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The molecular structure of the anti-aging agent J147 [systematic name: (E)-N-(2,4-dimethylphenyl)-2,2,2-trifluoro-N′-(3-methoxybenzylidene)acetohydrazide], C18H17F3N2O2, has been determined at 150 K. The crystal structure corresponds to the minimum-energy conformation in the gas phase calculated by density functional theory (DFT). 15 other conformations have been calculated and compared with the minimum, denoted 1111. NMR spectroscopic data have been obtained and compared with those from Gauge Independent Atomic Orbital (GIAO) calculations. DFT calculations allow the reduction of the 16 possible rotamers to the four most stable (i.e. 1111, 1112, 1121 and 1222); in addition, the calculated barriers connecting these minima are low enough to permit their interconversion. Comparison of the NMR spectroscopic results, both experimental and calculated, point to the 1121 isomer being present in chloroform solution.
Supporting information
CCDC reference: 1869097
Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
(
E)-
N-(2,4-Dimethylphenyl)-2,2,2-trifluoro-
N'-(3-methoxybenzylidene)acetohydrazide
top
Crystal data top
C18H17F3N2O2 | F(000) = 728 |
Mr = 350.33 | Dx = 1.376 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
a = 15.0494 (3) Å | Cell parameters from 8396 reflections |
b = 14.2369 (3) Å | θ = 6.4–73.4° |
c = 7.9898 (2) Å | µ = 0.97 mm−1 |
β = 99.025 (2)° | T = 150 K |
V = 1690.68 (7) Å3 | Block, colourless |
Z = 4 | 0.2 × 0.08 × 0.02 mm |
Data collection top
Rigaku Oxford Diffraction SuperNova diffractometer with a dual
source (Cu at zero) equipped with an AtlasS2 CCD area detector | 5945 independent reflections |
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source | 4685 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.037 |
Detector resolution: 5.3046 pixels mm-1 | θmax = 73.5°, θmin = 3.0° |
ω scans | h = −18→18 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018) | k = −17→17 |
Tmin = 0.792, Tmax = 1.000 | l = −9→9 |
5945 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: iterative |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0644P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
5945 reflections | Δρmax = 0.21 e Å−3 |
230 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refined as a 2-component twin. The twin ratio is 75:25.
The twin components are related by a rotation = 179.9993 deg around the
following vectors:
