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Volume 69 
Part 12 
Page o1821  
December 2013  

Received 4 November 2013
Accepted 15 November 2013
Online 23 November 2013

Key indicators
Single-crystal X-ray study
T = 133 K
Mean [sigma](C-C) = 0.003 Å
R = 0.025
wR = 0.065
Data-to-parameter ratio = 17.7
Details
Open access

2-(6-Bromo­benzo[d]thia­zol-2-yl)-5,5-di­methyl­thia­zol-4(5H)-one

aInstitut für Organische Chemie und Makromolekulare Chemie, Universität Jena, Humboldtstr. 10, 07743 Jena, Germany, and bInstitut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität, Jena, Humboldt-Str. 8, 07743 Jena, Germany
Correspondence e-mail: c6bera@rz.uni-jena.de

The title compound, C12H9BrN2OS2, was obtained by reacting 6-bromo­benzo[d]thia­zole-2-carbo­nitrile in iso-propanol with ethyl 2-mercapto-2-methyl­propano­ate at reflux temperature for several hours. The resulting di­methyl­oxyluciferin derivative shows partial double-bond character of the carbon-carbon bond between the two heterocyclic moieties [C-C = 1.461 (3) Å]. This double bond restricts rotation around this C-C axis, therefore leading to an almost planar mol­ecular structure [N-C-C-S torsion angle = 9.7 (3)°]. The five-membered thiazoline ring is not completely planar as a result of the bulky S atom [C-S-C-C torsion angle = 5.17 (12)°].

Related literature

For the chemi- and bioluminescence of firefly luciferin and related compounds, see: Jung et al. (1975[Jung, J., Chin, C.-A. & Song, P.-S. (1975). J. Am. Chem. Soc. 97, 3949-3954.]); White et al. (1961[White, E. H., Capra, F. M., Field, G. F. & McElroy, W. D. (1961). J. Am. Chem. Soc. 83, 2402-2403.], 1979[White, E. H., Steinmetz, M. G., Miano, J. D., Wildes, P. D. & Morland, R. (1979). J. Am. Chem. Soc. 101, 3199-3208.]); Branchini et al. (2002[Branchini, B. R., Murtiashaw, M. H., Magyar, R. A., Portier, N. C., Ruggiero, M. C. & Stroh, J. G. (2002). J. Am. Chem. Soc. 124, 2112-2113.]). For structural modifications of firefly luciferin, see: Meroni et al. (2009[Meroni, G., Rajabi, M. & Santaniello, E. (2009). Arkivoc, pp. 265-288.]); McCutcheon et al. (2012[McCutcheon, D. C., Paley, M. A., Steinhardt, R. C. & Prescher, J. A. (2012). J. Am. Chem. Soc. 134, 7604-7607.]); Branchini et al. (2012[Branchini, B. R., Woodroofe, C. C., Meisenheimer, P. L., Klaubert, D. H., Kovic, Y., Rosenberg, J. C., Behney, C. E. & Southworth, T. L. (2012). Biochemistry, 51, 9807-9813.]); Würfel (2012[Würfel, H. (2012). PhD thesis, Friedrich-Schiller-University Jena, Germany.]). Luciferin and related structures are widely used in clinical and biochemical applications, see: Schäffer (1987a[Schäffer, J. M. (1987a). US patent US 4665022.],b[Schäffer, J. M. (1987b). Chem. Abstr.107, 55320.]); Kricka (1988[Kricka, L. J. (1988). Anal. Biochem. 175, 14-21.]); Josel et al. (1994a[Josel, H.-P., Herrmann, R., Klein, C. & Heindl, D. (1994a). German patent DE 4210759.],b[Josel, H.-P., Herrmann, R., Klein, C. & Heindl, D. (1994b). Chem. Abstr. 120, 164160.]); Shinde et al. (2006[Shinde, R., Perkins, J. & Contag, C. H. (2006). Biochemistry, 45, 11103-11112.]). For details of the synthetic procedure, see: Armarego & Chai (2009[Armarego, W. L. & Chai, C. L. (2009). Purification of Laboratory Chemicals, 6th ed. Amsterdam, Boston, Heidelberg, London, New York, Oxford, Paris, San Diego, San Francisco, Singapore, Sydney, Tokyo: Elsevier.]); Bardsley et al. (2009a[Bardsley, K., Agyemang, D. O. & Pei, T. (2009a). US patent US20090232747A1.],b[Bardsley, K., Agyemang, D. O. & Pei, T. (2009b). Chem. Abstr. 151, 366000.]); Würfel et al. (2012[Würfel, H., Weiss, D., Beckert, R. & Güther, A. (2012). J. Sulfur Chem. 33, 9-16.]).

