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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1686.
Published online 2008 August 6. doi:  10.1107/S1600536808022010
PMCID: PMC2960686

(6aR,10aR)-6,6,9-Trimethyl-3-pentyl-6a,7,8,10a-tetra­hydro-6H-benzo[c]­chromen-1-yl 4-methyl­benzene­sulfonate

Abstract

In the crystal structure of the title compound, C28H36O4S, the p-tolyl ring is inclined at 35.8° to the aromatic ring. The cyclohexene ring adopts a boat conformation and the heterocyclic ring is in a slightly distorted screw boat conformation.

Related literature

For the physiological actions of tetra­hydro­cannabinol (Δ9—THC), the most psychologically active constituent of Cannabis sativa, see: Mechoulam & Gaoni (1967 [triangle]). For the synthesis of Δ9—THC-tosyl­ate, see: Duchek (2004 [triangle]).

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Object name is e-64-o1686-scheme1.jpg

Experimental

Crystal data

  • C28H36O4S
  • M r = 468.63
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1686-efi1.jpg
  • a = 9.8759 (2) Å
  • b = 13.2996 (2) Å
  • c = 19.1500 (3) Å
  • V = 2515.27 (7) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 1.39 mm−1
  • T = 100 K
  • 0.19 × 0.17 × 0.16 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: none
  • 47731 measured reflections
  • 4562 independent reflections
  • 4438 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 0.069
  • S = 1.04
  • 4562 reflections
  • 303 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.24 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1965 Friedel pairs
  • Flack parameter: 0.023 (11)

Data collection: SMART (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2003 [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: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808022010/nc2105sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022010/nc2105Isup2.hkl

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

Acknowledgments

The authors thank Desmond Slade, John R. Duchek and David J. Kimmich for their valuable contributions, and the Center for Disease Control and Prevention, USA, for providing financial assistance (CDC cooperative agreements 1UO1 CI000211-03 and 1UO1 CI000362-01). This investigation was conducted in a facility constructed with support from Research Facilities Improvement Program grant No. C06 Rr-14503-01 from the National Center for Research Resources, National Institutes of Health. The project was also supported in part by the National Institute on Drug Abuse, contract No. N01DA-5-7746.

supplementary crystallographic information

Experimental

Δ9 – Tetrahydrocannabinol tosylate (p-tosyl-Δ9—THC), was synthesized according to Duchek (2004).

Refinement

All H atoms were located in difference maps and treated as riding atoms, with the following distance restraints: C—H = 0.93 Å, Uiso=1.2Ueq (C) for Csp2, C—H = 0.98 Å, Uiso = 1.2Ueq (C) for CH, C—H = 0.97 Å, Uiso = 1.2Ueq (C) for CH2, C—H = 0.96 Å, Uiso = 1.5Ueq (C) for CH3.

Figures

Fig. 1.
Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level.

Crystal data

C28H36O4SF000 = 1008
Mr = 468.63Dx = 1.238 Mg m3
Orthorhombic, P212121Cu Kα radiation λ = 1.54178 Å
Hall symbol: P 2ac 2abCell parameters from 9942 reflections
a = 9.8759 (2) Åθ = 4.1–67.4º
b = 13.2996 (2) ŵ = 1.39 mm1
c = 19.1500 (3) ÅT = 100 K
V = 2515.27 (7) Å3Blocks, colourless
Z = 40.19 × 0.17 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer4438 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 100 Kθmax = 68.0º
[var phi] and ω scansθmin = 4.1º
Absorption correction: noneh = −11→11
47731 measured reflectionsk = −15→15
4562 independent reflectionsl = −23→23

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.027  w = 1/[σ2(Fo2) + (0.0429P)2 + 0.4744P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.069(Δ/σ)max = 0.002
S = 1.04Δρmax = 0.25 e Å3
4562 reflectionsΔρmin = −0.24 e Å3
303 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1965 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.023 (11)

