Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103021309/gg1187sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103021309/gg1187Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103021309/gg1187IIsup3.hkl |
CCDC references: 226135; 226136
Both compounds were obtained from Key Organics Ltd and crystals were grown from ethanol solution.
All H atoms were included in the refinement, at calculated positions, in the riding-model approximation, with C—H distances of 0.95 Å (Ar—H). The isotropic displacement parameters were set equal to 1.25Ueq of the carrier atom. The high weighting values for both (I) and (II) were the result of the soft poor-quality crystals obtained. There is no discernible disorder in the CF3 group in the structure of (II).
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998) for (I); DENZO (Otwinowski & Minor, 1997 and COLLECT (Hooft, 1998) for (II). For both compounds, cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.
C13H7ClF3NO2S | Z = 2 |
Mr = 333.71 | F(000) = 336 |
Triclinic, P1 | Dx = 1.645 Mg m−3 |
Hall symbol: -P 1 | Melting point: ? K K |
a = 7.1953 (14) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.4763 (17) Å | Cell parameters from 2771 reflections |
c = 11.811 (2) Å | θ = 2.9–30.5° |
α = 84.35 (3)° | µ = 0.48 mm−1 |
β = 88.05 (3)° | T = 150 K |
γ = 70.06 (3)° | Needle, yellow |
V = 673.8 (2) Å3 | 0.20 × 0.06 × 0.06 mm |
Nonius KappaCCD area-detector diffractometer | 2336 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 1564 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.0°, θmin = 3.0° |
ϕ and ω scans | h = −8→8 |
Absorption correction: multi-scan SORTAV (Blessing, 1995) | k = −9→10 |
Tmin = 0.911, Tmax = 0.972 | l = −14→14 |
4967 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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.202 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.1266P)2] where P = (Fo2 + 2Fc2)/3 |
2336 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C13H7ClF3NO2S | γ = 70.06 (3)° |
Mr = 333.71 | V = 673.8 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.1953 (14) Å | Mo Kα radiation |
b = 8.4763 (17) Å | µ = 0.48 mm−1 |
c = 11.811 (2) Å | T = 150 K |
α = 84.35 (3)° | 0.20 × 0.06 × 0.06 mm |
β = 88.05 (3)° |
Nonius KappaCCD area-detector diffractometer | 2336 independent reflections |
Absorption correction: multi-scan SORTAV (Blessing, 1995) | 1564 reflections with I > 2σ(I) |
Tmin = 0.911, Tmax = 0.972 | Rint = 0.057 |
4967 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.202 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.36 e Å−3 |
2336 reflections | Δρmin = −0.34 e Å−3 |
190 parameters |
Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) − 6.1676 (0.0067) x + 1.0443 (0.0131) y + 3.2430 (0.0171) z = 0.9122 (0.0148) * 0.0113 (0.0026) C1 * −0.0117 (0.0026) C2 * −0.0006 (0.0027) C3 * 0.0131 (0.0027) C4 * −0.0132 (0.0026) C5 * 0.0010 (0.0027) C6 Rms deviation of fitted atoms = 0.0101 0.4458 (0.0122) x + 6.3194 (0.0096) y − 6.5896 (0.0169) z = 4.5579 (0.0087) Angle to previous plane (with approximate e.s.d.) = 83.11 (0.13) * −0.0008 (0.0026) C7 * 0.0021 (0.0028) C8 * −0.0027 (0.0028) C9 * 0.0020 (0.0029) C10 * −0.0006 (0.0029) C11 * 0.0000 (0.0027) C12 Rms deviation of fitted atoms = 0.0017 |
x | y | z | Uiso*/Ueq | ||
C1 | 0.1761 (5) | 0.8402 (4) | 0.3492 (3) | 0.0450 (9) | |
C2 | 0.2390 (5) | 0.8915 (4) | 0.4451 (3) | 0.0463 (9) | |
N21 | 0.2727 (5) | 1.0537 (4) | 0.4400 (3) | 0.0584 (9) | |
O21 | 0.2988 (6) | 1.1188 (4) | 0.3469 (3) | 0.0901 (12) | |
O22 | 0.2784 (5) | 1.1130 (4) | 0.5284 (3) | 0.0763 (10) | |
C3 | 0.2751 (6) | 0.7952 (5) | 0.5482 (3) | 0.0483 (9) | |
H3 | 0.3157 | 0.8355 | 0.6119 | 0.060* | |
C4 | 0.2517 (5) | 0.6398 (4) | 0.5581 (3) | 0.0469 (9) | |
C41 | 0.2794 (7) | 0.5381 (5) | 0.6695 (3) | 0.0568 (10) | |
F41 | 0.3657 (5) | 0.3737 (3) | 0.6601 (2) | 0.0834 (9) | |
F42 | 0.1060 (4) | 0.5509 (4) | 0.7204 (2) | 0.0799 (8) | |
F43 | 0.3844 (6) | 0.5801 (4) | 0.7423 (2) | 0.1055 (12) | |
C5 | 0.1965 (6) | 0.5824 (5) | 0.4633 (3) | 0.0490 (9) | |
H5 | 0.1854 | 0.4734 | 0.4687 | 0.061* | |
C6 | 0.1574 (6) | 0.6808 (5) | 0.3618 (3) | 0.0501 (9) | |
H6 | 0.1167 | 0.6396 | 0.2985 | 0.063* | |
S1 | 0.11982 (18) | 0.97010 (13) | 0.22007 (9) | 0.0611 (4) | |
C7 | −0.0167 (6) | 0.8736 (5) | 0.1451 (3) | 0.0518 (10) | |
C8 | −0.2161 (7) | 0.9094 (5) | 0.1655 (3) | 0.0600 (11) | |
H8 | −0.2778 | 0.9767 | 0.2251 | 0.075* | |
C9 | −0.3266 (7) | 0.8480 (5) | 0.0999 (3) | 0.0613 (11) | |
H9 | −0.4637 | 0.8715 | 0.1141 | 0.077* | |
C10 | −0.2344 (7) | 0.7524 (5) | 0.0137 (3) | 0.0574 (11) | |
Cl1 | −0.3736 (2) | 0.67802 (16) | −0.07093 (10) | 0.0868 (5) | |
C11 | −0.0369 (7) | 0.7156 (5) | −0.0078 (3) | 0.0624 (11) | |
H11 | 0.0244 | 0.6486 | −0.0676 | 0.078* | |
C12 | 0.0719 (7) | 0.7770 (5) | 0.0584 (3) | 0.0583 (11) | |
H12 | 0.2091 | 0.7525 | 0.0440 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.037 (2) | 0.0461 (19) | 0.053 (2) | −0.0154 (17) | −0.0030 (16) | −0.0029 (16) |
C2 | 0.038 (2) | 0.0404 (19) | 0.061 (2) | −0.0138 (16) | 0.0003 (17) | −0.0061 (17) |
N21 | 0.049 (2) | 0.0504 (19) | 0.081 (2) | −0.0223 (17) | −0.0082 (18) | −0.008 (2) |
O21 | 0.122 (3) | 0.078 (2) | 0.091 (2) | −0.065 (2) | −0.030 (2) | 0.0214 (19) |
O22 | 0.087 (3) | 0.0611 (19) | 0.093 (2) | −0.0350 (18) | 0.0043 (18) | −0.0296 (17) |
C3 | 0.042 (2) | 0.054 (2) | 0.049 (2) | −0.0148 (18) | −0.0004 (16) | −0.0118 (17) |
C4 | 0.040 (2) | 0.050 (2) | 0.050 (2) | −0.0134 (17) | −0.0012 (16) | −0.0057 (17) |
C41 | 0.056 (3) | 0.062 (3) | 0.054 (2) | −0.022 (2) | −0.003 (2) | −0.0057 (19) |
F41 | 0.097 (2) | 0.0613 (16) | 0.0732 (16) | −0.0066 (15) | −0.0007 (15) | 0.0087 (13) |
F42 | 0.072 (2) | 0.0955 (19) | 0.0659 (15) | −0.0247 (15) | 0.0150 (14) | 0.0025 (13) |
