4-Cyano-3-fluoro­phenyl (2E)-3-(3-meth­oxy-4-pentyl­oxyphen­yl)acrylate

The two mol­ecules in the asymmetric unit of the title compound, C₂₂H₂₂NO₄F, differ in the orientation of the 4-cyano-3-fluoro­benzene ring with respect to the acrylate linkage. In one of the mol­ecules, the pent­yloxy chain has an extended conformation and in the other it is folded. The mol­ecules are linked into a three-dimensional framework by C—H... O and C—H...F hydrogen bonds, and by π–π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in main residue
• R factor = 0.058
• wR factor = 0.173
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.74 Ratio
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.61 Ratio

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.06 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C42
PLAT301_ALERT_3_C Main Residue  Disorder .........................       3.00 Perc.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C2     -   C3     ...       1.38 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C2     -   C7     ...       1.38 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C3     -   C4     ...       1.37 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C6     -   C7     ...       1.37 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C24    -   C25    ...       1.38 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C25    -   C26    ...       1.36 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.43 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C23    -   C24    ...       1.44 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C22 H22 F N O4

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
  17 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  11 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

The nematic isotropic transition temperature of compounds containing a fluoro atom at the ortho- or meta- position with respect to the cyano-group on a phenyl ring are only slightly lower than the corresponding esters with an F atom (Kelly et al., 1984). However, the viscosity and driving voltage needed for the new esters are remarkably higher than those of the analogous non-fluoro-substituted phenyl esters. In order to obtain liquid-crystal materials with excellent properties (Sung et al., 2004), the title compound, (I), was synthesized. We report here the crystal structure of (I).

The asymmetric unit of (I) contains two crystallographically independent molecules. The corresponding bond lengths and angles of these two molecules agree with each other (Table 1) but they differ in the orientation of the 4-cyano-3-fluorobenzene ring with respect to the acrylate linkage (Fig. 1). The dihedral angle between C2–C7 and O1/O2/C8–C10 planes is 74.93 (9)° and that between C24–C29 and O5/O6/C30–C32 planes is 68.28 (8)°. Also, the torsion angles O3—C17—C18—C19 [177.8 (2)°] and O7—C39—C40—C41 [60.7 (3)°] indicate that in one of the molecules the pentyloxy chain is in an extended configuration and in the other it is folded. In both the molecules, the methoxybenzene ring is nearly coplanar with the acrylate linkage. The torsion angles C8—C9—C10—C11 [−178.5 (3)°] and C30—C31—C32—C33 [176.9 (2)°] indicate the trans configuration of the double bonds.

In the crystal structure, molecules are linked into a three-dimensional framework by C—H···O and C—H···F hydrogen bonds (Table 2). The packing is further stabilized by π–π interactions involving the C2–C7 and C24–C29 benzene rings at (x, y, z) and (x − 1, y, 1 + z), respectively, with a centroid–centroid distance of 3.788 (2) Å.

S2. Experimental

1-Bromopentane (4.53 g, 0.03 mol) in ethanol (30 ml) was added dropwise to a solution of 3-(4-hydroxy-3-methoxyphenyl)acrylic acid (1.94 g, 0.01 mol) in 17.0% KOH solution (10 ml). The mixture was refluxed for 24 h and extra KOH solution was added to remove the additional products. The mixture was then acidified to give a white precipitate, which was filtered and recrystallized from ethanol to obtain 3-(4-pentyloxyphenyl)acrylic acid. 3-(4-pentyloxyphenyl)acrylic acid (0.79 g) and 1,3-dicyclohexylcarbodiimide (0.62 g) were dissolved in tetrahydrofuran (THF, 20 ml) and a solution of 2-fluoro-4-hydroxybenzonitrile (0.68 g) and 4-dimethylaminopyridine (0.01 g) in THF (20 ml) was added. The mixture was stirred at room temperature for 24 h and then filtered. Colourless single crystals of (I) suitable for X-ray diffraction study were obtained by slow evaporation of a THF/ethanol (1:4 v/v) solution over a period of 2 d.

S3. Refinement

In both independent molecules, the F atom was found to be disordered over two positions, suggesting two different orientations for the 4-cyano-3-fluorobenzene ring. The occupancies of the disordered positions F1/F1' (and F2/F2') were refined to 0.791 (4)/0.209 (4). The C—F distances were restrained to be equal and the U^ij components of the disordered atoms were approximated to isotropic behaviour. H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å and with U_iso(H) = 1.2–1.5U_eq(C).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures

Fig. 1. The two independent molecules of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme. The F atom in each molecule is disordered over two positions and both positions are shown.

