3-Methyl 5-[(S)-2-methyl­butyl] 4-[2-(di­fluoro­methoxy)­phenyl]-2,6-di­methyl-1,4-di­hydropyridine-3,5-di­carboxyl­ate

The crystal structure of the title compound, C₂₂H₂₇F₂NO₅, contains two diastereomers, related by a pseudo-glide plane. Owing to the addition of the di­fluoro­methoxy­phenyl moiety, the di­hydro­pyridine ring is somewhat deformed from planarity. The packing involves a two-dimensional network created by C—H...O and N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.046
• wR factor = 0.095
• Data-to-parameter ratio = 8.4

checkCIF results

No syntax errors found


 Alert Level B:



PLAT_112  Alert B ADDSYM Detects Additional (Pseudo) Symm. Elem.          c

Author response: The additional symmetry is pseudo symmetry. The molecules concerned are diastereomers and can therefore not be related by a symmetry element. This pseudo symmetrie is discussed in the Comment, and illustrated in Figure 2.

PLAT_113  Alert B ADDSYM suggests Pseudo/New Spacegroup ........       Pc

Author response: See previous VRF.

 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.50
         From the CIF: _reflns_number_total               4617
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         4870
         Completeness (_total/calc)             94.80%
          Alert C: < 95% complete

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.50
         From the CIF: _reflns_number_total               4617
         Count of symmetry unique reflns         4870
         Completeness (_total/calc)             94.80%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured         0
         Fraction of Friedel pairs measured     0.000
         Are heavy atom types Z>Si present           no
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 2 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

In order to investigate the stereochemical course of the Candida rugosa lipase mediated kinetic resolution of 3-acyloxymethyl-4-aryl-1,4-dihydropyridine-3,5-dicarboxylates, a derivative containing a second chiral centre of known configuration was prepared. This would allow the determination of the relative configuration of the chiral centre at C⁴ (labeled C3 and C25 in the presented structure). The enzymatically prepared carboxylic acid (1) was esterified to (S)-2-methyl-1-butanol, giving the title compound, (2), and its crystal structure was determined. However, since the starting material was not entirely stereochemically pure, there was a risk that the two diastereomers would preferentially crystallize together. This indeed proved to be the case, as is shown in Fig. 1. Later, compound (2) was prepared in stereochemically pure form. Unfortunately, we could not obtain crystals suitable for a structure determination from this material.

The asymmetric unit contains two molecules, which are diastereomers with configuration (R,S) and (S,S) at (C3,C9) and (C25,C31), respectively. These configurations have been assigned with reference to the known (S)-configuration of atoms C9 and C31. The diastereomers have adopted conformations which are related by an inversion operation, with the exception of the 2-methylbutyl moiety. This is illustrated in Fig. 2, which displays a fit of molecule (1) and the inverted molecule (2). In the crystal, the molecules are related by a pseudo-c-glide plane, with exception of the 2-methylbutyl moiety. The unit cell displays a pseudo-monoclinic geometry, with the pseudo-glide plane parallel to the a and c axes. The best-fit between the molecules is obtained by a rotation of -176° over the rotary-inversion axis [-0.018,-1.000,0.042], combined with a shift of 7.226 Å (i.e. 0.48c) in the direction [0.002,-0.096,-1.000]. The unit weight r.m.s. fit is 0.31 Å, with the largest deviations for atoms C9, C10 and C12 of molecule (1).

Addition of the difluoromethoxyphenyl moiety to the dihydropyridine ring results in a slight deformation from planarity towards a sofa conformation in both diastereomers. The relevant asymmetry parameters (Duax & Norton, 1975) are ΔC_s[N1] = 2.2 (4)° for molecule (1) and ΔC_s[N2] = 1.8 (4)° for molecule (2); all other asymmetry parameters are at least 10°. The total puckering amplitude (Cremer & Pople, 1975) of the dihydropyridine ring is 0.177 (3) Å in molecule (1) and 0.173 (3) Å in molecule (2). The phenyl rings show total puckering amplitudes of 0.029 (3) and 0.019 (3) for molecules (1) and (2), respectively. For these rings, all asymmetry parameters are less then 5°. Hydrogenation of the pyridine N atom apparently has no influence on its hybridization (sp²) or the planarity of this part of the six-membered ring. The bond distances along the dihydropyridine rings indicate delocalization of the formal double bonds of the C═C—N—C═C fragment (see Table 1).

Crystal packing involves the formation of chains, parallel to the c axis, consisting of molecules connected by N—H···O hydrogen bonds (see Fig. 3 and Table 2). Each chain consists of an alternation of both diastereomers. The unitary graph set is DD, the binary graph set is C₂²[12] (Bernstein et al., 1995). Two neighbouring chains are connected by C—H···O hydrogen bonds linking the F₂OCH moiety to the O═C acceptor of the carboxylate moiety. These hydrogen bonds form links between equal stereoisomers. Both types of hydrogen bond together create a two-dimensional network of hydrogen-bonded molecules, with main axes a and c.

S2. Experimental

The title compound was prepared from 284 mg (0.808 mmol) of 4-[2-(difluoromethoxy)phenyl]-5-(methoxycarbonyl)-2,6-dimethyl-1,4-dihydro- 3-pyridinecarboxylic acid, (1), by reaction of its acid chloride with 0.262 ml (2.41 mmol) of (S)-2-methyl-1-butanol, using the method of Sobolev et al. (2002). The crude product was flash chromatographed on silica gel with ethyl acetate/petroleum ether (b.p. 313–333 K, 1:3), purified again on silica gel with petroleum ether (b.p. 313–333 K)/chloroform/isopropyl alcohol (20:5:2) and crystallized from ethanol to give 276 mg (81%) as pale-yellow crystals: m.p. 406–407 K; ¹H NMR (CDCl₃, 200 MHz): δ 0.83 (t, 3H, J = 7.3 Hz, CH₃), 0.85 (d, 3H, J = 7.4 Hz, CH₃), 0.95–1.16 (m, 1H, CH₂), 1.19–1.40 (m, 1H, CH₂), 1.60–1.76 (m, 1H, CH), 2.28 (s, 3H, CH₃), 2.30 (s, 3H, CH₃), 3.59 (s, 3H, CH₃), 3.77 (dd, 1H, J = 10.8, 6.9 Hz, CH₂), 3.89 (dd, 1H, J = 10.8, 6.4 Hz, CH₂), 5.25 (s, 1H, CH), 5.60 (br s, 1H, NH), 6.46 (dd, 1H, J_H—F = 75.6, 75.8 Hz, OCHF₂), 6.95- 7.13 (m, 3H, Ar—H), 7.35 (dd, 1H, J = 2.2, 7.3 Hz, Ar—H). MS m/z: 423 (M⁺, 9), 352 (10), 336 (5), 308 (9), 284 (6), 281 (15), 280 (100), 211 (4), 210 (36); HRMS calculated for C₂₂H₂₇F₂O₅: 423.1857, found 423.1853. Crystals suitable for X-ray analysis were obtained by recrystallization from hexane containing a small amount of methanol.

