Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049926/sj2376sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049926/sj2376Isup2.hkl |
CCDC reference: 667366
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.041
- wR factor = 0.113
- Data-to-parameter ratio = 16.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT142_ALERT_4_C su on b - Axis Small or Missing (x 100000) ..... 10 Ang. PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 100 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 5
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Ethyl 2-[5-(4-bromophenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate (729 mg, 1.8 mmol) was added to a solution of potassium hydroxide (561 mg, 10.0 mmol) in water (15 ml) and methanol (15 ml), and the mixture was heated at 343 K for 4 h, then cooled. Water was added, and the solution was washed with chloroform. 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 87%, m.p. 476–477 K; Rf = 0.81 (ethyl acetate)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a dilute solution of the title compound in acetone at room temperature.
H atoms of the carboxyl groups were found in a difference Fourier map and refined freely with isotropic displacement parameters. The other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å for aromatic H atoms, 0.96 Å for methyl H atoms and 0.97 Å for methylene H atoms, and with Uiso(H) = 1.2Ueq(C) for aromatic and methylene H atoms and Uiso(H) =1.5Ueq(C) for methyl H atoms.
As part of our ongoing studies on the synthesis and structure of 2-(5-aryl-3-methylsulfanyl-1-benzofuran-2-yl)acetic acid derivatives, we have recently described ethyl 2-[5-(4-hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate (Choi et al., 2006) and 2-(3-methylsulfanyl-5-phenyl-1-benzofuran-2-yl)acetic acid (Choi et al., 2007). Herein we report the molecular and crystal structure of the title compound, 2-[5-(4-bromophenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetic acid which crystallizes with two unique molecules, A & B, in the asymmetric unit (Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.019 Å, for A, and 0.013 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 plane of the benzofuran and the plane of the 4-bromophenyl ring are 50.22 (8)° in A and 35.4 (1)° in B, respectively. The methyl groups (S1—CH3 in A and S2—CH3 in B) are tilted towards the plane of the benzofuran systems [99.5 (2)°, A and 100.8 (2)°, B]. The molecular packing (Fig. 2) is stabilized by a C—H···O hydrogen bond (Table 1 and Fig. 2), between a methyl H and the C═O unit, i.e. C17—H17B···O2i. Further stability comes from a weak Br···O interaction (Fig. 2) (Politzer et al., 2007) between the bromine atom and the oxygen of a neighbouring C═O unit, with a Br2···O6ii distance of 3.284 (2) Å (Symmetry codes as in Fig. 2). Classical inversion-related O3—H35···O5i and O6—H36···O2i hydrogen bonds link the carboxyl groups from two symmetry-independent molecules (Table 1 and Fig. 2).