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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 andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

xyzUiso*/Ueq
S10.46490 (3)0.05656 (2)1.076895 (17)0.01846 (9)
C10.47927 (14)0.18406 (10)0.97409 (7)0.0172 (3)
C20.47639 (14)0.28371 (11)0.99381 (7)0.0187 (3)
H20.52050.30461.03420.022*
C30.40657 (14)0.35294 (11)0.95249 (7)0.0186 (3)
C40.34101 (15)0.31759 (11)0.89315 (7)0.0189 (3)
H40.29110.36210.86590.023*
C70.39042 (17)−0.07962 (11)0.78957 (8)0.0262 (3)
H7A0.3350−0.11820.82160.031*
H7B0.3527−0.08690.74310.031*
C90.61971 (16)−0.07895 (11)0.84941 (8)0.0244 (3)
C100.57509 (15)−0.00757 (11)0.89264 (7)0.0207 (3)
H100.63260.01520.92770.025*
C80.53477 (18)−0.11963 (12)0.79053 (8)0.0291 (3)
H8A0.5319−0.19230.79410.035*
H8B0.5780−0.10290.74660.035*
C60.25642 (15)0.08708 (11)0.79805 (8)0.0213 (3)
C4A0.34857 (14)0.21680 (11)0.87368 (7)0.0184 (3)
C10A0.43477 (14)0.03799 (10)0.88715 (7)0.0189 (3)
H10A0.3732−0.00340.91520.023*
C10B0.42230 (14)0.14608 (10)0.91271 (7)0.0178 (3)
C190.40283 (15)0.14829 (10)1.13478 (7)0.0176 (3)
C200.47260 (15)0.16732 (11)1.19667 (7)0.0208 (3)
H200.55320.13401.20650.025*
C240.28354 (15)0.19860 (11)1.11914 (7)0.0199 (3)
H240.23710.18511.07790.024*
C210.42018 (16)0.23624 (12)1.24306 (8)0.0228 (3)
H210.46490.24781.28500.027*
C140.40301 (15)0.46315 (10)0.97123 (7)0.0216 (3)
H14A0.43230.47131.01930.026*
H14B0.31050.48720.96790.026*
C110.13920 (16)0.05062 (12)0.84292 (8)0.0264 (3)
H11A0.16220.05790.89140.040*
H11B0.1214−0.01890.83290.040*
H11C0.06000.08980.83280.040*
C230.23487 (16)0.26903 (11)1.16577 (8)0.0221 (3)
H230.15590.30401.15510.027*
C220.30153 (15)0.28894 (11)1.22843 (8)0.0210 (3)
C180.5664 (2)0.77077 (13)1.03217 (10)0.0409 (5)
H18A0.59920.81270.99510.061*
H18B0.62050.78121.07320.061*
H18C0.47380.78761.04220.061*
C250.24424 (18)0.36377 (13)1.27916 (9)0.0301 (4)
H25A0.16750.33491.30250.045*
H25B0.21660.42311.25440.045*
H25C0.31210.38121.31300.045*
C150.49335 (15)0.52705 (10)0.92386 (8)0.0227 (3)
H15A0.46200.52080.87610.027*
H15B0.58520.50130.92580.027*
C170.57512 (18)0.66107 (12)1.01015 (9)0.0293 (4)
H17A0.54190.61911.04790.035*
H17B0.66930.64381.00220.035*
C160.49424 (17)0.63855 (11)0.94437 (8)0.0260 (3)
H16A0.53170.67730.90600.031*
H16B0.40160.66060.95130.031*
C120.21926 (17)0.08792 (12)0.72084 (8)0.0273 (3)
H12A0.14540.13360.71330.041*
H12B0.19280.02150.70670.041*
H12C0.29610.10910.69390.041*
O20.55008 (10)0.11806 (7)1.01992 (5)0.0185 (2)
O30.56579 (11)−0.00225 (8)1.11089 (5)0.0271 (2)