S3. Refinement

Due to the absence of significant anomalous dispersion, the absolute structure could not be determined reliably. The configuration of C9 and thereby also that of C31 was set equal to S, consistent with the starting materials used. The measured reflections reduced to 9040 unique reflections with an R_int of 0.0742. After merging of the Friedel pairs, the 4617 reflections reported above remained. H atoms of the N—H moieties were located on a difference Fourier map and their coordinates and isotropic displacement parameters were refined. All other H atoms were included at calculated positions, riding on their carrier atoms. Isotropic displacement parameters of H atoms bonded to C atoms were coupled to the equivalent isotropic displacement parameter of their carrier atoms by a fixed factor of 1.5 (methyl H atoms) or 1.2 (other H atoms).

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: PLATON.

Figures

	Fig. 1. View of the title compound with the atom-numbering scheme. H atoms have been omitted for clarity. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. (a) molecule (1), the (R,S)-stereoisomer (b) molecule (2), the (S,S)-stereoisomer.
	Fig. 2. Fit of molecule (1) [configuration (R,S), green] on the inverted molecule (2) [configuration (R,R), red; N·B. this configuration is not present in the crystal]. H atoms have been omitted for clarity.
	Fig. 3. N—H···O bonded chains (parallel to c) of alternating diasteromers, linked into a two-dimensional network by soft C—H···O interactions (parallel to a).

3-Methyl 5-[(S)-2-methylbutyl] 4-[2-(difluoromethoxy)phenyl]-2,6-dimethyl-1,4-dihydropyridine- 3,5-dicarboxylate

Crystal data

C22H27F2NO5	Z = 2
Mr = 423.45	F(000) = 448
Triclinic, P1	Quoted _cell_measurement_* data items refer to the initial cell determination. The cell parameters as reported in _cell_* are based on the complete data set.
Hall symbol: P 1	Dx = 1.330 Mg m^−3
a = 8.2340 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.7827 (18) Å	Cell parameters from 367 reflections
c = 14.9145 (18) Å	θ = 1.6–25.0°
α = 89.299 (11)°	µ = 0.11 mm^−1
β = 78.697 (11)°	T = 150 K
γ = 89.906 (7)°	Needle, colourless
V = 1057.6 (3) Å^3	0.3 × 0.1 × 0.1 mm

