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Acta Crystallogr Sect E Struct Rep Online. 2009 March 1; 65(Pt 3): o606.
Published online 2009 February 25. doi:  10.1107/S1600536809005959
PMCID: PMC2968474

4-(4-Bromo­phenyl)-2-methyl-2,6-di­phenyl-2H-thio­pyran

Abstract

The six-membered thio­pyran ring in the title compound, C24H19BrS, adopts an approximate envelope conformation, with the S atom displaced by 0.26 (1) Å and the 2-methyl­ene C atom by −0.54 (1) Å from the plane of the other four sp 2-hydridized C atoms. The methyl substituent on the methyl­ene carbon lies in a pseudo-axial position with the phenyl ring in a pseudo-equatorial position.

Related literature

For the background to 4-alkyl-2,4,6-triaryl-4H-thio­pyrans, see: Rahmani et al. (2009 [triangle]). For the general synthesis from a Grignard reaction, see: Suld & Price (1962 [triangle]).

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Object name is e-65-0o606-scheme1.jpg

Experimental

Crystal data

  • C24H19BrS
  • M r = 419.36
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o606-efi1.jpg
  • a = 23.3348 (8) Å
  • b = 5.9991 (2) Å
  • c = 13.6866 (5) Å
  • V = 1916.0 (1) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.26 mm−1
  • T = 115 K
  • 0.40 × 0.15 × 0.05 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.465, T max = 0.895
  • 16215 measured reflections
  • 4407 independent reflections
  • 3017 reflections with I > 2σ(I)
  • R int = 0.093

Refinement

  • R[F 2 > 2σ(F 2)] = 0.075
  • wR(F 2) = 0.190
  • S = 1.09
  • 4407 reflections
  • 236 parameters
  • 145 restraints
  • H-atom parameters constrained
  • Δρmax = 1.53 e Å−3
  • Δρmin = −0.91 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 2108 Friedel pairs
  • Flack parameter: 0.01 (2)

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809005959/sj2581sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005959/sj2581Isup2.hkl

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

Acknowledgments

We thank the Iranian Research Organization for Science and Technology and the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

The compound was obtained as the rearranged product from the reaction of methyl magnesium bromide and 4-(4-bromophenyl)-2,6-diphenyl thiopyrylium perchlorate in dry ether under an argon atmosphere according to a reported method (Suld & Price, 1962). The product was isolated by TLC on neutral alumina (petroleum ether 40–60 °C) and purified by recrystalization from ethanol.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

The final difference Fourier map had a large peak/deep hole in the vicinity of the bromine.

Figures

Fig. 1.
Thermal ellisoid plot (Barbour, 2001) of C24H19BrS; probability levels are set at 70% and H-atoms are drawn as spheres of arbitrary radius.

