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Acta Cryst. (2009). E65, o2621    [ doi:10.1107/S1600536809038410 ]

10-Ethynyl-2,3,6,6a,9,10-hexahydro-1H-6,9-methanopyrrolo[2,1-i][2,1]benzothiazol-10-ol 5,5-dioxide

B. O. Patrick, H. Liang, S. Canesi and M. A. Ciufolini

Abstract top

In the title compound, C13H15NO3S, the sole classical hydrogen-bond donor is involved in an intramolecular O-H...N hydrogen bond. In the crystal structure, pairs of molecules related by inversion centres are linked by pairs of weak intermolecular C-H...O interactions; these centrosymmetric pairs are, in turn, linked further by weak intermolecular C-H...O interactions, forming two-dimensional sheets oriented parallel to (101).

Comment top

The oxidative amidation of phenols offers interesting opportunities in the synthesis of nitrogenous substances. We employed spirocyclization of phenolic sulfonamides to prepare a tricyclic intermediate in the ongoing research on the synthesis of himandrine and related alkaloids (Liang et al., 2008; Ciufolini et al., 2007). The molecular stucture of the title compound is shown in Fig.1. In the crystal structure, pairs of molecules for related by inversion centres are linked by weak intermolecular C—H···O interactions (Table 1, Fig. 2). These centrosymmetric pairs, are in turn, linked further by weak intermolecular C—H···O interactions to form 2-D sheets oriented parallel to the (101) plane, as shown in Fig.3.

Related literature top

For background information, see: Ciufolini et al. (2007); Liang & Ciufolini (2008).

Experimental top

Potassium carbonate (137 mg, 0.99 mmol) was added to a solution of 10- [(trimethylsilyl)ethynyl]-2,3,6,6a,9,10-hexahydro-1H-6,9-methanopyrrolo [2,1-i][2,1]benzisothiazol-10-ol 5,5-dioxide (110 mg, 0.33 mmol) in MeOH (1 ml). Upon the completion of the reaction, the mixture was concentrated and dried over high vacuum. Chromatography of the residue (EtOAc / hexanes = 1 / 2) gave 78 mg (0.29 mmol, 89%) product as a colourless solid. X-ray quality single crystals were obtained by slow evaporation of a dichloromethane/hexanes (1:2v/v) solution of the title compound over two weeks.