Data collection

Nonius KappaCCD area-detector diffractometer	3257 reflections with I > 2σ(I)
Radiation source: Rotating Anode	Rint = 0.084
Graphite monochromator	θmax = 27.5°, θmin = 1.4°
Detector resolution: 18.4 pixels mm^-1	h = −10→10
ϕ scans, and ω scans with κ offset	k = −11→11
21160 measured reflections	l = −19→19
4617 independent reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0468P)^2] where P = (Fo^2 + 2Fc^2)/3
4617 reflections	(Δ/σ)max = 0.002
549 parameters	Δρmax = 0.17 e Å^−3
3 restraints	Δρmin = −0.23 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F^{2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F}2, conventional R-factors R are based on F, with F set to zero for negative F^{2. The observed criterion of F}2 > σ(F^{2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F}2 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
F1	0.7760 (3)	−0.0537 (2)	0.88624 (13)	0.0496 (8)
F2	0.7747 (3)	−0.2814 (3)	0.84126 (17)	0.0693 (10)
O1	0.9384 (3)	0.2567 (3)	0.54029 (14)	0.0321 (8)
O2	0.7558 (3)	0.3528 (3)	0.65755 (14)	0.0316 (7)
O3	0.9633 (3)	−0.1194 (2)	0.76922 (14)	0.0306 (7)
O4	1.5299 (3)	0.0194 (4)	0.71809 (18)	0.0554 (10)
O5	1.4461 (3)	0.0231 (3)	0.58531 (14)	0.0341 (8)
N1	1.0523 (4)	0.1878 (3)	0.83573 (19)	0.0315 (10)
C1	0.9455 (4)	0.2382 (4)	0.7810 (2)	0.0298 (11)
C2	0.9850 (4)	0.2140 (4)	0.6898 (2)	0.0259 (10)
C3	1.1333 (4)	0.1149 (4)	0.6482 (2)	0.0259 (10)
C4	1.2536 (4)	0.0949 (4)	0.7129 (2)	0.0284 (10)
C5	1.2060 (4)	0.1266 (4)	0.8033 (2)	0.0306 (11)
C6	0.7972 (5)	0.3174 (4)	0.8334 (2)	0.0398 (11)
C7	0.8940 (4)	0.2748 (3)	0.6225 (2)	0.0257 (11)
C8	0.6499 (4)	0.4010 (4)	0.5948 (2)	0.0326 (11)
C9	0.5407 (4)	0.5300 (4)	0.6363 (2)	0.0297 (11)
C10	0.4362 (6)	0.4884 (5)	0.7275 (3)	0.0655 (17)
C11	0.3398 (7)	0.6188 (7)	0.7769 (3)	0.093 (3)
C12	0.4350 (5)	0.5820 (5)	0.5690 (3)	0.0476 (14)
C13	1.0798 (4)	−0.0387 (3)	0.6159 (2)	0.0254 (10)
C14	0.9981 (4)	−0.1507 (4)	0.6749 (2)	0.0266 (10)
C15	0.9598 (4)	−0.2905 (4)	0.6442 (2)	0.0355 (12)
C16	0.9941 (4)	−0.3197 (4)	0.5517 (2)	0.0374 (12)
C17	1.0698 (4)	−0.2104 (4)	0.4910 (2)	0.0368 (11)
C18	1.1124 (4)	−0.0729 (4)	0.5233 (2)	0.0308 (11)
C19	0.8023 (5)	−0.1366 (4)	0.8103 (2)	0.0369 (11)
C20	1.4205 (4)	0.0418 (4)	0.6763 (2)	0.0327 (11)
C21	1.6072 (5)	−0.0337 (4)	0.5429 (3)	0.0415 (12)
C22	1.3056 (5)	0.1025 (5)	0.8765 (2)	0.0414 (13)
F3	0.7921 (3)	0.7777 (2)	0.34946 (14)	0.0483 (8)
F4	0.7794 (3)	0.5392 (2)	0.38152 (13)	0.0500 (8)
O6	0.9447 (3)	0.2447 (3)	0.04224 (14)	0.0326 (8)
O7	0.7614 (3)	0.1551 (3)	0.16247 (14)	0.0311 (7)
O8	0.9706 (3)	0.6164 (2)	0.26849 (13)	0.0281 (7)
O9	1.5375 (3)	0.4940 (3)	0.21486 (18)	0.0501 (10)
O10	1.4531 (3)	0.4807 (3)	0.08184 (15)	0.0376 (8)
N2	1.0653 (3)	0.3085 (3)	0.33527 (18)	0.0273 (9)
C23	0.9573 (4)	0.2605 (4)	0.2821 (2)	0.0278 (11)
C24	0.9945 (4)	0.2889 (4)	0.1904 (2)	0.0262 (10)
C25	1.1413 (4)	0.3884 (3)	0.1479 (2)	0.0249 (10)
C26	1.2628 (4)	0.4056 (3)	0.2118 (2)	0.0270 (10)
C27	1.2181 (4)	0.3708 (3)	0.3021 (2)	0.0268 (10)
C28	0.8102 (5)	0.1784 (4)	0.3358 (2)	0.0379 (11)
C29	0.9010 (4)	0.2294 (3)	0.1250 (2)	0.0249 (10)
C30	0.6540 (4)	0.1078 (4)	0.1015 (2)	0.0328 (11)
C31	0.4940 (4)	0.0512 (4)	0.1600 (2)	0.0340 (11)
C32	0.5194 (4)	−0.0847 (4)	0.2202 (2)	0.0367 (12)
C33	0.3659 (5)	−0.1369 (5)	0.2858 (3)	0.0580 (17)
C34	0.3743 (5)	0.0154 (5)	0.0976 (3)	0.0543 (17)
C35	1.0862 (4)	0.5422 (3)	0.1151 (2)	0.0245 (10)
C36	1.0053 (4)	0.6523 (4)	0.1743 (2)	0.0256 (10)
C37	0.9637 (4)	0.7929 (4)	0.1432 (2)	0.0324 (11)
C38	0.9987 (4)	0.8259 (4)	0.0514 (2)	0.0340 (11)
C39	1.0740 (4)	0.7194 (4)	−0.0093 (2)	0.0369 (11)
C40	1.1180 (4)	0.5799 (4)	0.0229 (2)	0.0339 (11)
C41	0.8112 (4)	0.6375 (4)	0.3100 (2)	0.0330 (11)
C42	1.4283 (4)	0.4641 (4)	0.1737 (2)	0.0314 (11)
C43	1.6091 (5)	0.5467 (4)	0.0375 (3)	0.0454 (12)
C44	1.3208 (5)	0.3918 (4)	0.3740 (2)	0.0391 (11)
H1	1.027 (6)	0.197 (5)	0.901 (3)	0.072 (14)*
H3	1.19410	0.17040	0.59280	0.0310*
H6A	0.80260	0.42590	0.81690	0.0600*
H6B	0.79470	0.30550	0.89910	0.0600*
H6C	0.69670	0.27290	0.81860	0.0600*
H8A	0.58060	0.31450	0.58270	0.0390*
H8B	0.71900	0.43470	0.53600	0.0390*
H9	0.61400	0.61670	0.64550	0.0360*
H10A	0.50910	0.44530	0.76690	0.0790*
H10B	0.35740	0.40780	0.71850	0.0790*
H11A	0.41400	0.70550	0.77810	0.1400*
H11B	0.29160	0.58700	0.83970	0.1400*
H11C	0.25110	0.64860	0.74510	0.1400*
H12A	0.50580	0.60030	0.50890	0.0720*
H12B	0.37740	0.67630	0.59060	0.0720*
H12C	0.35350	0.50290	0.56400	0.0720*
H15	0.90990	−0.36670	0.68640	0.0430*
H16	0.96550	−0.41520	0.53000	0.0450*
H17	1.09240	−0.22960	0.42720	0.0440*
H18	1.16610	0.00120	0.48070	0.0370*
H19	0.72610	−0.10640	0.76860	0.0440*
H21A	1.69250	0.03980	0.55100	0.0620*
H21B	1.61100	−0.04840	0.47750	0.0620*
H21C	1.62760	−0.13120	0.57140	0.0620*
H22A	1.34990	−0.00130	0.87300	0.0620*
H22B	1.23450	0.11760	0.93660	0.0620*
H22C	1.39730	0.17570	0.86770	0.0620*
H2	1.038 (5)	0.301 (4)	0.395 (3)	0.045 (11)*
H25	1.20130	0.33440	0.09260	0.0300*
H28A	0.70880	0.22020	0.32000	0.0570*
H28B	0.80700	0.19130	0.40130	0.0570*
H28C	0.81840	0.06980	0.32120	0.0570*
H30A	0.70730	0.02570	0.06120	0.0390*
H30B	0.63190	0.19470	0.06270	0.0390*
H31	0.44560	0.13600	0.20090	0.0400*
H32A	0.56270	−0.17080	0.18030	0.0440*
