The title compound, C
18H
14F
4N
2O
2S·CHCl
3, forms a one-dimensional hydrogen-bonded chain
via a single O—H
N interaction; the chain runs approximately along the [110] axis. The two benzene rings are almost parallel to one another, forming a dihedral angle of 8.43 (8)°.
Supporting information
CCDC reference: 287444
Key indicators
- Single-crystal X-ray study
- T = 253 K
- Mean (C-C) = 0.003 Å
- Disorder in main residue
- R factor = 0.047
- wR factor = 0.089
- Data-to-parameter ratio = 14.6
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C11
Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
PLAT213_ALERT_2_C Atom F32 has ADP max/min Ratio ............. 3.20 prolat
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for S1
PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for Cl31
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C19
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.11
PLAT301_ALERT_3_C Main Residue Disorder ......................... 10.00 Perc.
PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 43.00 Perc.
PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C8 - C9 ... 1.45 Ang.
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
9 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
5 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
3 ALERT type 4 Improvement, methodology, query or suggestion
2-Hydroxy-2-methyl-3-p-tolylsulfanyl-propionic acid (36.5 g, 159 mmol), 2-trifluoromethyl-4-aminobenzonitrile (38.0 g, 200 mmol) and N,N-dimethyl acetamide (300 ml) were mixed in a 500 ml three-necked bottle and stirred at 263 K. Thionyl chloride (12 ml, 164 mmol) was then added dropwise to the solution and the resulting mixture was kept for 30 min at 258–263 K and then allowed to react for 24 h. After that time, the reaction solution was poured into ice–water (600 ml) and extracted with CH2Cl2 (Volume?). The organic part was washed with HCl (3 M, 4 × 300 ml), NaCl (saturated solution, 2 × 150 ml), NaHCO3 (saturated solution, 3 × 150 ml) and NaCl (saturated solution, 2 × 150 ml), and dried over anhydrous MgSO4. Compound (I) was recovered after vacuum distillation. The final product was recrystallized from a mixture of toluene and petroleum ether (5:1) (yield 26 g, 41%) (Thurlow, 1998; Sepp-Lorenzino & Slovin, 2000). Finally, compound (I) was recrystallized from chloroform, giving colourless crystals suitable for X-ray diffraction.
The Cl atoms of the chloroform molecule and the F atoms of the CF3 group were found to be disordered. Each atom was split over two sites and the site occupancy factors were roughly refined with the sums constrained to 1, and then fixed. H atoms belonging to the hydroxy and amido groups and to the CHCl3 molecule were located in difference maps and included in the refinement with as-found constrained O—H, N—H and C—H bond lengths. Other H atoms were placed in calculated positions and refined using a riding model. Constrained C—H bond lengths are 0.98 Å for aromatic CH, 0.97 Å for methylene CH2 and 0.96 Å for methyl CH3. For all H atoms, Uiso(H) values were refined and then fixed in the final cycles.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: Crystal Structure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: Crystal Structure.