Crystal data

C24H19BrSF(000) = 856
Mr = 419.36Dx = 1.454 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 2506 reflections
a = 23.3348 (8) Åθ = 2.3–22.9°
b = 5.9991 (2) ŵ = 2.26 mm1
c = 13.6866 (5) ÅT = 115 K
V = 1916.0 (1) Å3Prism, pale yellow
Z = 40.40 × 0.15 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer4407 independent reflections
Radiation source: fine-focus sealed tube3017 reflections with I > 2σ(I)
graphiteRint = 0.093
ω scansθmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −30→29
Tmin = 0.465, Tmax = 0.895k = −7→7
16215 measured reflectionsl = −17→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.075H-atom parameters constrained
wR(F2) = 0.190w = 1/[σ2(Fo2) + (0.0672P)2 + 10.0175P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max = 0.001
4407 reflectionsΔρmax = 1.53 e Å3
236 parametersΔρmin = −0.91 e Å3
145 restraintsAbsolute structure: Flack (1983), 2108 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.01 (2)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Br10.55183 (4)0.84726 (15)0.50001 (7)0.0381 (3)
S10.76405 (9)−0.1684 (4)0.84041 (14)0.0245 (4)
C10.7867 (4)−0.2735 (13)0.6484 (6)0.0260 (18)
H1A0.8005−0.22730.58380.039*
H1B0.7469−0.32460.64310.039*
H1C0.8107−0.39520.67300.039*
C20.7898 (3)−0.0738 (13)0.7196 (5)0.0198 (16)
C30.7503 (3)0.1075 (12)0.6851 (5)0.0206 (17)
H30.76690.23720.65710.025*
C40.6924 (3)0.0971 (13)0.6915 (5)0.0191 (16)
C50.6643 (3)−0.0773 (13)0.7470 (5)0.0183 (16)
H50.6252−0.10830.73320.022*
C60.6907 (4)−0.1988 (12)0.8174 (5)0.0204 (17)
C70.8509 (3)0.0024 (14)0.7371 (5)0.0202 (17)
C80.8986 (4)−0.1115 (16)0.7095 (6)0.032 (2)
H80.8937−0.24940.67640.039*
C90.9534 (4)−0.0388 (16)0.7267 (6)0.033 (2)
H90.9852−0.12340.70390.040*
C100.9623 (4)0.1547 (18)0.7762 (7)0.034 (2)
H101.00000.20160.79220.041*
C110.9148 (4)0.2837 (15)0.8034 (6)0.0263 (19)
H110.92060.42380.83420.032*
C120.8604 (4)0.2107 (13)0.7863 (5)0.0225 (17)
H120.82870.29790.80690.027*
C130.6567 (3)0.2668 (12)0.6448 (5)0.0168 (15)
C140.6740 (4)0.3678 (14)0.5562 (5)0.0236 (17)
H140.70810.31870.52530.028*
C150.6422 (3)0.5366 (13)0.5137 (6)0.0274 (18)
H150.65520.60580.45530.033*
C160.5923 (4)0.6028 (14)0.5560 (6)0.0276 (19)
