2-(3-Ethyl­sulfanyl-5-phenyl-1-benzofuran-2-yl)acetic acid

Choi, H.D.; Seo, P.J.; Son, B.W.; Lee, U.

doi:10.1107/S160053680903253X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2212

doi:10.1107/S160053680903253X

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2-(3-Ethylsulfanyl-5-phenyl-1-benzofuran-2-yl)acetic acid

Hong Dae Choi,^a Pil Ja Seo,^a Byeng Wha Son ^b and Uk Lee ^b ^*

^aDepartment of Chemistry, Dongeui University, San 24 Kaya-dong Busanjin-gu, Busan 614-714, Republic of Korea, and ^bDepartment of Chemistry, Pukyong National University, 599-1 Daeyeon 3-dong, Nam-gu, Busan 608-737, Republic of Korea
^*Correspondence e-mail: uklee@pknu.ac.kr

(Received 14 August 2009; accepted 17 August 2009; online 22 August 2009)

The title compound, C₁₈H₁₆O₃S, crystallizes with two symmetry-independent molecules in the asymmetric unit. The phenyl rings are rotated out of the benzofuran planes, making dihedral angles of 43.38 (7) and 56.13 (6)° in the two molecules. The carboxyl groups are involved in inversion-related intermolecular O—H⋯O hydrogen bonds, which link the molecules into centrosymmetric dimers. These dimers are further packed into stacks along the b axis by weak non-classical intermolecular C—H⋯O hydrogen bonds. The crystal structure also exhibits intermolecular C—H⋯π interactions, and two aromatic π–π interactions between the furan rings of neighbouring benzofuran systems; the centroid–centroid distances are 3.500 (3) and 3.605 (3) Å.

Related literature

For the crystal structures of similar 2-(5-aryl-1-benzofuran-2-yl)acetic acid derivatives, see: Choi et al. (2007a ,b ). For the pharmacological activity of benzofuran compounds, see: Howlett et al. (1999 ); Twyman & Allsop (1999 ).

Experimental

Crystal data

C₁₈H₁₆O₃S
M_r = 312.37
Monoclinic, P 2₁ /n
a = 12.4250 (7) Å
b = 11.7823 (7) Å
c = 21.2426 (13) Å
β = 93.021 (1)°
V = 3105.5 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 293 K
0.40 × 0.40 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.918, T_max = 0.958
18961 measured reflections
7033 independent reflections
4490 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.116
S = 1.02
7033 reflections
405 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O3ⁱ	0.92 (2)	1.73 (2)	2.643 (2)	174 (3)
O5—H5O⋯O6ⁱⁱ	0.92 (2)	1.68 (2)	2.602 (2)	175 (4)
C6—H6⋯O5ⁱⁱⁱ	0.93	2.57	3.461 (3)	161
C24—H24⋯O3	0.93	2.57	3.480 (3)	165
C12—H12⋯Cg4^iv	0.93	2.91	3.561 (3)	131
C30—H30⋯Cg2^v	0.93	2.80	3.506 (3)	133
Symmetry codes: (i) -x, -y+2, -z+1; (ii) -x+1, -y+1, -z+1; (iii) x, y+1, z; (iv) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ . Cg2 and Cg4 are the centroids of the C2–C7 and the C20–C25 benzene rings, respectively.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903253X/nk2002sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680903253X/nk2002Isup2.hkl

checkCIF report

Comment top

The benzofuran ring systems have attracted considerable interest in the view of their pharmacological properties (Howlett et al., 1999; Twyman & Allsop, 1999). As a part of our ongoing studies on the synthesis and structures of 2-(5-aryl-1-benzofuran-2-yl)acetic acid analogues, the crystal structure of 2-(3-methylsulfanyl-5-phenyl-1-benzofuran-2-yl)acetic acid (Choi et al., 2007a) and 2-[5-(4-bromophenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetic acid (Choi et al., 2007b) have been described in the literature. Here we report the crystal structure of the title compound, which has two unique molecules in the asymmetric unit (further marked as A and B) (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.006 (2) Å for A, and 0.024 (2) Å for B, respectively, from the least-squares plane defined by the nine constituent atoms. In the title compound, the dihedral angles formed by the phenyl ring and the plane of the benzofuran fragment are 43.38 (7) in A and 56.13 (6)° in B, respectively. In the crystal structure, the carboxylic acid groups are involved in inversion-related intermolecular O–H···O hydrogen bonds, which link the molecules into centrosymmetric dimers. These dimers are further packed into stacks along the b axis by non-classical intermolecular C–H···O hydrogen bonds (Table 1 and Fig. 2). The crystal structure (Fig. 3) is further stabilized by intermolecular C–H···π interactions between the phenyl H atom and the benzene ring of the adjacent molecule, with a C12–H12···Cg4^iv and a C30–H30···Cg2^v (Table 1; Cg2 and Cg4 are the centroids of the C2-C7 and the C20-C25 benzene rings, respectively). The crystal packing (Fig. 3) also shows two aromatic π–π interactions between the furan rings of the adjacent benzofuran molecules, with a Cg1···Cg1^vii and a Cg3···Cg3^viii distances of 3.500 (3) and 3.605 (3) Å, respectively (Cg1 and Cg3 are the centroids of the C1/C2/C7/O1/C8 and the C19/C20/C25/O4/C26 furan rings, respectively).

