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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2011 Apr 7;67(Pt 5):o1047. doi: 10.1107/S1600536811011792

rac-2,2′-(Thiane-2,6-di­yl)bis­[1-(4-bromo­phen­yl)ethanone]

Li-Qiang Liu a,*, Jing-Kui Yang a
PMCID: PMC3089314  PMID: 21754374

Abstract

In the title compound, C21H20Br2O2S, prepared by the reaction of 1,9-bis­(4-bromo­phen­yl)nona-2,7-diene-1,9-dione with sodium sulfide nona­hydrate in acetonitrile, the six-membered thio­pyran ring has a chair conformation while the H atoms ortho to the S atom adopt a cis configuration. The dihedral angle between the two benzene rings is 2.59 (8)°.

Related literature

For the synthesis of 1,9-bis­(4-bromo­phen­yl)nona-2,7-diene-1,9-dione, see: Yang, Cauble et al. (2004 ▶); Yang, Felton et al. (2004 ▶). For the synthesis of compounds containing sulfur, see: Knapp et al. (2002 ▶); Yao et al. (2003 ▶); Oliveira et al. (1999 ▶). For applications of natural products containing sulfur, see: Qi et al. (2004 ▶); Zhang & Zhang (2006 ▶); Barco et al. (2006 ▶).graphic file with name e-67-o1047-scheme1.jpg

Experimental

Crystal data

  • C21H20Br2O2S

  • M r = 496.25

  • Triclinic, Inline graphic

  • a = 6.484 (4) Å

  • b = 12.970 (5) Å

  • c = 13.076 (4) Å

  • α = 71.14 (3)°

  • β = 79.45 (4)°

  • γ = 79.52 (4)°

  • V = 1014.1 (7) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 4.11 mm−1

  • T = 295 K

  • 0.40 × 0.30 × 0.20 mm

Data collection

  • Siemens P4 four-circle diffractometer

  • Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.381, T max = 0.459

  • 4549 measured reflections

  • 3548 independent reflections

  • 2220 reflections with I > 2σ(I)

  • R int = 0.032

  • 3 standard reflections every 97 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055

  • wR(F 2) = 0.112

  • S = 1.07

  • 3548 reflections

  • 235 parameters

  • H-atom parameters constrained

  • Δρmax = 0.51 e Å−3

  • Δρmin = −0.41 e Å−3

Data collection: XSCANS (Bruker, 1997 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011792/zs2103sup1.cif

e-67-o1047-sup1.cif (17.7KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011792/zs2103Isup2.hkl

e-67-o1047-Isup2.hkl (174KB, hkl)

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Enhanced figure: interactive version of Fig. 1

Acknowledgments

This research was supported by the NSFC·SRF for ROCS, SEM, the Present Fund of GUCAS and the Opening Fund of the Laboratory of Organic Solids, CAS, China

supplementary crystallographic information

Comment

The mothods for the synthesis of compounds containing sulfur have been described (Knapp et al., 2002; Yao et al., 2003; Oliveira et al. 1999). Natural products containing sulfur often have biological activity, so that the methods for their synthesis have received considerable attention among researchers. In this paper, we report the structure of the title compound C21H20Br2O2S (I), prepared by the reaction of 1,9-bis(4-bromophenyl)nona-2,7-diene-1,9-dione with sodium sulfide nonahydrate in acetonitrile. In the crystal, the six-membered thiopyran ring has a chair conformation with the H atoms ortho to the S (H9 and H13) adopting a cis configuration (Fig. 1). The dihedral angle between the benzene rings on the substituent chains is 2.59 (8)°.

Experimental

The reaction mixture of 1,9-bis(4-bromophenyl)nona-2,7-diene-1,9-dione (100 mg, 0.20 mmol) with sodium sulfide nonahydrate (67 mg, 0.28 mmol) in 50 ml of acetonitrile was stirred for 11 days at room temperature, affording the title compound (20 mg; yield 32%). Colorless single crystals were obtained by slow evaporation of an ethyl acetate solution in air.

Refinement

All hydrogen atoms were generated geometically with C—H bond distances of 0.93–0.98 Å according to criteria described in the SHELXTL manual (Bruker, 1997). These were included in the refinement with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.

Fig. 1.