N-[4-Cyano-3-(trifluoromethyl)phenyl]-3-(4-fluorophenylsulfanyl)-2-hydroxy- 2-methylpropionamide chloroform solvate
top
Crystal data top
C18H14F4N2O2S·CHCl3 | Z = 2 |
Mr = 517.75 | F(000) = 524.00 |
Triclinic, P1 | Dx = 1.561 Mg m−3 |
Hall symbol: -P 1 | Melting point: 390(1) K |
a = 8.8442 (9) Å | Mo Kα radiation, λ = 0.7107 Å |
b = 10.4591 (9) Å | Cell parameters from 4876 reflections |
c = 13.319 (1) Å | θ = 2.2–27.5° |
α = 110.718 (4)° | µ = 0.56 mm−1 |
β = 90.895 (2)° | T = 253 K |
γ = 105.595 (2)° | Block, colourless |
V = 1101.5 (2) Å3 | 0.42 × 0.33 × 0.28 mm |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 3260 reflections with F2 > 2σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.025 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −11→11 |
Tmin = 0.738, Tmax = 0.854 | k = −13→13 |
9744 measured reflections | l = −17→17 |
4896 independent reflections | |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[0.0002Fo2 + 3σ(Fo2) + 0.5]/(4Fo2) |
wR(F2) = 0.089 | (Δ/σ)max = 0.010 |
S = 0.96 | Δρmax = 0.39 e Å−3 |
4892 reflections | Δρmin = −0.38 e Å−3 |
334 parameters | |
Crystal data top
C18H14F4N2O2S·CHCl3 | γ = 105.595 (2)° |
Mr = 517.75 | V = 1101.5 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.8442 (9) Å | Mo Kα radiation |
b = 10.4591 (9) Å | µ = 0.56 mm−1 |
c = 13.319 (1) Å | T = 253 K |
α = 110.718 (4)° | 0.42 × 0.33 × 0.28 mm |
β = 90.895 (2)° | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 4896 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3260 reflections with F2 > 2σ(F2) |
Tmin = 0.738, Tmax = 0.854 | Rint = 0.025 |
9744 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 334 parameters |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.39 e Å−3 |
4892 reflections | Δρmin = −0.38 e Å−3 |
Special details top
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY |
Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cl11 | 1.2062 (2) | 0.8504 (2) | 0.4380 (1) | 0.0960 (5) | 0.70 |
Cl12 | 1.1429 (8) | 0.8661 (8) | 0.4300 (6) | 0.172 (3) | 0.30 |
Cl21 | 1.0358 (2) | 0.9036 (2) | 0.6305 (1) | 0.1095 (5) | 0.80 |
Cl22 | 1.017 (2) | 0.923 (1) | 0.5951 (6) | 0.166 (4) | 0.20 |
Cl31 | 0.9634 (3) | 0.6151 (2) | 0.4646 (2) | 0.1167 (8) | 0.50 |
Cl32 | 0.9101 (3) | 0.6728 (2) | 0.4393 (2) | 0.1071 (7) | 0.50 |
S1 | 0.29974 (8) | 0.17911 (6) | 0.16587 (5) | 0.0675 (2) | |
F4 | 0.5753 (2) | 0.7802 (1) | 0.4490 (1) | 0.1209 (7) | |
F11 | 1.0834 (8) | 0.0945 (2) | −0.1285 (6) | 0.117 (2) | 0.60 |
F12 | 1.114 (1) | 0.0985 (3) | −0.1135 (7) | 0.078 (2) | 0.40 |
F21 | 1.2803 (3) | 0.272 (1) | −0.0626 (8) | 0.069 (2) | 0.40 |
F22 | 1.2746 (3) | 0.2951 (7) | −0.0757 (6) | 0.131 (2) | 0.60 |
F31 | 1.092 (1) | 0.276 (1) | −0.1613 (5) | 0.117 (2) | 0.70 |
F32 | 1.041 (2) | 0.234 (2) | −0.1663 (8) | 0.106 (4) | 0.30 |
O1 | 0.4501 (1) | −0.0655 (1) | 0.09616 (9) | 0.0475 (4) | |
O2 | 0.6803 (2) | 0.2435 (1) | 0.3121 (1) | 0.0509 (4) | |
N1 | 0.7076 (2) | 0.1402 (1) | 0.1344 (1) | 0.0418 (4) | |
N2 | 1.3224 (2) | 0.6270 (2) | 0.0573 (2) | 0.0659 (6) | |
C1 | 0.3477 (2) | 0.0824 (2) | 0.2440 (2) | 0.0505 (6) | |
C2 | 0.4850 (2) | 0.0225 (2) | 0.2082 (1) | 0.0399 (5) | |
C3 | 0.5171 (3) | −0.0599 (2) | 0.2764 (2) | 0.0530 (6) | |
