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Volume 59 
Part 1 
Pages m17-m19  
January 2003  

Received 12 November 2002
Accepted 2 December 2002
Online 19 December 2002


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© International Union of Crystallography 2003

Key indicators
Single-crystal X-ray study
T = 180 K
Mean [sigma](C-C) = 0.004 Å
R = 0.017
wR = 0.046
Data-to-parameter ratio = 11.1
Details

Aquadichloro(2,9-dimethyl-1,10-phenanthroline-[kappa]2N,N')copper(II)

Pascale Lemoine,a* Bernard Viossata,b and Jean-Claude Daranc

aLaboratoire de Cristallographie et RMN Biologiques, UMR 8015 CNRS, Faculté des Sciences Pharmaceutiques et Biologiques de Paris V, 4 Avenue de l'Observatoire, 75270 Paris Cedex 06, France,bLaboratoire de Chimie Générale, Faculté de Médecine et de Pharmacie, 34 rue du Jardin des Plantes, BP199, 86005 Poitiers Cedex, France, and cLaboratoire de Chimie de Coordination, UPR 8241 CNRS, 205 route de Narbonne 31077 Toulouse Cedex 04, France
Correspondence e-mail: lemoine@pharmacie.univ-paris5.fr

The crystal structure of the title compound, [CuCl2(C14H12N2)(H2O)], previously reported by Preston & Kennard [J. Chem. Soc. A (1969[Preston, H. S. & Kennard, C. H. L. (1969). J. Chem. Soc. A, pp. 2955-2958.]). pp. 2955-2958], has been redetermined. The recognition of an inversion twin allowed a much better refinement.

Comment

The asymmetric unit of the title compound, (I[link]), contains one monomeric five-coordinate copper complex. The Cu atom is coordinated by one 2,9-dimethyl-1,10-phenanthroline (neocuproine) ligand via both N atoms, two Cl- anions and to one water molecule. The complex exhibits a distorted square pyramidal geometry about the copper(II) atom, with the apical position occupied by atom N10 from the neocuproine ligand. The Cu atom is displaced by 0.3074 (6) Å out of the basal plane defined by atoms N1, Cl1, Cl2 and OW1. An alternative description of this molecule would be trigonal bipyramidal, with atoms N1 and OW1 in axial positions [OW1 Cu1 N1 171.50 (8)°; the Cu atom is 0.0327 (3) Å out of the equatorial plane]. However, analysis of the [tau] factor, proposed by Addison & Rao (1984[Addison, A. W. & Rao, T. N. (1984). J. Chem. Soc. Dalton Trans. pp. 1349-1356.]) for five-coordinate copper complexes, makes the description as distorted square pyramidal more correct, with a [tau] value of 0.267 ([tau] square pyramidal = 0.0, [tau] trigonal bipyramidal = 1.0).[link]

[Scheme 1]

The crystal packing is characterized by two hydrogen bonds [OW-HW1...Cl1i: 3.088 (2) Å, 159 (3)°; OW-HW2...Cl2ii 3.029 (2) Å, 162 (3)°; symmetry codes: (i) -x, y + ½, -z; (ii) -x, y - ½, -z]; these interactions result in chains parallel to the b axis. The neocuproine least-squares planes are linked by [\pi−\pi] stacking interactions, related, in pairs, by the twofold screw axis, with an average spacing of 3.153 Å (symmetry code: 1-x, -½ + y, 1 - z).

[Figure 1]
Figure 1
Perspective view of the asymmetric unit, showing the atomic numbering. Displacement ellipsoids are at the 50% probability level.
[Figure 2]
Figure 2
The [pi]-[pi]-stacking interactions between neocuproine ligands.
[Figure 3]
Figure 3
The molecular packing, showing chains formed by hydrogen bonds.

Experimental

The title compound was synthesized according to Preston & Kennard (1969[Preston, H. S. & Kennard, C. H. L. (1969). J. Chem. Soc. A, pp. 2955-2958.]). Green parallelepiped crystals were obtained by recrystallization from methanol.