O40.35208 (11)0.00985 (8)1.04341 (5)0.0240 (2)
C130.75923 (18)−0.12306 (14)0.85622 (9)0.0344 (4)
H13A0.8061−0.09080.89400.052*
H13B0.8084−0.11270.81360.052*
H13C0.7523−0.19380.86540.052*
C6A0.38882 (15)0.03099 (10)0.81073 (7)0.0201 (3)
H6A0.45820.06470.78270.024*
O10.28074 (11)0.19339 (8)0.81346 (5)0.0207 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.02166 (17)0.01704 (15)0.01669 (15)0.00077 (14)0.00114 (13)0.00015 (13)
C10.0154 (7)0.0200 (7)0.0162 (6)−0.0006 (6)0.0033 (5)0.0013 (5)
C20.0174 (7)0.0236 (7)0.0149 (6)−0.0041 (6)0.0019 (5)−0.0024 (5)
C30.0178 (7)0.0188 (7)0.0191 (7)−0.0019 (6)0.0064 (5)−0.0007 (5)
C40.0189 (7)0.0188 (7)0.0190 (7)−0.0008 (6)0.0023 (5)0.0015 (6)
C70.0351 (9)0.0208 (8)0.0227 (7)−0.0001 (7)−0.0047 (6)−0.0053 (6)
C90.0272 (8)0.0229 (8)0.0231 (7)0.0022 (6)0.0012 (6)−0.0001 (6)
C100.0240 (7)0.0203 (7)0.0177 (6)0.0003 (6)−0.0006 (5)−0.0013 (6)
C80.0382 (9)0.0228 (7)0.0263 (8)0.0047 (7)0.0008 (7)−0.0079 (6)
C60.0252 (8)0.0166 (7)0.0221 (7)−0.0025 (6)−0.0026 (6)−0.0028 (5)
C4A0.0174 (7)0.0215 (7)0.0162 (7)−0.0024 (6)0.0029 (5)−0.0014 (5)
C10A0.0221 (7)0.0184 (7)0.0161 (6)−0.0019 (6)0.0006 (5)−0.0014 (5)
C10B0.0172 (7)0.0182 (7)0.0179 (7)−0.0019 (5)0.0027 (5)−0.0010 (5)
C190.0195 (7)0.0185 (7)0.0148 (6)−0.0010 (6)0.0024 (5)0.0011 (5)
C200.0174 (7)0.0258 (7)0.0193 (7)0.0010 (6)−0.0017 (6)0.0014 (5)
C240.0197 (7)0.0230 (7)0.0169 (7)−0.0010 (6)−0.0026 (6)0.0006 (5)
C210.0223 (8)0.0286 (8)0.0175 (7)−0.0048 (6)−0.0032 (6)−0.0024 (6)
C140.0220 (7)0.0203 (7)0.0225 (7)−0.0008 (6)0.0022 (6)−0.0038 (5)
C110.0233 (8)0.0255 (7)0.0303 (8)−0.0017 (7)−0.0014 (6)−0.0008 (6)
C230.0197 (7)0.0242 (7)0.0225 (7)0.0039 (6)−0.0001 (6)0.0031 (6)
C220.0224 (8)0.0187 (7)0.0220 (7)−0.0032 (6)0.0024 (6)0.0006 (6)
C180.0586 (13)0.0257 (8)0.0384 (10)−0.0098 (8)0.0003 (9)−0.0062 (7)
C250.0326 (9)0.0304 (8)0.0273 (8)0.0026 (7)−0.0007 (7)−0.0070 (7)
C150.0264 (7)0.0193 (7)0.0224 (7)−0.0013 (6)0.0000 (6)−0.0009 (6)
C170.0332 (9)0.0217 (8)0.0329 (9)−0.0040 (7)−0.0023 (7)−0.0014 (6)
C160.0321 (9)0.0176 (7)0.0284 (8)−0.0006 (6)−0.0016 (6)0.0021 (6)
C120.0336 (9)0.0248 (7)0.0235 (8)0.0005 (7)−0.0070 (6)−0.0050 (6)
O20.0180 (5)0.0210 (5)0.0164 (5)0.0007 (4)0.0003 (4)−0.0004 (4)
O30.0329 (6)0.0244 (5)0.0242 (5)0.0065 (5)0.0008 (4)0.0025 (4)
O40.0277 (6)0.0222 (5)0.0220 (5)−0.0061 (4)0.0039 (4)−0.0029 (4)
C130.0325 (9)0.0362 (9)0.0346 (9)0.0108 (7)0.0016 (7)−0.0088 (7)
C6A0.0232 (8)0.0195 (7)0.0175 (7)−0.0032 (6)0.0007 (6)−0.0031 (5)
O10.0271 (5)0.0172 (5)0.0179 (5)−0.0009 (4)−0.0047 (4)−0.0017 (4)

