5-Amino-1-phenyl-3-trifluoro­methyl-1H-pyrazole-4-carboxylic acid

Caruso, F.; Raimondi, M.V.; Daidone, G.; Pettinari, C.; Rossi, M.

doi:10.1107/S1600536809032188

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2173

doi:10.1107/S1600536809032188

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5-Amino-1-phenyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid

Francesco Caruso,^a ^* Maria Valeria Raimondi,^b Giuseppe Daidone,^b Claudio Pettinari ^c and Miriam Rossi ^d

^aIstituto Chimica Biomolecolare CNR, Ple Aldo Moro 5, 00185 Rome, Italy, ^bDipartimento Chimica e Tecnologie Farmaceutiche, Universita di Palermo, Via Archirafi 32 90123, Palermo, Italy, ^cDipartimento Chimica, Universita di Camerino, Via Sant'Agostino 1, 62032 MC, Italy, and ^dDepartment of Chemistry, Vassar College, Poughkeepsie, NY 12604-0484, USA
^*Correspondence e-mail: caruso@vassar.edu

(Received 15 June 2009; accepted 13 August 2009; online 15 August 2009)

In the title compound, C₁₁H₈F₃N₃O₂, there are two molecules in the asymmetric unit wherein the phenyl rings make dihedral angles of 65.3 (2) and 85.6 (2)° with the pyrazole rings. In the crystal, pairs of molecules are held together by O—H⋯O hydrogen bonds between the carboxyl groups, forming a centrosymmetric dimer with an R²₂(8) motif. Intramolecular N—H⋯O interactions are also present.

Related literature

For general background, see: Caruso & Rossi (2004 ); Maggio et al., (2008 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₁H₈F₃N₃O₂
M_r = 271.20
Monoclinic, P 2₁ /n
a = 9.757 (3) Å
b = 10.740 (3) Å
c = 21.277 (6) Å
β = 93.716 (3)°
V = 2225 (1) Å³
Z = 8
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 125 K
0.30 × 0.18 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.957, T_max = 0.993
20692 measured reflections
3772 independent reflections
2737 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.140
S = 1.01
3772 reflections
368 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N53—H531⋯O52	0.85 (4)	2.20 (4)	2.808 (3)	128 (3)
O51—H51⋯O2ⁱ	0.94 (4)	1.75 (4)	2.687 (3)	177 (4)
N3—H31⋯O2	0.90 (4)	2.20 (4)	2.873 (3)	132 (3)
O1—H1⋯O52ⁱⁱ	0.91 (4)	1.67 (4)	2.580 (3)	176 (4)
Symmetry codes: (i) x, y-1, z-1; (ii) x, y+1, z+1.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809032188/bx2218sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809032188/bx2218Isup2.hkl

checkCIF report

Comment top

We report here the structure of the title compound (I), isolated during attempts to synthesize Ti(C₅H₅)₂(C₁₁H₇F₃N₃O₂)₂. In the title compound C₁₁H₈F₃N₃O₂, there are two molecules in the asymmetric unit that differ in the dihedral angle formed between the phenyl and pyrazole rings, 65.3 (2) and 85.6 (2)°. The pairs of molecules are held together by O—H···O hydrogen bonds between the carboxyl groups, forming a centrosymmetric dimer with an R²₂(8) motif, Fig. 2. (Bernstein et al., 1995) . Related compounds of this ligand show antiproliferative and apoptotic effects against K562, K562-R (imatinib mesilate resistant), HL60 and multidrug resistant HL60 cell lines (Maggio et al., 2008).