Related literature top

For the crystal structures of similar 2-(5-aryl-1-benzofuran-2-yl)acetic acid derivatives, see: Choi et al. (2007a,b). For the pharmacological activity of benzofuran compounds, see: Howlett et al. (1999); Twyman & Allsop (1999). Cg2 and Cg4 are the centroids of the C2–C7 and the C20–C25 benzene rings, respectively.

Experimental top

Ethyl 2-(3-ethylsulfanyl-5-phenyl-1-benzofuran-2-yl)acetate (374 mg, 1.1 mmol) was added to a solution of potassium hydroxide (309 mg, 5.5 mmol) in water (20 ml) and methanol (20 ml), and the mixture was refluxed for 6h, then cooled. Water was added, and the solution was extracted with dichloromethane. The aqueous layer was acidified to pH 1 with concentrated hydrochloric acid and then extracted with chloroform, dried over magnesium sulfate, filtered and concentrated under vacuum. The residue was purified by column chromatography (ethyl acetate) to afford the title compound as a colorless solid [yield 80%, m.p. 413-414 K; R_f = 0.79 (ethyl acetate)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in diisopropyl ether at room temperature.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small cycles of arbitrary radius.
	Fig. 2. O–H···O and C–H···O hydrogen bonds (dotted lines) in the title compound. [Symmetry code: (i) - x, - y + 2, - z + 1; (ii) - x + 1, - y + 1, - z + 1; (iii) x, y + 1, z; (vi) x, y - 1, z.]
	Fig. 3. C–H···π and π–π interactions (dotted lines) in the title compound. Cg denotes the ring centroids. [Symmetry code: (iv) x + 1/2, - y + 3/2, z + 1/2; (v) x - 1/2, - y + 3/2, z - 1/2; (vii) -x + 1, -y + 2, -z + 1; (viii) - x, -y + 1, -z + 1; (ix) - x + 1/2, y + 1/2, -z + 1/2; (x) -x + 1/2, y - 1/2, -z + 3/2.]

2-(3-Ethylsulfanyl-5-phenyl-1-benzofuran-2-yl)acetic acid top

Crystal data top

C₁₈H₁₆O₃S	F(000) = 1312
M_r = 312.37	D_x = 1.336 Mg m⁻³
Monoclinic, P2₁/n	Melting point = 413–414 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 12.4250 (7) Å	Cell parameters from 5569 reflections
b = 11.7823 (7) Å	θ = 2.4–27.2°
c = 21.2426 (13) Å	µ = 0.22 mm⁻¹
β = 93.021 (1)°	T = 293 K
V = 3105.5 (3) Å³	Block, colorless
Z = 8	0.40 × 0.40 × 0.20 mm

Data collection top

Bruker SMART CCD diffractometer	7033 independent reflections
Radiation source: fine-focus sealed tube	4490 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.5°, θ_min = 1.9°
ϕ and ω scans	h = −16→14
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→15
T_min = 0.918, T_max = 0.958	l = −22→27
18961 measured reflections

Refinement top

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)] = 0.044	Hydrogen site location: difference Fourier map
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0418P)² + 1.3759P] where P = (F_o² + 2F_c²)/3
7033 reflections	(Δ/σ)_max < 0.001
405 parameters	Δρ_max = 0.27 e Å⁻³
2 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₈H₁₆O₃S	V = 3105.5 (3) Å³
M_r = 312.37	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.4250 (7) Å	µ = 0.22 mm⁻¹
b = 11.7823 (7) Å	T = 293 K
c = 21.2426 (13) Å	0.40 × 0.40 × 0.20 mm
β = 93.021 (1)°

