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Volume 69 
Part 5 
Pages m275-m276  
May 2013  

Received 3 April 2013
Accepted 10 April 2013
Online 20 April 2013

Key indicators
Single-crystal X-ray study
T = 296 K
Mean [sigma](C-C) = 0.007 Å
R = 0.050
wR = 0.122
Data-to-parameter ratio = 21.3
Details
Open access

Tris([mu]4-azepane-1-carbodithioato)bis([mu]3-azepane-1-carbodithioato)-[mu]9-bromido-tetra-[mu]2-bromido-octacopper(I)copper(II)

aDepartment of Chemistry, Faculty of Science and Engineering, Kinki University, Higashi-Osaka, Osaka 577-8502, Japan, and bPRESTO, Japan Science and Technology Agency (JST), Japan
Correspondence e-mail: okubo_t@chem.kindai.ac.jp

The reaction of Cu(Hm-dtc)2 (H2m-dtc is azepane-1-carbodithioic acid), CuBr2 and methyl isothiocyanate yielded the title mixed-valence nonanuclear CuI/CuII compound, [Cu9Br5(C7H12NS2)5] or [CuI8CuIIBr5(Hm-dtc)5], encapsulating a bromide anion in the center of the Cu9Br4S10 cluster cage. The cage consists of a mononuclear CuII unit [Cu(Hm-dtc)2], three [mu]4-bridging Hm-dtc- ligands, eight CuI ions with distorted tetrahedral or trigonal pyramidal coordination geometries and four [mu]2-bridging bromide anions. The incorporated central bromide anion interacts with nine Cu ions with shorter Cu-Br separations than the sum of the van der Waals radii for Cu and Br.

Related literature

For copper clusters with dithiocarbamate ligands, see: Cardell et al. (2006[Cardell, D., Hogarth, G. & Faulkner, S. (2006). Inorg. Chim. Acta, 359, 1321-1324.]); Okubo, Kuwamoto et al. (2011[Okubo, T., Kuwamoto, H., Kim, K. H., Hayami, S., Yamano, A., Shiro, M., Maekawa, M. & Kuroda-Sowa, T. (2011). Inorg. Chem. 50, 2708-2710.]); Liao et al. (2012[Liao, P. K., Fang, C. S., Edwards, A. J., Kahlal, S., Saillard, J. Y. & Liu, C. W. (2012). Inorg. Chem. 51, 6577-6591.]). For coordination polymers with dithiocarbamate ligands, see: Golding et al. (1974[Golding, R. M., Rae, A. D. & Sulligoi, L. (1974). Inorg. Chem. 13, 2499-2504.]); Hendrickson et al. (1975[Hendrickson, A. R., Martin, R. L. & Taylor, D. (1975). J. Chem. Soc. Chem. Commun. pp. 843-844.]); Okubo et al. (2010[Okubo, T., Tanaka, N., Kim, K. H., Yone, H., Maekawa, M. & Kuroda-Sowa, T. (2010). Inorg. Chem. 49, 3700-3702.]); Okubo, Tanaka et al. (2011[Okubo, T., Tanaka, N., Kim, K. H., Anma, H., Seki, S., Saeki, A., Maekawa, M. & Kuroda-Sowa, T. (2011). Dalton Trans. 40, 2218-2224.]). For pmononuclear copper complexes with dithiocarbamate ligands, see: Jian et al. (1999[Jian, F., Wang, Z., Bai, Z., You, X., Fun, H.-K., Chinnakali, K. & Razak, I. R. (1999). Polyhedron, 18, 3401-3406.]); Ngo et al. (2003[Ngo, S. C., Banger, K. K., DelaRosa, M. J., Toscano, P. J. & Welch, J. T. (2003). Polyhedron, 22, 1575-1583.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu9Br5(C7H12NS2)5]

  • Mr = 1842.93

  • Monoclinic, P 21 /c

  • a = 12.5728 (6) Å

  • b = 19.5997 (7) Å

  • c = 22.9708 (8) Å

  • [beta] = 107.0411 (12)°

  • V = 5412.0 (4) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 7.59 mm-1

  • T = 296 K

  • 0.90 × 0.60 × 0.10 mm

Data collection
  • Rigaku R-AXIS RAPID diffractometer

  • Absorption correction: multi-scan (ABSCOR; Rigaku, 1995[Rigaku (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.241, Tmax = 0.468

