Methyl 7-chloro-2-ethyl-sulfanyl-6-fluoro-4-oxo-4H-thio-chromene-3-carboxyl-ate.

In the title compound, C(13)H(10)ClFO(3)S(2), the two-ring system is essentially planar, the mean plane of the benzene ring being inclined at 6.0 (2)° to the plane of the remaining four atoms. The ethyl-sulfanyl group is almost coplanar with the two rings [dihedral angle = 6.4 (2)°], while the carboxyl-ate group is almost perpendicular to it [dihedral angle = 72.4 (2)°]. In the crystal structure, inter-molecular C-H⋯O and C-H⋯F hydrogen bonds link the mol-ecules in a stacked arrangement along the a axis.

Related literature

For related compounds containing a 4H-thio­chromen-4-one fragment, see: Adams et al. (1991 ▶); Nakazumi et al. (1992 ▶); Weiss et al. (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C13H10ClFO3S2

M = 332.78

Triclinic,

a = 7.6740 (15) Å

b = 9.3880 (19) Å

c = 10.368 (2) Å

α = 85.18 (3)°

β = 80.93 (3)°

γ = 71.24 (3)°

V = 698.0 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.59 mm−1

T = 293 K

0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.892, T max = 0.944

2735 measured reflections

2531 independent reflections

1908 reflections with I > 2σ(I)

R int = 0.016

3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.138

S = 1.00

2531 reflections

181 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.31 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810002667/zq2029sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002667/zq2029Isup2.hkl

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

C13H10ClFO3S2	Z = 2
Mr = 332.78	F(000) = 340
Triclinic, P1	Dx = 1.583 Mg m−3
Hall symbol: -P 1	Melting point: 421 K
a = 7.6740 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3880 (19) Å	Cell parameters from 25 reflections
c = 10.368 (2) Å	θ = 10–13°
α = 85.18 (3)°	µ = 0.59 mm−1
β = 80.93 (3)°	T = 293 K
γ = 71.24 (3)°	Block, colourless
V = 698.0 (2) Å3	0.20 × 0.10 × 0.10 mm

Enraf–Nonius CAD-4 diffractometer	1908 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.016
graphite	θmax = 25.3°, θmin = 2.0°
ω/2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = −10→11
Tmin = 0.892, Tmax = 0.944	l = −12→12
2735 measured reflections	3 standard reflections every 200 reflections
2531 independent reflections	intensity decay: 1%

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.085P)2] where P = (Fo2 + 2Fc2)/3
2531 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.31 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
Cl	0.32919 (13)	0.43804 (11)	−0.25035 (9)	0.0614 (3)
F	−0.0661 (3)	0.5608 (2)	−0.2592 (2)	0.0679 (6)
S1	0.13971 (10)	0.07054 (9)	0.12622 (8)	0.0409 (3)
S2	−0.04493 (12)	−0.08554 (10)	0.33572 (9)	0.0515 (3)
O1	−0.4369 (3)	0.3010 (3)	0.0513 (2)	0.0541 (6)
O2	−0.4884 (3)	0.2281 (3)	0.3453 (2)	0.0572 (7)
O3	−0.4571 (4)	0.0067 (3)	0.2676 (3)	0.0738 (8)
C1	0.0642 (4)	0.2176 (3)	0.0132 (3)	0.0353 (7)
C2	0.2053 (4)	0.2628 (3)	−0.0640 (3)	0.0403 (7)
H2A	0.3289	0.2153	−0.0531	0.048*
C3	0.1606 (4)	0.3769 (3)	−0.1554 (3)	0.0409 (7)
C4	−0.0260 (5)	0.4468 (4)	−0.1690 (3)	0.0460 (8)
C5	−0.1641 (4)	0.4052 (3)	−0.0954 (3)	0.0433 (8)
H5A	−0.2871	0.4546	−0.1070	0.052*
C6	−0.1220 (4)	0.2881 (3)	−0.0019 (3)	0.0357 (7)
C7	−0.2770 (4)	0.2453 (3)	0.0767 (3)	0.0394 (7)
C8	−0.2374 (4)	0.1375 (3)	0.1842 (3)	0.0364 (7)
C9	−0.0653 (4)	0.0524 (3)	0.2103 (3)	0.0359 (7)
C10	0.1994 (4)	−0.1669 (4)	0.3475 (3)	0.0478 (8)
H10A	0.2680	−0.2038	0.2638	0.057*
H10B	0.2482	−0.0928	0.3750	0.057*
C11	0.2151 (5)	−0.2962 (4)	0.4489 (4)	0.0616 (10)
H11A	0.3432	−0.3439	0.4593	0.092*
H11B	0.1659	−0.3683	0.4203	0.092*
H11C	0.1459	−0.2578	0.5310	0.092*
C12	−0.4059 (4)	0.1142 (4)	0.2676 (3)	0.0435 (8)
C13	−0.6523 (5)	0.2191 (5)	0.4322 (4)	0.0650 (11)
H13A	−0.7010	0.3066	0.4843	0.097*
H13B	−0.6200	0.1305	0.4882	0.097*
H13C	−0.7445	0.2141	0.3815	0.097*

