Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101008216/bm1449sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101008216/bm1449IIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101008216/bm1449IIIsup3.hkl |
CCDC references: 174810; 174811
Compounds (II) and (III) were made by displacement of halide by the appropriate thiol from the corresponding 2-halogenoacetophenone. Crystals of (II) were obtained directly from the reaction mixture and those of (III) were obtained by slow evaporation from an acetone solution.
For (II), the H atoms attached to C12 were located in a circular difference synthesis, the methyl group was thereafter treated as a rotating rigid group with Uiso(H) = 1.5Ueq(C12). Other H atoms were placed in calculated positions and allowed to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).
For both compounds, data collection: DIF4 (Stoe & Cie, 1990a); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1990b); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. A view of (II) and (III) with atom-numbering schemes. Displacement ellipsoids enclose 50% probability surfaces. |
C14H12OS | F(000) = 480 |
Mr = 228.30 | Dx = 1.284 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
a = 9.0151 (7) Å | Cell parameters from 48 reflections |
b = 12.7805 (14) Å | θ = 20–22° |
c = 10.6400 (12) Å | µ = 2.22 mm−1 |
β = 105.497 (7)° | T = 293 K |
V = 1181.3 (2) Å3 | Block, colourless |
Z = 4 | 0.58 × 0.47 × 0.39 mm |
Stoe Stadi-4 four-circle diffractometer | 1754 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.033 |
Graphite monochromator | θmax = 70.0°, θmin = 5.1° |
ω/θ scans | h = −10→10 |
Absorption correction: ψ scans (North et al., 1968) | k = −4→15 |
Tmin = 0.331, Tmax = 0.420 | l = −6→12 |
3137 measured reflections | 3 standard reflections every 60 min |
2070 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: see text |
R[F2 > 2σ(F2)] = 0.039 | See text |
wR(F2) = 0.110 | w = 1/[σ2(Fo2) + (0.0571P)2 + 0.297P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
2070 reflections | Δρmax = 0.30 e Å−3 |
147 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0107 (9) |
C14H12OS | V = 1181.3 (2) Å3 |
Mr = 228.30 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 9.0151 (7) Å | µ = 2.22 mm−1 |
b = 12.7805 (14) Å | T = 293 K |
c = 10.6400 (12) Å | 0.58 × 0.47 × 0.39 mm |
β = 105.497 (7)° |
Stoe Stadi-4 four-circle diffractometer | 1754 reflections with I > 2σ(I) |
Absorption correction: ψ scans (North et al., 1968) | Rint = 0.033 |
Tmin = 0.331, Tmax = 0.420 | 3 standard reflections every 60 min |
3137 measured reflections | intensity decay: none |