  • 50620 measured reflections

  • 12284 independent reflections

  • 10468 reflections with I > 2[sigma](I)

  • Rint = 0.078

Refinement
  • R[F2 > 2[sigma](F2)] = 0.050

  • wR(F2) = 0.122

  • S = 1.03

  • 12284 reflections

  • 577 parameters

  • H-atom parameters constrained

  • [Delta][rho]max = 2.35 e Å-3

  • [Delta][rho]min = -1.54 e Å-3

Table 1
Selected bond lengths (Å)

Br1-Cu3 2.6912 (8)
Br2-Cu2 2.3748 (7)
Br2-Cu6 2.4201 (6)
Br3-Cu3 2.4149 (6)
Br3-Cu7 2.3993 (7)
Br4-Cu5 2.3748 (7)
Br4-Cu9 2.4414 (7)
Br5-Cu4 2.3705 (7)
Br5-Cu8 2.3962 (6)
Cu1-S1 2.3087 (10)
Cu1-S2 2.3208 (13)
Cu1-S3 2.3122 (10)
Cu1-S4 2.3322 (13)
Cu2-S1 2.2805 (12)
Cu2-S5 2.2623 (14)
Cu3-S2 2.3216 (11)
Cu3-S7 2.2711 (10)
Cu4-S3 2.2645 (11)
Cu4-S7 2.2619 (14)
Cu5-S4 2.3110 (12)
Cu5-S5 2.2447 (10)
Cu6-S6 2.2805 (15)
Cu6-S9 2.2537 (12)
Cu7-S8 2.2480 (11)
Cu7-S9 2.2788 (13)
Cu8-S8 2.3043 (15)
Cu8-S10 2.2647 (13)
Cu9-S6 2.2771 (11)
Cu9-S10 2.2705 (12)

Data collection: RAPID-AUTO (Rigaku, 2006[Rigaku (2006). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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: CrystalStructure (Rigaku, 2010[Rigaku (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan.]); software used to prepare material for publication: CrystalStructure.


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS5263 ).


Acknowledgements

This work was partly supported by a Grant-in-Aid for Science Research from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

References

Cardell, D., Hogarth, G. & Faulkner, S. (2006). Inorg. Chim. Acta, 359, 1321-1324.  [ISI] [CSD] [CrossRef] [ChemPort]
Golding, R. M., Rae, A. D. & Sulligoi, L. (1974). Inorg. Chem. 13, 2499-2504.  [CrossRef] [ChemPort] [ISI]
Hendrickson, A. R., Martin, R. L. & Taylor, D. (1975). J. Chem. Soc. Chem. Commun. pp. 843-844.  [CrossRef] [ISI]
Jian, F., Wang, Z., Bai, Z., You, X., Fun, H.-K., Chinnakali, K. & Razak, I. R. (1999). Polyhedron, 18, 3401-3406.  [ISI] [CSD] [CrossRef] [ChemPort]
Liao, P. K., Fang, C. S., Edwards, A. J., Kahlal, S., Saillard, J. Y. & Liu, C. W. (2012). Inorg. Chem. 51, 6577-6591.  [ISI] [CSD] [CrossRef] [ChemPort] [PubMed]
Ngo, S. C., Banger, K. K., DelaRosa, M. J., Toscano, P. J. & Welch, J. T. (2003). Polyhedron, 22, 1575-1583.  [ISI] [CSD] [CrossRef] [ChemPort]
Okubo, T., Kuwamoto, H., Kim, K. H., Hayami, S., Yamano, A., Shiro, M., Maekawa, M. & Kuroda-Sowa, T. (2011). Inorg. Chem. 50, 2708-2710.  [ISI] [CSD] [CrossRef] [ChemPort] [PubMed]
Okubo, T., Tanaka, N., Kim, K. H., Anma, H., Seki, S., Saeki, A., Maekawa, M. & Kuroda-Sowa, T. (2011). Dalton Trans. 40, 2218-2224.  [CSD] [CrossRef] [ChemPort] [PubMed]
Okubo, T., Tanaka, N., Kim, K. H., Yone, H., Maekawa, M. & Kuroda-Sowa, T. (2010). Inorg. Chem. 49, 3700-3702.  [ISI] [CSD] [CrossRef] [ChemPort] [PubMed]
Rigaku (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Rigaku (2006). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [details]


Acta Cryst (2013). E69, m275-m276   [ doi:10.1107/S1600536813009938 ]

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