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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o57.
Published online 2007 December 6. doi:  10.1107/S1600536807058084
PMCID: PMC2915015

(1R,4R,7S)-1,7-Dimethyl-7-(phenyl­sulfonyl­meth­yl)spiro­[bicyclo­[2.2.1]heptane-2,2′-1,3-dioxolane]

Abstract

In the title compound, C18H24O4S, the chiral bicyclo­[2.2.1]heptane group is not symmetrical due to the influence of the substituents. The angle between the three-atom bridge plane and the four-atom planes of the boat-shaped six-membered ring are 55.07 (19) and 56.24 (19)°. The bridgehead angle is 92.75 (17)°.

Related literature

For related literature, see: Antczak et al. (1987 [triangle]); García Martínez et al. (2004 [triangle]); Gorichko et al. (2002 [triangle]); Kuo & Money (1988 [triangle]); Money (1985 [triangle]); Tanyeli et al. (2004 [triangle]); Trost et al. (1979 [triangle]); Vaillancourt & Albizati (1993 [triangle]). For related structures, see: Bear & Trotter (1975 [triangle]); Cullen et al. (1988 [triangle]); Komarov et al. (1997 [triangle]); Takasu et al. (2000 [triangle]).

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Object name is e-64-00o57-scheme1.jpg

Experimental

Crystal data

  • C18H24O4S
  • M r = 336.43
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-00o57-efi1.jpg
  • a = 10.5420 (2) Å
  • b = 11.7946 (2) Å
  • c = 13.2997 (3) Å
  • V = 1653.67 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.21 mm−1
  • T = 294 (2) K
  • 0.22 × 0.20 × 0.12 mm

Data collection

  • Bruker APEX CCD area-detector diffractometer
  • Absorption correction: none
  • 8969 measured reflections
  • 3080 independent reflections
  • 2595 reflections with I > 2σ(I)
  • R int = 0.033

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.083
  • S = 1.01
  • 3080 reflections
  • 211 parameters
  • H-atom parameters constrained
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.20 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1307 Friedel pairs
  • Flack parameter: 0.09 (9)

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 2000 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807058084/hg2344sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807058084/hg2344Isup2.hkl

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

Acknowledgments

We acknowledge financial support from the Research Fund for the New Faculty at the State Key Laboratory of Applied Organic Chemstry.

supplementary crystallographic information

Comment

The uniqueness of the bicyclic structure of camphor is illustrated by a wide variety of intriguing structure transformations that frequently involve fascinating rearrangement processes (Money, 1985; García Martínez et al., 2004). Studies towards these transformations have produced much chemical knowledge on theoretical and mechanistic aspects of organic chemistry in the past century and offered synthetically useful chiral building blocks (Kuo & Money, 1988; Vaillancourt & Albizati, 1993) and chiral ligands (Tanyeli et al., 2004; Gorichko et al., 2002; Komarov et al., 1997) from readily available natural camphor. Some related X-ray structures (Beta & Trotter, 1975; Cullen et al., 1988; Takasu et al., 2000; Antczak et al., 1987) have been obtained.

The chiral bicyclo[2.2.1]heptane group is not symmetrical due to the influence of the substituents. The angles between the three-atom bridge plane, C10, C13, C14 and the four-atom planes (C9, C10, C14, C18 and C10, C11, C12, C14) of the boat-shaped six-membered ring are 55.07 (19) and 56.24 (19)° while the bridgehead angle is 92.75 (17)°.