F43 | 0.148 (3) | 0.125 (3) | 0.0725 (16) | −0.087 (2) | −0.0542 (18) | 0.0192 (17) |
C5 | 0.048 (2) | 0.047 (2) | 0.055 (2) | −0.0200 (18) | −0.0019 (17) | −0.0030 (18) |
C6 | 0.051 (3) | 0.049 (2) | 0.050 (2) | −0.0168 (18) | −0.0076 (17) | −0.0032 (17) |
S1 | 0.0686 (8) | 0.0588 (7) | 0.0605 (7) | −0.0303 (6) | −0.0128 (5) | 0.0082 (5) |
C7 | 0.055 (3) | 0.052 (2) | 0.0475 (19) | −0.0181 (19) | −0.0078 (18) | 0.0045 (17) |
C8 | 0.058 (3) | 0.071 (3) | 0.045 (2) | −0.014 (2) | −0.0024 (19) | −0.0036 (19) |
C9 | 0.049 (3) | 0.073 (3) | 0.057 (2) | −0.016 (2) | −0.0029 (19) | 0.000 (2) |
C10 | 0.061 (3) | 0.054 (2) | 0.053 (2) | −0.014 (2) | −0.0209 (19) | 0.0056 (18) |
Cl1 | 0.0876 (11) | 0.0801 (9) | 0.0929 (9) | −0.0236 (7) | −0.0352 (7) | −0.0155 (7) |
C11 | 0.071 (3) | 0.056 (2) | 0.056 (2) | −0.016 (2) | 0.001 (2) | −0.007 (2) |
C12 | 0.052 (3) | 0.057 (2) | 0.060 (2) | −0.014 (2) | 0.002 (2) | 0.003 (2) |
C1—C2 | 1.394 (5) | C5—H5 | 0.95 |
C1—C6 | 1.396 (5) | C6—H6 | 0.95 |
C1—S1 | 1.763 (4) | S1—C7 | 1.780 (4) |
C2—C3 | 1.378 (5) | C7—C12 | 1.375 (6) |
C2—N21 | 1.470 (5) | C7—C8 | 1.379 (6) |
N21—O22 | 1.210 (4) | C8—C9 | 1.381 (6) |
N21—O21 | 1.219 (4) | C8—H8 | 0.95 |
C3—C4 | 1.377 (5) | C9—C10 | 1.372 (6) |
C3—H3 | 0.95 | C9—H9 | 0.95 |
C4—C5 | 1.385 (5) | C10—C11 | 1.367 (6) |
C4—C41 | 1.481 (5) | C10—Cl1 | 1.739 (4) |
C41—F43 | 1.313 (5) | C11—C12 | 1.376 (6) |
C41—F41 | 1.332 (5) | C11—H11 | 0.95 |
C41—F42 | 1.341 (5) | C12—H12 | 0.95 |
C5—C6 | 1.371 (5) | ||
C2—C1—C6 | 116.1 (3) | C4—C5—H5 | 119.6 |
C2—C1—S1 | 122.0 (3) | C5—C6—C1 | 121.5 (3) |
C6—C1—S1 | 121.9 (3) | C5—C6—H6 | 119.2 |
C3—C2—C1 | 122.9 (3) | C1—C6—H6 | 119.2 |
C3—C2—N21 | 116.3 (3) | C1—S1—C7 | 102.55 (17) |
C1—C2—N21 | 120.7 (3) | C12—C7—C8 | 119.7 (4) |
O22—N21—O21 | 123.5 (3) | C12—C7—S1 | 119.8 (3) |
O22—N21—C2 | 118.4 (4) | C8—C7—S1 | 120.2 (3) |
O21—N21—C2 | 118.0 (3) | C7—C8—C9 | 120.4 (4) |
C4—C3—C2 | 119.4 (3) | C7—C8—H8 | 119.8 |
C4—C3—H3 | 120.3 | C9—C8—H8 | 119.8 |
C2—C3—H3 | 120.3 | C10—C9—C8 | 118.7 (4) |
C3—C4—C5 | 119.2 (3) | C10—C9—H9 | 120.7 |
C3—C4—C41 | 120.3 (3) | C8—C9—H9 | 120.7 |
C5—C4—C41 | 120.6 (3) | C11—C10—C9 | 121.7 (4) |
F43—C41—F41 | 107.0 (4) | C11—C10—Cl1 | 119.4 (3) |
F43—C41—F42 | 106.6 (3) | C9—C10—Cl1 | 118.9 (4) |
F41—C41—F42 | 104.3 (3) | C10—C11—C12 | 119.1 (4) |
F43—C41—C4 | 114.0 (3) | C10—C11—H11 | 120.4 |
F41—C41—C4 | 112.6 (3) | C12—C11—H11 | 120.4 |
F42—C41—C4 | 111.7 (3) | C7—C12—C11 | 120.4 (4) |
C6—C5—C4 | 120.8 (3) | C7—C12—H12 | 119.8 |
C6—C5—H5 | 119.6 | C11—C12—H12 | 119.8 |
C6—C1—C2—C3 | −2.1 (6) | C41—C4—C5—C6 | 175.5 (4) |
S1—C1—C2—C3 | 177.0 (3) | C4—C5—C6—C1 | 1.5 (6) |
C6—C1—C2—N21 | 177.1 (3) | C2—C1—C6—C5 | 0.8 (6) |
S1—C1—C2—N21 | −3.8 (5) | S1—C1—C6—C5 | −178.2 (3) |
C3—C2—N21—O22 | −18.9 (5) | C2—C1—S1—C7 | −163.6 (3) |
C1—C2—N21—O22 | 161.8 (4) | C6—C1—S1—C7 | 15.4 (4) |