For the crystal structures of similar benzofuran compounds, see: Choi et al. (2006, 2007). For a review of halogen bonding, see: Politzer, et al. (2007).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C17H13BrO3S | Z = 4 |
Mr = 377.24 | F(000) = 760 |
Triclinic, P1 | Dx = 1.580 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7531 (1) Å | Cell parameters from 6878 reflections |
b = 10.8299 (1) Å | θ = 2.4–26.1° |
c = 19.5621 (2) Å | µ = 2.73 mm−1 |
α = 104.131 (1)° | T = 298 K |
β = 93.631 (1)° | Block, colourless |
γ = 92.870 (1)° | 0.40 × 0.22 × 0.17 mm |
V = 1585.99 (3) Å3 |
Bruker SMART CCD diffractometer | 6889 independent reflections |
Radiation source: fine-focus sealed tube | 5128 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.0°, θmin = 1.1° |
φ and ω scans | h = −9→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | k = −13→13 |
Tmin = 0.482, Tmax = 0.637 | l = −24→24 |
29666 measured reflections |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0468P)2 + 1.5959P] where P = (Fo2 + 2Fc2)/3 |
6889 reflections | (Δ/σ)max < 0.001 |
407 parameters | Δρmax = 0.98 e Å−3 |
0 restraints | Δρmin = −0.82 e Å−3 |
C17H13BrO3S | γ = 92.870 (1)° |
Mr = 377.24 | V = 1585.99 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 7.7531 (1) Å | Mo Kα radiation |
b = 10.8299 (1) Å | µ = 2.73 mm−1 |
c = 19.5621 (2) Å | T = 298 K |
α = 104.131 (1)° | 0.40 × 0.22 × 0.17 mm |
β = 93.631 (1)° |
Bruker SMART CCD diffractometer | 6889 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 5128 reflections with I > 2σ(I) |
Tmin = 0.482, Tmax = 0.637 | Rint = 0.019 |
29666 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.98 e Å−3 |
6889 reflections | Δρmin = −0.82 e Å−3 |
407 parameters |
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 | ||
Br1 | 0.60522 (6) | 0.18122 (4) | 0.49776 (2) | 0.07480 (15) | |
Br2 | 0.76860 (7) | 0.72243 (5) | 0.72068 (2) | 0.08609 (17) | |
S1 | 1.25540 (10) | 0.03549 (8) | 0.06637 (5) | 0.0514 (2) | |
S2 | 1.33833 (11) | 0.73058 (10) | 0.28286 (5) | 0.0626 (2) | |
O1 | 0.9335 (3) | −0.27217 (19) | 0.00294 (10) | 0.0443 (5) | |
O2 | 1.3988 (3) | −0.2684 (2) | −0.12497 (12) | 0.0577 (6) | |
O3 | 1.3216 (4) | −0.3477 (3) | −0.03577 (14) | 0.0674 (7) | |
H35 | 1.406 (8) | −0.389 (5) | −0.045 (3) | 0.13 (2)* | |
O4 | 0.9304 (3) | 0.5069 (2) | 0.18828 (11) | 0.0527 (5) | |
O5 | 1.4056 (3) | 0.4862 (2) | 0.06232 (12) | 0.0558 (6) | |
O6 | 1.3168 (4) | 0.3951 (3) | 0.14457 (13) | 0.0630 (7) | |
H36 | 1.391 (6) | 0.358 (4) | 0.135 (2) | 0.087 (16)* | |
