Crystal structure of 2,3-bis(5-bromo-3-methylthiophen

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Ζ. Kristallogr. NCS 224 (2009) 691-692 / DOI 10.1524/ncrs.2009.0304

691

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Crystal structure of 2,3-bis(5-bromo-3-methylthiophen-2yl)benzo[b]thiophene, CigH^nSa Xiaochuan Li*·1, Bingcai Wang1, Young-Α Son*·", Jiange Wang111 and Sheng Wang1TV ' Henan Normal University, College of Chemistry and Environmental Science, Xinxiang, Henan, 453007, P. R. China " Chungnam National University, Department of Advanced Organic Materials and Textile System Engineering, Daejeon 305-764, South Korea 111 Luoyang Normal University, College of Chemistry and Chemical Engineering, Luoyang, Henan, 471022, P. R. China ,v Zhanjiang Normal University, School of Chemistry Science & Technology, Zhanjiang, Guangdong, 524048, P. R. China Received September 28, 2009, accepted and available on-line October 5, 2009; CCDC no. 1267/2787

H18A

thiophen-2-yl)benzo[b]thiophene (90 mg, 0.276 mmol) in acetic acid (20 mL) and chloroform (20 mL) at 0°C, N-bromosuccinimide (NBS) (117.6 mg, 0.662 mol) was slowly added. The reaction mixture was stirred for 3 h at 0 °C in the dark. After filtered, the fíltrate was neutralized and extracted with ether. The ether extract was washed with water, saturated NaCl, dried over Mg 2 S04, filtered and concentrated. Column chromatography on silica gel with petroleum ether afforded 123 mg of the target compound in 92 % yield. Colorless block-shaped single crystals suitable for X-ray diffraction was obtained by slow evaporation of its solution in hexane. NMR data are available in the CIF.

Experimental details All H atoms attached to C were fixed geometrically and treated as riding with d(C—H) = 0.96 Â (methyl) or 0.93 Λ (aromatic) with f/iso(H) = 1.5 i/eq(methyl) or l/iso(H) = 1.2 i/eq(aromatic).

Discussion

Abstract Ci8Hi2Br2S3, monoclinic, />12i/cl (no. 14), a = 11.948(2) Â, b = 7.985(1) Â, c = 19.863(3) k,ß = 105.998(2)°, V= 1821.6 Â 3 , Z = 4, Rgt(F) = 0.037, wRnf(F) = 0.100, Γ =296 Κ.

Source of material 2,3-Bis(5-bromo-3-methylthiophen-2-yl)benzo[b]thiophene was synthesized by brominatíon of 2,3-bis(3-methylthiophen-2yl)benzo[b]thiophene, which was obtained according to our early published method [1]. To a stirred solution of 2,3- bis(3-methyl* Correspondence authors (e-mail: [email protected], yason @cnu.ac.kr)

The tide crystal structure is built up from CieHi2Br2S3 molecule (figure, top). The crystal packing is generated only one kind of hydroen bond (C6-H6—Br2\ symmetry code i: 2-x,0.5+y,l .5-z). The donor-acceptor distance is 3.193(1) Â with the bond angle 149.4(3)°. The prevalent interactions observed in the crystal are C-Η -π interactions including intra- and intermolecular interactions. The intramolecular C-H—jr interactions are C 1 3 H13C—π" (C2/C3/C8/C7/S1, symmetry code ii: x,y¿), C18Η180··π" (C2/C3/C8/C7/S1 ), and C13-H13A—π" (C14/C15/ C16/C17/S3). The local configurations correspond to type V interactions [2]. The typical parallel conformation of the packed molecules in the crystals is stabilized by the intra- molecular C-H- jr interactions. The parallel conformation of the two thiophene rings leads to the lost of the photochromic reactivity of the crystals [3]. Four kinds of intermolecular C-Η· - π interactions are observed (figure, bottom): C18-H18C···:*'" (C2/C3/C8/ C7/S1, symmeüy code iii: *,1.5-y,0.5+z), Ο Ι β - Η Ι β Β - π 0 (ClC6), C4-H4—jr" (C1-C6), and C5-H5· - ^ (C2/C3/C8/C7/S1). The first one is a typical C-Η—π interaction observed in the crystal. The hydrogen atom is directly above the center of the heterocycle, which indicates that the hydrogen atom is being attracted in the direction of the ring centre. The C18 -centroid distance is 3.638(5) Â and the bond angle is 122.3(1)°. This corresponds to a type-I interaction [2]. The other three intermolecular C-Η—π interactions belong to the type Π. Therefore, the molecules are packed together mainly by the stronger intermolecular C-Η—π interactions and the molecular structure are further stabilized by intramolecular C - Η -π interactions. Unauthenticated Download Date | 3/31/18 8:55 PM

