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Volume 67 
Part 6 
Pages m793-m794  
June 2011  

Received 17 May 2011
Accepted 19 May 2011
Online 25 May 2011

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Key indicators
Single-crystal X-ray study
T = 295 K
Mean [sigma](C-C) = 0.004 Å
Disorder in main residue
R = 0.035
wR = 0.089
Data-to-parameter ratio = 19.6
Details
Open access

Bis(3-methylpyridinium) tetra(chlorido/bromido)cuprate(II)

Young-Inn Kim,a Hyun-Soo Lima and Sung Kwon Kangb*

aDepartment of Chemistry Education and Interdisciplinary Program of Advanced Information and Display Materials, Pusan National University, Pusan 609-735, Republic of Korea, and bDepartment of Chemistry, Chungnam National University, Daejeon 305-764, Republic of Korea
Correspondence e-mail: skkang@cnu.ac.kr

The structure of the title salt, (C6H8N)2[CuCl3.4Br0.6], consists of two 3-methylpyridinium cations and a distorted tetrahedral [CuCl3.4Br0.6]2- dianion. Substitutional disorder with Br is exhibited for three of the Cl atoms of the anion, giving a mixed chloride/bromide cuprate(II) anion. In the crystal, intermolecular N-H...Cl hydrogen bonds link two cations to one anion, forming a three-ion aggregate. These are connected into a supramolecular chain along the b axis via [pi]-[pi] interactions between the pyridinium rings [centroid-centroid distance = 3.743 (3) Å].

Related literature

For general background to the geometry of the tetrahalidocuprate(II) species, see: Solomon et al. (1992[Solomon, E. I., Baldwin, M. J. & Lowery, M. D. (1992). Chem. Rev. 92, 521-542.]); Kim et al. (2001[Kim, Y. J., Kim, S. O., Kim, Y. I. & Choi, S. N. (2001). Inorg. Chem. 40, 4481-4484.]); Panja et al. (2005[Panja, A., Goswami, S., Shaikh, N., Roy, P., Manassero, M., Butcher, R. J. & Banerjee, P. (2005). Polyhedron, 24, 2921-2932.]); Sengottvelan et al. (2009[Sengottvelan, N., Lee, Y.-S., Lim, H.-S., Kim, Y.-I. & Kang, S. K. (2009). Acta Cryst. E65, m384.]). For its magnetic properties, see: Lee et al. (2004[Lee, Y. K., Park, S. M., Kang, S. K., Kim, Y. I. & Choi, S. N. (2004). Bull. Korean Chem. Soc. 25, 823-828.]); Turnbull et al. (2005[Turnbull, M. M., Landee, C. P. & Wells, B. M. (2005). Coord. Chem. Rev. 249, 2567-2576.]); Shapiro et al. (2007[Shapiro, A., Landee, C. P., Turnbull, M. M., Jornet, J., Deumal, M., Novoa, J. J., Robb, M. A. & Lewis, W. (2007). J. Am. Chem. Soc. 129, 952-959.]). CuBr42- ions usually show less distortion from the ideal tetrahedral geometry compared with CuCl42- ions, see: Edwards et al. (2011[Edwards, K., Herringer, S. N., Parent, A. R., Provost, M., Shortsleeves, K. C., Turnbull, M. M. & Dawe, L. N. (2011). Inorg. Chim. Acta, 368, 141-151.]); AlDaman & Haddad (2011[AlDaman, M. A. & Haddad, S. F. (2011). J. Mol. Struct. 985, 27-33.]).

[Scheme 1]

Experimental

Crystal data

  • (C6H8N)2[CuBr0.60Cl3.40]

  • Mr = 420.28

  • Monoclinic, P 21 /n

  • a = 9.0617 (18) Å

  • b = 13.259 (3) Å

  • c = 14.060 (3) Å

  • [beta] = 102.47 (3)°

  • V = 1649.4 (6) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 3.32 mm-1

  • T = 295 K

  • 0.19 × 0.15 × 0.15 mm
Data collection

  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2002[Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.560, Tmax = 0.610

  • 17556 measured reflections

  • 4094 independent reflections

  • 2621 reflections with I > 2[sigma](I)

  • Rint = 0.039
Refinement

  • R[F2 > 2[sigma](F2)] = 0.035

  • wR(F2) = 0.089

  • S = 1.03

  • 4094 reflections

  • 209 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • [Delta][rho]max = 0.34 e Å-3

  • [Delta][rho]min = -0.41 e Å-3

Table 1
Selected geometric parameters (Å, °)

Cu1-Cl2 2.232 (8)
Cu1-Cl4 2.248 (10)
Cu1-Cl5 2.2604 (8)
Cu1-Cl3 2.273 (3)
Cl2-Cu1-Cl4 97.5 (3)
Cl2-Cu1-Cl5 135.34 (14)
Cl4-Cu1-Cl5 99.0 (3)
Cl2-Cu1-Cl3 100.2 (2)
Cl4-Cu1-Cl3 135.8 (2)
Cl5-Cu1-Cl3 96.18 (8)

Table 2
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
N1-H1...Cl5 0.76 (3) 2.50 (3) 3.158 (3) 145 (3)
N8-H8...Cl3 0.82 (3) 2.53 (3) 3.245 (4) 147 (3)
N8-H8...Cl5 0.82 (3) 2.72 (3) 3.332 (3) 133 (3)

Data collection: SMART (Bruker, 2002[Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2002[Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2745 ).

Acknowledgements

This work was supported by a 2-Year Research Grant of Pusan National University.

References

AlDaman, M. A. & Haddad, S. F. (2011). J. Mol. Struct. 985, 27-33.
Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.
Edwards, K., Herringer, S. N., Parent, A. R., Provost, M., Shortsleeves, K. C., Turnbull, M. M. & Dawe, L. N. (2011). Inorg. Chim. Acta, 368, 141-151.  [ChemPort]
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  [CrossRef] [details]
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.  [CrossRef] [ChemPort] [details]
Kim, Y. J., Kim, S. O., Kim, Y. I. & Choi, S. N. (2001). Inorg. Chem. 40, 4481-4484.  [ISI] [PubMed] [ChemPort]
Lee, Y. K., Park, S. M., Kang, S. K., Kim, Y. I. & Choi, S. N. (2004). Bull. Korean Chem. Soc. 25, 823-828.  [ChemPort]
Panja, A., Goswami, S., Shaikh, N., Roy, P., Manassero, M., Butcher, R. J. & Banerjee, P. (2005). Polyhedron, 24, 2921-2932.  [ChemPort]
Sengottvelan, N., Lee, Y.-S., Lim, H.-S., Kim, Y.-I. & Kang, S. K. (2009). Acta Cryst. E65, m384.  [CSD] [CrossRef] [details]
Shapiro, A., Landee, C. P., Turnbull, M. M., Jornet, J., Deumal, M., Novoa, J. J., Robb, M. A. & Lewis, W. (2007). J. Am. Chem. Soc. 129, 952-959.  [ISI] [PubMed] [ChemPort]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Solomon, E. I., Baldwin, M. J. & Lowery, M. D. (1992). Chem. Rev. 92, 521-542.  [CrossRef] [ChemPort]
Turnbull, M. M., Landee, C. P. & Wells, B. M. (2005). Coord. Chem. Rev. 249, 2567-2576.  [ISI] [CrossRef] [ChemPort]

Acta Cryst (2011). E67, m793-m794   [ doi:10.1107/S1600536811019076 ]

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