Geometric parameters (Å, °)

S1—O31.4243 (11)C20—H200.9300
S1—O41.4277 (11)C24—C231.380 (2)
S1—O21.6022 (10)C24—H240.9300
S1—C191.7586 (14)C21—C221.394 (2)
C1—C21.3783 (19)C21—H210.9300
C1—C10B1.3976 (19)C14—C151.5301 (19)
C1—O21.4247 (17)C14—H14A0.9700
C2—C31.396 (2)C14—H14B0.9700
C2—H20.9300C11—H11A0.9600
C3—C41.390 (2)C11—H11B0.9600
C3—C141.5095 (19)C11—H11C0.9600
C4—C4A1.393 (2)C23—C221.394 (2)
C4—H40.9300C23—H230.9300
C7—C81.522 (2)C22—C251.501 (2)
C7—C6A1.5260 (19)C18—C171.521 (2)
C7—H7A0.9700C18—H18A0.9600
C7—H7B0.9700C18—H18B0.9600
C9—C101.335 (2)C18—H18C0.9600
C9—C131.503 (2)C25—H25A0.9600
C9—C81.506 (2)C25—H25B0.9600
C10—C10A1.516 (2)C25—H25C0.9600
C10—H100.9300C15—C161.5341 (19)
C8—H8A0.9700C15—H15A0.9700
C8—H8B0.9700C15—H15B0.9700
C6—O11.4643 (17)C17—C161.521 (2)
C6—C111.521 (2)C17—H17A0.9700
C6—C121.523 (2)C17—H17B0.9700
C6—C6A1.525 (2)C16—H16A0.9700
C4A—O11.3694 (17)C16—H16B0.9700
C4A—C10B1.405 (2)C12—H12A0.9600
C10A—C10B1.5236 (18)C12—H12B0.9600
C10A—C6A1.5350 (18)C12—H12C0.9600
C10A—H10A0.9800C13—H13A0.9600
C19—C241.388 (2)C13—H13B0.9600
C19—C201.394 (2)C13—H13C0.9600
C20—C211.377 (2)C6A—H6A0.9800
O3—S1—O4120.81 (7)C3—C14—H14A109.1
O3—S1—O2102.96 (6)C15—C14—H14A109.1
O4—S1—O2109.03 (6)C3—C14—H14B109.1
O3—S1—C19109.68 (7)C15—C14—H14B109.1
O4—S1—C19108.24 (7)H14A—C14—H14B107.8
O2—S1—C19104.96 (6)C6—C11—H11A109.5
C2—C1—C10B124.73 (13)C6—C11—H11B109.5
C2—C1—O2115.71 (12)H11A—C11—H11B109.5
C10B—C1—O2119.53 (12)C6—C11—H11C109.5
C1—C2—C3119.27 (13)H11A—C11—H11C109.5
C1—C2—H2120.4H11B—C11—H11C109.5
C3—C2—H2120.4C24—C23—C22121.41 (14)
C4—C3—C2118.06 (13)C24—C23—H23119.3
C4—C3—C14120.79 (13)C22—C23—H23119.3
C2—C3—C14121.14 (13)C21—C22—C23118.32 (14)
C3—C4—C4A121.28 (14)C21—C22—C25121.34 (14)
C3—C4—H4119.4C23—C22—C25120.32 (14)
C4A—C4—H4119.4C17—C18—H18A109.5
C8—C7—C6A110.09 (13)C17—C18—H18B109.5
C8—C7—H7A109.6H18A—C18—H18B109.5
C6A—C7—H7A109.6C17—C18—H18C109.5
C8—C7—H7B109.6H18A—C18—H18C109.5
C6A—C7—H7B109.6H18B—C18—H18C109.5
H7A—C7—H7B108.2C22—C25—H25A109.5
C10—C9—C13121.77 (15)C22—C25—H25B109.5
C10—C9—C8122.42 (14)H25A—C25—H25B109.5
