Ethyl 5-hy-droxy-6-oxo-4-phenyl-5,6-dihydro-4H-cyclo-penta-[b]thio-phene-5-carboxyl-ate.

In the title mol-ecule, C(16)H(14)O(4)S, the dihydro-cyclo-penta-thio-phenone ring system is almost planar, with an r.m.s. deviation of 0.060 Å from the best fit plane through all nine non-H atoms. The cyclo-penta-none ring adopts a severely flattened envelope conformation with the C atom carrying the OH and ethylcarboxylate substituents at the flap. This atom lies only 0.185 (3) Å from the plane through the other four C atoms. The phenyl substituent is inclined at 43.37 (5)° to the dihydro-cyclo-penta-thio-phenone mean plane. In the crystal, mol-ecules are linked by pairs of O-H⋯O hydrogen bonds, forming inversion dimers with R(2) (2)(10) ring motifs. Weak C-H⋯O hydrogen bonds also link mol-ecules into chains along c, while an approximately orthogonal set of C-H⋯O contacts form chains along b, resulting in layers lying parallel to (100). Inversion dimers also form through weaker R(2) (2)(12) C-H⋯S contacts, which combine with C-H⋯O contacts to form stacks along b.

Related literature

For details of conducting thio­phene polymers, see: Anquetil et al. (2003 ▶). For related structures, see: Bonini et al. (2004 ▶); Chang et al. (2004 ▶). For details of the Cambridge Structural Database, see: Allen (2002 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For standard bond lengths, see Allen et al. (1987 ▶). For the preparation of a precursor used in the synthesis, see: Yang (2009 ▶).

Experimental

Crystal data

C16H14O4S

M = 302.33

Triclinic,

a = 7.7407 (4) Å

b = 9.1005 (4) Å

c = 10.5035 (5) Å

α = 84.840 (3)°

β = 80.929 (3)°

γ = 88.086 (3)°

V = 727.56 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.24 mm−1

T = 91 K

0.45 × 0.35 × 0.25 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2011 ▶) T min = 0.672, T max = 0.745

13007 measured reflections

2584 independent reflections

2233 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.079

S = 1.07

2584 reflections

194 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: APEX2 and SAINT (Bruker, 2011 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶) and TITAN2000 (Hunter & Simpson, 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and TITAN2000; molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶), PLATON (Spek, 2009 ▶) and publCIF (Westrip 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811037032/su2314sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037032/su2314Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811037032/su2314Isup3.cml

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

C16H14O4S	Z = 2
Mr = 302.33	F(000) = 316
Triclinic, P1	Dx = 1.380 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7407 (4) Å	Cell parameters from 4122 reflections
b = 9.1005 (4) Å	θ = 2.7–24.9°
c = 10.5035 (5) Å	µ = 0.24 mm−1
α = 84.840 (3)°	T = 91 K
β = 80.929 (3)°	Block, colourless
γ = 88.086 (3)°	0.45 × 0.35 × 0.25 mm
V = 727.56 (6) Å3

Bruker APEXII CCD area-detector diffractometer	2584 independent reflections
Radiation source: fine-focus sealed tube	2233 reflections with I > 2σ(I)
graphite	Rint = 0.035
φ and ω scans	θmax = 25.2°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2011)	h = −9→9
Tmin = 0.672, Tmax = 0.745	k = −10→10
13007 measured reflections	l = −12→12

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0322P)2 + 0.3338P] where P = (Fo2 + 2Fc2)/3
2584 reflections	(Δ/σ)max < 0.001
194 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

Experimental. Spectroscopic data for the title compound: 1H NMR (δ p.p.m., CDCl3, 400 MHz): 8.08 (1H, d, J = 4.8 Hz, CHS), 7.35–7.28 (5H, m, phenyl H), 7.16 (1H, d, J = 4.8 Hz, CHCHS), 4.73 (1H, s, CHC6H5), 4.37 (1H, s, OH), 3.82 & 3.62 [2 x (1H, m, CH2)], 0.85 (3H, t, J = 7 Hz, CH3). IR ν(CO) 1737, 1703 cm-1 .