H32B	0.60480	−0.05780	0.25570	0.0440*
H33A	0.31680	−0.05070	0.32260	0.0870*
H33B	0.39530	−0.21690	0.32620	0.0870*
H33C	0.28590	−0.17710	0.25140	0.0870*
H34A	0.36590	0.10360	0.05780	0.0810*
H34B	0.26490	−0.00780	0.13460	0.0810*
H34C	0.41480	−0.07270	0.06000	0.0810*
H37	0.91110	0.86660	0.18530	0.0390*
H38	0.97070	0.92280	0.02970	0.0410*
H39	1.09580	0.74110	−0.07310	0.0440*
H40	1.17180	0.50760	−0.01980	0.0410*
H41	0.73370	0.62250	0.26690	0.0400*
H43A	1.62010	0.64850	0.06190	0.0680*
H43B	1.61290	0.55430	−0.02850	0.0680*
H43C	1.70010	0.48210	0.04910	0.0680*
H44A	1.42010	0.32810	0.35990	0.0590*
H44B	1.25570	0.36210	0.43390	0.0590*
H44C	1.35330	0.49890	0.37510	0.0590*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0529 (15)	0.0587 (14)	0.0312 (11)	−0.0045 (11)	0.0067 (10)	−0.0047 (10)
F2	0.0818 (19)	0.0487 (15)	0.0623 (16)	−0.0225 (13)	0.0230 (13)	0.0038 (12)
O1	0.0407 (15)	0.0380 (14)	0.0176 (12)	0.0058 (11)	−0.0055 (10)	−0.0010 (9)
O2	0.0343 (14)	0.0384 (13)	0.0218 (11)	0.0111 (11)	−0.0051 (10)	−0.0019 (9)
O3	0.0287 (14)	0.0397 (13)	0.0222 (11)	−0.0063 (10)	−0.0025 (10)	0.0048 (10)
O4	0.0384 (17)	0.086 (2)	0.0445 (16)	0.0146 (15)	−0.0150 (13)	0.0012 (14)
O5	0.0280 (14)	0.0421 (14)	0.0296 (13)	0.0021 (11)	0.0005 (10)	−0.0015 (10)
N1	0.0382 (19)	0.0370 (17)	0.0193 (15)	0.0012 (13)	−0.0057 (12)	−0.0003 (12)
C1	0.036 (2)	0.0267 (18)	0.0264 (18)	0.0002 (15)	−0.0052 (15)	0.0001 (13)
C2	0.0285 (19)	0.0274 (17)	0.0205 (16)	0.0006 (14)	−0.0015 (13)	0.0002 (13)
C3	0.0269 (19)	0.0280 (17)	0.0214 (16)	−0.0013 (13)	−0.0017 (13)	0.0012 (12)
C4	0.032 (2)	0.0274 (17)	0.0266 (17)	−0.0014 (14)	−0.0077 (14)	−0.0005 (13)
C5	0.033 (2)	0.0296 (18)	0.0304 (18)	−0.0037 (15)	−0.0094 (15)	0.0030 (14)
C6	0.051 (2)	0.048 (2)	0.0199 (17)	0.0117 (18)	−0.0056 (16)	−0.0027 (15)
C7	0.031 (2)	0.0215 (17)	0.0247 (18)	−0.0021 (14)	−0.0056 (14)	0.0011 (13)
C8	0.034 (2)	0.039 (2)	0.0263 (17)	0.0042 (15)	−0.0097 (15)	−0.0015 (14)
C9	0.028 (2)	0.0364 (19)	0.0261 (17)	0.0013 (15)	−0.0088 (14)	−0.0006 (14)
C10	0.064 (3)	0.069 (3)	0.051 (3)	0.030 (2)	0.018 (2)	0.023 (2)
C11	0.107 (5)	0.121 (5)	0.039 (3)	0.072 (4)	0.017 (3)	0.006 (3)
C12	0.043 (2)	0.057 (3)	0.046 (2)	0.0127 (19)	−0.0159 (18)	−0.0084 (18)
C13	0.0234 (18)	0.0272 (17)	0.0259 (16)	0.0021 (13)	−0.0057 (13)	−0.0005 (13)
C14	0.0216 (18)	0.0345 (18)	0.0246 (17)	0.0038 (14)	−0.0066 (14)	−0.0008 (14)
C15	0.032 (2)	0.035 (2)	0.039 (2)	−0.0026 (16)	−0.0057 (16)	−0.0016 (15)
C16	0.033 (2)	0.038 (2)	0.041 (2)	−0.0061 (16)	−0.0065 (17)	−0.0091 (16)
C17	0.040 (2)	0.042 (2)	0.0291 (18)	0.0002 (17)	−0.0084 (16)	−0.0077 (15)
C18	0.028 (2)	0.039 (2)	0.0245 (17)	−0.0004 (15)	−0.0026 (14)	−0.0015 (14)
C19	0.036 (2)	0.045 (2)	0.0291 (19)	0.0013 (17)	−0.0049 (16)	0.0012 (16)
C20	0.031 (2)	0.0345 (19)	0.0331 (19)	−0.0041 (15)	−0.0081 (16)	0.0052 (14)
C21	0.030 (2)	0.044 (2)	0.046 (2)	0.0014 (16)	0.0041 (16)	−0.0043 (17)
C22	0.042 (2)	0.060 (3)	0.0250 (18)	−0.0017 (18)	−0.0136 (16)	−0.0001 (16)
F3	0.0560 (15)	0.0463 (13)	0.0390 (12)	0.0176 (11)	−0.0003 (10)	−0.0099 (9)
F4	0.0547 (15)	0.0554 (14)	0.0319 (11)	0.0069 (11)	0.0102 (10)	0.0128 (9)
O6	0.0411 (15)	0.0366 (13)	0.0194 (12)	−0.0046 (10)	−0.0045 (10)	0.0003 (10)
O7	0.0344 (14)	0.0393 (13)	0.0204 (11)	−0.0080 (11)	−0.0075 (10)	0.0015 (9)
O8	0.0299 (14)	0.0328 (12)	0.0208 (11)	0.0049 (10)	−0.0030 (10)	−0.0002 (9)
O9	0.0366 (16)	0.0669 (19)	0.0473 (16)	−0.0160 (13)	−0.0094 (13)	0.0016 (13)
O10	0.0333 (15)	0.0433 (14)	0.0320 (13)	−0.0031 (11)	0.0034 (11)	0.0026 (10)
N2	0.0332 (18)	0.0301 (15)	0.0186 (15)	−0.0024 (12)	−0.0048 (12)	0.0001 (11)
C23	0.033 (2)	0.0262 (17)	0.0244 (18)	−0.0017 (14)	−0.0059 (15)	−0.0013 (13)
C24	0.0267 (19)	0.0289 (17)	0.0224 (16)	0.0014 (14)	−0.0033 (13)	−0.0008 (13)
C25	0.0252 (18)	0.0253 (17)	0.0226 (16)	0.0033 (13)	−0.0011 (13)	−0.0011 (12)
C26	0.029 (2)	0.0246 (17)	0.0269 (17)	0.0041 (14)	−0.0042 (14)	0.0002 (13)
C27	0.027 (2)	0.0248 (17)	0.0295 (17)	0.0039 (14)	−0.0074 (14)	−0.0007 (13)
C28	0.049 (2)	0.044 (2)	0.0191 (17)	−0.0162 (18)	−0.0029 (15)	−0.0001 (15)
C29	0.031 (2)	0.0203 (16)	0.0237 (17)	0.0018 (14)	−0.0059 (14)	0.0003 (12)
C30	0.037 (2)	0.037 (2)	0.0271 (17)	−0.0012 (16)	−0.0124 (15)	−0.0033 (14)
C31	0.031 (2)	0.040 (2)	0.0337 (19)	0.0026 (15)	−0.0129 (16)	−0.0035 (15)
C32	0.034 (2)	0.039 (2)	0.037 (2)	−0.0042 (16)	−0.0072 (16)	0.0024 (16)
C33	0.048 (3)	0.062 (3)	0.058 (3)	−0.010 (2)	0.004 (2)	0.008 (2)
C34	0.042 (3)	0.071 (3)	0.055 (3)	−0.005 (2)	−0.022 (2)	−0.001 (2)
C35	0.0185 (18)	0.0264 (16)	0.0279 (17)	−0.0030 (13)	−0.0026 (13)	0.0007 (13)
C36	0.0190 (18)	0.0313 (18)	0.0259 (16)	−0.0016 (13)	−0.0033 (13)	0.0028 (13)
C37	0.031 (2)	0.033 (2)	0.0322 (19)	0.0042 (15)	−0.0038 (15)	−0.0007 (14)
C38	0.031 (2)	0.0326 (19)	0.0358 (19)	0.0027 (15)	−0.0011 (15)	0.0110 (15)
C39	0.040 (2)	0.041 (2)	0.0262 (18)	0.0065 (17)	0.0017 (15)	0.0084 (15)
C40	0.038 (2)	0.037 (2)	0.0235 (17)	0.0040 (16)	0.0017 (14)	0.0041 (14)
C41	0.035 (2)	0.040 (2)	0.0225 (17)	0.0010 (16)	−0.0017 (15)	−0.0012 (14)
C42	0.031 (2)	0.0283 (18)	0.0336 (19)	0.0021 (15)	−0.0032 (16)	−0.0038 (14)
C43	0.040 (2)	0.043 (2)	0.045 (2)	−0.0052 (18)	0.0118 (18)	0.0026 (18)
C44	0.044 (2)	0.047 (2)	0.0296 (18)	0.0001 (17)	−0.0152 (16)	0.0007 (16)