Related literature top

For general background, see: Caruso & Rossi (2004); Maggio et al., (2008). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

The synthesis of title compound has been described by Maggio et al., 2008. The title compound was reacted with titanocene dichloride, (C₅H₅)₂TiCl₂. Elemental analysis {C, 53.50, H, 3.37, N, 11.70%. Found: C, 53.66, H, 3.45, N, 11.54%} indicated formation of Cp₂Ti(ligand)₂,= Ti(C₅H₅)₂(C₁₁H₇F₃N₃O₂)₂, ligand = 5-amino-1-phenyl-3- (trifluoromethyl)-1H-pyrazole-4-carboxylate. Melting point 190–195°C. IR(nujol, cm-1): 3439w, 3332w (N—H), 3049w (Carom-H), 1661 s, 1611 s (COO), 1537 s, 1486 s (C=N + C=C). 1H NMR (CDCl₃): 5.59br (10H, Ti—C₅H₅), 6.40br, 6.60br (6H, –NH₂), 7.55 mbr (10H, Carom-H). Good solubility in chloroform, methanol, dimethylsulfoxide; lower solubilty in acetonitrile; insoluble in water. Upon recrystallization flat needles were obtained, they were studied to determine its crystal and molecular structure and revealed only the ligand. Ligand cleavage is a non unusual feature for Ti complexes that show a marked tendency to evolve towards titanium dioxide (Caruso & Rossi, 2004). The title compound synthesis has been described (Maggio et al.). Related compounds of this ligand show antiproliferative and apoptotic effects against K562, K562—R (imatinib mesilate resistant), HL60 and multidrug resistant HL60 cell lines (Maggio et al., 2008).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radii and the intramolecular hydrogen bond is shown as dashed lines.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a cyclic R²₂(8) pattern. [Symmetry code: (i) x, y + 1, z + 1].

5-Amino-1-phenyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid top

Crystal data top

C₁₁H₈F₃N₃O₂	F(000) = 1104
M_r = 271.20	D_x = 1.619 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3829 reflections
a = 9.757 (3) Å	θ = 2.2–22.3°
b = 10.740 (3) Å	µ = 0.15 mm⁻¹
c = 21.277 (6) Å	T = 125 K
β = 93.716 (3)°	Flat needle, pale yellow
V = 2225 (1) Å³	0.30 × 0.18 × 0.05 mm
Z = 8

Data collection top

Bruker APEXII CCD diffractometer	3772 independent reflections
Radiation source: fine-focus sealed tube	2737 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
ϕ and ω scans	θ_max = 24.7°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −11→11
T_min = 0.957, T_max = 0.993	k = −12→12
20692 measured reflections	l = −25→24

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.140	w = 1/[σ²(F_o²) + (0.0233P)² + 1.9621P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
3772 reflections	Δρ_max = 0.43 e Å⁻³
368 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0099 (12)

Crystal data top

C₁₁H₈F₃N₃O₂	V = 2225 (1) Å³
M_r = 271.20	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.757 (3) Å	µ = 0.15 mm⁻¹
b = 10.740 (3) Å	T = 125 K
c = 21.277 (6) Å	0.30 × 0.18 × 0.05 mm
β = 93.716 (3)°