2070 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.110 | See text |
S = 1.07 | Δρmax = 0.30 e Å−3 |
2070 reflections | Δρmin = −0.19 e Å−3 |
147 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 | ||
C1 | 0.9941 (2) | 0.37915 (15) | 0.10751 (17) | 0.0437 (4) | |
C11 | 0.9209 (2) | 0.28736 (16) | 0.02984 (19) | 0.0518 (5) | |
O11 | 0.79066 (19) | 0.26176 (13) | 0.02729 (18) | 0.0729 (5) | |
C12 | 1.0095 (3) | 0.2247 (2) | −0.0446 (3) | 0.0801 (8) | |
H12A | 1.0990 | 0.1951 | 0.0151 | 0.120* | |
H12B | 1.0408 | 0.2693 | −0.1055 | 0.120* | |
H12C | 0.9456 | 0.1695 | −0.0910 | 0.120* | |
C2 | 0.9116 (2) | 0.44574 (15) | 0.17073 (17) | 0.0430 (4) | |
S21 | 0.71436 (5) | 0.42206 (4) | 0.15644 (5) | 0.0572 (2) | |
C22 | 0.6611 (2) | 0.52844 (16) | 0.24334 (19) | 0.0487 (5) | |
C23 | 0.5953 (3) | 0.61685 (19) | 0.1771 (2) | 0.0625 (6) | |
H23 | 0.5923 | 0.6252 | 0.0896 | 0.075* | |
C24 | 0.5339 (3) | 0.6931 (2) | 0.2403 (3) | 0.0743 (7) | |
H24 | 0.4893 | 0.7524 | 0.1950 | 0.089* | |
C25 | 0.5384 (3) | 0.6819 (2) | 0.3695 (3) | 0.0670 (6) | |
H25 | 0.4964 | 0.7331 | 0.4118 | 0.080* | |
C26 | 0.6055 (3) | 0.5944 (2) | 0.4358 (2) | 0.0663 (6) | |
H26 | 0.6105 | 0.5872 | 0.5239 | 0.080* | |
C27 | 0.6653 (2) | 0.51726 (19) | 0.3734 (2) | 0.0576 (5) | |
H27 | 0.7085 | 0.4576 | 0.4188 | 0.069* | |
C3 | 0.9885 (2) | 0.52901 (17) | 0.24371 (19) | 0.0512 (5) | |
H3 | 0.9354 | 0.5731 | 0.2860 | 0.061* | |
C4 | 1.1424 (2) | 0.54780 (19) | 0.2548 (2) | 0.0596 (6) | |
H4 | 1.1916 | 0.6039 | 0.3044 | 0.072* | |
C5 | 1.2232 (2) | 0.4838 (2) | 0.1927 (2) | 0.0635 (6) | |
H5 | 1.3266 | 0.4966 | 0.1995 | 0.076* | |
C6 | 1.1497 (2) | 0.40116 (18) | 0.1208 (2) | 0.0554 (5) | |
H6 | 1.2050 | 0.3580 | 0.0793 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0437 (10) | 0.0464 (10) | 0.0400 (9) | 0.0013 (8) | 0.0096 (8) | 0.0057 (8) |
C11 | 0.0579 (12) | 0.0464 (11) | 0.0507 (10) | 0.0017 (9) | 0.0142 (9) | 0.0030 (9) |
O11 | 0.0691 (10) | 0.0651 (10) | 0.0878 (11) | −0.0200 (8) | 0.0268 (9) | −0.0218 (9) |
C12 | 0.0855 (18) | 0.0669 (15) | 0.0932 (19) | −0.0034 (13) | 0.0332 (15) | −0.0246 (14) |
C2 | 0.0408 (9) | 0.0482 (10) | 0.0389 (9) | −0.0024 (8) | 0.0087 (7) | 0.0041 (8) |
S21 | 0.0431 (3) | 0.0636 (4) | 0.0671 (4) | −0.0118 (2) | 0.0187 (2) | −0.0156 (3) |
C22 | 0.0361 (9) | 0.0565 (12) | 0.0542 (11) | −0.0042 (8) | 0.0133 (8) | −0.0007 (9) |
C23 | 0.0619 (13) | 0.0664 (14) | 0.0573 (12) | −0.0016 (11) | 0.0124 (10) | 0.0078 (11) |
C24 | 0.0686 (15) | 0.0582 (14) | 0.0894 (18) | 0.0085 (12) | 0.0094 (13) | 0.0072 (13) |
