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X-ray powder diffraction data for copper(II), bis[(2E)-3-methoxy-2-[(2,6-dimethylphenyl)imino]-4-[(2,6-dimethylphenyl)imino-κN]-3-pentanolato-κO] complex

Published online by Cambridge University Press:  29 May 2013

R. Pažout ,
J. Maixner ,
A.S. Jones  and
J. Merna
R. Pažout*
Affiliation:
Central Laboratories, Institute of Chemical Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic
J. Maixner
Affiliation:
Central Laboratories, Institute of Chemical Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic
A.S. Jones
Affiliation:
Department of Polymers, Institute of Chemical Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic
J. Merna
Affiliation:
Department of Polymers, Institute of Chemical Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic
*
a) Author to whom correspondence should be addressed. Electronic mail: richard.pazout@vscht.cz

Abstract

X-ray powder diffraction data, unit-cell parameters, and space group for a new bis(β-diiminato) Cu(II) complex, C44H54CuN4O4, are reported [a = 8.683(3) Å, b = 11.216(3) Å, c = 11.753(4) Å, α = 66.27(3), β = 84.61(3), γ = 78.85(3), unit-cell volume V = 1027.77 Å3, Z = 1, and space group P-1]. All measured lines were indexed and are consistent with the P-1 space group. No detectable impurity was observed.

Keywords

X-ray powder diffractionbis(β-diiminato) Cu(II) complex

Information

Type
New Diffraction Data
Information
Powder Diffraction , Volume 28 , Issue 4 , December 2013 , pp. 296 - 298
Copyright
Copyright © International Centre for Diffraction Data 2013 

I. INTRODUCTION

Copper(II), bis[(2E)-3-methoxy-2-[(2,6-dimethylphenyl)imino]-4-[(2,6-dimethylphenyl) imino-κN]-3-pentanolato-κO] complex (Figure 1) is a reaction intermediate in the synthesis of keto-β − diimine ligands (Yokota et al., Reference Yokota, Tachi and Itoh2002). The complexation of these ligands to nickel leads to the formation of efficient catalysts for olefin polymerization (Azoulay et al., Reference Azoulay, Schneider, Galland and Bazan2009) similarly to more frequently used α − diimine complexes of Ni and Pd (Johnson et al., Reference Johnson, Killian and Brookhart1995). These keto-β-diimine Ni complexes allow the living polymerization of ethylene and higher olefins leading to polyolefins with the controlled molar mass.

Figure 1.

Structural formula of the title compound, copper(II), bis[(2E)-3-methoxy-2-[(2,6-dimethylphenyl)imino]-4-[(2,6-dimethylphenyl) imino-κN]-3-pentanolato-κO] complex.

II. EXPERIMENTAL

A. Sample preparation

Preparation of Cu(II) complex is based on oxidative degradation of β-diimine by copper acetate under aerobic conditions reported by Yokota et al. (Reference Yokota, Tachi and Itoh2002).

Starting compounds for the synthesis were a β-diimine ligand, prepared according to Feldman et al. (Reference Feldman, McLain, Parthasarathy, Marshall, Calabrese and Arthur1997), and copper(II) acetate monohydrated yielding a copper(II) β-diimine complex. The copper(II) β-diimine complex was converted to the title complex (copper(II), bis[(2E)-3-methoxy-2-[(2,6-dimethylphenyl)imino]-4-[(2,6-dimethylphenyl)imino-κN]-3-pentanolato-κO]) by a reaction with molecular oxygen.

B. Diffraction data collection and reduction

The diffraction pattern for the title compound was collected at room temperature using an X'Pert PRO θ–θ powder diffractometer with parafocusing Bragg–Brentano geometry and CuKα 1 radiation (λ = 1.5406 Å, generator setting: 40 kV, 30 mA). An ultrafast X'Celerator detector was employed to collect XRD data over the angular range from 4 to 60° 2θ with a step size of 0.017° 2θ and a counting time of 20.32 s/step. The experimental powder diffraction pattern is depicted in Figure 2. The software package HighScore PlusV3.0d of PANalytical, Almelo, Netherlands was used to smooth the data, to fit the background, and to eliminate the Kα 2 component. The top of the smoothed peak method was used to determine the peak positions and intensities of the diffraction peaks.

