Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105000545/fg1802sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105000545/fg1802Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105000545/fg1802IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105000545/fg1802IIIsup4.hkl |
CCDC references: 264819; 264820; 264821
Compound (I) was synthesized by refluxing benzoic acid in methanol, as described by Johnson (1977). The oily product was cooled in a refrigerator, and the solid which formed was grown from solution in acetone to afford colourless single crystals suitable for X-ray diffraction [m. p. 331–332 K (semi-solid; Johnson, 1977)]. Spectroscopic analysis: 1H NMR (Solvent?, δ, p.p.m.): 3.93 (s, 3 H, CH3O), 7.08–7.13 (m, 2 H, Ph), 7.27 (dd, 1 H, J = 9 and 0.9 Hz, NO2—Ph), 7.63 (dd, 1 H, J = 7.8 and 1.5 Hz, CF3—Ph), 7.82 (d, 1 H, J = 1.8 Hz, CF3—Ph), 8.05 (d, 1 H, J = 9 Hz, NO2—Ph). Compound (II) was sythesized according to the procedure of Li et al. (2001), by stirring 2-chloro-5-(3-H-2,6-dioxo-4-trifluoromethyl-3,6-dihydro- 2H-pyrimidin-1-yl)-benzoic acid methyl ester, Na2CO3 and iodomethane in dimethylformamide for 4 h at room temperature. After pouring the reaction mixture into water, the precipitate which formed was filtered off and recrystallized from chloroform, which gave colourless single crystals suitable for X-ray diffraction (m.p. 441–442 K). Analysis, C14H10ClF3N2O4 requires: C 46.36, H 2.78, N 7.72%; found: C 46.39, H 2.61, N 7.70%; 1H NMR (Solvent:, δ, p.p.m.): 3.55 (s, 3 H, CH3N), 3.91 (s, 3 H, CH3O), 6.37 (s, 1 H, py), 7.29 (d, 1 H, J = 8.9 Hz, Ph), 7.59 (d, 1 H, J = 8.9 Hz, Ph), 7.79 (d, 1 H, J = 2.4 Hz, Ph). Compound (III) was synthesized by refluxing 4-chloro-2-fluoro-5-prop-2-ynyloxy-phenylamine with the corresponding anhydride in acetic acid for 1 h, as described by Lange et al. (1991). The crude products were purified by silica-gel column chromatography and then grown from solution in acetone, to afford colourless single crystals suitable for X-ray diffraction [m.p. 379–380 K; literature value 361–394 K (Lange et al., 1991)]. Spectroscopic analysis: 1H NMR (Solvent?, δ, p.p.m.): 2.57 (t, 1 H, J = 2.4 Hz, C*CH), 2.89–3.15 (m, 5 H), 4.72 (d, 2 H, J = 2.4 Hz, CH2C*C), 6.84 (d, 1 H, J = 6.6 Hz, Ph), 7.29 (d, 1 H, J = 9 Hz, Ph).
For all three compounds, possible H-atom sites were revealed in difference maps. H atoms were subsequently allowed for in the refinements as riding atoms, with C—H = 0.93, 0.97 and 0.98 Å, with Uiso(H) = 1.2Ueq(parent atom). For (I), both CF3 groups have the F atoms unequally disordered over two main orientations. This was modelled with DFIX restraints [C—F 1.33 (5) and F···F 2.08 (5) Å) and tied occupancy parameters, which refined to 0.827 (10)/0.173 (10) and 0.858 (9)/0.142 (9). Each triplet of minor-occupancy F atoms was refined with a common Uiso value [final values 0.111 (7) and 0.122 (8) Å2]. Compound (III) has disorder of the piperidine C4 atom, with concomitant disorder of the F atoms bonded to C7 (which was not disordered). Initial refinement of tied occupancy parameters for the disordered C4 site led to values which did not differ significantly from 0.5 and, in the final refinement cycles, the occupancies of the two components (labelled C4 and C4A) were set at 0.5. The six 0.5-occupancy F atoms (labelled F71–F73 and F71A–F73A) were refined without restraints.
For all compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) in WinGX (Farrugia, 1999); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
C15H9ClF3NO5 | Dx = 1.566 Mg m−3 |
Mr = 375.68 | Melting point: 332(1) K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 19.280 (5) Å | Cell parameters from 997 reflections |
b = 9.715 (3) Å | θ = 2.3–19.5° |
c = 18.050 (5) Å | µ = 0.30 mm−1 |
β = 109.509 (5)° | T = 293 K |
V = 3186.8 (15) Å3 | Prism, colourless |
Z = 8 | 0.44 × 0.36 × 0.26 mm |
F(000) = 1520 |
Bruker SMART CCD area-detector diffractometer | 5616 independent reflections |
Radiation source: fine-focus sealed tube | 2057 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.087 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −22→14 |
Tmin = 0.853, Tmax = 0.925 | k = −11→11 |
16078 measured reflections | l = −21→21 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 0.87 | w = 1/[σ2(Fo2) + (0.0715P)2] where P = (Fo2 + 2Fc2)/3 |
5616 reflections | (Δ/σ)max < 0.001 |
475 parameters | Δρmax = 0.19 e Å−3 |
18 restraints | Δρmin = −0.21 e Å−3 |
C15H9ClF3NO5 | V = 3186.8 (15) Å3 |
Mr = 375.68 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 19.280 (5) Å | µ = 0.30 mm−1 |
b = 9.715 (3) Å | T = 293 K |
c = 18.050 (5) Å | 0.44 × 0.36 × 0.26 mm |
β = 109.509 (5)° |
Bruker SMART CCD area-detector diffractometer | 5616 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2057 reflections with I > 2σ(I) |
Tmin = 0.853, Tmax = 0.925 | Rint = 0.087 |
16078 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 18 restraints |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 0.87 | Δρmax = 0.19 e Å−3 |
5616 reflections | Δρmin = −0.21 e Å−3 |
475 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 | Occ. (<1) | |
Cl1 | 0.29501 (10) | 0.76114 (13) | 0.60249 (9) | 0.1354 (6) | |
F71 | 0.3742 (4) | 0.5081 (6) | 0.9148 (2) | 0.182 (3) | 0.827 (10) |
F72 | 0.4480 (3) | 0.5082 (11) | 0.8546 (3) | 0.201 (4) | 0.827 (10) |
F73 | 0.3870 (4) | 0.3284 (5) | 0.8584 (3) | 0.173 (3) | 0.827 (10) |
O1 | 0.15154 (19) | 0.6484 (3) | 0.5910 (2) | 0.1265 (14) | |
O2 | 0.2045 (2) | 0.2603 (3) | 0.3961 (2) | 0.1263 (14) | |
O3 | 0.12343 (16) | 0.1541 (3) | 0.43781 (17) | 0.0833 (9) | |
O4 | 0.0453 (3) | 0.2812 (4) | 0.2907 (2) | 0.1469 (18) | |
O5 | −0.0419 (2) | 0.4212 (5) | 0.2694 (2) | 0.1589 (19) | |
N1 | 0.0164 (3) | 0.3783 (6) | 0.3102 (3) | 0.1002 (14) | |
C1 | 0.2089 (3) | 0.5935 (5) | 0.6511 (3) | 0.0799 (14) | |
C2 | 0.2784 (3) | 0.6437 (4) | 0.6657 (3) | 0.0704 (12) | |
C3 | 0.3358 (3) | 0.6018 (4) | 0.7306 (3) | 0.0721 (12) | |
H3 | 0.3826 | 0.6386 | 0.7412 | 0.086* | |
C4 | 0.3225 (3) | 0.5050 (5) | 0.7790 (3) | 0.0683 (12) | |
C5 | 0.2541 (4) | 0.4511 (5) | 0.7642 (3) | 0.0919 (15) | |
H5 | 0.2459 | 0.3844 | 0.7973 | 0.110* | |
C6 | 0.1974 (3) | 0.4958 (6) | 0.7003 (4) | 0.0993 (17) | |
H6 | 0.1506 | 0.4593 | 0.6903 | 0.119* | |
C7 | 0.3834 (4) | 0.4605 (7) | 0.8502 (4) | 0.1063 (18) | |
C11 | 0.1191 (2) | 0.3911 (4) | 0.4351 (2) | 0.0630 (11) | |
C12 | 0.0562 (3) | 0.4491 (5) | 0.3831 (3) | 0.0708 (12) | |
C13 | 0.0277 (2) | 0.5701 (5) | 0.3992 (3) | 0.0846 (14) | |
H13 | −0.0140 | 0.6080 | 0.3625 | 0.102* | |
C14 | 0.0606 (2) | 0.6348 (5) | 0.4689 (3) | 0.0872 (14) | |
H14 | 0.0413 | 0.7164 | 0.4808 | 0.105* | |
C15 | 0.1227 (2) | 0.5778 (5) | 0.5216 (3) | 0.0780 (13) | |
C16 | 0.1525 (2) | 0.4573 (4) | 0.5050 (2) | 0.0688 (12) | |
H16 | 0.1951 | 0.4213 | 0.5411 | 0.083* | |
C17 | 0.1532 (3) | 0.2617 (5) | 0.4197 (2) | 0.0704 (12) | |
C18 | 0.1502 (3) | 0.0228 (4) | 0.4218 (3) | 0.1033 (17) | |
H18A | 0.1378 | 0.0112 | 0.3661 | 0.155* | |
H18B | 0.1280 | −0.0494 | 0.4425 | 0.155* | |
H18C | 0.2027 | 0.0193 | 0.4463 | 0.155* | |
F74 | 0.4198 (13) | 0.539 (2) | 0.8858 (12) | 0.111 (7)* | 0.173 (10) |