Refinement top

H atoms boned to C atoms were placed in calculated positions with C-H = 0.93-1.00Å and included in the refinement with Uiso(H) = 1.2Ueq(C). The hydroxyl H atom was refined indpendently with an isotropic displacement parameter.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. A centrosymmetric pair of molecules with weak intermolecular C—H···O interactions shown as dashed lines.
[Figure 3] Fig. 3. Part of the crystal structure of the title compound, showing C-H···O hydrogen-bonded (dashed lines) sheets parallel to the (101) plane.
10-Ethynyl-2,3,6,6a,9,10-hexahydro-1H-6,9- methanopyrrolo[2,1-i][2,1]benzothiazol-10-ol 5,5-dioxide top
Crystal data top
C13H15NO3SF(000) = 1120
Mr = 265.32Dx = 1.463 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 6461 reflections
a = 24.113 (3) Åθ = 2.7–28.1°
b = 6.6202 (7) ŵ = 0.27 mm−1
c = 15.111 (2) ÅT = 173 K
β = 92.625 (5)°Prism, colourless
V = 2409.6 (5) Å30.35 × 0.27 × 0.18 mm
Z = 8
Data collection top
Bruker X8 APEXII
diffractometer		2889 independent reflections
Radiation source: fine-focus sealed tube2523 reflections with I > 2σ(I)
graphiteRint = 0.030
φ and ω scansθmax = 28.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		h = −31→30
Tmin = 0.877, Tmax = 0.963k = −7→8
13946 measured reflectionsl = −19→19
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0543P)2 + 1.8974P]
where P = (Fo2 + 2Fc2)/3
2889 reflections(Δ/σ)max = 0.001
167 parametersΔρmax = 0.33 e Å−3
0 restraintsΔρmin = −0.42 e Å−3
Crystal data top
C13H15NO3SV = 2409.6 (5) Å3
Mr = 265.32Z = 8
Monoclinic, C2/cMo Kα radiation
a = 24.113 (3) ŵ = 0.27 mm−1
b = 6.6202 (7) ÅT = 173 K
c = 15.111 (2) Å0.35 × 0.27 × 0.18 mm
β = 92.625 (5)°
Data collection top
Bruker X8 APEXII
diffractometer		2523 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		Rint = 0.030
Tmin = 0.877, Tmax = 0.963θmax = 28.0°
13946 measured reflectionsStandard reflections: 0
2889 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.095Δρmax = 0.33 e Å−3
S = 1.03Δρmin = −0.42 e Å−3
2889 reflectionsAbsolute structure: ?
167 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.08386 (6)0.8014 (2)0.24477 (10)0.0260 (3)
H10.08040.80170.18190.031*
C20.10447 (6)0.6218 (2)0.29734 (9)0.0227 (3)
H20.11370.50770.25730.027*
C30.15678 (6)0.69210 (19)0.35283 (9)0.0167 (3)
C40.07087 (6)0.9590 (2)0.29339 (10)0.0241 (3)
H40.05801.08260.26810.029*
C50.13832 (5)0.86156 (19)0.41981 (8)0.0143 (2)
C60.07809 (5)0.9277 (2)0.39197 (9)0.0179 (3)
H60.06691.05070.42520.021*
C70.05869 (6)0.5588 (2)0.36090 (10)0.0246 (3)
H7A0.02510.51440.32610.030*
H7B0.07200.44460.39850.030*
C80.04457 (6)0.7400 (2)0.41948 (9)0.0192 (3)
H80.00380.76820.41630.023*
C100.17913 (6)1.0368 (2)0.43416 (9)0.0197 (3)
H10A0.21770.99260.42520.024*
H10B0.16981.14970.39310.024*
C110.17199 (6)1.0997 (2)0.53035 (10)0.0258 (3)
H11A0.20461.17610.55430.031*
H11B0.13821.18270.53610.031*
C120.16678 (6)0.8971 (2)0.57668 (9)0.0238 (3)
H12A0.20380.83890.59190.029*