4-Cyano-3-fluorophenyl (2E)-3-(3-methoxy-4-pentyloxyphenyl)acrylate

Crystal data

C22H22FNO4	Z = 4
Mr = 383.41	F(000) = 808
Triclinic, P1	Dx = 1.255 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.193 (4) Å	Cell parameters from 1724 reflections
b = 12.506 (4) Å	θ = 2.3–22.6°
c = 14.449 (5) Å	µ = 0.09 mm^−1
α = 82.348 (7)°	T = 293 K
β = 68.816 (6)°	Plate, colourless
γ = 83.036 (7)°	0.41 × 0.18 × 0.09 mm
V = 2029.7 (12) Å^3

Data collection

Simens SMART 1000 CCD area-detector diffractometer	7827 independent reflections
Radiation source: fine-focus sealed tube	3944 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 8.33 pixels mm^-1	θmax = 26.1°, θmin = 1.5°
ω scans	h = −13→15
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −15→14
Tmin = 0.963, Tmax = 0.992	l = −9→17
11493 measured 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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.173	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0777P)^2] where P = (Fo^2 + 2Fc^2)/3
7827 reflections	(Δ/σ)max = 0.001
524 parameters	Δρmax = 0.21 e Å^−3
30 restraints	Δρmin = −0.18 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)
F1	−0.52447 (19)	0.7156 (2)	0.48049 (19)	0.1228 (11)	0.791 (4)
F2	0.94123 (17)	0.62599 (18)	−0.52135 (16)	0.0909 (9)	0.791 (4)
F1'	−0.2424 (11)	0.9091 (10)	0.5023 (9)	0.162 (5)	0.209 (4)
F2'	0.6731 (8)	0.3841 (7)	−0.4855 (7)	0.105 (4)	0.209 (4)
O1	−0.14351 (17)	0.68708 (14)	0.24252 (14)	0.0765 (6)
O2	−0.14778 (18)	0.83171 (16)	0.13515 (15)	0.0866 (7)
O3	0.39423 (16)	0.32152 (14)	−0.15097 (14)	0.0718 (6)
O4	0.33680 (15)	0.50914 (14)	−0.22390 (13)	0.0696 (5)
O5	0.58363 (16)	0.63792 (14)	−0.25299 (14)	0.0755 (6)
O6	0.60108 (18)	0.49287 (16)	−0.14967 (14)	0.0854 (7)
O7	0.04807 (14)	0.96600 (13)	0.17973 (13)	0.0639 (5)
O8	0.12322 (15)	0.77764 (13)	0.23663 (13)	0.0642 (5)
N1	−0.5416 (3)	0.9028 (3)	0.6432 (2)	0.1282 (12)
N2	0.9559 (2)	0.4219 (2)	−0.66425 (19)	0.0937 (9)
C1	−0.4744 (3)	0.8693 (3)	0.5734 (3)	0.0881 (10)
C2	−0.3888 (3)	0.8262 (2)	0.4865 (2)	0.0698 (8)
C3	−0.4164 (3)	0.7495 (3)	0.4403 (2)	0.0768 (9)
H3	−0.4925	0.7269	0.4661	0.092*	0.209 (4)
C4	−0.3375 (3)	0.7051 (2)	0.3581 (2)	0.0741 (8)
H4	−0.3589	0.6533	0.3286	0.089*
C5	−0.2264 (2)	0.7390 (2)	0.3207 (2)	0.0622 (7)
C6	−0.1935 (3)	0.8152 (2)	0.3630 (2)	0.0816 (9)
H6	−0.1174	0.8378	0.3366	0.098*
C7	−0.2755 (3)	0.8575 (3)	0.4453 (3)	0.0866 (10)
H7	−0.2537	0.9093	0.4745	0.104*	0.791 (4)
C8	−0.1052 (2)	0.7432 (2)	0.1501 (2)	0.0609 (7)
C9	−0.0117 (2)	0.6812 (2)	0.0793 (2)	0.0623 (7)