C1 | 1.0950 (4) | −0.0895 (3) | 0.05385 (15) | 0.0388 (6) | |
C2 | 0.9754 (3) | −0.1131 (3) | 0.10368 (15) | 0.0378 (6) | |
C3 | 0.9381 (4) | −0.0489 (3) | 0.17147 (14) | 0.0394 (6) | |
H3 | 0.9978 | 0.0282 | 0.1945 | 0.047* | |
C4 | 0.8100 (4) | −0.1024 (3) | 0.20400 (15) | 0.0404 (6) | |
C5 | 0.7238 (4) | −0.2198 (3) | 0.16914 (16) | 0.0457 (7) | |
H5 | 0.6416 | −0.2561 | 0.1923 | 0.055* | |
C6 | 0.7572 (4) | −0.2834 (3) | 0.10136 (16) | 0.0467 (7) | |
H6 | 0.6983 | −0.3606 | 0.0781 | 0.056* | |
C7 | 0.8821 (4) | −0.2261 (3) | 0.07034 (14) | 0.0394 (6) | |
C8 | 1.0620 (4) | −0.1855 (3) | −0.00486 (15) | 0.0413 (6) | |
C9 | 0.7624 (4) | −0.0338 (3) | 0.27527 (15) | 0.0430 (6) | |
C10 | 0.7279 (5) | 0.0940 (3) | 0.28954 (17) | 0.0544 (8) | |
H10 | 0.7366 | 0.1374 | 0.2542 | 0.065* | |
C11 | 0.6808 (5) | 0.1584 (3) | 0.35513 (18) | 0.0584 (8) | |
H11 | 0.6566 | 0.2439 | 0.3637 | 0.070* | |
C12 | 0.6703 (4) | 0.0941 (3) | 0.40722 (16) | 0.0511 (8) | |
C13 | 0.7044 (4) | −0.0320 (3) | 0.39538 (17) | 0.0547 (8) | |
H13 | 0.6977 | −0.0741 | 0.4314 | 0.066* | |
C14 | 0.7491 (4) | −0.0962 (3) | 0.32900 (16) | 0.0501 (7) | |
H14 | 0.7704 | −0.1822 | 0.3205 | 0.060* | |
C15 | 1.1362 (4) | −0.2090 (3) | −0.07483 (16) | 0.0470 (7) | |
H15A | 1.1598 | −0.1275 | −0.0859 | 0.056* | |
H15B | 1.0499 | −0.2580 | −0.1105 | 0.056* | |
C16 | 1.2989 (4) | −0.2782 (3) | −0.07950 (15) | 0.0430 (6) | |
C17 | 1.4235 (5) | −0.0275 (5) | 0.1136 (3) | 0.0887 (14) | |
H17A | 1.3829 | −0.0393 | 0.1571 | 0.133* | |
H17B | 1.5241 | 0.0313 | 0.1237 | 0.133* | |
H17C | 1.4530 | −0.1079 | 0.0851 | 0.133* | |
C18 | 1.1413 (4) | 0.6404 (3) | 0.25681 (16) | 0.0467 (7) | |
C19 | 1.0116 (4) | 0.6135 (3) | 0.30190 (15) | 0.0413 (6) | |
C20 | 0.9929 (4) | 0.6474 (3) | 0.37435 (15) | 0.0428 (6) | |
H20 | 1.0772 | 0.7006 | 0.4051 | 0.051* | |
C21 | 0.8478 (4) | 0.6011 (3) | 0.39999 (15) | 0.0455 (7) | |
C22 | 0.7219 (4) | 0.5223 (3) | 0.35249 (18) | 0.0576 (8) | |
H22 | 0.6235 | 0.4931 | 0.3702 | 0.069* | |
C23 | 0.7373 (5) | 0.4859 (4) | 0.28023 (18) | 0.0608 (9) | |
H23 | 0.6527 | 0.4335 | 0.2492 | 0.073* | |
C24 | 0.8854 (4) | 0.5322 (3) | 0.25728 (16) | 0.0475 (7) | |
C25 | 1.0861 (4) | 0.5761 (3) | 0.19068 (16) | 0.0467 (7) | |
C26 | 0.8272 (4) | 0.6325 (3) | 0.47745 (16) | 0.0467 (7) | |
C27 | 0.8862 (4) | 0.7505 (3) | 0.52105 (16) | 0.0520 (8) | |
H27 | 0.9382 | 0.8116 | 0.5015 | 0.062* | |
C28 | 0.8687 (5) | 0.7789 (3) | 0.59368 (18) | 0.0584 (8) | |
H28 | 0.9078 | 0.8584 | 0.6224 | 0.070* | |
C29 | 0.7931 (5) | 0.6879 (4) | 0.62205 (17) | 0.0578 (9) | |
C30 | 0.7355 (5) | 0.5696 (4) | 0.58056 (19) | 0.0605 (9) | |
H30 | 0.6859 | 0.5083 | 0.6007 | 0.073* | |
C31 | 0.7523 (5) | 0.5428 (3) | 0.50844 (18) | 0.0576 (8) | |
H31 | 0.7125 | 0.4630 | 0.4802 | 0.069* | |
