Journal article
Dipicolylamine Complexes of Copper(II): Two Different Coordination Geometries in the Same Unit Cell of Cu(Dipica)(2)(BF(4))(2)
Inorganic chemistry, v 35(2), pp 467-471
17 Jan 1996
PMID: 11666231
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Abstract
Bright blue Cu(Dipica)(2)(BF(4))(2) crystallizes in the monoclinic space group P2(1)/n, with unit cell parameters a = 23.406(6) Å, b = 9.338(2) Å, c = 25.573(7) Å, beta = 95.39(2) degrees, and Z = 8. The structure was solved by conventional Patterson and Fourier methods. The R and R(w) values for 5282 observed reflections were 7.06% and 9.10% respectively. Two structurally different complex cations are present in the same unit cell, one hexacoordinate and the other pentacoordinate. In the hexacoordinate cation, the two tridentate bis(2'-picolyl)amine ligands are trans-facially coordinated with two pyridine nitrogens and the two secondary amine nitrogens situated on four positions in a plane [Cu-N(pyr) = 2.189(6), 2.146(6) Å; Cu-N(sat) = 2.207(6), 2.201(5) Å]. The remaining two pyridine nitrogens constitute the axis [Cu-N(pyr) = 2.035(5), 2.038(5) Å] in an equatorially expanded pseudooctahedral geometry. The pentacoordinate cation possesses a square-pyramidal configuration, the two secondary nitrogens being mutually cis, with one Dipica equatorially tridentate [Cu-N(pyr) = 2.044(5), 2.027(5) Å, Cu-N(sat) = 1.995(5) Å]. The other Dipica functions as a bidentate ligand, with one of the pyridine nitrogens occupying the equator [Cu-N(pyr) = 1.986(5) Å] and the aliphatic nitrogen defining the axial copper position [Cu-N(sat) = 2.344(5) Å]. Its second pyridine is uncoordinated but hydrogen-bonded to the coordinated NH of the other ligand. Solution properties offer no clear distinction between the two cation stereochemistries. The ternary chelates [Cu(Dipica)(Acac)]ClO(4) and [Cu(Dipica)(Bipy)](ClO(4))(2) are also described.
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Details
- Title
- Dipicolylamine Complexes of Copper(II): Two Different Coordination Geometries in the Same Unit Cell of Cu(Dipica)(2)(BF(4))(2)
- Creators
- Mallayan Palaniandavar - Departments of Chemistry, Drexel University, Philadelphia, Pennsylvania 19104, and Howard University, Washington, D.C. 20059.Raymond J. ButcherAnthony W. Addison - Drexel University
- Publication Details
- Inorganic chemistry, v 35(2), pp 467-471
- Publisher
- American Chemical Society; Washington, DC
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:A1996TR24000032
- Scopus ID
- 2-s2.0-0000700250
- Other Identifier
- 991019168267804721
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- Collaboration types
- Domestic collaboration
- Web of Science research areas
- Chemistry, Inorganic & Nuclear