Geometric parameters (Å, º)

F1—C19	1.335 (4)	C15—H15	0.9498
F2—C19	1.352 (4)	C16—H16	0.9491
F3—C41	1.367 (4)	C17—H17	0.9502
F4—C41	1.349 (4)	C18—H18	0.9505
O1—C7	1.221 (4)	C19—H19	0.9996
O2—C8	1.458 (4)	C21—H21C	0.9802
O2—C7	1.346 (4)	C21—H21B	0.9799
O3—C19	1.355 (5)	C21—H21A	0.9804
O3—C14	1.410 (4)	C22—H22B	0.9802
O4—C20	1.206 (4)	C22—H22C	0.9805
O5—C20	1.344 (4)	C22—H22A	0.9795
O5—C21	1.444 (5)	N2—C23	1.372 (4)
O6—C29	1.222 (4)	N2—C27	1.371 (4)
O7—C30	1.452 (4)	C23—C24	1.362 (4)
O7—C29	1.342 (4)	C23—C28	1.496 (5)
O8—C41	1.350 (4)	C24—C25	1.522 (5)
O8—C36	1.409 (4)	C24—C29	1.458 (4)
O9—C42	1.215 (4)	C25—C35	1.529 (4)
O10—C42	1.351 (4)	C25—C26	1.520 (5)
O10—C43	1.443 (5)	C26—C42	1.461 (5)
N1—C1	1.381 (4)	C26—C27	1.356 (4)
N1—C5	1.374 (5)	C27—C44	1.503 (5)
N1—H1	0.96 (4)	C30—C31	1.512 (5)
N2—H2	0.88 (4)	C31—C32	1.524 (5)
C1—C2	1.354 (4)	C31—C34	1.518 (5)
C1—C6	1.491 (5)	C32—C33	1.507 (5)
C2—C7	1.461 (4)	C35—C40	1.385 (4)
C2—C3	1.532 (5)	C35—C36	1.395 (4)
C3—C4	1.521 (5)	C36—C37	1.380 (5)
C3—C13	1.532 (4)	C37—C38	1.370 (4)
C4—C20	1.454 (5)	C38—C39	1.370 (5)
C4—C5	1.360 (4)	C39—C40	1.384 (5)
C5—C22	1.501 (5)	C25—H25	0.9992
C8—C9	1.507 (5)	C28—H28A	0.9805
C9—C12	1.518 (5)	C28—H28B	0.9800
C9—C10	1.501 (5)	C28—H28C	0.9802
C10—C11	1.508 (7)	C30—H30A	0.9899
C13—C14	1.394 (4)	C30—H30B	0.9902
C13—C18	1.391 (4)	C31—H31	1.0002
C14—C15	1.374 (5)	C32—H32A	0.9900
C15—C16	1.380 (4)	C32—H32B	0.9900
C16—C17	1.374 (5)	C33—H33A	0.9798
C17—C18	1.377 (5)	C33—H33B	0.9806
C3—H3	0.9999	C33—H33C	0.9795
C6—H6A	0.9802	C34—H34A	0.9807
C6—H6B	0.9804	C34—H34B	0.9800
C6—H6C	0.9803	C34—H34C	0.9802
C8—H8B	0.9895	C37—H37	0.9504
C8—H8A	0.9902	C38—H38	0.9508
C9—H9	0.9997	C39—H39	0.9501
C10—H10A	0.9904	C40—H40	0.9505
C10—H10B	0.9890	C41—H41	1.0005
C11—H11B	0.9803	C43—H43A	0.9804
C11—H11A	0.9796	C43—H43B	0.9802
C11—H11C	0.9793	C43—H43C	0.9799
C12—H12B	0.9798	C44—H44A	0.9797
C12—H12C	0.9803	C44—H44B	0.9801
C12—H12A	0.9804	C44—H44C	0.9796
F1···N1	3.090 (4)	C42···H44C	2.9652
F1···C1	3.168 (4)	C42···H44A	2.9982
F1···C6	3.341 (4)	C42···H31^vi	2.9123
F2···C15	3.036 (4)	C44···H12C^vi	3.0696
F2···C43^i	3.323 (5)	H1···H6B	2.1406
F3···C37	3.125 (4)	H1···O6^ii	2.13 (4)
F4···N2	3.083 (3)	H1···H22B	2.0075
F4···C8	3.363 (4)	H2···O1	2.19 (4)
F4···C23	3.092 (4)	H2···H28B	2.1186
F4···C28	3.249 (4)	H2···H44B	2.0631
F1···H30A^ii	2.6608	H3···H18	2.2956
F2···H43B^i	2.5600	H3···O1	2.4995
F2···H6A^iii	2.6041	H3···O5	2.4281
F2···H15	2.4833	H6A···O2	2.5702
F3···H21B^iv	2.6741	H6A···F2^v	2.6041
F3···H28C^v	2.5972	H6B···O6^ii	2.7151
F3···H32B^v	2.6851	H6B···H1	2.1406
F3···H37	2.5651	H6C···C7	3.0545
F4···H12A	2.7048	H6C···H10A	2.3883
F4···H8B	2.4287	H6C···H22C^viii	2.5742
O1···C18	3.218 (4)	H6C···O2	2.4496
O1···C13	3.129 (4)	H8A···O5^viii	2.7871
O1···N2	3.060 (3)	H8A···H10B	2.5938
O2···C6	2.724 (4)	H8A···H12C	2.5486
O3···C5	3.059 (4)	H8A···H21A^viii	2.5967
O3···N1	3.026 (3)	H8A···C20^viii	2.9377
O3···C1	3.149 (4)	H8B···O1	2.3969
O3···C4	3.025 (4)	H8B···H12A	2.3698
O3···C2	3.137 (4)	H8B···F4	2.4287
O4···C22	2.802 (4)	H8B···H16^v	2.4084
O4···C19^vi	3.155 (5)	H9···H21C^iv	2.4553
O5···C18	3.184 (4)	H9···H11A	2.4471
O5···C13	3.010 (4)	H9···C15^v	2.9593
O6···N1^vii	3.080 (4)	H10A···O2	2.4849
O6···C40	3.259 (4)	H10A···C6	2.9596
O6···C35	3.153 (4)	H10A···H6C	2.3883
O7···C28	2.703 (4)	H10B···C4^viii	2.8863
O8···C23	3.131 (4)	H10B···H8A	2.5938
O8···C26	3.026 (4)	H10B···H12C	2.4475
O8···C27	3.069 (4)	H10B···C5^viii	2.9272
O8···N2	3.024 (3)	H11A···H9	2.4471
O8···C24	3.108 (4)	H11B···C40^xii	2.8245
O9···C44	2.814 (4)	H11B···H39^xii	2.3101
O9···C41^vi	3.160 (4)	H11B···C39^xii	2.8478
O10···C40	3.173 (4)	H11B···H40^xii	2.2376
O10···C35	3.013 (4)	H11C···C14^iv	3.0563
O1···H21A^viii	2.7627	H11C···H12B	2.3448
O1···H8B	2.3969	H11C···C12	2.8300
O1···H16^v	2.8905	H12A···H8B	2.3698
O1···H2	2.19 (4)	H12A···F4	2.7048
O1···H28B	2.5900	H12B···C11	2.7749
O1···H3	2.4995	H12B···H11C	2.3448
O2···H15^v	2.8486	H12C···H8A	2.5486
O2···H6C	2.4496	H12C···H10B	2.4475
O2···H10A	2.4849	H12C···C44^viii	3.0696
O2···H6A	2.5702	H12C···H44B^viii	2.5724
O4···H22A	2.4932	H15···C19	2.7798
O4···H21A	2.5917	H15···F2	2.4833
O4···H22C	2.6778	H15···O2^iii	2.8486
O4···H19^vi	2.2020	H16···O1^iii	2.8905
O4···H21C	2.5614	H16···C7^iii	3.0426
O5···H8A^vi	2.7871	H16···C8^iii	3.0470
O5···H3	2.4281	H16···H8B^iii	2.4084
O6···H1^vii	2.13 (4)	H17···C33^vi	2.8782
O6···H25	2.5082	H18···H33A^vi	2.4870
O6···H30A	2.7171	H18···H3	2.2956
O6···H22B^vii	2.8254	H19···C15	2.9023
O6···H38^iii	2.8406	H19···O4^viii	2.2020
O6···H43C^viii	2.8853	H21A···O1^vi	2.7627
O6···H6B^vii	2.7151	H21A···O4	2.5917
O6···H30B	2.5714	H21A···H28B^vi	2.5982
O7···H28A	2.3807	H21A···C7^vi	2.9847
O7···H37^iii	2.8616	H21A···H8A^vi	2.5967
O7···H32B	2.5167	H21B···F3^xiii	2.6741
O7···H28C	2.6033	H21C···O4	2.5614
O9···H41^vi	2.2372	H21C···C12^xiii	2.9830
O9···H43A	2.6129	H21C···H9^xiii	2.4553
O9···H43C	2.5737	H22A···O4	2.4932
O9···H44A	2.6162	H22A···C20	2.8970
O9···H44C	2.5681	H22B···H34A^ix	2.2834
O10···H25	2.4184	H22B···O6^ii	2.8254
O10···H30B^vi	2.8981	H22B···H1	2.0075