C32 | 1.1614 (4) | 0.5649 (3) | 0.12150 (16) | 0.0518 (8) | |
H32A | 1.2035 | 0.6493 | 0.1188 | 0.062* | |
H32B | 1.0700 | 0.5345 | 0.0841 | 0.062* | |
C33 | 1.3073 (4) | 0.4775 (3) | 0.10812 (14) | 0.0415 (6) | |
C34 | 1.2640 (6) | 0.8890 (4) | 0.3101 (3) | 0.0804 (12) | |
H34A | 1.1966 | 0.9078 | 0.2715 | 0.121* | |
H34B | 1.3620 | 0.9499 | 0.3241 | 0.121* | |
H34C | 1.1939 | 0.8938 | 0.3493 | 0.121* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0754 (3) | 0.0850 (3) | 0.0525 (2) | −0.0104 (2) | 0.02318 (18) | −0.00634 (18) |
Br2 | 0.0983 (3) | 0.1191 (4) | 0.0429 (2) | 0.0032 (3) | 0.0189 (2) | 0.0216 (2) |
S1 | 0.0423 (4) | 0.0513 (4) | 0.0666 (5) | −0.0002 (3) | 0.0061 (4) | 0.0262 (4) |
S2 | 0.0398 (4) | 0.0817 (6) | 0.0665 (5) | 0.0022 (4) | 0.0152 (4) | 0.0164 (5) |
O1 | 0.0474 (12) | 0.0433 (11) | 0.0421 (11) | 0.0041 (9) | 0.0105 (9) | 0.0083 (8) |
O2 | 0.0580 (14) | 0.0611 (14) | 0.0626 (14) | 0.0147 (11) | 0.0258 (11) | 0.0244 (11) |
O3 | 0.0770 (18) | 0.0798 (18) | 0.0624 (15) | 0.0411 (15) | 0.0278 (13) | 0.0375 (13) |
O4 | 0.0582 (14) | 0.0560 (13) | 0.0403 (11) | 0.0047 (11) | 0.0111 (10) | 0.0031 (9) |
O5 | 0.0593 (14) | 0.0645 (14) | 0.0569 (13) | 0.0217 (11) | 0.0290 (11) | 0.0306 (11) |
O6 | 0.0748 (18) | 0.0715 (16) | 0.0590 (15) | 0.0333 (14) | 0.0339 (13) | 0.0346 (13) |
C1 | 0.0353 (14) | 0.0411 (15) | 0.0443 (15) | 0.0077 (11) | 0.0068 (12) | 0.0170 (12) |
C2 | 0.0332 (14) | 0.0406 (15) | 0.0422 (14) | 0.0043 (11) | 0.0034 (11) | 0.0148 (12) |
C3 | 0.0388 (15) | 0.0400 (15) | 0.0401 (14) | 0.0029 (12) | 0.0010 (12) | 0.0117 (12) |
C4 | 0.0396 (15) | 0.0446 (16) | 0.0399 (14) | 0.0094 (12) | 0.0057 (12) | 0.0139 (12) |
C5 | 0.0409 (16) | 0.0488 (17) | 0.0508 (17) | 0.0038 (13) | 0.0128 (13) | 0.0162 (14) |
C6 | 0.0452 (17) | 0.0413 (16) | 0.0529 (17) | −0.0023 (13) | 0.0079 (14) | 0.0105 (13) |
C7 | 0.0397 (15) | 0.0419 (15) | 0.0372 (14) | 0.0073 (12) | 0.0061 (11) | 0.0093 (12) |
C8 | 0.0413 (16) | 0.0433 (15) | 0.0453 (15) | 0.0128 (12) | 0.0112 (12) | 0.0186 (13) |
C9 | 0.0374 (15) | 0.0530 (17) | 0.0406 (15) | 0.0062 (13) | 0.0052 (12) | 0.0140 (13) |
C10 | 0.070 (2) | 0.0508 (18) | 0.0448 (17) | 0.0076 (16) | 0.0078 (15) | 0.0150 (14) |
C11 | 0.069 (2) | 0.0480 (18) | 0.0548 (19) | 0.0068 (16) | 0.0102 (17) | 0.0042 (15) |
C12 | 0.0441 (17) | 0.063 (2) | 0.0410 (16) | −0.0003 (14) | 0.0096 (13) | 0.0020 (14) |
C13 | 0.0520 (19) | 0.072 (2) | 0.0450 (17) | 0.0044 (16) | 0.0122 (14) | 0.0217 (16) |
C14 | 0.0503 (18) | 0.0548 (18) | 0.0506 (17) | 0.0131 (14) | 0.0132 (14) | 0.0190 (14) |
C15 | 0.0512 (18) | 0.0527 (17) | 0.0426 (15) | 0.0147 (14) | 0.0102 (13) | 0.0182 (13) |
C16 | 0.0505 (17) | 0.0404 (15) | 0.0404 (15) | 0.0080 (13) | 0.0119 (13) | 0.0114 (12) |