Experimental

The title compound was prepared by the reaction of sodium benzenesulfinate with (+)-8-bromocamphor (Bear & Trotter, 1975) ketal through the literature method (Trost et al., 1979). Single crystals suitable for X-ray determination were obtained by slow evaporation of a EtOAc solution over a period of several days. IR (film): 3063, 2961, 2883, 1586, 1478, 1448, 1306, 1145, 1084, 1053, 1023, 972, 742, 691 cm-1; 1H NMR (400 MHz, CDCl3): 7.93 (d, J=7.2 Hz, 2H), 7.65 (t, J=8.5 Hz, 1H), 7.56 (t, J=8.0 Hz, 2H), 4.12 (d, J=14.7 Hz, 1H), 3.91–3.86 (m, 1H), 3.84–3.81(m, 1H), 3.76–3.70 (m, 2H), 2.90 (d, J=14.7 Hz, 1H), 2.11 (dt, J=3.4, 13.7 Hz, 1H), 1.94–1.89 (m, 1H), 1.77–1.75 (m, 1H), 1.52 (d, J=13.9 Hz, 1H), 1.37–1.26 (m, 3H), 1.23 (s, 3H), 0.89 (s, 3H) p.p.m.; EIMS m/z (%): 336 (M+, 0.6), 321 (3.3), 272 (1), 235 (1), 181 (38), 125 (3), 109 (14), 95 (100); HRMS (ESI): calcd. for C18H25SO4+ [M+H]+: 337.1468, found: 337.1460.

Refinement

All H atoms were placed geometrically (C—H values were set to 0.98, 0.97, 0.96 and 0.93 A° for atoms CH, CH2, CH3, and CH (phenyl), respectively) and refined with a riding model, with Uiso(H) = 1.2 or 1.5 times Ueq(C), or1.5 Ueq(O).

Figures

Fig. 1.
The independent components of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C18H24O4SF000 = 720
Mr = 336.43Dx = 1.351 Mg m3
Orthorhombic, P212121Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2482 reflections
a = 10.5420 (2) Åθ = 2.3–22.9º
b = 11.7946 (2) ŵ = 0.21 mm1
c = 13.2997 (3) ÅT = 294 (2) K
V = 1653.67 (6) Å3Block, colorless
Z = 40.22 × 0.20 × 0.12 mm

Data collection

Bruker APEX CCD area-detector diffractometer2595 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.033
Monochromator: graphiteθmax = 25.5º
T = 294(2) Kθmin = 2.3º
phi and ω scansh = −12→10
Absorption correction: nonek = −14→14
8969 measured reflectionsl = −14→16
3080 independent reflections

Refinement

Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0351P)2 + 0.3259P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.036(Δ/σ)max = 0.001
wR(F2) = 0.083Δρmax = 0.18 e Å3
S = 1.01Δρmin = −0.20 e Å3
3080 reflectionsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
211 parametersExtinction coefficient: 0.0024 (6)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1307 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.09 (9)
Hydrogen site location: inferred from neighbouring sites

Special details

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.

