In the title acids, C
15H
14O
4S, (I), and C
16H
16O
4S, (II), respectively, the angle between the planes of the benzene ring and the carboxyl group is 13.7 (1)° for (I) and 21.3 (1)° for (II). The molecular structures are stabilized by intramolecular C—H
O hydrogen bonds. The crystal packing is stabilized by a single O—H
O hydrogen bond in both compounds, in which the O and H atoms are ordered; H
O 1.87 Å for (I) and 1.83 Å for (II), O
O 2.680 (2) Å for (I) and 2.652 (3) Å for (II), and O—H
O 172° for (I) and 175° for (II). The hydrogen bond forms a cyclic dimer, with graph-set descriptor
R(8), about a centre of symmetry.
Supporting information
CCDC references: 171578; 171579
The title compounds were prepared by the alkylation of methyl 2-phenylsulfonyl
methylbenzoate with the corresponding alkyl iodides in the presence of sodium
hydride in dry dimethylsulfoxide at room temperature. The ester group suffered
hydrolysis under the reaction conditions. Compounds (I) and (II) were
recrystallized from ethyl acetate and hexane by slow evaporation.
All H atoms were geometrically fixed with C—H = 0.93–0.98 Å and O—H =
0.82 Å, and allowed to ride on the corresponding parent atoms, with
Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O). Are these the
correct constraints?
Data collection: SMART (Siemens, 1996) for (I); CAD-4 Software (Enraf-Nonius, 1989) for (II). Cell refinement: SAINT (Siemens, 1996) for (I); CAD-4 Software for (II). Data reduction: SAINT for (I); SDP (Frenz, 1989) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELX97 and PARST (Nardelli, 1995).
(I) 2-[1-(Phenylsulfonyl)ethyl]benzoic acid
top
Crystal data top
C15H14O4S | F(000) = 608 |
Mr = 290.32 | Dx = 1.432 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.8969 (3) Å | Cell parameters from 7690 reflections |
b = 8.5064 (1) Å | θ = 2.9–28.4° |
c = 13.0472 (3) Å | µ = 0.25 mm−1 |
β = 109.803 (1)° | T = 293 K |
V = 1346.71 (5) Å3 | Block, colourless |
Z = 4 | 0.38 × 0.28 × 0.24 mm |
Data collection top
Siemens SMART CCD area-detector diffractometer | 2293 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.050 |
Graphite monochromator | θmax = 28.3°, θmin = 2.9° |
ω scans | h = −17→16 |
9552 measured reflections | k = −9→11 |
3352 independent reflections | l = −13→17 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0693P)2] where P = (Fo2 + 2Fc2)/3 |
3352 reflections | (Δ/σ)max = 0.001 |
183 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
Crystal data top
C15H14O4S | V = 1346.71 (5) Å3 |
Mr = 290.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.8969 (3) Å | µ = 0.25 mm−1 |
b = 8.5064 (1) Å | T = 293 K |
c = 13.0472 (3) Å | 0.38 × 0.28 × 0.24 mm |
β = 109.803 (1)° | |
Data collection top
Siemens SMART CCD area-detector diffractometer | 2293 reflections with I > 2σ(I) |
9552 measured reflections | Rint = 0.050 |
3352 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.30 e Å−3 |
3352 reflections | Δρmin = −0.57 e Å−3 |
183 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.78809 (4) | 0.48405 (5) | 0.03251 (4) | 0.03726 (16) | |
C1 | 0.78032 (13) | 0.05270 (19) | 0.07200 (14) | 0.0307 (4) | |
C2 | 0.83321 (14) | 0.17356 (19) | 0.03421 (14) | 0.0305 (4) | |
