2-[4-(2-{5-tert-Butyl-2-chloro-3-[2-(3-pentyl-1,3-benzothia­zol-2-yl­idene)ethyl­idene]cyclo­hex-1-en­yl}ethen­yl)-3-cyano-5,5-dimethyl­furan-2-yl­idene]malono­nitrile

Gainsford, G.J.; Ashraf, M.; Kay, A.J.

doi:10.1107/S1600536812050842

Volume 69
Part 1
Pages o120-o121
January 2013

Received 21 November 2012
Accepted 13 December 2012
Online 22 December 2012

Key indicators
Single-crystal X-ray study
T = 116 K
Mean (C-C) = 0.006 Å
Disorder in main residue
R = 0.059
wR = 0.177
Data-to-parameter ratio = 13.2
Details

2-[4-(2-{5-tert-Butyl-2-chloro-3-[2-(3-pentyl-1,3-benzothiazol-2-ylidene)ethylidene]cyclohex-1-enyl}ethenyl)-3-cyano-5,5-dimethylfuran-2-ylidene]malononitrile

Graeme J. Gainsford,^a ^* Mohamed Ashraf ^a and Andrew J. Kay ^a

^aIndustrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand
Correspondence e-mail: g.gainsford@irl.cri.nz

In the title molecule, C₃₆H₃₉ClN₄OS, the non-aromatic part of the cyclohex-1-enyl ring and the attached tert-butyl group are disordered over two conformations with occupancy ratios of 0.52 (3):0.48 (3) and 0.53 (3):0.47 (3), respectively. The polyene chain single- and double-bond dimensions contrast with a closely related compound [Bouit et al. (2007). Chem. Mater. 19, 5325-5335] with an approximate 19° twist between donor and acceptor ends of the molecule, related to the additional intramolecular C-HS interaction. In the title compound, the molecules pack into dimeric units about centres of symmetry utilizing weak C-HN(cyano) and C-HO attractive interactions, building both chain and ring motifs about the centres [R₂²(8) and R₂²(9)]. Adjacent dimeric sets then form a herringbone configuration.

Related literature

For general background to our ongoing research involving the development of organic non-linear optical (NLO) chromophores, see: Kay et al. (2004); Bhuiyan et al. (2011). For related structures, see: Bouit et al. (2007, 2008); Gainsford et al. (2008). For a description of the Cambridge Structural Database, see: Allen (2002). For the BLA parameter, see: Marder et al. (1993).

Experimental

Crystal data

C₃₆H₃₉ClN₄OS
M_r = 611.22
Monoclinic, P 2₁ /n
a = 8.6293 (5) Å
b = 20.1267 (11) Å
c = 19.5299 (11) Å
= 102.236 (4)°
V = 3314.9 (3) Å³
Z = 4
Mo K radiation
= 0.21 mm^-1
T = 116 K
0.71 × 0.30 × 0.10 mm

Data collection

Bruker-Nonius APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (Blessing, 1995) and SADABS (Bruker, 2005) T_min = 0.614, T_max = 0.746
32003 measured reflections
5943 independent reflections
3121 reflections with I > 2(I)
R_int = 0.106

Refinement

R[F² > 2(F²)] = 0.059
wR(F²) = 0.177
S = 1.01
5943 reflections
451 parameters
75 restraints
H atoms treated by a mixture of independent and constrained refinement
_max = 0.45 e Å^-3
_min = -0.29 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
C9-H9AO1ⁱ	0.98	2.59	3.494 (6)	154
C32-H32AN2ⁱⁱ	0.98	2.73	3.702 (5)	166
C33-H33BN1ⁱⁱ	0.98	2.65	3.539 (6)	150
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2431 ).

Acknowledgements

We thank Drs J. Wikaira & C. Fitchett of the University of Canterbury, New Zealand, for the data collection.

References

Allen, F. H. (2002). Acta Cryst. B58, 380-388.
Bhuiyan, M. D. H., Ashraf, M., Teshome, A., Gainsford, G. J., Kay, A. J., Asselberghs, I. & Clays, K. (2011). Dyes Pigm. 89, 177-187.
Blessing, R. H. (1995). Acta Cryst. A51, 33-38.
Bouit, P.-A., Di Piazza, E., Rigaut, S., Le Guennic, B., Aronica, B., Toupet, L., Andraud, C. & Maury, O. (2008). Org. Lett. 10, 4159-4162.
Bouit, P.-A., Wetzel, G., Berginc, G., Loiseaux, B., Toupet, L., Feneyrou, P., Bretonniere, Y., Kamada, K., Maury, O. & Andraud, C. (2007). Chem. Mater. 19, 5325-5335.
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.
Gainsford, G. J., Bhuiyan, M. D. H. & Kay, A. J. (2008). Acta Cryst. C64, o616-o619.
Kay, A. J., Woolhouse, A. D., Zhao, Y. & Clays, K. (2004). J. Mater. Chem. 45, 1321-1330.
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.
Marder, S. R., Perry, J. W., Tiemann, B. G., Gorman, C. B., Gilmour, S., Biddle, S. L. & Bourhill, G. (1993). J. Am. Chem. Soc. 115, 2524-2526.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Spek, A. L. (2009). Acta Cryst. D65, 148-155.