10-Ethynyl-2,3,6,6a,9,10-hexa-hydro-1H-6,9-methano-pyrrolo[2,1-i][2,1]benzo-thia-zol-10-ol 5,5-dioxide.

In the title compound, C(13)H(15)NO(3)S, the sole classical hydrogen-bond donor is involved in an intra-molecular O-H⋯N hydrogen bond. In the crystal structure, pairs of mol-ecules related by inversion centres are linked by pairs of weak inter-molecular C-H⋯O inter-actions; these centrosymmetric pairs are, in turn, linked further by weak inter-molecular C-H⋯O inter-actions, forming two-dimensional sheets oriented parallel to (101).

Related literature

For background to our ongoing research on the synthesis of himandrine and related alkaloids, see: Ciufolini et al. (2007 ▶); Liang & Ciufolini (2008 ▶).

Experimental

Crystal data

C13H15NO3S

M = 265.32

Monoclinic,

a = 24.113 (3) Å

b = 6.6202 (7) Å

c = 15.111 (2) Å

β = 92.625 (5)°

V = 2409.6 (5) Å3

Z = 8

Mo Kα radiation

μ = 0.27 mm−1

T = 173 K

0.35 × 0.27 × 0.18 mm

Data collection

Bruker X8 APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.877, T max = 0.963

13946 measured reflections

2889 independent reflections

2523 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.095

S = 1.03

2889 reflections

167 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; 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 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809038410/lh2908sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038410/lh2908Isup2.hkl

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

C13H15NO3S	F(000) = 1120
Mr = 265.32	Dx = 1.463 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6461 reflections
a = 24.113 (3) Å	θ = 2.7–28.1°
b = 6.6202 (7) Å	µ = 0.27 mm−1
c = 15.111 (2) Å	T = 173 K
β = 92.625 (5)°	Prism, colourless
V = 2409.6 (5) Å3	0.35 × 0.27 × 0.18 mm
Z = 8

Bruker X8 APEXII diffractometer	2889 independent reflections
Radiation source: fine-focus sealed tube	2523 reflections with I > 2σ(I)
graphite	Rint = 0.030
φ and ω scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −31→30
Tmin = 0.877, Tmax = 0.963	k = −7→8
13946 measured reflections	l = −19→19

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095	H 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 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.08386 (6)	0.8014 (2)	0.24477 (10)	0.0260 (3)
H1	0.0804	0.8017	0.1819	0.031*
C2	0.10447 (6)	0.6218 (2)	0.29734 (9)	0.0227 (3)
H2	0.1137	0.5077	0.2573	0.027*
C3	0.15678 (6)	0.69210 (19)	0.35283 (9)	0.0167 (3)
C4	0.07087 (6)	0.9590 (2)	0.29339 (10)	0.0241 (3)
H4	0.0580	1.0826	0.2681	0.029*
C5	0.13832 (5)	0.86156 (19)	0.41981 (8)	0.0143 (2)
C6	0.07809 (5)	0.9277 (2)	0.39197 (9)	0.0179 (3)
H6	0.0669	1.0507	0.4252	0.021*
C7	0.05869 (6)	0.5588 (2)	0.36090 (10)	0.0246 (3)
H7A	0.0251	0.5144	0.3261	0.030*
H7B	0.0720	0.4446	0.3985	0.030*
C8	0.04457 (6)	0.7400 (2)	0.41948 (9)	0.0192 (3)
H8	0.0038	0.7682	0.4163	0.023*
C10	0.17913 (6)	1.0368 (2)	0.43416 (9)	0.0197 (3)
H10A	0.2177	0.9926	0.4252	0.024*
H10B	0.1698	1.1497	0.3931	0.024*
C11	0.17199 (6)	1.0997 (2)	0.53035 (10)	0.0258 (3)
H11A	0.2046	1.1761	0.5543	0.031*
H11B	0.1382	1.1827	0.5361	0.031*
C12	0.16678 (6)	0.8971 (2)	0.57668 (9)	0.0238 (3)
H12A	0.2038	0.8389	0.5919	0.029*
H12B	0.1462	0.9112	0.6315	0.029*
C17	0.19816 (6)	0.7687 (2)	0.29199 (9)	0.0187 (3)
C18	0.23235 (6)	0.8204 (2)	0.24254 (10)	0.0237 (3)
H18	0.2597	0.8618	0.2030	0.028*
N13	0.13541 (5)	0.76842 (17)	0.51039 (7)	0.0166 (2)
O9	0.18201 (4)	0.52655 (15)	0.39984 (7)	0.0242 (2)
O15	0.04568 (4)	0.85899 (19)	0.58703 (7)	0.0300 (3)
O16	0.06809 (5)	0.50367 (17)	0.56167 (8)	0.0316 (3)
S14	0.069910 (13)	0.70937 (5)	0.53140 (2)	0.01917 (11)
H9O	0.1739 (10)	0.542 (3)	0.4521 (16)	0.049 (6)*