Reciprocal space (hkl): 0.9591 -0.0004 -0.2832
Direct space (uvw) : 1.0000 -0.0000 -0.0000 More twin information from Crysalis Pro is shown below
HKLF 5 merged RINT ANALYSIS FOR ALL HKLF5 REFLECTIONS
Components measured unique redundancy F2/sig(F2) Rint Rsigma
——————————————————————–
1,2 40817 6202 6.58 13.10 0.037 0.049 RINT ANALYSIS FOR OVERLAPPED REFLECTIONS
Components measured unique redundancy F2/sig(F2) Rint Rsigma
——————————————————————–
1,2 15535 2329 6.67 16.27 0.034 0.042 RINT ANALYSIS FOR ISOLATED REFLECTIONS
Component measured unique redundancy F2/sig(F2) Rint Rsigma
——————————————————————–
1 12639 1940 6.51 15.24 0.035 0.042
2 12643 1933 6.54 7.05 0.061 0.103 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.79743 (10) | 0.55247 (11) | 0.5015 (2) | 0.0310 (3) | |
F1A | 0.80312 (7) | 0.52484 (8) | 0.66192 (12) | 0.0429 (2) | |
F1B | 0.86916 (6) | 0.52092 (7) | 0.44165 (14) | 0.0426 (3) | |
F1C | 0.80174 (6) | 0.64552 (7) | 0.50186 (15) | 0.0465 (3) | |
C2 | 0.70649 (9) | 0.52283 (11) | 0.39492 (18) | 0.0269 (3) | |
O2 | 0.65540 (7) | 0.58383 (8) | 0.33280 (15) | 0.0346 (3) | |
N3 | 0.68799 (8) | 0.42978 (9) | 0.38228 (16) | 0.0274 (3) | |
N4 | 0.75575 (8) | 0.36869 (9) | 0.45448 (16) | 0.0275 (3) | |
C5 | 0.74210 (9) | 0.28083 (11) | 0.43262 (19) | 0.0292 (3) | |
H5 | 0.687429 | 0.258876 | 0.368883 | 0.035* | |
C6 | 0.81146 (9) | 0.21384 (10) | 0.50661 (19) | 0.0279 (3) | |
C7 | 0.88960 (10) | 0.24511 (11) | 0.61040 (18) | 0.0291 (3) | |
H7 | 0.898622 | 0.310195 | 0.633233 | 0.035* | |
C8 | 0.95351 (10) | 0.18023 (11) | 0.6793 (2) | 0.0325 (3) | |
O8 | 1.03238 (8) | 0.20262 (9) | 0.77993 (18) | 0.0448 (3) | |
C9 | 0.94022 (11) | 0.08438 (12) | 0.6455 (2) | 0.0369 (4) | |
H9 | 0.984103 | 0.040119 | 0.693868 | 0.044* | |
C10 | 0.86373 (11) | 0.05411 (12) | 0.5422 (2) | 0.0371 (4) | |
H10 | 0.855136 | −0.010989 | 0.519015 | 0.045* | |
C11 | 0.79887 (10) | 0.11852 (11) | 0.4717 (2) | 0.0328 (3) | |
H11 | 0.746236 | 0.097521 | 0.399995 | 0.039* | |
C12 | 0.59850 (9) | 0.40011 (10) | 0.30719 (19) | 0.0261 (3) | |
C13 | 0.53748 (9) | 0.37550 (10) | 0.41401 (19) | 0.0268 (3) | |
C13A | 0.56160 (11) | 0.37566 (12) | 0.6041 (2) | 0.0350 (3) | |
H13A | 0.600629 | 0.321894 | 0.640011 | 0.052* | |
H13B | 0.506618 | 0.371151 | 0.655018 | 0.052* | |
H13C | 0.593278 | 0.434026 | 0.640896 | 0.052* | |
C14 | 0.45046 (9) | 0.35210 (11) | 0.3373 (2) | 0.0286 (3) | |
H14 | 0.407817 | 0.333806 | 0.407057 | 0.034* | |