C17 | 0.057 (2) | 0.092 (3) | 0.126 (4) | −0.009 (2) | −0.028 (2) | 0.056 (3) |
C18 | 0.0409 (16) | 0.0550 (18) | 0.0450 (16) | 0.0101 (13) | 0.0128 (13) | 0.0100 (13) |
C19 | 0.0365 (15) | 0.0447 (15) | 0.0432 (15) | 0.0091 (12) | 0.0116 (12) | 0.0084 (12) |
C20 | 0.0400 (15) | 0.0469 (16) | 0.0399 (15) | 0.0054 (12) | 0.0070 (12) | 0.0065 (12) |
C21 | 0.0444 (17) | 0.0496 (17) | 0.0429 (16) | 0.0065 (13) | 0.0110 (13) | 0.0097 (13) |
C22 | 0.0489 (19) | 0.067 (2) | 0.0546 (19) | −0.0065 (16) | 0.0157 (15) | 0.0094 (16) |
C23 | 0.054 (2) | 0.069 (2) | 0.0516 (19) | −0.0123 (17) | 0.0082 (15) | 0.0011 (16) |
C24 | 0.0515 (18) | 0.0481 (17) | 0.0407 (15) | 0.0061 (14) | 0.0102 (13) | 0.0046 (13) |
C25 | 0.0475 (17) | 0.0493 (17) | 0.0460 (16) | 0.0162 (14) | 0.0160 (13) | 0.0112 (13) |
C26 | 0.0427 (16) | 0.0531 (18) | 0.0464 (16) | 0.0085 (13) | 0.0137 (13) | 0.0126 (14) |
C27 | 0.0568 (19) | 0.0534 (18) | 0.0465 (17) | 0.0010 (15) | 0.0106 (14) | 0.0128 (14) |
C28 | 0.063 (2) | 0.063 (2) | 0.0476 (18) | 0.0027 (17) | 0.0095 (16) | 0.0091 (16) |
C29 | 0.057 (2) | 0.080 (2) | 0.0408 (17) | 0.0138 (18) | 0.0131 (15) | 0.0187 (17) |
C30 | 0.064 (2) | 0.068 (2) | 0.057 (2) | 0.0071 (18) | 0.0176 (17) | 0.0276 (18) |
C31 | 0.063 (2) | 0.0557 (19) | 0.0552 (19) | 0.0024 (16) | 0.0165 (16) | 0.0135 (15) |
C32 | 0.060 (2) | 0.0585 (19) | 0.0417 (16) | 0.0217 (16) | 0.0171 (14) | 0.0144 (14) |
C33 | 0.0471 (16) | 0.0445 (16) | 0.0335 (14) | 0.0076 (13) | 0.0082 (12) | 0.0085 (12) |
C34 | 0.065 (3) | 0.069 (3) | 0.105 (3) | −0.006 (2) | −0.009 (2) | 0.024 (2) |
Br1—C12 | 1.904 (3) | C13—H13 | 0.9300 |
Br2—C29 | 1.897 (3) | C14—H14 | 0.9300 |
Br2—O6i | 3.284 (2) | C15—C16 | 1.496 (4) |
S1—C1 | 1.752 (3) | C15—H15A | 0.9700 |
S1—C17 | 1.806 (4) | C15—H15B | 0.9700 |
S2—C18 | 1.748 (3) | C17—H17A | 0.9600 |
S2—C34 | 1.804 (4) | C17—H17B | 0.9600 |
O1—C8 | 1.376 (3) | C17—H17C | 0.9600 |
O1—C7 | 1.382 (3) | C18—C25 | 1.342 (4) |
O2—C16 | 1.236 (3) | C18—C19 | 1.443 (4) |
O3—C16 | 1.279 (4) | C19—C24 | 1.387 (4) |
O3—H35 | 0.82 (6) | C19—C20 | 1.393 (4) |
O4—C25 | 1.381 (4) | C20—C21 | 1.381 (4) |
O4—C24 | 1.381 (3) | C20—H20 | 0.9300 |
O5—C33 | 1.230 (3) | C21—C22 | 1.399 (5) |
O6—C33 | 1.273 (4) | C21—C26 | 1.490 (4) |
O6—H36 | 0.73 (5) | C22—C23 | 1.386 (5) |
C1—C8 | 1.348 (4) | C22—H22 | 0.9300 |
C1—C2 | 1.445 (4) | C23—C24 | 1.375 (5) |
C2—C7 | 1.382 (4) | C23—H23 | 0.9300 |
C2—C3 | 1.394 (4) | C25—C32 | 1.488 (4) |
C3—C4 | 1.388 (4) | C26—C31 | 1.387 (4) |
C3—H3 | 0.9300 | C26—C27 | 1.389 (4) |
C4—C5 | 1.401 (4) | C27—C28 | 1.395 (4) |
C4—C9 | 1.490 (4) | C27—H27 | 0.9300 |
C5—C6 | 1.384 (4) | C28—C29 | 1.368 (5) |
C5—H5 | 0.9300 | C28—H28 | 0.9300 |
C6—C7 | 1.374 (4) | C29—C30 | 1.374 (5) |
C6—H6 | 0.9300 | C30—C31 | 1.385 (5) |
C8—C15 | 1.488 (4) | C30—H30 | 0.9300 |