F75 | 0.4347 (10) | 0.377 (2) | 0.8287 (8) | 0.111 (7)* | 0.173 (10) |
F76 | 0.3558 (8) | 0.370 (3) | 0.8897 (10) | 0.111 (7)* | 0.173 (10) |
Cl1A | 0.21997 (9) | 0.73650 (13) | 0.38441 (8) | 0.1254 (6) | |
F71A | 0.0891 (2) | 0.5237 (5) | 0.0679 (2) | 0.136 (2) | 0.858 (9) |
F72A | 0.0348 (2) | 0.4778 (8) | 0.1478 (3) | 0.166 (3) | 0.858 (9) |
F73A | 0.0949 (2) | 0.3220 (5) | 0.1122 (3) | 0.154 (2) | 0.858 (9) |
O1A | 0.35465 (18) | 0.6238 (3) | 0.3665 (2) | 0.0954 (10) | |
O2A | 0.30895 (19) | 0.2834 (3) | 0.5934 (2) | 0.1195 (14) | |
O3A | 0.39627 (16) | 0.1812 (3) | 0.55869 (15) | 0.0762 (8) | |
O4A | 0.4648 (3) | 0.3438 (5) | 0.6969 (2) | 0.160 (2) | |
O5A | 0.5256 (2) | 0.5276 (5) | 0.7190 (2) | 0.1477 (17) | |
N1A | 0.4807 (2) | 0.4506 (6) | 0.6756 (3) | 0.0982 (14) | |
C1A | 0.2902 (3) | 0.5716 (5) | 0.3137 (3) | 0.0719 (12) | |
C2A | 0.2231 (3) | 0.6224 (4) | 0.3125 (3) | 0.0715 (12) | |
C3A | 0.1598 (3) | 0.5844 (4) | 0.2536 (3) | 0.0741 (12) | |
H3A | 0.1148 | 0.6218 | 0.2516 | 0.089* | |
C4A | 0.1630 (3) | 0.4920 (5) | 0.1982 (3) | 0.0706 (12) | |
C5A | 0.2289 (3) | 0.4390 (5) | 0.2008 (3) | 0.0868 (14) | |
H5A | 0.2309 | 0.3759 | 0.1629 | 0.104* | |
C6A | 0.2928 (3) | 0.4773 (5) | 0.2588 (3) | 0.0848 (14) | |
H6A | 0.3375 | 0.4391 | 0.2605 | 0.102* | |
C7A | 0.0950 (4) | 0.4560 (7) | 0.1323 (4) | 0.1022 (18) | |
C11A | 0.3872 (2) | 0.4171 (4) | 0.5452 (2) | 0.0569 (10) | |
C12A | 0.4432 (2) | 0.4951 (5) | 0.5947 (3) | 0.0681 (12) | |
C13A | 0.4678 (2) | 0.6134 (5) | 0.5700 (3) | 0.0863 (14) | |
H13A | 0.5053 | 0.6649 | 0.6050 | 0.104* | |
C14A | 0.4368 (3) | 0.6546 (4) | 0.4938 (3) | 0.0859 (14) | |
H14A | 0.4535 | 0.7338 | 0.4762 | 0.103* | |
C15A | 0.3804 (2) | 0.5780 (4) | 0.4428 (3) | 0.0691 (12) | |
C16A | 0.3551 (2) | 0.4605 (4) | 0.4682 (2) | 0.0624 (11) | |
H16A | 0.3165 | 0.4106 | 0.4338 | 0.075* | |
C17A | 0.3590 (3) | 0.2881 (5) | 0.5692 (2) | 0.0665 (11) | |
C18A | 0.3754 (3) | 0.0499 (4) | 0.5823 (3) | 0.0954 (15) | |
H18D | 0.3877 | 0.0480 | 0.6384 | 0.143* | |
H18E | 0.4014 | −0.0223 | 0.5663 | 0.143* | |
H18F | 0.3234 | 0.0367 | 0.5578 | 0.143* | |
F74A | 0.0498 (11) | 0.584 (2) | 0.1057 (13) | 0.122 (8)* | 0.142 (9) |
F75A | 0.0499 (12) | 0.383 (3) | 0.1554 (12) | 0.122 (8)* | 0.142 (9) |
F76A | 0.1050 (9) | 0.393 (4) | 0.0825 (12) | 0.122 (8)* | 0.142 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.2095 (18) | 0.0896 (9) | 0.1154 (12) | 0.0051 (10) | 0.0651 (11) | 0.0311 (8) |
F71 | 0.286 (7) | 0.193 (6) | 0.057 (3) | 0.089 (5) | 0.044 (3) | 0.014 (3) |
F72 | 0.093 (4) | 0.349 (11) | 0.126 (4) | −0.008 (5) | −0.009 (3) | 0.055 (5) |
F73 | 0.185 (5) | 0.108 (4) | 0.184 (5) | 0.073 (3) | 0.006 (4) | 0.018 (3) |
O1 | 0.119 (3) | 0.088 (2) | 0.122 (3) | 0.054 (2) | −0.027 (2) | −0.038 (2) |
O2 | 0.125 (3) | 0.105 (3) | 0.189 (4) | −0.034 (2) | 0.106 (3) | −0.058 (2) |
O3 | 0.099 (2) | 0.0573 (18) | 0.112 (2) | 0.0063 (18) | 0.060 (2) | 0.0059 (17) |
O4 | 0.188 (5) | 0.117 (3) | 0.088 (3) | 0.022 (3) | −0.017 (3) | −0.018 (2) |
O5 | 0.094 (3) | 0.251 (5) | 0.098 (3) | 0.031 (3) | −0.012 (2) | −0.037 (3) |
N1 | 0.088 (4) | 0.124 (4) | 0.078 (4) | 0.003 (4) | 0.014 (3) | 0.012 (3) |
C1 | 0.078 (4) | 0.065 (3) | 0.086 (4) | 0.014 (3) | 0.014 (3) | −0.025 (3) |
C2 | 0.099 (4) | 0.046 (3) | 0.069 (3) | 0.008 (3) | 0.032 (3) | −0.005 (2) |
C3 | 0.082 (4) | 0.066 (3) | 0.074 (3) | −0.006 (3) | 0.033 (3) | −0.014 (3) |
C4 | 0.083 (4) | 0.071 (3) | 0.056 (3) | 0.009 (3) | 0.031 (3) | −0.003 (3) |
C5 | 0.109 (5) | 0.087 (4) | 0.101 (4) | −0.003 (4) | 0.064 (4) | 0.005 (3) |
C6 | 0.077 (4) | 0.092 (4) | 0.139 (5) | −0.012 (3) | 0.049 (4) | −0.014 (4) |
C7 | 0.150 (7) | 0.088 (5) | 0.087 (5) | 0.018 (5) | 0.047 (5) | 0.002 (4) |
C11 | 0.064 (3) | 0.062 (3) | 0.062 (3) | −0.007 (3) | 0.019 (2) | −0.001 (2) |
C12 | 0.065 (3) | 0.074 (3) | 0.065 (3) | −0.014 (3) | 0.010 (3) | −0.001 (3) |
C13 | 0.066 (3) | 0.086 (4) | 0.087 (4) | 0.010 (3) | 0.006 (3) | 0.016 (3) |
C14 | 0.066 (3) | 0.067 (3) | 0.111 (4) | 0.021 (3) | 0.007 (3) | 0.006 (3) |
C15 | 0.072 (3) | 0.064 (3) | 0.087 (4) | 0.012 (3) | 0.012 (3) | −0.008 (3) |
C16 | 0.060 (3) | 0.059 (3) | 0.075 (3) | 0.011 (2) | 0.005 (2) | −0.003 (2) |
C17 | 0.065 (3) | 0.078 (3) | 0.072 (3) | −0.009 (3) | 0.027 (3) | −0.016 (3) |
C18 | 0.132 (5) | 0.069 (3) | 0.119 (4) | 0.020 (3) | 0.057 (4) | −0.013 (3) |
Cl1A | 0.1726 (15) | 0.0890 (9) | 0.1181 (11) | 0.0154 (9) | 0.0531 (10) | −0.0283 (8) |
F71A | 0.161 (4) | 0.151 (4) | 0.072 (3) | −0.024 (3) | 0.008 (2) | 0.024 (2) |
F72A | 0.086 (3) | 0.276 (8) | 0.124 (4) | −0.003 (3) | 0.018 (3) | −0.009 (4) |
F73A | 0.150 (4) | 0.115 (4) | 0.163 (4) | −0.055 (3) | 0.006 (3) | −0.013 (3) |
O1A | 0.100 (3) | 0.089 (2) | 0.089 (2) | −0.035 (2) | 0.020 (2) | 0.0201 (19) |
O2A | 0.103 (3) | 0.120 (3) | 0.171 (4) | 0.033 (2) | 0.093 (3) | 0.062 (2) |
O3A | 0.093 (2) | 0.0669 (19) | 0.078 (2) | 0.0029 (18) | 0.0420 (17) | 0.0004 (16) |
O4A | 0.236 (6) | 0.129 (3) | 0.067 (3) | −0.017 (4) | −0.014 (3) | 0.006 (3) |
O5A | 0.106 (3) | 0.219 (5) | 0.090 (3) | −0.047 (3) | −0.004 (2) | −0.035 (3) |
N1A | 0.084 (3) | 0.129 (4) | 0.069 (4) | 0.001 (3) | 0.009 (3) | −0.028 (3) |
C1A | 0.080 (4) | 0.065 (3) | 0.074 (3) | −0.016 (3) | 0.030 (3) | 0.015 (3) |
C2A | 0.105 (4) | 0.053 (3) | 0.066 (3) | 0.004 (3) | 0.041 (3) | 0.007 (2) |
C3A | 0.071 (3) | 0.076 (3) | 0.079 (3) | 0.012 (3) | 0.030 (3) | 0.017 (3) |
C4A | 0.073 (4) | 0.085 (3) | 0.061 (3) | −0.010 (3) | 0.033 (3) | 0.000 (3) |
C5A | 0.108 (4) | 0.091 (3) | 0.075 (4) | −0.015 (4) | 0.050 (3) | −0.014 (3) |
C6A | 0.085 (4) | 0.092 (4) | 0.092 (4) | 0.005 (3) | 0.049 (3) | 0.002 (3) |
C7A | 0.104 (5) | 0.130 (6) | 0.081 (5) | −0.015 (4) | 0.043 (4) | −0.001 (4) |
C11A | 0.050 (3) | 0.066 (3) | 0.057 (3) | −0.002 (2) | 0.021 (2) | −0.007 (2) |
C12A | 0.052 (3) | 0.082 (3) | 0.066 (3) | 0.002 (3) | 0.015 (3) | −0.017 (3) |
C13A | 0.063 (3) | 0.090 (4) | 0.100 (4) | −0.017 (3) | 0.020 (3) | −0.034 (3) |
C14A | 0.081 (4) | 0.063 (3) | 0.117 (4) | −0.020 (3) | 0.037 (3) | −0.014 (3) |
C15A | 0.063 (3) | 0.058 (3) | 0.085 (4) | −0.011 (2) | 0.023 (3) | −0.003 (3) |
C16A | 0.066 (3) | 0.057 (3) | 0.068 (3) | −0.014 (2) | 0.026 (2) | −0.008 (2) |
C17A | 0.062 (3) | 0.081 (3) | 0.056 (3) | 0.007 (3) | 0.020 (2) | 0.012 (2) |
C18A | 0.131 (4) | 0.072 (3) | 0.085 (3) | 0.002 (3) | 0.040 (3) | 0.019 (3) |
Cl1—C2 | 1.717 (4) | Cl1A—C2A | 1.723 (4) |
F71—F74 | 1.20 (3) | F71A—C7A | 1.308 (6) |
F71—C7 | 1.320 (7) | F71A—F76A | 1.31 (3) |
F71—F76 | 1.43 (3) | F71A—F74A | 1.32 (3) |
F72—F74 | 0.95 (3) | F72A—F75A | 0.96 (3) |
F72—C7 | 1.305 (8) | F72A—C7A | 1.301 (6) |
F72—F75 | 1.35 (2) | F72A—F74A | 1.37 (2) |
F73—F76 | 1.03 (2) | F73A—F76A | 0.93 (3) |
F73—C7 | 1.291 (7) | F73A—C7A | 1.350 (7) |
F73—F75 | 1.30 (2) | F73A—F75A | 1.47 (3) |
O1—C1 | 1.373 (5) | O1A—C15A | 1.373 (5) |
O1—C15 | 1.373 (5) | O1A—C1A | 1.386 (5) |
O2—C17 | 1.199 (4) | O2A—C17A | 1.186 (4) |
O3—C17 | 1.287 (5) | O3A—C17A | 1.312 (5) |
O3—C18 | 1.440 (4) | O3A—C18A | 1.444 (4) |
O4—N1 | 1.206 (5) | O4A—N1A | 1.183 (5) |
O5—N1 | 1.194 (5) | O5A—N1A | 1.212 (5) |
N1—C12 | 1.455 (6) | N1A—C12A | 1.462 (6) |
C1—C2 | 1.366 (6) | C1A—C6A | 1.363 (6) |