C25 | 0.0522 (12) | 0.0635 (14) | 0.0865 (17) | −0.0006 (11) | 0.0204 (12) | −0.0158 (13) |
C26 | 0.0649 (14) | 0.0795 (17) | 0.0602 (13) | −0.0020 (12) | 0.0266 (11) | −0.0056 (12) |
C27 | 0.0542 (12) | 0.0624 (13) | 0.0579 (12) | 0.0046 (10) | 0.0177 (10) | 0.0074 (10) |
C3 | 0.0470 (10) | 0.0589 (12) | 0.0479 (10) | −0.0054 (9) | 0.0129 (8) | −0.0079 (9) |
C4 | 0.0456 (11) | 0.0707 (14) | 0.0578 (12) | −0.0146 (10) | 0.0056 (9) | −0.0113 (11) |
C5 | 0.0386 (10) | 0.0817 (16) | 0.0691 (13) | −0.0076 (10) | 0.0125 (10) | −0.0061 (12) |
C6 | 0.0457 (11) | 0.0649 (13) | 0.0568 (11) | 0.0054 (9) | 0.0160 (9) | 0.0009 (10) |
C1—C6 | 1.400 (3) | C4—C5 | 1.376 (3) |
C1—C2 | 1.414 (3) | C5—C6 | 1.367 (3) |
C1—C11 | 1.484 (3) | C3—H3 | 0.93 |
C11—O11 | 1.213 (2) | C4—H4 | 0.93 |
C11—C12 | 1.498 (3) | C5—H5 | 0.93 |
C2—C3 | 1.389 (3) | C6—H6 | 0.93 |
C2—S21 | 1.7694 (18) | C12—H12A | 0.96 |
S21—C22 | 1.781 (2) | C12—H12B | 0.96 |
C22—C23 | 1.379 (3) | C12—H12C | 0.96 |
C22—C27 | 1.382 (3) | C23—H23 | 0.93 |
C23—C24 | 1.381 (3) | C24—H24 | 0.93 |
C24—C25 | 1.372 (4) | C25—H25 | 0.93 |
C25—C26 | 1.374 (4) | C26—H26 | 0.93 |
C26—C27 | 1.376 (3) | C27—H27 | 0.93 |
C3—C4 | 1.381 (3) | ||
C6—C1—C2 | 118.13 (18) | C2—C3—H3 | 118.7 |
C6—C1—C11 | 119.97 (17) | C5—C4—H4 | 119.8 |
C2—C1—C11 | 121.90 (17) | C3—C4—H4 | 119.5 |
O11—C11—C1 | 120.64 (18) | C6—C5—H5 | 120.4 |
O11—C11—C12 | 119.6 (2) | C4—C5—H5 | 120.4 |
C1—C11—C12 | 119.76 (19) | C5—C6—H6 | 118.9 |
C3—C2—C1 | 118.64 (17) | C1—C6—H6 | 118.1 |
C3—C2—S21 | 121.30 (15) | C11—C12—H12A | 108.9 |
C1—C2—S21 | 120.06 (14) | C11—C12—H12B | 110.0 |
C2—S21—C22 | 103.24 (9) | H12A—C12—H12B | 109.5 |
C23—C22—C27 | 119.3 (2) | C11—C12—H12C | 109.5 |
C23—C22—S21 | 119.92 (16) | H12A—C12—H12C | 109.5 |
C27—C22—S21 | 120.14 (17) | H12B—C12—H12C | 109.5 |
C22—C23—C24 | 120.2 (2) | C22—C23—H23 | 119.9 |
C25—C24—C23 | 120.4 (2) | C24—C23—H23 | 120.0 |
C24—C25—C26 | 119.4 (2) | C25—C24—H24 | 119.8 |
C25—C26—C27 | 120.7 (2) | C23—C24—H24 | 119.6 |
C26—C27—C22 | 120.0 (2) | C24—C25—H25 | 121.3 |
C4—C3—C2 | 121.42 (19) | C26—C25—H25 | 120.8 |
C5—C4—C3 | 120.2 (2) | C25—C26—H26 | 119.1 |
C6—C5—C4 | 119.25 (19) | C27—C26—H26 | 119.7 |
C5—C6—C1 | 122.32 (19) | C26—C27—H27 | 120.0 |
C4—C3—H3 | 119.6 | C22—C27—H27 | 120.0 |
C15H14OS | Dx = 1.304 Mg m−3 |
Mr = 242.32 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, Pbca | Cell parameters from 150 reflections |
a = 7.8838 (18) Å | θ = 20–22° |
b = 14.719 (3) Å | µ = 2.15 mm−1 |
c = 21.277 (4) Å | T = 150 K |
V = 2469.1 (9) Å3 | Block, colourless |
Z = 8 | 0.54 × 0.18 × 0.12 mm |
F(000) = 1024 |
