2-[N-(2,4-Difluoro­phen­yl)carbamo­yl]-3,4,5,6-tetra­fluoro­benzoic acid

Guo, D.; Nichol, G.S.; Cain, J.P.; Yalkowsky, S.H.

doi:10.1107/S1600536809038306

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2644

https://doi.org/10.1107/S1600536809038306

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2-[N-(2,4-Difluorophenyl)carbamoyl]-3,4,5,6-tetrafluorobenzoic acid

Duoli Guo,^a ^* Gary S. Nichol,^b James P. Cain ^b and Samuel H. Yalkowsky ^a

^aCollege of Pharmacy, The University of Arizona, 1295 N. Martin Avenue, Tucson, AZ 85721, USA, and ^bDepartment of Chemistry and Biochemistry, The University of Arizona, 1306 E. University Boulevard, Tucson, AZ 85721, USA
^*Correspondence e-mail: guod@pharmacy.arizona.edu

(Received 14 September 2009; accepted 21 September 2009; online 3 October 2009)

The title compound, C₁₄H₅F₆NO₃, was synthesized by condensation of tetrafluorophthalic anhydride and 2,4-difluoroaniline. It was then recrystallized from hexane to give a nonmerohedral twin with two crystallographically unique molecules in the asymmetric unit. The refined twin fraction is 0.460 (3). Torsional differences between the aryl rings and the central amide group account for the presence of two unique molecules. The compound packs as double tapes formed by O—H⋯O and N—H⋯O hydrogen-bonding interactions between each unique molecule and its symmetry equivalents.

Related literature

For the synthesis of a related structure, see: Collin et al. (2001 ). For antitumor effects of thalidomide analogs, see: Ng et al. (2004 ).

Experimental

Crystal data

C₁₄H₅F₆NO₃
M_r = 349.19
Triclinic, $[P \overline 1]$
a = 7.5293 (4) Å
b = 7.6795 (5) Å
c = 24.1969 (15) Å
α = 89.809 (5)°
β = 82.747 (4)°
γ = 68.712 (4)°
V = 1291.83 (13) Å³
Z = 4
Cu Kα radiation
μ = 1.65 mm⁻¹
T = 100 K
0.27 × 0.19 × 0.09 mm

Data collection

Bruker Kappa APEXII DUO CCD diffractometer
Absorption correction: multi-scan (TWINABS; Sheldrick, 1996 ) T_min = 0.664, T_max = 0.868
7781 measured reflections
3296 independent reflections
2467 reflections with I > 2σ(I)
R_int = 0.074
θ_max = 58.5°

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.182
S = 0.99
3296 reflections
434 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1ⁱ	0.84	1.84	2.666 (6)	168
N1—H1⋯O2ⁱⁱ	0.88	2.09	2.902 (7)	154
O53—H53⋯O51ⁱⁱⁱ	0.84	1.84	2.675 (6)	170
N51—H51⋯O52^iv	0.88	2.07	2.902 (8)	157
Symmetry codes: (i) -x+2, -y, -z; (ii) -x+1, -y+1, -z; (iii) -x+2, -y-1, -z+1; (iv) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809038306/bt5063sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809038306/bt5063Isup2.hkl

checkCIF report

Comment top

Analogs of thalidomide have demonstrated promising anti-cancer activity (Ng et al., 2004). Inhibition of the angiogenesis activity of 2-(2,4-difluorophenyl)-4,5,6,7-tetrafluoroisoindoline-1,3-dione led us to synthesize and test the activity of its degradation product, 2-(2,4-difluorophenylcarbamoyl)-3,4,5,6-tetrafluorobenzoic acid, (I). In the course of doing so we determined its crystal structure.

Compound (I) was recrystallized from hexane to yield, concomitantly, small needle and prism-like crystals. Both crystal morphologies have the same unit cell parameters and data were collected on a prism crystal. Although the crystal was reasonably large the diffraction was phenomenally weak. With 60 second exposures using Cu radiation data could only be observed up to a resolution of 1 Å; the dataset was truncated at this resolution. The diffraction pattern is a non-merohedral twin with a refined twin fraction ration of 0.460 (3). A room temperature redetermination of the unit cell, using a fresh crystal, showed that twinning was still present and does not result from flash-cooling to 100 K.

