(5S,11aS)-5-Hydro-per-oxy-1,5,11,11a-tetra-hydro-[1]benzothieno[3,2-f]indol-izin-3(2H)-one.

The absolute configuration of the title compound, C14H13NO3S, was assigned from the synthesis and confirmed by the structure determination. The central six-membered ring of the indolizine moiety adopts an envelope conformation, with the greatest deviation from the mean plane of the ring being 0.661 (2) Å for the bridgehead C atom. The benzothiene ring attached to the indolizine ring system is planar to within 0.008 (2) Å. In the crystal, mol-ecules form chains parallel to the b axis via O-H⋯O hydrogen bonds.

Related literature

For background to indolizines and their biological activity, see: Malonne et al. (1998 ▶); Medda et al. (2003 ▶); Sonnet et al. (2000 ▶); Campagna et al. (1990 ▶); Pearson & Guo (2001 ▶). For their synthesis, see: Šafář et al. (2009a ▶,b ▶). For compounds with similar properties, see: Švorc et al. (2008 ▶, 2009 ▶). For IR spectroscopy on similar compounds, see: Šafář et al. (2009a ▶). For conformational analysis, see: Nardelli (1983 ▶).

Experimental

Crystal data

C14H13NO3S

M = 275.31

Monoclinic,

a = 7.8040 (5) Å

b = 7.9800 (4) Å

c = 10.2903 (5) Å

β = 99.458 (5)°

V = 632.13 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.26 mm−1

T = 295 K

0.25 × 0.20 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur (Ruby, Gemi) diffractometer

Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009 ▶), based on expressions derived by Clark & Reid (1995 ▶)] T min = 0.947, T max = 0.974

21595 measured reflections

2555 independent reflections

2162 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.068

S = 1.00

2555 reflections

176 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.13 e Å−3

Δρmin = −0.14 e Å−3

Absolute structure: Flack (1983 ▶), 1185 Friedel pairs

Flack parameter: −0.05 (6)

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND, (Brandenburg, 2001 ▶), PLATON (Spek, 2009 ▶) and WinGX (Farrugia, 1999 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812045394/bg2481sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812045394/bg2481Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812045394/bg2481Isup3.cml

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

C14H13NO3S	F(000) = 288
Mr = 275.31	Dx = 1.446 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 10799 reflections
a = 7.8040 (5) Å	θ = 3.2–29.6°
b = 7.9800 (4) Å	µ = 0.26 mm−1
c = 10.2903 (5) Å	T = 295 K
β = 99.458 (5)°	Block, colourless
V = 632.13 (6) Å3	0.25 × 0.20 × 0.15 mm
Z = 2

Oxford Diffraction Xcalibur (Ruby, Gemi) diffractometer	2555 independent reflections
Radiation source: fine-focus sealed tube	2162 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 10.4340 pixels mm-1	θmax = 26.4°, θmin = 4.4°
ω scans	h = −9→9
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)]	k = −9→9
Tmin = 0.947, Tmax = 0.974	l = −12→12
21595 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.068	w = 1/[σ2(Fo2) + (0.0441P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
2555 reflections	Δρmax = 0.13 e Å−3
176 parameters	Δρmin = −0.14 e Å−3
2 restraints	Absolute structure: Flack (1983), 1185 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.05 (6)