O1 | 0.59096 (10) | 0.10876 (17) | −0.03430 (13) | 0.0527 (4) | |
C7 | 0.65802 (15) | 0.0380 (2) | 0.04011 (16) | 0.0349 (4) | |
C8 | 0.77233 (14) | 0.30243 (19) | −0.04315 (15) | 0.0324 (4) | |
H8 | 0.6938 | 0.2754 | −0.0695 | 0.039* | |
C10 | 0.69326 (15) | 0.6102 (2) | −0.06069 (15) | 0.0353 (4) | |
O2 | 0.75019 (14) | 0.45641 (19) | 0.12232 (12) | 0.0600 (4) | |
O3 | 0.62727 (12) | −0.0617 (2) | 0.10068 (14) | 0.0628 (5) | |
H3 | 0.5607 | −0.0768 | 0.0740 | 0.094* | |
C6 | 0.84428 (16) | −0.0622 (2) | 0.14186 (16) | 0.0395 (4) | |
H6 | 0.8096 | −0.1428 | 0.1659 | 0.047* | |
O4 | 0.89691 (11) | 0.54596 (17) | 0.05446 (14) | 0.0565 (4) | |
C5 | 0.95799 (16) | −0.0581 (2) | 0.17582 (17) | 0.0451 (5) | |
H5 | 0.9993 | −0.1357 | 0.2220 | 0.054* | |
C9 | 0.80833 (17) | 0.3230 (2) | −0.14254 (16) | 0.0467 (5) | |
H9A | 0.8839 | 0.3565 | −0.1193 | 0.070* | |
H9B | 0.7628 | 0.4008 | −0.1902 | 0.070* | |
H9C | 0.8010 | 0.2248 | −0.1806 | 0.070* | |
C15 | 0.72894 (18) | 0.7206 (2) | −0.11904 (18) | 0.0499 (5) | |
H15 | 0.8036 | 0.7311 | −0.1087 | 0.060* | |
C4 | 1.00946 (16) | 0.0611 (2) | 0.14104 (18) | 0.0470 (5) | |
H4 | 1.0860 | 0.0655 | 0.1651 | 0.056* | |
C3 | 0.94848 (15) | 0.1748 (2) | 0.07054 (17) | 0.0415 (5) | |
H3A | 0.9848 | 0.2537 | 0.0468 | 0.050* | |
C11 | 0.58196 (17) | 0.5938 (3) | −0.0773 (2) | 0.0533 (6) | |
H11 | 0.5580 | 0.5182 | −0.0389 | 0.064* | |
C12 | 0.50703 (19) | 0.6897 (3) | −0.1505 (2) | 0.0636 (7) | |
H12 | 0.4323 | 0.6799 | −0.1609 | 0.076* | |
C13 | 0.5417 (2) | 0.7990 (3) | −0.2077 (2) | 0.0634 (7) | |
H13 | 0.4904 | 0.8633 | −0.2573 | 0.076* | |
C14 | 0.6523 (2) | 0.8153 (3) | −0.1930 (2) | 0.0631 (7) | |
H14 | 0.6753 | 0.8899 | −0.2328 | 0.076* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0417 (3) | 0.0345 (2) | 0.0340 (3) | −0.00012 (19) | 0.0109 (2) | −0.00078 (19) |
C1 | 0.0310 (9) | 0.0317 (8) | 0.0290 (9) | −0.0012 (7) | 0.0097 (7) | −0.0040 (7) |
C2 | 0.0296 (8) | 0.0320 (9) | 0.0292 (9) | −0.0003 (7) | 0.0089 (7) | −0.0024 (7) |
O1 | 0.0327 (7) | 0.0583 (9) | 0.0627 (10) | −0.0071 (6) | 0.0103 (7) | 0.0207 (8) |
C7 | 0.0352 (9) | 0.0335 (9) | 0.0364 (11) | −0.0058 (7) | 0.0127 (8) | −0.0007 (8) |
C8 | 0.0307 (9) | 0.0313 (8) | 0.0335 (10) | −0.0030 (7) | 0.0087 (8) | 0.0017 (7) |
C10 | 0.0389 (10) | 0.0320 (9) | 0.0372 (11) | 0.0005 (7) | 0.0156 (8) | −0.0029 (7) |
O2 | 0.0877 (12) | 0.0609 (9) | 0.0396 (9) | 0.0154 (8) | 0.0325 (9) | 0.0047 (7) |
O3 | 0.0396 (8) | 0.0751 (11) | 0.0701 (11) | −0.0114 (7) | 0.0140 (8) | 0.0328 (9) |
C6 | 0.0445 (11) | 0.0358 (9) | 0.0391 (11) | 0.0001 (8) | 0.0153 (9) | 0.0039 (8) |
O4 | 0.0388 (8) | 0.0448 (8) | 0.0716 (11) | −0.0100 (6) | −0.0001 (7) | −0.0062 (7) |
C5 | 0.0437 (11) | 0.0455 (11) | 0.0423 (12) | 0.0125 (8) | 0.0096 (10) | 0.0078 (9) |
C9 | 0.0571 (13) | 0.0499 (11) | 0.0360 (11) | 0.0068 (10) | 0.0196 (10) | 0.0037 (9) |
C15 | 0.0482 (12) | 0.0441 (11) | 0.0604 (15) | −0.0039 (9) | 0.0224 (11) | 0.0077 (10) |
C4 | 0.0297 (9) | 0.0540 (12) | 0.0528 (13) | 0.0051 (8) | 0.0081 (9) | 0.0039 (10) |
C3 | 0.0325 (9) | 0.0422 (10) | 0.0488 (12) | −0.0020 (8) | 0.0126 (9) | 0.0043 (9) |
C11 | 0.0461 (12) | 0.0499 (12) | 0.0715 (16) | 0.0034 (10) | 0.0302 (11) | 0.0077 (11) |