Stoe Stadi-4 four-circle diffractometer | 1520 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.011 |
Graphite monochromator | θmax = 59.9°, θmin = 4.2° |
ω/θ scans | h = −8→6 |
Absorption correction: ψ scans (North et al., 1968) | k = −15→16 |
Tmin = 0.429, Tmax = 0.581 | l = −23→17 |
2272 measured reflections | 3 standard reflections every 60 min |
1790 independent reflections | intensity decay: 1% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.033 | All H-atom parameters refined |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0545P)2 + 0.689P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
1790 reflections | Δρmax = 0.19 e Å−3 |
211 parameters | Δρmin = −0.30 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0026 (2) |
C15H14OS | V = 2469.1 (9) Å3 |
Mr = 242.32 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 7.8838 (18) Å | µ = 2.15 mm−1 |
b = 14.719 (3) Å | T = 150 K |
c = 21.277 (4) Å | 0.54 × 0.18 × 0.12 mm |
Stoe Stadi-4 four-circle diffractometer | 1520 reflections with I > 2σ(I) |
Absorption correction: ψ scans (North et al., 1968) | Rint = 0.011 |
Tmin = 0.429, Tmax = 0.581 | θmax = 59.9° |
2272 measured reflections | 3 standard reflections every 60 min |
1790 independent reflections | intensity decay: 1% |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.087 | All H-atom parameters refined |
S = 1.02 | Δρmax = 0.19 e Å−3 |
1790 reflections | Δρmin = −0.30 e Å−3 |
211 parameters |
Experimental. Data were collected to 2θmax = 120° because of the presence of a low-temperature unit. |
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 | ||
C1 | 0.1098 (2) | 0.54262 (13) | 0.21073 (9) | 0.0250 (5) | |
C11 | 0.0473 (3) | 0.45532 (13) | 0.23716 (9) | 0.0289 (5) | |
O11 | −0.0116 (2) | 0.39745 (10) | 0.20286 (7) | 0.0433 (4) | |
C12 | 0.0611 (3) | 0.43843 (19) | 0.30664 (11) | 0.0378 (6) | |
H12A | 0.028 (5) | 0.379 (3) | 0.3148 (15) | 0.098 (12)* | |
H12B | 0.003 (4) | 0.479 (2) | 0.3301 (14) | 0.086 (11)* | |
H12C | 0.179 (4) | 0.4493 (19) | 0.3216 (14) | 0.073 (10)* | |
C2 | 0.1637 (2) | 0.54871 (12) | 0.14744 (9) | 0.0235 (5) | |
C3 | 0.2257 (3) | 0.63192 (13) | 0.12562 (10) | 0.0287 (5) | |
H3A | 0.261 (3) | 0.6370 (13) | 0.0833 (10) | 0.022 (5)* | |
C4 | 0.2301 (3) | 0.70738 (14) | 0.16445 (11) | 0.0337 (5) | |
H4A | 0.274 (3) | 0.7627 (17) | 0.1489 (11) | 0.047 (7)* | |
C5 | 0.1723 (3) | 0.70216 (15) | 0.22569 (11) | 0.0358 (6) | |
H5A | 0.176 (3) | 0.7521 (16) | 0.2519 (12) | 0.042 (6)* | |
C6 | 0.1152 (3) | 0.62014 (14) | 0.24819 (11) | 0.0319 (5) | |
H6A | 0.080 (3) | 0.6146 (14) | 0.2894 (10) | 0.029 (6)* | |
