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Acta Crystallogr Sect E Struct Rep Online. 2009 March 1; 65(Pt 3): o603.
Published online 2009 February 25. doi:  10.1107/S1600536809005911
PMCID: PMC2968509

4-Methyl-2,4,6-triphenyl-4H-thio­pyran

Abstract

The six-membered thio­pyran ring in the title compound, C24H20S, adopts a flattened boat conformation, with the S atom displaced by 0.273 (2) Å and the 3-methyl­ene C atom by 0.294 (3) Å from the plane of the other four sp 2-hydridized C atoms. The methyl group on the methyl­ene carbon lies in a axial position with the phenyl equatorial.

Related literature

2,4,4,6-Tetraaryl- or 4-alkyl-2,4,6-triaryl-4H-thio­pyrans undergo UV-induced isomerization to form aryl-migrated 2H-thio­pyrans; for a discussion of the photoisomerization mechanism, see: Pirelahi et al. (2004 [triangle]); Pirelahi & Rahmani (1997 [triangle]). 4-Methyl-2,4,6-triphenyl-4H-thio­pyran does not react in the solid state, but in solution is converted to 4-methyl-2,3,6-triphenyl-2H-thio­pyran; see: Mori & Maeda (1991 [triangle]). For the synthesis, see: Suld & Price (1962 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o603-scheme1.jpg

Experimental

Crystal data

  • C24H20S
  • M r = 340.46
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o603-efi1.jpg
  • a = 9.8737 (2) Å
  • b = 22.5282 (4) Å
  • c = 9.2288 (2) Å
  • β = 118.987 (1)°
  • V = 1795.67 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.18 mm−1
  • T = 115 K
  • 0.35 × 0.20 × 0.10 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.917, T max = 0.982
  • 8464 measured reflections
  • 3883 independent reflections
  • 3698 reflections with I > σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.072
  • S = 1.03
  • 3883 reflections
  • 227 parameters
  • 2 restraints
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.18 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1825 Friedel pairs
  • Flack parameter: 0.00 (5)

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/S1600536809005911/sj2578sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005911/sj2578Isup2.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 synthesized by the reaction of methyl magnesium bromide and 2,4,6-triphenylthiopyrylium 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).

Figures

Fig. 1.
Thermal ellisoid plot (Barbour, 2001) of C24H20S; probability levels are set at 70% and H-atoms are drawn as spheres of arbitrary radius.

Crystal data

C24H20SF(000) = 720
Mr = 340.46Dx = 1.259 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 4067 reflections
a = 9.8737 (2) Åθ = 2.5–28.0°
b = 22.5282 (4) ŵ = 0.18 mm1
c = 9.2288 (2) ÅT = 115 K
β = 118.987 (1)°Prism, colorless
V = 1795.67 (6) Å30.35 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer3883 independent reflections
Radiation source: fine-focus sealed tube3698 reflections with I > σ(I)
graphiteRint = 0.024
ω scansθmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −12→12
Tmin = 0.917, Tmax = 0.982k = −29→29
8464 measured reflectionsl = −11→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.072w = 1/[σ2(Fo2) + (0.0401P)2 + 0.2571P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
3883 reflectionsΔρmax = 0.28 e Å3
227 parametersΔρmin = −0.17 e Å3
2 restraintsAbsolute structure: Flack (1983), 1825 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.00 (5)