N1···O6^ii	3.080 (4)	H22B···C34^ix	2.9873
N1···O3	3.026 (3)	H22C···C20	3.0718
N1···F1	3.090 (4)	H22C···H6C^vi	2.5742
N2···O8	3.024 (3)	H22C···O4	2.6778
N2···O1	3.060 (3)	H25···O6	2.5082
N2···F4	3.083 (3)	H25···O10	2.4184
C1···C19	3.492 (5)	H25···H34A^vi	2.4405
C1···O3	3.149 (4)	H25···H40	2.2977
C1···F1	3.168 (4)	H28A···O7	2.3807
C2···O3	3.137 (4)	H28A···C29	3.0265
C4···O3	3.025 (4)	H28A···H44A^viii	2.5209
C5···O3	3.059 (4)	H28B···O1	2.5900
C6···F1	3.341 (4)	H28B···H2	2.1186
C6···O2	2.724 (4)	H28B···H21A^viii	2.5982
C8···F4	3.363 (4)	H28C···F3^iii	2.5972
C13···O5	3.010 (4)	H28C···O7	2.6033
C13···O1	3.129 (4)	H28C···H32B	2.4516
C15···F2	3.036 (4)	H30A···F1^vii	2.6608
C17···C33^vi	3.572 (5)	H30A···O6	2.7171
C18···O1	3.218 (4)	H30A···C38^iii	2.9517
C18···O5	3.184 (4)	H30A···H32A	2.5795
C19···C1	3.492 (5)	H30A···H34C	2.5636
C19···O4^viii	3.155 (5)	H30A···H38^iii	2.3121
C22···O4	2.802 (4)	H30B···O6	2.5714
C22···C34^ix	3.528 (5)	H30B···O10^viii	2.8981
C23···C41	3.522 (5)	H30B···H34A	2.3479
C23···O8	3.131 (4)	H30B···H43C^viii	2.5837
C23···F4	3.092 (4)	H31···C26^viii	2.7929
C24···O8	3.108 (4)	H31···C27^viii	2.9991
C26···O8	3.026 (4)	H31···C42^viii	2.9123
C27···O8	3.069 (4)	H31···H33A	2.5073
C28···O7	2.703 (4)	H32A···H30A	2.5795
C28···F4	3.249 (4)	H32A···H34C	2.5020
C33···C17^viii	3.572 (5)	H32A···H43A^xvi	2.3663
C34···C22^x	3.528 (5)	H32B···F3^iii	2.6851
C35···O6	3.153 (4)	H32B···O7	2.5167
C35···O10	3.013 (4)	H32B···C28	3.0749
C37···F3	3.125 (4)	H32B···H28C	2.4516
C40···O6	3.259 (4)	H33A···H18^viii	2.4870
C40···O10	3.173 (4)	H33A···H31	2.5073
C41···C23	3.522 (5)	H33B···H44C^xvi	2.5964
C41···O9^viii	3.160 (4)	H33C···C34	2.8115
C43···F2^xi	3.323 (5)	H33C···H34B	2.3085
C44···O9	2.814 (4)	H34A···C22^x	2.8434
C4···H10B^vi	2.8863	H34A···H22B^x	2.2834
C5···H10B^vi	2.9272	H34A···H25^viii	2.4405
C6···H10A	2.9596	H34A···H30B	2.3479
C7···H6C	3.0545	H34B···C33	2.7807
C7···H21A^viii	2.9847	H34B···C37^xvi	3.0191
C7···H16^v	3.0426	H34B···C38^xvi	3.0981
C8···H16^v	3.0470	H34B···H33C	2.3085
C11···H39^xii	2.9129	H34C···H30A	2.5636
C11···H12B	2.7749	H34C···H32A	2.5020
C12···H21C^iv	2.9830	H37···F3	2.5651
C12···H11C	2.8300	H37···O7^v	2.8616
C14···H11C^xiii	3.0563	H37···C41	2.7383
C15···H19	2.9023	H38···O6^v	2.8406
C15···H9^iii	2.9593	H38···C29^v	3.0610
C19···H15	2.7798	H38···C30^v	3.0856
C20···H8A^vi	2.9377	H38···H30A^v	2.3121
C20···H22A	2.8970	H39···C11^xv	2.9129
C20···H22C	3.0718	H39···H11B^xv	2.3101
C22···H34A^ix	2.8434	H40···H11B^xv	2.2376
C26···H31^vi	2.7929	H40···H25	2.2977
C27···H31^vi	2.9991	H41···O9^viii	2.2372
C28···H32B	3.0749	H41···C37	2.7932
C29···H43C^viii	3.0990	H43A···O9	2.6129
C29···H38^iii	3.0610	H43A···H32A^xiv	2.3663
C29···H28A	3.0265	H43B···F2^xi	2.5600
C30···H38^iii	3.0856	H43C···O6^vi	2.8853
C33···H17^viii	2.8782	H43C···O9	2.5737
C33···H34B	2.7807	H43C···C29^vi	3.0990
C34···H33C	2.8115	H43C···H30B^vi	2.5837
C34···H22B^x	2.9873	H44A···O9	2.6162
C37···H34B^xiv	3.0191	H44A···C42	2.9982
C37···H41	2.7932	H44A···H28A^vi	2.5209
C38···H34B^xiv	3.0981	H44B···H2	2.0631
C38···H30A^v	2.9517	H44B···H12C^vi	2.5724
C39···H11B^xv	2.8478	H44C···O9	2.5681
C40···H11B^xv	2.8245	H44C···C42	2.9652
C41···H37	2.7383	H44C···H33B^xiv	2.5964
C7—O2—C8	117.5 (2)	H22B—C22—H22C	109.47
C14—O3—C19	114.7 (3)	C5—C22—H22A	109.52
C20—O5—C21	116.0 (3)	C5—C22—H22B	109.41
C29—O7—C30	117.3 (2)	C5—C22—H22C	109.44
C36—O8—C41	114.6 (2)	H22A—C22—H22B	109.49
C42—O10—C43	116.5 (3)	H22A—C22—H22C	109.50
C1—N1—C5	124.3 (3)	N2—C23—C24	118.9 (3)
C1—N1—H1	122 (3)	C24—C23—C28	128.2 (3)
C5—N1—H1	113 (3)	N2—C23—C28	112.9 (3)
C23—N2—C27	124.7 (3)	C23—C24—C29	124.4 (3)
C27—N2—H2	115 (3)	C23—C24—C25	121.3 (3)
C23—N2—H2	120 (3)	C25—C24—C29	114.3 (3)
C2—C1—C6	128.1 (3)	C24—C25—C35	111.9 (3)
N1—C1—C2	119.0 (3)	C24—C25—C26	111.5 (2)
N1—C1—C6	112.9 (3)	C26—C25—C35	112.2 (2)
C1—C2—C7	125.1 (3)	C27—C26—C42	120.8 (3)
C1—C2—C3	121.2 (3)	C25—C26—C27	121.0 (3)
C3—C2—C7	113.6 (2)	C25—C26—C42	118.2 (3)
C4—C3—C13	111.6 (3)	N2—C27—C44	113.6 (3)
C2—C3—C13	112.2 (3)	N2—C27—C26	119.6 (3)
C2—C3—C4	111.8 (3)	C26—C27—C44	126.8 (3)
C5—C4—C20	120.6 (3)	O6—C29—C24	123.4 (3)
C3—C4—C20	118.8 (3)	O6—C29—O7	121.8 (3)
C3—C4—C5	120.6 (3)	O7—C29—C24	114.9 (3)
N1—C5—C22	113.1 (3)	O7—C30—C31	107.6 (2)
N1—C5—C4	120.0 (3)	C30—C31—C34	108.2 (3)
C4—C5—C22	126.9 (3)	C30—C31—C32	112.7 (3)
O1—C7—O2	121.8 (3)	C32—C31—C34	112.0 (3)
O2—C7—C2	115.1 (3)	C31—C32—C33	114.8 (3)
O1—C7—C2	123.1 (3)	C25—C35—C36	123.2 (3)
O2—C8—C9	109.5 (2)	C36—C35—C40	116.3 (3)
C8—C9—C12	108.8 (3)	C25—C35—C40	120.5 (3)
C8—C9—C10	112.7 (3)	O8—C36—C37	120.6 (3)
C10—C9—C12	111.5 (3)	C35—C36—C37	122.0 (3)
C9—C10—C11	114.7 (4)	O8—C36—C35	117.4 (3)
C14—C13—C18	116.3 (3)	C36—C37—C38	119.7 (3)
C3—C13—C14	123.6 (3)	C37—C38—C39	120.1 (3)
C3—C13—C18	120.2 (3)	C38—C39—C40	119.6 (3)
O3—C14—C13	117.6 (3)	C35—C40—C39	122.2 (3)
C13—C14—C15	122.1 (3)	F3—C41—O8	110.2 (3)
O3—C14—C15	120.2 (3)	F4—C41—O8	107.1 (3)
C14—C15—C16	119.7 (3)	F3—C41—F4	104.0 (2)
C15—C16—C17	120.0 (3)	O10—C42—C26	111.8 (3)