The structure features two crystallographically independent molecules in the asymmetric unit. The structural discussion is limited to molecule A (atoms F1 > C14) with equivalent results for molecule B (F51 > C14) presented in square brackets. The asymmetric unit is shown in Figure 1. Figure 2 shows an overlay of both molecules,formed by overlaying the central amide group.Molecular dimensions are unexceptional. The plane of the more highly-substituted aryl ring is rotated by 69.41 (5)° [69.64 (4)°] from the amide group, and the carboxylic acid group is rotated by 58.70 (2)° [61.10 (3)°] from the aryl ring. The plane of the second aryl ring is rotated by 70.25 (4)° [66.54 (4)°] from the amide group. As can be see from Figure 3 and from the direction of rotation is different for each molecule, most easily appreciated by considering the torsion angle N1–C1–C2–C3 - 49.0 (8)° [48.5 (10)°] (similar magnitude, opposite direction).

As shown in Figures 3 and 4 the compound packs as a double tape structure with each crystallographically unique molecule hydrogen-bonded to its symmetry equivalents via O–H···O and N–H···O hydrogen bonding interactions. Each tape runs parallel to the a axis.

Related literature top

For the synthesis of a related structure, see Collin et al. (2001). For antitumor effects of thalidomide analogs, see Ng et al. (2004).

Experimental top

Compound (I) was synthesized by coupling tetraflurophthalic anhydride (1 g, 4.54 mmol) and 2,4-difluoroaniline (0.59 g, 4.54 mmol) using 4-dimethylaminopyridine (56 mg, 0.454 mmol) as the catalyst and dry dichloromethane (10 ml) as the solvent. The mixture was stirred at ambient temperature for 72 h. After evaporation of the solvent, the reaction mixture was partitioned between ethyl acetate and 2 N HCl. The aqueous phase was then extracted twice more with ethyl acetate. The combined extracts were evaporated to a solid in vacuo. The solid was treated with diethyl ether at room temperature and the undissolved residue was discarded. The remaining solution was evaporated to give a white powder, which was recrystallized from hexane.

Structure description top

For the synthesis of a related structure, see Collin et al. (2001). For antitumor effects of thalidomide analogs, see Ng et al. (2004).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Version 2.2; Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top

	Fig. 1. The asymmetric unit of (I) with displacment ellipsoids at the 50% probability level.
	Fig. 2. An overlay of the amide groups of molecules A (green) and B (blue) with an r.m.s. deviation of 0.0149 Å.
	Fig. 3. Hydrogen bonding interactions (blue dotted lines; red dotted lines indicate hydrogen bonding continuation) in (I).
	Fig. 4. A b-axis projection of the crystal packing in (I). The colour scheme is that used in Figure 2.

2-[N-(2,4-Difluorophenyl)carbamoyl]-3,4,5,6-tetrafluorobenzoic acid top

Crystal data top

C₁₄H₅F₆NO₃	Z = 4
M_r = 349.19	F(000) = 696
Triclinic, P1	D_x = 1.795 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 7.5293 (4) Å	Cell parameters from 617 reflections
b = 7.6795 (5) Å	θ = 3.7–56.9°
c = 24.1969 (15) Å	µ = 1.65 mm⁻¹
α = 89.809 (5)°	T = 100 K
β = 82.747 (4)°	Prism, colorless
γ = 68.712 (4)°	0.27 × 0.19 × 0.09 mm
V = 1291.83 (13) Å³

Data collection top

Bruker Kappa APEXII DUO CCD diffractometer	3296 independent reflections
Radiation source: microsource	2467 reflections with I > 2σ(I)
Silicon monochromator	R_int = 0.074
φ and ω scans	θ_max = 58.5°, θ_min = 1.8°
Absorption correction: multi-scan (TWINABS; Sheldrick, 1996)	h = −8→8
T_min = 0.664, T_max = 0.868	k = −8→8
7781 measured reflections	l = 0→26