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The molecular conformation of the title compound showing 35% probability displacement ellipsoids and the atom numbering scheme

Crystal data

C21H20Br2O2S Z = 2
Mr = 496.25 F(000) = 496
Triclinic, P1 Dx = 1.625 Mg m−3
Hall symbol: -P 1 Mo Kα radiation, λ = 0.71073 Å
a = 6.484 (4) Å Cell parameters from 45 reflections
b = 12.970 (5) Å θ = 5.6–12.4°
c = 13.076 (4) Å µ = 4.11 mm−1
α = 71.14 (3)° T = 295 K
β = 79.45 (4)° Prism, colorless
γ = 79.52 (4)° 0.40 × 0.30 × 0.20 mm
V = 1014.1 (7) Å3
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Data collection

Siemens P4 four-circle diffractometer 2220 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube Rint = 0.032
graphite θmax = 25.1°, θmin = 2.0°
ω scans h = −1→7
Absorption correction: ψ scan (North et al., 1968) k = −14→14
Tmin = 0.381, Tmax = 0.459 l = −15→15
4549 measured reflections 3 standard reflections every 97 reflections
3548 independent reflections intensity decay: none
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Refinement

Refinement on F2 Primary atom site location: structure-invariant direct methods
Least-squares matrix: full Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055 Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112 H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.001P)2 + 2.0P] where P = (Fo2 + 2Fc2)/3
3548 reflections (Δ/σ)max = 0.001
235 parameters Δρmax = 0.51 e Å−3
0 restraints Δρmin = −0.41 e Å−3
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Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
Br1 0.47955 (9) 1.39832 (4) 0.65329 (4) 0.08336 (16)
Br2 0.87756 (10) 0.46636 (4) −0.19734 (4) 0.09195 (19)
S1 0.35503 (17) 0.97967 (9) 0.19248 (8) 0.0594 (3)
O1 −0.0519 (5) 1.2370 (2) 0.3377 (2) 0.0755 (9)
O2 0.0963 (5) 0.8256 (2) −0.0195 (2) 0.0740 (9)
C1 0.2190 (6) 1.2490 (3) 0.4300 (3) 0.0477 (10)
C2 0.4267 (6) 1.2193 (3) 0.4523 (3) 0.0596 (12)
H2A 0.5153 1.1687 0.4220 0.071*
C3 0.5051 (7) 1.2633 (3) 0.5185 (3) 0.0673 (13)
H3A 0.6453 1.2438 0.5316 0.081*
C4 0.3711 (6) 1.3365 (3) 0.5645 (3) 0.0559 (11)
C5 0.1643 (7) 1.3678 (3) 0.5447 (3) 0.0597 (12)
H5A 0.0760 1.4175 0.5764 0.072*
C6 0.0894 (7) 1.3245 (3) 0.4772 (3) 0.0568 (12)
H6A −0.0499 1.3460 0.4630 0.068*
C7 0.1259 (7) 1.2030 (3) 0.3601 (3) 0.0543 (11)
C8 0.2614 (6) 1.1124 (3) 0.3196 (3) 0.0557 (11)
H8A 0.3138 1.0552 0.3815 0.067*
H8B 0.3829 1.1420 0.2711 0.067*
C9 0.1493 (6) 1.0605 (3) 0.2598 (3) 0.0494 (10)
H9A 0.0776 1.1190 0.2042 0.059*
C10 −0.0111 (6) 0.9885 (3) 0.3336 (3) 0.0601 (12)
H10A −0.1162 1.0322 0.3709 0.072*
H10B 0.0599 0.9303 0.3884 0.072*
C11 −0.1229 (6) 0.9372 (3) 0.2727 (3) 0.0650 (13)
H11A −0.2286 0.8956 0.3238 0.078*
H11B −0.1954 0.9953 0.2184 0.078*