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

xyzUiso*/Ueq
C10.8521 (3)0.4745 (2)0.8698 (2)0.0553 (7)
H10.91410.41850.86710.066*
C20.7480 (3)0.4684 (2)0.8078 (2)0.0573 (8)
H20.73960.40830.76300.069*
C30.6567 (3)0.5508 (2)0.81181 (19)0.0559 (7)
H30.58690.54640.76930.067*
C40.6670 (2)0.6412 (2)0.87884 (18)0.0460 (6)
H40.60500.69720.88140.055*
C50.7711 (2)0.64549 (17)0.94106 (17)0.0366 (5)
C60.8644 (3)0.5640 (2)0.93635 (18)0.0458 (6)
H60.93530.56900.97770.055*
C70.9448 (3)1.1891 (2)1.1304 (2)0.0520 (7)
H7A1.03161.20091.10880.062*
H7B0.94161.18901.20330.062*
C80.8581 (3)1.2769 (2)1.08728 (18)0.0543 (7)
H8A0.78171.28461.12730.065*
H8B0.89991.35001.08290.065*
C90.8317 (2)1.11268 (18)0.99706 (16)0.0393 (6)
C100.8975 (2)1.06072 (19)0.90376 (17)0.0386 (6)
C110.8356 (3)1.1177 (2)0.81204 (18)0.0526 (7)
H11A0.88111.09900.75090.063*
H11B0.83421.19950.81990.063*
C120.7000 (3)1.0694 (2)0.80945 (18)0.0545 (7)
H12A0.68381.02960.74690.065*
H12B0.63731.12890.81770.065*
C130.8356 (2)0.93875 (18)0.89830 (16)0.0352 (5)
C140.6987 (2)0.9872 (2)0.89958 (17)0.0420 (6)
H140.63190.92950.89670.050*
C151.0411 (2)1.0690 (2)0.9064 (2)0.0567 (7)
H15C1.07571.03430.84720.085*
H15A1.07261.03070.96500.085*
H15B1.06571.14740.90870.085*
C160.8700 (3)0.8742 (2)0.80203 (17)0.0474 (6)
H16B0.95950.85910.80130.071*
H16C0.84780.91920.74450.071*
H16A0.82420.80390.80000.071*
C170.8764 (2)0.86578 (17)0.98851 (17)0.0353 (5)
H17B0.88970.91721.04440.042*
H17A0.95870.83400.97190.042*
C180.6982 (2)1.0590 (2)0.99592 (17)0.0440 (6)
H18B0.68471.01211.05490.053*
H18A0.63291.11680.99330.053*
O10.65482 (17)0.79178 (14)1.05340 (14)0.0596 (5)
O20.8532 (2)0.70566 (14)1.11702 (12)0.0606 (5)
O30.83048 (18)1.23328 (13)0.99050 (12)0.0545 (5)
O40.89416 (16)1.08703 (13)1.08999 (11)0.0438 (4)
S10.78162 (6)0.75224 (5)1.03435 (4)0.04187 (16)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0658 (19)0.0410 (14)0.0590 (17)0.0034 (14)0.0122 (16)−0.0026 (13)
C20.077 (2)0.0501 (16)0.0452 (15)−0.0175 (16)0.0103 (15)−0.0074 (12)
C30.0596 (18)0.0666 (18)0.0417 (14)−0.0257 (17)−0.0051 (13)0.0071 (13)
C40.0445 (15)0.0467 (14)0.0468 (15)−0.0053 (12)0.0025 (12)0.0061 (11)
C50.0384 (13)0.0340 (12)0.0375 (12)−0.0076 (11)0.0056 (11)0.0016 (9)
C60.0477 (16)0.0437 (13)0.0461 (15)−0.0036 (13)−0.0010 (12)−0.0001 (11)
C70.0631 (18)0.0451 (14)0.0476 (15)−0.0054 (14)−0.0085 (13)−0.0096 (13)
C80.0682 (18)0.0419 (15)0.0529 (15)0.0028 (13)−0.0070 (14)−0.0101 (11)
C90.0514 (15)0.0297 (11)0.0368 (12)0.0014 (11)−0.0056 (11)0.0007 (9)
C100.0434 (14)0.0358 (12)0.0366 (13)−0.0043 (11)0.0009 (11)0.0030 (10)
C110.080 (2)0.0418 (14)0.0361 (13)−0.0009 (15)−0.0051 (13)0.0042 (11)
C120.067 (2)0.0502 (15)0.0459 (15)0.0102 (14)−0.0169 (14)−0.0006 (12)
C130.0398 (13)0.0350 (11)0.0307 (11)−0.0037 (10)0.0021 (10)0.0001 (10)
C140.0392 (14)0.0460 (13)0.0407 (13)0.0013 (11)−0.0061 (11)−0.0040 (11)
C150.0490 (16)0.0571 (17)0.0639 (18)−0.0137 (13)0.0117 (14)−0.0007 (15)
C160.0586 (17)0.0426 (14)0.0411 (14)−0.0023 (13)0.0081 (12)−0.0013 (11)
C170.0338 (12)0.0321 (11)0.0400 (13)−0.0032 (10)0.0017 (10)−0.0028 (9)
C180.0429 (15)0.0452 (13)0.0439 (13)0.0074 (12)0.0008 (11)−0.0031 (11)
O10.0523 (11)0.0550 (10)0.0717 (12)−0.0074 (9)0.0261 (10)−0.0081 (9)
O20.0968 (15)0.0496 (10)0.0354 (9)−0.0141 (10)−0.0086 (10)0.0099 (8)
O30.0854 (13)0.0322 (9)0.0459 (9)0.0029 (9)−0.0093 (9)−0.0005 (7)
O40.0614 (11)0.0349 (9)0.0351 (9)−0.0056 (8)−0.0094 (8)−0.0003 (7)
S10.0523 (4)0.0367 (3)0.0367 (3)−0.0066 (3)0.0075 (3)0.0005 (3)