C13—C9—C8115.81 (13)C22—C25—H25C109.5
C9—C10—C10A122.90 (14)H25A—C25—H25C109.5
C9—C10—H10118.6H25B—C25—H25C109.5
C10A—C10—H10118.6C14—C15—C16112.86 (12)
C9—C8—C7113.91 (13)C14—C15—H15A109.0
C9—C8—H8A108.8C16—C15—H15A109.0
C7—C8—H8A108.8C14—C15—H15B109.0
C9—C8—H8B108.8C16—C15—H15B109.0
C7—C8—H8B108.8H15A—C15—H15B107.8
H8A—C8—H8B107.7C18—C17—C16112.87 (14)
O1—C6—C11108.59 (12)C18—C17—H17A109.0
O1—C6—C12103.19 (12)C16—C17—H17A109.0
C11—C6—C12111.55 (13)C18—C17—H17B109.0
O1—C6—C6A107.43 (11)C16—C17—H17B109.0
C11—C6—C6A114.00 (12)H17A—C17—H17B107.8
C12—C6—C6A111.40 (12)C17—C16—C15113.92 (13)
O1—C4A—C4114.70 (13)C17—C16—H16A108.8
O1—C4A—C10B123.32 (13)C15—C16—H16A108.8
C4—C4A—C10B121.97 (13)C17—C16—H16B108.8
C10—C10A—C10B115.39 (12)C15—C16—H16B108.8
C10—C10A—C6A108.19 (11)H16A—C16—H16B107.7
C10B—C10A—C6A109.85 (11)C6—C12—H12A109.5
C10—C10A—H10A107.7C6—C12—H12B109.5
C10B—C10A—H10A107.7H12A—C12—H12B109.5
C6A—C10A—H10A107.7C6—C12—H12C109.5
C1—C10B—C4A114.47 (13)H12A—C12—H12C109.5
C1—C10B—C10A125.35 (13)H12B—C12—H12C109.5
C4A—C10B—C10A120.18 (12)C1—O2—S1118.44 (8)
C24—C19—C20121.03 (13)C9—C13—H13A109.5
C24—C19—S1119.63 (11)C9—C13—H13B109.5
C20—C19—S1119.31 (11)H13A—C13—H13B109.5
C21—C20—C19118.91 (14)C9—C13—H13C109.5
C21—C20—H20120.5H13A—C13—H13C109.5
C19—C20—H20120.5H13B—C13—H13C109.5
C23—C24—C19118.90 (13)C6—C6A—C7115.99 (12)
C23—C24—H24120.5C6—C6A—C10A112.07 (12)
C19—C24—H24120.5C7—C6A—C10A107.98 (12)
C20—C21—C22121.40 (14)C6—C6A—H6A106.8
C20—C21—H21119.3C7—C6A—H6A106.8
C22—C21—H21119.3C10A—C6A—H6A106.8
C3—C14—C15112.63 (12)C4A—O1—C6118.01 (11)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NC2105).

References

  • Bruker (2003). SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2005). SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Duchek, J. R. (2004). US Patent No. 2006/0094774-A1.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Mechoulam, R. & Gaoni, Y. (1967). Fortschr. Chem. Org. Naturst.25, 175–213. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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