H12B0.14620.91120.63150.029*
C170.19816 (6)0.7687 (2)0.29199 (9)0.0187 (3)
C180.23235 (6)0.8204 (2)0.24254 (10)0.0237 (3)
H180.25970.86180.20300.028*
N130.13541 (5)0.76842 (17)0.51039 (7)0.0166 (2)
O90.18201 (4)0.52655 (15)0.39984 (7)0.0242 (2)
O150.04568 (4)0.85899 (19)0.58703 (7)0.0300 (3)
O160.06809 (5)0.50367 (17)0.56167 (8)0.0316 (3)
S140.069910 (13)0.70937 (5)0.53140 (2)0.01917 (11)
H9O0.1739 (10)0.542 (3)0.4521 (16)0.049 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0192 (7)0.0402 (9)0.0183 (7)−0.0073 (6)−0.0010 (5)0.0025 (6)
C20.0242 (7)0.0233 (7)0.0210 (7)−0.0070 (6)0.0053 (5)−0.0054 (5)
C30.0182 (6)0.0136 (6)0.0187 (6)0.0007 (5)0.0044 (5)0.0015 (5)
C40.0178 (6)0.0313 (8)0.0228 (7)0.0008 (6)−0.0017 (5)0.0094 (6)
C50.0148 (6)0.0128 (6)0.0156 (6)0.0005 (5)0.0023 (4)0.0017 (5)
C60.0152 (6)0.0180 (6)0.0205 (6)0.0021 (5)0.0012 (5)0.0031 (5)
C70.0235 (7)0.0255 (7)0.0252 (7)−0.0096 (6)0.0052 (6)−0.0040 (6)
C80.0149 (6)0.0239 (7)0.0188 (6)−0.0023 (5)0.0015 (5)0.0018 (5)
C100.0200 (6)0.0163 (6)0.0228 (7)−0.0038 (5)0.0026 (5)−0.0006 (5)
C110.0277 (7)0.0236 (7)0.0261 (7)−0.0062 (6)0.0012 (6)−0.0059 (6)
C120.0223 (7)0.0293 (8)0.0194 (7)−0.0024 (6)−0.0020 (5)−0.0013 (6)
C170.0187 (6)0.0164 (6)0.0209 (6)0.0019 (5)0.0022 (5)−0.0003 (5)
C180.0231 (7)0.0232 (7)0.0252 (7)−0.0003 (5)0.0067 (6)0.0016 (6)
N130.0147 (5)0.0194 (6)0.0160 (5)−0.0001 (4)0.0027 (4)0.0027 (4)
O90.0301 (5)0.0163 (5)0.0271 (6)0.0078 (4)0.0097 (4)0.0062 (4)
O150.0232 (5)0.0426 (7)0.0248 (5)0.0037 (5)0.0081 (4)−0.0073 (5)
O160.0286 (6)0.0307 (6)0.0357 (6)−0.0060 (5)0.0048 (5)0.0151 (5)
S140.01614 (17)0.0232 (2)0.01853 (18)−0.00074 (12)0.00492 (12)0.00346 (12)
Geometric parameters (Å, °) top
C1—C41.322 (2)C7—H7B0.9900
C1—C21.501 (2)C8—S141.7832 (14)
C1—H10.9500C8—H81.0000
C2—C71.5532 (19)C10—C111.529 (2)
C2—C31.5536 (19)C10—H10A0.9900
C2—H21.0000C10—H10B0.9900
C3—O91.4269 (16)C11—C121.521 (2)
C3—C171.4770 (18)C11—H11A0.9900
C3—C51.5882 (17)C11—H11B0.9900
C4—C61.5062 (19)C12—N131.4938 (18)
C4—H40.9500C12—H12A0.9900
C5—N131.5057 (16)C12—H12B0.9900
C5—C101.5304 (18)C17—C181.188 (2)
C5—C61.5563 (17)C18—H180.9500
C6—C81.5497 (18)N13—S141.6716 (11)
C6—H61.0000O9—H9O0.83 (2)
C7—C81.538 (2)O15—S141.4402 (11)
C7—H7A0.9900O16—S141.4378 (11)
C4—C1—C2114.33 (13)C7—C8—C6109.82 (11)
C4—C1—H1122.8C7—C8—S14112.45 (10)
C2—C1—H1122.8C6—C8—S14100.68 (9)
C1—C2—C7108.20 (12)C7—C8—H8111.2
C1—C2—C3106.82 (11)C6—C8—H8111.2
C7—C2—C3109.22 (11)S14—C8—H8111.2
C1—C2—H2110.8C11—C10—C5103.97 (11)
C7—C2—H2110.8C11—C10—H10A111.0
C3—C2—H2110.8C5—C10—H10A111.0
O9—C3—C17106.79 (11)C11—C10—H10B111.0
O9—C3—C2110.84 (11)C5—C10—H10B111.0
C17—C3—C2108.77 (11)H10A—C10—H10B109.0
O9—C3—C5110.54 (10)C12—C11—C10102.28 (11)
C17—C3—C5111.79 (10)C12—C11—H11A111.3
C2—C3—C5108.13 (10)C10—C11—H11A111.3
C1—C4—C6114.92 (13)C12—C11—H11B111.3
C1—C4—H4122.5C10—C11—H11B111.3
C6—C4—H4122.5H11A—C11—H11B109.2
N13—C5—C10103.78 (10)N13—C12—C11104.12 (11)
N13—C5—C6106.21 (10)N13—C12—H12A110.9
C10—C5—C6114.26 (11)C11—C12—H12A110.9