C4 | 0.6341 (2) | 0.1476 (2) | 0.2239 (1) | 0.0382 (5) | |
C5 | 0.8428 (2) | 0.2384 (2) | 0.1241 (1) | 0.0378 (5) | |
C6 | 0.9007 (2) | 0.3776 (2) | 0.1980 (1) | 0.0485 (6) | |
C7 | 1.0292 (2) | 0.4711 (2) | 0.1784 (1) | 0.0491 (6) | |
C8 | 1.1023 (2) | 0.4287 (2) | 0.0867 (1) | 0.0393 (5) | |
C9 | 1.2283 (2) | 0.5361 (2) | 0.0681 (2) | 0.0471 (6) | |
C10 | 1.0473 (2) | 0.2868 (2) | 0.0147 (1) | 0.0378 (5) | |
C11 | 1.1237 (2) | 0.2332 (1) | −0.0851 (2) | 0.0539 (7) | |
C12 | 0.9196 (2) | 0.1936 (2) | 0.0341 (1) | 0.0389 (5) | |
C13 | 0.3847 (2) | 0.3598 (2) | 0.2522 (2) | 0.0517 (6) | |
C14 | 0.3347 (3) | 0.4153 (3) | 0.3517 (2) | 0.0672 (8) | |
C15 | 0.3985 (3) | 0.5561 (3) | 0.4186 (2) | 0.0731 (9) | |
C16 | 0.5099 (4) | 0.6404 (3) | 0.3832 (2) | 0.0784 (9) | |
C17 | 0.5615 (3) | 0.5922 (3) | 0.2851 (2) | 0.080 (1) | |
C18 | 0.4983 (3) | 0.4503 (3) | 0.2190 (2) | 0.0656 (8) | |
C19 | 1.0889 (3) | 0.7859 (2) | 0.5206 (2) | 0.0822 (9) | |
H2 | 0.3749 | 0.1468 | 0.3191 | 0.058* | |
H3 | 0.2552 | 0.0035 | 0.2373 | 0.058* | |
H6 | 0.8509 | 0.4099 | 0.2639 | 0.053* | |
H7 | 1.0690 | 0.5697 | 0.2307 | 0.053* | |
H12 | 0.8823 | 0.0940 | −0.0166 | 0.044* | |
H14 | 0.2519 | 0.3527 | 0.3754 | 0.082* | |
H15 | 0.3636 | 0.5940 | 0.4898 | 0.090* | |
H17 | 0.6427 | 0.6568 | 0.2619 | 0.102* | |
H18 | 0.5339 | 0.4137 | 0.1479 | 0.085* | |
H19 | 1.1278 | 0.7374 | 0.5588 | 0.094* | |
H31 | 0.5450 | 0.0031 | 0.3509 | 0.064* | |
H32 | 0.6029 | −0.0980 | 0.2514 | 0.065* | |
H33 | 0.4242 | −0.1368 | 0.2696 | 0.065* | |
H101 | 0.4167 | −0.1595 | 0.0834 | 0.053* | |
H111 | 0.6655 | 0.0661 | 0.0770 | 0.045* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl11 | 0.094 (1) | 0.101 (1) | 0.092 (1) | 0.0254 (8) | 0.0354 (7) | 0.0359 (7) |
Cl12 | 0.255 (8) | 0.203 (5) | 0.158 (4) | 0.140 (5) | 0.101 (5) | 0.126 (4) |
Cl21 | 0.0899 (8) | 0.129 (1) | 0.0675 (9) | 0.0435 (8) | 0.0094 (6) | −0.0205 (9) |
Cl22 | 0.26 (1) | 0.196 (7) | 0.101 (6) | 0.152 (7) | 0.082 (6) | 0.058 (5) |
Cl31 | 0.124 (2) | 0.101 (2) | 0.080 (1) | 0.008 (1) | 0.030 (1) | −0.002 (1) |
Cl32 | 0.079 (1) | 0.114 (2) | 0.069 (1) | −0.006 (1) | 0.0094 (9) | −0.010 (1) |
S1 | 0.0756 (4) | 0.0606 (4) | 0.0607 (4) | 0.0246 (3) | −0.0138 (3) | 0.0134 (3) |
F4 | 0.172 (2) | 0.0521 (9) | 0.116 (1) | 0.016 (1) | −0.010 (1) | 0.0183 (9) |
F11 | 0.117 (4) | 0.061 (3) | 0.102 (4) | −0.021 (2) | 0.071 (3) | −0.022 (2) |
F12 | 0.132 (6) | 0.060 (4) | 0.077 (4) | 0.070 (4) | 0.047 (4) | 0.035 (4) |
F21 | 0.036 (4) | 0.115 (5) | 0.075 (4) | 0.042 (4) | 0.017 (3) | 0.040 (4) |
F22 | 0.087 (4) | 0.102 (3) | 0.123 (5) | −0.024 (3) | 0.068 (3) | −0.018 (3) |
F31 | 0.154 (4) | 0.187 (6) | 0.077 (3) | 0.104 (4) | 0.055 (2) | 0.088 (3) |
F32 | 0.17 (1) | 0.16 (1) | 0.036 (4) | 0.11 (1) | 0.050 (5) | 0.044 (5) |
O1 | 0.0578 (8) | 0.0340 (7) | 0.0381 (7) | −0.0012 (6) | 0.0059 (6) | 0.0096 (6) |
O2 | 0.0571 (9) | 0.0470 (8) | 0.0346 (7) | 0.0022 (6) | 0.0040 (6) | 0.0086 (6) |
N1 | 0.0437 (9) | 0.0341 (8) | 0.0342 (8) | −0.0009 (7) | 0.0053 (7) | 0.0061 (7) |
N2 | 0.062 (1) | 0.049 (1) | 0.078 (1) | −0.0031 (9) | 0.008 (1) | 0.028 (1) |
C1 | 0.045 (1) | 0.051 (1) | 0.050 (1) | 0.0080 (9) | 0.009 (1) | 0.017 (1) |
C2 | 0.045 (1) | 0.036 (1) | 0.033 (1) | 0.0052 (8) | 0.0055 (8) | 0.0121 (8) |