C15 | 0.42381 (9) | 0.35456 (10) | 0.1622 (2) | 0.0283 (3) | |
C15A | 0.32796 (10) | 0.33260 (12) | 0.0862 (2) | 0.0371 (4) | |
H15A | 0.311125 | 0.271072 | 0.126430 | 0.056* | |
H15C | 0.322498 | 0.331594 | −0.037665 | 0.056* | |
H15B | 0.287938 | 0.380841 | 0.120305 | 0.056* | |
C16 | 0.48731 (10) | 0.37919 (11) | 0.0605 (2) | 0.0309 (3) | |
H16 | 0.470708 | 0.380628 | −0.059150 | 0.037* | |
C17 | 0.57474 (10) | 0.40166 (11) | 0.1329 (2) | 0.0303 (3) | |
H17 | 0.617961 | 0.417993 | 0.063091 | 0.036* | |
C18 | 1.05443 (11) | 0.29985 (13) | 0.7989 (3) | 0.0445 (4) | |
H18A | 1.052627 | 0.328445 | 0.686869 | 0.067* | |
H18B | 1.114964 | 0.306629 | 0.863909 | 0.067* | |
H18C | 1.010847 | 0.331309 | 0.859057 | 0.067* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0286 (7) | 0.0266 (8) | 0.0363 (8) | −0.0010 (6) | 0.0004 (6) | 0.0005 (6) |
F1A | 0.0474 (5) | 0.0470 (6) | 0.0305 (5) | −0.0026 (4) | −0.0060 (4) | 0.0000 (4) |
F1B | 0.0270 (4) | 0.0430 (6) | 0.0587 (6) | −0.0025 (4) | 0.0091 (4) | −0.0025 (5) |
F1C | 0.0396 (5) | 0.0269 (5) | 0.0667 (7) | −0.0045 (4) | −0.0115 (5) | −0.0011 (5) |
C2 | 0.0259 (6) | 0.0274 (7) | 0.0269 (7) | −0.0006 (5) | 0.0027 (5) | 0.0003 (6) |
O2 | 0.0336 (5) | 0.0257 (6) | 0.0411 (6) | 0.0028 (4) | −0.0044 (5) | 0.0037 (5) |
N3 | 0.0234 (5) | 0.0240 (6) | 0.0326 (7) | 0.0016 (4) | −0.0020 (5) | 0.0027 (5) |
N4 | 0.0237 (5) | 0.0266 (7) | 0.0311 (6) | 0.0039 (5) | 0.0005 (5) | 0.0027 (5) |
C5 | 0.0274 (6) | 0.0283 (8) | 0.0305 (8) | 0.0017 (5) | 0.0001 (5) | −0.0008 (6) |
C6 | 0.0287 (7) | 0.0263 (7) | 0.0289 (7) | 0.0024 (5) | 0.0051 (5) | 0.0002 (6) |
C7 | 0.0292 (7) | 0.0235 (8) | 0.0345 (7) | 0.0016 (5) | 0.0042 (5) | −0.0001 (7) |
C8 | 0.0272 (7) | 0.0309 (8) | 0.0382 (8) | 0.0014 (6) | 0.0016 (6) | 0.0025 (6) |
O8 | 0.0332 (6) | 0.0319 (7) | 0.0627 (9) | 0.0019 (5) | −0.0129 (5) | 0.0040 (6) |
C9 | 0.0361 (8) | 0.0273 (8) | 0.0465 (10) | 0.0080 (6) | 0.0036 (7) | 0.0063 (7) |
C10 | 0.0409 (8) | 0.0245 (8) | 0.0449 (9) | 0.0020 (6) | 0.0035 (7) | 0.0000 (7) |
C11 | 0.0333 (7) | 0.0284 (8) | 0.0355 (8) | 0.0001 (6) | 0.0019 (6) | −0.0023 (6) |
C12 | 0.0247 (6) | 0.0218 (7) | 0.0302 (8) | 0.0017 (5) | −0.0006 (5) | 0.0007 (5) |
C13 | 0.0293 (7) | 0.0218 (7) | 0.0281 (7) | 0.0025 (5) | 0.0009 (5) | 0.0017 (6) |
C13A | 0.0350 (7) | 0.0391 (9) | 0.0294 (8) | −0.0005 (6) | 0.0005 (6) | 0.0035 (7) |
C14 | 0.0273 (6) | 0.0249 (7) | 0.0333 (8) | −0.0005 (5) | 0.0037 (6) | 0.0028 (6) |