N13—C5—C3108.43 (10)N13—C12—H12B110.9
C10—C5—C3115.39 (10)C11—C12—H12B110.9
C6—C5—C3108.17 (10)H12A—C12—H12B109.0
C4—C6—C8109.72 (12)C18—C17—C3176.65 (15)
C4—C6—C5111.73 (11)C17—C18—H18180.0
C8—C6—C5101.16 (10)C12—N13—C5109.44 (10)
C4—C6—H6111.3C12—N13—S14117.37 (9)
C8—C6—H6111.3C5—N13—S14110.62 (8)
C5—C6—H6111.3C3—O9—H9O105.3 (16)
C8—C7—C2109.18 (11)O16—S14—O15116.53 (7)
C8—C7—H7A109.8O16—S14—N13108.95 (6)
C2—C7—H7A109.8O15—S14—N13111.24 (6)
C8—C7—H7B109.8O16—S14—C8113.28 (7)
C2—C7—H7B109.8O15—S14—C8110.17 (7)
H7A—C7—H7B108.3N13—S14—C894.53 (6)
C4—C1—C2—C758.42 (16)C5—C6—C8—C7−67.18 (13)
C4—C1—C2—C3−59.07 (15)C4—C6—C8—S14169.71 (9)
C1—C2—C3—O9−175.33 (11)C5—C6—C8—S1451.57 (10)
C7—C2—C3—O967.86 (14)N13—C5—C10—C11−29.30 (13)
C1—C2—C3—C17−58.21 (14)C6—C5—C10—C1185.90 (13)
C7—C2—C3—C17−175.02 (12)C3—C5—C10—C11−147.76 (11)
C1—C2—C3—C563.37 (13)C5—C10—C11—C1240.51 (14)
C7—C2—C3—C5−53.44 (14)C10—C11—C12—N13−35.77 (14)
C2—C1—C4—C6−1.13 (18)O9—C3—C17—C1835 (3)
O9—C3—C5—N13−18.73 (14)C2—C3—C17—C18−85 (3)
C17—C3—C5—N13−137.54 (11)C5—C3—C17—C18156 (3)
C2—C3—C5—N13102.76 (11)C11—C12—N13—C518.13 (14)
O9—C3—C5—C1097.12 (13)C11—C12—N13—S14−108.98 (11)
C17—C3—C5—C10−21.69 (16)C10—C5—N13—C126.98 (13)
C2—C3—C5—C10−141.39 (11)C6—C5—N13—C12−113.80 (12)
O9—C3—C5—C6−133.51 (11)C3—C5—N13—C12130.14 (11)
C17—C3—C5—C6107.68 (12)C10—C5—N13—S14137.81 (9)
C2—C3—C5—C6−12.02 (13)C6—C5—N13—S1417.02 (12)
C1—C4—C6—C8−55.26 (16)C3—C5—N13—S14−99.03 (10)
C1—C4—C6—C556.10 (17)C12—N13—S14—O16−103.72 (11)
N13—C5—C6—C4−161.09 (11)C5—N13—S14—O16129.74 (9)
C10—C5—C6—C485.14 (14)C12—N13—S14—O1526.08 (12)
C3—C5—C6—C4−44.87 (14)C5—N13—S14—O15−100.46 (9)
N13—C5—C6—C8−44.42 (12)C12—N13—S14—C8139.77 (10)
C10—C5—C6—C8−158.19 (11)C5—N13—S14—C813.23 (10)
C3—C5—C6—C871.81 (12)C7—C8—S14—O16−34.96 (11)
C1—C2—C7—C8−56.73 (15)C6—C8—S14—O16−151.79 (9)
C3—C2—C7—C859.20 (15)C7—C8—S14—O15−167.50 (9)
C2—C7—C8—C63.27 (16)C6—C8—S14—O1575.67 (10)
C2—C7—C8—S14−107.96 (12)C7—C8—S14—N1377.91 (10)
C4—C6—C8—C750.96 (15)C6—C8—S14—N13−38.92 (9)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O9—H9O···N130.83 (2)1.99 (2)2.606 (1)131 (2)
C8—H8···O16i1.002.533.183 (2)123
C18—H18···O9ii0.952.403.341 (2)169
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O9—H9O···N130.83 (2)1.99 (2)2.606 (1)131 (2)
C8—H8···O16i1.002.533.183 (2)123
C18—H18···O9ii0.952.403.341 (2)169
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+1/2.
Acknowledgements top

Financial support by the University of British Columbia, the Canada Research Chair Program, NSERC, CIHR, and Merck Frosst Canada, Ltd, is gratefully acknowledged.

references
References top

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Ciufolini, M. A., Braun, N. A., Canesi, S., Ousmer, M., Chang, J. & Chai, D. (2007). Synthesis, pp. 3759–3772.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Liang, H. & Ciufolini, M. A. (2008). J. Org. Chem. 73, 4299–4301.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.