C3 | 0.062 (1) | 0.049 (1) | 0.050 (1) | 0.011 (1) | 0.009 (1) | 0.025 (1) |
C4 | 0.042 (1) | 0.036 (1) | 0.035 (1) | 0.0087 (8) | 0.0046 (8) | 0.0138 (8) |
C5 | 0.038 (1) | 0.035 (1) | 0.036 (1) | 0.0043 (8) | 0.0019 (8) | 0.0127 (8) |
C6 | 0.052 (1) | 0.039 (1) | 0.042 (1) | 0.0036 (9) | 0.0110 (9) | 0.0067 (9) |
C7 | 0.053 (1) | 0.031 (1) | 0.047 (1) | −0.0002 (9) | 0.006 (1) | 0.0055 (9) |
C8 | 0.035 (1) | 0.036 (1) | 0.043 (1) | 0.0031 (8) | 0.0042 (8) | 0.0159 (8) |
C9 | 0.045 (1) | 0.040 (1) | 0.050 (1) | 0.0050 (9) | 0.0022 (9) | 0.0150 (9) |
C10 | 0.035 (1) | 0.039 (1) | 0.039 (1) | 0.0081 (8) | 0.0040 (8) | 0.0154 (8) |
C11 | 0.056 (2) | 0.046 (1) | 0.052 (1) | 0.006 (1) | 0.016 (1) | 0.015 (1) |
C12 | 0.039 (1) | 0.0319 (9) | 0.037 (1) | 0.0034 (8) | 0.0003 (8) | 0.0082 (8) |
C13 | 0.051 (1) | 0.056 (1) | 0.053 (1) | 0.023 (1) | 0.004 (1) | 0.022 (1) |
C14 | 0.073 (2) | 0.062 (1) | 0.071 (2) | 0.025 (1) | 0.025 (1) | 0.026 (1) |
C15 | 0.100 (2) | 0.061 (2) | 0.065 (2) | 0.038 (1) | 0.020 (1) | 0.021 (1) |
C16 | 0.107 (2) | 0.051 (2) | 0.075 (2) | 0.024 (1) | −0.003 (2) | 0.021 (1) |
C17 | 0.089 (2) | 0.062 (2) | 0.103 (2) | 0.014 (1) | 0.019 (2) | 0.051 (2) |
C18 | 0.074 (2) | 0.077 (2) | 0.061 (1) | 0.034 (1) | 0.017 (1) | 0.036 (1) |
C19 | 0.091 (2) | 0.088 (2) | 0.052 (1) | 0.024 (1) | 0.012 (1) | 0.011 (1) |
Geometric parameters (Å, º) top
Cl11—C19 | 1.711 (3) | C7—C8 | 1.379 (3) |
Cl12—C19 | 1.705 (9) | C8—C9 | 1.448 (3) |
Cl21—C19 | 1.713 (3) | C8—C10 | 1.396 (2) |
Cl22—C19 | 1.72 (1) | C10—C11 | 1.498 (3) |
Cl31—C19 | 1.716 (3) | C10—C12 | 1.374 (3) |
Cl32—C19 | 1.763 (3) | C13—C14 | 1.378 (3) |
S1—C1 | 1.801 (3) | C13—C18 | 1.379 (3) |
S1—C13 | 1.769 (2) | C14—C15 | 1.375 (3) |
F4—C16 | 1.365 (2) | C15—C16 | 1.346 (4) |
F11—C11 | 1.300 (2) | C16—C17 | 1.358 (4) |
F12—C11 | 1.302 (4) | C17—C18 | 1.380 (3) |
F21—C11 | 1.330 (3) | O1—H101 | 0.8978 |
F22—C11 | 1.299 (3) | N1—H111 | 0.8599 |
F31—C11 | 1.30 (1) | C1—H2 | 0.9700 |
F32—C11 | 1.30 (2) | C1—H3 | 0.9700 |
O1—C2 | 1.425 (2) | C3—H31 | 0.9600 |
O2—C4 | 1.218 (2) | C3—H32 | 0.9600 |
N1—C4 | 1.354 (2) | C3—H33 | 0.9600 |
N1—C5 | 1.396 (2) | C6—H6 | 0.9800 |
N2—C9 | 1.137 (3) | C7—H7 | 0.9800 |
C1—C2 | 1.521 (3) | C12—H12 | 0.9800 |
C2—C3 | 1.525 (3) | C14—H14 | 0.9800 |
C2—C4 | 1.537 (2) | C15—H15 | 0.9800 |
C5—C6 | 1.386 (2) | C17—H17 | 0.9800 |
C5—C12 | 1.385 (3) | C18—H18 | 0.9800 |
C6—C7 | 1.382 (3) | C19—H19 | 0.9507 |
| | | |
Cl11···Cl21 | 2.952 (3) | S1···H111vi | 3.4239 |
Cl11···Cl22 | 2.72 (1) | F4···H2x | 2.9029 |
Cl11···Cl31 | 2.932 (3) | F4···H15 | 2.5326 |
Cl11···Cl32 | 2.778 (3) | F4···H17 | 2.5324 |
Cl11···F4i | 3.545 (3) | F4···H31iv | 3.1136 |
Cl12···Cl21 | 2.779 (8) | F4···H31x | 3.2373 |
Cl12···Cl22 | 2.44 (1) | F4···H32iv | 3.2913 |
Cl12···Cl31 | 2.875 (9) | F4···H33iv | 3.1998 |
Cl12···Cl32 | 2.508 (8) | F11···H3vi | 3.0473 |
Cl21···Cl31 | 2.932 (2) | F11···H12 | 2.3382 |
Cl21···Cl32 | 2.769 (2) | F12···H3vi | 3.3537 |
Cl21···F11ii | 3.072 (6) | F12···H12 | 2.4386 |
Cl21···F12ii | 3.242 (8) | F21···H18i | 3.1876 |
Cl21···F32ii | 3.55 (2) | F22···H18i | 3.3629 |
Cl22···Cl31 | 2.97 (1) | F31···H3vi | 3.4609 |
Cl22···Cl32 | 2.612 (8) | F31···H12 | 3.4034 |
Cl22···F11ii | 3.44 (1) | F32···H3vi | 2.9493 |