C12 | 0.0425 (12) | 0.0588 (14) | 0.0848 (19) | 0.0100 (10) | 0.0154 (13) | −0.0040 (13) |
C13 | 0.0707 (17) | 0.0514 (13) | 0.0537 (15) | 0.0186 (12) | 0.0025 (13) | 0.0002 (11) |
C14 | 0.0806 (18) | 0.0477 (13) | 0.0603 (16) | 0.0029 (12) | 0.0230 (13) | 0.0158 (11) |
Geometric parameters (Å, º) top
S1—O4 | 1.434 (2) | C5—C4 | 1.371 (3) |
S1—O2 | 1.434 (2) | C5—H5 | 0.9300 |
S1—C10 | 1.7656 (19) | C9—H9A | 0.9600 |
S1—C8 | 1.8074 (18) | C9—H9B | 0.9600 |
C1—C6 | 1.399 (2) | C9—H9C | 0.9600 |
C1—C2 | 1.412 (2) | C15—C14 | 1.382 (3) |
C1—C7 | 1.494 (2) | C15—H15 | 0.9300 |
C2—C3 | 1.399 (2) | C4—C3 | 1.382 (3) |
C2—C8 | 1.517 (2) | C4—H4 | 0.9300 |
O1—C7 | 1.218 (2) | C3—H3A | 0.9300 |
C7—O3 | 1.309 (2) | C11—C12 | 1.373 (3) |
C8—C9 | 1.528 (3) | C11—H11 | 0.9300 |
C8—H8 | 0.9800 | C12—C13 | 1.359 (4) |
C10—C15 | 1.382 (3) | C12—H12 | 0.9300 |
C10—C11 | 1.384 (3) | C13—C14 | 1.380 (3) |
O3—H3 | 0.8200 | C13—H13 | 0.9300 |
C6—C5 | 1.381 (3) | C14—H14 | 0.9300 |
C6—H6 | 0.9300 | | |
| | | |
O4—S1—O2 | 118.59 (11) | C4—C5—H5 | 120.2 |
O4—S1—C10 | 108.48 (9) | C6—C5—H5 | 120.2 |
O2—S1—C10 | 108.3 (1) | C8—C9—H9A | 109.5 |
O4—S1—C8 | 110.14 (9) | C8—C9—H9B | 109.5 |
O2—S1—C8 | 107.45 (9) | H9A—C9—H9B | 109.5 |
C10—S1—C8 | 102.69 (8) | C8—C9—H9C | 109.5 |
C6—C1—C2 | 119.23 (16) | H9A—C9—H9C | 109.5 |
C6—C1—C7 | 117.20 (16) | H9B—C9—H9C | 109.5 |
C2—C1—C7 | 123.57 (15) | C10—C15—C14 | 119.2 (2) |
C3—C2—C1 | 118.09 (16) | C10—C15—H15 | 120.4 |
C3—C2—C8 | 118.1 (2) | C14—C15—H15 | 120.4 |
C1—C2—C8 | 123.8 (2) | C5—C4—C3 | 120.51 (18) |
O1—C7—O3 | 121.5 (2) | C5—C4—H4 | 119.7 |
O1—C7—C1 | 125.3 (2) | C3—C4—H4 | 119.7 |
O3—C7—C1 | 113.2 (2) | C4—C3—C2 | 121.36 (18) |
C2—C8—C9 | 114.20 (15) | C4—C3—H3A | 119.3 |
C2—C8—S1 | 108.5 (1) | C2—C3—H3A | 119.3 |
C9—C8—S1 | 110.8 (1) | C12—C11—C10 | 119.8 (2) |
C2—C8—H8 | 107.7 | C12—C11—H11 | 120.1 |
C9—C8—H8 | 107.7 | C10—C11—H11 | 120.1 |
S1—C8—H8 | 107.7 | C13—C12—C11 | 120.2 (2) |
C15—C10—C11 | 120.20 (19) | C13—C12—H12 | 119.9 |
C15—C10—S1 | 120.66 (15) | C11—C12—H12 | 119.9 |
C11—C10—S1 | 119.10 (15) | C12—C13—C14 | 120.6 (2) |
C7—O3—H3 | 109.5 | C12—C13—H13 | 119.7 |
C5—C6—C1 | 121.27 (18) | C14—C13—H13 | 119.7 |
C5—C6—H6 | 119.4 | C13—C14—C15 | 120.0 (2) |
C1—C6—H6 | 119.4 | C13—C14—H14 | 120.0 |
C4—C5—C6 | 119.54 (18) | C15—C14—H14 | 120.0 |
| | | |
C6—C1—C2—C3 | −1.3 (3) | C8—S1—C10—C15 | −101.33 (17) |
C7—C1—C2—C3 | 179.70 (17) | O4—S1—C10—C11 | −166.76 (17) |
C6—C1—C2—C8 | 178.92 (16) | O2—S1—C10—C11 | −36.81 (19) |
C7—C1—C2—C8 | −0.1 (3) | C8—S1—C10—C11 | 76.66 (17) |
C6—C1—C7—O1 | −165.62 (19) | C2—C1—C6—C5 | 1.0 (3) |
C2—C1—C7—O1 | 13.4 (3) | C7—C1—C6—C5 | −179.91 (18) |
C6—C1—C7—O3 | 14.0 (3) | C1—C6—C5—C4 | 0.4 (3) |
C2—C1—C7—O3 | −166.95 (18) | C11—C10—C15—C14 | 0.7 (3) |
C3—C2—C8—C9 | 51.6 (2) | S1—C10—C15—C14 | 178.68 (17) |
C1—C2—C8—C9 | −128.65 (18) | C6—C5—C4—C3 | −1.5 (3) |
C3—C2—C8—S1 | −72.54 (19) | C5—C4—C3—C2 | 1.2 (3) |
C1—C2—C8—S1 | 107.2 (2) | C1—C2—C3—C4 | 0.2 (3) |
O4—S1—C8—C2 | 75.2 (1) | C8—C2—C3—C4 | −179.97 (18) |
O2—S1—C8—C2 | −55.3 (1) | C15—C10—C11—C12 | −1.2 (3) |
C10—S1—C8—C2 | −169.4 (1) | S1—C10—C11—C12 | −179.20 (18) |