H9	0.0206	0.7134	0.0145	0.075*
C10	0.0312 (2)	0.5828 (2)	0.09986 (19)	0.0574 (7)
H10	−0.0039	0.5519	0.1648	0.069*
C11	0.1264 (2)	0.5158 (2)	0.0343 (2)	0.0572 (7)
C12	0.1855 (2)	0.5483 (2)	−0.0660 (2)	0.0566 (7)
H12	0.1643	0.6158	−0.0931	0.068*
C13	0.2742 (2)	0.4830 (2)	−0.1254 (2)	0.0566 (7)
C14	0.3070 (2)	0.3811 (2)	−0.0857 (2)	0.0603 (7)
C15	0.2496 (2)	0.3486 (2)	0.0127 (2)	0.0705 (8)
H15	0.2709	0.2811	0.0397	0.085*
C16	0.1602 (2)	0.4152 (2)	0.0724 (2)	0.0701 (8)
H16	0.1223	0.3918	0.1391	0.084*
C17	0.4311 (2)	0.2164 (2)	−0.1142 (2)	0.0736 (8)
H17A	0.3644	0.1723	−0.0866	0.088*
H17B	0.4612	0.2230	−0.0618	0.088*
C18	0.5247 (3)	0.1642 (2)	−0.1974 (2)	0.0792 (9)
H18A	0.5892	0.2108	−0.2267	0.095*
H18B	0.4930	0.1564	−0.2486	0.095*
C19	0.5718 (2)	0.0543 (2)	−0.1640 (2)	0.0800 (9)
H19A	0.5077	0.0071	−0.1374	0.096*
H19B	0.5996	0.0620	−0.1104	0.096*
C20	0.6712 (3)	0.0012 (3)	−0.2459 (3)	0.1021 (12)
H20A	0.6449	−0.0029	−0.3011	0.123*
H20B	0.7372	0.0463	−0.2699	0.123*
C21	0.7124 (3)	−0.1093 (3)	−0.2136 (4)	0.1384 (18)
H21A	0.7754	−0.1384	−0.2686	0.208*
H21B	0.6482	−0.1551	−0.1914	0.208*
H21C	0.7402	−0.1058	−0.1599	0.208*
C22	0.3033 (3)	0.6103 (2)	−0.2692 (2)	0.0785 (9)
H22A	0.3533	0.6192	−0.3381	0.118*
H22B	0.3115	0.6682	−0.2353	0.118*
H22C	0.2227	0.6113	−0.2648	0.118*
C23	0.8910 (3)	0.4571 (2)	−0.5942 (2)	0.0686 (8)
C24	0.8103 (2)	0.5010 (2)	−0.50500 (18)	0.0574 (7)
C25	0.8389 (2)	0.5862 (2)	−0.4692 (2)	0.0648 (8)
H25	0.9110	0.6152	−0.5040	0.078*	0.209 (4)
C26	0.7662 (2)	0.6297 (2)	−0.3852 (2)	0.0682 (8)
H26	0.7879	0.6873	−0.3626	0.082*
C27	0.6603 (2)	0.5870 (2)	−0.33438 (19)	0.0615 (7)
C28	0.6282 (2)	0.5011 (2)	−0.3659 (2)	0.0667 (8)
H28	0.5564	0.4722	−0.3301	0.080*
C29	0.7032 (2)	0.4584 (3)	−0.4510 (2)	0.0687 (8)
H29	0.6820	0.4000	−0.4727	0.082*	0.791 (4)
C30	0.5550 (2)	0.5810 (2)	−0.1603 (2)	0.0610 (7)
C31	0.4653 (2)	0.6389 (2)	−0.0839 (2)	0.0595 (7)
H31	0.4415	0.6058	−0.0189	0.071*
C32	0.4146 (2)	0.7361 (2)	−0.10010 (18)	0.0533 (6)
H32	0.4424	0.7692	−0.1649	0.064*
C33	0.3200 (2)	0.79674 (19)	−0.02741 (18)	0.0484 (6)
C34	0.26920 (19)	0.75488 (18)	0.07238 (18)	0.0492 (6)
H34	0.2970	0.6870	0.0935	0.059*
C35	0.1793 (2)	0.81224 (19)	0.13930 (18)	0.0496 (6)
C36	0.1371 (2)	0.91545 (19)	0.1079 (2)	0.0518 (6)
C37	0.1868 (2)	0.9575 (2)	0.0103 (2)	0.0601 (7)
H37	0.1601	1.0259	−0.0108	0.072*
C38	0.2768 (2)	0.8977 (2)	−0.05636 (19)	0.0567 (7)
H38	0.3090	0.9264	−0.1224	0.068*
C39	−0.0018 (2)	1.0693 (2)	0.1512 (2)	0.0745 (9)
H39A	−0.0302	1.0635	0.0975	0.089*
H39B	0.0572	1.1216	0.1283	0.089*