	U11	U22	U33	U12	U13	U23
Cl	0.0607 (6)	0.0691 (6)	0.0557 (6)	−0.0309 (5)	0.0054 (4)	0.0070 (4)
F	0.0703 (15)	0.0607 (13)	0.0659 (13)	−0.0157 (11)	−0.0153 (11)	0.0271 (11)
S1	0.0278 (4)	0.0440 (5)	0.0476 (5)	−0.0082 (3)	−0.0062 (3)	0.0060 (3)
S2	0.0359 (5)	0.0571 (6)	0.0557 (5)	−0.0118 (4)	−0.0047 (4)	0.0164 (4)
O1	0.0323 (12)	0.0591 (15)	0.0699 (16)	−0.0121 (11)	−0.0163 (11)	0.0109 (12)
O2	0.0491 (14)	0.0657 (16)	0.0583 (15)	−0.0270 (12)	0.0139 (12)	−0.0153 (12)
O3	0.0476 (15)	0.0571 (16)	0.119 (2)	−0.0274 (13)	0.0101 (15)	−0.0153 (16)
C1	0.0362 (16)	0.0339 (16)	0.0375 (16)	−0.0114 (13)	−0.0077 (13)	−0.0044 (13)
C2	0.0356 (16)	0.0406 (17)	0.0454 (18)	−0.0115 (14)	−0.0061 (14)	−0.0058 (14)
C3	0.0462 (18)	0.0416 (17)	0.0374 (16)	−0.0179 (15)	−0.0024 (14)	−0.0040 (14)
C4	0.057 (2)	0.0418 (18)	0.0398 (18)	−0.0144 (16)	−0.0116 (16)	0.0019 (14)
C5	0.0384 (17)	0.0396 (18)	0.0499 (19)	−0.0059 (14)	−0.0125 (15)	−0.0032 (15)
C6	0.0349 (16)	0.0340 (15)	0.0384 (16)	−0.0088 (13)	−0.0075 (13)	−0.0052 (12)
C7	0.0306 (16)	0.0392 (17)	0.0467 (18)	−0.0071 (13)	−0.0068 (14)	−0.0048 (14)
C8	0.0293 (15)	0.0395 (16)	0.0429 (17)	−0.0133 (13)	−0.0051 (13)	−0.0050 (13)
C9	0.0346 (16)	0.0373 (16)	0.0369 (16)	−0.0127 (13)	−0.0044 (13)	−0.0025 (13)
C10	0.0395 (18)	0.050 (2)	0.054 (2)	−0.0131 (15)	−0.0134 (15)	0.0088 (16)
C11	0.054 (2)	0.063 (2)	0.065 (2)	−0.0148 (19)	−0.0194 (19)	0.0168 (19)
C12	0.0283 (16)	0.0442 (18)	0.058 (2)	−0.0108 (14)	−0.0100 (14)	0.0046 (16)
C13	0.049 (2)	0.079 (3)	0.059 (2)	−0.019 (2)	0.0107 (18)	0.002 (2)