O4—S1—C8—C9 | −51.0 (2) | C10—C11—C12—C13 | 0.9 (4) |
O2—S1—C8—C9 | 178.6 (1) | C11—C12—C13—C14 | −0.2 (4) |
C10—S1—C8—C9 | 64.44 (14) | C12—C13—C14—C15 | −0.3 (4) |
O4—S1—C10—C15 | 15.3 (2) | C10—C15—C14—C13 | 0.1 (3) |
O2—S1—C10—C15 | 145.2 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O3 | 0.93 | 2.32 | 2.665 (2) | 102 |
C8—H8···O1 | 0.98 | 2.10 | 2.895 (2) | 138 |
O3—H3···O1i | 0.82 | 1.87 | 2.680 (2) | 172 |
Symmetry code: (i) −x+1, −y, −z. |
(II) 2-[1-(Phenylsulfonyl)propyl]benzoic acid
top
Crystal data top
C16H16O4S | Z = 2 |
Mr = 304.35 | F(000) = 320 |
Triclinic, P1 | Dx = 1.390 Mg m−3 |
a = 7.4805 (10) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.5125 (9) Å | Cell parameters from 25 reflections |
c = 14.4853 (18) Å | θ = 2.8–25.0° |
α = 94.634 (9)° | µ = 0.24 mm−1 |
β = 91.807 (1)° | T = 293 K |
γ = 116.020 (8)° | Block, colourless |
V = 727.09 (16) Å3 | 0.40 × 0.30 × 0.26 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.016 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.8° |
Graphite monochromator | h = −8→8 |
w/2θ scans | k = −8→8 |
2625 measured reflections | l = 0→17 |
2518 independent reflections | 3 standard reflections every 300 min |
2004 reflections with I > 2σ(I) | intensity decay: 1% |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0549P)2 + 0.1743P] where P = (Fo2 + 2Fc2)/3 |
2518 reflections | (Δ/σ)max < 0.001 |
192 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C16H16O4S | γ = 116.020 (8)° |
Mr = 304.35 | V = 727.09 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.4805 (10) Å | Mo Kα radiation |
b = 7.5125 (9) Å | µ = 0.24 mm−1 |
c = 14.4853 (18) Å | T = 293 K |
α = 94.634 (9)° | 0.40 × 0.30 × 0.26 mm |
β = 91.807 (1)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.016 |
2625 measured reflections | 3 standard reflections every 300 min |
2518 independent reflections | intensity decay: 1% |
2004 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.28 e Å−3 |
2518 reflections | Δρmin = −0.19 e Å−3 |
192 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.20708 (8) | 0.44293 (8) | 0.16910 (4) | 0.04162 (19) | |
O1 | 0.3803 (2) | 0.5780 (2) | 0.42924 (12) | 0.0561 (5) | |
O2 | 0.2830 (3) | 0.3211 (2) | 0.21172 (12) | 0.0603 (5) | |
O3 | 0.2600 (3) | 0.2837 (3) | 0.48350 (13) | 0.0654 (5) | |
H3 | 0.3736 | 0.3305 | 0.5082 | 0.098* | |
O4 | 0.0334 (2) | 0.3469 (2) | 0.10488 (11) | 0.0559 (5) | |
C1 | 0.0374 (3) | 0.3470 (3) | 0.38971 (14) | 0.0374 (5) | |
C2 | −0.0049 (3) | 0.4326 (3) | 0.31428 (14) | 0.0371 (5) | |
C3 | −0.2037 (3) | 0.3623 (3) | 0.28149 (17) | 0.0494 (6) | |
H3A | −0.2340 | 0.4178 | 0.2318 | 0.059* | |
C4 | −0.3568 (3) | 0.2135 (4) | 0.32024 (18) | 0.0561 (6) | |
H4 | −0.4882 | 0.1711 | 0.2973 | 0.067* | |
C5 | −0.3145 (4) | 0.1279 (4) | 0.39295 (18) | 0.0564 (6) | |
H5 | −0.4172 | 0.0263 | 0.4190 | 0.068* | |
C6 | −0.1199 (3) | 0.1931 (3) | 0.42713 (16) | 0.0489 (6) | |
H6 | −0.0922 | 0.1338 | 0.4760 | 0.059* | |
C7 | 0.2418 (3) | 0.4146 (3) | 0.43423 (14) | 0.0411 (5) | |
C8 | 0.1556 (3) | 0.5853 (3) | 0.26256 (14) | 0.0377 (5) | |
H8 | 0.2763 | 0.6521 | 0.3049 | 0.045* | |
C9 | 0.1063 (3) | 0.7462 (3) | 0.22693 (15) | 0.0441 (5) | |
H9A | 0.2163 | 0.8339 | 0.1939 | 0.053* | |