Data collection top

Bruker APEXII CCD diffractometer	3772 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2737 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.993	R_int = 0.072
20692 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.43 e Å⁻³
3772 reflections	Δρ_min = −0.32 e Å⁻³
368 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	1.0029 (2)	0.57631 (18)	0.86748 (8)	0.0449 (5)
F2	0.88145 (19)	0.61681 (17)	0.94547 (8)	0.0402 (5)
F3	1.03719 (18)	0.74508 (17)	0.91981 (8)	0.0410 (5)
F51	0.5059 (2)	0.47366 (17)	0.12944 (8)	0.0417 (5)
F52	0.62681 (18)	0.41822 (16)	0.05332 (8)	0.0380 (5)
F53	0.43613 (17)	0.32665 (16)	0.06739 (7)	0.0361 (5)
O1	0.8071 (2)	0.8727 (2)	0.96933 (9)	0.0323 (5)
O2	0.6443 (2)	0.98989 (19)	0.91963 (9)	0.0295 (5)
O51	0.6194 (2)	0.1440 (2)	0.01774 (9)	0.0312 (5)
O52	0.7542 (2)	0.00154 (19)	0.06715 (9)	0.0343 (5)
N1	0.7329 (2)	0.7741 (2)	0.76427 (10)	0.0268 (6)
N2	0.8258 (2)	0.6935 (2)	0.79385 (10)	0.0283 (6)
N3	0.5911 (3)	0.9467 (2)	0.78704 (13)	0.0301 (6)
N51	0.7186 (2)	0.2162 (2)	0.22548 (10)	0.0263 (6)
N52	0.6454 (3)	0.3151 (2)	0.19957 (10)	0.0274 (6)
N53	0.8148 (3)	0.0243 (3)	0.19747 (13)	0.0334 (7)
C1	0.6874 (3)	0.7528 (3)	0.70017 (12)	0.0280 (7)
C2	0.6161 (3)	0.6448 (3)	0.68442 (13)	0.0307 (7)
H2	0.5971	0.5859	0.7160	0.037*
C3	0.5730 (3)	0.6233 (3)	0.62231 (13)	0.0340 (8)
H3	0.5244	0.5491	0.6111	0.041*
C4	0.6001 (3)	0.7086 (3)	0.57672 (14)	0.0385 (8)
H4	0.5702	0.6932	0.5340	0.046*
C5	0.6705 (4)	0.8163 (3)	0.59258 (14)	0.0412 (8)
H5	0.6886	0.8751	0.5608	0.049*
C6	0.7154 (3)	0.8395 (3)	0.65493 (13)	0.0350 (8)
H6	0.7643	0.9135	0.6661	0.042*
C7	0.8382 (3)	0.7328 (3)	0.85250 (13)	0.0269 (7)
C8	0.7540 (3)	0.8365 (3)	0.86272 (12)	0.0258 (7)
C9	0.6881 (3)	0.8604 (3)	0.80423 (12)	0.0253 (6)
C10	0.7303 (3)	0.9061 (3)	0.91922 (13)	0.0265 (7)
C11	0.9388 (3)	0.6684 (3)	0.89644 (14)	0.0333 (7)
C51	0.7711 (3)	0.2189 (3)	0.28986 (12)	0.0258 (7)
C52	0.6897 (3)	0.1791 (3)	0.33664 (13)	0.0303 (7)
H52	0.5997	0.1485	0.3264	0.036*
C53	0.7412 (3)	0.1847 (3)	0.39859 (14)	0.0341 (7)
H53	0.6865	0.1572	0.4313	0.041*
C54	0.8717 (3)	0.2301 (3)	0.41322 (13)	0.0344 (8)
H54	0.9060	0.2352	0.4560	0.041*
C55	0.9524 (3)	0.2681 (3)	0.36596 (14)	0.0343 (7)
H55	1.0429	0.2976	0.3761	0.041*
C56	0.9021 (3)	0.2632 (3)	0.30386 (14)	0.0319 (7)
H56	0.9570	0.2901	0.2712	0.038*
C57	0.6225 (3)	0.2847 (3)	0.13997 (12)	0.0253 (6)
C58	0.6793 (3)	0.1676 (3)	0.12543 (12)	0.0256 (7)
C59	0.7408 (3)	0.1272 (3)	0.18279 (12)	0.0262 (7)
C60	0.6867 (3)	0.0985 (3)	0.06813 (13)	0.0277 (7)
C61	0.5484 (3)	0.3755 (3)	0.09757 (13)	0.0286 (7)
H1	0.792 (4)	0.918 (4)	1.004 (2)	0.076 (14)*
H30	0.597 (4)	0.987 (4)	0.748 (2)	0.066 (12)*
H31	0.579 (4)	1.000 (3)	0.8190 (17)	0.047 (10)*
H51	0.628 (4)	0.087 (4)	−0.0156 (19)	0.067 (12)*
H530	0.830 (3)	0.001 (3)	0.2381 (17)	0.041 (9)*
H531	0.807 (4)	−0.029 (3)	0.1682 (18)	0.047 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0527 (12)	0.0511 (12)	0.0302 (10)	0.0212 (10)	−0.0019 (8)	−0.0080 (8)