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

xyzUiso*/Ueq
S10.49977 (4)0.892322 (17)0.49963 (4)0.01993 (9)
C10.48277 (17)0.87133 (6)0.67575 (18)0.0169 (3)
C20.37550 (18)0.83350 (7)0.66660 (19)0.0197 (3)
H20.37400.82590.76710.024*
C30.25547 (17)0.80107 (7)0.51476 (19)0.0187 (3)
C40.22225 (18)0.83423 (7)0.35828 (18)0.0180 (3)
H40.12280.82830.26510.022*
C50.31709 (16)0.87086 (6)0.33675 (17)0.0156 (3)
C60.3178 (2)0.73921 (7)0.5054 (2)0.0252 (4)
H6A0.34870.71780.60920.038*
H6B0.40750.74370.48790.038*
H6C0.23660.71680.41310.038*
C70.59735 (17)0.90088 (7)0.83149 (19)0.0174 (3)
C80.55816 (18)0.91435 (7)0.95401 (19)0.0210 (3)
H80.45850.90410.93790.025*
C90.66275 (19)0.94253 (7)1.0990 (2)0.0241 (3)
H90.63410.95171.18100.029*
C100.8091 (2)0.95738 (7)1.1249 (2)0.0236 (4)
H100.88090.97661.22450.028*
C110.84996 (18)0.94407 (7)1.0045 (2)0.0237 (3)
H110.95030.95401.02210.028*
C120.74509 (18)0.91643 (7)0.85877 (19)0.0207 (3)
H120.77380.90790.77650.025*
C130.10640 (17)0.79667 (7)0.52855 (18)0.0183 (3)
C140.0894 (2)0.75238 (8)0.6233 (2)0.0255 (3)
H140.16790.72310.67420.031*
C15−0.0402 (2)0.75009 (8)0.6451 (2)0.0294 (4)
H15−0.04870.71980.71180.035*
C16−0.1572 (2)0.79169 (8)0.5702 (2)0.0284 (4)
H16−0.24650.78990.58360.034*
C17−0.14174 (19)0.83609 (8)0.47516 (19)0.0257 (4)
H17−0.22120.86490.42320.031*
C18−0.01103 (19)0.83879 (7)0.45533 (18)0.0222 (3)
H18−0.00160.86980.39100.027*
C190.27339 (17)0.89872 (7)0.17441 (18)0.0165 (3)
C200.18705 (18)0.86626 (7)0.02926 (18)0.0191 (3)
H200.16580.82550.03590.023*
C210.13179 (19)0.89302 (7)−0.1250 (2)0.0222 (3)
H210.07290.8706−0.22300.027*
C220.16242 (19)0.95233 (8)−0.1358 (2)0.0238 (4)
H220.12320.9708−0.24120.029*
C230.25068 (19)0.98482 (7)0.0078 (2)0.0242 (3)
H230.27221.02550.00050.029*
C240.30752 (18)0.95805 (7)0.16187 (18)0.0192 (3)
H240.37000.98020.25940.023*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.01477 (16)0.02749 (19)0.01650 (17)−0.00309 (16)0.00676 (13)−0.00013 (15)
C10.0159 (7)0.0177 (7)0.0151 (7)0.0022 (6)0.0060 (6)0.0015 (6)
C20.0202 (7)0.0213 (8)0.0151 (7)0.0008 (6)0.0067 (6)0.0030 (6)
C30.0183 (7)0.0174 (7)0.0179 (7)−0.0021 (6)0.0069 (6)0.0014 (5)
C40.0177 (7)0.0189 (7)0.0146 (7)−0.0021 (6)0.0056 (6)−0.0022 (6)
C50.0144 (7)0.0154 (7)0.0151 (7)0.0006 (5)0.0056 (6)−0.0027 (5)
C60.0260 (9)0.0207 (8)0.0305 (9)0.0010 (7)0.0150 (7)0.0016 (7)
C70.0144 (7)0.0168 (7)0.0159 (7)0.0014 (6)0.0032 (6)0.0022 (5)
C80.0149 (7)0.0237 (8)0.0219 (8)−0.0006 (6)0.0070 (6)−0.0016 (6)
C90.0233 (8)0.0294 (8)0.0197 (8)0.0019 (7)0.0105 (6)−0.0021 (6)
C100.0203 (8)0.0216 (8)0.0206 (8)−0.0008 (7)0.0034 (6)−0.0044 (6)
C110.0167 (7)0.0261 (8)0.0250 (8)−0.0027 (6)0.0075 (6)−0.0014 (6)
C120.0201 (8)0.0237 (8)0.0190 (8)−0.0008 (6)0.0100 (6)0.0002 (6)
C130.0172 (7)0.0187 (7)0.0153 (7)−0.0034 (6)0.0048 (6)−0.0022 (5)
C140.0258 (8)0.0221 (8)0.0262 (8)−0.0006 (7)0.0107 (7)0.0051 (6)
C150.0318 (9)0.0282 (9)0.0302 (9)−0.0090 (7)0.0167 (8)0.0027 (7)
C160.0208 (8)0.0378 (10)0.0267 (9)−0.0079 (7)0.0115 (7)−0.0065 (7)
C170.0198 (8)0.0340 (9)0.0182 (8)0.0035 (7)0.0050 (6)−0.0011 (6)
C180.0246 (8)0.0228 (8)0.0166 (8)−0.0005 (6)0.0079 (7)0.0008 (5)
C190.0140 (7)0.0203 (7)0.0165 (8)0.0010 (6)0.0084 (6)−0.0008 (6)
C200.0188 (7)0.0198 (7)0.0202 (8)−0.0007 (6)0.0106 (6)−0.0012 (6)
C210.0184 (8)0.0318 (9)0.0166 (8)−0.0006 (6)0.0086 (6)−0.0019 (6)
C220.0195 (8)0.0346 (9)0.0197 (8)0.0068 (7)0.0113 (7)0.0079 (7)
C230.0262 (8)0.0216 (8)0.0314 (9)−0.0006 (7)0.0191 (7)0.0027 (6)
C240.0182 (7)0.0222 (8)0.0192 (8)−0.0019 (6)0.0106 (6)−0.0027 (6)