H9B | −0.0112 | 0.6839 | 0.1837 | 0.053* | |
C10 | 0.0687 (4) | 0.8674 (4) | 0.30598 (17) | 0.0550 (6) | |
H10A | −0.0538 | 0.7858 | 0.3319 | 0.082* | |
H10B | 0.0592 | 0.9796 | 0.2830 | 0.082* | |
H10C | 0.1768 | 0.9136 | 0.3531 | 0.082* | |
C11 | 0.3998 (3) | 0.6215 (3) | 0.11182 (15) | 0.0383 (5) | |
C12 | 0.5860 (3) | 0.7331 (3) | 0.15787 (17) | 0.0486 (6) | |
H12 | 0.6107 | 0.7158 | 0.2190 | 0.058* | |
C13 | 0.7347 (3) | 0.8709 (4) | 0.11141 (19) | 0.0550 (6) | |
H13 | 0.8600 | 0.9485 | 0.1418 | 0.066* | |
C14 | 0.6984 (4) | 0.8939 (4) | 0.02084 (19) | 0.0551 (6) | |
H14 | 0.7999 | 0.9852 | −0.0103 | 0.066* | |
C15 | 0.5130 (4) | 0.7828 (4) | −0.02414 (17) | 0.0514 (6) | |
H15 | 0.4896 | 0.7990 | −0.0856 | 0.062* | |
C16 | 0.3613 (3) | 0.6473 (3) | 0.02139 (15) | 0.0446 (5) | |
H16 | 0.2347 | 0.5743 | −0.0085 | 0.053* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0417 (3) | 0.0341 (3) | 0.0467 (3) | 0.0141 (2) | 0.0052 (2) | 0.0067 (2) |
O1 | 0.0477 (10) | 0.0464 (10) | 0.0633 (11) | 0.0102 (8) | −0.0162 (8) | 0.0170 (8) |
O2 | 0.0758 (12) | 0.0514 (10) | 0.0719 (12) | 0.0401 (9) | 0.0239 (9) | 0.0268 (9) |
O3 | 0.0529 (11) | 0.0533 (10) | 0.0794 (13) | 0.0122 (8) | −0.0198 (9) | 0.0273 (9) |
O4 | 0.0447 (9) | 0.0477 (9) | 0.0539 (10) | 0.0031 (8) | −0.0003 (8) | −0.0063 (8) |
C1 | 0.0414 (12) | 0.0378 (11) | 0.0338 (11) | 0.0182 (10) | 0.0030 (9) | 0.0032 (9) |
C2 | 0.0355 (11) | 0.0367 (11) | 0.0369 (11) | 0.0141 (9) | 0.0012 (9) | 0.0033 (9) |
C3 | 0.0391 (13) | 0.0542 (14) | 0.0528 (14) | 0.0185 (11) | −0.0034 (10) | 0.0104 (11) |
C4 | 0.0338 (12) | 0.0625 (16) | 0.0657 (16) | 0.0155 (12) | 0.0012 (11) | 0.0090 (13) |
C5 | 0.0422 (14) | 0.0572 (15) | 0.0598 (16) | 0.0113 (12) | 0.0144 (12) | 0.0125 (12) |
C6 | 0.0502 (14) | 0.0509 (14) | 0.0430 (13) | 0.0185 (11) | 0.0072 (11) | 0.0123 (11) |
C7 | 0.0472 (13) | 0.0403 (12) | 0.0363 (12) | 0.0199 (11) | −0.0003 (10) | 0.0062 (9) |
C8 | 0.0365 (11) | 0.0363 (11) | 0.0364 (11) | 0.0130 (9) | −0.0036 (9) | 0.0047 (9) |
C9 | 0.0504 (13) | 0.0395 (12) | 0.0443 (13) | 0.0215 (11) | 0.0004 (10) | 0.0069 (10) |
C10 | 0.0661 (16) | 0.0462 (14) | 0.0548 (15) | 0.0269 (12) | 0.0072 (12) | 0.0039 (11) |
C11 | 0.0375 (11) | 0.0343 (11) | 0.0445 (12) | 0.0167 (9) | 0.0047 (9) | 0.0059 (9) |
C12 | 0.0424 (13) | 0.0462 (13) | 0.0541 (14) | 0.0165 (11) | −0.0030 (11) | 0.0095 (11) |
C13 | 0.0366 (13) | 0.0460 (14) | 0.0766 (18) | 0.0130 (11) | −0.0002 (12) | 0.0085 (12) |
C14 | 0.0526 (15) | 0.0443 (13) | 0.0725 (18) | 0.0222 (12) | 0.0217 (13) | 0.0181 (12) |
C15 | 0.0637 (16) | 0.0523 (14) | 0.0438 (13) | 0.0293 (13) | 0.0104 (12) | 0.0111 (11) |
C16 | 0.0469 (13) | 0.0411 (12) | 0.0457 (13) | 0.0196 (10) | 0.0022 (10) | 0.0046 (10) |
Geometric parameters (Å, º) top
S1—O2 | 1.437 (2) | C8—C9 | 1.531 (3) |
S1—O4 | 1.438 (2) | C8—H8 | 0.9800 |
S1—C11 | 1.767 (2) | C9—C10 | 1.515 (3) |
S1—C8 | 1.813 (2) | C9—H9A | 0.9700 |
O1—C7 | 1.220 (3) | C9—H9B | 0.9700 |
O3—C7 | 1.311 (2) | C10—H10A | 0.9600 |
O3—H3 | 0.8200 | C10—H10B | 0.9600 |
C1—C6 | 1.401 (3) | C10—H10C | 0.9600 |
C1—C2 | 1.407 (3) | C11—C12 | 1.384 (3) |
C1—C7 | 1.488 (3) | C11—C16 | 1.379 (3) |
C2—C3 | 1.393 (3) | C12—C13 | 1.382 (3) |
