Three trifluoro­methyl-substituted protoporphyrinogen IX oxidase inhibitors

The structures of methyl 5-[2-chloro-4-(trifluoro­methyl)phenoxy]-2-nitro­benzoate, C₁₅H₉ClF₃N₃O₅, (I), methyl 2-chloro-5-[3-methyl-2,6-dioxo-4-(trifluoro­methyl)-1,2,3,6-tetrahydro­pyrimidin-1-yl]benzoate, C₁₄H₁₀ClF₃N₂O₄, (II), and 2-[4-chloro-2-fluoro-5-(prop-2-ynyloxy)phenyl]-4-(trifluoro­methyl)piperidine-2,6-dione, C₁₅H₁₀ClF₄NO₃, (III), are similar in their dihedral angles and in the distances between the farthest two atoms. There are two independent molecules in the structure of (I). The dihedral angles between the two aromatic rings in each molecule in (I), between the benzene and tetrahydro­pyrimidine rings in (II), and between the benzene ring and the five-atom planar portion of the piperidine-2,6-dione ring in (III) are 80.78 (11)/89.75 (11), 89.13 (9) and 87.52 (13)°, respectively. The distances between the farthest two atoms, viz. O...F in the two molecules of (I), and Cl...F in (II) and (III), are 11.763 (7)/11.953 (6), 10.734 (10) and 10.889 (9) Å, respectively. In all three crystal structures, the molecules are linked to generate sheets of molecules via C—H...O interactions.

S1. Comment

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).

S2. Experimental

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).

S3. Refinement

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 U_iso(H) = 1.2U_eq(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 U_iso value [final values 0.111 (7) and 0.122 (8) Ų]. 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.

Computing details

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.

Figures

	Fig. 1. A view of the two independent molecules of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. The F atoms of the CF3 groups are unequally disordered over two orientations; for clarity, only the major orientation is shown in each case.
	Fig. 2. A view of a chain of molecules of (I), linked by weak C—H···O interactions along [100]. Atoms labelled with an asterisk (*) or a hash (#) are at the symmetry positions (−x, 1 − y, 1 − z) and (1 − x, 1 − y, 1 − z), respectively.
	Fig. 3. A view of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. A view showing part of a sheet of molecules of (II), linked by weak C—H···O interactions in the (101) plane. Atoms labelled with an asterisk (*), hash (#) or dollar ($) are at the symmetry positions (−x, −y, 1 − z), (1/2 − x, y − 1/2, 1/2 − z) and (1/2 − x, 1/2 + y, 1/2 − z), respectively.
	Fig. 5. A view of (III), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. The C4—C7F3 moiety is disordered equally over two sites; for clarity, only one of these is shown.
	Fig. 6. A view showing part of a sheet of molecules of (III), linked by C—H···O interactions in the (010) plane. Atoms labelled with an asterisk (*), hash (#), dollar ($), ampersand (&) or `at' symbol (@) are at the symmetry positions (x, y, z − 1), (1/2 − x, y, z − 1/2), (1 − x, 1 − y, 1/2 + z), (1 − x, 1 − y, z − 1/2) and (1/2 − x, y, 1/2 + z), respectively.

(I) methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate

Crystal data

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) Å^3	Prism, colourless
Z = 8	0.44 × 0.36 × 0.26 mm
F(000) = 1520

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.163	H-atom parameters constrained
S = 0.87	w = 1/[σ^2(Fo^2) + (0.0715P)^2] where P = (Fo^2 + 2Fc^2)/3
5616 reflections	(Δ/σ)max < 0.001
475 parameters	Δρmax = 0.19 e Å^−3
18 restraints	Δρmin = −0.21 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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···O5^i	0.93	2.70	3.323 (6)	125
C6A—H6A···O5A^ii	0.93	2.56	3.389 (6)	149
C5—H5···O2^iii	0.93	2.60	3.511 (6)	167
C5A—H5A···O2A^iv	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.

(II) methyl 2-chloro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin- 1-yl]benzoate

Crystal data

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) Å^3	Prism, colourless
Z = 4	0.26 × 0.22 × 0.16 mm
F(000) = 736

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.0399P)^2 + 1.2049P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0072 (12)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2^i	0.93	2.51	3.427 (4)	169
C16—H16···O3^ii	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.

(III) 2-[4-chloro-2-fluoro-5-(prop-2-ynyloxy)phenyl]-4-(trifluoromethyl)piperidine- 2,6-dione

Crystal data

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) Å^3	T = 293 K
Z = 4	Block, colourless
F(000) = 736	0.40 × 0.38 × 0.28 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.124	w = 1/[σ^2(Fo^2) + (0.055P)^2 + 0.3451P] where P = (Fo^2 + 2Fc^2)/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)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···O2^i	0.93	2.49	3.287 (7)	143
C17—H17B···O2^ii	0.97	2.52	3.359 (4)	145
C4—H4···O1^iii	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.