C16—C17—C18	119.5 (3)	O9—C42—O10	120.7 (3)
C13—C18—C17	122.4 (3)	O9—C42—C26	127.4 (3)
F1—C19—O3	107.8 (3)	C24—C25—H25	106.95
F2—C19—O3	109.8 (3)	C26—C25—H25	106.87
F1—C19—F2	104.0 (2)	C35—C25—H25	106.92
O4—C20—O5	121.0 (3)	C23—C28—H28A	109.46
O5—C20—C4	111.9 (3)	C23—C28—H28B	109.48
O4—C20—C4	127.1 (3)	C23—C28—H28C	109.45
C13—C3—H3	106.95	H28A—C28—H28B	109.54
C2—C3—H3	106.95	H28A—C28—H28C	109.42
C4—C3—H3	107.00	H28B—C28—H28C	109.47
C1—C6—H6A	109.47	O7—C30—H30A	110.18
H6A—C6—H6C	109.43	O7—C30—H30B	110.20
H6B—C6—H6C	109.49	C31—C30—H30A	110.20
C1—C6—H6C	109.44	C31—C30—H30B	110.17
C1—C6—H6B	109.51	H30A—C30—H30B	108.46
H6A—C6—H6B	109.48	C30—C31—H31	107.88
O2—C8—H8B	109.76	C32—C31—H31	107.94
O2—C8—H8A	109.80	C34—C31—H31	107.88
C9—C8—H8B	109.79	C31—C32—H32A	108.58
H8A—C8—H8B	108.25	C31—C32—H32B	108.54
C9—C8—H8A	109.78	C33—C32—H32A	108.56
C12—C9—H9	107.91	C33—C32—H32B	108.63
C10—C9—H9	107.95	H32A—C32—H32B	107.54
C8—C9—H9	107.84	C32—C33—H33A	109.47
C9—C10—H10B	108.63	C32—C33—H33B	109.46
C11—C10—H10B	108.62	C32—C33—H33C	109.52
H10A—C10—H10B	107.57	H33A—C33—H33B	109.40
C9—C10—H10A	108.56	H33A—C33—H33C	109.51
C11—C10—H10A	108.56	H33B—C33—H33C	109.48
C10—C11—H11C	109.48	C31—C34—H34A	109.49
H11A—C11—H11B	109.45	C31—C34—H34B	109.52
C10—C11—H11A	109.50	C31—C34—H34C	109.47
C10—C11—H11B	109.46	H34A—C34—H34B	109.46
H11A—C11—H11C	109.47	H34A—C34—H34C	109.44
H11B—C11—H11C	109.46	H34B—C34—H34C	109.45
C9—C12—H12C	109.43	C36—C37—H37	120.12
H12A—C12—H12C	109.45	C38—C37—H37	120.13
H12B—C12—H12C	109.49	C37—C38—H38	120.02
H12A—C12—H12B	109.45	C39—C38—H38	119.87
C9—C12—H12B	109.49	C38—C39—H39	120.24
C9—C12—H12A	109.52	C40—C39—H39	120.18
C14—C15—H15	120.20	C35—C40—H40	118.97
C16—C15—H15	120.11	C39—C40—H40	118.80
C15—C16—H16	120.04	F3—C41—H41	111.71
C17—C16—H16	120.01	F4—C41—H41	111.71
C16—C17—H17	120.21	O8—C41—H41	111.75
C18—C17—H17	120.27	O10—C43—H43A	109.45
C17—C18—H18	118.72	O10—C43—H43B	109.43
C13—C18—H18	118.91	O10—C43—H43C	109.45
O3—C19—H19	111.65	H43A—C43—H43B	109.54
F1—C19—H19	111.58	H43A—C43—H43C	109.43
F2—C19—H19	111.65	H43B—C43—H43C	109.54
O5—C21—H21B	109.49	C27—C44—H44A	109.49
H21A—C21—H21C	109.43	C27—C44—H44B	109.43
O5—C21—H21A	109.50	C27—C44—H44C	109.44
O5—C21—H21C	109.52	H44A—C44—H44B	109.48
H21A—C21—H21B	109.50	H44A—C44—H44C	109.53
H21B—C21—H21C	109.39	H44B—C44—H44C	109.45
C7—O2—C8—C9	−159.7 (3)	C3—C4—C20—O5	2.5 (4)
O2—C8—C9—C10	−57.5 (4)	C3—C4—C20—O4	−179.6 (4)
C8—C9—C10—C11	173.1 (4)	O2—C8—C9—C12	178.3 (3)
C29—O7—C30—C31	−170.7 (3)	C12—C9—C10—C11	−64.2 (5)
O7—C30—C31—C32	−60.9 (3)	C18—C13—C14—C15	3.5 (5)
C30—C31—C32—C33	174.9 (3)	C3—C13—C18—C17	178.7 (3)
C8—O2—C7—O1	6.7 (4)	C14—C13—C18—C17	−1.2 (5)
C8—O2—C7—C2	−173.1 (3)	C3—C13—C14—O3	0.1 (5)
C19—O3—C14—C13	126.2 (3)	C3—C13—C14—C15	−176.4 (3)
C19—O3—C14—C15	−57.3 (4)	C18—C13—C14—O3	180.0 (3)
C14—O3—C19—F1	−157.8 (2)	O3—C14—C15—C16	179.9 (3)
C14—O3—C19—F2	89.5 (3)	C13—C14—C15—C16	−3.7 (5)
C21—O5—C20—O4	3.7 (5)	C14—C15—C16—C17	1.5 (5)
C21—O5—C20—C4	−178.3 (3)	C15—C16—C17—C18	0.7 (5)
C30—O7—C29—C24	173.5 (3)	C16—C17—C18—C13	−0.8 (5)
C30—O7—C29—O6	−6.7 (4)	N2—C23—C24—C25	−7.4 (5)
C36—O8—C41—F4	152.2 (2)	C28—C23—C24—C29	−6.2 (6)
C41—O8—C36—C35	−128.1 (3)	N2—C23—C24—C29	172.7 (3)
C41—O8—C36—C37	53.5 (4)	C28—C23—C24—C25	173.7 (3)
C36—O8—C41—F3	−95.2 (3)	C29—C24—C25—C35	71.1 (3)
C43—O10—C42—O9	−4.9 (5)	C23—C24—C29—O6	−173.2 (3)
C43—O10—C42—C26	176.3 (3)	C23—C24—C29—O7	6.7 (5)
C1—N1—C5—C22	171.6 (3)	C25—C24—C29—O6	6.9 (5)
C5—N1—C1—C6	−172.5 (3)	C25—C24—C29—O7	−173.2 (3)
C5—N1—C1—C2	6.6 (5)	C23—C24—C25—C26	17.9 (4)
C1—N1—C5—C4	−8.2 (5)	C23—C24—C25—C35	−108.8 (4)
C23—N2—C27—C44	−171.4 (3)	C29—C24—C25—C26	−162.2 (3)
C23—N2—C27—C26	8.1 (4)	C24—C25—C26—C42	164.8 (3)
C27—N2—C23—C24	−6.8 (5)	C35—C25—C26—C27	109.9 (3)
C27—N2—C23—C28	172.2 (3)	C35—C25—C26—C42	−68.7 (3)
C6—C1—C2—C7	5.9 (6)	C24—C25—C35—C36	66.4 (4)
N1—C1—C2—C7	−173.0 (3)	C24—C25—C35—C40	−114.7 (3)
N1—C1—C2—C3	7.9 (5)	C26—C25—C35—C36	−59.9 (4)
C6—C1—C2—C3	−173.2 (3)	C24—C25—C26—C27	−16.6 (4)
C7—C2—C3—C4	162.3 (3)	C26—C25—C35—C40	119.0 (3)
C1—C2—C3—C13	107.8 (4)	C42—C26—C27—C44	2.9 (5)
C1—C2—C7—O2	−4.0 (5)	C25—C26—C42—O9	175.2 (3)
C7—C2—C3—C13	−71.4 (3)	C42—C26—C27—N2	−176.5 (3)
C1—C2—C7—O1	176.2 (3)	C27—C26—C42—O9	−3.4 (5)
C1—C2—C3—C4	−18.4 (5)	C27—C26—C42—O10	175.3 (3)
C3—C2—C7—O1	−4.6 (5)	C25—C26—C42—O10	−6.1 (4)
C3—C2—C7—O2	175.2 (3)	C25—C26—C27—N2	4.9 (4)
C2—C3—C4—C5	16.8 (5)	C25—C26—C27—C44	−175.7 (3)
C13—C3—C4—C20	70.4 (4)	O7—C30—C31—C34	174.7 (3)
C2—C3—C4—C20	−163.0 (3)	C34—C31—C32—C33	−62.7 (4)
C13—C3—C4—C5	−109.8 (4)	C40—C35—C36—O8	179.6 (3)
C2—C3—C13—C14	−66.1 (4)	C25—C35—C36—O8	−1.4 (5)
C4—C3—C13—C14	60.2 (4)	C25—C35—C36—C37	177.0 (3)
C4—C3—C13—C18	−119.7 (3)	C36—C35—C40—C39	0.7 (5)
C2—C3—C13—C18	114.0 (3)	C40—C35—C36—C37	−1.9 (5)
C3—C4—C5—N1	−4.8 (5)	C25—C35—C40—C39	−178.3 (3)
C3—C4—C5—C22	175.4 (3)	C35—C36—C37—C38	1.5 (5)
C20—C4—C5—C22	−4.8 (6)	O8—C36—C37—C38	179.9 (3)
C5—C4—C20—O4	0.6 (6)	C36—C37—C38—C39	0.3 (5)
C20—C4—C5—N1	175.0 (3)	C37—C38—C39—C40	−1.6 (5)
C5—C4—C20—O5	−177.3 (3)	C38—C39—C40—C35	1.1 (5)