C2—C8 | 1.518 (3) | C12—H12 | 0.9300 |
C3—C4 | 1.377 (3) | C13—C14 | 1.371 (4) |
C3—H3A | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.374 (3) | C14—C15 | 1.372 (3) |
C4—H4 | 0.9300 | C14—H14 | 0.9300 |
C5—C6 | 1.377 (3) | C15—C16 | 1.379 (3) |
C5—H5 | 0.9300 | C15—H15 | 0.9300 |
C6—H6 | 0.9300 | C16—H16 | 0.9300 |
| | | |
O2—S1—O4 | 118.47 (11) | C9—C8—H8 | 107.7 |
O2—S1—C11 | 108.79 (10) | S1—C8—H8 | 107.7 |
O4—S1—C11 | 108.1 (1) | C10—C9—C8 | 111.36 (18) |
O2—S1—C8 | 106.8 (1) | C10—C9—H9A | 109.4 |
O4—S1—C8 | 108.8 (1) | C8—C9—H9A | 109.4 |
C11—S1—C8 | 105.2 (1) | C10—C9—H9B | 109.4 |
C7—O3—H3 | 109.5 | C8—C9—H9B | 109.4 |
C6—C1—C2 | 119.08 (19) | H9A—C9—H9B | 108.0 |
C6—C1—C7 | 117.51 (19) | C9—C10—H10A | 109.5 |
C2—C1—C7 | 123.39 (18) | C9—C10—H10B | 109.5 |
C3—C2—C1 | 117.93 (19) | H10A—C10—H10B | 109.5 |
C3—C2—C8 | 118.64 (19) | C9—C10—H10C | 109.5 |
C1—C2—C8 | 123.25 (18) | H10A—C10—H10C | 109.5 |
C4—C3—C2 | 122.2 (2) | H10B—C10—H10C | 109.5 |
C4—C3—H3A | 118.9 | C12—C11—C16 | 121.0 (2) |
C2—C3—H3A | 118.9 | C12—C11—S1 | 119.92 (17) |
C3—C4—C5 | 119.7 (2) | C16—C11—S1 | 119.10 (17) |
C3—C4—H4 | 120.2 | C11—C12—C13 | 118.8 (2) |
C5—C4—H4 | 120.2 | C11—C12—H12 | 120.6 |
C4—C5—C6 | 119.8 (2) | C13—C12—H12 | 120.6 |
C4—C5—H5 | 120.1 | C14—C13—C12 | 120.4 (2) |
C6—C5—H5 | 120.1 | C14—C13—H13 | 119.8 |
C5—C6—C1 | 121.3 (2) | C12—C13—H13 | 119.8 |
C5—C6—H6 | 119.4 | C13—C14—C15 | 120.3 (2) |
C1—C6—H6 | 119.4 | C13—C14—H14 | 119.8 |
O1—C7—O3 | 121.8 (2) | C15—C14—H14 | 119.8 |
O1—C7—C1 | 124.5 (2) | C16—C15—C14 | 120.3 (2) |
O3—C7—C1 | 113.7 (2) | C16—C15—H15 | 119.8 |
C2—C8—C9 | 115.77 (17) | C14—C15—H15 | 119.8 |
C2—C8—S1 | 105.6 (1) | C15—C16—C11 | 119.1 (2) |
C9—C8—S1 | 111.9 (1) | C15—C16—H16 | 120.4 |
C2—C8—H8 | 107.7 | C11—C16—H16 | 120.4 |
| | | |
C6—C1—C2—C3 | 1.4 (3) | C11—S1—C8—C2 | −178.1 (1) |
C7—C1—C2—C3 | −177.04 (19) | O2—S1—C8—C9 | 170.6 (2) |
C6—C1—C2—C8 | −173.70 (19) | O4—S1—C8—C9 | −60.5 (2) |
C7—C1—C2—C8 | 7.9 (3) | C11—S1—C8—C9 | 55.1 (2) |
C1—C2—C3—C4 | −0.2 (3) | C2—C8—C9—C10 | 60.3 (2) |
C8—C2—C3—C4 | 175.1 (2) | S1—C8—C9—C10 | −178.58 (16) |
C2—C3—C4—C5 | −0.9 (4) | O2—S1—C11—C12 | −48.9 (2) |
C3—C4—C5—C6 | 0.7 (4) | O4—S1—C11—C12 | −178.7 (2) |
C4—C5—C6—C1 | 0.5 (4) | C8—S1—C11—C12 | 65.2 (2) |
C2—C1—C6—C5 | −1.6 (3) | O2—S1—C11—C16 | 131.2 (2) |
C7—C1—C6—C5 | 176.9 (2) | O4—S1—C11—C16 | 1.4 (2) |
C6—C1—C7—O1 | −157.2 (2) | C8—S1—C11—C16 | −114.7 (2) |
C2—C1—C7—O1 | 21.2 (3) | C16—C11—C12—C13 | −0.5 (3) |
C6—C1—C7—O3 | 20.3 (3) | S1—C11—C12—C13 | 179.6 (2) |
C2—C1—C7—O3 | −161.2 (2) | C11—C12—C13—C14 | −1.0 (4) |
C3—C2—C8—C9 | 39.7 (3) | C12—C13—C14—C15 | 1.2 (4) |
C1—C2—C8—C9 | −145.3 (2) | C13—C14—C15—C16 | 0.2 (4) |
C3—C2—C8—S1 | −84.7 (2) | C14—C15—C16—C11 | −1.6 (3) |
C1—C2—C8—S1 | 90.3 (2) | C12—C11—C16—C15 | 1.8 (3) |
O2—S1—C8—C2 | −62.6 (2) | S1—C11—C16—C15 | −178.3 (2) |
O4—S1—C8—C2 | 66.3 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O3 | 0.93 | 2.36 | 2.695 (3) | 101 |
C8—H8···O1 | 0.98 | 2.15 | 2.917 (3) | 134 |
C16—H16···O4 | 0.93 | 2.50 | 2.887 (3) | 105 |
O3—H3···O1i | 0.82 | 1.83 | 2.652 (3) | 175 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C15H14O4S | C16H16O4S |