F2	0.0541 (12)	0.0421 (11)	0.0240 (9)	0.0044 (9)	0.0002 (8)	0.0061 (8)
F3	0.0383 (11)	0.0534 (12)	0.0302 (10)	−0.0014 (9)	−0.0061 (8)	−0.0047 (8)
F51	0.0600 (12)	0.0355 (11)	0.0290 (10)	0.0142 (9)	−0.0017 (9)	−0.0026 (8)
F52	0.0473 (11)	0.0392 (11)	0.0280 (9)	−0.0021 (9)	0.0055 (8)	0.0098 (8)
F53	0.0368 (10)	0.0450 (11)	0.0255 (9)	0.0005 (8)	−0.0054 (8)	0.0025 (8)
O1	0.0468 (13)	0.0355 (13)	0.0141 (10)	0.0050 (10)	−0.0018 (9)	−0.0034 (9)
O2	0.0381 (12)	0.0312 (12)	0.0191 (10)	0.0040 (10)	0.0009 (8)	−0.0016 (8)
O51	0.0446 (13)	0.0341 (12)	0.0145 (10)	0.0059 (10)	−0.0013 (9)	−0.0016 (9)
O52	0.0547 (14)	0.0304 (12)	0.0171 (10)	0.0095 (11)	−0.0016 (9)	−0.0027 (8)
N1	0.0323 (14)	0.0339 (14)	0.0140 (11)	0.0015 (11)	−0.0012 (10)	−0.0020 (10)
N2	0.0310 (14)	0.0353 (15)	0.0184 (12)	0.0013 (11)	−0.0004 (10)	−0.0021 (10)
N3	0.0386 (15)	0.0329 (15)	0.0187 (13)	0.0037 (12)	0.0008 (11)	−0.0015 (12)
N51	0.0364 (14)	0.0264 (13)	0.0158 (12)	0.0009 (11)	−0.0012 (10)	−0.0018 (10)
N52	0.0363 (14)	0.0285 (14)	0.0169 (12)	0.0022 (11)	−0.0016 (10)	−0.0004 (10)
N53	0.0501 (17)	0.0324 (16)	0.0170 (14)	0.0067 (13)	−0.0026 (12)	−0.0009 (12)
C1	0.0320 (16)	0.0357 (18)	0.0162 (14)	0.0050 (14)	0.0012 (12)	−0.0017 (12)
C2	0.0316 (16)	0.0389 (19)	0.0212 (15)	0.0045 (14)	−0.0010 (12)	−0.0017 (13)
C3	0.0328 (17)	0.042 (2)	0.0268 (16)	0.0037 (15)	−0.0016 (13)	−0.0096 (14)
C4	0.0422 (19)	0.051 (2)	0.0219 (16)	0.0123 (16)	−0.0039 (14)	−0.0082 (15)
C5	0.052 (2)	0.050 (2)	0.0224 (16)	0.0114 (17)	0.0047 (14)	0.0059 (15)
C6	0.0403 (18)	0.0407 (19)	0.0243 (16)	0.0009 (15)	0.0036 (13)	−0.0014 (14)
C7	0.0329 (16)	0.0304 (17)	0.0172 (14)	−0.0030 (13)	0.0007 (12)	0.0010 (12)
C8	0.0346 (16)	0.0274 (16)	0.0153 (14)	−0.0040 (13)	0.0015 (12)	−0.0009 (12)
C9	0.0300 (16)	0.0262 (16)	0.0200 (14)	−0.0032 (13)	0.0029 (12)	−0.0019 (12)
C10	0.0352 (17)	0.0258 (16)	0.0183 (14)	−0.0067 (14)	0.0000 (12)	0.0012 (12)
C11	0.0389 (18)	0.0370 (18)	0.0236 (16)	0.0012 (15)	−0.0002 (13)	−0.0021 (14)
C51	0.0333 (16)	0.0267 (16)	0.0169 (14)	0.0001 (13)	−0.0028 (12)	−0.0021 (12)
C52	0.0317 (16)	0.0367 (18)	0.0227 (15)	0.0003 (14)	0.0030 (12)	0.0007 (13)
C53	0.0415 (19)	0.0408 (19)	0.0205 (15)	0.0057 (15)	0.0055 (13)	0.0016 (13)
C54	0.0443 (19)	0.0393 (19)	0.0185 (15)	0.0069 (15)	−0.0074 (13)	−0.0042 (13)
C55	0.0364 (18)	0.0350 (19)	0.0307 (17)	−0.0008 (14)	−0.0047 (14)	−0.0044 (14)
C56	0.0370 (18)	0.0348 (18)	0.0242 (16)	−0.0050 (14)	0.0049 (13)	−0.0027 (13)
C57	0.0336 (16)	0.0254 (16)	0.0168 (14)	−0.0027 (13)	0.0006 (12)	−0.0002 (12)
C58	0.0360 (17)	0.0243 (16)	0.0164 (14)	−0.0035 (13)	0.0021 (12)	−0.0008 (11)
C59	0.0318 (16)	0.0280 (17)	0.0191 (14)	−0.0014 (13)	0.0036 (12)	−0.0015 (12)
C60	0.0362 (17)	0.0297 (18)	0.0170 (15)	−0.0045 (14)	0.0001 (12)	−0.0013 (12)
C61	0.0359 (17)	0.0289 (17)	0.0209 (15)	0.0004 (13)	0.0015 (13)	−0.0048 (12)