C3—C2—N21—O21 | 159.1 (4) | C1—S1—C7—C12 | −103.7 (3) |
C1—C2—N21—O21 | −20.2 (6) | C1—S1—C7—C8 | 83.1 (4) |
C1—C2—C3—C4 | 1.0 (6) | C12—C7—C8—C9 | 0.4 (6) |
N21—C2—C3—C4 | −178.2 (3) | S1—C7—C8—C9 | 173.6 (3) |
C2—C3—C4—C5 | 1.4 (6) | C7—C8—C9—C10 | −0.6 (6) |
C2—C3—C4—C41 | −176.8 (3) | C8—C9—C10—C11 | 0.6 (6) |
C3—C4—C41—F43 | −20.7 (6) | C8—C9—C10—Cl1 | −178.8 (3) |
C5—C4—C41—F43 | 161.2 (4) | C9—C10—C11—C12 | −0.4 (6) |
C3—C4—C41—F41 | −142.8 (4) | Cl1—C10—C11—C12 | 179.0 (3) |
C5—C4—C41—F41 | 39.1 (5) | C8—C7—C12—C11 | −0.2 (6) |
C3—C4—C41—F42 | 100.2 (4) | S1—C7—C12—C11 | −173.5 (3) |
C5—C4—C41—F42 | −77.9 (5) | C10—C11—C12—C7 | 0.2 (6) |
C3—C4—C5—C6 | −2.6 (6) |
C13H7ClF3NO2S | F(000) = 672 |
Mr = 333.71 | Dx = 1.583 Mg m−3 |
Monoclinic, P21/n | Melting point: ? K K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 12.335 (3) Å | Cell parameters from 11965 reflections |
b = 9.2477 (18) Å | θ = 2.9–27.5° |
c = 12.929 (3) Å | µ = 0.46 mm−1 |
β = 108.32 (3)° | T = 568 K |
V = 1400.1 (5) Å3 | Plate, colourless |
Z = 4 | 0.30 × 0.27 × 0.02 mm |
Nonius KappaCCD area-detector diffractometer | 3183 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 1305 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.091 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −15→15 |
Absorption correction: multi-scan SORTAV (Blessing, 1995) | k = −11→11 |
Tmin = 0.875, Tmax = 0.991 | l = −16→16 |
10187 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.083 | H-atom parameters constrained |
wR(F2) = 0.258 | w = 1/[σ2(Fo2) + (0.1331P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
3183 reflections | Δρmax = 0.66 e Å−3 |
191 parameters | Δρmin = −0.39 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.051 (8) |
C13H7ClF3NO2S | V = 1400.1 (5) Å3 |
Mr = 333.71 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.335 (3) Å | µ = 0.46 mm−1 |
b = 9.2477 (18) Å | T = 568 K |
c = 12.929 (3) Å | 0.30 × 0.27 × 0.02 mm |
β = 108.32 (3)° |
Nonius KappaCCD area-detector diffractometer | 3183 independent reflections |
Absorption correction: multi-scan SORTAV (Blessing, 1995) | 1305 reflections with I > 2σ(I) |
Tmin = 0.875, Tmax = 0.991 | Rint = 0.091 |
10187 measured reflections |
R[F2 > 2σ(F2)] = 0.083 | 0 restraints |
wR(F2) = 0.258 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.66 e Å−3 |
3183 reflections | Δρmin = −0.39 e Å−3 |
191 parameters |
Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 8.3347 (0.0172) x + 6.8117 (0.0120) y − 2.3852 (0.0241) z = 5.2963 (0.0183) * 0.0084 (0.0031) C1 * −0.0057 (0.0031) C2 * 0.0012 (0.0029) C3 * 0.0008 (0.0029) C4 * 0.0020 (0.0031) C5 * −0.0067 (0.0032) C6 Rms deviation of fitted atoms = 0.0051 6.8408 (0.0229) x − 7.6930 (0.0120) y − 2.5004 (0.0256) z = 2.4145 (0.0250) Angle to previous plane (with approximate e.s.d.) = 76.20 (0.12) * 0.0053 (0.0031) C7 * −0.0016 (0.0033) C8 * −0.0060 (0.0033) C9 * 0.0099 (0.0033) C10 * −0.0060 (0.0033) C11 * −0.0016 (0.0032) C12 Rms deviation of fitted atoms = 0.0058 |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7970 (4) | 0.0018 (5) | 0.5659 (3) | 0.0637 (12) | |