Cl31···C6 | 3.470 (3) | F32···H12 | 3.0241 |
Cl32···F4 | 3.427 (3) | O1···H2 | 3.2219 |
Cl32···C6 | 3.563 (3) | O1···H3 | 2.6146 |
Cl32···C16 | 3.506 (4) | O1···H12vi | 3.0102 |
Cl32···C17 | 3.408 (4) | O1···H31 | 3.2546 |
S1···F21iii | 3.52 (1) | O1···H32 | 2.6212 |
S1···O1 | 3.060 (2) | O1···H33 | 2.6619 |
S1···C2 | 2.784 (2) | O1···H111 | 2.1083 |
S1···C4 | 3.175 (2) | O1···H111vi | 2.5060 |
S1···C14 | 2.750 (2) | O2···H2 | 2.6333 |
S1···C18 | 2.738 (2) | O2···H6 | 2.2642 |
F4···Cl11iii | 3.545 (3) | O2···H15x | 2.6864 |
F4···C3iv | 3.390 (3) | O2···H31 | 2.7091 |
F4···C14 | 3.581 (3) | O2···H32 | 3.2406 |
F4···C15 | 2.333 (3) | O2···H111 | 3.0010 |
F4···C17 | 2.339 (3) | N1···H6 | 2.6658 |
F4···C18 | 3.598 (3) | N1···H12 | 2.5452 |
F11···Cl21v | 3.072 (6) | N1···H18 | 3.5480 |
F11···Cl22v | 3.44 (1) | N1···H32 | 3.3227 |
F11···F21 | 2.077 (7) | N1···H101 | 3.3176 |
F11···F22 | 2.184 (7) | N1···H101vi | 3.1782 |
F11···F31 | 2.08 (1) | N2···H7 | 3.3370 |
F11···F32 | 1.83 (2) | N2···H32viii | 3.4371 |
F11···C10 | 2.332 (5) | N2···H33viii | 2.9483 |
F11···C12 | 2.679 (7) | N2···H101viii | 2.0603 |
F12···Cl21v | 3.242 (8) | C1···H12vi | 3.2475 |
F12···F21 | 1.892 (9) | C1···H14 | 3.0989 |
F12···F22 | 2.043 (8) | C1···H31 | 2.7011 |
F12···F31 | 2.22 (1) | C1···H32 | 3.3286 |
F12···F32 | 2.03 (2) | C1···H33 | 2.6856 |
F12···C8 | 3.569 (6) | C1···H101 | 2.8968 |
F12···C10 | 2.329 (7) | C2···H2 | 2.0465 |
F12···C12 | 2.73 (1) | C2···H3 | 2.0454 |
F21···S1i | 3.52 (1) | C2···H31 | 2.0574 |
F21···F31 | 2.12 (1) | C2···H32 | 2.0508 |
F21···F32 | 2.37 (2) | C2···H33 | 2.0569 |
F21···N2 | 3.392 (9) | C2···H101 | 1.9652 |
F21···C8 | 2.880 (8) | C2···H111 | 2.4630 |
F21···C9 | 2.858 (9) | C3···H2 | 2.6817 |
F21···C10 | 2.335 (6) | C3···H3 | 2.6656 |
F21···C12 | 3.461 (6) | C3···H17ix | 3.3798 |
F22···F31 | 1.89 (1) | C3···H101 | 2.4529 |
F22···F32 | 2.19 (2) | C3···H111 | 3.4878 |
F22···N2 | 3.194 (7) | C4···H2 | 2.6363 |
F22···C8 | 2.840 (6) | C4···H3 | 3.3202 |
F22···C9 | 2.712 (7) | C4···H6 | 2.7557 |
F22···C10 | 2.357 (5) | C4···H18 | 3.5846 |
F22···C12 | 3.546 (5) | C4···H31 | 2.6411 |
F31···C8 | 3.106 (7) | C4···H32 | 2.6637 |
F31···C9 | 3.230 (7) | C4···H33 | 3.3184 |
F31···C10 | 2.351 (8) | C4···H101 | 3.1346 |
F31···C12 | 3.293 (9) | C4···H111 | 1.8956 |
F32···Cl21v | 3.55 (2) | C5···H6 | 2.0625 |
F32···C8 | 3.21 (1) | C5···H7 | 3.2752 |
F32···C9 | 3.54 (1) | C5···H12 | 2.0537 |
F32···C10 | 2.27 (1) | C5···H101vi | 3.2803 |
F32···C12 | 3.02 (1) | C5···H111 | 1.9360 |
O1···O1vi | 3.335 (2) | C6···H7 | 2.0477 |
O1···O2 | 3.545 (1) | C6···H12 | 3.2751 |
O1···N1 | 2.575 (2) | C6···H18 | 3.4473 |
O1···N1vi | 3.093 (2) | C6···H111 | 3.1739 |
O1···N2vii | 2.956 (2) | C7···H6 | 2.0549 |
O1···C1 | 2.397 (2) | C8···H6 | 3.2879 |
O1···C3 | 2.440 (3) | C8···H7 | 2.0470 |
O1···C4 | 2.406 (2) | C8···H12 | 3.2834 |
O1···C5vi | 3.475 (2) | C9···H7 | 2.5731 |
O1···C12vi | 3.364 (2) | C9···H18i | 3.5780 |
O2···N1 | 2.275 (2) | C9···H33viii | 3.4755 |
O2···C1 | 2.913 (2) | C9···H101viii | 3.1040 |
O2···C2 | 2.399 (2) | C10···H7 | 3.2747 |
O2···C3 | 2.971 (2) | C10···H12 | 2.0431 |
O2···C5 | 2.897 (2) | C11···H12 | 2.6157 |
O2···C6 | 2.864 (3) | C12···H3vi | 3.5420 |
O2···C13 | 3.359 (3) | C12···H6 | 3.2797 |