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.182	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.1222P)²] where P = (F_o² + 2F_c²)/3
3296 reflections	(Δ/σ)_max < 0.001
434 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₁₄H₅F₆NO₃	γ = 68.712 (4)°
M_r = 349.19	V = 1291.83 (13) Å³
Triclinic, P1	Z = 4
a = 7.5293 (4) Å	Cu Kα radiation
b = 7.6795 (5) Å	µ = 1.65 mm⁻¹
c = 24.1969 (15) Å	T = 100 K
α = 89.809 (5)°	0.27 × 0.19 × 0.09 mm
β = 82.747 (4)°

Data collection top

Bruker Kappa APEXII DUO CCD diffractometer	3296 independent reflections
Absorption correction: multi-scan (TWINABS; Sheldrick, 1996)	2467 reflections with I > 2σ(I)
T_min = 0.664, T_max = 0.868	R_int = 0.074
7781 measured reflections	θ_max = 58.5°

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.182	H-atom parameters constrained
S = 0.99	Δρ_max = 0.40 e Å⁻³
3296 reflections	Δρ_min = −0.43 e Å⁻³
434 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
F1	0.6312 (6)	0.7940 (5)	0.07802 (17)	0.0314 (10)
F2	0.5202 (6)	0.7903 (6)	0.18695 (17)	0.0342 (11)
F3	0.5293 (7)	0.4660 (6)	0.23442 (17)	0.0380 (12)
F4	0.6469 (7)	0.1469 (6)	0.17134 (17)	0.0368 (11)
F5	0.8026 (6)	0.3185 (6)	−0.11126 (18)	0.0310 (10)
F6	0.9832 (7)	0.7035 (7)	−0.23925 (18)	0.0441 (13)
O1	0.9457 (6)	0.3317 (6)	−0.0108 (2)	0.0233 (11)
O2	0.6865 (7)	0.1123 (7)	0.01592 (19)	0.0252 (12)
O3	0.9119 (7)	−0.0116 (6)	0.0722 (2)	0.0279 (12)
H3	0.9411	−0.1078	0.0513	0.034*
N1	0.6934 (8)	0.5969 (8)	−0.0258 (2)	0.0208 (13)
H1	0.5782	0.6737	−0.0115	0.025*
C1	0.7927 (10)	0.4594 (10)	0.0057 (3)	0.0221 (17)
C2	0.7033 (10)	0.4683 (10)	0.0659 (3)	0.0233 (17)
C3	0.6390 (10)	0.6307 (10)	0.0997 (3)	0.0252 (17)
C4	0.5817 (10)	0.6302 (10)	0.1557 (3)	0.0257 (17)
C5	0.5853 (11)	0.4681 (11)	0.1803 (3)	0.0270 (18)
C6	0.6523 (11)	0.3034 (10)	0.1465 (3)	0.0289 (19)
C7	0.7083 (10)	0.3010 (10)	0.0908 (3)	0.0210 (16)
C8	0.7685 (10)	0.1238 (10)	0.0551 (3)	0.0229 (16)
C9	0.7661 (10)	0.6233 (10)	−0.0807 (3)	0.0216 (16)
C10	0.8250 (11)	0.4836 (10)	−0.1232 (3)	0.0285 (18)
C11	0.8983 (11)	0.5061 (10)	−0.1755 (3)	0.0288 (18)
H11	0.9396	0.4074	−0.2032	0.035*
C12	0.9107 (11)	0.6748 (12)	−0.1869 (3)	0.032 (2)
C13	0.8517 (11)	0.8235 (11)	−0.1472 (3)	0.0289 (18)
H13	0.8582	0.9414	−0.1566	0.035*
C14	0.7839 (11)	0.7933 (11)	−0.0938 (3)	0.0285 (18)
H14	0.7487	0.8899	−0.0655	0.034*