692

Ci 8 Hi2Br 2 S3

Table 1. Data collection and handling.

Table 2. Atomic coordinates and displacement parameters (in Ä2).

Crystal: Wavelength: μ· Diffractometer, scan mode: 20max: N(hklhmsmá. Nihklhrnyx·· Criterion for /ot». N(hkl)p: N(param)nñntá'· Programs:

Atom

Site

χ

H(l) H(4) H(5) H(6) H(U) H(13A) H(13B) H(13C) H06) H(18A) H(18B) H(18C)

4e 4e 4e 4e 4e 4e 4« 4e 4« 4e 4e 4e

0.2363 0.5490 0.3684 0.2137 0.9533 0.8067 0.7799 0.6806 0.7934 0.5276 0.6207 0.5513

colorless block, size 0.18 χ 0.29 χ 0.40 mm Mo Ka radiation (0.71073 Â) 47.89 cm"1 ΒrakerSMART CCD, φ/ω 51° 13439,3398 /ote > 2 o(Iobs), 2378 210 SHELX-90 [4], SHELXS-97 [5], SHELXL-97 [6], SHELXTL [7], DIAMOND [8]

y 0.2688 0.0005 0.0072 0.1398 -0.1407 -0.0453 -0.2186 -0.0854 0.3875 0.2920 0.1672 0.1217

ζ 0.8019 0.7502 0.6696 0.6962 0.9372 1.0329 0.9948 0.9865 1.1609 1.0982 1.1423 1.0653

í/iso

0.069 0.061 0.077 0.084 0.062 0.102 0.102 0.102 0.057 0.104 0.104 0.104

Table 3. Atomic coordinates and displacement parameters (in Â2). Atom

Site

X

BtO) Br(2) C(l) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(IO) COD C(12) C(13) C(14) C(15) C(16) C(17) C(18) S(l) S(2) S(3)

4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e

1.02388(5) -0.01222(8) 0.98723(4) 0.55944(7) 0.2990(4) 0.2169(6) 0.4095(3) 0.2166(5) 0.5048(3) 0.1375(5) 0.4876(4) 0.0565(5) 0.3794(4) 0.0591(6) 0.2863(4) 0.1395(6) 0.5916(3) 0.2397(5) 0.6094(3) 0.1515(5) 0.7228(3) 0.0786(5) 0.7921(4) -0.0293(5) 0.8966(4) -0.0687(5) 0.9047(4) 0.0086(6) 0.7621(4) -0.1012(6) 0.6785(3) 0.2991(5) 0.6793(4) 0.2949(5) 0.7786(4) 0.3781(5) 0.8482(4) 0.4414(5) 0.5862(5) 0.2113(6) 0.44831(9) 0.3073(1) 0.78717(9) 0.1334(1) 0.79913(9) 0.4028(2)

y

ζ

Un

Un

t/33

Un

0.80860(3) 1.11091(3) 0.7914(3) 0.8394(2) 0.8246(2) 0.7607(2) 0.7129(3) 0.7290(3) 0.9372(2) 0.8821(2) 0.8814(2) 0.9285(2) 0.9111(2) 0.8530(2) 0.9914(3) 1.0002(2) 1.0692(2) 1.1126(2) 1.0764(2) 1.0962(2) 0.92213(6) 0.81636(5) 0.98858(6)

0.0631(3) 0.0542(3) 0.040(2) 0.037(2) 0.034(2) 0.048(2) 0.065(3) 0.049(3) 0.038(2) 0.037(2) 0.036(2) 0.046(2) 0.044(2) 0.039(2) 0.065(3) 0.039(2) 0.057(3) 0.057(3) 0.043(2) 0.097(4) 0.0397(6) 0.0447(6) 0.0455(6)