C170.5729 (4)0.5021 (14)0.6414 (5)0.0223 (17)
H170.53760.54740.66980.027*
C180.6048 (4)0.3370 (14)0.6844 (6)0.0230 (17)
H180.59120.26910.74270.028*
C190.6600 (4)−0.3593 (13)0.8826 (5)0.0222 (17)
C200.6058 (4)−0.2976 (14)0.9198 (6)0.0258 (19)
H200.5896−0.15640.90460.031*
C210.5766 (4)−0.4471 (14)0.9787 (5)0.0284 (19)
H210.5393−0.41061.00170.034*
C220.6007 (4)−0.6463 (15)1.0043 (8)0.0363 (19)
H220.5808−0.74361.04730.044*
C230.6542 (4)−0.7082 (13)0.9679 (6)0.0259 (19)
H230.6702−0.84890.98430.031*
C240.6841 (4)−0.5623 (13)0.9073 (5)0.0214 (17)
H240.7209−0.60210.88310.026*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0382 (5)0.0361 (4)0.0401 (5)0.0017 (4)−0.0071 (5)0.0148 (5)
S10.0254 (10)0.0295 (11)0.0186 (9)−0.0016 (9)−0.0016 (8)0.0090 (9)
C10.041 (5)0.014 (4)0.023 (4)−0.005 (3)−0.002 (4)0.000 (3)
C20.029 (4)0.015 (3)0.016 (3)0.004 (3)0.001 (3)0.001 (3)
C30.027 (4)0.021 (4)0.014 (3)0.001 (3)−0.003 (3)0.005 (3)
C40.031 (4)0.018 (4)0.008 (3)−0.002 (3)−0.003 (3)0.006 (3)
C50.023 (4)0.016 (4)0.016 (3)−0.002 (3)0.001 (3)0.000 (3)
C60.031 (4)0.015 (4)0.015 (3)0.000 (3)−0.001 (3)0.002 (3)
C70.031 (4)0.020 (4)0.010 (3)0.004 (3)0.000 (3)0.007 (3)
C80.028 (4)0.041 (5)0.028 (4)0.004 (4)0.003 (3)0.010 (4)
C90.028 (4)0.042 (5)0.028 (4)0.005 (4)0.005 (4)0.005 (4)
C100.020 (4)0.047 (5)0.036 (4)−0.007 (4)−0.004 (3)0.010 (4)
C110.032 (5)0.023 (4)0.024 (4)−0.001 (4)−0.002 (4)0.010 (3)
C120.033 (4)0.020 (4)0.015 (3)0.002 (3)0.005 (3)0.004 (3)
C130.022 (4)0.014 (3)0.015 (3)−0.002 (3)−0.004 (3)0.004 (3)
C140.025 (4)0.030 (4)0.016 (3)−0.004 (3)−0.002 (3)0.004 (3)
C150.036 (4)0.029 (4)0.017 (4)−0.006 (3)−0.001 (3)0.010 (3)
C160.035 (5)0.024 (4)0.024 (4)−0.004 (3)0.002 (4)0.012 (3)
C170.029 (4)0.025 (4)0.013 (3)0.001 (3)−0.001 (3)0.007 (3)
C180.025 (4)0.026 (4)0.017 (3)−0.007 (3)−0.001 (3)0.010 (3)
C190.032 (4)0.019 (4)0.016 (3)−0.004 (3)−0.004 (3)0.002 (3)
C200.032 (4)0.025 (4)0.020 (3)−0.002 (3)−0.001 (3)0.007 (3)
C210.032 (4)0.032 (4)0.022 (4)−0.002 (3)−0.001 (3)0.006 (3)
C220.043 (4)0.041 (4)0.025 (3)−0.018 (4)−0.006 (5)0.009 (4)
C230.046 (5)0.010 (4)0.022 (4)−0.003 (3)−0.006 (3)0.006 (3)
C240.031 (4)0.020 (4)0.013 (3)0.000 (3)−0.002 (3)0.002 (3)

