 1 , a = 9.414(2), b = 15.929(3), c = 10.180(2) Å, Z = 4, R 1 = 0.0286. II is monoclinic, C 2/ c , a = 14.463(3), b = 19.154(4), c = 13.724(3) Å, β = 120.90(3), Z = 12, R 1 = 0.0890. Structure I consists of [Mn(NO 3 ) 3 ] – sheets with NO + cations between them. Two types of Mn atoms have CN Mn = 7 and 8. Structure II is ionic containing isolated [Co(NO 3 ) 4 ]‐anions and NO + cations with CN Co = 8. Crystals of Mn(NO 3 ) 2 ( III ) and Co(NO 3 ) 2 ( IV ) were obtained by concentration of metal nitrate hydrate solutions in 100% HNO 3 in a desiccator with P 2 O 5 . III is cubic, Pa 3, a = 7.527(2) Å, Z = 4, R 1 = 0.0987. IV is trigonal, R 3, a = 10.500(2), c = 12.837(3) Å, Z = 12, R 1 = 0.0354. The three dimensional structure III is isotypic to the strontium and barium dinitrates. Structure IV contains a three dimensional network of interconnected Co(NO 3 ) 6/3 units with a distorted octahedral coordination environment of Co atoms. General correlations between central atom coordination and coordination modes of NO 3 groups are discussed.