0.1110(5) 0.0872(4) 0.048(3) 0.035(2) 0.032(2) 0.045(2) 0.058(3) 0.060(3) 0.033(2) 0.032(2) 0.037(2) 0.037(2) 0.046(2) 0.057(3) 0.064(3) 0.035(2) 0.037(2) 0.047(2) 0.047(2) 0.067(3) 0.0522(6) 0.0574(6) 0.0637(7)

0.0896(4) 0.0691(3) 0.077(3) 0.059(3) 0.044(2) 0.054(3) 0.057(3) 0.082(4) 0.046(2) 0.043(2) 0.044(2) 0.050(2) 0.060(3) 0.057(3) 0.074(3) 0.046(2) 0.047(2) 0.036(2) 0.043(2) 0.056(3) 0.0612(7) 0.0450(6) 0.0435(6)

0.0191(3) -0.0154(3) -0.003(2) -0.004(2) -0.003(2) -0.002(2) -0.011(3) -0.009(2) -0.000(2) -0.002(2) 0.000(2) -0.000(2) 0.008(2) 0.004(2) 0.011(2) 0.000(2) 0.002(2) -0.001(2) -0.000(2) -0.020(3) 0.0043(5) 0.0058(5) -0.0123(5)

Un 0.0379(3) 0.0023(2) 0.006(2) 0.010(2) 0.005(2) 0.005(2) -0.006(2) -0.014(3) 0.011(2) 0.010(2) 0.006(2) 0.007(2) 0.005(2) 0.011(2) 0.017(3) 0.012(2) 0.022(2) 0.009(2) 0.004(2) 0.040(3) 0.0168(5) 0.0132(5) 0.0133(5)

t/23

-0.0108(3) -0.0096(3) 0.000(2) 0.006(2) 0.003(2) -0.005(2) -0.010(2) 0.003(3) 0.002(2) 0.001(2) -0.006(2) -0.003(2) -0.006(2) -0.012(2) 0.026(3) -0.004(2) 0.002(2) -0.003(2) -0.004(2) 0.003(3) -0.0031(5) -0.0005(5) -0.0045(5)

Acknowledgments. This work was supported by the National Natural Science Foundation of China for the Youth (grant nos. 20702011 and 20802065), the Startup Fund of Henan Normal University (grant no. 051004), the Science Foundation for the Youth of Henan Normal University (grant no. 2006033), and the Natural Science Foundation of Henan Provincial Education Office (grant no. 2007150022).

References 1. Li, X.; Ma, Y.; Wang, B.; Li, G.: "Lock and Key control" of Photochromic Reactivity by Controlling the Oxidation/Reduction State. Org. Lett. 10 (2008) 3639-3642. 2. Malone, J. F.; Murray, C. M.; Charlton, M. H.; Docherty, R.; Laveiy, A. J.: X-H-w (phenyl) interactions theoretical and crystallographic observations. J. Chem. Soc. Faraday Trans. 93 (1997) 3429-3436. 3. Kobatake, S.; Uchida, K.; Tsuchida, E.; Irie, M.: Single-crystalline photochromism of diaiylethenes: reactivity — structure relationship. Chem. Commun. 23 (2002) 2804-5805. 4. Sheldrick, G. M.: Phase annealing in SHELX-90: direct methods for larger structures. Acta Crystallogr. A46 (1990) 467-473.

5. Sheldrick, G. M.: SHELXS-97. Program for the Solution of Crystal Structures. University of Göttingen, Germany 1997. 6. Sheldrick, G. M.: SHELXL-97. Program for the Refinement of Crystal Structures. University of Göttingen, Germany 1997. 7. Sheldrick, G. M.: SHELXTL. Structure Determination Software Suite. Version 6.14. Broker AXS, Madison, Wisconsin, USA 2000. 8. Brandenburg, K.: DIAMOND. Visual Crystal Structure Information System. Version 2.0f. Crystal Impact, Bonn, Germany 1998.

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