C1—C6 | 1.368 (6) | C1A—C2A | 1.377 (6) |
C2—C3 | 1.378 (5) | C2A—C3A | 1.375 (6) |
C3—C4 | 1.365 (5) | C3A—C4A | 1.361 (5) |
C3—H3 | 0.9300 | C3A—H3A | 0.9300 |
C4—C5 | 1.360 (6) | C4A—C5A | 1.357 (6) |
C4—C7 | 1.487 (7) | C4A—C7A | 1.488 (7) |
C5—C6 | 1.367 (6) | C5A—C6A | 1.373 (6) |
C5—H5 | 0.9300 | C5A—H5A | 0.9300 |
C6—H6 | 0.9300 | C6A—H6A | 0.9300 |
C7—F74 | 1.09 (2) | C7A—F76A | 1.15 (2) |
C7—F76 | 1.350 (19) | C7A—F75A | 1.29 (3) |
C7—F75 | 1.427 (19) | C7A—F74A | 1.51 (2) |
C11—C16 | 1.370 (5) | C11A—C12A | 1.376 (5) |
C11—C12 | 1.382 (5) | C11A—C16A | 1.385 (5) |
C11—C17 | 1.487 (5) | C11A—C17A | 1.487 (5) |
C12—C13 | 1.369 (6) | C12A—C13A | 1.373 (6) |
C13—C14 | 1.360 (6) | C13A—C14A | 1.365 (6) |
C13—H13 | 0.9300 | C13A—H13A | 0.9300 |
C14—C15 | 1.372 (5) | C14A—C15A | 1.384 (5) |
C14—H14 | 0.9300 | C14A—H14A | 0.9300 |
C15—C16 | 1.380 (5) | C15A—C16A | 1.380 (5) |
C16—H16 | 0.9300 | C16A—H16A | 0.9300 |
C18—H18A | 0.9600 | C18A—H18D | 0.9600 |
C18—H18B | 0.9600 | C18A—H18E | 0.9600 |
C18—H18C | 0.9600 | C18A—H18F | 0.9600 |
F74—F71—C7 | 50.8 (10) | C7A—F71A—F76A | 52.3 (10) |
F74—F71—F76 | 103.6 (14) | C7A—F71A—F74A | 70.0 (10) |
C7—F71—F76 | 58.8 (8) | F76A—F71A—F74A | 117.7 (16) |
F74—F72—C7 | 54.9 (14) | F75A—F72A—C7A | 67.9 (17) |
F74—F72—F75 | 115 (2) | F75A—F72A—F74A | 134 (2) |
C7—F72—F75 | 65.0 (10) | C7A—F72A—F74A | 68.6 (11) |
F76—F73—C7 | 70.0 (13) | F76A—F73A—C7A | 57.2 (15) |
F76—F73—F75 | 134.8 (18) | F76A—F73A—F75A | 106.1 (19) |
C7—F73—F75 | 66.9 (9) | C7A—F73A—F75A | 54.4 (9) |
C1—O1—C15 | 120.0 (3) | C15A—O1A—C1A | 120.9 (3) |
C17—O3—C18 | 116.6 (3) | C17A—O3A—C18A | 115.9 (3) |
O5—N1—O4 | 121.7 (6) | O4A—N1A—O5A | 122.5 (5) |
O5—N1—C12 | 119.7 (5) | O4A—N1A—C12A | 119.3 (5) |
O4—N1—C12 | 118.6 (5) | O5A—N1A—C12A | 118.2 (5) |
C2—C1—C6 | 118.9 (5) | C6A—C1A—C2A | 119.5 (5) |
C2—C1—O1 | 119.5 (6) | C6A—C1A—O1A | 120.2 (5) |
C6—C1—O1 | 121.4 (6) | C2A—C1A—O1A | 120.1 (5) |
C1—C2—C3 | 121.0 (4) | C3A—C2A—C1A | 120.1 (4) |
C1—C2—Cl1 | 119.9 (5) | C3A—C2A—Cl1A | 120.7 (4) |
C3—C2—Cl1 | 119.1 (4) | C1A—C2A—Cl1A | 119.2 (4) |
C4—C3—C2 | 118.6 (4) | C4A—C3A—C2A | 119.9 (4) |
C4—C3—H3 | 120.7 | C4A—C3A—H3A | 120.0 |
C2—C3—H3 | 120.7 | C2A—C3A—H3A | 120.0 |
C5—C4—C3 | 121.1 (5) | C5A—C4A—C3A | 119.8 (4) |
C5—C4—C7 | 119.5 (5) | C5A—C4A—C7A | 120.2 (5) |
C3—C4—C7 | 119.4 (5) | C3A—C4A—C7A | 119.9 (5) |
C4—C5—C6 | 119.6 (5) | C4A—C5A—C6A | 121.0 (4) |
C4—C5—H5 | 120.2 | C4A—C5A—H5A | 119.5 |
C6—C5—H5 | 120.2 | C6A—C5A—H5A | 119.5 |
C5—C6—C1 | 120.7 (5) | C1A—C6A—C5A | 119.6 (5) |
C5—C6—H6 | 119.6 | C1A—C6A—H6A | 120.2 |
C1—C6—H6 | 119.6 | C5A—C6A—H6A | 120.2 |
F74—C7—F73 | 128.9 (11) | F76A—C7A—F75A | 105.5 (18) |
F74—C7—F72 | 45.7 (16) | F76A—C7A—F72A | 130.4 (10) |
F73—C7—F72 | 109.4 (7) | F75A—C7A—F72A | 43.5 (13) |
F74—C7—F71 | 58.9 (16) | F76A—C7A—F71A | 63.9 (18) |
F73—C7—F71 | 105.4 (6) | F75A—C7A—F71A | 133.9 (9) |
F72—C7—F71 | 103.3 (8) | F72A—C7A—F71A | 106.9 (6) |
F74—C7—F76 | 115.8 (16) | F76A—C7A—F73A | 42.9 (17) |
F73—C7—F76 | 46.0 (10) | F75A—C7A—F73A | 67.6 (14) |
F72—C7—F76 | 137.4 (8) | F72A—C7A—F73A | 107.1 (6) |
F71—C7—F76 | 64.5 (11) | F71A—C7A—F73A | 104.7 (5) |
F74—C7—F75 | 100.8 (18) | F76A—C7A—C4A | 114.5 (9) |
F73—C7—F75 | 56.8 (9) | F75A—C7A—C4A | 112.2 (8) |
F72—C7—F75 | 58.9 (10) | F72A—C7A—C4A | 113.6 (5) |
F71—C7—F75 | 138.5 (7) | F71A—C7A—C4A | 112.6 (5) |
F76—C7—F75 | 101.8 (14) | F73A—C7A—C4A | 111.3 (6) |
F74—C7—C4 | 118.4 (9) | F76A—C7A—F74A | 114.7 (18) |
F73—C7—C4 | 112.6 (6) | F75A—C7A—F74A | 100.1 (16) |
F72—C7—C4 | 114.3 (5) | F72A—C7A—F74A | 58.0 (11) |
F71—C7—C4 | 111.1 (6) | F71A—C7A—F74A | 55.3 (11) |
F76—C7—C4 | 108.0 (8) | F73A—C7A—F74A | 139.8 (7) |
F75—C7—C4 | 110.4 (7) | C4A—C7A—F74A | 108.7 (7) |
C16—C11—C12 | 118.0 (4) | C12A—C11A—C16A | 118.3 (4) |
C16—C11—C17 | 117.9 (4) | C12A—C11A—C17A | 124.0 (4) |
C12—C11—C17 | 124.1 (4) | C16A—C11A—C17A | 117.7 (4) |
C13—C12—C11 | 121.9 (4) | C13A—C12A—C11A | 122.2 (4) |
C13—C12—N1 | 118.1 (5) | C13A—C12A—N1A | 117.5 (5) |
C11—C12—N1 | 120.0 (5) | C11A—C12A—N1A | 120.3 (5) |
C14—C13—C12 | 119.8 (4) | C14A—C13A—C12A | 119.3 (4) |
C14—C13—H13 | 120.1 | C14A—C13A—H13A | 120.3 |
C12—C13—H13 | 120.1 | C12A—C13A—H13A | 120.3 |
C13—C14—C15 | 118.9 (4) | C13A—C14A—C15A | 119.7 (4) |
C13—C14—H14 | 120.5 | C13A—C14A—H14A | 120.1 |
C15—C14—H14 | 120.5 | C15A—C14A—H14A | 120.2 |
C14—C15—O1 | 115.0 (4) | O1A—C15A—C16A | 123.5 (4) |
C14—C15—C16 | 121.5 (4) | O1A—C15A—C14A | 115.7 (4) |
O1—C15—C16 | 123.4 (4) | C16A—C15A—C14A | 120.7 (4) |
C11—C16—C15 | 119.8 (4) | C15A—C16A—C11A | 119.7 (4) |
C11—C16—H16 | 120.1 | C15A—C16A—H16A | 120.1 |
C15—C16—H16 | 120.1 | C11A—C16A—H16A | 120.1 |
O2—C17—O3 | 124.9 (4) | O2A—C17A—O3A | 125.1 (4) |
O2—C17—C11 | 122.9 (4) | O2A—C17A—C11A | 124.1 (4) |
O3—C17—C11 | 112.1 (4) | O3A—C17A—C11A | 110.7 (4) |
O3—C18—H18A | 109.5 | O3A—C18A—H18D | 109.5 |
O3—C18—H18B | 109.5 | O3A—C18A—H18E | 109.5 |
H18A—C18—H18B | 109.5 | H18D—C18A—H18E | 109.5 |
O3—C18—H18C | 109.5 | O3A—C18A—H18F | 109.5 |
H18A—C18—H18C | 109.5 | H18D—C18A—H18F | 109.5 |
H18B—C18—H18C | 109.5 | H18E—C18A—H18F | 109.5 |
F72—F74—C7 | 79.3 (18) | F71A—F74A—F72A | 102.3 (15) |
F72—F74—F71 | 146 (3) | F71A—F74A—C7A | 54.7 (9) |
C7—F74—F71 | 70.2 (18) | F72A—F74A—C7A | 53.5 (8) |
F73—F75—F72 | 106.3 (14) | F72A—F75A—C7A | 68.7 (14) |
F73—F75—C7 | 56.3 (9) | F72A—F75A—F73A | 121 (2) |
F72—F75—C7 | 56.0 (8) | C7A—F75A—F73A | 58.0 (13) |
F73—F76—C7 | 64.0 (10) | F73A—F76A—C7A | 79.8 (19) |
F73—F76—F71 | 114.3 (17) | F73A—F76A—F71A | 139 (3) |
C7—F76—F71 | 56.7 (9) | C7A—F76A—F71A | 63.8 (16) |
C15—O1—C1—C2 | 103.8 (5) | C15A—O1A—C1A—C6A | −102.8 (5) |
C15—O1—C1—C6 | −80.8 (6) | C15A—O1A—C1A—C2A | 82.0 (5) |
C6—C1—C2—C3 | −2.8 (6) | C6A—C1A—C2A—C3A | −3.9 (6) |
O1—C1—C2—C3 | 172.8 (4) | O1A—C1A—C2A—C3A | 171.3 (4) |
C6—C1—C2—Cl1 | 177.3 (3) | C6A—C1A—C2A—Cl1A | 177.5 (3) |
O1—C1—C2—Cl1 | −7.1 (5) | O1A—C1A—C2A—Cl1A | −7.3 (5) |
C1—C2—C3—C4 | 2.3 (6) | C1A—C2A—C3A—C4A | 2.8 (6) |
Cl1—C2—C3—C4 | −177.9 (3) | Cl1A—C2A—C3A—C4A | −178.6 (3) |
C2—C3—C4—C5 | −0.4 (6) | C2A—C3A—C4A—C5A | −0.8 (6) |
C2—C3—C4—C7 | −178.8 (4) | C2A—C3A—C4A—C7A | −177.1 (4) |
C3—C4—C5—C6 | −0.8 (7) | C3A—C4A—C5A—C6A | 0.0 (7) |
C7—C4—C5—C6 | 177.6 (5) | C7A—C4A—C5A—C6A | 176.3 (5) |
C4—C5—C6—C1 | 0.3 (7) | C2A—C1A—C6A—C5A | 3.1 (6) |
C2—C1—C6—C5 | 1.5 (7) | O1A—C1A—C6A—C5A | −172.1 (4) |
O1—C1—C6—C5 | −174.0 (4) | C4A—C5A—C6A—C1A | −1.2 (7) |
F76—F73—C7—F74 | 90 (2) | F75A—F72A—C7A—F76A | 67 (3) |
F75—F73—C7—F74 | −76 (2) | F74A—F72A—C7A—F76A | −97 (3) |
F76—F73—C7—F72 | 138.1 (10) | F74A—F72A—C7A—F75A | −164.0 (14) |
F75—F73—C7—F72 | −28.0 (8) | F75A—F72A—C7A—F71A | 137.2 (13) |
F76—F73—C7—F71 | 27.7 (10) | F74A—F72A—C7A—F71A | −26.8 (8) |
F75—F73—C7—F71 | −138.4 (9) | F75A—F72A—C7A—F73A | 25.4 (12) |
F75—F73—C7—F76 | −166.1 (11) | F74A—F72A—C7A—F73A | −138.6 (9) |
F76—F73—C7—F75 | 166.1 (11) | F75A—F72A—C7A—C4A | −98.0 (12) |
F76—F73—C7—C4 | −93.6 (10) | F74A—F72A—C7A—C4A | 98.0 (9) |
F75—F73—C7—C4 | 100.3 (8) | F75A—F72A—C7A—F74A | 164.0 (14) |
F75—F72—C7—F74 | 153.2 (15) | F74A—F71A—C7A—F76A | 154.9 (12) |
F74—F72—C7—F73 | −125.9 (14) | F76A—F71A—C7A—F75A | −87 (2) |