C40	−0.1019 (3)	1.1042 (2)	0.2411 (3)	0.0863 (10)
H40A	−0.1604	1.0514	0.2618	0.104*
H40B	−0.1389	1.1727	0.2227	0.104*
C41	−0.0657 (3)	1.1170 (3)	0.3290 (3)	0.0978 (11)
H41A	−0.0297	1.0481	0.3478	0.117*
H41B	−0.0062	1.1688	0.3077	0.117*
C42	−0.1646 (4)	1.1536 (3)	0.4192 (3)	0.1199 (14)
H42A	−0.2268	1.1047	0.4387	0.144*
H42B	−0.1970	1.2252	0.4025	0.144*
C43	−0.1239 (5)	1.1571 (4)	0.5065 (3)	0.181 (2)
H43A	−0.1893	1.1815	0.5624	0.272*
H43B	−0.0629	1.2061	0.4877	0.272*
H43C	−0.0937	1.0860	0.5245	0.272*
C44	0.1620 (2)	0.6734 (2)	0.2716 (2)	0.0725 (8)
H44A	0.1165	0.6580	0.3410	0.109*
H44B	0.2439	0.6720	0.2633	0.109*
H44C	0.1517	0.6198	0.2342	0.109*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0607 (15)	0.191 (3)	0.106 (2)	−0.0397 (15)	0.0060 (14)	−0.0493 (18)
F2	0.0645 (14)	0.1103 (17)	0.0782 (16)	−0.0234 (11)	0.0041 (11)	−0.0103 (13)
F1'	0.151 (8)	0.156 (8)	0.167 (9)	−0.047 (6)	−0.020 (7)	−0.044 (7)
F2'	0.102 (6)	0.114 (6)	0.088 (6)	−0.034 (5)	0.000 (5)	−0.046 (5)
O1	0.0819 (13)	0.0599 (11)	0.0585 (13)	0.0139 (10)	0.0017 (10)	0.0016 (10)
O2	0.0985 (15)	0.0685 (13)	0.0706 (14)	0.0216 (11)	−0.0160 (12)	0.0050 (11)
O3	0.0666 (12)	0.0677 (12)	0.0683 (13)	0.0103 (9)	−0.0118 (10)	−0.0112 (10)
O4	0.0664 (12)	0.0688 (12)	0.0549 (12)	0.0009 (9)	−0.0012 (10)	−0.0047 (10)
O5	0.0777 (13)	0.0683 (12)	0.0495 (12)	0.0123 (10)	0.0078 (10)	−0.0024 (10)
O6	0.0950 (15)	0.0813 (14)	0.0571 (13)	0.0334 (12)	−0.0122 (11)	−0.0066 (11)
O7	0.0600 (11)	0.0568 (11)	0.0645 (12)	0.0152 (8)	−0.0133 (9)	−0.0123 (9)
O8	0.0635 (11)	0.0619 (11)	0.0457 (11)	0.0096 (9)	0.0009 (9)	−0.0023 (9)
N1	0.115 (3)	0.154 (3)	0.088 (2)	0.018 (2)	−0.001 (2)	−0.040 (2)
N2	0.0887 (19)	0.116 (2)	0.0536 (16)	0.0006 (16)	0.0039 (14)	−0.0191 (16)
C1	0.087 (2)	0.095 (2)	0.064 (2)	0.0111 (18)	−0.0086 (19)	−0.0137 (19)
C2	0.067 (2)	0.0685 (19)	0.0610 (19)	0.0070 (15)	−0.0122 (16)	−0.0039 (16)
C3	0.0605 (19)	0.099 (2)	0.061 (2)	−0.0088 (17)	−0.0086 (16)	−0.0082 (18)
C4	0.070 (2)	0.088 (2)	0.0605 (19)	−0.0057 (16)	−0.0158 (16)	−0.0158 (17)
C5	0.0624 (18)	0.0529 (16)	0.0543 (17)	0.0092 (13)	−0.0066 (14)	0.0001 (14)
C6	0.0660 (19)	0.072 (2)	0.086 (2)	−0.0110 (16)	0.0017 (17)	−0.0111 (19)
C7	0.088 (2)	0.074 (2)	0.089 (3)	−0.0131 (18)	−0.012 (2)	−0.0248 (19)
C8	0.0592 (17)	0.0611 (18)	0.0551 (18)	−0.0030 (14)	−0.0133 (14)	−0.0020 (15)
C9	0.0598 (17)	0.0643 (17)	0.0554 (18)	−0.0058 (14)	−0.0119 (14)	−0.0031 (14)
C10	0.0528 (15)	0.0654 (18)	0.0492 (16)	−0.0085 (13)	−0.0108 (13)	−0.0058 (14)
C11	0.0536 (16)	0.0626 (17)	0.0527 (17)	−0.0048 (13)	−0.0137 (14)	−0.0108 (14)