Crystal data

  • [CuCl2(C14H12N2)(H2O)]

  • Mr = 360.71

  • Monoclinic, P21

  • a = 9.462 (1) Å

  • b = 8.093 (1) Å

  • c = 9.823 (1) Å

  • [beta] = 105.38 (1)°

  • V = 725.3 (1) Å3

  • Z = 2

  • Dx = 1.652 Mg m-3

  • Dm = 1.63 (2) Mg m-3

  • Dm measured by flotation in CCl4/C2H4Br2

  • Mo K[alpha] radiation

  • Cell parameters from 5681 reflections

  • [theta] = 2.2-26.1°

  • [mu] = 1.87 mm-1

  • T = 180 (2) K

  • Parallelepiped, green

  • 0.30 × 0.25 × 0.20 mm
Data collection

  • Stoe IPDS diffractometer

  • [varphi] scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.511, Tmax = 0.569

  • 5663 measured reflections

  • 2499 independent reflections

  • 2425 reflections with I > 2[sigma](I)

  • Rint = 0.018

  • [theta]max = 26.1°

  • h = -10 [rightwards arrow] 10

  • k = -9 [rightwards arrow] 9

  • l = -12 [rightwards arrow] 12
Refinement

  • Refinement on F2

  • R[F2 > 2[sigma](F2)] = 0.017

  • wR(F2) = 0.046

  • S = 1.05

  • 2499 reflections

  • 225 parameters

  • All H-atom parameters refined

  • w = 1/[[sigma]2(Fo2) + (0.0354P)2] where P = (Fo2 + 2Fc2)/3

  • ([Delta]/[sigma])max < 0.001

  • [Delta][rho]max = 0.27 e Å-3

  • [Delta][rho]min = -0.21 e Å-3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 951 Friedel pairs

  • Flack parameter = 0.538 (8)

Table 1
Selected geometric parameters (Å, °)

Cu-OW 1.9582 (15)
Cu-N1 1.9911 (15)
Cu-N10 2.230 (2)
Cu-Cl2 2.3017 (5)
Cu-Cl1 2.3026 (6)
OW-Cu-N1 171.44 (7)
OW-Cu-N10 107.34 (7)
N1-Cu-N10 79.98 (7)
OW-Cu-Cl2 87.57 (5)
N1-Cu-Cl2 86.68 (6)
N10-Cu-Cl2 100.57 (5)
OW-Cu-Cl1 87.77 (6)
N1-Cu-Cl1 94.84 (5)
N10-Cu-Cl1 103.92 (5)
Cl2-Cu-Cl1 155.36 (2)
C2-N1-Cu 123.98 (15)
C14-N1-Cu 114.81 (11)
C9-N10-Cu 133.46 (16)
C11-N10-Cu 107.36 (14)

Table 2
Hydrogen-bonding geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
OW-HW1...Cl1i 0.77 (4) 2.36 (4) 3.0882 (17) 159 (3)
OW-HW2...Cl2ii 0.75 (4) 2.31 (4) 3.0286 (17) 162 (3)
Symmetry codes: (i) [-x,{\script{1\over 2}}+y,-z]; (ii) [-x,y-{\script{1\over 2}},-z].

H atoms were located from difference Fourier maps and freely refined; a common displacement parameter was refined for all H atoms. The refinement of the Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) parameter [x = 0.538 (8)] clearly indicates the occurrence of an inversion twin.

Data collection: IPDS Software (Stoe & Cie, 1996[Stoe & Cie (1996). IPDS Manual (Version 2.75) and X-RED (Revision 1.08). Stoe & Cie, Darmstadt, Germany.]); cell refinement: IPDS Software; data reduction: XRED (Stoe & Cie, 1996[Stoe & Cie (1996). IPDS Manual (Version 2.75) and X-RED (Revision 1.08). Stoe & Cie, Darmstadt, Germany.]); program(s) used to solve structure: SIR92 (Altomare et al., 1999[Altomare, A., Burla, M. C., Camalli, M., Cascarano, G., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115-119.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.]); molecular graphics: CAMERON (Watkin et al., 1996[Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.]); software used to prepare material for publication: WinGX (Version 1.63.02; Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

References

Addison, A. W. & Rao, T. N. (1984). J. Chem. Soc. Dalton Trans. pp. 1349-1356. [CrossRef]
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115-119. [CrossRef] [ChemPort] [details]
Blessing, R. H. (1995). Acta Cryst. A51, 33-38. [CrossRef] [details]
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838. [CrossRef] [details]
Flack, H. D. (1983). Acta Cryst. A39, 876-881. [CrossRef] [ChemPort] [details]
Preston, H. S. & Kennard, C. H. L. (1969). J. Chem. Soc. A, pp. 2955-2958.
Stoe & Cie (1996). IPDS Manual (Version 2.75) and X-RED (Revision 1.08). Stoe & Cie, Darmstadt, Germany.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.

Acta Cryst (2003). E59, m17-m19   [ doi:10.1107/S1600536802022249 ]