O2···C18 | 3.538 (4) | C12···H101vi | 3.2113 |
N1···O1vi | 3.093 (2) | C12···H111 | 2.4742 |
N1···C1 | 3.516 (3) | C13···H2 | 2.6584 |
N1···C2 | 2.443 (2) | C13···H3 | 3.5234 |
N1···C3 | 3.435 (3) | C13···H14 | 2.0433 |
N1···C6 | 2.447 (2) | C13···H15 | 3.2905 |
N1···C12 | 2.378 (2) | C13···H17 | 3.2813 |
N2···O1viii | 2.956 (2) | C13···H18 | 2.0499 |
N2···C3viii | 3.501 (2) | C14···H2 | 2.8073 |
N2···C7 | 3.421 (3) | C14···H15 | 2.0587 |
N2···C8 | 2.583 (3) | C14···H15x | 3.4201 |
N2···C10 | 3.574 (2) | C14···H18 | 3.2567 |
C1···C3 | 2.506 (4) | C15···H14 | 2.0408 |
C1···C4 | 2.485 (3) | C15···H15x | 3.3806 |
C1···C13 | 2.792 (3) | C15···H17 | 3.2558 |
C1···C14 | 3.298 (3) | C15···H19iii | 3.5905 |
C3···F4ix | 3.390 (3) | C16···H14 | 3.2175 |
C3···N2vii | 3.501 (2) | C16···H15 | 2.0333 |
C3···C4 | 2.481 (3) | C16···H17 | 2.0402 |
C4···C5 | 2.470 (3) | C16···H18 | 3.2439 |
C4···C6 | 3.005 (3) | C16···H33iv | 3.4211 |
C4···C13 | 3.464 (3) | C17···H6 | 3.5400 |
C5···O1vi | 3.475 (2) | C17···H15 | 3.2602 |
C5···C7 | 2.393 (2) | C17···H18 | 2.0524 |
C5···C8 | 2.785 (2) | C17···H32iv | 3.3513 |
C5···C10 | 2.401 (3) | C17···H33iv | 3.4364 |
C6···C8 | 2.407 (3) | C18···H6 | 3.3301 |
C6···C10 | 2.769 (3) | C18···H14 | 3.2528 |
C6···C12 | 2.390 (2) | C18···H17 | 2.0596 |
C7···C9 | 2.421 (3) | C19···H14x | 3.5083 |
C7···C10 | 2.388 (2) | C19···H15i | 3.4879 |
C7···C12 | 2.747 (2) | H2···F4x | 2.9029 |
C8···C11 | 2.523 (2) | H3···Cl11vii | 3.5477 |
C8···C12 | 2.400 (2) | H3···Cl12vii | 3.3996 |
C9···C10 | 2.505 (2) | H3···Cl21x | 3.3079 |
C9···C11 | 2.974 (2) | H3···Cl22x | 3.3646 |
C9···C18i | 3.581 (4) | H3···F11vi | 3.0473 |
C11···C12 | 2.471 (3) | H3···F12vi | 3.3537 |
C12···O1vi | 3.364 (2) | H3···F31vi | 3.4609 |
C13···C15 | 2.404 (3) | H3···F32vi | 2.9493 |
C13···C16 | 2.730 (3) | H3···C12vi | 3.5420 |
C13···C17 | 2.393 (3) | H12···S1vi | 2.8481 |
C14···C16 | 2.332 (3) | H12···O1vi | 3.0102 |
C14···C17 | 2.730 (4) | H12···C1vi | 3.2475 |
C14···C18 | 2.367 (4) | H14···Cl21x | 3.1371 |
C15···C15x | 3.479 (5) | H14···Cl22x | 3.3596 |
C15···C17 | 2.376 (4) | H14···Cl31x | 2.8714 |
C15···C18 | 2.755 (4) | H14···Cl32x | 2.9306 |
C16···C18 | 2.356 (3) | H14···C19x | 3.5083 |
C18···C9iii | 3.581 (4) | H15···Cl11iii | 3.5905 |
Cl11···H3viii | 3.5477 | H15···Cl31x | 3.3327 |
Cl11···H7 | 3.1565 | H15···Cl32x | 3.5835 |
Cl11···H15i | 3.5905 | H15···O2x | 2.6864 |
Cl11···H19 | 2.3246 | H15···C14x | 3.4201 |
Cl11···H31viii | 3.4236 | H15···C15x | 3.3806 |
Cl11···H33viii | 2.9960 | H15···C19iii | 3.4879 |
Cl12···H3viii | 3.3996 | H17···C3iv | 3.3798 |
Cl12···H7 | 3.1806 | H18···F21iii | 3.1876 |
Cl12···H19 | 2.5129 | H18···F22iii | 3.3629 |
Cl12···H33viii | 3.3035 | H18···C9iii | 3.5780 |
Cl21···H3x | 3.3079 | H19···C15i | 3.5905 |
Cl21···H14x | 3.1371 | H31···Cl11vii | 3.4236 |
Cl21···H19 | 2.0506 | H31···F4ix | 3.1136 |
Cl22···H3x | 3.3646 | H31···F4x | 3.2373 |
Cl22···H14x | 3.3596 | H32···F4ix | 3.2913 |
Cl22···H19 | 2.3115 | H32···N2vii | 3.4371 |
Cl31···H6 | 2.7294 | H32···C17ix | 3.3513 |
Cl31···H7 | 3.1757 | H33···Cl11vii | 2.9960 |
Cl31···H14x | 2.8714 | H33···Cl12vii | 3.3035 |
Cl31···H15x | 3.3327 | H33···F4ix | 3.1998 |
Cl31···H19 | 1.7701 | H33···N2vii | 2.9483 |