Figure 2.

X-ray powder diffraction pattern of the title compound using CuKα 1 radiation (λ = 1.5406 Å).

Automatic indexing of the experimental XRD pattern was done using DICVOL04 (Boultif and Louër, Reference Boultif and Louër2004).

III. RESULTS

The experimental powder diffraction pattern is depicted in Figure 2. Automatic indexing results obtained by DICVOL04 (Table 1) show that the title compound is triclinic with a space group P-1 and unit-cell parameters: a = 8.683(3) Å, b = 11.216(3) Å, c = 11.753(4) Å, α = 66.27(3), β = 84.61(3), γ = 78.85(3), unit-cell volume V = 1027.77 Å3, and Z = 1. The figures of merits are F 20 = 115.3(0.0062, 28) (Smith and Snyder, Reference Smith and Snyder1979) and M 20 = 40.8 (de Wolf, Reference De Wolff1968). All lines were indexed and are consistent with the P-1 space group.

Table I.

Indexed X-ray powder diffraction data for the title compound, C44H54CuN4O4l.. Only the peaks with I rel of 1 or greater are presented [a = 8.683(3) Å, b = 11.216(3) Å, c = 11.753(4) Å, α = 66.27(3), β = 84.61(3), γ = 78.85(3), unit-cell volume V = 1027.77 Å3, Z = 1, and space group P-1]. All measured lines were indexed and are consistent with the P-1 space group. The d-values were calculated using CuKα 1 radiation (λ = 1.5406 Å).

ACKNOWLEDGEMENT

This work was supported by the grant TA 03011394 of the Technological Agency of the Czech Republic.

References

Azoulay, J. D., Schneider, Y., Galland, G. B., and Bazan, G. C. (2009). “Living polymerization of ethylene and α-olefins using a nickel α-keto-β-diimine initiator,” Chem. Commun. 41, 6177.Google Scholar
Boultif, A. and Louër, D. (2004). “Powder pattern indexing with the dichotomy method,” J. Appl. Crystallogr. 37, 724–731.Google Scholar
De Wolff, P. M. (1968). “A simplified criterion for the reliability of a powder pattern indexing,” J. Appl. Crystallogr. 1, 108–113.CrossRefGoogle Scholar
Feldman, J., McLain, S. J., Parthasarathy, A., Marshall, W. J., Calabrese, J. C., and Arthur, S. D. (1997). “Electrophilic metal precursors and a beta-diimine ligand for nickel(II)- and palladium(II)-catalyzed ethylene polymerizations,” Organometallics 16, 1514–1516.Google Scholar
Johnson, L. K., Killian, C. M., and Brookhart, M. (1995). “New Pd(Ii)-based and Ni(Ii)-based catalysts for polymerization of ethylene and alpha-olefins,” J. Am. Chem. Soc. 117, 6414–6415.CrossRefGoogle Scholar
Smith, G. S. and Snyder, R. L. (1979). “FN: A criterion for rating powder diffraction patterns and evaluating the reliability of powder indexing,” J. Appl. Crystallogr. 12, 60–65.Google Scholar
Yokota, S., Tachi, Y., and Itoh, S. (2002). “Oxidative degradation of β-diketiminate ligand in copper(II) and zinc(II) complexes,” Inorg. Chem. 41, 1342–1344.Google Scholar
Figure 0

Figure 1. Structural formula of the title compound, copper(II), bis[(2E)-3-methoxy-2-[(2,6-dimethylphenyl)imino]-4-[(2,6-dimethylphenyl) imino-κN]-3-pentanolato-κO] complex.

Figure 1

Figure 2. X-ray powder diffraction pattern of the title compound using CuKα1 radiation (λ = 1.5406 Å).

Figure 2

Table I. Indexed X-ray powder diffraction data for the title compound, C44H54CuN4O4l.. Only the peaks with Irel of 1 or greater are presented [a = 8.683(3) Å, b = 11.216(3) Å, c = 11.753(4) Å, α = 66.27(3), β = 84.61(3), γ = 78.85(3), unit-cell volume V = 1027.77 Å3, Z = 1, and space group P-1]. All measured lines were indexed and are consistent with the P-1 space group. The d-values were calculated using CuKα1 radiation (λ = 1.5406 Å).