S21 | 0.15434 (6) | 0.45227 (3) | 0.09782 (2) | 0.0243 (2) | |
C21 | 0.2889 (3) | 0.48540 (15) | 0.03213 (10) | 0.0298 (5) | |
H21A | 0.397 (3) | 0.5042 (16) | 0.0495 (10) | 0.036 (6)* | |
H21B | 0.237 (3) | 0.5364 (15) | 0.0090 (11) | 0.037 (6)* | |
C22 | 0.3101 (2) | 0.40234 (13) | −0.00845 (9) | 0.0246 (5) | |
C23 | 0.4131 (3) | 0.33112 (14) | 0.01019 (10) | 0.0310 (5) | |
H23A | 0.468 (3) | 0.3350 (15) | 0.0476 (11) | 0.043 (7)* | |
C24 | 0.4301 (3) | 0.25422 (16) | −0.02655 (10) | 0.0361 (5) | |
H24A | 0.508 (3) | 0.2056 (16) | −0.0124 (11) | 0.052 (7)* | |
C25 | 0.3421 (3) | 0.24734 (16) | −0.08266 (10) | 0.0348 (5) | |
H25A | 0.353 (3) | 0.1945 (18) | −0.1078 (12) | 0.057 (8)* | |
C26 | 0.2370 (3) | 0.31730 (16) | −0.10132 (10) | 0.0338 (5) | |
H26A | 0.177 (3) | 0.3141 (15) | −0.1394 (11) | 0.035 (6)* | |
C27 | 0.2221 (3) | 0.39448 (15) | −0.06478 (9) | 0.0291 (5) | |
H27A | 0.148 (3) | 0.4426 (16) | −0.0750 (12) | 0.044 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0223 (10) | 0.0263 (11) | 0.0264 (11) | 0.0025 (8) | −0.0011 (8) | −0.0039 (8) |
C11 | 0.0255 (10) | 0.0320 (11) | 0.0292 (11) | 0.0005 (9) | 0.0063 (9) | −0.0010 (9) |
O11 | 0.0592 (10) | 0.0367 (9) | 0.0341 (8) | −0.0190 (8) | 0.0076 (8) | −0.0053 (7) |
C12 | 0.0410 (14) | 0.0414 (14) | 0.0311 (12) | −0.0008 (12) | 0.0053 (11) | 0.0039 (11) |
C2 | 0.0214 (10) | 0.0207 (10) | 0.0284 (11) | 0.0033 (8) | −0.0034 (8) | −0.0012 (8) |
C3 | 0.0331 (11) | 0.0248 (11) | 0.0282 (12) | −0.0001 (9) | −0.0008 (10) | 0.0005 (9) |
C4 | 0.0391 (13) | 0.0224 (11) | 0.0395 (13) | 0.0000 (10) | −0.0085 (10) | 0.0004 (10) |
C5 | 0.0438 (13) | 0.0255 (12) | 0.0380 (13) | 0.0034 (10) | −0.0070 (10) | −0.0095 (10) |
C6 | 0.0341 (11) | 0.0346 (12) | 0.0270 (11) | 0.0030 (10) | −0.0004 (9) | −0.0063 (10) |
S21 | 0.0278 (3) | 0.0212 (3) | 0.0240 (3) | −0.0011 (2) | 0.0030 (2) | −0.00262 (19) |
C21 | 0.0349 (12) | 0.0271 (11) | 0.0272 (11) | −0.0049 (10) | 0.0059 (9) | 0.0011 (9) |
C22 | 0.0253 (10) | 0.0261 (10) | 0.0223 (10) | −0.0014 (9) | 0.0060 (8) | −0.0010 (8) |
C23 | 0.0311 (11) | 0.0382 (13) | 0.0238 (11) | 0.0022 (10) | 0.0003 (9) | −0.0001 (10) |
C24 | 0.0375 (12) | 0.0355 (12) | 0.0353 (11) | 0.0099 (11) | 0.0042 (10) | 0.0000 (10) |
C25 | 0.0371 (12) | 0.0354 (12) | 0.0320 (11) | 0.0011 (11) | 0.0099 (10) | −0.0086 (10) |
C26 | 0.0311 (11) | 0.0467 (13) | 0.0238 (11) | −0.0042 (11) | 0.0014 (10) | −0.0042 (10) |
C27 | 0.0275 (11) | 0.0340 (12) | 0.0257 (11) | 0.0046 (10) | 0.0030 (9) | 0.0026 (9) |
C1—C6 | 1.393 (3) | C6—H6A | 0.92 (2) |
C1—C2 | 1.415 (3) | S21—C21 | 1.821 (2) |
C1—C11 | 1.487 (3) | C21—C22 | 1.506 (3) |