Cl32···H6 | 2.8165 | H33···C9vii | 3.4755 |
Cl32···H7 | 3.1100 | H33···C16ix | 3.4211 |
Cl32···H14x | 2.9306 | H33···C17ix | 3.4364 |
Cl32···H15x | 3.5835 | H101···N1vi | 3.1782 |
Cl32···H17 | 3.2456 | H101···N2vii | 2.0603 |
Cl32···H19 | 2.2677 | H101···C5vi | 3.2803 |
S1···H2 | 2.2994 | H101···C9vii | 3.1040 |
S1···H3 | 2.3010 | H101···C12vi | 3.2113 |
S1···H12vi | 2.8481 | H111···S1vi | 3.4239 |
S1···H14 | 2.8507 | H111···O1vi | 2.5060 |
S1···H18 | 2.8401 | | |
| | | |
Cl11—C19—Cl21 | 119.1 (1) | C7—C8—C9 | 117.8 (1) |
Cl11—C19—Cl22 | 105.2 (4) | C10—C8—C9 | 123.4 (2) |
Cl11—C19—Cl31 | 117.6 (1) | C8—C10—C11 | 121.3 (2) |
Cl11—C19—Cl32 | 106.2 (2) | C8—C10—C12 | 120.0 (2) |
Cl12—C19—Cl21 | 108.7 (3) | C12—C10—C11 | 118.7 (1) |
Cl12—C19—Cl31 | 114.3 (2) | C18—C13—C14 | 118.3 (2) |
Cl21—C19—Cl31 | 117.5 (2) | C13—C14—C15 | 121.7 (2) |
Cl21—C19—Cl32 | 105.6 (2) | C13—C18—C17 | 120.4 (2) |
Cl22—C19—Cl31 | 119.7 (4) | C14—C15—C16 | 118.0 (2) |
S1—C1—C2 | 113.6 (2) | C15—C16—C17 | 122.9 (2) |
C13—S1—C1 | 102.9 (1) | C16—C17—C18 | 118.7 (3) |
S1—C13—C14 | 121.3 (2) | Cl11—C19—H19 | 118.9327 |
S1—C13—C18 | 120.3 (2) | Cl12—C19—H19 | 140.5302 |
F4—C16—C17 | 118.4 (2) | Cl21—C19—H19 | 96.4389 |
F4—C16—C15 | 118.7 (2) | Cl22—C19—H19 | 117.0419 |
F11—C11—F21 | 104.3 (5) | Cl31—C19—H19 | 77.3166 |
F11—C11—F22 | 114.3 (5) | Cl32—C19—H19 | 109.6825 |
F11—C11—F31 | 106.1 (5) | S1—C1—H2 | 108.3710 |
F12—C11—F22 | 103.5 (6) | S1—C1—H3 | 108.4947 |
F12—C11—F31 | 117.1 (6) | H101—O1—C2 | 113.6427 |
F12—C11—C10 | 112.4 (5) | H111—N1—C4 | 115.9415 |
F21—C11—F31 | 107.7 (6) | H111—N1—C5 | 116.2185 |
F21—C11—F32 | 128.4 (9) | H2—C1—C2 | 108.4686 |
F21—C11—C10 | 111.2 (4) | H3—C1—C2 | 108.3745 |
F22—C11—F32 | 114.8 (8) | H3—C1—H2 | 109.4548 |
F22—C11—C10 | 114.7 (3) | C2—C3—H31 | 109.6748 |
F31—C11—C10 | 114.1 (4) | C2—C3—H32 | 109.1022 |
F32—C11—C10 | 108.3 (7) | C2—C3—H33 | 109.6251 |
O1—C2—C1 | 108.9 (2) | H32—C3—H31 | 109.4779 |
O1—C2—C4 | 108.6 (1) | H33—C3—H31 | 109.4741 |
O1—C2—C3 | 111.6 (1) | H33—C3—H32 | 109.4726 |
O2—C4—C2 | 120.6 (2) | C5—C6—H6 | 120.3401 |
O2—C4—N1 | 124.2 (2) | C5—C12—H12 | 119.5708 |
N1—C4—C2 | 115.2 (1) | C6—C7—H7 | 119.2658 |
C5—N1—C4 | 127.8 (1) | H6—C6—C7 | 119.9811 |
N1—C5—C6 | 123.2 (2) | H7—C7—C8 | 119.3980 |
N1—C5—C12 | 117.6 (1) | C10—C12—H12 | 119.4789 |
N2—C9—C8 | 175.4 (2) | C13—C14—H14 | 119.1366 |
C1—C2—C4 | 108.7 (2) | C13—C18—H18 | 119.7595 |
C1—C2—C3 | 110.7 (2) | H14—C14—C15 | 119.2082 |
C4—C2—C3 | 108.3 (2) | C14—C15—H15 | 120.9946 |
C12—C5—C6 | 119.2 (2) | H15—C15—C16 | 121.0356 |
C5—C6—C7 | 119.7 (2) | C16—C17—H17 | 120.6299 |
C5—C12—C10 | 121.0 (1) | H17—C17—C18 | 120.6217 |
C6—C7—C8 | 121.3 (1) | C17—C18—H18 | 119.8896 |
C7—C8—C10 | 118.7 (2) | | |
| | | |
C13—S1—C1—C2 | −102.3 (1) | C7—C8—C10—C11 | −178.6 (2) |
C1—S1—C13—C14 | −62.2 (2) | C8—C10—C11—F11 | 164.7 (4) |
C5—N1—C4—O2 | −2.0 (4) | C8—C10—C11—F12 | 149.4 (5) |
C5—N1—C4—C2 | 179.0 (2) | C8—C10—C11—F21 | 48.0 (6) |
C4—N1—C5—C6 | −16.9 (3) | C8—C10—C11—F22 | 31.6 (5) |
S1—C1—C2—O1 | −56.0 (2) | C8—C10—C11—F31 | −74.2 (4) |
O1—C2—C4—O2 | 174.4 (2) | C8—C10—C11—F32 | −98.1 (9) |
O1—C2—C4—N1 | −6.6 (3) | C8—C10—C12—C5 | 0.6 (3) |
C1—C2—C4—O2 | 56.1 (3) | S1—C13—C14—C15 | −179.1 (3) |