Geometric parameters (Å, º) top

F1—C11	1.341 (3)	C2—C3	1.380 (4)
F2—C11	1.336 (3)	C2—H2	0.9500
F3—C11	1.336 (4)	C3—C4	1.372 (5)
F51—C61	1.335 (3)	C3—H3	0.9500
F52—C61	1.333 (3)	C4—C5	1.376 (5)
F53—C61	1.340 (3)	C4—H4	0.9500
O1—C10	1.313 (3)	C5—C6	1.392 (4)
O1—H1	0.91 (4)	C5—H5	0.9500
O2—C10	1.231 (3)	C6—H6	0.9500
O51—C60	1.315 (3)	C7—C8	1.410 (4)
O51—H51	0.94 (4)	C7—C11	1.482 (4)
O52—C60	1.232 (4)	C8—C9	1.387 (4)
N1—C9	1.350 (4)	C8—C10	1.447 (4)
N1—N2	1.376 (3)	C51—C56	1.379 (4)
N1—C1	1.425 (3)	C51—C52	1.380 (4)
N2—C7	1.316 (4)	C52—C53	1.381 (4)
N3—C9	1.358 (4)	C52—H52	0.9500
N3—H30	0.95 (4)	C53—C54	1.381 (5)
N3—H31	0.90 (4)	C53—H53	0.9500
N51—C59	1.346 (4)	C54—C55	1.378 (4)
N51—N52	1.376 (3)	C54—H54	0.9500
N51—C51	1.431 (3)	C55—C56	1.380 (4)
N52—C57	1.315 (3)	C55—H55	0.9500
N53—C59	1.346 (4)	C56—H56	0.9500
N53—H530	0.90 (3)	C57—C58	1.416 (4)
N53—H531	0.85 (4)	C57—C61	1.484 (4)
C1—C6	1.379 (4)	C58—C59	1.393 (4)
C1—C2	1.383 (4)	C58—C60	1.433 (4)