F75—F72—C7—F73 | 27.3 (8) | F74A—F71A—C7A—F75A | 68 (2) |
F74—F72—C7—F71 | −14.1 (13) | F76A—F71A—C7A—F72A | −127.2 (11) |
F75—F72—C7—F71 | 139.1 (8) | F74A—F71A—C7A—F72A | 27.7 (8) |
F74—F72—C7—F76 | −81 (2) | F76A—F71A—C7A—F73A | −13.8 (10) |
F75—F72—C7—F76 | 72 (2) | F74A—F71A—C7A—F73A | 141.1 (9) |
F74—F72—C7—F75 | −153.2 (15) | F76A—F71A—C7A—C4A | 107.3 (11) |
F74—F72—C7—C4 | 106.8 (12) | F74A—F71A—C7A—C4A | −97.8 (8) |
F75—F72—C7—C4 | −100.0 (8) | F76A—F71A—C7A—F74A | −154.9 (12) |
F76—F71—C7—F74 | −148.2 (12) | F75A—F73A—C7A—F76A | −150.3 (15) |
F74—F71—C7—F73 | 126.5 (12) | F76A—F73A—C7A—F75A | 150.3 (15) |
F76—F71—C7—F73 | −21.7 (8) | F76A—F73A—C7A—F72A | 131.7 (14) |
F74—F71—C7—F72 | 11.7 (11) | F75A—F73A—C7A—F72A | −18.6 (8) |
F76—F71—C7—F72 | −136.5 (9) | F76A—F73A—C7A—F71A | 18.4 (13) |
F74—F71—C7—F76 | 148.2 (12) | F75A—F73A—C7A—F71A | −131.9 (9) |
F74—F71—C7—F75 | 70 (2) | F76A—F73A—C7A—C4A | −103.6 (12) |
F76—F71—C7—F75 | −78.7 (19) | F75A—F73A—C7A—C4A | 106.2 (9) |
F74—F71—C7—C4 | −111.3 (10) | F76A—F73A—C7A—F74A | 71 (2) |
F76—F71—C7—C4 | 100.5 (9) | F75A—F73A—C7A—F74A | −79 (2) |
C5—C4—C7—F74 | −135 (2) | C5A—C4A—C7A—F76A | −7 (2) |
C3—C4—C7—F74 | 43 (2) | C3A—C4A—C7A—F76A | 169 (2) |
C5—C4—C7—F73 | 48.0 (8) | C5A—C4A—C7A—F75A | 113.1 (18) |
C3—C4—C7—F73 | −133.6 (7) | C3A—C4A—C7A—F75A | −70.7 (18) |
C5—C4—C7—F72 | 173.6 (8) | C5A—C4A—C7A—F72A | 160.5 (6) |
C3—C4—C7—F72 | −8.0 (10) | C3A—C4A—C7A—F72A | −23.3 (8) |
C5—C4—C7—F71 | −70.0 (8) | C5A—C4A—C7A—F71A | −77.7 (7) |
C3—C4—C7—F71 | 108.4 (7) | C3A—C4A—C7A—F71A | 98.5 (6) |
C5—C4—C7—F76 | −1.1 (15) | C5A—C4A—C7A—F73A | 39.5 (8) |
C3—C4—C7—F76 | 177.3 (14) | C3A—C4A—C7A—F73A | −144.3 (6) |
C5—C4—C7—F75 | 109.4 (13) | C5A—C4A—C7A—F74A | −137.1 (14) |
C3—C4—C7—F75 | −72.1 (14) | C3A—C4A—C7A—F74A | 39.2 (15) |
C16—C11—C12—C13 | 1.1 (6) | C16A—C11A—C12A—C13A | 0.0 (6) |
C17—C11—C12—C13 | −178.5 (4) | C17A—C11A—C12A—C13A | 179.7 (4) |
C16—C11—C12—N1 | −176.4 (4) | C16A—C11A—C12A—N1A | −177.7 (3) |
C17—C11—C12—N1 | 4.0 (6) | C17A—C11A—C12A—N1A | 2.0 (6) |
O5—N1—C12—C13 | −5.3 (7) | O4A—N1A—C12A—C13A | −174.1 (5) |
O4—N1—C12—C13 | 171.0 (5) | O5A—N1A—C12A—C13A | 8.0 (6) |
O5—N1—C12—C11 | 172.3 (5) | O4A—N1A—C12A—C11A | 3.7 (7) |
O4—N1—C12—C11 | −11.5 (7) | O5A—N1A—C12A—C11A | −174.2 (4) |
C11—C12—C13—C14 | −1.7 (7) | C11A—C12A—C13A—C14A | −1.1 (6) |
N1—C12—C13—C14 | 175.8 (4) | N1A—C12A—C13A—C14A | 176.7 (4) |
C12—C13—C14—C15 | 1.0 (7) | C12A—C13A—C14A—C15A | 1.0 (6) |
C13—C14—C15—O1 | −178.9 (4) | C1A—O1A—C15A—C16A | 14.4 (6) |
C13—C14—C15—C16 | 0.4 (7) | C1A—O1A—C15A—C14A | −168.2 (4) |
C1—O1—C15—C14 | 173.2 (5) | C13A—C14A—C15A—O1A | −177.4 (4) |
C1—O1—C15—C16 | −6.1 (7) | C13A—C14A—C15A—C16A | 0.1 (6) |
C12—C11—C16—C15 | 0.4 (6) | O1A—C15A—C16A—C11A | 176.1 (4) |
C17—C11—C16—C15 | 179.9 (4) | C14A—C15A—C16A—C11A | −1.2 (6) |
C14—C15—C16—C11 | −1.1 (7) | C12A—C11A—C16A—C15A | 1.1 (5) |
O1—C15—C16—C11 | 178.2 (4) | C17A—C11A—C16A—C15A | −178.6 (4) |
C18—O3—C17—O2 | −5.6 (7) | C18A—O3A—C17A—O2A | −3.0 (6) |
C18—O3—C17—C11 | 177.3 (4) | C18A—O3A—C17A—C11A | 178.1 (3) |
C16—C11—C17—O2 | −81.3 (6) | C12A—C11A—C17A—O2A | 92.3 (5) |
C12—C11—C17—O2 | 98.2 (5) | C16A—C11A—C17A—O2A | −87.9 (5) |
C16—C11—C17—O3 | 95.9 (4) | C12A—C11A—C17A—O3A | −88.8 (4) |
C12—C11—C17—O3 | −84.6 (5) | C16A—C11A—C17A—O3A | 90.9 (4) |
F75—F72—F74—C7 | −26.8 (12) | C7A—F71A—F74A—F72A | −25.6 (6) |
C7—F72—F74—F71 | 27.5 (18) | F76A—F71A—F74A—F72A | −3.3 (11) |
F75—F72—F74—F71 | 1 (3) | F76A—F71A—F74A—C7A | 22.3 (8) |
F73—C7—F74—F72 | 79 (2) | F75A—F72A—F74A—F71A | 5.3 (15) |
F71—C7—F74—F72 | 164.0 (14) | C7A—F72A—F74A—F71A | 26.0 (6) |
F76—C7—F74—F72 | 132.1 (14) | F75A—F72A—F74A—C7A | −20.7 (13) |
F75—C7—F74—F72 | 23.2 (14) | F76A—C7A—F74A—F71A | −24.8 (16) |
C4—C7—F74—F72 | −97.2 (12) | F75A—C7A—F74A—F71A | −137.2 (11) |
F73—C7—F74—F71 | −84.9 (18) | F72A—C7A—F74A—F71A | −148.3 (8) |
F72—C7—F74—F71 | −164.0 (14) | F73A—C7A—F74A—F71A | −70.1 (19) |
F76—C7—F74—F71 | −31.9 (14) | C4A—C7A—F74A—F71A | 105.0 (6) |
F75—C7—F74—F71 | −140.8 (10) | F76A—C7A—F74A—F72A | 123.6 (16) |
C4—C7—F74—F71 | 98.8 (13) | F75A—C7A—F74A—F72A | 11.1 (11) |
C7—F71—F74—F72 | −28.8 (19) | F71A—C7A—F74A—F72A | 148.3 (8) |
F76—F71—F74—F72 | −1 (2) | F73A—C7A—F74A—F72A | 78 (2) |
F76—F71—F74—C7 | 27.6 (9) | C4A—C7A—F74A—F72A | −106.7 (6) |
F76—F73—F75—F72 | 8.0 (15) | F74A—F72A—F75A—C7A | 20.8 (13) |
C7—F73—F75—F72 | 26.5 (6) | C7A—F72A—F75A—F73A | −26.0 (9) |
F76—F73—F75—C7 | −18.5 (13) | F74A—F72A—F75A—F73A | −5.2 (19) |
F74—F72—F75—F73 | −2.6 (13) | F76A—C7A—F75A—F72A | −133.2 (16) |
C7—F72—F75—F73 | −26.6 (6) | F71A—C7A—F75A—F72A | −65 (2) |
F74—F72—F75—C7 | 24.0 (10) | F73A—C7A—F75A—F72A | −153.7 (11) |
F74—C7—F75—F73 | 129.7 (13) | C4A—C7A—F75A—F72A | 101.4 (9) |
F72—C7—F75—F73 | 148.9 (8) | F74A—C7A—F75A—F72A | −13.7 (13) |
F71—C7—F75—F73 | 74.9 (18) | F76A—C7A—F75A—F73A | 20.5 (14) |
F76—C7—F75—F73 | 10.2 (9) | F72A—C7A—F75A—F73A | 153.7 (11) |
C4—C7—F75—F73 | −104.3 (8) | F71A—C7A—F75A—F73A | 89.1 (18) |
F74—C7—F75—F72 | −19.2 (13) | C4A—C7A—F75A—F73A | −104.9 (9) |
F73—C7—F75—F72 | −148.9 (8) | F74A—C7A—F75A—F73A | 139.9 (9) |
F71—C7—F75—F72 | −74.0 (19) | F76A—F73A—F75A—F72A | 3.1 (16) |
F76—C7—F75—F72 | −138.7 (10) | C7A—F73A—F75A—F72A | 28.8 (10) |
C4—C7—F75—F72 | 106.8 (7) | F76A—F73A—F75A—C7A | −25.7 (10) |
F75—F73—F76—C7 | 18.1 (12) | F75A—F73A—F76A—C7A | 24.8 (10) |
C7—F73—F76—F71 | −27.1 (8) | C7A—F73A—F76A—F71A | −27.5 (14) |
F75—F73—F76—F71 | −9.0 (17) | F75A—F73A—F76A—F71A | −3 (2) |
F74—C7—F76—F73 | −120.1 (17) | F75A—C7A—F76A—F73A | −28.4 (15) |
F72—C7—F76—F73 | −68.4 (19) | F72A—C7A—F76A—F73A | −70 (2) |
F71—C7—F76—F73 | −150.2 (9) | F71A—C7A—F76A—F73A | −160.2 (13) |
F75—C7—F76—F73 | −11.8 (10) | C4A—C7A—F76A—F73A | 95.5 (12) |
C4—C7—F76—F73 | 104.4 (7) | F74A—C7A—F76A—F73A | −137.6 (14) |
F74—C7—F76—F71 | 30.1 (14) | F75A—C7A—F76A—F71A | 131.8 (12) |
F73—C7—F76—F71 | 150.2 (9) | F72A—C7A—F76A—F71A | 91 (2) |
F72—C7—F76—F71 | 81.8 (18) | F73A—C7A—F76A—F71A | 160.2 (13) |
F75—C7—F76—F71 | 138.4 (9) | C4A—C7A—F76A—F71A | −104.3 (10) |
C4—C7—F76—F71 | −105.4 (7) | F74A—C7A—F76A—F71A | 22.6 (13) |
F74—F71—F76—F73 | 4.5 (13) | C7A—F71A—F76A—F73A | 30.5 (16) |
C7—F71—F76—F73 | 29.3 (8) | F74A—F71A—F76A—F73A | 4 (2) |
F74—F71—F76—C7 | −24.8 (8) | F74A—F71A—F76A—C7A | −26.7 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···O2A | 0.93 | 2.47 | 3.359 (5) | 159 |
C16A—H16A···O2 | 0.93 | 2.51 | 3.373 (5) | 155 |
C6—H6···O5i | 0.93 | 2.70 | 3.323 (6) | 125 |
C6A—H6A···O5Aii | 0.93 | 2.56 | 3.389 (6) | 149 |
C5—H5···O2iii | 0.93 | 2.60 | 3.511 (6) | 167 |
C5A—H5A···O2Aiv | 0.93 | 2.74 | 3.578 (6) | 151 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z+1/2; (iv) x, −y+1/2, z−1/2. |
C14H10ClF3N2O4 | Dx = 1.606 Mg m−3 |
Mr = 362.69 | Melting point: 443(1) K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 14.326 (13) Å | Cell parameters from 823 reflections |
b = 7.802 (7) Å | θ = 2.5–25.4° |
c = 14.337 (13) Å | µ = 0.31 mm−1 |
β = 110.599 (15)° | T = 293 K |
V = 1500 (2) Å3 | Prism, colourless |
Z = 4 | 0.26 × 0.22 × 0.16 mm |
F(000) = 736 |
Bruker SMART CCD area-detector diffractometer | 2646 independent reflections |