[Scheme 1]

Experimental

Crystal data
  • C12H9BrN2OS2

  • Mr = 341.24

  • Monoclinic, P 21 /c

  • a = 12.8246 (3) Å

  • b = 11.9115 (3) Å

  • c = 8.5375 (2) Å

  • [beta] = 99.735 (1)°

  • V = 1285.41 (5) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 3.51 mm-1

  • T = 133 K

  • 0.06 × 0.05 × 0.04 mm

Data collection
  • Nonius KappaCCD diffractometer

  • 7856 measured reflections

  • 2927 independent reflections

  • 2676 reflections with I > 2[sigma](I)

  • Rint = 0.033

Refinement
  • R[F2 > 2[sigma](F2)] = 0.025

  • wR(F2) = 0.065

  • S = 1.02

  • 2927 reflections

  • 165 parameters

  • H-atom parameters constrained

  • [Delta][rho]max = 0.44 e Å-3

  • [Delta][rho]min = -0.40 e Å-3

Data collection: COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by Carter, C. W. Jr & Sweet, R. M., pp. 307-326. New York: Academic Press.]); data reduction: DENZO; 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: XP in SHELXTL/PC (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IM2444 ).


Acknowledgements

The authors thank Roche Diagnostics GmbH, Penzberg, for financial support.

References

Armarego, W. L. & Chai, C. L. (2009). Purification of Laboratory Chemicals, 6th ed. Amsterdam, Boston, Heidelberg, London, New York, Oxford, Paris, San Diego, San Francisco, Singapore, Sydney, Tokyo: Elsevier.
Bardsley, K., Agyemang, D. O. & Pei, T. (2009a). US patent US20090232747A1.
Bardsley, K., Agyemang, D. O. & Pei, T. (2009b). Chem. Abstr. 151, 366000.
Branchini, B. R., Murtiashaw, M. H., Magyar, R. A., Portier, N. C., Ruggiero, M. C. & Stroh, J. G. (2002). J. Am. Chem. Soc. 124, 2112-2113.  [Web of Science] [CrossRef] [PubMed] [ChemPort]
Branchini, B. R., Woodroofe, C. C., Meisenheimer, P. L., Klaubert, D. H., Kovic, Y., Rosenberg, J. C., Behney, C. E. & Southworth, T. L. (2012). Biochemistry, 51, 9807-9813.  [Web of Science] [PubMed]
Josel, H.-P., Herrmann, R., Klein, C. & Heindl, D. (1994a). German patent DE 4210759.
Josel, H.-P., Herrmann, R., Klein, C. & Heindl, D. (1994b). Chem. Abstr. 120, 164160.
Jung, J., Chin, C.-A. & Song, P.-S. (1975). J. Am. Chem. Soc. 97, 3949-3954.  [CrossRef] [Web of Science]
Kricka, L. J. (1988). Anal. Biochem. 175, 14-21.  [CrossRef] [ChemPort] [PubMed] [Web of Science]
McCutcheon, D. C., Paley, M. A., Steinhardt, R. C. & Prescher, J. A. (2012). J. Am. Chem. Soc. 134, 7604-7607.  [Web of Science] [CrossRef] [ChemPort] [PubMed]
Meroni, G., Rajabi, M. & Santaniello, E. (2009). Arkivoc, pp. 265-288.  [CrossRef]
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by Carter, C. W. Jr & Sweet, R. M., pp. 307-326. New York: Academic Press.
Schäffer, J. M. (1987a). US patent US 4665022.
Schäffer, J. M. (1987b). Chem. Abstr.107, 55320.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [IUCr Journals]
Shinde, R., Perkins, J. & Contag, C. H. (2006). Biochemistry, 45, 11103-11112.  [Web of Science] [CrossRef] [PubMed] [ChemPort]
White, E. H., Capra, F. M., Field, G. F. & McElroy, W. D. (1961). J. Am. Chem. Soc. 83, 2402-2403.  [CrossRef] [ChemPort] [Web of Science]
White, E. H., Steinmetz, M. G., Miano, J. D., Wildes, P. D. & Morland, R. (1979). J. Am. Chem. Soc. 101, 3199-3208.
Würfel, H. (2012). PhD thesis, Friedrich-Schiller-University Jena, Germany.
Würfel, H., Weiss, D., Beckert, R. & Güther, A. (2012). J. Sulfur Chem. 33, 9-16.


Acta Cryst (2013). E69, o1821  [ doi:10.1107/S1600536813031334 ]

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