C9—C10 | 1.386 (4) | C31—H31 | 0.9300 |
C9—C14 | 1.388 (4) | C32—C33 | 1.506 (4) |
C10—C11 | 1.384 (4) | C32—H32A | 0.9700 |
C10—H10 | 0.9300 | C32—H32B | 0.9700 |
C11—C12 | 1.372 (5) | C34—H34A | 0.9600 |
C11—H11 | 0.9300 | C34—H34B | 0.9600 |
C12—C13 | 1.371 (5) | C34—H34C | 0.9600 |
C13—C14 | 1.389 (4) | ||
C1—S1—C17 | 99.5 (2) | S1—C17—H17C | 109.5 |
C18—S2—C34 | 100.8 (2) | H17A—C17—H17C | 109.5 |
C8—O1—C7 | 105.4 (2) | H17B—C17—H17C | 109.5 |
C16—O3—H35 | 109 (4) | C25—C18—C19 | 106.5 (3) |
C25—O4—C24 | 105.5 (2) | C25—C18—S2 | 126.2 (2) |
C33—O6—H36 | 110 (4) | C19—C18—S2 | 127.2 (2) |
C8—C1—C2 | 106.2 (2) | C24—C19—C20 | 119.2 (3) |
C8—C1—S1 | 126.0 (2) | C24—C19—C18 | 105.6 (3) |
C2—C1—S1 | 127.8 (2) | C20—C19—C18 | 135.1 (3) |
C7—C2—C3 | 119.3 (2) | C21—C20—C19 | 119.3 (3) |
C7—C2—C1 | 105.6 (2) | C21—C20—H20 | 120.4 |
C3—C2—C1 | 135.0 (3) | C19—C20—H20 | 120.4 |
C4—C3—C2 | 118.7 (3) | C20—C21—C22 | 119.2 (3) |
C4—C3—H3 | 120.7 | C20—C21—C26 | 120.4 (3) |
C2—C3—H3 | 120.7 | C22—C21—C26 | 120.4 (3) |
C3—C4—C5 | 119.9 (3) | C23—C22—C21 | 122.9 (3) |
C3—C4—C9 | 120.0 (3) | C23—C22—H22 | 118.5 |
C5—C4—C9 | 120.1 (3) | C21—C22—H22 | 118.5 |
C6—C5—C4 | 122.1 (3) | C24—C23—C22 | 115.8 (3) |
C6—C5—H5 | 119.0 | C24—C23—H23 | 122.1 |
C4—C5—H5 | 119.0 | C22—C23—H23 | 122.1 |
C7—C6—C5 | 116.3 (3) | C23—C24—O4 | 126.1 (3) |
C7—C6—H6 | 121.8 | C23—C24—C19 | 123.5 (3) |
C5—C6—H6 | 121.8 | O4—C24—C19 | 110.4 (3) |
C6—C7—C2 | 123.7 (3) | C18—C25—O4 | 112.1 (2) |
C6—C7—O1 | 125.8 (3) | C18—C25—C32 | 132.4 (3) |
C2—C7—O1 | 110.6 (2) | O4—C25—C32 | 115.6 (3) |
C1—C8—O1 | 112.1 (2) | C31—C26—C27 | 118.0 (3) |
C1—C8—C15 | 131.0 (3) | C31—C26—C21 | 120.6 (3) |
O1—C8—C15 | 116.9 (3) | C27—C26—C21 | 121.4 (3) |
C10—C9—C14 | 118.1 (3) | C26—C27—C28 | 121.2 (3) |
C10—C9—C4 | 120.9 (3) | C26—C27—H27 | 119.4 |
C14—C9—C4 | 121.0 (3) | C28—C27—H27 | 119.4 |
C11—C10—C9 | 121.5 (3) | C29—C28—C27 | 119.0 (3) |
C11—C10—H10 | 119.2 | C29—C28—H28 | 120.5 |
C9—C10—H10 | 119.2 | C27—C28—H28 | 120.5 |
C12—C11—C10 | 118.8 (3) | C28—C29—C30 | 121.3 (3) |
C12—C11—H11 | 120.6 | C28—C29—Br2 | 120.2 (3) |
C10—C11—H11 | 120.6 | C30—C29—Br2 | 118.4 (3) |
C13—C12—C11 | 121.4 (3) | C29—C30—C31 | 119.2 (3) |
C13—C12—Br1 | 119.2 (2) | C29—C30—H30 | 120.4 |
C11—C12—Br1 | 119.4 (3) | C31—C30—H30 | 120.4 |
C12—C13—C14 | 119.2 (3) | C30—C31—C26 | 121.4 (3) |
C12—C13—H13 | 120.4 | C30—C31—H31 | 119.3 |
C14—C13—H13 | 120.4 | C26—C31—H31 | 119.3 |
C9—C14—C13 | 120.9 (3) | C25—C32—C33 | 115.1 (3) |
C9—C14—H14 | 119.6 | C25—C32—H32A | 108.5 |
C13—C14—H14 | 119.6 | C33—C32—H32A | 108.5 |
C8—C15—C16 | 114.9 (2) | C25—C32—H32B | 108.5 |
C8—C15—H15A | 108.6 | C33—C32—H32B | 108.5 |
C16—C15—H15A | 108.6 | H32A—C32—H32B | 107.5 |
C8—C15—H15B | 108.6 | O5—C33—O6 | 124.0 (3) |