C15 | 0.0277 (7) | 0.0209 (7) | 0.0346 (8) | 0.0015 (5) | −0.0003 (6) | −0.0014 (6) |
C15A | 0.0293 (7) | 0.0371 (9) | 0.0422 (9) | −0.0019 (6) | −0.0030 (6) | −0.0052 (7) |
C16 | 0.0326 (7) | 0.0314 (8) | 0.0269 (7) | 0.0011 (6) | −0.0010 (6) | −0.0005 (6) |
C17 | 0.0296 (7) | 0.0310 (8) | 0.0300 (8) | 0.0003 (6) | 0.0036 (6) | 0.0027 (6) |
C18 | 0.0346 (8) | 0.0351 (10) | 0.0592 (12) | −0.0045 (7) | −0.0067 (8) | 0.0017 (8) |
Geometric parameters (Å, º) top
C1—F1A | 1.3303 (19) | C11—H11 | 0.9500 |
C1—F1B | 1.3260 (18) | C12—C13 | 1.393 (2) |
C1—F1C | 1.3262 (18) | C12—C17 | 1.382 (2) |
C1—C2 | 1.5527 (19) | C13—C13A | 1.505 (2) |
C2—O2 | 1.2133 (18) | C13—C14 | 1.396 (2) |
C2—N3 | 1.354 (2) | C13A—H13A | 0.9800 |
N3—N4 | 1.3944 (16) | C13A—H13B | 0.9800 |
N3—C12 | 1.4487 (17) | C13A—H13C | 0.9800 |
N4—C5 | 1.275 (2) | C14—H14 | 0.9500 |
C5—H5 | 0.9500 | C14—C15 | 1.394 (2) |
C5—C6 | 1.468 (2) | C15—C15A | 1.5076 (19) |
C6—C7 | 1.401 (2) | C15—C16 | 1.393 (2) |
C6—C11 | 1.392 (2) | C15A—H15A | 0.9800 |
C7—H7 | 0.9500 | C15A—H15C | 0.9800 |
C7—C8 | 1.384 (2) | C15A—H15B | 0.9800 |
C8—O8 | 1.3629 (19) | C16—H16 | 0.9500 |
C8—C9 | 1.399 (2) | C16—C17 | 1.389 (2) |
O8—C18 | 1.426 (2) | C17—H17 | 0.9500 |
C9—H9 | 0.9500 | C18—H18A | 0.9800 |
C9—C10 | 1.376 (2) | C18—H18B | 0.9800 |
C10—H10 | 0.9500 | C18—H18C | 0.9800 |
C10—C11 | 1.393 (2) | | |
| | | |
F1A—C1—C2 | 111.48 (12) | C17—C12—N3 | 119.30 (13) |
F1B—C1—F1A | 108.32 (12) | C17—C12—C13 | 122.00 (13) |
F1B—C1—F1C | 107.26 (12) | C12—C13—C13A | 122.68 (13) |
F1B—C1—C2 | 114.04 (13) | C12—C13—C14 | 117.01 (13) |
F1C—C1—F1A | 107.32 (13) | C14—C13—C13A | 120.30 (14) |
F1C—C1—C2 | 108.13 (12) | C13—C13A—H13A | 109.5 |
O2—C2—C1 | 118.51 (13) | C13—C13A—H13B | 109.5 |
O2—C2—N3 | 124.06 (13) | C13—C13A—H13C | 109.5 |
N3—C2—C1 | 117.39 (12) | H13A—C13A—H13B | 109.5 |
C2—N3—N4 | 116.80 (11) | H13A—C13A—H13C | 109.5 |
C2—N3—C12 | 118.88 (11) | H13B—C13A—H13C | 109.5 |
N4—N3—C12 | 124.16 (12) | C13—C14—H14 | 118.8 |
C5—N4—N3 | 117.62 (12) | C15—C14—C13 | 122.48 (13) |
N4—C5—H5 | 120.2 | C15—C14—H14 | 118.8 |
N4—C5—C6 | 119.54 (13) | C14—C15—C15A | 120.39 (14) |
C6—C5—H5 | 120.2 | C16—C15—C14 | 118.42 (13) |
C7—C6—C5 | 120.64 (13) | C16—C15—C15A | 121.18 (14) |
C11—C6—C5 | 119.12 (13) | C15—C15A—H15A | 109.5 |
C11—C6—C7 | 120.24 (14) | C15—C15A—H15C | 109.5 |
C6—C7—H7 | 120.3 | C15—C15A—H15B | 109.5 |
C8—C7—C6 | 119.33 (14) | H15A—C15A—H15C | 109.5 |
C8—C7—H7 | 120.3 | H15A—C15A—H15B | 109.5 |