	U11	U22	U33	U12	U13	U23
C1	0.0192 (7)	0.0402 (9)	0.0183 (7)	−0.0073 (6)	−0.0010 (5)	0.0025 (6)
C2	0.0242 (7)	0.0233 (7)	0.0210 (7)	−0.0070 (6)	0.0053 (5)	−0.0054 (5)
C3	0.0182 (6)	0.0136 (6)	0.0187 (6)	0.0007 (5)	0.0044 (5)	0.0015 (5)
C4	0.0178 (6)	0.0313 (8)	0.0228 (7)	0.0008 (6)	−0.0017 (5)	0.0094 (6)
C5	0.0148 (6)	0.0128 (6)	0.0156 (6)	0.0005 (5)	0.0023 (4)	0.0017 (5)
C6	0.0152 (6)	0.0180 (6)	0.0205 (6)	0.0021 (5)	0.0012 (5)	0.0031 (5)
C7	0.0235 (7)	0.0255 (7)	0.0252 (7)	−0.0096 (6)	0.0052 (6)	−0.0040 (6)
C8	0.0149 (6)	0.0239 (7)	0.0188 (6)	−0.0023 (5)	0.0015 (5)	0.0018 (5)
C10	0.0200 (6)	0.0163 (6)	0.0228 (7)	−0.0038 (5)	0.0026 (5)	−0.0006 (5)
C11	0.0277 (7)	0.0236 (7)	0.0261 (7)	−0.0062 (6)	0.0012 (6)	−0.0059 (6)
C12	0.0223 (7)	0.0293 (8)	0.0194 (7)	−0.0024 (6)	−0.0020 (5)	−0.0013 (6)
C17	0.0187 (6)	0.0164 (6)	0.0209 (6)	0.0019 (5)	0.0022 (5)	−0.0003 (5)
C18	0.0231 (7)	0.0232 (7)	0.0252 (7)	−0.0003 (5)	0.0067 (6)	0.0016 (6)
N13	0.0147 (5)	0.0194 (6)	0.0160 (5)	−0.0001 (4)	0.0027 (4)	0.0027 (4)
O9	0.0301 (5)	0.0163 (5)	0.0271 (6)	0.0078 (4)	0.0097 (4)	0.0062 (4)
O15	0.0232 (5)	0.0426 (7)	0.0248 (5)	0.0037 (5)	0.0081 (4)	−0.0073 (5)
O16	0.0286 (6)	0.0307 (6)	0.0357 (6)	−0.0060 (5)	0.0048 (5)	0.0151 (5)
S14	0.01614 (17)	0.0232 (2)	0.01853 (18)	−0.00074 (12)	0.00492 (12)	0.00346 (12)