Data collection top

Bruker SMART CCD diffractometer	7033 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4490 reflections with I > 2σ(I)
T_min = 0.918, T_max = 0.958	R_int = 0.051
18961 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	2 restraints
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.27 e Å⁻³
7033 reflections	Δρ_min = −0.35 e Å⁻³
405 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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

	x	y	z	U_iso*/U_eq
S1	0.42821 (4)	0.74794 (5)	0.56883 (3)	0.03157 (15)
S2	0.09978 (5)	0.26751 (5)	0.45920 (3)	0.03627 (16)
O1	0.35424 (11)	1.06793 (13)	0.52955 (7)	0.0307 (3)
O2	0.12491 (13)	0.98536 (16)	0.54306 (7)	0.0429 (4)
H2O	0.054 (2)	1.005 (3)	0.5462 (16)	0.102 (13)*
O3	0.07580 (12)	0.94865 (15)	0.44307 (7)	0.0366 (4)
O4	0.13576 (11)	0.60092 (13)	0.46153 (7)	0.0316 (4)
O5	0.42194 (12)	0.46922 (13)	0.56302 (7)	0.0314 (4)
H5O	0.493 (2)	0.481 (3)	0.5539 (17)	0.116 (14)*
O6	0.37647 (12)	0.50831 (14)	0.46214 (7)	0.0353 (4)
C1	0.41378 (16)	0.89499 (18)	0.56241 (9)	0.0254 (5)
C2	0.47608 (16)	0.98018 (18)	0.59689 (9)	0.0248 (5)
C3	0.55970 (16)	0.97787 (18)	0.64336 (9)	0.0265 (5)
H3	0.5871	0.9091	0.6585	0.032*
C4	0.60141 (16)	1.08000 (18)	0.66661 (10)	0.0271 (5)
C5	0.55883 (17)	1.18297 (19)	0.64317 (10)	0.0330 (5)
H5	0.5874	1.2507	0.6591	0.040*
C6	0.47558 (18)	1.1869 (2)	0.59704 (11)	0.0343 (5)
H6	0.4477	1.2554	0.5816	0.041*
C7	0.43644 (16)	1.08408 (19)	0.57530 (10)	0.0282 (5)
C8	0.34212 (16)	0.95192 (19)	0.52408 (10)	0.0275 (5)
C9	0.25729 (16)	0.9119 (2)	0.47742 (10)	0.0311 (5)
H9A	0.2575	0.8295	0.4776	0.037*
H9B	0.2764	0.9363	0.4358	0.037*
C10	0.14441 (17)	0.95190 (18)	0.48781 (10)	0.0272 (5)
C11	0.69182 (16)	1.07951 (19)	0.71553 (10)	0.0287 (5)
C12	0.69211 (17)	1.0048 (2)	0.76654 (10)	0.0313 (5)
H12	0.6349	0.9547	0.7702	0.038*
C13	0.77631 (18)	1.0042 (2)	0.81172 (10)	0.0363 (6)
H13	0.7749	0.9545	0.8457	0.044*
C14	0.86258 (19)	1.0771 (2)	0.80665 (11)	0.0412 (6)
H14	0.9195	1.0762	0.8369	0.049*
C15	0.86381 (19)	1.1513 (2)	0.75639 (11)	0.0440 (6)
H15	0.9218	1.2003	0.7528	0.053*
C16	0.77908 (18)	1.1532 (2)	0.71117 (11)	0.0369 (6)
H16	0.7804	1.2039	0.6777	0.044*
C17	0.3695 (2)	0.7258 (2)	0.64445 (11)	0.0388 (6)
H17A	0.3726	0.6456	0.6547	0.047*
H17B	0.4122	0.7662	0.6768	0.047*
C18	0.2544 (2)	0.7653 (2)	0.64531 (12)	0.0441 (6)
H18A	0.2113	0.7246	0.6140	0.053*
H18B	0.2509	0.8451	0.6363	0.053*