Mr | 290.32 | 304.35 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 12.8969 (3), 8.5064 (1), 13.0472 (3) | 7.4805 (10), 7.5125 (9), 14.4853 (18) |
α, β, γ (°) | 90, 109.803 (1), 90 | 94.634 (9), 91.807 (1), 116.020 (8) |
V (Å3) | 1346.71 (5) | 727.09 (16) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.25 | 0.24 |
Crystal size (mm) | 0.38 × 0.28 × 0.24 | 0.40 × 0.30 × 0.26 |
|
Data collection |
Diffractometer | Siemens SMART CCD area-detector diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9552, 3352, 2293 | 2625, 2518, 2004 |
Rint | 0.050 | 0.016 |
(sin θ/λ)max (Å−1) | 0.667 | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.124, 0.94 | 0.040, 0.107, 1.01 |
No. of reflections | 3352 | 2518 |
No. of parameters | 183 | 192 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.57 | 0.28, −0.19 |
Selected geometric parameters (Å, º) for (I) topS1—O4 | 1.434 (2) | O1—C7 | 1.218 (2) |
S1—O2 | 1.434 (2) | C7—O3 | 1.309 (2) |
| | | |
O4—S1—C10 | 108.48 (9) | O1—C7—C1 | 125.3 (2) |
O2—S1—C10 | 108.3 (1) | O3—C7—C1 | 113.2 (2) |
O4—S1—C8 | 110.14 (9) | C2—C8—S1 | 108.5 (1) |
O2—S1—C8 | 107.45 (9) | C9—C8—S1 | 110.8 (1) |
O1—C7—O3 | 121.5 (2) | | |
| | | |
O4—S1—C8—C2 | 75.2 (1) | O2—S1—C8—C9 | 178.6 (1) |
O2—S1—C8—C2 | −55.3 (1) | O4—S1—C10—C15 | 15.3 (2) |
O4—S1—C8—C9 | −51.0 (2) | O2—S1—C10—C15 | 145.2 (2) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O3 | 0.93 | 2.32 | 2.665 (2) | 102 |
C8—H8···O1 | 0.98 | 2.10 | 2.895 (2) | 138 |
O3—H3···O1i | 0.82 | 1.87 | 2.680 (2) | 172 |
Symmetry code: (i) −x+1, −y, −z. |
Selected geometric parameters (Å, º) for (II) topS1—O2 | 1.437 (2) | O1—C7 | 1.220 (3) |
S1—O4 | 1.438 (2) | O3—C7 | 1.311 (2) |
S1—C11 | 1.767 (2) | | |
| | | |
O4—S1—C11 | 108.1 (1) | O1—C7—C1 | 124.5 (2) |
O2—S1—C8 | 106.8 (1) | O3—C7—C1 | 113.7 (2) |
O4—S1—C8 | 108.8 (1) | C2—C8—S1 | 105.6 (1) |
O1—C7—O3 | 121.8 (2) | C9—C8—S1 | 111.9 (1) |
| | | |
O2—S1—C8—C2 | −62.6 (2) | O4—S1—C11—C12 | −178.7 (2) |
O4—S1—C8—C2 | 66.3 (2) | C8—S1—C11—C12 | 65.2 (2) |
C11—S1—C8—C2 | −178.1 (1) | O2—S1—C11—C16 | 131.2 (2) |
O2—S1—C8—C9 | 170.6 (2) | O4—S1—C11—C16 | 1.4 (2) |
O4—S1—C8—C9 | −60.5 (2) | C8—S1—C11—C16 | −114.7 (2) |
C11—S1—C8—C9 | 55.1 (2) | S1—C11—C12—C13 | 179.6 (2) |
O2—S1—C11—C12 | −48.9 (2) | S1—C11—C16—C15 | −178.3 (2) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O3 | 0.93 | 2.36 | 2.695 (3) | 101 |
C8—H8···O1 | 0.98 | 2.15 | 2.917 (3) | 134 |
C16—H16···O4 | 0.93 | 2.50 | 2.887 (3) | 105 |
O3—H3···O1i | 0.82 | 1.83 | 2.652 (3) | 175 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
The title compounds, (I) and (II), are potential intermediates for the synthesis of 2-alkylbenzoic acid starting from o-toluic acid. Sulfates, sulfones, thiols, sulfonamides and sulfoxides are some of the compounds that belong to this class, and many of these exihibit insecticidal, germicidal or antimicrobial activities (Krishnaiah et al., 1995; De Benedetti et al., 1985; Dupont et al., 1978). Sulfur-containing compounds, for the most part, act as simple narcotics (Schultz et al., 2001). A series of acyclic sulfones have been identified as high-affinity selective 5-HT(2 A) receptor antagonists (Fletcher