C11—O11 | 1.214 (2) | C21—H21A | 0.97 (2) |
C11—C12 | 1.503 (3) | C21—H21B | 0.99 (2) |
C12—H12A | 0.93 (4) | C22—C23 | 1.384 (3) |
C12—H12B | 0.90 (3) | C22—C27 | 1.389 (3) |
C12—H12C | 1.00 (3) | C23—C24 | 1.382 (3) |
C2—C3 | 1.398 (3) | C23—H23A | 0.91 (2) |
C2—S21 | 1.7706 (19) | C24—C25 | 1.384 (3) |
C3—C4 | 1.385 (3) | C24—H24A | 0.99 (2) |
C3—H3A | 0.95 (2) | C25—C26 | 1.380 (3) |
C4—C5 | 1.382 (3) | C25—H25A | 0.95 (3) |
C4—H4A | 0.94 (2) | C26—C27 | 1.382 (3) |
C5—C6 | 1.375 (3) | C26—H26A | 0.94 (2) |
C5—H5A | 0.92 (3) | C27—H27A | 0.94 (2) |
C6—C1—C2 | 118.92 (18) | C1—C6—H6A | 117.6 (13) |
C6—C1—C11 | 120.13 (18) | C2—S21—C21 | 102.62 (10) |
C2—C1—C11 | 120.95 (17) | C22—C21—S21 | 106.68 (14) |
O11—C11—C1 | 120.40 (18) | C22—C21—H21A | 110.6 (13) |
O11—C11—C12 | 120.2 (2) | S21—C21—H21A | 107.3 (12) |
C1—C11—C12 | 119.40 (19) | C22—C21—H21B | 112.2 (13) |
C11—C12—H12A | 109 (2) | S21—C21—H21B | 110.1 (14) |
C11—C12—H12B | 113 (2) | H21A—C21—H21B | 109.8 (19) |
H12A—C12—H12B | 112 (3) | C23—C22—C27 | 118.49 (19) |
C11—C12—H12C | 110.7 (18) | C23—C22—C21 | 121.02 (18) |
H12A—C12—H12C | 111 (3) | C27—C22—C21 | 120.46 (19) |
H12B—C12—H12C | 101 (3) | C24—C23—C22 | 120.98 (19) |
C3—C2—C1 | 118.46 (17) | C24—C23—H23A | 120.2 (15) |
C3—C2—S21 | 121.27 (15) | C22—C23—H23A | 118.8 (15) |
C1—C2—S21 | 120.27 (14) | C23—C24—C25 | 120.0 (2) |
C4—C3—C2 | 120.90 (19) | C23—C24—H24A | 118.6 (14) |
C4—C3—H3A | 119.8 (12) | C25—C24—H24A | 121.4 (14) |
C2—C3—H3A | 119.3 (12) | C26—C25—C24 | 119.6 (2) |
C5—C4—C3 | 120.6 (2) | C26—C25—H25A | 120.4 (16) |
C5—C4—H4A | 119.9 (15) | C24—C25—H25A | 120.0 (16) |
C3—C4—H4A | 119.5 (15) | C25—C26—C27 | 120.2 (2) |
C6—C5—C4 | 119.0 (2) | C25—C26—H26A | 120.8 (13) |
C6—C5—H5A | 119.8 (15) | C27—C26—H26A | 119.0 (14) |
C4—C5—H5A | 121.1 (15) | C26—C27—C22 | 120.8 (2) |
C5—C6—C1 | 122.0 (2) | C26—C27—H27A | 122.7 (15) |
C5—C6—H6A | 120.4 (13) | C22—C27—H27A | 116.4 (15) |
Experimental details
(II) | (III) | |
Crystal data | ||
Chemical formula | C14H12OS | C15H14OS |
Mr | 228.30 | 242.32 |
Crystal system, space group | Monoclinic, P21/c | Orthorhombic, Pbca |
Temperature (K) | 293 | 150 |
a, b, c (Å) | 9.0151 (7), 12.7805 (14), 10.6400 (12) | 7.8838 (18), 14.719 (3), 21.277 (4) |
α, β, γ (°) | 90, 105.497 (7), 90 | 90, 90, 90 |
V (Å3) | 1181.3 (2) | 2469.1 (9) |
Z | 4 | 8 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 2.22 | 2.15 |
Crystal size (mm) | 0.58 × 0.47 × 0.39 | 0.54 × 0.18 × 0.12 |
Data collection | ||
Diffractometer | Stoe Stadi-4 four-circle diffractometer | Stoe Stadi-4 four-circle diffractometer |