F51	0.7042 (6)	0.2634 (6)	0.41888 (17)	0.0305 (10)
F52	0.6881 (7)	0.2199 (6)	0.31022 (18)	0.0402 (12)
F53	0.7306 (6)	−0.1187 (6)	0.26531 (18)	0.0383 (11)
F54	0.7893 (7)	−0.4145 (6)	0.33004 (18)	0.0350 (11)
F55	0.6962 (6)	−0.1608 (5)	0.60603 (17)	0.0311 (11)
F56	0.8200 (6)	0.2169 (6)	0.73646 (18)	0.0413 (12)
O51	0.9354 (7)	−0.1677 (7)	0.5081 (2)	0.0264 (12)
O52	0.6925 (7)	−0.3957 (7)	0.4849 (2)	0.0259 (12)
O53	0.9737 (7)	−0.5342 (6)	0.4286 (2)	0.0279 (12)
H53	0.9875	−0.6255	0.4491	0.034*
N51	0.6738 (9)	0.1005 (8)	0.5249 (2)	0.0251 (14)
H51	0.5713	0.1778	0.5119	0.030*
C51	0.7952 (11)	−0.0447 (10)	0.4919 (3)	0.0245 (17)
C52	0.7609 (10)	−0.0563 (10)	0.4324 (3)	0.0253 (17)
C53	0.7284 (11)	0.0938 (10)	0.3988 (3)	0.0269 (17)
C54	0.7213 (11)	0.0727 (10)	0.3424 (3)	0.0270 (18)
C55	0.7409 (11)	−0.1006 (11)	0.3196 (3)	0.0268 (18)
C56	0.7748 (10)	−0.2496 (10)	0.3531 (3)	0.0236 (17)
C57	0.7811 (10)	−0.2303 (10)	0.4091 (3)	0.0221 (17)
C58	0.8084 (11)	−0.3979 (10)	0.4460 (3)	0.0246 (17)
C59	0.7037 (11)	0.1344 (10)	0.5794 (3)	0.0272 (18)
C60	0.7205 (10)	0.0006 (10)	0.6193 (3)	0.0252 (17)
C61	0.7593 (11)	0.0240 (11)	0.6723 (3)	0.0307 (18)
H61	0.7755	−0.0707	0.6986	0.037*
C62	0.7733 (12)	0.1938 (11)	0.6849 (3)	0.032 (2)
C63	0.7495 (11)	0.3315 (11)	0.6487 (3)	0.0299 (19)
H63	0.7575	0.4470	0.6595	0.036*
C64	0.7138 (11)	0.3034 (11)	0.5961 (3)	0.0300 (18)
H64	0.6955	0.4007	0.5706	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.040 (3)	0.024 (2)	0.032 (2)	−0.014 (2)	−0.003 (2)	−0.0027 (19)
F2	0.040 (3)	0.029 (2)	0.032 (2)	−0.010 (2)	−0.005 (2)	−0.006 (2)
F3	0.047 (3)	0.033 (3)	0.022 (2)	−0.002 (2)	−0.001 (2)	0.0010 (19)
F4	0.052 (3)	0.021 (2)	0.032 (2)	−0.008 (2)	−0.002 (2)	0.0045 (19)
F5	0.029 (2)	0.027 (2)	0.038 (3)	−0.010 (2)	−0.013 (2)	0.0016 (19)
F6	0.052 (3)	0.051 (3)	0.023 (2)	−0.016 (2)	0.006 (2)	0.007 (2)
O1	0.015 (3)	0.018 (3)	0.034 (3)	−0.002 (2)	−0.005 (2)	−0.006 (2)
O2	0.024 (3)	0.027 (3)	0.028 (3)	−0.013 (2)	−0.003 (2)	−0.003 (2)
O3	0.035 (3)	0.014 (3)	0.033 (3)	−0.004 (2)	−0.015 (2)	−0.001 (2)
N1	0.005 (3)	0.024 (3)	0.031 (3)	−0.001 (2)	−0.009 (3)	0.005 (3)
C1	0.027 (4)	0.019 (4)	0.030 (4)	−0.016 (4)	−0.011 (3)	−0.001 (3)
C2	0.019 (4)	0.033 (4)	0.029 (4)	−0.020 (3)	−0.009 (3)	0.001 (3)
C3	0.016 (4)	0.018 (4)	0.038 (4)	−0.003 (3)	−0.005 (4)	0.001 (3)