Cl—C3	1.719 (3)	C5—C6	1.394 (4)
F—C4	1.352 (4)	C5—H5A	0.9300
S1—C9	1.726 (3)	C6—C7	1.480 (4)
S1—C1	1.744 (3)	C7—C8	1.441 (4)
S2—C9	1.744 (3)	C8—C9	1.362 (4)
S2—C10	1.802 (3)	C8—C12	1.505 (4)
O1—C7	1.231 (4)	C10—C11	1.524 (4)
O2—C12	1.320 (4)	C10—H10A	0.9700
O2—C13	1.448 (4)	C10—H10B	0.9700
O3—C12	1.195 (4)	C11—H11A	0.9600
C1—C6	1.396 (4)	C11—H11B	0.9600
C1—C2	1.400 (4)	C11—H11C	0.9600
C2—C3	1.363 (4)	C13—H13A	0.9600
C2—H2A	0.9300	C13—H13B	0.9600
C3—C4	1.394 (5)	C13—H13C	0.9600
C4—C5	1.349 (5)
C9—S1—C1	103.12 (15)	C7—C8—C12	114.8 (3)
C9—S2—C10	106.87 (15)	C8—C9—S1	124.2 (2)
C12—O2—C13	116.1 (3)	C8—C9—S2	119.3 (2)
C6—C1—C2	120.8 (3)	S1—C9—S2	116.45 (17)
C6—C1—S1	124.0 (2)	C11—C10—S2	105.9 (2)
C2—C1—S1	115.1 (2)	C11—C10—H10A	110.6
C3—C2—C1	119.7 (3)	S2—C10—H10A	110.6
C3—C2—H2A	120.2	C11—C10—H10B	110.6
C1—C2—H2A	120.2	S2—C10—H10B	110.6
C2—C3—C4	118.9 (3)	H10A—C10—H10B	108.7
C2—C3—Cl	121.1 (3)	C10—C11—H11A	109.5
C4—C3—Cl	119.9 (3)	C10—C11—H11B	109.5
C5—C4—F	120.0 (3)	H11A—C11—H11B	109.5
C5—C4—C3	122.4 (3)	C10—C11—H11C	109.5
F—C4—C3	117.5 (3)	H11A—C11—H11C	109.5
C4—C5—C6	119.8 (3)	H11B—C11—H11C	109.5
C4—C5—H5A	120.1	O3—C12—O2	123.8 (3)
C6—C5—H5A	120.1	O3—C12—C8	125.7 (3)
C5—C6—C1	118.4 (3)	O2—C12—C8	110.4 (3)
C5—C6—C7	118.3 (3)	O2—C13—H13A	109.5
C1—C6—C7	123.3 (3)	O2—C13—H13B	109.5
O1—C7—C8	120.6 (3)	H13A—C13—H13B	109.5
O1—C7—C6	120.7 (3)	O2—C13—H13C	109.5
C8—C7—C6	118.7 (3)	H13A—C13—H13C	109.5
C9—C8—C7	125.9 (3)	H13B—C13—H13C	109.5
C9—C8—C12	119.1 (3)
C9—S1—C1—C6	−3.7 (3)	C1—C6—C7—C8	7.3 (4)
C9—S1—C1—C2	176.1 (2)	O1—C7—C8—C9	169.8 (3)
C6—C1—C2—C3	−0.2 (4)	C6—C7—C8—C9	−10.5 (5)
S1—C1—C2—C3	180.0 (2)	O1—C7—C8—C12	−6.3 (4)
C1—C2—C3—C4	0.5 (4)	C6—C7—C8—C12	173.4 (3)
C1—C2—C3—Cl	178.9 (2)	C7—C8—C9—S1	6.0 (5)
C2—C3—C4—C5	−0.3 (5)	C12—C8—C9—S1	−178.0 (2)
Cl—C3—C4—C5	−178.8 (3)	C7—C8—C9—S2	−173.7 (2)
C2—C3—C4—F	179.2 (3)	C12—C8—C9—S2	2.3 (4)
Cl—C3—C4—F	0.7 (4)	C1—S1—C9—C8	1.0 (3)
F—C4—C5—C6	−179.6 (3)	C1—S1—C9—S2	−179.22 (16)
C3—C4—C5—C6	−0.2 (5)	C10—S2—C9—C8	−176.9 (2)
C4—C5—C6—C1	0.5 (5)	C10—S2—C9—S1	3.3 (2)
C4—C5—C6—C7	−179.8 (3)	C9—S2—C10—C11	−175.0 (2)
C2—C1—C6—C5	−0.3 (4)	C13—O2—C12—O3	−1.3 (5)
S1—C1—C6—C5	179.6 (2)	C13—O2—C12—C8	−179.4 (3)
C2—C1—C6—C7	180.0 (3)	C9—C8—C12—O3	−70.7 (5)
S1—C1—C6—C7	−0.1 (4)	C7—C8—C12—O3	105.7 (4)
C5—C6—C7—O1	7.3 (4)	C9—C8—C12—O2	107.4 (3)
C1—C6—C7—O1	−173.0 (3)	C7—C8—C12—O2	−76.2 (3)
C5—C6—C7—C8	−172.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1i	0.93	2.60	3.292 (4)	132
C13—H13C···Fii	0.96	2.52	3.144 (5)	123

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1i	0.93	2.60	3.292 (4)	132
C13—H13C⋯Fii	0.96	2.52	3.144 (5)	123

Symmetry codes: (i) ; (ii) .