Radiation source: fine-focus sealed tube | 2007 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→17 |
Tmin = 0.806, Tmax = 1.000 | k = −9→9 |
7542 measured reflections | l = −17→15 |
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)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.0399P)2 + 1.2049P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.006 |
2646 reflections | Δρmax = 0.26 e Å−3 |
220 parameters | Δρmin = −0.34 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0072 (12) |
C14H10ClF3N2O4 | V = 1500 (2) Å3 |
Mr = 362.69 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.326 (13) Å | µ = 0.31 mm−1 |
b = 7.802 (7) Å | T = 293 K |
c = 14.337 (13) Å | 0.26 × 0.22 × 0.16 mm |
β = 110.599 (15)° |
Bruker SMART CCD area-detector diffractometer | 2646 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2007 reflections with I > 2σ(I) |
Tmin = 0.806, Tmax = 1.000 | Rint = 0.022 |
7542 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.26 e Å−3 |
2646 reflections | Δρmin = −0.34 e Å−3 |
220 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 | ||
Cl1 | 0.07694 (7) | 0.88697 (10) | 0.19239 (6) | 0.0751 (3) | |
F71 | 0.21795 (16) | −0.1887 (2) | 0.68455 (15) | 0.0899 (7) | |
F72 | 0.32208 (15) | −0.0282 (2) | 0.78845 (11) | 0.0697 (5) | |
F73 | 0.36128 (17) | −0.1549 (3) | 0.67724 (14) | 0.0861 (7) | |
O1 | 0.33607 (14) | 0.4512 (3) | 0.55205 (15) | 0.0635 (6) | |
O2 | 0.02759 (13) | 0.2154 (3) | 0.43625 (14) | 0.0581 (5) | |
O3 | 0.1805 (2) | 0.6179 (3) | 0.11095 (17) | 0.0864 (8) | |
O4 | 0.12446 (17) | 0.3650 (3) | 0.13431 (14) | 0.0606 (6) | |
N1 | 0.18198 (14) | 0.3337 (2) | 0.49334 (13) | 0.0349 (5) | |
N3 | 0.31324 (14) | 0.2012 (3) | 0.62138 (14) | 0.0391 (5) | |
C2 | 0.28141 (18) | 0.3369 (3) | 0.55551 (17) | 0.0394 (6) | |
C4 | 0.24823 (18) | 0.0740 (3) | 0.62383 (17) | 0.0370 (6) | |
C5 | 0.15265 (19) | 0.0750 (3) | 0.56586 (18) | 0.0419 (6) | |
H5 | 0.1108 | −0.0120 | 0.5720 | 0.050* | |
C6 | 0.11304 (18) | 0.2085 (3) | 0.49387 (18) | 0.0394 (6) | |
C7 | 0.2883 (2) | −0.0737 (4) | 0.6940 (2) | 0.0499 (7) | |
C8 | 0.4187 (2) | 0.2073 (5) | 0.6862 (2) | 0.0699 (10) | |
H8A | 0.4290 | 0.1339 | 0.7427 | 0.105* | |
H8B | 0.4364 | 0.3227 | 0.7086 | 0.105* | |
H8C | 0.4595 | 0.1691 | 0.6496 | 0.105* | |
C11 | 0.14032 (17) | 0.5648 (3) | 0.25663 (17) | 0.0372 (6) | |
C12 | 0.10602 (19) | 0.7209 (3) | 0.27755 (19) | 0.0435 (6) | |
C13 | 0.0911 (2) | 0.7464 (4) | 0.3663 (2) | 0.0512 (7) | |
H13 | 0.0653 | 0.8502 | 0.3782 | 0.061* | |
C14 | 0.1139 (2) | 0.6196 (3) | 0.43735 (19) | 0.0466 (6) | |
H14 | 0.1036 | 0.6367 | 0.4972 | 0.056* | |
C15 | 0.15216 (17) | 0.4672 (3) | 0.41879 (17) | 0.0357 (5) | |
C16 | 0.16351 (17) | 0.4382 (3) | 0.32921 (17) | 0.0357 (5) | |
H16 | 0.1870 | 0.3326 | 0.3169 | 0.043* | |
C17 | 0.15162 (19) | 0.5245 (4) | 0.15984 (18) | 0.0439 (6) | |
C18 | 0.1284 (3) | 0.3052 (5) | 0.0407 (2) | 0.0793 (11) | |
H18A | 0.1937 | 0.3255 | 0.0386 | 0.119* | |
H18B | 0.0798 | 0.3655 | −0.0130 | 0.119* | |
H18C | 0.1142 | 0.1846 | 0.0340 | 0.119* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0942 (7) | 0.0516 (5) | 0.0700 (5) | 0.0180 (4) | 0.0171 (5) | 0.0255 (4) |
F71 | 0.1013 (16) | 0.0612 (12) | 0.0870 (14) | −0.0221 (11) | 0.0081 (12) | 0.0321 (10) |
F72 | 0.1064 (14) | 0.0615 (11) | 0.0346 (9) | 0.0083 (10) | 0.0165 (9) | 0.0090 (8) |
F73 | 0.1133 (16) | 0.0802 (13) | 0.0721 (12) | 0.0521 (12) | 0.0416 (12) | 0.0223 (11) |
O1 | 0.0468 (11) | 0.0647 (13) | 0.0636 (13) | −0.0223 (10) | 0.0001 (9) | 0.0202 (11) |
O2 | 0.0398 (11) | 0.0680 (13) | 0.0560 (12) | −0.0102 (9) | 0.0036 (9) | 0.0113 (10) |
O3 | 0.135 (2) | 0.0793 (17) | 0.0610 (14) | −0.0390 (16) | 0.0538 (15) | −0.0009 (12) |
O4 | 0.0907 (16) | 0.0538 (12) | 0.0506 (12) | −0.0072 (11) | 0.0415 (11) | −0.0092 (9) |
N1 | 0.0352 (10) | 0.0373 (11) | 0.0301 (10) | −0.0024 (9) | 0.0090 (8) | 0.0011 (9) |
N3 | 0.0338 (11) | 0.0482 (12) | 0.0319 (10) | −0.0021 (9) | 0.0072 (8) | 0.0063 (9) |
C2 | 0.0377 (13) | 0.0437 (14) | 0.0334 (13) | −0.0072 (12) | 0.0081 (11) | 0.0026 (11) |
C4 | 0.0464 (14) | 0.0378 (13) | 0.0296 (12) | −0.0010 (11) | 0.0167 (11) | −0.0012 (10) |
C5 | 0.0470 (15) | 0.0398 (14) | 0.0393 (13) | −0.0096 (11) | 0.0156 (12) | 0.0015 (11) |
C6 | 0.0383 (14) | 0.0445 (14) | 0.0351 (13) | −0.0061 (11) | 0.0124 (11) | −0.0029 (11) |
C7 | 0.0642 (18) | 0.0450 (15) | 0.0412 (15) | 0.0033 (14) | 0.0192 (13) | 0.0047 (12) |
C8 | 0.0397 (16) | 0.090 (2) | 0.066 (2) | −0.0078 (16) | 0.0002 (14) | 0.0288 (18) |
C11 | 0.0359 (13) | 0.0386 (13) | 0.0337 (12) | −0.0026 (10) | 0.0083 (10) | 0.0027 (10) |
C12 | 0.0435 (14) | 0.0369 (14) | 0.0417 (14) | 0.0028 (11) | 0.0044 (11) | 0.0061 (11) |
C13 | 0.0572 (17) | 0.0403 (15) | 0.0501 (16) | 0.0136 (13) | 0.0114 (13) | −0.0036 (12) |
C14 | 0.0522 (15) | 0.0480 (16) | 0.0389 (14) | 0.0069 (13) | 0.0152 (12) | −0.0063 (12) |
C15 | 0.0364 (13) | 0.0362 (13) | 0.0316 (12) | −0.0016 (10) | 0.0083 (10) | 0.0008 (10) |
C16 | 0.0365 (12) | 0.0332 (12) | 0.0357 (13) | 0.0024 (10) | 0.0106 (10) | 0.0003 (10) |
C17 | 0.0433 (14) | 0.0496 (16) | 0.0371 (13) | −0.0015 (12) | 0.0121 (12) | 0.0059 (12) |
C18 | 0.103 (3) | 0.090 (3) | 0.0538 (19) | 0.004 (2) | 0.0383 (19) | −0.0206 (18) |
Cl1—C12 | 1.728 (3) | C5—H5 | 0.9300 |
F71—C7 | 1.321 (3) | C8—H8A | 0.9600 |
F72—C7 | 1.316 (3) | C8—H8B | 0.9600 |
F73—C7 | 1.315 (3) | C8—H8C | 0.9600 |
O1—C2 | 1.199 (3) | C11—C12 | 1.385 (4) |
O2—C6 | 1.213 (3) | C11—C16 | 1.387 (3) |
O3—C17 | 1.182 (3) | C11—C17 | 1.486 (4) |
O4—C17 | 1.317 (3) | C12—C13 | 1.377 (4) |
O4—C18 | 1.441 (4) | C13—C14 | 1.375 (4) |
N1—C2 | 1.390 (3) | C13—H13 | 0.9300 |
N1—C6 | 1.391 (3) | C14—C15 | 1.374 (4) |
N1—C15 | 1.445 (3) | C14—H14 | 0.9300 |
N3—C4 | 1.370 (3) | C15—C16 | 1.369 (3) |
N3—C2 | 1.385 (3) | C16—H16 | 0.9300 |
N3—C8 | 1.470 (3) | C18—H18A | 0.9600 |
C4—C5 | 1.329 (4) | C18—H18B | 0.9600 |
C4—C7 | 1.504 (4) | C18—H18C | 0.9600 |
C5—C6 | 1.435 (4) | ||
C17—O4—C18 | 117.4 (2) | H8A—C8—H8C | 109.5 |
C2—N1—C6 | 125.4 (2) | H8B—C8—H8C | 109.5 |
C2—N1—C15 | 115.53 (19) | C12—C11—C16 | 118.2 (2) |
C6—N1—C15 | 118.98 (19) | C12—C11—C17 | 123.5 (2) |
C4—N3—C2 | 120.5 (2) | C16—C11—C17 | 118.3 (2) |
C4—N3—C8 | 124.3 (2) | C13—C12—C11 | 120.6 (2) |
C2—N3—C8 | 115.1 (2) | C13—C12—Cl1 | 117.9 (2) |
O1—C2—N3 | 122.2 (2) | C11—C12—Cl1 | 121.5 (2) |
O1—C2—N1 | 121.6 (2) | C14—C13—C12 | 120.5 (2) |
N3—C2—N1 | 116.2 (2) | C14—C13—H13 | 119.8 |
C5—C4—N3 | 122.7 (2) | C12—C13—H13 | 119.8 |
C5—C4—C7 | 119.3 (2) | C15—C14—C13 | 119.1 (2) |
N3—C4—C7 | 118.0 (2) | C15—C14—H14 | 120.5 |
C4—C5—C6 | 120.9 (2) | C13—C14—H14 | 120.5 |
C4—C5—H5 | 119.5 | C16—C15—C14 | 120.8 (2) |
C6—C5—H5 | 119.5 | C16—C15—N1 | 118.2 (2) |
O2—C6—N1 | 120.9 (2) | C14—C15—N1 | 121.0 (2) |
O2—C6—C5 | 124.8 (2) | C15—C16—C11 | 120.6 (2) |
N1—C6—C5 | 114.3 (2) | C15—C16—H16 | 119.7 |
F73—C7—F72 | 106.9 (2) | C11—C16—H16 | 119.7 |
F73—C7—F71 | 106.3 (3) | O3—C17—O4 | 123.3 (3) |
F72—C7—F71 | 106.2 (2) | O3—C17—C11 | 126.8 (3) |
F73—C7—C4 | 112.8 (2) | O4—C17—C11 | 109.9 (2) |
F72—C7—C4 | 113.4 (2) | O4—C18—H18A | 109.5 |
F71—C7—C4 | 110.7 (2) | O4—C18—H18B | 109.5 |