C2 | 0.7821 (3) | −0.0210 (5) | 0.4550 (3) | 0.0629 (12) | |
C21 | 0.6917 (5) | 0.0536 (8) | 0.3679 (4) | 0.0952 (18) | |
F21 | 0.6899 (4) | 0.0160 (6) | 0.2701 (2) | 0.176 (2) | |
F22 | 0.5880 (3) | 0.0260 (5) | 0.3713 (3) | 0.1478 (17) | |
F23 | 0.6955 (4) | 0.1928 (5) | 0.3732 (3) | 0.1572 (18) | |
C3 | 0.8520 (4) | −0.1162 (5) | 0.4242 (3) | 0.0649 (12) | |
H3 | 0.8427 | −0.1299 | 0.3507 | 0.081* | |
C4 | 0.9351 (3) | −0.1910 (5) | 0.5012 (3) | 0.0573 (11) | |
N41 | 1.0086 (3) | −0.2915 (5) | 0.4693 (3) | 0.0806 (12) | |
O41 | 0.9996 (3) | −0.3004 (5) | 0.3724 (3) | 0.0975 (13) | |
O42 | 1.0762 (4) | −0.3634 (6) | 0.5392 (3) | 0.1267 (18) | |
C5 | 0.9510 (4) | −0.1721 (5) | 0.6101 (3) | 0.0675 (12) | |
H5 | 1.0079 | −0.2227 | 0.6619 | 0.084* | |
C6 | 0.8816 (4) | −0.0776 (5) | 0.6414 (3) | 0.0675 (13) | |
H6 | 0.8914 | −0.0661 | 0.7152 | 0.084* | |
S1 | 0.71112 (13) | 0.12763 (19) | 0.60618 (10) | 0.1004 (7) | |
C7 | 0.7642 (4) | 0.1212 (5) | 0.7501 (3) | 0.0646 (12) | |
C8 | 0.8640 (4) | 0.1929 (6) | 0.8055 (4) | 0.0754 (14) | |
H8 | 0.9050 | 0.2420 | 0.7671 | 0.094* | |
C9 | 0.9023 (4) | 0.1911 (6) | 0.9174 (4) | 0.0780 (14) | |
H9 | 0.9689 | 0.2398 | 0.9553 | 0.097* | |
C10 | 0.8420 (4) | 0.1175 (6) | 0.9725 (3) | 0.0745 (14) | |
Cl1 | 0.88837 (16) | 0.1151 (2) | 1.11375 (11) | 0.1304 (8) | |
C11 | 0.7416 (4) | 0.0479 (5) | 0.9185 (4) | 0.0787 (14) | |
H11 | 0.7001 | 0.0002 | 0.9570 | 0.098* | |
C12 | 0.7042 (4) | 0.0501 (5) | 0.8075 (4) | 0.0769 (14) | |
H12 | 0.6368 | 0.0026 | 0.7701 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.061 (2) | 0.074 (3) | 0.051 (2) | 0.003 (2) | 0.011 (2) | −0.006 (2) |
C2 | 0.057 (2) | 0.081 (3) | 0.047 (2) | 0.000 (2) | 0.0112 (19) | −0.004 (2) |
C21 | 0.099 (4) | 0.113 (6) | 0.055 (3) | 0.018 (4) | −0.002 (3) | 0.004 (3) |
F21 | 0.184 (4) | 0.275 (6) | 0.0488 (17) | 0.114 (4) | 0.006 (2) | 0.001 (2) |
F22 | 0.078 (2) | 0.210 (5) | 0.125 (3) | 0.029 (3) | −0.013 (2) | 0.003 (3) |
F23 | 0.200 (4) | 0.112 (4) | 0.110 (3) | 0.029 (3) | −0.021 (3) | 0.033 (2) |
C3 | 0.064 (2) | 0.080 (3) | 0.051 (2) | −0.014 (2) | 0.019 (2) | −0.009 (2) |
C4 | 0.054 (2) | 0.066 (3) | 0.055 (2) | −0.004 (2) | 0.022 (2) | −0.011 (2) |
N41 | 0.073 (3) | 0.099 (4) | 0.074 (3) | −0.005 (2) | 0.029 (2) | −0.020 (2) |
O41 | 0.099 (2) | 0.128 (4) | 0.076 (2) | 0.001 (2) | 0.0430 (19) | −0.021 (2) |
O42 | 0.124 (3) | 0.164 (5) | 0.091 (3) | 0.073 (3) | 0.031 (3) | −0.012 (3) |
C5 | 0.065 (2) | 0.080 (3) | 0.055 (2) | 0.009 (2) | 0.015 (2) | −0.007 (2) |
C6 | 0.073 (3) | 0.078 (3) | 0.048 (2) | 0.008 (2) | 0.015 (2) | −0.010 (2) |
S1 | 0.1028 (11) | 0.1272 (15) | 0.0601 (8) | 0.0528 (9) | 0.0096 (7) | −0.0097 (7) |