C16—C15—H15B | 108.6 | O5—C33—C32 | 119.5 (3) |
H15A—C15—H15B | 107.5 | O6—C33—C32 | 116.4 (3) |
O2—C16—O3 | 124.4 (3) | S2—C34—H34A | 109.5 |
O2—C16—C15 | 119.7 (3) | S2—C34—H34B | 109.5 |
O3—C16—C15 | 115.9 (3) | H34A—C34—H34B | 109.5 |
S1—C17—H17A | 109.5 | S2—C34—H34C | 109.5 |
S1—C17—H17B | 109.5 | H34A—C34—H34C | 109.5 |
H17A—C17—H17B | 109.5 | H34B—C34—H34C | 109.5 |
C17—S1—C1—C8 | −97.1 (3) | C34—S2—C18—C25 | 113.1 (3) |
C17—S1—C1—C2 | 81.3 (3) | C34—S2—C18—C19 | −71.2 (3) |
C8—C1—C2—C7 | 1.8 (3) | C25—C18—C19—C24 | 0.1 (3) |
S1—C1—C2—C7 | −176.9 (2) | S2—C18—C19—C24 | −176.3 (2) |
C8—C1—C2—C3 | −177.0 (3) | C25—C18—C19—C20 | 178.4 (3) |
S1—C1—C2—C3 | 4.3 (5) | S2—C18—C19—C20 | 2.0 (5) |
C7—C2—C3—C4 | 1.3 (4) | C24—C19—C20—C21 | −1.0 (4) |
C1—C2—C3—C4 | 180.0 (3) | C18—C19—C20—C21 | −179.1 (3) |
C2—C3—C4—C5 | 1.3 (4) | C19—C20—C21—C22 | −0.7 (4) |
C2—C3—C4—C9 | −177.6 (2) | C19—C20—C21—C26 | 178.0 (3) |
C3—C4—C5—C6 | −2.5 (4) | C20—C21—C22—C23 | 1.3 (5) |
C9—C4—C5—C6 | 176.4 (3) | C26—C21—C22—C23 | −177.4 (3) |
C4—C5—C6—C7 | 1.1 (4) | C21—C22—C23—C24 | −0.1 (6) |
C5—C6—C7—C2 | 1.6 (4) | C22—C23—C24—O4 | 178.6 (3) |
C5—C6—C7—O1 | −179.0 (3) | C22—C23—C24—C19 | −1.8 (5) |
C3—C2—C7—C6 | −2.8 (4) | C25—O4—C24—C23 | 178.5 (3) |
C1—C2—C7—C6 | 178.2 (3) | C25—O4—C24—C19 | −1.1 (3) |
C3—C2—C7—O1 | 177.7 (2) | C20—C19—C24—C23 | 2.4 (5) |
C1—C2—C7—O1 | −1.4 (3) | C18—C19—C24—C23 | −179.0 (3) |
C8—O1—C7—C6 | −179.1 (3) | C20—C19—C24—O4 | −178.0 (3) |
C8—O1—C7—C2 | 0.4 (3) | C18—C19—C24—O4 | 0.6 (3) |
C2—C1—C8—O1 | −1.7 (3) | C19—C18—C25—O4 | −0.8 (3) |
S1—C1—C8—O1 | 177.03 (19) | S2—C18—C25—O4 | 175.7 (2) |
C2—C1—C8—C15 | 176.2 (3) | C19—C18—C25—C32 | −179.9 (3) |
S1—C1—C8—C15 | −5.1 (5) | S2—C18—C25—C32 | −3.4 (5) |
C7—O1—C8—C1 | 0.8 (3) | C24—O4—C25—C18 | 1.2 (3) |
C7—O1—C8—C15 | −177.4 (2) | C24—O4—C25—C32 | −179.6 (3) |
C3—C4—C9—C10 | 49.0 (4) | C20—C21—C26—C31 | −143.1 (3) |
C5—C4—C9—C10 | −129.9 (3) | C22—C21—C26—C31 | 35.7 (5) |
C3—C4—C9—C14 | −131.8 (3) | C20—C21—C26—C27 | 35.2 (4) |
C5—C4—C9—C14 | 49.3 (4) | C22—C21—C26—C27 | −146.0 (3) |
C14—C9—C10—C11 | −0.3 (5) | C31—C26—C27—C28 | −0.8 (5) |
C4—C9—C10—C11 | 178.9 (3) | C21—C26—C27—C28 | −179.2 (3) |
C9—C10—C11—C12 | 0.8 (5) | C26—C27—C28—C29 | 0.5 (5) |
C10—C11—C12—C13 | −0.4 (5) | C27—C28—C29—C30 | 0.4 (5) |
C10—C11—C12—Br1 | −179.9 (3) | C27—C28—C29—Br2 | 179.5 (3) |
C11—C12—C13—C14 | −0.5 (5) | C28—C29—C30—C31 | −0.9 (6) |
Br1—C12—C13—C14 | 178.9 (2) | Br2—C29—C30—C31 | 180.0 (3) |
C10—C9—C14—C13 | −0.7 (5) | C29—C30—C31—C26 | 0.5 (5) |
C4—C9—C14—C13 | −179.9 (3) | C27—C26—C31—C30 | 0.3 (5) |
C12—C13—C14—C9 | 1.1 (5) | C21—C26—C31—C30 | 178.7 (3) |
C1—C8—C15—C16 | 86.6 (4) | C18—C25—C32—C33 | 77.1 (4) |
O1—C8—C15—C16 | −95.7 (3) | O4—C25—C32—C33 | −102.0 (3) |