H18C	0.2276	0.7513	0.6862	0.053*
C19	0.09835 (16)	0.41459 (19)	0.44545 (10)	0.0272 (5)
C20	0.03217 (15)	0.47991 (18)	0.40052 (9)	0.0249 (5)
C21	−0.04696 (15)	0.45394 (18)	0.35359 (9)	0.0260 (5)
H21	−0.0636	0.3789	0.3436	0.031*
C22	−0.10028 (16)	0.54269 (19)	0.32209 (9)	0.0262 (5)
C23	−0.07088 (17)	0.65529 (19)	0.33561 (10)	0.0300 (5)
H23	−0.1065	0.7135	0.3135	0.036*
C24	0.00971 (17)	0.68284 (19)	0.38098 (10)	0.0323 (5)
H24	0.0298	0.7575	0.3894	0.039*
C25	0.05787 (16)	0.59262 (19)	0.41258 (9)	0.0268 (5)
C26	0.15723 (16)	0.4906 (2)	0.48009 (10)	0.0294 (5)
C27	0.23707 (16)	0.4758 (2)	0.53380 (10)	0.0343 (5)
H27A	0.2263	0.4018	0.5524	0.041*
H27B	0.2232	0.5324	0.5655	0.041*
C28	0.35276 (17)	0.48548 (18)	0.51715 (9)	0.0258 (5)
C29	−0.19404 (16)	0.51884 (19)	0.27720 (10)	0.0279 (5)
C30	−0.18684 (18)	0.44420 (19)	0.22683 (10)	0.0316 (5)
H30	−0.1214	0.4094	0.2198	0.038*
C31	−0.27602 (19)	0.4213 (2)	0.18717 (11)	0.0384 (6)
H31	−0.2700	0.3727	0.1531	0.046*
C32	−0.37435 (19)	0.4708 (2)	0.19823 (11)	0.0409 (6)
H32	−0.4347	0.4541	0.1721	0.049*
C33	−0.38292 (18)	0.5449 (2)	0.24798 (11)	0.0390 (6)
H33	−0.4489	0.5783	0.2553	0.047*
C34	−0.29342 (17)	0.5695 (2)	0.28696 (10)	0.0339 (5)
H34	−0.2994	0.6203	0.3201	0.041*
C35	0.1906 (2)	0.2174 (2)	0.40061 (12)	0.0438 (6)
H35A	0.2462	0.2740	0.3956	0.053*
H35B	0.2256	0.1485	0.4161	0.053*
C36	0.1365 (3)	0.1937 (3)	0.33772 (13)	0.0640 (8)
H36A	0.1025	0.2616	0.3216	0.077*
H36B	0.0830	0.1357	0.3418	0.077*
H36C	0.1890	0.1685	0.3093	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0307 (3)	0.0256 (3)	0.0383 (3)	0.0037 (2)	0.0005 (2)	−0.0017 (2)
S2	0.0380 (3)	0.0335 (3)	0.0378 (3)	0.0016 (3)	0.0059 (3)	0.0099 (3)
O1	0.0293 (8)	0.0282 (9)	0.0342 (8)	0.0021 (7)	−0.0007 (6)	0.0067 (7)
O2	0.0287 (9)	0.0706 (13)	0.0294 (9)	0.0054 (9)	−0.0003 (7)	−0.0133 (8)
O3	0.0310 (9)	0.0518 (11)	0.0262 (8)	0.0020 (8)	−0.0051 (7)	−0.0036 (7)
O4	0.0277 (8)	0.0346 (9)	0.0319 (8)	−0.0012 (7)	−0.0023 (6)	−0.0039 (7)
O5	0.0272 (8)	0.0363 (9)	0.0304 (8)	0.0015 (7)	−0.0027 (7)	0.0053 (7)
O6	0.0303 (8)	0.0525 (11)	0.0232 (8)	0.0004 (8)	0.0012 (6)	0.0001 (7)
C1	0.0229 (10)	0.0266 (11)	0.0271 (11)	0.0009 (9)	0.0043 (8)	0.0016 (9)
C2	0.0205 (10)	0.0260 (12)	0.0285 (11)	0.0001 (9)	0.0064 (8)	0.0032 (9)
C3	0.0228 (10)	0.0275 (12)	0.0294 (11)	0.0022 (9)	0.0046 (9)	0.0029 (9)
C4	0.0233 (10)	0.0299 (12)	0.0289 (11)	−0.0010 (9)	0.0072 (9)	−0.0011 (9)