C1—C4	1.322 (2)	C7—H7B	0.9900
C1—C2	1.501 (2)	C8—S14	1.7832 (14)
C1—H1	0.9500	C8—H8	1.0000
C2—C7	1.5532 (19)	C10—C11	1.529 (2)
C2—C3	1.5536 (19)	C10—H10A	0.9900
C2—H2	1.0000	C10—H10B	0.9900
C3—O9	1.4269 (16)	C11—C12	1.521 (2)
C3—C17	1.4770 (18)	C11—H11A	0.9900
C3—C5	1.5882 (17)	C11—H11B	0.9900
C4—C6	1.5062 (19)	C12—N13	1.4938 (18)
C4—H4	0.9500	C12—H12A	0.9900
C5—N13	1.5057 (16)	C12—H12B	0.9900
C5—C10	1.5304 (18)	C17—C18	1.188 (2)
C5—C6	1.5563 (17)	C18—H18	0.9500
C6—C8	1.5497 (18)	N13—S14	1.6716 (11)
C6—H6	1.0000	O9—H9O	0.83 (2)
C7—C8	1.538 (2)	O15—S14	1.4402 (11)
C7—H7A	0.9900	O16—S14	1.4378 (11)
C4—C1—C2	114.33 (13)	C7—C8—C6	109.82 (11)
C4—C1—H1	122.8	C7—C8—S14	112.45 (10)
C2—C1—H1	122.8	C6—C8—S14	100.68 (9)
C1—C2—C7	108.20 (12)	C7—C8—H8	111.2
C1—C2—C3	106.82 (11)	C6—C8—H8	111.2
C7—C2—C3	109.22 (11)	S14—C8—H8	111.2
C1—C2—H2	110.8	C11—C10—C5	103.97 (11)
C7—C2—H2	110.8	C11—C10—H10A	111.0
C3—C2—H2	110.8	C5—C10—H10A	111.0
O9—C3—C17	106.79 (11)	C11—C10—H10B	111.0
O9—C3—C2	110.84 (11)	C5—C10—H10B	111.0
C17—C3—C2	108.77 (11)	H10A—C10—H10B	109.0
O9—C3—C5	110.54 (10)	C12—C11—C10	102.28 (11)
C17—C3—C5	111.79 (10)	C12—C11—H11A	111.3
C2—C3—C5	108.13 (10)	C10—C11—H11A	111.3
C1—C4—C6	114.92 (13)	C12—C11—H11B	111.3
C1—C4—H4	122.5	C10—C11—H11B	111.3
C6—C4—H4	122.5	H11A—C11—H11B	109.2
N13—C5—C10	103.78 (10)	N13—C12—C11	104.12 (11)
N13—C5—C6	106.21 (10)	N13—C12—H12A	110.9
C10—C5—C6	114.26 (11)	C11—C12—H12A	110.9
N13—C5—C3	108.43 (10)	N13—C12—H12B	110.9
C10—C5—C3	115.39 (10)	C11—C12—H12B	110.9
C6—C5—C3	108.17 (10)	H12A—C12—H12B	109.0
C4—C6—C8	109.72 (12)	C18—C17—C3	176.65 (15)
C4—C6—C5	111.73 (11)	C17—C18—H18	180.0
C8—C6—C5	101.16 (10)	C12—N13—C5	109.44 (10)
C4—C6—H6	111.3	C12—N13—S14	117.37 (9)
C8—C6—H6	111.3	C5—N13—S14	110.62 (8)
C5—C6—H6	111.3	C3—O9—H9O	105.3 (16)
C8—C7—C2	109.18 (11)	O16—S14—O15	116.53 (7)
C8—C7—H7A	109.8	O16—S14—N13	108.95 (6)
C2—C7—H7A	109.8	O15—S14—N13	111.24 (6)
C8—C7—H7B	109.8	O16—S14—C8	113.28 (7)
C2—C7—H7B	109.8	O15—S14—C8	110.17 (7)
H7A—C7—H7B	108.3	N13—S14—C8	94.53 (6)
C4—C1—C2—C7	58.42 (16)	C5—C6—C8—C7	−67.18 (13)
C4—C1—C2—C3	−59.07 (15)	C4—C6—C8—S14	169.71 (9)
C1—C2—C3—O9	−175.33 (11)	C5—C6—C8—S14	51.57 (10)
C7—C2—C3—O9	67.86 (14)	N13—C5—C10—C11	−29.30 (13)
C1—C2—C3—C17	−58.21 (14)	C6—C5—C10—C11	85.90 (13)
C7—C2—C3—C17	−175.02 (12)	C3—C5—C10—C11	−147.76 (11)
C1—C2—C3—C5	63.37 (13)	C5—C10—C11—C12	40.51 (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—C18	35 (3)
O9—C3—C5—N13	−18.73 (14)	C2—C3—C17—C18	−85 (3)
C17—C3—C5—N13	−137.54 (11)	C5—C3—C17—C18	156 (3)
C2—C3—C5—N13	102.76 (11)	C11—C12—N13—C5	18.13 (14)
O9—C3—C5—C10	97.12 (13)	C11—C12—N13—S14	−108.98 (11)
C17—C3—C5—C10	−21.69 (16)	C10—C5—N13—C12	6.98 (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—C12	130.14 (11)
C17—C3—C5—C6	107.68 (12)	C10—C5—N13—S14	137.81 (9)
C2—C3—C5—C6	−12.02 (13)	C6—C5—N13—S14	17.02 (12)
C1—C4—C6—C8	−55.26 (16)	C3—C5—N13—S14	−99.03 (10)
C1—C4—C6—C5	56.10 (17)	C12—N13—S14—O16	−103.72 (11)
N13—C5—C6—C4	−161.09 (11)	C5—N13—S14—O16	129.74 (9)
C10—C5—C6—C4	85.14 (14)	C12—N13—S14—O15	26.08 (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—C8	139.77 (10)
C10—C5—C6—C8	−158.19 (11)	C5—N13—S14—C8	13.23 (10)
C3—C5—C6—C8	71.81 (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—C8	59.20 (15)	C7—C8—S14—O15	−167.50 (9)
C2—C7—C8—C6	3.27 (16)	C6—C8—S14—O15	75.67 (10)
C2—C7—C8—S14	−107.96 (12)	C7—C8—S14—N13	77.91 (10)
C4—C6—C8—C7	50.96 (15)	C6—C8—S14—N13	−38.92 (9)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9O···N13	0.83 (2)	1.99 (2)	2.606 (1)	131 (2)
C8—H8···O16i	1.00	2.53	3.183 (2)	123
C18—H18···O9ii	0.95	2.40	3.341 (2)	169

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9O⋯N13	0.83 (2)	1.99 (2)	2.606 (1)	131 (2)
C8—H8⋯O16i	1.00	2.53	3.183 (2)	123
C18—H18⋯O9ii	0.95	2.40	3.341 (2)	169

Symmetry codes: (i) ; (ii) .