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
S1	0.31491 (5)	0.47012 (4)	0.41577 (4)	0.01868 (13)
C1	0.2877 (2)	0.33654 (18)	0.54308 (16)	0.0206 (4)
H1	0.3238	0.2366	0.5349	0.025*
C2	0.2095 (2)	0.38688 (18)	0.65715 (16)	0.0185 (4)
H2	0.1850	0.3271	0.7365	0.022*
C3	0.1697 (2)	0.53999 (17)	0.64162 (15)	0.0149 (3)
C4	0.2184 (2)	0.59827 (17)	0.51632 (15)	0.0155 (3)
C5	0.1669 (2)	0.75165 (17)	0.49802 (15)	0.0154 (3)
O5	0.17464 (15)	0.83394 (12)	0.39918 (10)	0.0204 (3)
C6	0.0911 (2)	0.79820 (17)	0.63548 (15)	0.0152 (3)
O6	−0.07237 (14)	0.86931 (13)	0.63575 (12)	0.0203 (3)
H6	−0.064 (3)	0.959 (2)	0.6268 (19)	0.030*
C7	0.0721 (2)	0.65116 (17)	0.72591 (15)	0.0158 (3)
H7	−0.0542	0.6251	0.7382	0.019*
C8	0.1173 (2)	0.66251 (18)	0.86036 (15)	0.0174 (4)
C9	0.2418 (2)	0.57266 (19)	0.91240 (16)	0.0228 (4)
H9	0.3044	0.5001	0.8629	0.027*
C10	0.2752 (3)	0.5886 (2)	1.03705 (17)	0.0293 (4)
H10	0.3582	0.5247	1.0728	0.035*
C11	0.1892 (3)	0.6958 (2)	1.10879 (17)	0.0292 (4)
H11	0.2145	0.7074	1.1929	0.035*
C12	0.0658 (3)	0.78667 (19)	1.05765 (17)	0.0272 (4)
H12	0.0067	0.8614	1.1064	0.033*
C13	0.0281 (2)	0.76864 (18)	0.93510 (16)	0.0216 (4)
H13	−0.0595	0.8293	0.9017	0.026*
C14	0.2214 (2)	0.90456 (17)	0.67132 (14)	0.0147 (3)
O14	0.18207 (15)	1.02944 (12)	0.69500 (11)	0.0212 (3)
O15	0.38114 (14)	0.84388 (12)	0.66685 (11)	0.0200 (3)
C15	0.5156 (2)	0.9380 (2)	0.69937 (17)	0.0245 (4)
H15A	0.4980	1.0404	0.6625	0.029*
H15B	0.6326	0.9028	0.6600	0.029*
C16	0.5090 (3)	0.9368 (3)	0.8421 (2)	0.0471 (6)
H16A	0.3957	0.9768	0.8807	0.071*
H16B	0.6030	0.9975	0.8603	0.071*
H16C	0.5241	0.8353	0.8790	0.071*

	U11	U22	U33	U12	U13	U23
S1	0.0229 (2)	0.0171 (2)	0.0166 (2)	0.00254 (17)	−0.00388 (17)	−0.00395 (16)
C1	0.0247 (9)	0.0143 (8)	0.0237 (9)	0.0026 (7)	−0.0072 (7)	−0.0022 (7)
C2	0.0210 (9)	0.0167 (8)	0.0179 (8)	−0.0010 (7)	−0.0032 (7)	−0.0007 (7)
C3	0.0122 (8)	0.0167 (8)	0.0168 (8)	−0.0012 (6)	−0.0044 (6)	−0.0021 (6)
C4	0.0142 (8)	0.0158 (8)	0.0177 (8)	0.0005 (6)	−0.0046 (6)	−0.0038 (7)
C5	0.0120 (8)	0.0167 (8)	0.0185 (9)	−0.0017 (6)	−0.0051 (6)	−0.0023 (7)
O5	0.0252 (7)	0.0177 (6)	0.0184 (6)	0.0006 (5)	−0.0062 (5)	0.0014 (5)
C6	0.0115 (8)	0.0155 (8)	0.0189 (8)	0.0029 (6)	−0.0031 (6)	−0.0027 (7)
O6	0.0136 (6)	0.0150 (6)	0.0327 (7)	0.0042 (5)	−0.0057 (5)	−0.0029 (5)
C7	0.0128 (8)	0.0148 (8)	0.0198 (9)	−0.0012 (6)	−0.0022 (6)	−0.0008 (7)
C8	0.0174 (9)	0.0167 (8)	0.0169 (8)	−0.0037 (7)	0.0015 (7)	−0.0009 (7)
C9	0.0246 (9)	0.0243 (9)	0.0194 (9)	0.0031 (7)	−0.0023 (7)	−0.0050 (7)
C10	0.0317 (11)	0.0351 (11)	0.0220 (10)	0.0013 (9)	−0.0086 (8)	−0.0006 (8)
C11	0.0407 (11)	0.0329 (11)	0.0146 (9)	−0.0079 (9)	−0.0034 (8)	−0.0034 (8)
C12	0.0385 (11)	0.0207 (9)	0.0199 (9)	−0.0036 (8)	0.0070 (8)	−0.0066 (7)
C13	0.0234 (9)	0.0185 (9)	0.0212 (9)	−0.0008 (7)	0.0014 (7)	0.0001 (7)
C14	0.0163 (8)	0.0157 (8)	0.0116 (8)	−0.0006 (7)	−0.0003 (6)	−0.0006 (6)
O14	0.0220 (6)	0.0149 (6)	0.0270 (7)	0.0009 (5)	−0.0047 (5)	−0.0034 (5)
O15	0.0118 (6)	0.0222 (6)	0.0278 (7)	0.0012 (5)	−0.0050 (5)	−0.0098 (5)
C15	0.0139 (9)	0.0281 (10)	0.0334 (10)	−0.0044 (7)	−0.0040 (7)	−0.0113 (8)
C16	0.0419 (13)	0.0704 (16)	0.0341 (12)	−0.0203 (12)	−0.0160 (10)	−0.0069 (11)

