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Crystal structure of [Cu2(Edta)(Py)2(H2O)2] · 2H2O and [Cu(Im)6]{;Cu(Im)4[Cu(Edta)(Im)]2} · 6H2O, Products of the interaction of (Ethylenediaminetetraacetato)diaquadicopper(II) with pyridine and imidazole

Authors
  • Antsyshkina, A. S.1
  • Sadikov, G. G.1
  • Poznyak, A. L.2
  • Sergienko, V. S.1
  • 1 Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry, Leninskii pr. 31, Moscow, 119991, Russia , Moscow (Russia)
  • 2 National Academy of Sciences of Belarus, Institute of Molecular and Atomic Physics, ul. F. Skaryna, Minsk, 220072, Belarus , Minsk (Belarus)
Type
Published Article
Journal
Russian Journal of Inorganic Chemistry
Publisher
Nauka/Interperiodica
Publication Date
Feb 01, 2006
Volume
51
Issue
2
Pages
241–252
Identifiers
DOI: 10.1134/S0036023606020124
Source
Springer Nature
Keywords
License
Yellow

Abstract

The crystals of [Cu2(Edta)(Py)2(H2O)2] · 2H2O (I) and [Cu(Im)6]{;Cu(Im)4[Cu(Edta)(Im)]2} · 6H2O (II) were isolated as a result of the reaction of an aqueous solutions of Cu2(Edta) · 4H2O with pyridine or imidazole, respectively. The crystals were studied by X-ray diffraction. The crystals of I are monoclinic, a = 12.682 Å, b = 6.788 Å, c = 14.834 Å, β = 91.44°, Z = 2, space group P21/n. The crystals of II are triclinic, a = 9.118 Å, b = 14.889 Å, c = 15.130 Å, α = 72.59°, β = 72.94°, γ = 82.54°, Z = 1, space group P{ie241-1}. In the centrosymmetric binuclear complex molecule of I, an N atom and two O atoms of the Edta ligand are coordinated to each Cu atom (Cu-N, 2.046 Å; Cu-O, 1.941 and 1.954 Å). The N atom of the pyridine molecule (Cu-N, 1.993 Å) completes the base of an elongated tetragonal pyramid (4 + 1) with the O atom of the H2O molecule in the apex (Cu-O(w), 2.244 Å). The crystals of II are built of centrosymmetric complex cations [Cu(Im)6]2+ (Cu(1)-N, 2.469, 2.021, and 2.056 Å), centrosymmetric trinuclear complex anions {;Cu(Im)4[Cu(Edta)(Im)]2}2−, and crystal water molecules. In the anion, the central fragment [Cu(Im)4]2+ (Cu(2)-N, 1.985 and 2.023 Å) is bonded to two peripheral complexes [Cu(Edta)(Im)]2− through atoms O of the Edta ligand (Cu(2)-O, 2.615 Å). In the [Cu(Edta)(Im)]2− fragment of the complex anion, the Cu(3) atom is bonded to the Edta ligand through the two N atoms and three O atoms (Cu(3)-N, 1.970 and 2.071 Å; Cu(3)-O, 1.966, 1.969, and 2.238 Å) and with the imidazole molecule, through an N atom (Cu(3)-N, 2.397 Å). The coordination polyhedra of the three copper atoms (Cu(1)-Cu(3)) in the structure of II are elongated tetragonal bipyramids (4 + 2). In the structures studied, Edta4− is a hexadentate chelating/bridging ligand. However, the coordination mode of the ligand in these structures is different: in the binuclear complex I, the Edta ligand is coordinated to each Cu atom through an N atom and two O atoms with the formation of two chelate rings (symmetric (trans) coordination mode), whereas, in the trinuclear complex II, the Edta ligand is coordinated to the Cu(2) atom through an O atom and to the Cu(3) atom through the two N atoms and three O atoms with the formation of three chelate rings (asymmetric (cis) coordination mode).

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