N3—C8—H8A | 109.5 | H18A—C18—H18B | 109.5 |
N3—C8—H8B | 109.5 | O4—C18—H18C | 109.5 |
H8A—C8—H8B | 109.5 | H18A—C18—H18C | 109.5 |
N3—C8—H8C | 109.5 | H18B—C18—H18C | 109.5 |
C4—N3—C2—O1 | 179.3 (2) | N3—C4—C7—F71 | −177.2 (2) |
C8—N3—C2—O1 | −0.2 (4) | C16—C11—C12—C13 | −3.0 (4) |
C4—N3—C2—N1 | −0.6 (3) | C17—C11—C12—C13 | 175.7 (2) |
C8—N3—C2—N1 | 179.9 (2) | C16—C11—C12—Cl1 | 179.11 (19) |
C6—N1—C2—O1 | −178.5 (2) | C17—C11—C12—Cl1 | −2.2 (3) |
C15—N1—C2—O1 | 5.7 (3) | C11—C12—C13—C14 | 2.7 (4) |
C6—N1—C2—N3 | 1.4 (3) | Cl1—C12—C13—C14 | −179.3 (2) |
C15—N1—C2—N3 | −174.4 (2) | C12—C13—C14—C15 | 0.2 (4) |
C2—N3—C4—C5 | −1.3 (4) | C13—C14—C15—C16 | −2.9 (4) |
C8—N3—C4—C5 | 178.2 (3) | C13—C14—C15—N1 | 176.8 (2) |
C2—N3—C4—C7 | 177.5 (2) | C2—N1—C15—C16 | 87.7 (3) |
C8—N3—C4—C7 | −3.1 (4) | C6—N1—C15—C16 | −88.4 (3) |
N3—C4—C5—C6 | 2.4 (4) | C2—N1—C15—C14 | −92.0 (3) |
C7—C4—C5—C6 | −176.3 (2) | C6—N1—C15—C14 | 91.9 (3) |
C2—N1—C6—O2 | −179.5 (2) | C14—C15—C16—C11 | 2.6 (4) |
C15—N1—C6—O2 | −3.8 (3) | N1—C15—C16—C11 | −177.1 (2) |
C2—N1—C6—C5 | −0.3 (3) | C12—C11—C16—C15 | 0.3 (4) |
C15—N1—C6—C5 | 175.4 (2) | C17—C11—C16—C15 | −178.4 (2) |
C4—C5—C6—O2 | 177.6 (3) | C18—O4—C17—O3 | −1.5 (4) |
C4—C5—C6—N1 | −1.6 (3) | C18—O4—C17—C11 | 178.5 (2) |
C5—C4—C7—F73 | 120.6 (3) | C12—C11—C17—O3 | 38.9 (4) |
N3—C4—C7—F73 | −58.2 (3) | C16—C11—C17—O3 | −142.4 (3) |
C5—C4—C7—F72 | −117.7 (3) | C12—C11—C17—O4 | −141.1 (3) |
N3—C4—C7—F72 | 63.5 (3) | C16—C11—C17—O4 | 37.6 (3) |
C5—C4—C7—F71 | 1.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2i | 0.93 | 2.51 | 3.427 (4) | 169 |
C16—H16···O3ii | 0.93 | 2.47 | 3.260 (4) | 143 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1/2, y−1/2, −z+1/2. |
C15H10ClF4NO3 | Dx = 1.533 Mg m−3 |
Mr = 363.69 | Melting point: 380(1) K |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
a = 22.887 (9) Å | Cell parameters from 908 reflections |
b = 7.250 (3) Å | θ = 2.8–21.2° |
c = 9.497 (4) Å | µ = 0.30 mm−1 |
V = 1575.7 (11) Å3 | T = 293 K |
Z = 4 | Block, colourless |
F(000) = 736 | 0.40 × 0.38 × 0.28 mm |
Bruker SMART CCD area-detector diffractometer | 2725 independent reflections |
Radiation source: fine-focus sealed tube | 2022 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→27 |
Tmin = 0.853, Tmax = 0.919 | k = −8→8 |
7730 measured reflections | l = −11→11 |
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)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.124 | w = 1/[σ2(Fo2) + (0.055P)2 + 0.3451P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2725 reflections | Δρmax = 0.19 e Å−3 |
253 parameters | Δρmin = −0.18 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with how many Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.05 (12) |
C15H10ClF4NO3 | V = 1575.7 (11) Å3 |
Mr = 363.69 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 22.887 (9) Å | µ = 0.30 mm−1 |
b = 7.250 (3) Å | T = 293 K |
c = 9.497 (4) Å | 0.40 × 0.38 × 0.28 mm |
Bruker SMART CCD area-detector diffractometer | 2725 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2022 reflections with I > 2σ(I) |
Tmin = 0.853, Tmax = 0.919 | Rint = 0.053 |
7730 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.124 | Δρmax = 0.19 e Å−3 |
S = 1.05 | Δρmin = −0.18 e Å−3 |
2725 reflections | Absolute structure: Flack (1983), with how many Friedel pairs |
253 parameters | Absolute structure parameter: −0.05 (12) |
1 restraint |
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 | Occ. (<1) | |
Cl1 | 0.24602 (6) | 0.07128 (16) | 0.50000 (19) | 0.0991 (5) | |
F1 | 0.41739 (11) | 0.3028 (3) | 0.7791 (3) | 0.0851 (8) | |
O1 | 0.50000 (13) | 0.4401 (5) | 0.4929 (5) | 0.0995 (12) | |
O2 | 0.37221 (11) | 0.7646 (3) | 0.7528 (4) | 0.0722 (8) | |
O3 | 0.26586 (11) | 0.4022 (4) | 0.3420 (3) | 0.0701 (8) | |
N1 | 0.43490 (12) | 0.6065 (4) | 0.6168 (3) | 0.0471 (7) | |
C2 | 0.49118 (16) | 0.5708 (6) | 0.5654 (5) | 0.0640 (10) | 0.50 |
C3 | 0.53841 (18) | 0.7023 (7) | 0.6051 (6) | 0.0942 (18) | 0.50 |
H3A | 0.5743 | 0.6321 | 0.6148 | 0.113* | 0.50 |
H3B | 0.5439 | 0.7863 | 0.5267 | 0.113* | 0.50 |
C4 | 0.5317 (4) | 0.8122 (13) | 0.7305 (9) | 0.050 (2) | 0.50 |
H4 | 0.5410 | 0.7329 | 0.8110 | 0.061* | 0.50 |
C5 | 0.46863 (16) | 0.8788 (5) | 0.7498 (6) | 0.0716 (11) | 0.50 |
H5A | 0.4633 | 0.9105 | 0.8482 | 0.086* | 0.50 |
H5B | 0.4638 | 0.9912 | 0.6957 | 0.086* | 0.50 |
C6 | 0.42111 (15) | 0.7486 (4) | 0.7087 (4) | 0.0494 (8) | 0.50 |
C7 | 0.5720 (2) | 0.9764 (8) | 0.7370 (8) | 0.0853 (14) | 0.50 |
F71 | 0.5673 (4) | 1.0959 (13) | 0.6416 (12) | 0.106 (2) | 0.50 |
F72 | 0.6284 (3) | 0.9108 (10) | 0.7341 (9) | 0.0882 (18) | 0.50 |
F73 | 0.5690 (4) | 1.0556 (19) | 0.8647 (12) | 0.117 (3) | 0.50 |
C11 | 0.38914 (14) | 0.4772 (4) | 0.5833 (4) | 0.0471 (8) | |
C12 | 0.38129 (17) | 0.3264 (5) | 0.6665 (4) | 0.0582 (9) | |
C13 | 0.33749 (19) | 0.1999 (5) | 0.6425 (5) | 0.0682 (11) | |
H13 | 0.3329 | 0.0976 | 0.7007 | 0.082* | |
C14 | 0.30078 (16) | 0.2291 (5) | 0.5302 (5) | 0.0598 (10) | |
C15 | 0.30643 (15) | 0.3831 (5) | 0.4464 (4) | 0.0552 (9) | |
C16 | 0.35123 (15) | 0.5066 (5) | 0.4716 (4) | 0.0505 (8) | |
H16 | 0.3559 | 0.6091 | 0.4138 | 0.061* | |
C17 | 0.26144 (15) | 0.5750 (6) | 0.2734 (5) | 0.0714 (12) | |
H17A | 0.2676 | 0.6724 | 0.3417 | 0.086* | |
H17B | 0.2223 | 0.5887 | 0.2358 | 0.086* | |
C18 | 0.30325 (18) | 0.5958 (6) | 0.1598 (5) | 0.0674 (11) | |
C19 | 0.3355 (2) | 0.6130 (8) | 0.0667 (7) | 0.0939 (15) | |
H19 | 0.3614 | 0.6268 | −0.0080 | 0.113* | |
C2A | 0.49118 (16) | 0.5708 (6) | 0.5654 (5) | 0.0640 (10) | 0.50 |
C3A | 0.53841 (18) | 0.7023 (7) | 0.6051 (6) | 0.0942 (18) | 0.50 |
H3A1 | 0.5645 | 0.6406 | 0.6702 | 0.113* | 0.50 |
H3A2 | 0.5608 | 0.7314 | 0.5212 | 0.113* | 0.50 |
C4A | 0.5200 (4) | 0.8698 (15) | 0.6672 (12) | 0.063 (2) | 0.50 |
H4A | 0.5103 | 0.9467 | 0.5856 | 0.075* | 0.50 |
C5A | 0.46863 (16) | 0.8788 (5) | 0.7498 (6) | 0.0716 (11) | 0.50 |
H5A1 | 0.4534 | 1.0035 | 0.7450 | 0.086* | 0.50 |
H5A2 | 0.4791 | 0.8549 | 0.8471 | 0.086* | 0.50 |
C6A | 0.42111 (15) | 0.7486 (4) | 0.7087 (4) | 0.0494 (8) | 0.50 |
C7A | 0.5720 (2) | 0.9764 (8) | 0.7370 (8) | 0.0853 (14) | 0.50 |
F71A | 0.5530 (3) | 1.1556 (10) | 0.7580 (19) | 0.130 (3) | 0.50 |
F72A | 0.6130 (6) | 0.999 (2) | 0.6412 (18) | 0.176 (5) | 0.50 |
F73A | 0.5865 (5) | 0.9260 (16) | 0.8501 (17) | 0.150 (5) | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0866 (8) | 0.0809 (7) | 0.1298 (11) | −0.0384 (6) | 0.0084 (8) | −0.0115 (9) |
F1 | 0.1063 (18) | 0.0685 (13) | 0.0805 (18) | 0.0031 (12) | −0.0282 (16) | 0.0159 (13) |
O1 | 0.0676 (17) | 0.113 (3) | 0.118 (3) | 0.0031 (17) | 0.0111 (19) | −0.065 (3) |
O2 | 0.0556 (16) | 0.0640 (15) | 0.097 (2) | −0.0040 (12) | 0.0179 (16) | −0.0202 (16) |
O3 | 0.0567 (15) | 0.084 (2) | 0.0692 (18) | −0.0152 (13) | −0.0135 (14) | −0.0045 (17) |
N1 | 0.0473 (15) | 0.0494 (15) | 0.0445 (16) | 0.0001 (12) | −0.0048 (13) | −0.0046 (13) |
C2 | 0.051 (2) | 0.077 (3) | 0.064 (2) | 0.0024 (19) | 0.0037 (19) | −0.020 (2) |
C3 | 0.047 (2) | 0.120 (4) | 0.116 (4) | −0.012 (2) | 0.004 (2) | −0.055 (4) |
C4 | 0.052 (5) | 0.066 (5) | 0.033 (5) | −0.012 (4) | −0.004 (4) | 0.007 (4) |
C5 | 0.060 (2) | 0.060 (2) | 0.095 (3) | −0.0023 (17) | −0.003 (2) | −0.023 (2) |