Absorption correction | ψ scans (North et al., 1968) | ψ scans (North et al., 1968) |
Tmin, Tmax | 0.331, 0.420 | 0.429, 0.581 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3137, 2070, 1754 | 2272, 1790, 1520 |
Rint | 0.033 | 0.011 |
θmax (°) | 70.0 | 59.9 |
(sin θ/λ)max (Å−1) | 0.610 | 0.561 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.110, 1.07 | 0.033, 0.087, 1.02 |
No. of reflections | 2070 | 1790 |
No. of parameters | 147 | 211 |
H-atom treatment | See text | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.30, −0.19 | 0.19, −0.30 |
Computer programs: DIF4 (Stoe & Cie, 1990a), DIF4, REDU4 (Stoe & Cie, 1990b), SHELXTL (Sheldrick, 1997), SHELXTL.
C1—C6 | 1.400 (3) | C2—S21 | 1.7694 (18) |
C1—C2 | 1.414 (3) | S21—C22 | 1.781 (2) |
C1—C11 | 1.484 (3) | C3—C4 | 1.381 (3) |
C11—O11 | 1.213 (2) | C4—C5 | 1.376 (3) |
C11—C12 | 1.498 (3) | C5—C6 | 1.367 (3) |
C2—C3 | 1.389 (3) | ||
C6—C1—C2 | 118.13 (18) | C3—C2—S21 | 121.30 (15) |
C6—C1—C11 | 119.97 (17) | C1—C2—S21 | 120.06 (14) |
C2—C1—C11 | 121.90 (17) | C2—S21—C22 | 103.24 (9) |
O11—C11—C1 | 120.64 (18) | C4—C3—C2 | 121.42 (19) |
O11—C11—C12 | 119.6 (2) | C5—C4—C3 | 120.2 (2) |
C1—C11—C12 | 119.76 (19) | C6—C5—C4 | 119.25 (19) |
C3—C2—C1 | 118.64 (17) | C5—C6—C1 | 122.32 (19) |
C1—C6 | 1.393 (3) | C2—S21 | 1.7706 (19) |
C1—C2 | 1.415 (3) | C3—C4 | 1.385 (3) |
C1—C11 | 1.487 (3) | C4—C5 | 1.382 (3) |
C11—O11 | 1.214 (2) | C5—C6 | 1.375 (3) |
C11—C12 | 1.503 (3) | S21—C21 | 1.821 (2) |
C2—C3 | 1.398 (3) | ||
C6—C1—C2 | 118.92 (18) | C3—C2—S21 | 121.27 (15) |
C6—C1—C11 | 120.13 (18) | C1—C2—S21 | 120.27 (14) |
C2—C1—C11 | 120.95 (17) | C4—C3—C2 | 120.90 (19) |
O11—C11—C1 | 120.40 (18) | C5—C4—C3 | 120.6 (2) |
O11—C11—C12 | 120.2 (2) | C6—C5—C4 | 119.0 (2) |
C1—C11—C12 | 119.40 (19) | C5—C6—C1 | 122.0 (2) |
C3—C2—C1 | 118.46 (17) | C2—S21—C21 | 102.62 (10) |
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The crystal structure of 2-(phenylmethylthio)benzaldehyde, (I), was recently reported (Wong & Lee, 1995). In connection with the study of iminyl and thiophenoxyl radical cyclization reactions (Creed et al., 2001) we required the acetophenone derivatives (II) and (III) as starting materials. There is structural interest in related systems (Wong & Lee, 1995; Kucsman et al., 1984; Kucsman et al., 1986) because of the presence of a short S···O intramolecular distance which is suggestive of a weak interaction between the two heteroatoms. This can be represented by a contribution of the heterocyclic resonance form (Ia). Structural data on benzene derivatives containing ortho-disposed carbonyl and sulfur-containing substituents are rare; apart from aldehyde (I) the only relevant data available concern esters (IV)-(VII) and the diazo compound (VIII). We now report the crystal structures of the two related acetophenone derivatives. \sch
