The reactions of Cu(NO3)2·3H2O with pyridazine (pydz) in water and ethanol solutions have been investigated. In water, using a 1:1 salt: pydz molar ratio, the polymeric species catena-[Cu(μ-η2-pydz)(μ-OH)(μ-O 2NO)]·H2O 1 was obtained, whilst with a ratio of 1: 2 the trinuclear complex [Cu3(μ-η2-pydz)4(pydz) 2(μ-NO3)2(NO3)4] 2was isolated. In ethanol a different species 3, not yet characterized, was obtained on employing a ratio of 1:1. With a salt:pydz molar ratio close to 1:2 the trinuclear species 2 was recovered through a cleaner reaction, while, when a ratio of ca. 1:3 was used the mononuclear complex [Cu(pydz)3(O2NO)(NO3)] 4 was obtained. The structures of compounds 1 and 2 have been characterized by single-crystal X-ray analysis: 1, monoclinic, space group I2/m (no. 12), a = 10.239(1), b = 6.643(1), c = 12.363(2) Å, β = 103.74(1)°, Z = 4, R = 0.022 for 651 [Fo > 4σ(Fo)] reflections; 2, monoclinic, space group P21/n (no. 14), a = 8.957(2), b = 13.687(4), c = 14.945(4) Å, β = 96.06(2)°, Z = 2, R = 0.038 for 2430 [Fo > 4σ(Fo)] reflections. Compound 1 is a linear polymer [Cu ⋯ Cu 3.3215(5) Å], with each metal atom pair symmetrically bridged by a η2-pydz molecule, a hydroxide group and a nitrate. Compound 2 contains a linear trinuclear centrosymmetric array of copper atoms, with the two equivalent Cu ⋯ Cu interactions [3.4057(8) Å] symmetrically bridged by two η2-pydz molecules and a nitrate. Both 1 and 2 exhibit strong exchange coupling between the copper atoms, the room-temperature μeff being reduced to 1.08 1 and 2.62 μB 2.

Reactions of copper(II) nitrate with pyridazine (pydz) and crystal structures of catena-[Cu(μ-η2-pydz)(μ-OH)(μ-O 2NO)]·H2O and [Cu3(μ-η2-pydz)4(pydz) 2(μ-NO3)2(NO3)4] / L. Carlucci, G. Ciani, M. Moret, A. Sironi. - In: JOURNAL OF THE CHEMICAL SOCIETY DALTON TRANSACTIONS. - ISSN 0300-9246. - :16(1994), pp. 2397-2404. [10.1039/DT9940002397]

Reactions of copper(II) nitrate with pyridazine (pydz) and crystal structures of catena-[Cu(μ-η2-pydz)(μ-OH)(μ-O 2NO)]·H2O and [Cu3(μ-η2-pydz)4(pydz) 2(μ-NO3)2(NO3)4]

L. Carlucci
Primo
;
G. Ciani
Secondo
;
A. Sironi
Ultimo
1994

Abstract

The reactions of Cu(NO3)2·3H2O with pyridazine (pydz) in water and ethanol solutions have been investigated. In water, using a 1:1 salt: pydz molar ratio, the polymeric species catena-[Cu(μ-η2-pydz)(μ-OH)(μ-O 2NO)]·H2O 1 was obtained, whilst with a ratio of 1: 2 the trinuclear complex [Cu3(μ-η2-pydz)4(pydz) 2(μ-NO3)2(NO3)4] 2was isolated. In ethanol a different species 3, not yet characterized, was obtained on employing a ratio of 1:1. With a salt:pydz molar ratio close to 1:2 the trinuclear species 2 was recovered through a cleaner reaction, while, when a ratio of ca. 1:3 was used the mononuclear complex [Cu(pydz)3(O2NO)(NO3)] 4 was obtained. The structures of compounds 1 and 2 have been characterized by single-crystal X-ray analysis: 1, monoclinic, space group I2/m (no. 12), a = 10.239(1), b = 6.643(1), c = 12.363(2) Å, β = 103.74(1)°, Z = 4, R = 0.022 for 651 [Fo > 4σ(Fo)] reflections; 2, monoclinic, space group P21/n (no. 14), a = 8.957(2), b = 13.687(4), c = 14.945(4) Å, β = 96.06(2)°, Z = 2, R = 0.038 for 2430 [Fo > 4σ(Fo)] reflections. Compound 1 is a linear polymer [Cu ⋯ Cu 3.3215(5) Å], with each metal atom pair symmetrically bridged by a η2-pydz molecule, a hydroxide group and a nitrate. Compound 2 contains a linear trinuclear centrosymmetric array of copper atoms, with the two equivalent Cu ⋯ Cu interactions [3.4057(8) Å] symmetrically bridged by two η2-pydz molecules and a nitrate. Both 1 and 2 exhibit strong exchange coupling between the copper atoms, the room-temperature μeff being reduced to 1.08 1 and 2.62 μB 2.
Settore CHIM/03 - Chimica Generale e Inorganica
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/187190
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