Geometric parameters (Å, °)

S1—C51.7661 (14)C11—H110.9500
S1—C11.7772 (15)C12—H120.9500
C1—C21.330 (2)C13—C141.390 (2)
C1—C71.488 (2)C13—C181.393 (2)
C2—C31.514 (2)C14—C151.390 (2)
C2—H20.9500C14—H140.9500
C3—C41.514 (2)C15—C161.384 (3)
C3—C131.541 (2)C15—H150.9500
C3—C61.543 (2)C16—C171.386 (3)
C4—C51.333 (2)C16—H160.9500
C4—H40.9500C17—C181.390 (2)
C5—C191.483 (2)C17—H170.9500
C6—H6A0.9800C18—H180.9500
C6—H6B0.9800C19—C201.396 (2)
C6—H6C0.9800C19—C241.397 (2)
C7—C81.394 (2)C20—C211.391 (2)
C7—C121.399 (2)C20—H200.9500
C8—C91.386 (2)C21—C221.384 (2)
C8—H80.9500C21—H210.9500
C9—C101.387 (3)C22—C231.390 (2)
C9—H90.9500C22—H220.9500
C10—C111.386 (2)C23—C241.388 (2)
C10—H100.9500C23—H230.9500
C11—C121.386 (2)C24—H240.9500
C5—S1—C1101.27 (7)C11—C12—C7120.71 (15)
C2—C1—C7123.89 (14)C11—C12—H12119.6
C2—C1—S1122.53 (12)C7—C12—H12119.6
C7—C1—S1113.57 (11)C14—C13—C18117.92 (14)
C1—C2—C3127.59 (14)C14—C13—C3120.65 (14)
C1—C2—H2116.2C18—C13—C3121.32 (14)
C3—C2—H2116.2C15—C14—C13121.22 (16)
C4—C3—C2110.82 (12)C15—C14—H14119.4
C4—C3—C13109.66 (12)C13—C14—H14119.4
C2—C3—C13107.77 (13)C16—C15—C14120.43 (16)
C4—C3—C6107.47 (13)C16—C15—H15119.8
C2—C3—C6109.47 (13)C14—C15—H15119.8
C13—C3—C6111.67 (12)C15—C16—C17118.94 (16)
C5—C4—C3127.18 (13)C15—C16—H16120.5
C5—C4—H4116.4C17—C16—H16120.5
C3—C4—H4116.4C16—C17—C18120.56 (16)
C4—C5—C19122.09 (13)C16—C17—H17119.7
C4—C5—S1122.96 (11)C18—C17—H17119.7
C19—C5—S1114.91 (11)C17—C18—C13120.92 (15)
C3—C6—H6A109.5C17—C18—H18119.5
C3—C6—H6B109.5C13—C18—H18119.5
H6A—C6—H6B109.5C20—C19—C24118.78 (14)
C3—C6—H6C109.5C20—C19—C5119.41 (13)
H6A—C6—H6C109.5C24—C19—C5121.68 (13)
H6B—C6—H6C109.5C21—C20—C19120.60 (15)
C8—C7—C12118.32 (14)C21—C20—H20119.7
C8—C7—C1120.06 (14)C19—C20—H20119.7
C12—C7—C1121.62 (14)C22—C21—C20120.09 (15)
C9—C8—C7120.86 (15)C22—C21—H21120.0
C9—C8—H8119.6C20—C21—H21120.0
C7—C8—H8119.6C21—C22—C23119.82 (15)
C8—C9—C10120.22 (15)C21—C22—H22120.1
C8—C9—H9119.9C23—C22—H22120.1