C5	0.0308 (12)	0.0284 (12)	0.0400 (13)	−0.0057 (10)	0.0038 (10)	−0.0017 (10)
C6	0.0357 (13)	0.0258 (12)	0.0419 (13)	0.0027 (10)	0.0052 (10)	0.0066 (10)
C7	0.0241 (11)	0.0309 (12)	0.0296 (12)	−0.0004 (10)	0.0026 (9)	0.0042 (9)
C8	0.0241 (11)	0.0300 (12)	0.0288 (11)	0.0022 (9)	0.0049 (9)	0.0025 (9)
C9	0.0290 (11)	0.0367 (13)	0.0277 (12)	0.0031 (10)	0.0010 (9)	0.0009 (10)
C10	0.0298 (11)	0.0277 (12)	0.0241 (11)	−0.0016 (9)	−0.0003 (9)	0.0024 (9)
C11	0.0242 (11)	0.0325 (13)	0.0297 (12)	−0.0016 (9)	0.0045 (9)	−0.0065 (9)
C12	0.0266 (11)	0.0367 (13)	0.0311 (12)	−0.0024 (10)	0.0070 (9)	−0.0048 (10)
C13	0.0341 (13)	0.0451 (15)	0.0299 (12)	0.0029 (11)	0.0033 (10)	−0.0042 (11)
C14	0.0299 (12)	0.0603 (18)	0.0331 (13)	−0.0016 (12)	−0.0021 (10)	−0.0076 (12)
C15	0.0303 (13)	0.0567 (17)	0.0449 (15)	−0.0143 (12)	0.0022 (11)	−0.0062 (13)
C16	0.0329 (12)	0.0422 (15)	0.0361 (13)	−0.0069 (11)	0.0052 (10)	0.0010 (11)
C17	0.0535 (15)	0.0279 (13)	0.0345 (13)	−0.0050 (11)	−0.0033 (11)	0.0058 (10)
C18	0.0526 (16)	0.0373 (15)	0.0439 (14)	−0.0085 (12)	0.0185 (12)	0.0026 (11)
C19	0.0227 (10)	0.0312 (12)	0.0282 (11)	0.0026 (9)	0.0057 (9)	0.0036 (9)
C20	0.0191 (10)	0.0294 (12)	0.0268 (11)	0.0028 (9)	0.0061 (8)	0.0011 (9)
C21	0.0218 (10)	0.0270 (11)	0.0296 (11)	−0.0031 (9)	0.0063 (9)	−0.0010 (9)
C22	0.0226 (10)	0.0315 (12)	0.0249 (11)	0.0013 (9)	0.0056 (8)	0.0021 (9)
C23	0.0301 (11)	0.0278 (12)	0.0323 (12)	0.0050 (10)	0.0041 (9)	0.0052 (9)
C24	0.0312 (12)	0.0268 (12)	0.0388 (13)	−0.0014 (10)	0.0023 (10)	−0.0018 (10)
C25	0.0213 (10)	0.0332 (13)	0.0262 (11)	−0.0010 (9)	0.0028 (8)	−0.0027 (9)
C26	0.0228 (11)	0.0367 (13)	0.0289 (12)	0.0011 (10)	0.0038 (9)	0.0016 (10)
C27	0.0271 (11)	0.0487 (15)	0.0270 (12)	0.0003 (11)	0.0007 (9)	0.0008 (10)
C28	0.0280 (11)	0.0235 (11)	0.0255 (11)	0.0008 (9)	−0.0023 (9)	−0.0024 (9)
C29	0.0261 (11)	0.0312 (12)	0.0265 (11)	−0.0024 (9)	0.0024 (9)	0.0092 (9)
C30	0.0294 (12)	0.0332 (13)	0.0325 (12)	−0.0028 (10)	0.0049 (10)	0.0045 (10)
C31	0.0448 (14)	0.0383 (14)	0.0317 (13)	−0.0102 (12)	−0.0009 (11)	0.0041 (10)
C32	0.0331 (13)	0.0523 (17)	0.0364 (14)	−0.0140 (12)	−0.0085 (10)	0.0134 (12)
C33	0.0247 (12)	0.0546 (17)	0.0375 (14)	0.0010 (11)	0.0010 (10)	0.0135 (12)
C34	0.0301 (12)	0.0417 (14)	0.0301 (12)	0.0024 (11)	0.0028 (10)	0.0067 (10)
C35	0.0431 (14)	0.0326 (14)	0.0567 (16)	0.0088 (12)	0.0122 (12)	0.0058 (12)
C36	0.082 (2)	0.058 (2)	0.0526 (18)	0.0103 (17)	0.0174 (16)	−0.0032 (15)