C7 | 0.067 (3) | 0.067 (3) | 0.060 (2) | 0.012 (2) | 0.021 (2) | −0.009 (2) |
C8 | 0.081 (3) | 0.078 (4) | 0.076 (3) | −0.006 (3) | 0.039 (3) | −0.001 (3) |
C9 | 0.070 (3) | 0.091 (4) | 0.072 (3) | −0.013 (3) | 0.022 (2) | −0.022 (3) |
C10 | 0.088 (3) | 0.079 (4) | 0.061 (3) | 0.021 (3) | 0.031 (3) | 0.004 (2) |
Cl1 | 0.1476 (15) | 0.177 (2) | 0.0608 (8) | 0.0519 (13) | 0.0241 (9) | 0.0051 (9) |
C11 | 0.088 (3) | 0.069 (4) | 0.089 (3) | −0.006 (3) | 0.043 (3) | 0.005 (3) |
C12 | 0.066 (3) | 0.079 (4) | 0.087 (3) | −0.005 (2) | 0.025 (3) | −0.018 (3) |
C1—C6 | 1.393 (6) | C5—H5 | 0.93 |
C1—C2 | 1.403 (5) | C6—H6 | 0.93 |
C1—S1 | 1.759 (4) | S1—C7 | 1.769 (4) |
C2—C3 | 1.376 (6) | C7—C12 | 1.370 (6) |
C2—C21 | 1.483 (7) | C7—C8 | 1.383 (6) |
C21—F23 | 1.289 (7) | C8—C9 | 1.374 (6) |
C21—F21 | 1.304 (6) | C8—H8 | 0.93 |
C21—F22 | 1.319 (7) | C9—C10 | 1.363 (7) |
C3—C4 | 1.371 (6) | C9—H9 | 0.93 |
C3—H3 | 0.93 | C10—C11 | 1.376 (7) |
C4—C5 | 1.369 (5) | C10—Cl1 | 1.734 (4) |
C4—N41 | 1.447 (5) | C11—C12 | 1.363 (7) |
N41—O42 | 1.216 (5) | C11—H11 | 0.93 |
N41—O41 | 1.225 (4) | C12—H12 | 0.93 |
C5—C6 | 1.370 (6) | ||
C6—C1—C2 | 117.7 (4) | C6—C5—H5 | 120.5 |
C6—C1—S1 | 122.0 (3) | C5—C6—C1 | 122.0 (4) |
C2—C1—S1 | 120.3 (3) | C5—C6—H6 | 119.0 |
C3—C2—C1 | 120.0 (4) | C1—C6—H6 | 119.0 |
C3—C2—C21 | 117.8 (4) | C1—S1—C7 | 103.35 (19) |
C1—C2—C21 | 122.2 (4) | C12—C7—C8 | 119.7 (4) |
F23—C21—F21 | 107.9 (5) | C12—C7—S1 | 120.1 (4) |
F23—C21—F22 | 102.2 (5) | C8—C7—S1 | 120.2 (4) |
F21—C21—F22 | 105.1 (5) | C9—C8—C7 | 119.6 (4) |
F23—C21—C2 | 114.7 (5) | C9—C8—H8 | 120.2 |
F21—C21—C2 | 113.1 (5) | C7—C8—H8 | 120.2 |
F22—C21—C2 | 113.0 (5) | C10—C9—C8 | 119.6 (4) |
C4—C3—C2 | 120.4 (4) | C10—C9—H9 | 120.2 |
C4—C3—H3 | 119.8 | C8—C9—H9 | 120.2 |
C2—C3—H3 | 119.8 | C9—C10—C11 | 121.4 (4) |
C5—C4—C3 | 121.0 (4) | C9—C10—Cl1 | 120.2 (4) |
C5—C4—N41 | 118.4 (4) | C11—C10—Cl1 | 118.3 (4) |
C3—C4—N41 | 120.6 (4) | C12—C11—C10 | 118.7 (4) |
O42—N41—O41 | 122.9 (4) | C12—C11—H11 | 120.6 |
O42—N41—C4 | 119.0 (4) | C10—C11—H11 | 120.6 |
O41—N41—C4 | 118.1 (4) | C11—C12—C7 | 121.0 (4) |
C4—C5—C6 | 119.0 (4) | C11—C12—H12 | 119.5 |
C4—C5—H5 | 120.5 | C7—C12—H12 | 119.5 |
C6—C1—C2—C3 | −1.7 (6) | N41—C4—C5—C6 | −179.8 (4) |
S1—C1—C2—C3 | 177.9 (3) | C4—C5—C6—C1 | −1.2 (7) |
C6—C1—C2—C21 | 177.6 (5) | C2—C1—C6—C5 | 1.8 (7) |
S1—C1—C2—C21 | −2.8 (7) | S1—C1—C6—C5 | −177.8 (4) |
C3—C2—C21—F23 | −123.5 (6) | C6—C1—S1—C7 | 1.3 (5) |
C1—C2—C21—F23 | 57.2 (7) | C2—C1—S1—C7 | −178.3 (4) |
C3—C2—C21—F21 | 0.7 (8) | C1—S1—C7—C12 | −104.1 (4) |
C1—C2—C21—F21 | −178.6 (5) | C1—S1—C7—C8 | 78.6 (4) |
C3—C2—C21—F22 | 119.9 (5) | C12—C7—C8—C9 | 0.4 (7) |
C1—C2—C21—F22 | −59.4 (7) | S1—C7—C8—C9 | 177.8 (4) |
C1—C2—C3—C4 | 1.0 (6) | C7—C8—C9—C10 | 0.6 (7) |
C21—C2—C3—C4 | −178.3 (5) | C8—C9—C10—C11 | −1.8 (7) |
C2—C3—C4—C5 | −0.4 (6) | C8—C9—C10—Cl1 | −179.5 (4) |