et al., 2002). Para-amino,para-phenylsulfones are well known as antibacterial and antileprotic agents (McCullough & Maren, 1973; De Benedetti, 1992). The conformation about the S atom determines whether the pharmacological activity of the compound is mild or strong (McKenna et al., 1989). In order to obtain detailed information on their molecular conformation in the solid state, the pesent X-ray study on the title sulfones has been carried out and the results are presented here. \sch
Figs. 1 and 2 show the molecular structures of (I) and (II), respectively, with the atom-numbering schemes. In both compounds, the C—O distances are as expected. The S—C(phenyl) distances [1.766 (2) Å in (I) and 1.767 (2) Å in (II)] compare well with the literature value of 1.763 (9) Å for Car—SO2—C (Allen et al., 1987). The S1—C8 distances [1.806 (2) Å for (I) and 1.813 (2) Å for (II)] are longer than the literature value of 1.786 (18) Å for Csp3—SO2—C (Allen et al., 1987). The mean S═O distance of 1.436 (2) Å agrees well with the reported value of 1.436 (2) Å (Bocelli & Rizzoli, 1990; Jeyakanthan & Velmurugan, 1998).
The angular disposition of the bonds about the S1 atom in (I) and (II) shows significant deviation from that of a regular tetrahedron, with the largest deviation in the O—S—O angle for both (I) and (II). In both compounds, the widening of the O4—S1—O2 angle [to 118.6 (1)° in (I) and 118.4 (1)° in (II)], and the resulting narrowing of C—S—C from the ideal tetrahedral value [C10—S1—C8 in (I) to 102.6 (1)° and C11—S1—C8 in (II) to 105.2 (1)°], are attributed to the Thorpe-Ingold effect (Bassindale, 1984). The dihedral angles between the carboxyl group and the C1—C6 phenyl ring are 13.7 (1) and 21.3 (1)° in (I) and (II), respectively. In both compounds, the orientation of the carboxyl group with respect to the phenyl is influenced by C6—H6···O3 and C8—H8···O1 interactions (Tables 2 and 4). The interplanar angle between the phenyl rings in (I) is 9.2 (1)°. In the case of (II), this angle increases to 22.5 (1)°, due to the bulkier nature of the propyl group compared with the ethyl group. By changing the ethyl substituent for a propyl, the space group is changed and the volume per molecule increases by 26.9 Å3, corresponding to 7.98%.
The slight increases in the C7—C1—C2 [123.4 (2)° in (I) and 123.5 (2)° in (II)] and C1—C2—C8 [123.7 (2)° in (I) and 123.1 (2)° in (II)] angles in both compounds, from the ideal value of 120°, can be attributed to the steric interaction of the C7 and C8 substituents. The slight difference in the C2—C8—C9 bond angle between (I) and (II) is due to the slightly bulkier nature of the propyl group in (II) than the ethyl group in (I).
In addition to van der Waals interactions, there is one O—H···O intermolecular hydrogen bond in both compounds. Each of the hydrogen bonds in (I) and (II) participates in an eight-membered cyclic dimer arrangement, as shown in the packing diagrams (Figs.3 and 4), with an R22(8) ring descriptor (Bernstein et al., 1995). A similar pattern is also observed for 2-(isopropylthio)benzoic acid (Gerkin, 1999). The molecular structures of (I) and (II) are stabilized by intramolecular C—H···O hydrogen bonds.