Ethyl 3,3,3-trifluoro-2-hy­droxy-2-(5-meth­oxy-1H-indol-3-yl)propionate

Kadirova, Z.; Tolipov, S.; Fedorovskiy, O.; Bakhtiyar, I.; Parpiev, N.

doi:10.1107/S1600536811021489

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1619

doi:10.1107/S1600536811021489

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Ethyl 3,3,3-trifluoro-2-hydroxy-2-(5-methoxy-1H-indol-3-yl)propionate

Zukhra Kadirova,^a ^* Samat Tolipov,^b Oleg Fedorovskiy,^c Ibragimov Bakhtiyar ^b and Nusrat Parpiev ^d

^aTashkent Chemical–Technological Institute, Navoi St. 32, Tashkent 100011, Uzbekistan, ^bInstitute of Bioorganic Chemistry, Mirzo-Ulugbek St. 83, Tashkent 100125, Uzbekistan, ^cA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova St. 28, Moscow 119991, Russian Federation, and ^dNational University of Uzbekistan named by Mirzo Ulugbek, Chemical Faculty, Vuzgorodok, Tashkent 100123, Uzbekistan
^*Correspondence e-mail: zuhra_kadirova@yahoo.com

(Received 26 April 2011; accepted 3 June 2011; online 11 June 2011)

In the title compound, C₁₄H₁₄F₃NO₄, the 3,3,3-trifluoropyruvate fragment has a syn configuration and is noncoplanar with the indole plane [dihedral angle = 84.87 (5)°]. In the crystal, molecules form inversion-related dimers via pairs of intermolecular O—H⋯O hydrogen bonds. These dimers are connected by intermolecular N—H⋯O=C(CF₃) hydrogen bonds to form a two-dimensional network structure.

Related literature

For background on the synthesis and activity of trifluoropyruvates of indole, see: Nakamura et al. (2008 ); Abid et al. (2008 ). For the crystal structures of related compounds, see: Choudhury et al. (2004 ); Abid et al. (2008).

Experimental

Crystal data

C₁₄H₁₄F₃NO₄
M_r = 317.26
Monoclinic, P 2₁ /n
a = 9.6277 (4) Å
b = 15.9760 (6) Å
c = 9.9738 (4) Å
β = 109.314 (5)°
V = 1447.75 (10) Å³
Z = 4
Cu Kα radiation
μ = 1.15 mm⁻¹
T = 293 K
0.55 × 0.45 × 0.40 mm

Data collection

Oxford Diffraction Xcalibur Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.782, T_max = 1.000
5738 measured reflections
2911 independent reflections
2319 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.116
S = 1.06
2911 reflections
234 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.86 (2)	2.11 (2)	2.9166 (18)	156.8 (18)
O2—H2B⋯O3ⁱⁱ	0.80 (2)	2.03 (2)	2.7798 (17)	156 (2)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x, -y, -z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811021489/pk2322sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021489/pk2322Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811021489/pk2322Isup3.cml

checkCIF report

Comment top

3,3,3-Trifluoropyruvates have been used as efficient fluorinated building blocks in the synthesis of some biologically active trifluoromethylated compounds owing to the unique properties of the trifluoromethyl group, such as high electronegativity, electron density, steric hindrance and its hydrophobic character. The incorporation of a tertiary α-trifluoromethyl alcohol stereocenter (CF₃C*(OH)R₁R₂) into heterocycles could provide novel drug candidates with unusual biological activities as a result of the presence of the chiral tertiary α-trifluoromethyl alcohol functionality (Nakamura et al. 2008, Abid et al., 2008).

In this study we synthesized the 3,3,3-trifluoropyruvate derivative of indole, which is an analogue of indole alkaloids. The molecular structure is shown in Fig. 1.