C4	0.027 (4)	0.029 (4)	0.025 (4)	−0.013 (3)	−0.007 (3)	−0.007 (3)
C5	0.024 (4)	0.025 (4)	0.029 (4)	−0.004 (3)	−0.009 (3)	0.000 (3)
C6	0.030 (4)	0.022 (4)	0.036 (5)	−0.009 (4)	−0.009 (4)	0.015 (4)
C7	0.016 (4)	0.024 (4)	0.024 (4)	−0.008 (3)	−0.006 (3)	0.004 (3)
C8	0.023 (4)	0.028 (4)	0.021 (4)	−0.014 (3)	−0.001 (3)	0.002 (3)
C9	0.015 (4)	0.026 (4)	0.022 (4)	−0.004 (3)	−0.008 (3)	0.002 (3)
C10	0.031 (4)	0.026 (4)	0.031 (4)	−0.012 (4)	−0.005 (4)	0.005 (3)
C11	0.031 (4)	0.018 (4)	0.031 (4)	−0.002 (3)	−0.004 (4)	−0.005 (3)
C12	0.024 (4)	0.044 (5)	0.025 (4)	−0.009 (4)	−0.003 (3)	0.003 (4)
C13	0.027 (4)	0.024 (4)	0.038 (5)	−0.009 (3)	−0.011 (4)	0.012 (4)
C14	0.032 (4)	0.032 (4)	0.028 (4)	−0.015 (4)	−0.014 (3)	0.006 (4)
F51	0.035 (2)	0.022 (2)	0.036 (2)	−0.0108 (19)	−0.010 (2)	0.0055 (19)
F52	0.052 (3)	0.035 (3)	0.034 (3)	−0.015 (2)	−0.011 (2)	0.013 (2)
F53	0.047 (3)	0.042 (3)	0.027 (2)	−0.017 (2)	−0.007 (2)	0.005 (2)
F54	0.042 (3)	0.026 (2)	0.035 (3)	−0.007 (2)	−0.011 (2)	−0.005 (2)
F55	0.036 (2)	0.018 (2)	0.039 (3)	−0.010 (2)	0.000 (2)	0.0043 (19)
F56	0.036 (3)	0.051 (3)	0.036 (3)	−0.015 (2)	−0.007 (2)	−0.008 (2)
O51	0.031 (3)	0.019 (3)	0.031 (3)	−0.011 (3)	−0.006 (2)	0.001 (2)
O52	0.024 (3)	0.021 (3)	0.033 (3)	−0.008 (2)	−0.001 (3)	0.005 (2)
O53	0.023 (3)	0.020 (3)	0.041 (3)	−0.008 (2)	−0.004 (2)	0.009 (2)
N51	0.024 (3)	0.022 (3)	0.027 (3)	−0.005 (3)	−0.009 (3)	0.002 (3)
C51	0.029 (4)	0.024 (4)	0.028 (4)	−0.016 (4)	−0.009 (4)	0.010 (3)
C52	0.019 (4)	0.026 (4)	0.030 (4)	−0.006 (3)	−0.005 (3)	−0.002 (3)
C53	0.021 (4)	0.024 (4)	0.036 (5)	−0.008 (3)	−0.005 (4)	0.005 (4)
C54	0.022 (4)	0.024 (4)	0.033 (4)	−0.007 (3)	−0.005 (3)	0.018 (4)
C55	0.018 (4)	0.033 (5)	0.025 (4)	−0.002 (3)	−0.006 (3)	0.003 (4)
C56	0.018 (4)	0.026 (4)	0.032 (4)	−0.013 (3)	−0.007 (3)	−0.001 (4)
C57	0.014 (4)	0.022 (4)	0.028 (4)	−0.005 (3)	−0.003 (3)	0.006 (3)
C58	0.021 (4)	0.014 (4)	0.038 (5)	−0.003 (3)	−0.011 (4)	−0.001 (3)
C59	0.024 (4)	0.027 (4)	0.026 (4)	−0.004 (3)	−0.003 (3)	0.008 (3)
C60	0.015 (4)	0.018 (4)	0.041 (5)	−0.004 (3)	−0.005 (3)	−0.001 (3)
C61	0.031 (4)	0.028 (4)	0.028 (4)	−0.005 (3)	−0.004 (3)	0.003 (3)
C62	0.033 (5)	0.029 (5)	0.025 (4)	−0.001 (4)	−0.003 (4)	−0.003 (4)
C63	0.032 (5)	0.026 (4)	0.033 (4)	−0.011 (4)	−0.005 (4)	−0.003 (4)
C64	0.029 (4)	0.025 (4)	0.036 (5)	−0.010 (4)	−0.004 (4)	0.006 (4)