Geometric parameters (Å, °)

Br1—C161.905 (8)C11—C121.363 (12)
S1—C61.750 (8)C11—H110.9500
S1—C21.849 (8)C12—H120.9500
C1—C21.547 (11)C13—C181.391 (11)
C1—H1A0.9800C13—C141.414 (10)
C1—H1B0.9800C14—C151.383 (11)
C1—H1C0.9800C14—H140.9500
C2—C31.501 (10)C15—C161.360 (12)
C2—C71.516 (11)C15—H150.9500
C3—C41.356 (11)C16—C171.392 (11)
C3—H30.9500C17—C181.373 (11)
C4—C51.448 (10)C17—H170.9500
C4—C131.463 (10)C18—H180.9500
C5—C61.357 (11)C19—C241.383 (11)
C5—H50.9500C19—C201.414 (12)
C6—C191.495 (11)C20—C211.385 (11)
C7—C81.361 (12)C20—H200.9500
C7—C121.436 (11)C21—C221.366 (13)
C8—C91.372 (12)C21—H210.9500
C8—H80.9500C22—C231.395 (13)
C9—C101.360 (14)C22—H220.9500
C9—H90.9500C23—C241.393 (11)
C10—C111.402 (13)C23—H230.9500
C10—H100.9500C24—H240.9500
C6—S1—C2100.9 (4)C11—C12—C7120.3 (8)
C2—C1—H1A109.5C11—C12—H12119.8
C2—C1—H1B109.5C7—C12—H12119.8
H1A—C1—H1B109.5C18—C13—C14116.9 (7)
C2—C1—H1C109.5C18—C13—C4122.4 (6)
H1A—C1—H1C109.5C14—C13—C4120.7 (7)
H1B—C1—H1C109.5C15—C14—C13121.5 (8)
C3—C2—C7114.1 (7)C15—C14—H14119.3
C3—C2—C1109.5 (6)C13—C14—H14119.3
C7—C2—C1112.2 (7)C16—C15—C14119.5 (7)
C3—C2—S1107.7 (5)C16—C15—H15120.2
C7—C2—S1104.9 (5)C14—C15—H15120.2
C1—C2—S1108.1 (5)C15—C16—C17120.7 (8)
C4—C3—C2123.9 (7)C15—C16—Br1118.6 (6)
C4—C3—H3118.0C17—C16—Br1120.7 (7)
C2—C3—H3118.0C18—C17—C16119.8 (8)
C3—C4—C5121.2 (7)C18—C17—H17120.1
C3—C4—C13120.5 (7)C16—C17—H17120.1
C5—C4—C13118.3 (7)C17—C18—C13121.6 (7)
C6—C5—C4123.7 (7)C17—C18—H18119.2
C6—C5—H5118.1C13—C18—H18119.2
C4—C5—H5118.1C24—C19—C20120.4 (7)
C5—C6—C19123.6 (8)C24—C19—C6121.2 (8)
C5—C6—S1121.0 (6)C20—C19—C6118.4 (7)
C19—C6—S1115.3 (6)C21—C20—C19118.7 (8)
C8—C7—C12116.1 (8)C21—C20—H20120.6
C8—C7—C2125.1 (8)C19—C20—H20120.6
C12—C7—C2118.8 (7)C22—C21—C20120.9 (8)
C7—C8—C9123.8 (9)C22—C21—H21119.6
C7—C8—H8118.1C20—C21—H21119.6
C9—C8—H8118.1C21—C22—C23120.6 (9)
C10—C9—C8119.9 (9)C21—C22—H22119.7
C10—C9—H9120.1C23—C22—H22119.7
C8—C9—H9120.1C24—C23—C22119.6 (8)
C9—C10—C11118.9 (8)C24—C23—H23120.2
C9—C10—H10120.5C22—C23—H23120.2
C11—C10—H10120.5C19—C24—C23119.7 (8)
C12—C11—C10120.8 (9)C19—C24—H24120.2
C12—C11—H11119.6C23—C24—H24120.2
C10—C11—H11119.6
C6—S1—C2—C346.9 (6)C2—C7—C12—C11179.8 (7)
C6—S1—C2—C7168.8 (5)C3—C4—C13—C18−146.5 (8)
C6—S1—C2—C1−71.3 (6)C5—C4—C13—C1831.7 (11)
C7—C2—C3—C4−160.3 (7)C3—C4—C13—C1433.4 (11)
C1—C2—C3—C473.0 (9)C5—C4—C13—C14−148.5 (7)
S1—C2—C3—C4−44.3 (9)C18—C13—C14—C153.2 (12)
C2—C3—C4—C510.0 (11)C4—C13—C14—C15−176.6 (7)
C2—C3—C4—C13−171.9 (7)C13—C14—C15—C16−2.1 (13)
C3—C4—C5—C619.9 (12)C14—C15—C16—C17−0.2 (13)
C13—C4—C5—C6−158.2 (7)C14—C15—C16—Br1176.4 (6)
C4—C5—C6—C19172.4 (7)C15—C16—C17—C181.2 (13)
C4—C5—C6—S1−5.3 (11)Br1—C16—C17—C18−175.3 (7)
C2—S1—C6—C5−26.8 (7)C16—C17—C18—C130.0 (13)
C2—S1—C6—C19155.3 (6)C14—C13—C18—C17−2.2 (12)
C3—C2—C7—C8−136.8 (8)C4—C13—C18—C17177.7 (8)
C1—C2—C7—C8−11.5 (11)C5—C6—C19—C24139.8 (8)
S1—C2—C7—C8105.6 (8)S1—C6—C19—C24−42.3 (9)
C3—C2—C7—C1243.0 (9)C5—C6—C19—C20−40.9 (11)
C1—C2—C7—C12168.3 (6)S1—C6—C19—C20136.9 (7)
S1—C2—C7—C12−74.6 (7)C24—C19—C20—C21−1.9 (12)
C12—C7—C8—C90.4 (12)C6—C19—C20—C21178.8 (7)
C2—C7—C8—C9−179.8 (8)C19—C20—C21—C222.9 (13)
C7—C8—C9—C101.9 (13)C20—C21—C22—C23−3.0 (14)
C8—C9—C10—C11−4.1 (13)C21—C22—C23—C242.0 (13)
C9—C10—C11—C124.2 (13)C20—C19—C24—C231.0 (11)
C10—C11—C12—C7−1.9 (12)C6—C19—C24—C23−179.7 (7)
C8—C7—C12—C11−0.4 (11)C22—C23—C24—C19−1.0 (12)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2581).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Rahmani, H., Pirelahi, H. & Ng, S. W. (2009). Acta Cryst. E65, o603. [PMC free article] [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Suld, G. & Price, C. C. (1962). J. Am. Chem. Soc.84, 2090–2094.
  • Westrip, S. P. (2009). publCIF In preparation.

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