Geometric parameters (Å, º) top

S1—C1	1.746 (2)	C16—H16	0.9300
S1—C17	1.818 (2)	C17—C18	1.505 (3)
S2—C19	1.757 (2)	C17—H17A	0.9700
S2—C35	1.822 (2)	C17—H17B	0.9700
O1—C8	1.379 (3)	C18—H18A	0.9600
O1—C7	1.385 (2)	C18—H18B	0.9600
O2—C10	1.273 (2)	C18—H18C	0.9600
O2—H2O	0.92 (2)	C19—C26	1.350 (3)
O3—C10	1.243 (2)	C19—C20	1.448 (3)
O4—C26	1.380 (3)	C20—C25	1.387 (3)
O4—C25	1.386 (2)	C20—C21	1.397 (3)
O5—C28	1.279 (2)	C21—C22	1.390 (3)
O5—H5O	0.92 (2)	C21—H21	0.9300
O6—C28	1.249 (2)	C22—C23	1.402 (3)
C1—C8	1.353 (3)	C22—C29	1.493 (3)
C1—C2	1.443 (3)	C23—C24	1.391 (3)
C2—C7	1.388 (3)	C23—H23	0.9300
C2—C3	1.395 (3)	C24—C25	1.377 (3)
C3—C4	1.390 (3)	C24—H24	0.9300
C3—H3	0.9300	C26—C27	1.482 (3)
C4—C5	1.404 (3)	C27—C28	1.503 (3)
C4—C11	1.490 (3)	C27—H27A	0.9700
C5—C6	1.388 (3)	C27—H27B	0.9700
C5—H5	0.9300	C29—C30	1.392 (3)
C6—C7	1.376 (3)	C29—C34	1.397 (3)
C6—H6	0.9300	C30—C31	1.383 (3)
C8—C9	1.485 (3)	C30—H30	0.9300
C9—C10	1.507 (3)	C31—C32	1.385 (3)
C9—H9A	0.9700	C31—H31	0.9300
C9—H9B	0.9700	C32—C33	1.379 (3)
C11—C16	1.395 (3)	C32—H32	0.9300
C11—C12	1.396 (3)	C33—C34	1.382 (3)
C12—C13	1.382 (3)	C33—H33	0.9300
C12—H12	0.9300	C34—H34	0.9300
C13—C14	1.382 (3)	C35—C36	1.490 (4)
C13—H13	0.9300	C35—H35A	0.9700
C14—C15	1.380 (4)	C35—H35B	0.9700
C14—H14	0.9300	C36—H36A	0.9600
C15—C16	1.387 (3)	C36—H36B	0.9600
C15—H15	0.9300	C36—H36C	0.9600

C1—S1—C17	99.60 (10)	C17—C18—H18C	109.5
C19—S2—C35	101.98 (11)	H18A—C18—H18C	109.5
C8—O1—C7	105.57 (16)	H18B—C18—H18C	109.5
C10—O2—H2O	112 (2)	C26—C19—C20	106.23 (19)
C26—O4—C25	105.34 (16)	C26—C19—S2	124.28 (17)
C28—O5—H5O	115 (2)	C20—C19—S2	129.35 (16)
C8—C1—C2	106.20 (19)	C25—C20—C21	119.23 (19)
C8—C1—S1	126.92 (17)	C25—C20—C19	105.66 (18)
C2—C1—S1	126.88 (16)	C21—C20—C19	135.1 (2)
C7—C2—C3	119.26 (19)	C22—C21—C20	118.6 (2)
C7—C2—C1	105.91 (18)	C22—C21—H21	120.7
C3—C2—C1	134.8 (2)	C20—C21—H21	120.7
C4—C3—C2	119.0 (2)	C21—C22—C23	120.04 (19)
C4—C3—H3	120.5	C21—C22—C29	120.12 (19)
C2—C3—H3	120.5	C23—C22—C29	119.69 (19)
C3—C4—C5	119.69 (19)	C24—C23—C22	122.2 (2)
C3—C4—C11	119.8 (2)	C24—C23—H23	118.9
C5—C4—C11	120.5 (2)	C22—C23—H23	118.9
C6—C5—C4	122.2 (2)	C25—C24—C23	115.9 (2)
C6—C5—H5	118.9	C25—C24—H24	122.1
C4—C5—H5	118.9	C23—C24—H24	122.1
C7—C6—C5	116.4 (2)	C24—C25—O4	125.42 (19)
C7—C6—H6	121.8	C24—C25—C20	124.01 (19)
C5—C6—H6	121.8	O4—C25—C20	110.56 (18)
C6—C7—O1	126.2 (2)	C19—C26—O4	112.21 (18)
C6—C7—C2	123.5 (2)	C19—C26—C27	131.6 (2)
O1—C7—C2	110.25 (18)	O4—C26—C27	116.21 (19)
C1—C8—O1	112.04 (19)	C26—C27—C28	114.82 (18)
C1—C8—C9	131.7 (2)	C26—C27—H27A	108.6
O1—C8—C9	116.21 (18)	C28—C27—H27A	108.6
C8—C9—C10	115.85 (18)	C26—C27—H27B	108.6
C8—C9—H9A	108.3	C28—C27—H27B	108.6
C10—C9—H9A	108.3	H27A—C27—H27B	107.5
C8—C9—H9B	108.3	O6—C28—O5	124.23 (19)
C10—C9—H9B	108.3	O6—C28—C27	120.81 (18)
H9A—C9—H9B	107.4	O5—C28—C27	114.97 (18)
O3—C10—O2	123.9 (2)	C30—C29—C34	118.5 (2)
O3—C10—C9	118.97 (18)	C30—C29—C22	122.04 (19)
O2—C10—C9	117.10 (18)	C34—C29—C22	119.4 (2)
C16—C11—C12	118.3 (2)	C31—C30—C29	120.7 (2)
C16—C11—C4	120.7 (2)	C31—C30—H30	119.7
C12—C11—C4	120.99 (19)	C29—C30—H30	119.7
C13—C12—C11	120.9 (2)	C30—C31—C32	120.0 (2)
C13—C12—H12	119.6	C30—C31—H31	120.0
C11—C12—H12	119.6	C32—C31—H31	120.0
C12—C13—C14	120.3 (2)	C33—C32—C31	120.1 (2)
C12—C13—H13	119.9	C33—C32—H32	120.0
C14—C13—H13	119.9	C31—C32—H32	120.0
C15—C14—C13	119.6 (2)	C32—C33—C34	120.0 (2)
C15—C14—H14	120.2	C32—C33—H33	120.0
C13—C14—H14	120.2	C34—C33—H33	120.0
C14—C15—C16	120.4 (2)	C33—C34—C29	120.8 (2)
C14—C15—H15	119.8	C33—C34—H34	119.6
C16—C15—H15	119.8	C29—C34—H34	119.6
C15—C16—C11	120.5 (2)	C36—C35—S2	114.02 (19)
C15—C16—H16	119.7	C36—C35—H35A	108.7
C11—C16—H16	119.7	S2—C35—H35A	108.7
C18—C17—S1	113.11 (16)	C36—C35—H35B	108.7
C18—C17—H17A	109.0	S2—C35—H35B	108.7
S1—C17—H17A	109.0	H35A—C35—H35B	107.6
C18—C17—H17B	109.0	C35—C36—H36A	109.5
S1—C17—H17B	109.0	C35—C36—H36B	109.5
H17A—C17—H17B	107.8	H36A—C36—H36B	109.5
C17—C18—H18A	109.5	C35—C36—H36C	109.5
C17—C18—H18B	109.5	H36A—C36—H36C	109.5
H18A—C18—H18B	109.5	H36B—C36—H36C	109.5