C6 | 0.049 (2) | 0.0476 (18) | 0.052 (2) | 0.0001 (15) | 0.0006 (16) | 0.0001 (17) |
C7 | 0.068 (3) | 0.076 (3) | 0.111 (5) | −0.022 (3) | 0.009 (4) | −0.011 (4) |
F71 | 0.101 (6) | 0.091 (5) | 0.125 (6) | −0.052 (4) | −0.028 (5) | 0.038 (5) |
F72 | 0.053 (3) | 0.116 (5) | 0.096 (5) | −0.016 (3) | 0.004 (4) | −0.015 (4) |
F73 | 0.102 (6) | 0.126 (7) | 0.123 (7) | −0.044 (6) | 0.014 (5) | −0.054 (7) |
C11 | 0.0494 (18) | 0.0434 (18) | 0.048 (2) | 0.0028 (15) | 0.0006 (17) | −0.0077 (17) |
C12 | 0.065 (2) | 0.053 (2) | 0.057 (2) | 0.0045 (17) | −0.0067 (19) | −0.0021 (19) |
C13 | 0.086 (3) | 0.046 (2) | 0.072 (3) | −0.0014 (19) | 0.014 (3) | 0.004 (2) |
C14 | 0.055 (2) | 0.054 (2) | 0.071 (3) | −0.0095 (17) | 0.0076 (19) | −0.005 (2) |
C15 | 0.050 (2) | 0.062 (2) | 0.054 (2) | −0.0038 (17) | 0.0055 (17) | −0.0130 (18) |
C16 | 0.0482 (18) | 0.0542 (19) | 0.049 (2) | −0.0010 (15) | 0.0022 (16) | 0.0006 (17) |
C17 | 0.049 (2) | 0.083 (3) | 0.082 (3) | 0.0090 (18) | −0.020 (2) | −0.015 (3) |
C18 | 0.058 (2) | 0.077 (3) | 0.067 (3) | −0.003 (2) | −0.015 (2) | −0.002 (2) |
C19 | 0.083 (3) | 0.112 (4) | 0.088 (4) | −0.013 (3) | −0.005 (3) | 0.008 (3) |
C2A | 0.051 (2) | 0.077 (3) | 0.064 (2) | 0.0024 (19) | 0.0037 (19) | −0.020 (2) |
C3A | 0.047 (2) | 0.120 (4) | 0.116 (4) | −0.012 (2) | 0.004 (2) | −0.055 (4) |
C4A | 0.054 (5) | 0.081 (7) | 0.053 (6) | −0.019 (5) | 0.005 (5) | −0.005 (5) |
C5A | 0.060 (2) | 0.060 (2) | 0.095 (3) | −0.0023 (17) | −0.003 (2) | −0.023 (2) |
C6A | 0.049 (2) | 0.0476 (18) | 0.052 (2) | 0.0001 (15) | 0.0006 (16) | 0.0001 (17) |
C7A | 0.068 (3) | 0.076 (3) | 0.111 (5) | −0.022 (3) | 0.009 (4) | −0.011 (4) |
F71A | 0.108 (5) | 0.086 (5) | 0.195 (12) | −0.035 (4) | −0.032 (8) | 0.008 (7) |
F72A | 0.104 (7) | 0.213 (12) | 0.212 (13) | −0.087 (9) | 0.049 (9) | −0.035 (10) |
F73A | 0.142 (9) | 0.130 (7) | 0.179 (12) | −0.026 (6) | −0.113 (9) | 0.017 (8) |
Cl1—C14 | 1.721 (4) | C5—H5B | 0.9700 |
F1—C12 | 1.362 (4) | C7—F71 | 1.259 (10) |
O1—C2 | 1.189 (4) | C7—F73 | 1.343 (11) |
O2—C6 | 1.201 (4) | C7—F72 | 1.376 (9) |
O3—C15 | 1.366 (5) | C11—C12 | 1.361 (5) |
O3—C17 | 1.415 (5) | C11—C16 | 1.387 (5) |
N1—C6 | 1.386 (4) | C12—C13 | 1.378 (6) |
N1—C2 | 1.402 (5) | C13—C14 | 1.374 (6) |
N1—C11 | 1.441 (4) | C13—H13 | 0.9300 |
C2—C3 | 1.490 (6) | C14—C15 | 1.377 (6) |
C3—C4 | 1.441 (10) | C15—C16 | 1.383 (5) |
C3—H3A | 0.9700 | C16—H16 | 0.9300 |
C3—H3B | 0.9700 | C17—C18 | 1.450 (7) |
C4—C7 | 1.508 (10) | C17—H17A | 0.9700 |
C4—C5 | 1.533 (10) | C17—H17B | 0.9700 |
C4—H4 | 0.9800 | C18—C19 | 1.158 (7) |
C5—C6 | 1.492 (5) | C19—H19 | 0.9300 |
C5—H5A | 0.9700 | C4A—H4A | 0.9800 |
C15—O3—C17 | 118.2 (3) | F73—C7—F72 | 102.4 (8) |
C6—N1—C2 | 124.5 (3) | F71—C7—C4 | 117.5 (7) |
C6—N1—C11 | 117.2 (3) | F73—C7—C4 | 110.1 (7) |
C2—N1—C11 | 118.1 (3) | F72—C7—C4 | 107.5 (6) |
O1—C2—N1 | 120.3 (3) | C12—C11—C16 | 119.0 (3) |
O1—C2—C3 | 122.3 (4) | C12—C11—N1 | 119.4 (3) |
N1—C2—C3 | 117.4 (3) | C16—C11—N1 | 121.5 (3) |
C4—C3—C2 | 119.0 (5) | C11—C12—F1 | 118.4 (3) |
C4—C3—H3A | 107.6 | C11—C12—C13 | 122.4 (4) |
C2—C3—H3A | 107.6 | F1—C12—C13 | 119.2 (4) |
C4—C3—H3B | 107.6 | C14—C13—C12 | 118.0 (4) |
C2—C3—H3B | 107.6 | C14—C13—H13 | 121.0 |
H3A—C3—H3B | 107.0 | C12—C13—H13 | 121.0 |
C3—C4—C7 | 113.9 (7) | C13—C14—C15 | 121.1 (3) |
C3—C4—C5 | 112.0 (6) | C13—C14—Cl1 | 118.2 (3) |
C7—C4—C5 | 108.8 (7) | C15—C14—Cl1 | 120.7 (3) |
C3—C4—H4 | 107.3 | O3—C15—C14 | 116.0 (3) |
C7—C4—H4 | 107.3 | O3—C15—C16 | 124.3 (4) |
C5—C4—H4 | 107.3 | C14—C15—C16 | 119.7 (4) |
C6—C5—C4 | 117.1 (4) | C15—C16—C11 | 119.7 (3) |
C6—C5—H5A | 108.0 | C15—C16—H16 | 120.1 |
C4—C5—H5A | 108.0 | C11—C16—H16 | 120.1 |
C6—C5—H5B | 108.0 | O3—C17—C18 | 112.8 (3) |
C4—C5—H5B | 108.0 | O3—C17—H17A | 109.0 |
H5A—C5—H5B | 107.3 | C18—C17—H17A | 109.0 |
O2—C6—N1 | 120.2 (3) | O3—C17—H17B | 109.0 |
O2—C6—C5 | 121.8 (3) | C18—C17—H17B | 109.0 |
N1—C6—C5 | 118.0 (3) | H17A—C17—H17B | 107.8 |
F71—C7—F73 | 110.5 (8) | C19—C18—C17 | 178.3 (5) |
F71—C7—F72 | 107.7 (7) | C18—C19—H19 | 180.0 |
C6—N1—C2—O1 | 175.9 (4) | C2—N1—C11—C12 | 85.8 (4) |
C11—N1—C2—O1 | 2.2 (6) | C6—N1—C11—C16 | 89.0 (4) |
C6—N1—C2—C3 | −4.3 (6) | C2—N1—C11—C16 | −96.9 (4) |
C11—N1—C2—C3 | −177.9 (4) | C16—C11—C12—F1 | −177.5 (3) |
O1—C2—C3—C4 | −156.6 (6) | N1—C11—C12—F1 | −0.2 (5) |
N1—C2—C3—C4 | 23.5 (8) | C16—C11—C12—C13 | 1.0 (5) |
C2—C3—C4—C7 | −162.8 (6) | N1—C11—C12—C13 | 178.4 (3) |
C2—C3—C4—C5 | −38.8 (9) | C11—C12—C13—C14 | 0.0 (6) |
C3—C4—C5—C6 | 37.1 (8) | F1—C12—C13—C14 | 178.5 (3) |
C7—C4—C5—C6 | 163.9 (5) | C12—C13—C14—C15 | −1.9 (6) |
C2—N1—C6—O2 | −176.6 (4) | C12—C13—C14—Cl1 | 180.0 (3) |
C11—N1—C6—O2 | −2.9 (5) | C17—O3—C15—C14 | 166.3 (3) |
C2—N1—C6—C5 | 3.5 (5) | C17—O3—C15—C16 | −13.5 (5) |
C11—N1—C6—C5 | 177.2 (3) | C13—C14—C15—O3 | −177.0 (3) |
C4—C5—C6—O2 | 159.8 (5) | Cl1—C14—C15—O3 | 1.1 (5) |
C4—C5—C6—N1 | −20.4 (7) | C13—C14—C15—C16 | 2.8 (6) |
C3—C4—C7—F71 | 61.1 (11) | Cl1—C14—C15—C16 | −179.1 (3) |
C5—C4—C7—F71 | −64.6 (11) | O3—C15—C16—C11 | 178.0 (3) |
C3—C4—C7—F73 | −171.3 (10) | C14—C15—C16—C11 | −1.8 (5) |
C5—C4—C7—F73 | 63.1 (11) | C12—C11—C16—C15 | −0.1 (5) |
C3—C4—C7—F72 | −60.5 (9) | N1—C11—C16—C15 | −177.4 (3) |
C5—C4—C7—F72 | 173.9 (7) | C15—O3—C17—C18 | 84.3 (4) |
C6—N1—C11—C12 | −88.3 (4) | O3—C17—C18—C19 | 120 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···O2i | 0.93 | 2.49 | 3.287 (7) | 143 |
C17—H17B···O2ii | 0.97 | 2.52 | 3.359 (4) | 145 |
C4—H4···O1iii | 0.98 | 2.33 | 3.175 (10) | 144 |
Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, y, z−1/2; (iii) −x+1, −y+1, z+1/2. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C15H9ClF3NO5 | C14H10ClF3N2O4 | C15H10ClF4NO3 |
Mr | 375.68 | 362.69 | 363.69 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n | Orthorhombic, Pca21 |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 19.280 (5), 9.715 (3), 18.050 (5) | 14.326 (13), 7.802 (7), 14.337 (13) | 22.887 (9), 7.250 (3), 9.497 (4) |
α, β, γ (°) | 90, 109.509 (5), 90 | 90, 110.599 (15), 90 | 90, 90, 90 |
V (Å3) | 3186.8 (15) | 1500 (2) | 1575.7 (11) |
Z | 8 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.30 | 0.31 | 0.30 |
Crystal size (mm) | 0.44 × 0.36 × 0.26 | 0.26 × 0.22 × 0.16 | 0.40 × 0.38 × 0.28 |
Data collection | |||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.853, 0.925 | 0.806, 1.000 | 0.853, 0.919 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16078, 5616, 2057 | 7542, 2646, 2007 | 7730, 2725, 2022 |
Rint | 0.087 | 0.022 | 0.053 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 | 0.595 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.163, 0.87 | 0.039, 0.115, 1.10 | 0.047, 0.124, 1.05 |
No. of reflections | 5616 | 2646 | 2725 |
No. of parameters | 475 | 220 | 253 |
No. of restraints | 18 | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.21 | 0.26, −0.34 | 0.19, −0.18 |
Absolute structure | ? | ? | Flack (1983), with how many Friedel pairs |
Absolute structure parameter | ? | ? | −0.05 (12) |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997) in WinGX (Farrugia, 1999), PLATON (Spek, 2003), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···O2A | 0.93 | 2.47 | 3.359 (5) | 159 |