C12 0.0287 (6) 0.8618 (3) 0.2168 (3) 0.0588 (12)
H12A −0.0519 0.8293 0.1826 0.071*
H12B 0.0979 0.8027 0.2717 0.071*
C13 0.1970 (6) 0.9190 (3) 0.1311 (3) 0.0517 (11)
H13A 0.1284 0.9771 0.0739 0.062*
C14 0.3569 (6) 0.8426 (3) 0.0794 (3) 0.0561 (12)
H14A 0.4755 0.8815 0.0400 0.067*
H14B 0.4100 0.7805 0.1374 0.067*
C15 0.2757 (7) 0.7987 (3) 0.0020 (3) 0.0543 (12)
C16 0.4289 (6) 0.7209 (3) −0.0478 (3) 0.0530 (11)
C17 0.3596 (7) 0.6792 (3) −0.1196 (3) 0.0645 (13)
H17A 0.2225 0.7017 −0.1372 0.077*
C18 0.4938 (7) 0.6047 (3) −0.1650 (3) 0.0667 (13)
H18A 0.4479 0.5780 −0.2137 0.080*
C19 0.6922 (7) 0.5709 (3) −0.1379 (3) 0.0646 (13)
C20 0.7680 (8) 0.6127 (3) −0.0700 (3) 0.0719 (14)
H20A 0.9069 0.5912 −0.0550 0.086*
C21 0.6352 (7) 0.6872 (3) −0.0241 (3) 0.0657 (13)
H21A 0.6846 0.7148 0.0229 0.079*
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
Br1 0.1169 (4) 0.0718 (3) 0.0768 (3) −0.0107 (3) −0.0346 (3) −0.0323 (2)
Br2 0.1217 (5) 0.0730 (3) 0.0745 (3) 0.0071 (3) 0.0042 (3) −0.0334 (2)
S1 0.0517 (6) 0.0715 (6) 0.0667 (6) −0.0140 (5) −0.0006 (5) −0.0374 (5)
O1 0.0630 (18) 0.0824 (17) 0.0972 (18) 0.0060 (16) −0.0260 (15) −0.0490 (15)
O2 0.0769 (19) 0.0751 (17) 0.0793 (17) 0.0154 (16) −0.0348 (15) −0.0364 (14)
C1 0.051 (2) 0.0488 (19) 0.0465 (19) −0.0129 (18) −0.0055 (17) −0.0160 (16)
C2 0.049 (2) 0.067 (2) 0.067 (2) −0.004 (2) 0.000 (2) −0.0335 (19)
C3 0.063 (3) 0.075 (3) 0.074 (3) −0.010 (2) −0.014 (2) −0.033 (2)
C4 0.070 (3) 0.053 (2) 0.050 (2) −0.016 (2) −0.013 (2) −0.0154 (17)
C5 0.076 (3) 0.050 (2) 0.052 (2) 0.003 (2) −0.011 (2) −0.0193 (17)
C6 0.058 (3) 0.055 (2) 0.056 (2) −0.001 (2) −0.012 (2) −0.0159 (18)
C7 0.055 (2) 0.055 (2) 0.053 (2) −0.007 (2) −0.0016 (19) −0.0191 (17)
C8 0.056 (2) 0.060 (2) 0.058 (2) −0.013 (2) −0.0022 (19) −0.0272 (17)
C9 0.043 (2) 0.057 (2) 0.0519 (19) −0.0110 (18) −0.0026 (17) −0.0212 (17)
C10 0.056 (2) 0.064 (2) 0.061 (2) −0.012 (2) 0.004 (2) −0.0246 (19)
C11 0.052 (2) 0.070 (3) 0.072 (3) −0.017 (2) 0.000 (2) −0.019 (2)
C12 0.063 (3) 0.058 (2) 0.059 (2) −0.024 (2) −0.005 (2) −0.0159 (19)
C13 0.057 (2) 0.051 (2) 0.0507 (19) −0.0033 (19) −0.0162 (18) −0.0179 (16)
C14 0.063 (3) 0.055 (2) 0.055 (2) −0.010 (2) −0.011 (2) −0.0196 (18)
C15 0.072 (3) 0.0383 (19) 0.052 (2) −0.006 (2) −0.013 (2) −0.0118 (16)
C16 0.066 (3) 0.0443 (19) 0.051 (2) −0.0110 (19) −0.0120 (19) −0.0125 (17)
C17 0.074 (3) 0.065 (2) 0.060 (2) −0.010 (2) −0.016 (2) −0.0232 (19)
C18 0.080 (3) 0.068 (2) 0.064 (2) −0.016 (2) −0.011 (2) −0.0317 (19)
C19 0.083 (3) 0.054 (2) 0.053 (2) −0.007 (2) 0.001 (2) −0.0183 (19)
C20 0.078 (3) 0.063 (2) 0.074 (3) 0.004 (2) −0.013 (2) −0.026 (2)
C21 0.075 (3) 0.068 (2) 0.061 (2) −0.007 (2) −0.015 (2) −0.0262 (19)
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Geometric parameters (Å, °)