S1—C1	1.7164 (17)	C9—C10	1.395 (2)
S1—C4	1.7171 (16)	C9—H9	0.9500
C1—C2	1.365 (2)	C10—C11	1.376 (3)
C1—H1	0.9500	C10—H10	0.9500
C2—C3	1.417 (2)	C11—C12	1.384 (3)
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.374 (2)	C12—C13	1.389 (2)
C3—C7	1.509 (2)	C12—H12	0.9500
C4—C5	1.443 (2)	C13—H13	0.9500
C5—O5	1.2190 (19)	C14—O14	1.2041 (19)
C5—C6	1.560 (2)	C14—O15	1.3332 (19)
C6—O6	1.4018 (18)	O15—C15	1.4689 (19)
C6—C14	1.531 (2)	C15—C16	1.491 (3)
C6—C7	1.567 (2)	C15—H15A	0.9900
O6—H6	0.82 (2)	C15—H15B	0.9900
C7—C8	1.520 (2)	C16—H16A	0.9800
C7—H7	1.0000	C16—H16B	0.9800
C8—C9	1.389 (2)	C16—H16C	0.9800
C8—C13	1.395 (2)
C1—S1—C4	89.88 (8)	C8—C9—C10	120.27 (16)
C2—C1—S1	113.94 (13)	C8—C9—H9	119.9
C2—C1—H1	123.0	C10—C9—H9	119.9
S1—C1—H1	123.0	C11—C10—C9	120.64 (17)
C1—C2—C3	111.12 (15)	C11—C10—H10	119.7
C1—C2—H2	124.4	C9—C10—H10	119.7
C3—C2—H2	124.4	C10—C11—C12	119.60 (16)
C4—C3—C2	112.06 (14)	C10—C11—H11	120.2
C4—C3—C7	112.16 (14)	C12—C11—H11	120.2
C2—C3—C7	135.47 (15)	C11—C12—C13	120.06 (16)
C3—C4—C5	112.25 (14)	C11—C12—H12	120.0
C3—C4—S1	112.99 (12)	C13—C12—H12	120.0
C5—C4—S1	134.64 (13)	C12—C13—C8	120.82 (17)
O5—C5—C4	130.13 (15)	C12—C13—H13	119.6
O5—C5—C6	124.00 (14)	C8—C13—H13	119.6
C4—C5—C6	105.87 (13)	O14—C14—O15	125.38 (15)
O6—C6—C14	109.60 (13)	O14—C14—C6	122.73 (14)
O6—C6—C5	111.05 (12)	O15—C14—C6	111.83 (13)
C14—C6—C5	106.85 (12)	C14—O15—C15	115.81 (12)
O6—C6—C7	110.20 (12)	O15—C15—C16	111.60 (15)
C14—C6—C7	113.48 (12)	O15—C15—H15A	109.3
C5—C6—C7	105.56 (12)	C16—C15—H15A	109.3
C6—O6—H6	111.8 (14)	O15—C15—H15B	109.3
C3—C7—C8	119.14 (13)	C16—C15—H15B	109.3
C3—C7—C6	102.88 (12)	H15A—C15—H15B	108.0
C8—C7—C6	114.66 (13)	C15—C16—H16A	109.5
C3—C7—H7	106.4	C15—C16—H16B	109.5
C8—C7—H7	106.4	H16A—C16—H16B	109.5
C6—C7—H7	106.4	C15—C16—H16C	109.5
C9—C8—C13	118.56 (15)	H16A—C16—H16C	109.5
C9—C8—C7	123.45 (14)	H16B—C16—H16C	109.5
C13—C8—C7	117.99 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O14	0.82 (2)	2.27 (2)	2.6705 (16)	110.8 (16)
O6—H6···O5i	0.82 (2)	2.06 (2)	2.7973 (16)	150.5 (19)
C1—H1···O14ii	0.95	2.56	3.157 (2)	121
C11—H11···O5iii	0.95	2.52	3.386 (2)	152
C15—H15B···O6iv	0.99	2.27	3.206 (2)	157
C7—H7···S1v	1.00	2.97	3.7855 (16)	139
C12—H12···O14vi	0.95	2.61	3.497 (2)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6⋯O14	0.82 (2)	2.27 (2)	2.6705 (16)	110.8 (16)
O6—H6⋯O5i	0.82 (2)	2.06 (2)	2.7973 (16)	150.5 (19)
C1—H1⋯O14ii	0.95	2.56	3.157 (2)	121
C11—H11⋯O5iii	0.95	2.52	3.386 (2)	152
C15—H15B⋯O6iv	0.99	2.27	3.206 (2)	157
C7—H7⋯S1v	1.00	2.97	3.7855 (16)	139
C12—H12⋯O14vi	0.95	2.61	3.497 (2)	157

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .