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Volume 69 
Part 6 
Pages m307-m308  
June 2013  

Received 25 April 2013
Accepted 3 May 2013
Online 11 May 2013

Key indicators
Single-crystal X-ray study
T = 295 K
Mean [sigma](C-C) = 0.005 Å
Disorder in main residue
R = 0.029
wR = 0.087
Data-to-parameter ratio = 14.8
Details
Open access

Sodium bis(ethylenediamine)copper(II) tetracyanidocuprate(I)

aDepartment of Chemistry, Fordham University, 441 East Fordham Road, Bronx, NY 10458, USA, and bThe King's College, Briarcliff Manor, NY 10510, USA
Correspondence e-mail: pcorfield@fordham.edu

The title compound, Na[Cu(en)2][Cu(CN)4], where en represents ethylenediamine, NH2CH2CH2NH2, crystallizes as a salt with two distinct cations, Na+ and [CuIIen2]2+, and discrete [CuI(CN)4]3- anions. The anion geometry is tetrahedral, with angles at the copper atom ranging from 105.0 (1) to 115.4 (1)°. The Cu-C distances are in the range 1.976 (3) to 1.993 (3) Å. The divalent copper atom is coordinated by four N atoms of the two bidentate en ligands in a slightly distorted square-planar geometry. In the crystal, each sodium ion interacts with cyanide N atoms of four different anions, with Na-N distances lying in the narrow range of 2.344 (3) to 2.367 (3) Å, and an approximately tetrahedral arrangement around the sodium ions. The interacting sodium ions and [CuI(CN)4]3- anions form a three-dimensional network with channels which contain the [Cu(en)2]2+ cations. One of the chelate rings in the cation shows partial disorder between two different conformations and the C atoms were refined with occupancies in the ratio 0.817 (15):0.183 (15).

Related literature

The work presented here continues studies on mixed-valence copper cyanide complexes, see: Corfield et al. (2012[Corfield, P. W. R., Grillo, S. A. & Umstott, N. S. (2012). Acta Cryst. E68, m1532-m1533.]). Studies by others on similar complexes include Colacio et al. (2002[Colacio, E., Kivekas, R., Lloret, F., Sunberg, M., Suarez-Varela, J., Bardaji, M. & Laguna, A. (2002). Inorg. Chem. 47, 5141-5149.]) and Kim et al. (2005[Kim, D., Koo, J., Hong, C. S., Oh, S. & Do, Y. (2005). Inorg. Chem. 44, 4383-4390.]). For other results on the specific system CuI,II-CN-en, see: Williams et al. (1972[Williams, R. J., Larson, A. C. & Cromer, D. T. (1972). Acta Cryst. B28, 858-864.]) and Weiss et al. (2006[Weiss, R., Jansen, G., Boese, R. & Epple, M. (2006). J. Chem. Soc. Dalton Trans. pp. 1831-1835.]). We are aware of only one other detailed crystal structure describing the discrete [Cu(CN)4]3- anion, that reported for K3Cu(CN)4 in Roof et al. (1968[Roof, R. B., Larson, A. C. & Cromer, D. T. (1968). Acta Cryst. B24, 269-273.]). For molar conductance, see: Angelici (1977[Angelici, R. J. (1977). Synthesis and Techniques in Inorganic Chemistry, p. 17. Philadelphia: W. B. Saunders.]).

[Scheme 1]

Experimental

Crystal data
  • Na[Cu(C2H8N2)2][Cu(CN)4]

  • Mr = 374.36

  • Monoclinic, P 21 /c

  • a = 8.842 (1) Å

  • b = 10.743 (1) Å

  • c = 15.268 (3) Å

  • [beta] = 98.32 (1)°

  • V = 1435.0 (4) Å3

  • Z = 4

  • Cu K[alpha] radiation

  • [mu] = 3.94 mm-1

  • T = 295 K

  • 0.33 × 0.27 × 0.16 mm

Data collection
  • Enraf-Nonius CAD-4 diffractometer

  • Absorption correction: integration Busing & Levy (1957[Busing, W. R. & Levy, H. A. (1957). Acta Cryst. 10, 180-182.]) Tmin = 0.361, Tmax = 0.576