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
C2	−0.1152 (2)	0.0934 (2)	0.10939 (14)	0.0487 (4)
C3	−0.2994 (2)	0.1556 (3)	0.07868 (18)	0.0625 (5)
H3B	−0.3714	0.1014	0.1347	0.075*
H3A	−0.3483	0.1340	−0.0127	0.075*
C4	−0.2872 (2)	0.3432 (3)	0.1057 (2)	0.0662 (5)
H4B	−0.3852	0.3817	0.1447	0.079*
H4A	−0.2838	0.4054	0.0252	0.079*
C5	−0.1161 (2)	0.3639 (3)	0.20284 (16)	0.0527 (4)
H5	−0.0563	0.4666	0.1834	0.063*
C6	−0.1345 (2)	0.3584 (3)	0.34751 (18)	0.0584 (4)
H6B	−0.1750	0.4661	0.3741	0.070*
H6A	−0.2190	0.2739	0.3613	0.070*
C7	0.0371 (2)	0.31816 (19)	0.42819 (16)	0.0490 (4)
C8	0.2927 (2)	0.2798 (2)	0.60665 (15)	0.0497 (4)
C9	0.4223 (3)	0.2701 (3)	0.71705 (16)	0.0633 (5)
H9	0.4012	0.3056	0.7990	0.076*
C10	0.5810 (3)	0.2073 (3)	0.70255 (19)	0.0707 (6)
H10	0.6691	0.2028	0.7752	0.085*
C11	0.6131 (3)	0.1499 (3)	0.58133 (19)	0.0634 (5)
H11	0.7218	0.1064	0.5743	0.076*
C12	0.4862 (2)	0.1569 (2)	0.47181 (16)	0.0511 (4)
H12	0.5084	0.1174	0.3912	0.061*
C13	0.3233 (2)	0.22356 (19)	0.48218 (15)	0.0428 (4)
C14	0.17251 (19)	0.24634 (19)	0.38248 (14)	0.0412 (4)
C15	0.15873 (19)	0.1929 (2)	0.24080 (14)	0.0413 (4)
H15	0.1927	0.0751	0.2363	0.050*
N1	−0.01704 (17)	0.21547 (16)	0.17396 (12)	0.0447 (3)
O1	−0.06189 (17)	−0.04709 (17)	0.08604 (12)	0.0627 (3)
O2	0.27750 (15)	0.29669 (15)	0.18624 (11)	0.0513 (3)
O3	0.28192 (17)	0.23328 (18)	0.05339 (11)	0.0597 (3)
H3	0.207 (2)	0.299 (3)	0.013 (2)	0.098 (9)*
S1	0.08315 (6)	0.35880 (6)	0.59656 (4)	0.06228 (15)

	U11	U22	U33	U12	U13	U23
C2	0.0512 (10)	0.0610 (11)	0.0332 (7)	−0.0060 (9)	0.0043 (7)	0.0038 (8)
C3	0.0518 (11)	0.0782 (14)	0.0546 (10)	−0.0038 (10)	0.0001 (8)	0.0057 (9)
C4	0.0501 (10)	0.0692 (13)	0.0765 (12)	0.0052 (11)	0.0018 (9)	0.0209 (11)
C5	0.0440 (9)	0.0452 (9)	0.0699 (10)	0.0038 (9)	0.0121 (8)	0.0093 (9)
C6	0.0508 (9)	0.0560 (9)	0.0702 (10)	0.0095 (10)	0.0151 (8)	−0.0066 (10)
C7	0.0520 (10)	0.0446 (10)	0.0529 (9)	−0.0003 (8)	0.0156 (8)	−0.0048 (7)
C8	0.0679 (11)	0.0400 (8)	0.0435 (9)	0.0012 (8)	0.0161 (8)	0.0007 (7)
C9	0.0933 (15)	0.0563 (11)	0.0402 (9)	0.0050 (11)	0.0102 (9)	0.0006 (8)
C10	0.0872 (16)	0.0703 (14)	0.0492 (10)	0.0112 (12)	−0.0050 (10)	0.0097 (9)
C11	0.0673 (12)	0.0648 (12)	0.0560 (10)	0.0171 (10)	0.0042 (9)	0.0099 (9)
C12	0.0589 (11)	0.0514 (10)	0.0439 (9)	0.0086 (9)	0.0111 (8)	0.0041 (7)
C13	0.0549 (9)	0.0338 (8)	0.0411 (7)	−0.0015 (7)	0.0120 (7)	0.0016 (6)
C14	0.0467 (9)	0.0354 (8)	0.0433 (8)	−0.0009 (7)	0.0125 (7)	−0.0009 (6)
C15	0.0405 (8)	0.0433 (9)	0.0408 (8)	−0.0002 (7)	0.0084 (6)	0.0009 (6)
N1	0.0429 (7)	0.0457 (7)	0.0458 (7)	0.0001 (6)	0.0082 (6)	0.0021 (6)
O1	0.0674 (9)	0.0619 (8)	0.0554 (7)	−0.0007 (7)	0.0000 (6)	−0.0159 (6)
O2	0.0498 (6)	0.0609 (7)	0.0445 (6)	−0.0061 (5)	0.0121 (5)	0.0000 (5)
O3	0.0607 (8)	0.0756 (9)	0.0452 (7)	0.0118 (7)	0.0163 (6)	0.0007 (6)
S1	0.0745 (3)	0.0630 (3)	0.0537 (2)	0.0086 (3)	0.0234 (2)	−0.0118 (2)