Geometric parameters (Å, º) top

F1—C3	1.342 (8)	F51—C53	1.332 (8)
F2—C4	1.342 (8)	F52—C54	1.336 (8)
F3—C5	1.326 (8)	F53—C55	1.337 (9)
F4—C6	1.353 (8)	F54—C56	1.348 (8)
F5—C10	1.364 (8)	F55—C60	1.361 (8)
F6—C12	1.365 (9)	F56—C62	1.367 (9)
O1—C1	1.230 (9)	O51—C51	1.240 (8)
O2—C8	1.214 (8)	O52—C58	1.195 (9)
O3—H3	0.840	O53—H53	0.840
O3—C8	1.309 (8)	O53—C58	1.321 (9)
N1—H1	0.880	N51—H51	0.880
N1—C1	1.349 (9)	N51—C51	1.341 (10)
N1—C9	1.416 (9)	N51—C59	1.405 (10)
C1—C2	1.517 (10)	C51—C52	1.504 (10)
C2—C3	1.388 (10)	C52—C53	1.375 (11)
C2—C7	1.408 (10)	C52—C57	1.401 (10)
C3—C4	1.369 (10)	C53—C54	1.384 (11)
C4—C5	1.371 (11)	C54—C55	1.393 (11)
C5—C6	1.400 (11)	C55—C56	1.366 (11)
C6—C7	1.359 (11)	C56—C57	1.371 (11)
C7—C8	1.506 (10)	C57—C58	1.532 (10)
C9—C10	1.396 (11)	C59—C60	1.390 (10)
C9—C14	1.391 (10)	C59—C64	1.391 (11)
C10—C11	1.351 (10)	C60—C61	1.378 (11)
C11—H11	0.950	C61—H61	0.950
C11—C12	1.357 (11)	C61—C62	1.383 (11)
C12—C13	1.399 (11)	C62—C63	1.348 (11)
C13—H13	0.950	C63—H63	0.950
C13—C14	1.378 (11)	C63—C64	1.366 (11)
C14—H14	0.950	C64—H64	0.950

H3—O3—C8	109.5	H53—O53—C58	109.5
H1—N1—C1	118.5	H51—N51—C51	118.6
H1—N1—C9	118.5	H51—N51—C59	118.6
C1—N1—C9	123.0 (6)	C51—N51—C59	122.7 (6)
O1—C1—N1	125.2 (7)	O51—C51—N51	122.9 (6)
O1—C1—C2	119.4 (6)	O51—C51—C52	118.8 (7)
N1—C1—C2	115.4 (6)	N51—C51—C52	118.2 (6)
C1—C2—C3	122.6 (6)	C51—C52—C53	122.1 (7)
C1—C2—C7	118.8 (6)	C51—C52—C57	118.6 (6)
C3—C2—C7	118.1 (7)	C53—C52—C57	119.0 (7)
F1—C3—C2	120.4 (7)	F51—C53—C52	121.6 (6)
F1—C3—C4	118.0 (6)	F51—C53—C54	117.7 (7)
C2—C3—C4	121.6 (7)	C52—C53—C54	120.7 (7)
F2—C4—C3	119.8 (6)	F52—C54—C53	120.1 (7)
F2—C4—C5	119.4 (6)	F52—C54—C55	119.9 (7)
C3—C4—C5	120.8 (7)	C53—C54—C55	119.9 (7)
F3—C5—C4	121.4 (7)	F53—C55—C54	119.4 (7)
F3—C5—C6	120.7 (7)	F53—C55—C56	121.4 (7)
C4—C5—C6	117.9 (7)	C54—C55—C56	119.1 (7)
F4—C6—C5	116.7 (7)	F54—C56—C55	117.6 (6)
F4—C6—C7	120.9 (7)	F54—C56—C57	120.8 (7)
C5—C6—C7	122.3 (7)	C55—C56—C57	121.5 (7)
C2—C7—C6	119.4 (7)	C52—C57—C56	119.8 (7)
C2—C7—C8	119.5 (6)	C52—C57—C58	120.1 (6)
C6—C7—C8	121.0 (6)	C56—C57—C58	120.1 (7)
O2—C8—O3	125.7 (7)	O52—C58—O53	127.9 (7)
O2—C8—C7	122.0 (6)	O52—C58—C57	122.0 (7)
O3—C8—C7	112.3 (6)	O53—C58—C57	110.1 (7)
N1—C9—C10	122.7 (6)	N51—C59—C60	120.9 (7)
N1—C9—C14	119.7 (6)	N51—C59—C64	121.8 (7)
C10—C9—C14	117.5 (7)	C60—C59—C64	117.2 (7)
F5—C10—C9	118.0 (6)	F55—C60—C59	119.2 (6)
F5—C10—C11	118.8 (6)	F55—C60—C61	117.9 (7)
C9—C10—C11	123.2 (7)	C59—C60—C61	122.9 (7)
C10—C11—H11	121.2	C60—C61—H61	122.0
C10—C11—C12	117.6 (7)	C60—C61—C62	116.0 (7)
H11—C11—C12	121.2	H61—C61—C62	122.0
F6—C12—C11	119.5 (7)	F56—C62—C61	117.0 (7)
F6—C12—C13	117.6 (7)	F56—C62—C63	119.6 (7)
C11—C12—C13	122.9 (7)	C61—C62—C63	123.4 (7)
C12—C13—H13	121.1	C62—C63—H63	120.4
C12—C13—C14	117.8 (7)	C62—C63—C64	119.3 (7)
H13—C13—C14	121.1	H63—C63—C64	120.4
C9—C14—C13	120.9 (7)	C59—C64—C63	121.0 (7)
C9—C14—H14	119.6	C59—C64—H64	119.5
C13—C14—H14	119.6	C63—C64—H64	119.5