C12	0.0506 (15)	0.0573 (15)	0.0581 (18)	−0.0056 (12)	−0.0141 (13)	−0.0062 (14)
C13	0.0487 (15)	0.0623 (17)	0.0524 (17)	−0.0101 (13)	−0.0080 (13)	−0.0059 (14)
C14	0.0507 (15)	0.0664 (18)	0.0592 (19)	−0.0002 (13)	−0.0126 (14)	−0.0132 (15)
C15	0.0690 (19)	0.0682 (18)	0.064 (2)	0.0073 (15)	−0.0159 (16)	−0.0042 (16)
C16	0.0679 (18)	0.078 (2)	0.0530 (18)	0.0012 (15)	−0.0108 (15)	−0.0012 (15)
C17	0.0654 (18)	0.074 (2)	0.077 (2)	0.0067 (15)	−0.0202 (16)	−0.0146 (17)
C18	0.0689 (19)	0.080 (2)	0.083 (2)	0.0107 (16)	−0.0210 (17)	−0.0211 (18)
C19	0.0638 (18)	0.0681 (19)	0.105 (3)	0.0021 (15)	−0.0259 (18)	−0.0160 (18)
C20	0.093 (2)	0.083 (2)	0.128 (3)	0.0194 (19)	−0.035 (2)	−0.036 (2)
C21	0.098 (3)	0.085 (3)	0.229 (6)	0.012 (2)	−0.050 (3)	−0.043 (3)
C22	0.074 (2)	0.087 (2)	0.0597 (19)	0.0043 (16)	−0.0133 (16)	0.0053 (17)
C23	0.0643 (18)	0.084 (2)	0.0468 (17)	−0.0026 (15)	−0.0084 (15)	−0.0026 (16)
C24	0.0532 (16)	0.0701 (18)	0.0394 (15)	0.0036 (13)	−0.0085 (13)	−0.0026 (14)
C25	0.0489 (16)	0.0770 (19)	0.0499 (17)	−0.0066 (14)	0.0018 (14)	0.0044 (15)
C26	0.0663 (18)	0.0696 (18)	0.0551 (18)	−0.0037 (14)	−0.0047 (15)	−0.0083 (15)
C27	0.0585 (17)	0.0623 (17)	0.0437 (16)	0.0081 (14)	−0.0015 (13)	0.0045 (14)
C28	0.0500 (16)	0.078 (2)	0.0571 (18)	−0.0044 (14)	−0.0038 (14)	−0.0004 (16)
C29	0.0587 (18)	0.084 (2)	0.0514 (18)	−0.0009 (15)	−0.0071 (15)	−0.0043 (16)
C30	0.0580 (16)	0.0652 (18)	0.0475 (17)	0.0028 (14)	−0.0068 (13)	−0.0045 (14)
C31	0.0561 (16)	0.0659 (17)	0.0461 (16)	0.0034 (13)	−0.0082 (13)	−0.0055 (13)
C32	0.0479 (14)	0.0627 (16)	0.0429 (15)	−0.0071 (12)	−0.0081 (12)	−0.0029 (13)
C33	0.0447 (13)	0.0511 (15)	0.0467 (15)	−0.0036 (11)	−0.0119 (12)	−0.0072 (12)
C34	0.0467 (14)	0.0456 (14)	0.0501 (16)	−0.0010 (11)	−0.0110 (12)	−0.0062 (12)
C35	0.0457 (14)	0.0517 (15)	0.0456 (15)	−0.0006 (11)	−0.0092 (12)	−0.0076 (12)
C36	0.0469 (14)	0.0509 (15)	0.0566 (17)	0.0029 (11)	−0.0167 (13)	−0.0120 (13)
C37	0.0638 (17)	0.0516 (15)	0.0613 (19)	0.0047 (13)	−0.0218 (15)	−0.0024 (14)
C38	0.0587 (16)	0.0590 (16)	0.0472 (16)	−0.0040 (13)	−0.0148 (13)	0.0014 (13)
C39	0.0765 (19)	0.0641 (18)	0.080 (2)	0.0253 (15)	−0.0316 (17)	−0.0147 (16)
C40	0.078 (2)	0.074 (2)	0.098 (3)	0.0247 (16)	−0.025 (2)	−0.0232 (19)
C41	0.100 (3)	0.091 (2)	0.094 (3)	0.0089 (19)	−0.020 (2)	−0.035 (2)
C42	0.145 (4)	0.075 (2)	0.104 (3)	0.002 (2)	0.001 (3)	−0.023 (2)
C43	0.309 (7)	0.137 (4)	0.083 (3)	−0.008 (4)	−0.051 (4)	−0.024 (3)
C44	0.0756 (19)	0.0661 (18)	0.0531 (18)	0.0090 (15)	−0.0052 (15)	0.0087 (14)