The compound crystallizes as a racemate and the carboxy- and hydroxy- groups are syn to each other (torsion angle O2—C9—C10—O3 = 8.1 (2)°. The 3,3,3-trifluoropyruvate fragment is non-coplanar to the plane of the indole [torsion angles C8—C7—C9—C10, C6—C7—C9—C10, C6—C7—C9—O2, C8—C7—C9—O2 are 107.3 (2)°, -69.7 (2)°, 50.0 (2)°, and -133.0 (2)°, respectively)]. The methoxy-, hydroxy- and trifluoromethyl groups deviate from the indole plane by 0.061 (2), 0.854 (1) and 0.165 (2) Å, respectively. The bond distances C—C and C—N in the indole group are in the range 1.369–1.435 Å and 1.358–1.379 Å, respectively. Due to the concurrent influence of electron-withdrawing groups in the 3,3,3-trifluoropyruvate fragment, the EtO(O)C—C(O)CF₃ bond is elongated slightly to 1.554 (2) Å.

The fluorine does not readily accept hydrogen bonds and hence behaves differently from chlorine and bromine, but a signifcant number of compounds pack via weak interactions involving organic fluorine (Choudhury et al., 2004) and generate different packing motifs via F···F, C—H···F and C—F···π interactions. In the presence of a strong acceptor such as C=O, the C—H···O interaction takes priority over C—H···F. The molecules form inversion-related dimers via pairs of intermolecular O—H···O hydrogen bonds. These dimers are connected by intermolecular N—H···O═C(CF₃) hydrogen bonds to form a two-dimensional network structure.

Related literature top

For background on the synthesis and activity of trifluoropyruvates of indole, see: Nakamura et al. (2008); Abid et al. (2008). For the crystal structures of related compounds, see: Choudhury et al. (2004); Abid et al. (2008).

Experimental top

A solution of 0.170 g (0.001 mol) of ethyl 3,3,3-trifluoropyruvate in 10 ml of ether was added to a solution of 0.147 g (0.001 mol) of 5-methoxyindole in 10 ml ether, and stirred at room temperature for 24 h. The reaction was monitored by TLC. The reaction mixture was then evaporated under reduced pressure and the residue was purified by chromatography on silica gel (chloroform/ethylacetate=9:1); yield: 0.150 g (47%). The compound was crystallized from ethanolic solution by slow evaporation, giving colorless prism crystals suitable for X-ray diffraction analysis. ¹H NMR (300 MHz, dmso-d6): δ 1.11 (3H, t, CH₃); 4.22 (2H, q, CH₂, J_CH3—CH2 7,2 Hz); 3.72 (3H, s, O—CH₃), 6.78 (1H, d, aromatic, J_6–5 = 6.9 Hz), 7.17 (1H, s, aromatic), 7.32 (1H, d, aromatic), 7.37 (2H, s. br., OH, CH), 11.58 (1H, s. br., NH); ¹⁹F NMR (dmso-d6): 3.01 (s, CF₃); MS (m/z 317).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. A displacement ellipsoid plot drawn at the 50% probability level with H atoms shown as small spheres of arbitary radius.
	Fig. 2. A view of the crystal structure packing, showing part of the hydrogen bonding network.

Ethyl 3,3,3-trifluoro-2-hydroxy-2-(5-methoxy-1H-indol-3-yl)propionate top

Crystal data top

C₁₄H₁₄F₃NO₄	F(000) = 656
M_r = 317.26	D_x = 1.456 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 2319 reflections
a = 9.6277 (4) Å	θ = 5.5–75.5°
b = 15.9760 (6) Å	µ = 1.15 mm⁻¹
c = 9.9738 (4) Å	T = 293 K
β = 109.314 (5)°	Block, colourless
V = 1447.75 (10) Å³	0.55 × 0.45 × 0.40 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Ruby CCD diffractometer	2911 independent reflections
Radiation source: fine-focus sealed tube	2319 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 10.2576 pixels mm^-1	θ_max = 75.9°, θ_min = 5.5°
ω scans	h = −11→12
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −19→13
T_min = 0.782, T_max = 1.000	l = −12→12
5738 measured reflections