C9—N1—C1—O1	−7.7 (10)	C59—N51—C51—O51	5.3 (11)
C9—N1—C1—C2	172.3 (6)	C59—N51—C51—C52	−173.6 (6)
O1—C1—C2—C3	131.0 (7)	O51—C51—C52—C53	−130.4 (8)
O1—C1—C2—C7	−40.5 (9)	O51—C51—C52—C57	43.4 (10)
N1—C1—C2—C3	−49.0 (8)	N51—C51—C52—C53	48.5 (10)
N1—C1—C2—C7	139.5 (6)	N51—C51—C52—C57	−137.7 (7)
C1—C2—C3—F1	8.5 (10)	C51—C52—C53—F51	−7.6 (11)
C1—C2—C3—C4	−171.5 (7)	C51—C52—C53—C54	171.8 (7)
C7—C2—C3—F1	−180.0 (6)	C57—C52—C53—F51	178.6 (6)
C7—C2—C3—C4	0.0 (11)	C57—C52—C53—C54	−2.0 (12)
F1—C3—C4—F2	0.0 (10)	F51—C53—C54—F52	−1.1 (11)
F1—C3—C4—C5	179.7 (6)	F51—C53—C54—C55	−178.4 (6)
C2—C3—C4—F2	−180.0 (6)	C52—C53—C54—F52	179.5 (7)
C2—C3—C4—C5	−0.3 (11)	C52—C53—C54—C55	2.2 (12)
F2—C4—C5—F3	0.0 (11)	F52—C54—C55—F53	1.6 (11)
F2—C4—C5—C6	−179.3 (6)	F52—C54—C55—C56	−180.0 (7)
C3—C4—C5—F3	−179.7 (6)	C53—C54—C55—F53	178.9 (7)
C3—C4—C5—C6	1.1 (11)	C53—C54—C55—C56	−2.7 (11)
F3—C5—C6—F4	3.4 (10)	F53—C55—C56—F54	−2.8 (11)
F3—C5—C6—C7	179.1 (7)	F53—C55—C56—C57	−178.5 (6)
C4—C5—C6—F4	−177.4 (6)	C54—C55—C56—F54	178.8 (6)
C4—C5—C6—C7	−1.6 (11)	C54—C55—C56—C57	3.1 (11)
F4—C6—C7—C2	176.9 (6)	F54—C56—C57—C52	−178.4 (6)
F4—C6—C7—C8	−0.8 (11)	F54—C56—C57—C58	1.1 (10)
C5—C6—C7—C2	1.4 (11)	C55—C56—C57—C52	−2.9 (11)
C5—C6—C7—C8	−176.3 (7)	C55—C56—C57—C58	176.6 (7)
C1—C2—C7—C6	171.3 (6)	C51—C52—C57—C56	−171.7 (6)
C1—C2—C7—C8	−11.0 (9)	C51—C52—C57—C58	8.7 (10)
C3—C2—C7—C6	−0.6 (10)	C53—C52—C57—C56	2.3 (11)
C3—C2—C7—C8	177.2 (6)	C53—C52—C57—C58	−177.2 (7)
C2—C7—C8—O2	−57.0 (9)	C52—C57—C58—O52	59.1 (10)
C2—C7—C8—O3	124.7 (7)	C52—C57—C58—O53	−119.9 (7)
C6—C7—C8—O2	120.8 (8)	C56—C57—C58—O52	−120.4 (8)
C6—C7—C8—O3	−57.6 (9)	C56—C57—C58—O53	60.5 (9)
C1—N1—C9—C10	57.0 (9)	C51—N51—C59—C60	−57.9 (10)
C1—N1—C9—C14	−121.9 (7)	C51—N51—C59—C64	123.5 (8)
N1—C9—C10—F5	3.1 (10)	N51—C59—C60—F55	−3.9 (11)
N1—C9—C10—C11	−178.6 (7)	N51—C59—C60—C61	176.7 (7)
C14—C9—C10—F5	−178.0 (6)	C64—C59—C60—F55	174.8 (6)
C14—C9—C10—C11	0.3 (11)	C64—C59—C60—C61	−4.6 (11)
F5—C10—C11—C12	177.0 (6)	F55—C60—C61—C62	−176.8 (6)
C9—C10—C11—C12	−1.3 (11)	C59—C60—C61—C62	2.6 (11)
C10—C11—C12—F6	−179.7 (7)	C60—C61—C62—F56	−177.2 (7)
C10—C11—C12—C13	0.1 (11)	C60—C61—C62—C63	0.6 (12)
F6—C12—C13—C14	−178.1 (6)	F56—C62—C63—C64	176.3 (7)
C11—C12—C13—C14	2.1 (11)	C61—C62—C63—C64	−1.5 (12)
C12—C13—C14—C9	−3.1 (10)	C62—C63—C64—C59	−0.7 (12)
N1—C9—C14—C13	−179.1 (6)	N51—C59—C64—C63	−177.7 (7)
C10—C9—C14—C13	1.9 (10)	C60—C59—C64—C63	3.6 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1ⁱ	0.84	1.84	2.666 (6)	168
N1—H1···O2ⁱⁱ	0.88	2.09	2.902 (7)	154
O53—H53···O51ⁱⁱⁱ	0.84	1.84	2.675 (6)	170
N51—H51···O52^iv	0.88	2.07	2.902 (8)	157