Geometric parameters (Å, º)

F1—C3	1.330 (3)	C19—H19B	0.97
F2—C25	1.320 (3)	C20—C21	1.487 (4)
F1'—C7	1.305 (8)	C20—H20A	0.97
F2'—C29	1.259 (6)	C20—H20B	0.97
O1—C8	1.369 (3)	C21—H21A	0.96
O1—C5	1.390 (3)	C21—H21B	0.96
O2—C8	1.191 (3)	C21—H21C	0.96
O3—C14	1.358 (3)	C22—H22A	0.96
O3—C17	1.434 (3)	C22—H22B	0.96
O4—C13	1.367 (3)	C22—H22C	0.96
O4—C22	1.429 (3)	C23—C24	1.439 (4)
O5—C30	1.375 (3)	C24—C25	1.376 (4)
O5—C27	1.387 (3)	C24—C29	1.386 (4)
O6—C30	1.192 (3)	C25—C26	1.355 (4)
O7—C36	1.360 (3)	C25—H25	0.93
O7—C39	1.434 (3)	C26—C27	1.367 (4)
O8—C35	1.359 (3)	C26—H26	0.93
O8—C44	1.424 (3)	C27—C28	1.370 (4)
N1—C1	1.139 (4)	C28—C29	1.370 (4)
N2—C23	1.140 (3)	C28—H28	0.93
C1—C2	1.432 (4)	C29—H29	0.93
C2—C3	1.375 (4)	C30—C31	1.445 (3)
C2—C7	1.375 (4)	C31—C32	1.327 (3)
C3—C4	1.366 (4)	C31—H31	0.93
C3—H3	0.93	C32—C33	1.461 (3)
C4—C5	1.362 (4)	C32—H32	0.93
C4—H4	0.93	C33—C38	1.380 (3)
C5—C6	1.367 (4)	C33—C34	1.403 (3)
C6—C7	1.368 (4)	C34—C35	1.371 (3)
C6—H6	0.93	C34—H34	0.93
C7—H7	0.93	C35—C36	1.410 (3)
C8—C9	1.450 (3)	C36—C37	1.376 (4)
C9—C10	1.318 (3)	C37—C38	1.386 (3)
C9—H9	0.93	C37—H37	0.93
C10—C11	1.458 (3)	C38—H38	0.93
C10—H10	0.93	C39—C40	1.498 (4)
C11—C16	1.383 (3)	C39—H39A	0.97
C11—C12	1.394 (3)	C39—H39B	0.97
C12—C13	1.369 (3)	C40—C41	1.520 (4)
C12—H12	0.93	C40—H40A	0.97
C13—C14	1.400 (3)	C40—H40B	0.97
C14—C15	1.368 (4)	C41—C42	1.501 (4)
C15—C16	1.385 (3)	C41—H41A	0.97
C15—H15	0.93	C41—H41B	0.97
C16—H16	0.93	C42—C43	1.520 (6)
C17—C18	1.487 (4)	C42—H42A	0.97
C17—H17A	0.97	C42—H42B	0.97
C17—H17B	0.97	C43—H43A	0.96
C18—C19	1.511 (4)	C43—H43B	0.96
C18—H18A	0.97	C43—H43C	0.96
C18—H18B	0.97	C44—H44A	0.96
C19—C20	1.513 (4)	C44—H44B	0.96
C19—H19A	0.97	C44—H44C	0.96
C8—O1—C5	118.4 (2)	O4—C22—H22C	109.5
C14—O3—C17	117.9 (2)	H22A—C22—H22C	109.5
C13—O4—C22	117.3 (2)	H22B—C22—H22C	109.5
C30—O5—C27	118.3 (2)	N2—C23—C24	179.2 (3)
C36—O7—C39	117.8 (2)	C25—C24—C29	117.6 (3)
C35—O8—C44	116.97 (18)	C25—C24—C23	120.5 (3)
N1—C1—C2	179.1 (4)	C29—C24—C23	121.9 (3)
C3—C2—C7	116.3 (3)	F2—C25—C26	120.5 (3)
C3—C2—C1	121.0 (3)	F2—C25—C24	116.9 (3)
C7—C2—C1	122.7 (3)	C26—C25—C24	122.6 (3)
F1—C3—C4	119.4 (3)	C26—C25—H25	118.7
F1—C3—C2	117.4 (3)	C24—C25—H25	118.7
C4—C3—C2	123.1 (3)	C25—C26—C27	118.5 (3)
C4—C3—H3	118.4	C25—C26—H26	120.8
C2—C3—H3	118.4	C27—C26—H26	120.8
C5—C4—C3	117.9 (3)	C26—C27—C28	121.4 (3)
C5—C4—H4	121.0	C26—C27—O5	117.4 (3)
C3—C4—H4	121.0	C28—C27—O5	121.1 (3)
C4—C5—C6	121.8 (3)	C29—C28—C27	119.1 (3)
C4—C5—O1	117.7 (3)	C29—C28—H28	120.4
C6—C5—O1	120.2 (3)	C27—C28—H28	120.4
C5—C6—C7	118.2 (3)	F2'—C29—C28	120.7 (5)