C7—C8—C9 | 120.31 (14) | H15C—C15A—H15B | 109.5 |
O8—C8—C7 | 124.41 (15) | C15—C16—H16 | 119.8 |
O8—C8—C9 | 115.27 (14) | C17—C16—C15 | 120.46 (14) |
C8—O8—C18 | 117.16 (13) | C17—C16—H16 | 119.8 |
C8—C9—H9 | 119.9 | C12—C17—C16 | 119.62 (14) |
C10—C9—C8 | 120.13 (14) | C12—C17—H17 | 120.2 |
C10—C9—H9 | 119.9 | C16—C17—H17 | 120.2 |
C9—C10—H10 | 119.9 | O8—C18—H18A | 109.5 |
C9—C10—C11 | 120.25 (15) | O8—C18—H18B | 109.5 |
C11—C10—H10 | 119.9 | O8—C18—H18C | 109.5 |
C6—C11—C10 | 119.74 (14) | H18A—C18—H18B | 109.5 |
C6—C11—H11 | 120.1 | H18A—C18—H18C | 109.5 |
C10—C11—H11 | 120.1 | H18B—C18—H18C | 109.5 |
C13—C12—N3 | 118.62 (13) | | |
Calculated and experimental chemical shifts (δ, ppm) in CDCl3 (note that the
NMR atom numbering is different from the crystallographic atom numbering) topNMR atoms | X-ray atoms | 1111 | 1112 | 1121 | 1122 | Experimental |
C1 (C═O) | C2 | 155.8 | 156.2 | 156.0 | 156.0 | 157.3 (q), 2JF = 36 Hz |
C2 (CF3) | C1 | 121.2 | 121.1 | 121.1 | 121.1 | 117.2 (q), 1JF = 287 Hz |
C6 (C═N) | C5 | 141.2 | 140.8 | 141.1 | 141.1 | 143.9 |
H8 (C6—H) | H5 | 7.02 | 6.97 | 6.94 | 6.95 | 7.26 (under the solvent) |
C1' | C12 | 132.1 | 132.2 | 132.6 | 132.4 | 129.6 |
C2' | C13 | 140.1 | 140.1 | 140.4 | 140.2 | 136.2 |
C3' | C14 | 131.5 | 131.6 | 131.6 | 131.7 | 132.6 |
C4' | C15 | 142.4 | 142.3 | 142.3 | 142.4 | 140.9 |
C5' | C16 | 127.6 | 127.6 | 127.5 | 127.6 | 128.7 |
C6' | C17 | 129.3 | 129.5 | 129.6 | 129.5 | 128.5 |
C1'' | C6 | 136.1 | 136.2 | 135.8 | 136.4 | 134.7 |
C2'' | C7 | 104.7 | 115.0 | 110.0 | 120.4 | 111.7 |
C3'' | C8 | 161.4 | 160.7 | 160.4 | 160.4 | 159.9 |
C4'' | C9 | 121.1 | 109.7 | 119.7 | 108.6 | 121.2 |
C5'' | C10 | 128.6 | 128.7 | 129.8 | 129.7 | 129.8 |
C6'' | C11 | 122.6 | 122.1 | 118.1 | 117.7 | 117.1 |
C9 (Me-2') | C13a | 17.9 | 17.9 | 17.9 | 17.9 | 17.0 |
H10 (Me-2') | H13a | 2.03 | 2.03 | 2.04 | 2.03 | 2.09 |
C11 (Me-4') | C15a | 21.2 | 21.2 | 21.2 | 21.2 | 21.3 |
H12 (Me-4') | H15a | 2.40 | 2.41 | 2.39 | 2.40 | 2.42 |
C14 (O—Me) | C18 | 53.0 | 52.6 | 52.2 | 52.5 | 55.2 |
H15 (O—Me) | H18 | 3.78 | 3.69 | 3.54 | 3.63 | 3.83 |
H3' | H14 | 7.21 | 7.20 | 7.24 | 7.22 | 7.24 |
H5' | H16 | 7.17 | 7.18 | 7.17 | 7.19 | 7.21 |
H6' | H17 | 6.96 | 6.97 | 6.98 | 6.98 | 7.03 |
H2'' | H7 | 7.60 | 7.98 | 6.13 | 6.57 | 7.27 |
H4'' | H9 | 6.99 | 6.56 | 6.96 | 6.51 | 7.12 |
H5'' | H10 | 7.09 | 7.12 | 7.27 | 7.27 | 7.29 |
H6'' | H11 | 6.52 | 6.49 | 7.99 | 7.93 | 6.95 |
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