C10—O1—H1	114 (3)	O2—C10—C8	121.9 (3)
C60—O51—H51	108 (2)	O1—C10—C8	114.9 (3)
C9—N1—N2	112.0 (2)	F2—C11—F3	107.0 (2)
C9—N1—C1	128.2 (2)	F2—C11—F1	106.6 (2)
N2—N1—C1	119.5 (2)	F3—C11—F1	106.3 (2)
C7—N2—N1	104.4 (2)	F2—C11—C7	113.1 (3)
C9—N3—H30	118 (2)	F3—C11—C7	112.2 (3)
C9—N3—H31	110 (2)	F1—C11—C7	111.3 (2)
H30—N3—H31	114 (3)	C56—C51—C52	121.3 (3)
C59—N51—N52	112.3 (2)	C56—C51—N51	118.9 (3)
C59—N51—C51	126.7 (2)	C52—C51—N51	119.8 (3)
N52—N51—C51	120.8 (2)	C51—C52—C53	119.0 (3)
C57—N52—N51	104.2 (2)	C51—C52—H52	120.5
C59—N53—H530	120 (2)	C53—C52—H52	120.5
C59—N53—H531	111 (2)	C54—C53—C52	120.2 (3)
H530—N53—H531	121 (3)	C54—C53—H53	119.9
C6—C1—C2	121.1 (3)	C52—C53—H53	119.9
C6—C1—N1	119.8 (3)	C55—C54—C53	120.2 (3)
C2—C1—N1	119.1 (3)	C55—C54—H54	119.9
C3—C2—C1	119.3 (3)	C53—C54—H54	119.9
C3—C2—H2	120.3	C54—C55—C56	120.2 (3)
C1—C2—H2	120.3	C54—C55—H55	119.9
C4—C3—C2	120.3 (3)	C56—C55—H55	119.9
C4—C3—H3	119.9	C51—C56—C55	119.2 (3)
C2—C3—H3	119.9	C51—C56—H56	120.4
C3—C4—C5	120.3 (3)	C55—C56—H56	120.4
C3—C4—H4	119.9	N52—C57—C58	112.8 (2)
C5—C4—H4	119.9	N52—C57—C61	117.9 (2)
C4—C5—C6	120.3 (3)	C58—C57—C61	129.2 (2)
C4—C5—H5	119.8	C59—C58—C57	103.7 (2)
C6—C5—H5	119.8	C59—C58—C60	122.8 (3)
C1—C6—C5	118.7 (3)	C57—C58—C60	133.5 (3)
C1—C6—H6	120.6	N51—C59—N53	122.3 (3)
C5—C6—H6	120.6	N51—C59—C58	107.0 (2)
N2—C7—C8	112.4 (2)	N53—C59—C58	130.7 (3)
N2—C7—C11	117.7 (3)	O52—C60—O51	122.6 (3)
C8—C7—C11	129.8 (3)	O52—C60—C58	120.5 (3)
C9—C8—C7	104.4 (2)	O51—C60—C58	116.8 (3)
C9—C8—C10	124.1 (3)	F52—C61—F51	107.4 (2)
C7—C8—C10	131.5 (3)	F52—C61—F53	106.6 (2)
N1—C9—N3	123.2 (3)	F51—C61—F53	106.3 (2)
N1—C9—C8	106.7 (2)	F52—C61—C57	112.1 (2)
N3—C9—C8	130.0 (3)	F51—C61—C57	111.5 (2)
O2—C10—O1	123.2 (3)	F53—C61—C57	112.7 (2)