C5—C6—H6	120.9	F2'—C29—C24	118.3 (5)
C7—C6—H6	120.9	C28—C29—C24	120.9 (3)
F1'—C7—C6	120.3 (7)	C28—C29—H29	119.6
F1'—C7—C2	115.2 (6)	C24—C29—H29	119.6
C6—C7—C2	122.6 (3)	O6—C30—O5	120.6 (2)
C6—C7—H7	118.7	O6—C30—C31	126.8 (3)
C2—C7—H7	118.7	O5—C30—C31	112.6 (2)
O2—C8—O1	120.9 (2)	C32—C31—C30	124.4 (3)
O2—C8—C9	127.6 (3)	C32—C31—H31	117.8
O1—C8—C9	111.4 (2)	C30—C31—H31	117.8
C10—C9—C8	125.0 (3)	C31—C32—C33	127.2 (2)
C10—C9—H9	117.5	C31—C32—H32	116.4
C8—C9—H9	117.5	C33—C32—H32	116.4
C9—C10—C11	128.5 (3)	C38—C33—C34	118.0 (2)
C9—C10—H10	115.7	C38—C33—C32	120.1 (2)
C11—C10—H10	115.7	C34—C33—C32	121.9 (2)
C16—C11—C12	117.9 (2)	C35—C34—C33	121.2 (2)
C16—C11—C10	119.0 (2)	C35—C34—H34	119.4
C12—C11—C10	123.1 (2)	C33—C34—H34	119.4
C13—C12—C11	121.4 (3)	O8—C35—C34	125.4 (2)
C13—C12—H12	119.3	O8—C35—C36	114.9 (2)
C11—C12—H12	119.3	C34—C35—C36	119.7 (2)
O4—C13—C12	125.0 (2)	O7—C36—C37	125.1 (2)
O4—C13—C14	115.0 (2)	O7—C36—C35	115.3 (2)
C12—C13—C14	120.0 (2)	C37—C36—C35	119.6 (2)
O3—C14—C15	125.4 (3)	C36—C37—C38	119.8 (2)
O3—C14—C13	115.6 (2)	C36—C37—H37	120.1
C15—C14—C13	119.0 (2)	C38—C37—H37	120.1
C14—C15—C16	120.7 (3)	C33—C38—C37	121.7 (2)
C14—C15—H15	119.7	C33—C38—H38	119.1
C16—C15—H15	119.7	C37—C38—H38	119.1
C11—C16—C15	121.0 (3)	O7—C39—C40	107.4 (2)
C11—C16—H16	119.5	O7—C39—H39A	110.2
C15—C16—H16	119.5	C40—C39—H39A	110.2
O3—C17—C18	109.3 (2)	O7—C39—H39B	110.2
O3—C17—H17A	109.8	C40—C39—H39B	110.2
C18—C17—H17A	109.8	H39A—C39—H39B	108.5
O3—C17—H17B	109.8	C39—C40—C41	114.1 (3)
C18—C17—H17B	109.8	C39—C40—H40A	108.7
H17A—C17—H17B	108.3	C41—C40—H40A	108.7
C17—C18—C19	112.6 (3)	C39—C40—H40B	108.7
C17—C18—H18A	109.1	C41—C40—H40B	108.7
C19—C18—H18A	109.1	H40A—C40—H40B	107.6
C17—C18—H18B	109.1	C42—C41—C40	114.8 (3)
C19—C18—H18B	109.1	C42—C41—H41A	108.6
H18A—C18—H18B	107.8	C40—C41—H41A	108.6
C18—C19—C20	113.9 (3)	C42—C41—H41B	108.6
C18—C19—H19A	108.8	C40—C41—H41B	108.6
C20—C19—H19A	108.8	H41A—C41—H41B	107.5
C18—C19—H19B	108.8	C41—C42—C43	112.0 (4)
C20—C19—H19B	108.8	C41—C42—H42A	109.2
H19A—C19—H19B	107.7	C43—C42—H42A	109.2
C21—C20—C19	113.5 (3)	C41—C42—H42B	109.2
C21—C20—H20A	108.9	C43—C42—H42B	109.2
C19—C20—H20A	108.9	H42A—C42—H42B	107.9
C21—C20—H20B	108.9	C42—C43—H43A	109.5
C19—C20—H20B	108.9	C42—C43—H43B	109.5
H20A—C20—H20B	107.7	H43A—C43—H43B	109.5
C20—C21—H21A	109.5	C42—C43—H43C	109.5
C20—C21—H21B	109.5	H43A—C43—H43C	109.5
H21A—C21—H21B	109.5	H43B—C43—H43C	109.5
C20—C21—H21C	109.5	O8—C44—H44A	109.5
H21A—C21—H21C	109.5	O8—C44—H44B	109.5
H21B—C21—H21C	109.5	H44A—C44—H44B	109.5
O4—C22—H22A	109.5	O8—C44—H44C	109.5
O4—C22—H22B	109.5	H44A—C44—H44C	109.5