C10—C9—H9119.9C24—C23—C22120.22 (15)
C11—C10—C9119.59 (15)C24—C23—H23119.9
C11—C10—H10120.2C22—C23—H23119.9
C9—C10—H10120.2C23—C24—C19120.44 (14)
C12—C11—C10120.30 (15)C23—C24—H24119.8
C12—C11—H11119.9C19—C24—H24119.8
C10—C11—H11119.9
C5—S1—C1—C217.61 (15)C4—C3—C13—C14157.18 (14)
C5—S1—C1—C7−161.33 (11)C2—C3—C13—C14−82.11 (17)
C7—C1—C2—C3−179.48 (15)C6—C3—C13—C1438.2 (2)
S1—C1—C2—C31.7 (2)C4—C3—C13—C18−26.78 (19)
C1—C2—C3—C4−24.4 (2)C2—C3—C13—C1893.93 (16)
C1—C2—C3—C13−144.35 (16)C6—C3—C13—C18−145.80 (14)
C1—C2—C3—C694.01 (19)C18—C13—C14—C15−0.2 (2)
C2—C3—C4—C526.5 (2)C3—C13—C14—C15175.99 (16)
C13—C3—C4—C5145.30 (15)C13—C14—C15—C161.0 (3)
C6—C3—C4—C5−93.12 (19)C14—C15—C16—C17−0.9 (3)
C3—C4—C5—C19177.18 (14)C15—C16—C17—C180.0 (3)
C3—C4—C5—S1−5.5 (2)C16—C17—C18—C130.8 (2)
C1—S1—C5—C4−15.81 (15)C14—C13—C18—C17−0.7 (2)
C1—S1—C5—C19161.67 (11)C3—C13—C18—C17−176.85 (14)
C2—C1—C7—C8−31.3 (2)C4—C5—C19—C20−37.1 (2)
S1—C1—C7—C8147.59 (12)S1—C5—C19—C20145.37 (12)
C2—C1—C7—C12149.37 (16)C4—C5—C19—C24138.58 (16)
S1—C1—C7—C12−31.71 (19)S1—C5—C19—C24−38.92 (19)
C12—C7—C8—C90.1 (2)C24—C19—C20—C21−2.1 (2)
C1—C7—C8—C9−179.21 (15)C5—C19—C20—C21173.78 (14)
C7—C8—C9—C10−0.5 (3)C19—C20—C21—C220.1 (2)
C8—C9—C10—C110.2 (3)C20—C21—C22—C231.0 (2)
C9—C10—C11—C120.4 (3)C21—C22—C23—C24−0.3 (2)
C10—C11—C12—C7−0.8 (3)C22—C23—C24—C19−1.7 (2)
C8—C7—C12—C110.5 (2)C20—C19—C24—C232.8 (2)
C1—C7—C12—C11179.82 (15)C5—C19—C24—C23−172.93 (14)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2578).

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.
  • Mori, Y. & Maeda, K. (1991). J. Chem. Soc. Perkin Trans. 2, pp. 2061–2066.
  • Pirelahi, H., Atarodiekashani, A., Seyyedmoossavi, S. & Daryanavardedargahani, H. (2004). Monatsh. Chem.135, 973–978.
  • Pirelahi, H. & Rahmani, H. (1997). J. Photochem. Photobiol. A, 111, 15–21.
  • 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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