C16A—H16A···O2 | 0.93 | 2.51 | 3.373 (5) | 155 |
C6—H6···O5i | 0.93 | 2.70 | 3.323 (6) | 125 |
C6A—H6A···O5Aii | 0.93 | 2.56 | 3.389 (6) | 149 |
C5—H5···O2iii | 0.93 | 2.60 | 3.511 (6) | 167 |
C5A—H5A···O2Aiv | 0.93 | 2.74 | 3.578 (6) | 151 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z+1/2; (iv) x, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2i | 0.93 | 2.51 | 3.427 (4) | 169 |
C16—H16···O3ii | 0.93 | 2.47 | 3.260 (4) | 143 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1/2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···O2i | 0.93 | 2.49 | 3.287 (7) | 143 |
C17—H17B···O2ii | 0.97 | 2.52 | 3.359 (4) | 145 |
C4—H4···O1iii | 0.98 | 2.33 | 3.175 (10) | 144 |
Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, y, z−1/2; (iii) −x+1, −y+1, z+1/2. |
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The protoporphyrinogen-IX oxidase inhibitors are structurally very diverse, ranging from diphenylethers to 1-heterocyclyl-2,4,5-tetrasubstituted benzenes (Tomlin, 2003). They inhibit the activity of protoporphyrinogen-IX oxidase (PPO) by binding competitively to the same active site as the substrate protoporphyrinogen-IX (Matringe & Scalla, 1988; Duke et al., 1989).
In order to discover new herbicides and to study the interaction between the enzyme and its inhibitors, a number of groups have carried out studies of the structure–activity relationship (SAR) on herbicidal diphenylethers and 1-heterocyclyl-2,4,5-tetrasubstituted benzenes (Boger & Wakabayashi, 1999). The crystal structures of some PPO inhibitors have played an important role in SAR and QSAR (quantitative structure–activity relationship) studies, especially in three-dimensional-QSAR (three-dimensional quantitative structure–activity relationship) studies (Dayan & Allen, 2000; Kohno et al., 1993; Nandihalli et al., 1992).
At present, only six crystal structures of PPO inhibitors are available in the literature, namely 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoic acid (Acifluorfen; Kennard et al., 1987), 2-(4-chlorophenyl)-4,5,6,7-tetrahydro-isoindole-1,3-dione (Chlorophthalim), 3-(4-chloro-5-cyclopentyloxy-2-fluoro-phenyl)-5-isopropylidene-oxazolidine- 2,4-dione and 2-chloro-1-(3-ethoxy-4-nitro-phenoxy)-4-trifluoromethylbenzene (Kohno et al., 1993), and 2-(4-chloro-2-fluoro-5-prop-2-ynyloxy-phenyl)-4,5,6,7-tetrahydro-isoindole- 1,3-dione and 2-(4-chloro-2-fluoro-5-prop-2-ynyloxy-phenyl)-cis-3a,4,7,7a- tetrahydroisoindole-1,3-dione (Li et al., 2005). More crystal structures are needed, in a programme of three-dimensional-QSAR studies on PPO inhibitors carried out by our group, and we report here the crystal structures of 5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitro-benzoic acid methyl ester, (I), 2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin- 1-yl)-benzoic acid methyl ester, (II), and 2-(4-chloro-2-fluoro-5-prop-2-ynyloxy-phenyl)-4-trifluoromethyl-piperidine- 2,6-dione, (III), all of which contain a trifluoromethyl group, which is thought to be of biological importance, and all of which show high PPO-inhibiting activity and herbicidal activity (Li, 2005).
The asymmetric unit of (I) contains two independent molecules, as shown in Fig. 1. These are related by a pseudo-twofold axis at (1/4, y, 1/2). The conformations of the two molecules are similar, with the dihedral angles between the aromatic rings being 80.78 (11)° in one molecule and 89.75 (11)° in the other. Relevant torsion angles are C2—C1—O1—C15 103.8 (5)° and C2A—C1A—O1A—C15A 82.1 (6)°. The distances between the farthest two atoms are thought to be significant in terms of biological activity and are O5···F1 11.763 (7) Å and O5A···F71A 11.953 (6) Å. The planes of the carboxyl groups are rotated out of the associated aromatic ring by 83.44 (15)° and 88.78 (15)° for carboxyl groups C11/C17/O1/O2 and C11A/C17A/O1A/O2A, respectively; the corresponding out-of-plane rotation angles for the 2-nitro groups are 8.5 (4) and 6.5 (3)°. Compound (I) is the methyl ester of Acifluorfen (Kennard et al., 1987); the torsion angle corresponding to C2—C1—O1—C15 is 89.2° in Acifluorfen, and the corresponding longest O···F distance between a nitro O atom and the farthest F atom in Acifluorfen is 11.83 Å.
The packing of (I) is controlled by C—H···O hydrogen bonds. Checks using the program PLATON (Spek, 2003) show that there are no C—H···π or π–π interactions. The two molecules of the asymmetric unit are weakly linked by C—H···O interactions along C16—H16···O2A and C16A—H16A···O2 (Table 1), generating R22(10) rings (Bernstein et al., 1995). Molecules related by inversion centres at (0, 1/2, 1/2), (1/2, 1/2, 1/2), (1, 1/2, 1/2) etc. are then linked by further C—H···O interactions, involving C6—H6 and C6A—H6A and adjacent nitro O atoms (Table 1), generating R22(20) rings (Fig. 2), resulting in chains of rings along [100]. Parallel chains are propagated by the c-glide operation, and these chains are linked by C—H···O interactions involving C5—H5 and C5A—H5A with adjacent carboxyl O atoms (Table 1), to generate corrugated sheets in the (010) plane.
The molecular structure of (II) is shown in Fig. 3. The dihydropyrimidine ring adopts a planar conformation and the mean deviation from the plane is 0.0081 Å. The dihedral angle between the dihydropyrimidine and benzoate ring planes is 89.13 (9)°. The carboxyl group is rotated 38.84 (12)° about the C11—C17 bond out of the benzoate ring plane. The distance between the farthest two atoms, Cl1···F72, is 10.734 (10) Å.
Molecules of (II) are linked to form centrosymmetric R22(8) dimers via C—H···O interactions involving C5—H5 and an adjacent pyrimidine O atom (Table 2). Further C—H···O interactions involving C16—H16 and an adjacent (screw-axis related) carboxyl atom O3 (Table 2) generate sheets of molecules in the (101) plane (Fig. 4).
In compound (III) (Fig. 5), the piperidine-2,6-dione ring adopts an envelope conformation, with atom C4 disordered equally over two orientations (labelled C4 and C4A), with these atoms being 0.439 (1) and −0.333 (13) Å, respectively, from the plane of N1/C2/C3/C5/C6. The dihedral angle between the plane of these five atoms and the phenyl ring (C11–C16) is 87.52 (13)°. This conformation has atom F1 essentially equidistant from carbonyl atoms O1 and O2 [3.457 (5) and 3.513 (3) Å, respectively]. The orientation of the propargyl group relative to the aromatic ring is defined by the torsion angle C15—O3—C17—C18 84.3 (4)°. The distance between the farthest two atoms, Cl1···F71, is 10.889 (9) Å.
As was found in 2-(4-chloro-2-fluoro-5-prop-2-ynyloxy-phenyl)-cis- 3a,4,7,7a-tetrahydro-isoindole-1,3-dione (Li et al., 2005) there is also a well defined acetylenic C—H···O bond in (III) [C19—H19···O2i; symmetry code: (i) x, y, z − 1], which generates chains along [100] (Fig. 6). Adjacent chains are linked by C—H···O hydrogen bonds, involving the propargyl moiety C17—H17 with an adjacent piperidine carbonyl O atom, and also the piperidine C4—H4 with the other piperidine carbonyl O atom (Table 3). In this way, a sheet structure with R32(15) and R33(21) rings is propagated in the (010) plane (Fig. 6).