H22A—C22—H22B	109.5	H44B—C44—H44C	109.5
C7—C2—C3—F1	178.0 (3)	C29—C24—C25—F2	180.0 (2)
C1—C2—C3—F1	−1.4 (4)	C23—C24—C25—F2	1.4 (4)
C7—C2—C3—C4	0.3 (5)	C29—C24—C25—C26	−0.9 (4)
C1—C2—C3—C4	−179.2 (3)	C23—C24—C25—C26	−179.5 (3)
F1—C3—C4—C5	−177.9 (3)	F2—C25—C26—C27	179.0 (2)
C2—C3—C4—C5	−0.1 (5)	C24—C25—C26—C27	−0.1 (4)
C3—C4—C5—C6	−0.1 (4)	C25—C26—C27—C28	1.1 (4)
C3—C4—C5—O1	174.6 (2)	C25—C26—C27—O5	−175.2 (2)
C8—O1—C5—C4	110.4 (3)	C30—O5—C27—C26	−116.5 (3)
C8—O1—C5—C6	−74.8 (3)	C30—O5—C27—C28	67.2 (3)
C4—C5—C6—C7	0.2 (5)	C26—C27—C28—C29	−1.0 (4)
O1—C5—C6—C7	−174.4 (3)	O5—C27—C28—C29	175.2 (2)
C5—C6—C7—F1'	163.2 (8)	C27—C28—C29—F2'	−175.4 (6)
C5—C6—C7—C2	0.0 (5)	C27—C28—C29—C24	−0.1 (4)
C3—C2—C7—F1'	−164.2 (7)	C25—C24—C29—F2'	176.4 (6)
C1—C2—C7—F1'	15.2 (8)	C23—C24—C29—F2'	−5.0 (7)
C3—C2—C7—C6	−0.2 (5)	C25—C24—C29—C28	1.0 (4)
C1—C2—C7—C6	179.2 (3)	C23—C24—C29—C28	179.6 (2)
C5—O1—C8—O2	−5.3 (4)	C27—O5—C30—O6	4.9 (4)
C5—O1—C8—C9	174.8 (2)	C27—O5—C30—C31	−173.9 (2)
O2—C8—C9—C10	−179.2 (3)	O6—C30—C31—C32	−178.3 (3)
O1—C8—C9—C10	0.7 (4)	O5—C30—C31—C32	0.5 (4)
C8—C9—C10—C11	−178.5 (3)	C30—C31—C32—C33	176.9 (2)
C9—C10—C11—C16	177.9 (3)	C31—C32—C33—C38	179.8 (2)
C9—C10—C11—C12	−2.3 (4)	C31—C32—C33—C34	−1.1 (4)
C16—C11—C12—C13	0.1 (4)	C38—C33—C34—C35	0.1 (4)
C10—C11—C12—C13	−179.7 (2)	C32—C33—C34—C35	−179.1 (2)
C22—O4—C13—C12	−3.1 (4)	C44—O8—C35—C34	0.4 (4)
C22—O4—C13—C14	177.3 (2)	C44—O8—C35—C36	179.4 (2)
C11—C12—C13—O4	−179.5 (2)	C33—C34—C35—O8	178.7 (2)
C11—C12—C13—C14	0.1 (4)	C33—C34—C35—C36	−0.3 (4)
C17—O3—C14—C15	−0.9 (4)	C39—O7—C36—C37	2.8 (4)
C17—O3—C14—C13	−179.9 (2)	C39—O7—C36—C35	−177.4 (2)
O4—C13—C14—O3	−1.5 (3)	O8—C35—C36—O7	1.1 (3)
C12—C13—C14—O3	178.8 (2)	C34—C35—C36—O7	−179.8 (2)
O4—C13—C14—C15	179.4 (3)	O8—C35—C36—C37	−179.2 (2)
C12—C13—C14—C15	−0.3 (4)	C34—C35—C36—C37	−0.1 (4)
O3—C14—C15—C16	−178.9 (2)	O7—C36—C37—C38	−179.5 (2)
C13—C14—C15—C16	0.2 (4)	C35—C36—C37—C38	0.8 (4)
C12—C11—C16—C15	−0.3 (4)	C34—C33—C38—C37	0.6 (4)
C10—C11—C16—C15	179.6 (3)	C32—C33—C38—C37	179.7 (2)
C14—C15—C16—C11	0.1 (5)	C36—C37—C38—C33	−1.0 (4)
C14—O3—C17—C18	178.7 (2)	C36—O7—C39—C40	176.5 (2)
O3—C17—C18—C19	177.8 (2)	O7—C39—C40—C41	60.7 (3)
C17—C18—C19—C20	−177.3 (3)	C39—C40—C41—C42	179.1 (3)
C18—C19—C20—C21	−176.8 (3)	C40—C41—C42—C43	176.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C28—H28···O4	0.93	2.58	3.398 (3)	147
C31—H31···O6^i	0.93	2.48	3.410 (3)	174
C37—H37···O2^ii	0.93	2.39	3.246 (3)	153
C44—H44A···F2^iii	0.96	2.37	3.262 (4)	155

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+2, −z; (iii) x−1, y, z+1.