In (I)-(III), the C═O group is aligned s-Z to the ortho substituent. The angle between the best plane of the acetyl group and that of the aryl group to which it is attached is only 6.2 (4)° in (II), whereas it is 25.87 (16)° in (III); these compare with a corresponding angle of 4.4° in aldehyde (I). In (II) the phenyl rings are almost orthogonal to each other [88.29 (7)°], whereas in (I) and (III) the corresponding angles are 78.3 and 62.21 (5)°, respectively. The two Ar—S bonds in (II) are significantly different. The shorter [1.7694 (18) Å] is associated with the ring bearing the acetyl group; that associated with the unsubstituted phenyl group [1.781 (2) Å] is longer because the group is twisted out of the plane. Therefore even in the diarylsulfide (II), the lone pair of the sulfur atom interacts preferentially with the aryl ring carrying the acetyl group. These features would be expected if the cyclic resonance (###AUTHOR: OK to add this ?) form, e.g. (Ia), contributes to the overall structure.
The non-bonded S···O distance in (I) was reported to be unusually short at 2.804 (2) Å, and this was interpreted as indicating a weak interaction. The related distances in (II) and (III) are even shorter, at 2.6578 (18) and 2.7125 (17) Å, respectively. These are of a similar order of magnitude to related distances in structures (IV)–(VIII). However, these interactions are substantially weaker than in the 6,6a-dithiafurophthenes, where S···O distances can be as short as 2.287 Å (Saethre & Hordvik, 1975, CSD refcode: MAPTFU10).
The geometries of the disubstituted aryl rings in (I)-(III) are substantially distorted. The bond between the two substituents is the longest in each case: 1.408 (4), 1.414 (3) and 1.415 (3) Å, respectively, which may, in part, be rationalized by a contribution of resonance (###AUTHOR: OK to add this ?) structures of type (Ia). Similarly the shortest bond - differing from the largest by over 6σ in all three structures - is C5—C6 [1.361 (4), 1.367 (3) and 1.375 (3) Å in (I)-(III), respectively]. In (I)-(III) the bonds C3—C4 and C4—C5 are shorter than average, whereas C2—C3 and C1—C6 are longer than average. Intra-ring bond angles at the substituted sites in (II) and (III) are 118–119°, whereas the angles at C6 are around 122° in each case. The geometries of the S-phenyl group in (II) and the benzyl group in (III) are very regular.