C17—S1—C1—C8	−106.3 (2)	C35—S2—C19—C26	−99.5 (2)
C17—S1—C1—C2	73.8 (2)	C35—S2—C19—C20	85.5 (2)
C8—C1—C2—C7	−0.7 (2)	C26—C19—C20—C25	−0.1 (2)
S1—C1—C2—C7	179.23 (16)	S2—C19—C20—C25	175.61 (16)
C8—C1—C2—C3	178.9 (2)	C26—C19—C20—C21	−177.7 (2)
S1—C1—C2—C3	−1.2 (3)	S2—C19—C20—C21	−2.1 (4)
C7—C2—C3—C4	−0.3 (3)	C25—C20—C21—C22	−2.4 (3)
C1—C2—C3—C4	−179.8 (2)	C19—C20—C21—C22	175.0 (2)
C2—C3—C4—C5	0.1 (3)	C20—C21—C22—C23	2.9 (3)
C2—C3—C4—C11	−179.07 (18)	C20—C21—C22—C29	−172.70 (18)
C3—C4—C5—C6	0.0 (3)	C21—C22—C23—C24	−1.2 (3)
C11—C4—C5—C6	179.2 (2)	C29—C22—C23—C24	174.40 (19)
C4—C5—C6—C7	0.1 (3)	C22—C23—C24—C25	−1.0 (3)
C5—C6—C7—O1	−179.84 (19)	C23—C24—C25—O4	−176.59 (18)
C5—C6—C7—C2	−0.3 (3)	C23—C24—C25—C20	1.5 (3)
C8—O1—C7—C6	−179.2 (2)	C26—O4—C25—C24	177.8 (2)
C8—O1—C7—C2	1.2 (2)	C26—O4—C25—C20	−0.6 (2)
C3—C2—C7—C6	0.4 (3)	C21—C20—C25—C24	0.2 (3)
C1—C2—C7—C6	−180.0 (2)	C19—C20—C25—C24	−177.96 (19)
C3—C2—C7—O1	180.00 (17)	C21—C20—C25—O4	178.51 (17)
C1—C2—C7—O1	−0.3 (2)	C19—C20—C25—O4	0.4 (2)
C2—C1—C8—O1	1.5 (2)	C20—C19—C26—O4	−0.3 (2)
S1—C1—C8—O1	−178.41 (14)	S2—C19—C26—O4	−176.24 (14)
C2—C1—C8—C9	179.7 (2)	C20—C19—C26—C27	178.4 (2)
S1—C1—C8—C9	−0.2 (3)	S2—C19—C26—C27	2.5 (3)
C7—O1—C8—C1	−1.7 (2)	C25—O4—C26—C19	0.5 (2)
C7—O1—C8—C9	179.80 (17)	C25—O4—C26—C27	−178.42 (17)
C1—C8—C9—C10	122.9 (2)	C19—C26—C27—C28	102.0 (3)
O1—C8—C9—C10	−58.9 (3)	O4—C26—C27—C28	−79.3 (2)
C8—C9—C10—O3	160.6 (2)	C26—C27—C28—O6	2.4 (3)
C8—C9—C10—O2	−20.7 (3)	C26—C27—C28—O5	−177.9 (2)
C3—C4—C11—C16	136.0 (2)	C21—C22—C29—C30	−55.1 (3)
C5—C4—C11—C16	−43.2 (3)	C23—C22—C29—C30	129.3 (2)
C3—C4—C11—C12	−43.3 (3)	C21—C22—C29—C34	122.6 (2)
C5—C4—C11—C12	137.5 (2)	C23—C22—C29—C34	−53.0 (3)
C16—C11—C12—C13	0.4 (3)	C34—C29—C30—C31	0.4 (3)
C4—C11—C12—C13	179.7 (2)	C22—C29—C30—C31	178.1 (2)
C11—C12—C13—C14	−0.8 (3)	C29—C30—C31—C32	−1.5 (3)
C12—C13—C14—C15	0.5 (4)	C30—C31—C32—C33	1.4 (3)
C13—C14—C15—C16	0.1 (4)	C31—C32—C33—C34	−0.2 (4)
C14—C15—C16—C11	−0.5 (4)	C32—C33—C34—C29	−0.9 (3)
C12—C11—C16—C15	0.3 (3)	C30—C29—C34—C33	0.8 (3)
C4—C11—C16—C15	−179.1 (2)	C22—C29—C34—C33	−176.9 (2)
C1—S1—C17—C18	59.18 (19)	C19—S2—C35—C36	−86.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O3ⁱ	0.92 (2)	1.73 (2)	2.643 (2)	174 (3)
O5—H5O···O6ⁱⁱ	0.92 (2)	1.68 (2)	2.602 (2)	175 (4)
C6—H6···O5ⁱⁱⁱ	0.93	2.57	3.461 (3)	161
C24—H24···O3	0.93	2.57	3.480 (3)	165
C12—H12···Cg4^iv	0.93	2.91	3.561 (3)	131
C30—H30···Cg2^v	0.93	2.80	3.506 (3)	133