C2—O1	1.233 (2)	C8—C13	1.414 (2)
C2—N1	1.345 (2)	C8—S1	1.7400 (19)
C2—C3	1.505 (3)	C9—C10	1.366 (3)
C3—C4	1.523 (3)	C9—H9	0.9300
C3—H3B	0.9700	C10—C11	1.390 (3)
C3—H3A	0.9700	C10—H10	0.9300
C4—C5	1.539 (3)	C11—C12	1.374 (3)
C4—H4B	0.9700	C11—H11	0.9300
C4—H4A	0.9700	C12—C13	1.398 (2)
C5—N1	1.471 (2)	C12—H12	0.9300
C5—C6	1.519 (2)	C13—C14	1.440 (2)
C5—H5	0.9800	C14—C15	1.506 (2)
C6—C7	1.490 (2)	C15—O2	1.4252 (19)
C6—H6B	0.9700	C15—N1	1.441 (2)
C6—H6A	0.9700	C15—H15	0.9800
C7—C14	1.353 (2)	O2—O3	1.4634 (16)
C7—S1	1.7411 (17)	O3—H3	0.841 (2)
C8—C9	1.393 (3)
O1—C2—N1	124.86 (17)	C13—C8—S1	110.95 (13)
O1—C2—C3	126.89 (16)	C10—C9—C8	118.72 (16)
N1—C2—C3	108.17 (16)	C10—C9—H9	120.6
C2—C3—C4	104.88 (16)	C8—C9—H9	120.6
C2—C3—H3B	110.8	C9—C10—C11	121.29 (18)
C4—C3—H3B	110.8	C9—C10—H10	119.4
C2—C3—H3A	110.8	C11—C10—H10	119.4
C4—C3—H3A	110.8	C12—C11—C10	120.70 (18)
H3B—C3—H3A	108.8	C12—C11—H11	119.7
C3—C4—C5	104.22 (16)	C10—C11—H11	119.7
C3—C4—H4B	110.9	C11—C12—C13	119.67 (15)
C5—C4—H4B	110.9	C11—C12—H12	120.2
C3—C4—H4A	110.9	C13—C12—H12	120.2
C5—C4—H4A	110.9	C12—C13—C8	118.72 (15)
H4B—C4—H4A	108.9	C12—C13—C14	129.82 (14)
N1—C5—C6	108.21 (14)	C8—C13—C14	111.46 (14)
N1—C5—C4	102.19 (16)	C7—C14—C13	113.53 (14)
C6—C5—C4	114.92 (14)	C7—C14—C15	121.41 (14)
N1—C5—H5	110.4	C13—C14—C15	125.04 (13)
C6—C5—H5	110.4	O2—C15—N1	111.66 (12)
C4—C5—H5	110.4	O2—C15—C14	105.62 (12)
C7—C6—C5	109.33 (13)	N1—C15—C14	109.74 (12)
C7—C6—H6B	109.8	O2—C15—H15	109.9
C5—C6—H6B	109.8	N1—C15—H15	109.9
C7—C6—H6A	109.8	C14—C15—H15	109.9
C5—C6—H6A	109.8	C2—N1—C15	124.42 (15)
H6B—C6—H6A	108.3	C2—N1—C5	114.03 (14)
C14—C7—C6	125.42 (15)	C15—N1—C5	119.65 (13)
C14—C7—S1	112.32 (13)	C15—O2—O3	106.49 (11)
C6—C7—S1	122.26 (12)	O2—O3—H3	97.2 (18)
C9—C8—C13	120.88 (17)	C8—S1—C7	91.72 (7)
C9—C8—S1	128.16 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1i	0.84 (1)	1.86 (1)	2.6962 (19)	173 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1i	0.84 (1)	1.86 (1)	2.6962 (19)	173 (2)

Symmetry code: (i) .