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

Experimental details

Crystal data
Chemical formula	C₁₄H₅F₆NO₃
M_r	349.19
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.5293 (4), 7.6795 (5), 24.1969 (15)
α, β, γ (°)	89.809 (5), 82.747 (4), 68.712 (4)
V (Å³)	1291.83 (13)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.65
Crystal size (mm)	0.27 × 0.19 × 0.09

Data collection
Diffractometer	Bruker Kappa APEXII DUO CCD
Absorption correction	Multi-scan (TWINABS; Sheldrick, 1996)
T_min, T_max	0.664, 0.868
No. of measured, independent and observed [I > 2σ(I)] reflections	7781, 3296, 2467
R_int	0.074
θ_max (°)	58.5
(sin θ/λ)_max (Å⁻¹)	0.553

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.182, 0.99
No. of reflections	3296
No. of parameters	434
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.43

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Version 2.2; Macrae et al., 2008), SHELXTL (Sheldrick, 2008) and local programs.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1ⁱ	0.84	1.84	2.666 (6)	168.0
N1—H1···O2ⁱⁱ	0.88	2.09	2.902 (7)	153.5
O53—H53···O51ⁱⁱⁱ	0.84	1.84	2.675 (6)	169.6
N51—H51···O52^iv	0.88	2.07	2.902 (8)	156.6

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

Acknowledgements

We thank the National Science Foundation for funding the diffractometer purchase (grant No. CHE-0741837).

References

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