C2—C3—C4—N41 | 179.9 (4) | C9—C10—C11—C12 | 1.8 (7) |
C5—C4—N41—O42 | 5.3 (7) | Cl1—C10—C11—C12 | 179.6 (4) |
C3—C4—N41—O42 | −175.0 (5) | C10—C11—C12—C7 | −0.6 (7) |
C5—C4—N41—O41 | −174.9 (4) | C8—C7—C12—C11 | −0.5 (7) |
C3—C4—N41—O41 | 4.9 (6) | S1—C7—C12—C11 | −177.8 (4) |
C3—C4—C5—C6 | 0.5 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O41i | 0.93 | 2.50 | 3.397 (6) | 161 |
C11—H11···O42ii | 0.93 | 2.47 | 3.392 (6) | 174 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) x−1/2, −y−1/2, z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C13H7ClF3NO2S | C13H7ClF3NO2S |
Mr | 333.71 | 333.71 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n |
Temperature (K) | 150 | 568 |
a, b, c (Å) | 7.1953 (14), 8.4763 (17), 11.811 (2) | 12.335 (3), 9.2477 (18), 12.929 (3) |
α, β, γ (°) | 84.35 (3), 88.05 (3), 70.06 (3) | 90, 108.32 (3), 90 |
V (Å3) | 673.8 (2) | 1400.1 (5) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.48 | 0.46 |
Crystal size (mm) | 0.20 × 0.06 × 0.06 | 0.30 × 0.27 × 0.02 |
Data collection | ||
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan SORTAV (Blessing, 1995) | Multi-scan SORTAV (Blessing, 1995) |
Tmin, Tmax | 0.911, 0.972 | 0.875, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4967, 2336, 1564 | 10187, 3183, 1305 |
Rint | 0.057 | 0.091 |
(sin θ/λ)max (Å−1) | 0.595 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.202, 1.03 | 0.083, 0.258, 0.99 |
No. of reflections | 2336 | 3183 |
No. of parameters | 190 | 191 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.34 | 0.66, −0.39 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997 and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O41i | 0.93 | 2.50 | 3.397 (6) | 161.2 |
C11—H11···O42ii | 0.93 | 2.47 | 3.392 (6) | 173.6 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) x−1/2, −y−1/2, z+1/2. |
The crystal structure of the 1:1 molecular adduct of (+)-2-(3-methoxyphenoxy)propionic acid with (-)-2(3-bromophenoxy)propionic acid, determined by Karle & Karle (1966), was the first crystallographic example of a designed cocrystal. The idea behind this combination was based on the use of two chemically similar optically active compounds to prepare a quasi-racemate. The existence of such species had been identified previously, but by techniques other than crystallography [as reviewed by Fredga (1973)]. More recently, Wheeler and co-workers have published similar studies using phenoxy- (Hendi et al., 2001) or anilino-substituted propanoic acids (Fomulu et al., 2002a). In these structural studies, the components associate via a heteromolecular carboxylic acid dimer, giving each component a mutual site for strong hydrogen-bonding interaction. Opposing chirality in the two enantiomers is also essential when producing a quasi-racemate. Fomulu et al. (2002b) have also recently produced quasi-racemates using benzoyl-substituted benzyl amines.