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.116	w = 1/[σ²(F_o²) + (0.0607P)² + 0.1918P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2911 reflections	Δρ_max = 0.20 e Å⁻³
234 parameters	Δρ_min = −0.14 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: 0.0092 (10)

Crystal data top

C₁₄H₁₄F₃NO₄	V = 1447.75 (10) Å³
M_r = 317.26	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 9.6277 (4) Å	µ = 1.15 mm⁻¹
b = 15.9760 (6) Å	T = 293 K
c = 9.9738 (4) Å	0.55 × 0.45 × 0.40 mm
β = 109.314 (5)°

Data collection top

Oxford Diffraction Xcalibur Ruby CCD diffractometer	2911 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	2319 reflections with I > 2σ(I)
T_min = 0.782, T_max = 1.000	R_int = 0.018
5738 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.20 e Å⁻³
2911 reflections	Δρ_min = −0.14 e Å⁻³
234 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.

Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su'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 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	0.24919 (15)	0.21987 (8)	0.04081 (14)	0.0900 (4)
F2	0.24512 (15)	0.09413 (9)	−0.03770 (13)	0.0863 (4)
F3	0.42514 (12)	0.13538 (8)	0.14198 (14)	0.0805 (4)
O1	−0.16538 (14)	0.08409 (10)	0.51949 (16)	0.0773 (4)
O2	0.04297 (12)	0.12631 (7)	0.09810 (13)	0.0566 (3)
O3	0.12118 (13)	−0.03385 (7)	0.13702 (13)	0.0622 (3)
O4	0.34902 (11)	−0.00327 (7)	0.27903 (12)	0.0535 (3)
N1	0.34543 (16)	0.23072 (9)	0.50886 (17)	0.0590 (4)
C1	0.22216 (17)	0.19773 (10)	0.53026 (18)	0.0524 (4)
C2	0.1720 (2)	0.20300 (11)	0.6458 (2)	0.0627 (5)
C3	0.0439 (2)	0.16245 (13)	0.6367 (2)	0.0658 (5)
C4	−0.03659 (18)	0.11812 (11)	0.5139 (2)	0.0596 (4)
C5	0.01333 (17)	0.11079 (10)	0.40028 (19)	0.0528 (4)
C6	0.14673 (16)	0.15055 (9)	0.40867 (17)	0.0476 (4)
C7	0.23112 (16)	0.15638 (9)	0.31430 (17)	0.0479 (4)
C8	0.34965 (18)	0.20619 (10)	0.3800 (2)	0.0556 (4)
C9	0.19239 (16)	0.11127 (9)	0.17494 (17)	0.0475 (4)
C10	0.21565 (15)	0.01523 (9)	0.19510 (16)	0.0461 (4)
C11	0.3900 (2)	−0.09195 (11)	0.2897 (2)	0.0639 (5)
C12	0.4403 (3)	−0.11618 (14)	0.1696 (3)	0.0826 (6)
H12A	0.4697	−0.1739	0.1794	0.124*
H12B	0.5223	−0.0818	0.1702	0.124*
H12C	0.3613	−0.1085	0.0817	0.124*
