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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, Pca2 1 , a = 9.414(2), b = 15.929(3), c = 10.180(2) A Ê , Z = 4, R 1 = 0.0286. II is monoclinic, C2/c, a = 14.463(3), b = 19.154(4), c = 13.724(3) A Ê , b = 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) A Ê , Z = 4, R 1 = 0.0987. IV is trigonal, R 3, a = 10.500(2), c = 12.837(3) A Ê , 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. Wasserfreie Nitrate und Nitrosoniumnitratometallate von Mangan und Cobalt: M(NO 3 ) 2 , NO[Mn(NO 3 ) 3 ], und (NO) 2 [Co(NO 3 ) 4 ]: Synthese und Kristallstrukturen Inhaltsu È bersicht. Kristalline Verbindungen von NO[Mn-(NO 3 ) 3 ] (I) und (NO) 2 [Co(NO 3 ) 4 ] (II) wurden durch Umsetzung der entsprechenden Metalle mit flu È ssigem N 2 O 4 -Ethylacetat-Gemisch synthetisiert. I ist orthorhombisch, Pca2 1 , a = 9,414(2), b = 15,929(3), c = 10,180(2) A Ê , Z = 4, R 1 = 0,0286. II ist monoklin, C2/c, a = 14,463(3), b = 19,154(4), c = 13,724(3) A Ê , b = 120,90(3), Z = 12, R 1 = 0,0890. Die Struktur von I ist aus [Mn(NO 3 ) 3 ] ± -Schichten aufgebaut, zwischen denen sich NO + -Kationen befinden. Es existieren zwei Typen von verschieden koordinierten Mn-Atomen mit KZ Mn = 7 und 8. Die Struktur von II ist ionisch, aufgebaut aus isolierten [Co(NO 3 ) 4 ] 2± -Anionen und NO + -Kationen (KZ Co = 8). Die Kristalle von Mn(NO 3 ) 2 (III) und Co(NO 3 ) 2(IV) wurden im Exsiccator beim Konzentrieren der Lo È sungen von Metallnitrat-Hydraten in 100% HNO 3 in Anwesenheit von P 2 O 5 erhalten. III ist kubisch, Pa 3, a = 7,527(2) A Ê , Z = 4, R 1 = 0,0987. IV ist trigonal, R 3, a = 10,500(2), c = 12,837(3) A Ê , Z = 12, R 1 = 0,0354. Die dreidimensionale Struktur von III ist zu den entsprechenden Strontium-bzw. Bariumdinitraten isotyp. Die Struktur IV ist aus einem dreidimensionalen Geru È st von miteinander verknu È pften Co(NO 3 ) 6/3 -Einheiten mit verzerrt oktaedrischer Cobalt-Koordination aufgebaut. Allgemeine Korrelationen zwischen der Koordinationszahl der Metallatome und den Koordinationsmoden der NO 3 -Gruppen werden diskutiert.

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Blue crystals of a Cu(NO3)2 · H2O were synthesized by interaction of CuO with boiling 100% HNO3. Stable β‐Cu(NO3)2 modification was obtained by the sublimation of copper(II) nitrate in evacuated ampoule over the 150→100°C temperature gradient for 24 hr. According to X‐Ray single crystal analysis Cu(NO3)2 · H2O is monoclinic with a = 6.377(1), b = 8.548(1), c = 9.769(1) Å, β = 100.41(1)°, Z = 4, and space group P21/c. β‐modification Cu(NO3)2 is orthorhombic with a = 14.161(5), b = 7.516(3), c = 12.886(2) Å, Z = 12, and space group Pbcn. In the both structures Cu atoms are square coordinated by 4 O atoms at the distances ranging from 1.92 to 2.02 Å. In each structure there are also additional CuO bonds with the distance of 2.33 or 2.35 Å and some weaker ones with the distances in the range of 2.65–2.72 Å. In the Cu(NO3)2 · H2O structure the [CuO4] squares are connected by the bridging NO3 groups into zigzag chains, which are linked into layers by the longer CuO bonds. In the β‐Cu(NO3)2 structure the [CuO4] fragments of two types are joined by the bridging NO3 groups in a three‐dimensional framework. Some correlations were found between NO distances and coordination functions of O atoms.

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