We posed the question that if neither strong hydrogen-bonding sites nor chemical chirality were present, would, or could, two structurally similar chemical isomers still cocrystallize? To study this question, we chose isomeric pairs of compounds containing 3-nitrobenzotrifluoride, such that the nitro and trifluoromethyl groups were structurally interchanged. Both groups are known to be weak hydrogen-bond acceptors from strong hydrogen-bond donors (Allen et al., 1997; Brammer et al., 2001), but in the absence of such donors, the packing can only, if at all, be influenced by weak C—H interactions. A search of the April 2003 release of the Cambridge Structural Database (Allen, 2002) revealed 13 structures with a 3-nitrobenzotrifluoride moiety, although only four had one other substituent on the benzene ring, and two of these were bis(nitrotrifluoromethylphenyl) compounds that were bridged by either disulfide (Glidewell et al., 2000) or bis(sulfonyl)imide (Bombicz, 1995). Of the other two compounds, the additional substituents consisted of amine- (Glidewell et al., 2002) or amide-containing groups (He et al., 2001). Analyses of the crystal structures of the two individual components were essential in order to validate any comparisons to the cocrystal. Initial syntheses focused on thiophenol-substituted 3-nitrobenzotrifluoride. Again, the S atom in the thiophenol is not considered a strong hydrogen-bonding acceptor, and substituents on the thiophenol ring were limited to methyl and halogen groups. The first isomeric pair to simultaneously crystallize were 1-(4-chlorophenylsulfanyl)-2-nitro-4-(trifluoromethyl)benzene, (I), and 1-(4-chlorophenylsulfanyl)-4-nitro-2-(trifluoromethyl)benzene, (II), whose respective crystal structures are reported here.
The similar conformations of (I) and (II) are shown in Figs. 1 and 2, respectively. The compounds have a similar dihedral angle between the two benzene rings [83.1 (1) and 76.2 (1)°, respectively] but differ in their C6—C1—S1—C7 torsion angle [15.4 (4) and 1.3 (5)°, respectively]. The low torsion angle for (II) is a result of the orientation of the trifluoromethyl group and the lateral positions of atoms F22 and F23. The most significant difference between the two structures is in their packing, with (I) (Fig. 3) being triclinic P-1 and (II) (Fig. 4) being monoclinic P21/c. The 4-nitro group in (II) is involved in C—H···O interactions (Table 1), whereas no such associations are recorded in (I), nor are there any similar C—H close contacts recorded for either of the trifluoromethyl groups. However, in (I) there is a short contact [3.193 (5) Å] between atoms Cl1 and F43 (−1 + x, y, −1 + z). Attempts to cocrystallize (I) and (II) by dissolving equimolar amounts of each component in various solvents, with warming, and then allowing evaporation to dryness, led to the recrystallization in each case of the individual compounds. This result? was identified by distinct differences in the crystal morphology and the infrared analysis of each crystal type. The inability of (I) and (II) to cocrystallize may be due to the C—H···O interactions in (II), meaning that one molecule of (II) will preferentially associate with another molecule of (II) rather than a molecule of (I), thus propagating phase separation. Few conclusions can be drawn from just one isomeric pair, but the C—H···O interactions will be examined more closely as these studies into isomers of 3-nitrobenzotrifluoride progress.