C9—N1—N2—C7	−0.7 (3)	N2—C7—C11—F1	−0.1 (4)
C1—N1—N2—C7	−175.4 (2)	C8—C7—C11—F1	−177.2 (3)
C59—N51—N52—C57	0.2 (3)	C59—N51—C51—C56	83.1 (4)
C51—N51—N52—C57	175.8 (2)	N52—N51—C51—C56	−91.7 (3)
C9—N1—C1—C6	69.0 (4)	C59—N51—C51—C52	−97.9 (4)
N2—N1—C1—C6	−117.2 (3)	N52—N51—C51—C52	87.3 (3)
C9—N1—C1—C2	−111.3 (3)	C56—C51—C52—C53	0.3 (5)
N2—N1—C1—C2	62.5 (4)	N51—C51—C52—C53	−178.7 (3)
C6—C1—C2—C3	0.3 (4)	C51—C52—C53—C54	0.4 (5)
N1—C1—C2—C3	−179.4 (3)	C52—C53—C54—C55	−1.2 (5)
C1—C2—C3—C4	−0.3 (4)	C53—C54—C55—C56	1.3 (5)
C2—C3—C4—C5	0.0 (5)	C52—C51—C56—C55	−0.1 (5)
C3—C4—C5—C6	0.3 (5)	N51—C51—C56—C55	178.9 (3)
C2—C1—C6—C5	0.0 (5)	C54—C55—C56—C51	−0.6 (5)
N1—C1—C6—C5	179.6 (3)	N51—N52—C57—C58	−0.2 (3)
C4—C5—C6—C1	−0.3 (5)	N51—N52—C57—C61	−177.9 (2)
N1—N2—C7—C8	0.9 (3)	N52—C57—C58—C59	0.1 (3)
N1—N2—C7—C11	−176.6 (2)	C61—C57—C58—C59	177.5 (3)
N2—C7—C8—C9	−0.8 (3)	N52—C57—C58—C60	−176.8 (3)
C11—C7—C8—C9	176.3 (3)	C61—C57—C58—C60	0.6 (5)
N2—C7—C8—C10	177.1 (3)	N52—N51—C59—N53	177.5 (3)
C11—C7—C8—C10	−5.7 (5)	C51—N51—C59—N53	2.2 (5)
N2—N1—C9—N3	−176.8 (3)	N52—N51—C59—C58	−0.2 (3)
C1—N1—C9—N3	−2.6 (5)	C51—N51—C59—C58	−175.4 (3)
N2—N1—C9—C8	0.2 (3)	C57—C58—C59—N51	0.1 (3)
C1—N1—C9—C8	174.3 (3)	C60—C58—C59—N51	177.4 (3)
C7—C8—C9—N1	0.4 (3)	C57—C58—C59—N53	−177.3 (3)
C10—C8—C9—N1	−177.8 (3)	C60—C58—C59—N53	0.0 (5)
C7—C8—C9—N3	177.0 (3)	C59—C58—C60—O52	−3.2 (5)
C10—C8—C9—N3	−1.1 (5)	C57—C58—C60—O52	173.2 (3)
C9—C8—C10—O2	2.9 (5)	C59—C58—C60—O51	177.1 (3)
C7—C8—C10—O2	−174.7 (3)	C57—C58—C60—O51	−6.4 (5)
C9—C8—C10—O1	−177.2 (3)	N52—C57—C61—F52	115.3 (3)
C7—C8—C10—O1	5.2 (5)	C58—C57—C61—F52	−62.0 (4)
N2—C7—C11—F2	−120.1 (3)	N52—C57—C61—F51	−5.1 (4)
C8—C7—C11—F2	62.9 (4)	C58—C57—C61—F51	177.6 (3)
N2—C7—C11—F3	118.8 (3)	N52—C57—C61—F53	−124.5 (3)
C8—C7—C11—F3	−58.2 (4)	C58—C57—C61—F53	58.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N53—H531···O52	0.85 (4)	2.20 (4)	2.808 (3)	128 (3)
O51—H51···O2ⁱ	0.94 (4)	1.75 (4)	2.687 (3)	177 (4)
N3—H31···O2	0.90 (4)	2.20 (4)	2.873 (3)	132 (3)
O1—H1···O52ⁱⁱ	0.91 (4)	1.67 (4)	2.580 (3)	176 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₈F₃N₃O₂
M_r	271.20
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	125
a, b, c (Å)	9.757 (3), 10.740 (3), 21.277 (6)
β (°)	93.716 (3)
V (Å³)	2225 (1)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.30 × 0.18 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.957, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	20692, 3772, 2737
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.588

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.140, 1.01
No. of reflections	3772
No. of parameters	368
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.32

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N53—H531···O52	0.85 (4)	2.20 (4)	2.808 (3)	128 (3)
O51—H51···O2ⁱ	0.94 (4)	1.75 (4)	2.687 (3)	177 (4)
N3—H31···O2	0.90 (4)	2.20 (4)	2.873 (3)	132 (3)
O1—H1···O52ⁱⁱ	0.91 (4)	1.67 (4)	2.580 (3)	176 (4)

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

Acknowledgements

We acknowkledge US NSF grant No. 0521237 for the X-ray diffractometer.

References

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