C13	0.2798 (2)	0.14066 (12)	0.0805 (2)	0.0645 (5)
C14	−0.2605 (2)	0.04673 (16)	0.3932 (2)	0.0810 (6)
H14A	−0.3506	0.0303	0.4073	0.122*
H14B	−0.2137	−0.0017	0.3703	0.122*
H14C	−0.2815	0.0863	0.3166	0.122*
H1A	0.403 (2)	0.2684 (13)	0.559 (2)	0.066 (6)*
H2A	0.222 (2)	0.2317 (15)	0.724 (2)	0.079 (6)*
H2B	0.009 (2)	0.0882 (16)	0.045 (2)	0.079 (7)*
H3A	0.007 (2)	0.1646 (14)	0.715 (2)	0.075 (6)*
H5A	−0.0408 (19)	0.0778 (12)	0.3176 (19)	0.056 (5)*
H8A	0.430 (2)	0.2217 (12)	0.3467 (19)	0.059 (5)*
H11A	0.304 (2)	−0.1242 (13)	0.292 (2)	0.068 (6)*
H11B	0.473 (3)	−0.0959 (14)	0.378 (2)	0.079 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.1020 (9)	0.0653 (7)	0.0962 (9)	−0.0066 (6)	0.0240 (7)	0.0318 (6)
F2	0.0997 (9)	0.0956 (10)	0.0691 (7)	−0.0147 (7)	0.0352 (6)	−0.0033 (6)
F3	0.0560 (6)	0.0923 (9)	0.0963 (8)	−0.0088 (6)	0.0292 (6)	0.0143 (7)
O1	0.0549 (7)	0.0862 (10)	0.0964 (10)	−0.0112 (7)	0.0323 (7)	−0.0175 (8)
O2	0.0429 (6)	0.0470 (6)	0.0639 (7)	0.0081 (5)	−0.0037 (5)	−0.0038 (6)
O3	0.0518 (6)	0.0471 (6)	0.0710 (7)	−0.0071 (5)	−0.0022 (5)	0.0011 (5)
O4	0.0387 (5)	0.0429 (6)	0.0696 (7)	0.0059 (4)	0.0053 (5)	0.0037 (5)
N1	0.0492 (7)	0.0435 (7)	0.0687 (9)	−0.0106 (6)	−0.0014 (7)	−0.0051 (6)
C1	0.0448 (8)	0.0369 (7)	0.0645 (10)	0.0019 (6)	0.0032 (7)	−0.0040 (7)
C2	0.0611 (10)	0.0519 (10)	0.0645 (11)	0.0052 (8)	0.0066 (9)	−0.0157 (8)
C3	0.0611 (10)	0.0628 (11)	0.0724 (12)	0.0074 (9)	0.0204 (9)	−0.0139 (9)
C4	0.0469 (8)	0.0525 (9)	0.0774 (11)	0.0031 (7)	0.0179 (8)	−0.0085 (8)
C5	0.0420 (8)	0.0442 (8)	0.0648 (10)	−0.0021 (6)	0.0076 (7)	−0.0100 (7)
C6	0.0408 (7)	0.0331 (7)	0.0600 (9)	0.0026 (6)	0.0049 (6)	−0.0033 (6)
C7	0.0404 (7)	0.0358 (7)	0.0594 (9)	0.0005 (6)	0.0055 (6)	0.0032 (6)
C8	0.0437 (8)	0.0459 (9)	0.0673 (10)	−0.0053 (7)	0.0050 (7)	0.0068 (7)
C9	0.0365 (7)	0.0415 (8)	0.0563 (9)	0.0015 (6)	0.0042 (6)	0.0038 (6)
C10	0.0390 (7)	0.0426 (8)	0.0515 (8)	0.0001 (6)	0.0079 (6)	0.0010 (6)
C11	0.0521 (9)	0.0459 (9)	0.0860 (13)	0.0096 (8)	0.0125 (9)	0.0074 (9)
C12	0.0726 (13)	0.0660 (12)	0.1059 (17)	0.0106 (10)	0.0249 (12)	−0.0157 (12)
C13	0.0636 (10)	0.0580 (10)	0.0664 (11)	−0.0046 (8)	0.0139 (8)	0.0111 (9)
C14	0.0487 (10)	0.0883 (15)	0.1008 (16)	−0.0144 (10)	0.0176 (10)	−0.0043 (12)