Geometric parameters (Å, °)

C1—C21.375 (4)C10—C131.581 (3)
C1—C61.383 (3)C11—C121.540 (4)
C1—H10.9300C11—H11A0.9700
C2—C31.368 (4)C11—H11B0.9700
C2—H20.9300C12—C141.542 (3)
C3—C41.394 (4)C12—H12A0.9700
C3—H30.9300C12—H12B0.9700
C4—C51.375 (3)C13—C161.533 (3)
C4—H40.9300C13—C171.538 (3)
C5—C61.377 (3)C13—C141.553 (3)
C5—S11.771 (2)C14—C181.536 (3)
C6—H60.9300C14—H140.9800
C7—O41.422 (3)C15—H15C0.9600
C7—C81.496 (3)C15—H15A0.9600
C7—H7A0.9700C15—H15B0.9600
C7—H7B0.9700C16—H16B0.9600
C8—O31.417 (3)C16—H16C0.9600
C8—H8A0.9700C16—H16A0.9600
C8—H8B0.9700C17—S11.779 (2)
C9—O31.425 (3)C17—H17B0.9700
C9—O41.433 (3)C17—H17A0.9700
C9—C181.543 (3)C18—H18B0.9700
C9—C101.548 (3)C18—H18A0.9700
C10—C151.517 (3)O1—S11.4383 (18)
C10—C111.538 (3)O2—S11.4422 (18)
C2—C1—C6119.9 (3)C11—C12—H12A111.2
C2—C1—H1120.1C14—C12—H12A111.2
C6—C1—H1120.1C11—C12—H12B111.2
C3—C2—C1120.0 (2)C14—C12—H12B111.2
C3—C2—H2120.0H12A—C12—H12B109.1
C1—C2—H2120.0C16—C13—C17107.93 (18)
C2—C3—C4120.9 (3)C16—C13—C14114.30 (19)
C2—C3—H3119.5C17—C13—C14117.21 (19)
C4—C3—H3119.5C16—C13—C10113.13 (18)
C5—C4—C3118.3 (2)C17—C13—C10110.99 (18)
C5—C4—H4120.8C14—C13—C1092.75 (17)
C3—C4—H4120.8C18—C14—C12107.56 (18)
C4—C5—C6121.1 (2)C18—C14—C13102.43 (18)
C4—C5—S1119.86 (18)C12—C14—C13102.4 (2)
C6—C5—S1118.91 (18)C18—C14—H14114.4
C5—C6—C1119.7 (3)C12—C14—H14114.4
C5—C6—H6120.2C13—C14—H14114.4
C1—C6—H6120.2C10—C15—H15C109.5
O4—C7—C8102.25 (19)C10—C15—H15A109.5
O4—C7—H7A111.3H15C—C15—H15A109.5
C8—C7—H7A111.3C10—C15—H15B109.5
O4—C7—H7B111.3H15C—C15—H15B109.5
C8—C7—H7B111.3H15A—C15—H15B109.5
H7A—C7—H7B109.2C13—C16—H16B109.5
O3—C8—C7102.85 (19)C13—C16—H16C109.5
O3—C8—H8A111.2H16B—C16—H16C109.5
C7—C8—H8A111.2C13—C16—H16A109.5
O3—C8—H8B111.2H16B—C16—H16A109.5
C7—C8—H8B111.2H16C—C16—H16A109.5
H8A—C8—H8B109.1C13—C17—S1122.12 (16)
O3—C9—O4105.53 (17)C13—C17—H17B106.8
O3—C9—C18113.6 (2)S1—C17—H17B106.8
O4—C9—C18109.93 (18)C13—C17—H17A106.8
O3—C9—C10110.50 (18)S1—C17—H17A106.8
O4—C9—C10113.71 (18)H17B—C17—H17A106.6
C18—C9—C10103.77 (18)C14—C18—C9103.38 (19)
C15—C10—C11114.4 (2)C14—C18—H18B111.1
C15—C10—C9113.7 (2)C9—C18—H18B111.1