  • 5288 measured reflections

  • 2679 independent reflections

  • 2614 reflections with I > 2[sigma](I)

  • Rint = 0.024

  • 3 standard reflections every 120 min intensity decay: 11%

Refinement
  • R[F2 > 2[sigma](F2)] = 0.029

  • wR(F2) = 0.087

  • S = 1.19

  • 2679 reflections

  • 181 parameters

  • H-atom parameters constrained

  • [Delta][rho]max = 0.32 e Å-3

  • [Delta][rho]min = -0.20 e Å-3

Data collection: CAD-4 Software (Enraf-Nonius, 1994[Enraf-Nonius (1994). CAD-4 Software. Enraf-Nonius, Delft, The Netherlands.]); cell refinement: CAD-4 Software; data reduction followed procedures in Corfield et al. (1973[Corfield, P. W. R., Dabrowiak, J. C. & Gore, E. S. (1973). Inorg. Chem. 12, 1734-1740.]): data were averaged with a local version of SORTAV (Blessing, 1989[Blessing, R. H. (1989). J. Appl. Cryst. 22, 396-397.]); program(s) used to solve structure: locally modified program (Corfield, 1984[Corfield, P. W. R. (1984). Local versions of standard programs, written at The King's College.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and XABS2 (Parkin et al., 1995[Parkin, S., Moezzi, B. & Hope, H. (1995). J. Appl. Cryst. 28, 53-56.]); molecular graphics: ORTEPIII (Burnett & Johnson, 1996[Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.]); software used to prepare material for publication: SHELXL97.


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH5608 ).


Acknowledgements

We are grateful to Nancy McGuire and the X-Ray Lab then at Union Carbide in Tarrytown, NY, for use of their CAD-4 diffractometer. We thank Caryn Goodwin, Linda Kuzcko, Ruth Josenhans, John Oskam, and Nicholas Della Rocco for their assistance in this work. We also acknowledge gratefully an Atlantic Richfield Foundation grant from the Research Corporation, and funding from the Alumni Association of The King's College, where the experimental work was carried out.

References

Angelici, R. J. (1977). Synthesis and Techniques in Inorganic Chemistry, p. 17. Philadelphia: W. B. Saunders.
Blessing, R. H. (1989). J. Appl. Cryst. 22, 396-397.  [CrossRef] [details]
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
Busing, W. R. & Levy, H. A. (1957). Acta Cryst. 10, 180-182.  [CrossRef] [ChemPort] [details]
Colacio, E., Kivekas, R., Lloret, F., Sunberg, M., Suarez-Varela, J., Bardaji, M. & Laguna, A. (2002). Inorg. Chem. 47, 5141-5149.  [ISI] [CSD] [CrossRef]
Corfield, P. W. R. (1984). Local versions of standard programs, written at The King's College.
Corfield, P. W. R., Dabrowiak, J. C. & Gore, E. S. (1973). Inorg. Chem. 12, 1734-1740.  [CrossRef] [ChemPort] [ISI]
Corfield, P. W. R., Grillo, S. A. & Umstott, N. S. (2012). Acta Cryst. E68, m1532-m1533.  [CSD] [CrossRef] [ChemPort] [details]
Enraf-Nonius (1994). CAD-4 Software. Enraf-Nonius, Delft, The Netherlands.
Kim, D., Koo, J., Hong, C. S., Oh, S. & Do, Y. (2005). Inorg. Chem. 44, 4383-4390.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Parkin, S., Moezzi, B. & Hope, H. (1995). J. Appl. Cryst. 28, 53-56.  [CrossRef] [ChemPort] [ISI] [details]
Roof, R. B., Larson, A. C. & Cromer, D. T. (1968). Acta Cryst. B24, 269-273.  [CrossRef] [ChemPort] [details]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [details]
Weiss, R., Jansen, G., Boese, R. & Epple, M. (2006). J. Chem. Soc. Dalton Trans. pp. 1831-1835.
Williams, R. J., Larson, A. C. & Cromer, D. T. (1972). Acta Cryst. B28, 858-864.  [CrossRef] [ChemPort] [details]


Acta Cryst (2013). E69, m307-m308   [ doi:10.1107/S1600536813012075 ]

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