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z; (iv) x+1/2, −y+3/2, z+1/2; (v) x−1/2, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆O₃S
M_r	312.37
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	12.4250 (7), 11.7823 (7), 21.2426 (13)
β (°)	93.021 (1)
V (Å³)	3105.5 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.40 × 0.40 × 0.20

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.918, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	18961, 7033, 4490
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.116, 1.02
No. of reflections	7033
No. of parameters	405
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.35

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O3ⁱ	0.92 (2)	1.73 (2)	2.643 (2)	174 (3)
O5—H5O···O6ⁱⁱ	0.92 (2)	1.68 (2)	2.602 (2)	175 (4)
C6—H6···O5ⁱⁱⁱ	0.93	2.57	3.461 (3)	161.1
C24—H24···O3	0.93	2.57	3.480 (3)	164.7
C12—H12···Cg4^iv	0.93	2.91	3.561 (3)	130.8
C30—H30···Cg2^v	0.93	2.80	3.506 (3)	133.3

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z; (iv) x+1/2, −y+3/2, z+1/2; (v) x−1/2, −y+3/2, z−1/2.

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007a). Acta Cryst. E63, o3468. Web of Science CSD CrossRef IUCr Journals Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007b). Acta Cryst. E63, o4331. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Howlett, D. R., Perry, A. E., Godfrey, F., Swatton, J. E., Jennings, K. H., Spitzfaden, C., Wadsworth, H., Wood, S. J. & Markwell, R. E. (1999). Biochem. J. 340, 283–289. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Twyman, L. J. & Allsop, D. (1999). Tetrahedron Lett. 40, 9383–9384. Web of Science CrossRef CAS Google Scholar

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Volume 65| Part 9| September 2009| Page o2212

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