Symmetry codes: (i) x−1, y−1, z+1; (ii) x, y, z+1; (iii) x, y−1, z; (iv) x−1, y+1, z; (v) x, y+1, z; (vi) x+1, y, z; (vii) x, y, z−1; (viii) x−1, y, z; (ix) x+1, y, z+1; (x) x−1, y, z−1; (xi) x+1, y+1, z−1; (xii) x−1, y, z+1; (xiii) x+1, y−1, z; (xiv) x+1, y+1, z; (xv) x+1, y, z−1; (xvi) x−1, y−1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6^ii	0.96 (4)	2.13 (4)	3.080 (4)	171 (4)
N2—H2···O1	0.88 (4)	2.19 (4)	3.060 (3)	171 (4)
C8—H8B···F4	0.99	2.43	3.363 (4)	157
C10—H10A···O2	0.99	2.48	2.894 (5)	104
C15—H15···F2	0.95	2.48	3.036 (4)	117
C19—H19···O4^viii	1.00	2.20	3.155 (5)	159
C28—H28B···O1	0.98	2.59	3.494 (4)	153
C32—H32B···O7	0.99	2.52	2.906 (4)	103
C41—H41···O9^viii	1.00	2.24	3.160 (4)	153

Symmetry codes: (ii) x, y, z+1; (viii) x−1, y, z.