C1—C2—C4—N1 | −124.9 (2) | S1—C13—C18—C17 | 178.2 (3) |
N1—C5—C6—C7 | −175.7 (2) | C13—C14—C15—C16 | 1.5 (5) |
N1—C5—C12—C10 | 175.7 (2) | C14—C15—C16—F4 | −179.6 (3) |
C5—C6—C7—C8 | −0.4 (4) | F4—C16—C17—C18 | 178.7 (3) |
C6—C7—C8—C9 | 175.3 (2) | C16—C17—C18—C13 | 0.2 (4) |
Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z+1; (iii) x−1, y, z; (iv) x, y+1, z; (v) x, y−1, z−1; (vi) −x+1, −y, −z; (vii) x−1, y−1, z; (viii) x+1, y+1, z; (ix) x, y−1, z; (x) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H101···N2vii | 0.90 | 2.06 | 2.957 (3) | 175 |
N1—H111···O1vi | 0.86 | 2.51 | 3.094 (3) | 126 |
Symmetry codes: (vi) −x+1, −y, −z; (vii) x−1, y−1, z. |
Experimental details
Crystal data |
Chemical formula | C18H14F4N2O2S·CHCl3 |
Mr | 517.75 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 253 |
a, b, c (Å) | 8.8442 (9), 10.4591 (9), 13.319 (1) |
α, β, γ (°) | 110.718 (4), 90.895 (2), 105.595 (2) |
V (Å3) | 1101.5 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.56 |
Crystal size (mm) | 0.42 × 0.33 × 0.28 |
|
Data collection |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.738, 0.854 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 9744, 4896, 3260 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.089, 0.96 |
No. of reflections | 4892 |
No. of parameters | 334 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.38 |
Selected bond lengths (Å) topS1—C1 | 1.801 (3) | O2—C4 | 1.218 (2) |
S1—C13 | 1.769 (2) | N2—C9 | 1.137 (3) |
O1—C2 | 1.425 (2) | C8—C9 | 1.448 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H101···N2i | 0.90 | 2.06 | 2.957 (3) | 175 |
N1—H111···O1ii | 0.86 | 2.51 | 3.094 (3) | 126 |
Symmetry codes: (i) x−1, y−1, z; (ii) −x+1, −y, −z. |
The title compound, (I), was prepared as an intermediate in the synthesis of Bicalutamide [trademark name for N-(4-cyano-3-trifluoromethyl-phenyl)-3-(4-fluoro-benzensulfonyl)-2-hydroxy-2-methyl-propionamide], a nonsteroidal antiandrogen which acts on the male hormones (androgens) but which has no steroidal effects (Tucker et al., 1988; Xiao et al., 2003).
The crystal structure of (I) comprises one N-(4-cyano-3-trifluoromethyl-phenyl)-3-(4-fluoro-phenyl-sulfanyl)-2-hydroxy-2-methyl-propionamide molecule and one CHCl3 solvent molecule. The solvent molecule is disordered because there are no hydrogen-bonding interactions between CHCl3 and the main moiety. The two benzene ring mean planes are almost parallel to each other, forming a dihedral angle of 8.43 (8)°.
Intermolecular O—H···N hydrogen bonds (Table 2) link the molecules into infinite chains, approximately parallel to the [010] axis. Atom O1 belonging to the hydroxy group acts a donor, while N2 atom of the cyano group serves as an acceptor. Because of this hydrogen-bond interaction, the cyano group deviates slightly from the plane of the benzene ring (C5–C8/C10/C12); the deviations of atoms C9 and N2 from the mean plane are 0.123 and 0.250 Å, respectively. The cyano group is unconjugated with the benzene ring, resulting in a C8—C9 bond length of 1.448 (3) Å, long compared with the value expected for a formal Csp2—Csp bond (Reference for standard value?). The chain is further stabilized by weak intermolecular N1—H1···O1 interactions (Table 2) to form layers in the crystal structure.