C8—C15—C16—O2 | −157.5 (3) | C25—C32—C33—O5 | −161.6 (3) |
C8—C15—C16—O3 | 24.2 (4) | C25—C32—C33—O6 | 20.5 (4) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H35···O5ii | 0.82 (6) | 1.84 (6) | 2.659 (3) | 176 (6) |
O6—H36···O2ii | 0.73 (5) | 1.93 (5) | 2.655 (3) | 172 (5) |
C17—H17B···O2ii | 0.96 | 2.60 | 3.374 (5) | 138 |
Symmetry code: (ii) −x+3, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C17H13BrO3S |
Mr | 377.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 7.7531 (1), 10.8299 (1), 19.5621 (2) |
α, β, γ (°) | 104.131 (1), 93.631 (1), 92.870 (1) |
V (Å3) | 1585.99 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.73 |
Crystal size (mm) | 0.40 × 0.22 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.482, 0.637 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29666, 6889, 5128 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.113, 1.02 |
No. of reflections | 6889 |
No. of parameters | 407 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.98, −0.82 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H35···O5i | 0.82 (6) | 1.84 (6) | 2.659 (3) | 176 (6) |
O6—H36···O2i | 0.73 (5) | 1.93 (5) | 2.655 (3) | 172 (5) |
C17—H17B···O2i | 0.96 | 2.60 | 3.374 (5) | 137.8 |
Symmetry code: (i) −x+3, −y, −z. |
As part of our ongoing studies on the synthesis and structure of 2-(5-aryl-3-methylsulfanyl-1-benzofuran-2-yl)acetic acid derivatives, we have recently described ethyl 2-[5-(4-hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate (Choi et al., 2006) and 2-(3-methylsulfanyl-5-phenyl-1-benzofuran-2-yl)acetic acid (Choi et al., 2007). Herein we report the molecular and crystal structure of the title compound, 2-[5-(4-bromophenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetic acid which crystallizes with two unique molecules, A & B, in the asymmetric unit (Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.019 Å, for A, and 0.013 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 plane of the benzofuran and the plane of the 4-bromophenyl ring are 50.22 (8)° in A and 35.4 (1)° in B, respectively. The methyl groups (S1—CH3 in A and S2—CH3 in B) are tilted towards the plane of the benzofuran systems [99.5 (2)°, A and 100.8 (2)°, B]. The molecular packing (Fig. 2) is stabilized by a C—H···O hydrogen bond (Table 1 and Fig. 2), between a methyl H and the C═O unit, i.e. C17—H17B···O2i. Further stability comes from a weak Br···O interaction (Fig. 2) (Politzer et al., 2007) between the bromine atom and the oxygen of a neighbouring C═O unit, with a Br2···O6ii distance of 3.284 (2) Å (Symmetry codes as in Fig. 2). Classical inversion-related O3—H35···O5i and O6—H36···O2i hydrogen bonds link the carboxyl groups from two symmetry-independent molecules (Table 1 and Fig. 2).