Br1—C4 1.895 (4) C10—H10A 0.9700
Br2—C19 1.906 (4) C10—H10B 0.9700
S1—C9 1.819 (4) C11—C12 1.518 (6)
S1—C13 1.820 (4) C11—H11A 0.9700
O1—C7 1.210 (5) C11—H11B 0.9700
O2—C15 1.209 (5) C12—C13 1.518 (5)
C1—C2 1.389 (5) C12—H12A 0.9700
C1—C6 1.395 (5) C12—H12B 0.9700
C1—C7 1.497 (6) C13—C14 1.523 (5)
C2—C3 1.386 (6) C13—H13A 0.9800
C2—H2A 0.9300 C14—C15 1.517 (6)
C3—C4 1.377 (6) C14—H14A 0.9700
C3—H3A 0.9300 C14—H14B 0.9700
C4—C5 1.375 (6) C15—C16 1.500 (5)
C5—C6 1.381 (6) C16—C21 1.389 (6)
C5—H5A 0.9300 C16—C17 1.396 (6)
C6—H6A 0.9300 C17—C18 1.385 (6)
C7—C8 1.513 (5) C17—H17A 0.9300
C8—C9 1.523 (6) C18—C19 1.354 (6)
C8—H8A 0.9700 C18—H18A 0.9300
C8—H8B 0.9700 C19—C20 1.376 (7)
C9—C10 1.512 (5) C20—C21 1.385 (6)
C9—H9A 0.9800 C20—H20A 0.9300
C10—C11 1.528 (6) C21—H21A 0.9300
C9—S1—C13 101.01 (18) C12—C11—H11B 109.1
C2—C1—C6 117.9 (4) C10—C11—H11B 109.1
C2—C1—C7 123.7 (4) H11A—C11—H11B 107.8
C6—C1—C7 118.4 (4) C11—C12—C13 114.0 (3)
C3—C2—C1 121.6 (4) C11—C12—H12A 108.8
C3—C2—H2A 119.2 C13—C12—H12A 108.8
C1—C2—H2A 119.2 C11—C12—H12B 108.8
C4—C3—C2 118.6 (4) C13—C12—H12B 108.8
C4—C3—H3A 120.7 H12A—C12—H12B 107.7
C2—C3—H3A 120.7 C12—C13—C14 114.1 (3)
C5—C4—C3 121.6 (4) C12—C13—S1 110.2 (3)
C5—C4—Br1 119.8 (3) C14—C13—S1 104.6 (3)
C3—C4—Br1 118.6 (3) C12—C13—H13A 109.2
C4—C5—C6 119.1 (4) C14—C13—H13A 109.2
C4—C5—H5A 120.5 S1—C13—H13A 109.2
C6—C5—H5A 120.5 C15—C14—C13 116.0 (3)
C5—C6—C1 121.2 (4) C15—C14—H14A 108.3
C5—C6—H6A 119.4 C13—C14—H14A 108.3
C1—C6—H6A 119.4 C15—C14—H14B 108.3
O1—C7—C1 120.8 (4) C13—C14—H14B 108.3
O1—C7—C8 121.6 (4) H14A—C14—H14B 107.4
C1—C7—C8 117.6 (3) O2—C15—C16 121.3 (4)
C7—C8—C9 114.9 (3) O2—C15—C14 121.8 (4)
C7—C8—H8A 108.5 C16—C15—C14 117.0 (4)
C9—C8—H8A 108.5 C21—C16—C17 118.6 (4)
C7—C8—H8B 108.5 C21—C16—C15 122.9 (4)
C9—C8—H8B 108.5 C17—C16—C15 118.5 (4)
H8A—C8—H8B 107.5 C18—C17—C16 120.4 (4)
C10—C9—C8 113.7 (3) C18—C17—H17A 119.8
C10—C9—S1 110.1 (3) C16—C17—H17A 119.8
C8—C9—S1 106.4 (3) C19—C18—C17 119.6 (4)
C10—C9—H9A 108.8 C19—C18—H18A 120.2
C8—C9—H9A 108.8 C17—C18—H18A 120.2
S1—C9—H9A 108.8 C18—C19—C20 121.5 (4)
C9—C10—C11 113.2 (3) C18—C19—Br2 120.3 (4)
C9—C10—H10A 108.9 C20—C19—Br2 118.1 (4)
C11—C10—H10A 108.9 C19—C20—C21 119.3 (5)
C9—C10—H10B 108.9 C19—C20—H20A 120.4
C11—C10—H10B 108.9 C21—C20—H20A 120.4
H10A—C10—H10B 107.7 C20—C21—C16 120.5 (4)
C12—C11—C10 112.6 (3) C20—C21—H21A 119.8
C12—C11—H11A 109.1 C16—C21—H21A 119.8
C10—C11—H11A 109.1
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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZS2103).

References

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  2. Bruker (1997). XSCANS Bruker AXS Inc., Madison, Wisconsin, USA
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  4. North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  5. Oliveira, M. G., Soares, B. G., Santos, C. M. F., Diniz, M. F. & Dutra, R. C. L. (1999). Macromol. Rapid Commun. 20, 526–531.
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  7. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
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  11. Zhang, L. & Zhang, Y. J. (2006). Tetrahedron Lett. 47 775–778.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011792/zs2103sup1.cif

e-67-o1047-sup1.cif (17.7KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011792/zs2103Isup2.hkl

e-67-o1047-Isup2.hkl (174KB, hkl)

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Enhanced figure: interactive version of Fig. 1

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography

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