C11—C10—C9105.84 (19)C14—C18—H18A111.1
C15—C10—C13118.1 (2)C9—C18—H18A111.1
C11—C10—C13100.76 (18)H18B—C18—H18A109.1
C9—C10—C13102.27 (17)C8—O3—C9107.78 (17)
C10—C11—C12104.44 (19)C7—O4—C9108.65 (17)
C10—C11—H11A110.9O1—S1—O2118.38 (12)
C12—C11—H11A110.9O1—S1—C5107.19 (11)
C10—C11—H11B110.9O2—S1—C5107.22 (10)
C12—C11—H11B110.9O1—S1—C17109.78 (11)
H11A—C11—H11B108.9O2—S1—C17104.73 (11)
C11—C12—C14102.9 (2)C5—S1—C17109.29 (10)
C6—C1—C2—C30.0 (4)C11—C12—C14—C13−35.5 (2)
C1—C2—C3—C4−0.4 (4)C16—C13—C14—C18−172.69 (19)
C2—C3—C4—C5−0.1 (4)C17—C13—C14—C1859.6 (2)
C3—C4—C5—C61.2 (3)C10—C13—C14—C18−55.74 (19)
C3—C4—C5—S1−174.85 (17)C16—C13—C14—C12−61.3 (2)
C4—C5—C6—C1−1.7 (4)C17—C13—C14—C12170.99 (18)
S1—C5—C6—C1174.40 (19)C10—C13—C14—C1255.66 (19)
C2—C1—C6—C51.1 (4)C16—C13—C17—S1−81.5 (2)
O4—C7—C8—O3−35.5 (3)C14—C13—C17—S149.2 (3)
O3—C9—C10—C1576.8 (2)C10—C13—C17—S1153.97 (16)
O4—C9—C10—C15−41.6 (3)C12—C14—C18—C9−69.3 (2)
C18—C9—C10—C15−161.0 (2)C13—C14—C18—C938.2 (2)
O3—C9—C10—C11−49.6 (2)O3—C9—C18—C14117.2 (2)
O4—C9—C10—C11−168.02 (19)O4—C9—C18—C14−124.85 (18)
C18—C9—C10—C1172.6 (2)C10—C9—C18—C14−2.9 (2)
O3—C9—C10—C13−154.66 (19)C7—C8—O3—C931.9 (3)
O4—C9—C10—C1386.9 (2)O4—C9—O3—C8−15.7 (3)
C18—C9—C10—C13−32.5 (2)C18—C9—O3—C8104.8 (2)
C15—C10—C11—C12164.0 (2)C10—C9—O3—C8−139.0 (2)
C9—C10—C11—C12−69.9 (2)C8—C7—O4—C926.9 (3)
C13—C10—C11—C1236.2 (2)O3—C9—O4—C7−8.1 (2)
C10—C11—C12—C14−1.0 (3)C18—C9—O4—C7−131.0 (2)
C15—C10—C13—C16−62.9 (3)C10—C9—O4—C7113.2 (2)
C11—C10—C13—C1662.4 (2)C4—C5—S1—O121.5 (2)
C9—C10—C13—C16171.40 (19)C6—C5—S1—O1−154.61 (18)
C15—C10—C13—C1758.6 (3)C4—C5—S1—O2149.62 (19)
C11—C10—C13—C17−176.12 (19)C6—C5—S1—O2−26.5 (2)
C9—C10—C13—C17−67.1 (2)C4—C5—S1—C17−97.4 (2)
C15—C10—C13—C14179.1 (2)C6—C5—S1—C1786.5 (2)
C11—C10—C13—C14−55.55 (19)C13—C17—S1—O1−52.6 (2)
C9—C10—C13—C1453.46 (19)C13—C17—S1—O2179.28 (18)
C11—C12—C14—C1872.0 (2)C13—C17—S1—C564.7 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2344).

References

  • Antczak, K., Kingston, J. F. & Fallis, A. G. (1987). Can. J. Chem.65, 114–123.
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