Geometric parameters (Å, º) top

F1—C13	1.330 (2)	C4—C5	1.375 (3)
F2—C13	1.339 (2)	C5—C6	1.410 (2)
F3—C13	1.332 (2)	C5—H5A	0.972 (18)
O1—C4	1.372 (2)	C6—C7	1.436 (2)
O1—C14	1.421 (3)	C7—C8	1.367 (2)
O2—C9	1.4090 (17)	C7—C9	1.499 (2)
O2—H2B	0.80 (2)	C8—H8A	0.974 (18)
O3—C10	1.1954 (18)	C9—C13	1.530 (3)
O4—C10	1.3137 (17)	C9—C10	1.554 (2)
O4—C11	1.465 (2)	C11—C12	1.484 (3)
N1—C8	1.357 (2)	C11—H11A	0.98 (2)
N1—C1	1.378 (2)	C11—H11B	0.98 (2)
N1—H1A	0.86 (2)	C12—H12A	0.9600
C1—C2	1.391 (3)	C12—H12B	0.9600
C1—C6	1.408 (2)	C12—H12C	0.9600
C2—C3	1.369 (3)	C14—H14A	0.9600
C2—H2A	0.90 (2)	C14—H14B	0.9600
C3—C4	1.405 (3)	C14—H14C	0.9600
C3—H3A	0.97 (2)

C4—O1—C14	117.18 (16)	C7—C9—C13	113.86 (13)
C9—O2—H2B	110.4 (17)	O2—C9—C10	108.44 (12)
C10—O4—C11	116.54 (13)	C7—C9—C10	111.95 (13)
C8—N1—C1	109.48 (14)	C13—C9—C10	107.31 (14)
C8—N1—H1A	122.4 (13)	O3—C10—O4	126.01 (14)
C1—N1—H1A	127.1 (13)	O3—C10—C9	122.07 (13)
N1—C1—C2	131.13 (16)	O4—C10—C9	111.91 (12)
N1—C1—C6	107.25 (16)	O4—C11—C12	110.23 (17)
C2—C1—C6	121.60 (16)	O4—C11—H11A	107.4 (12)
C3—C2—C1	117.93 (17)	C12—C11—H11A	112.8 (12)
C3—C2—H2A	120.9 (14)	O4—C11—H11B	104.3 (13)
C1—C2—H2A	121.2 (14)	C12—C11—H11B	109.3 (13)
C2—C3—C4	121.43 (19)	H11A—C11—H11B	112.5 (17)
C2—C3—H3A	119.9 (13)	C11—C12—H12A	109.5
C4—C3—H3A	118.6 (13)	C11—C12—H12B	109.5
O1—C4—C5	124.53 (16)	H12A—C12—H12B	109.5
O1—C4—C3	114.21 (18)	C11—C12—H12C	109.5
C5—C4—C3	121.26 (17)	H12A—C12—H12C	109.5
C4—C5—C6	118.20 (15)	H12B—C12—H12C	109.5
C4—C5—H5A	120.7 (11)	F1—C13—F3	107.05 (16)
C6—C5—H5A	121.1 (11)	F1—C13—F2	107.46 (16)
C1—C6—C5	119.49 (16)	F3—C13—F2	106.77 (17)
C1—C6—C7	106.70 (14)	F1—C13—C9	111.24 (17)
C5—C6—C7	133.81 (15)	F3—C13—C9	113.91 (15)
C8—C7—C6	106.71 (15)	F2—C13—C9	110.11 (15)
C8—C7—C9	129.49 (16)	O1—C14—H14A	109.5
C6—C7—C9	123.74 (13)	O1—C14—H14B	109.5
N1—C8—C7	109.86 (16)	H14A—C14—H14B	109.5
N1—C8—H8A	121.8 (11)	O1—C14—H14C	109.5
C7—C8—H8A	128.3 (11)	H14A—C14—H14C	109.5
O2—C9—C7	108.57 (13)	H14B—C14—H14C	109.5
O2—C9—C13	106.46 (13)

C8—N1—C1—C2	178.10 (17)	C8—C7—C9—O2	−133.00 (17)
C8—N1—C1—C6	0.03 (18)	C6—C7—C9—O2	50.01 (18)
N1—C1—C2—C3	−179.49 (18)	C8—C7—C9—C13	−14.6 (2)
C6—C1—C2—C3	−1.7 (3)	C6—C7—C9—C13	168.40 (14)
C1—C2—C3—C4	−1.2 (3)	C8—C7—C9—C10	107.32 (18)
C14—O1—C4—C5	−7.2 (3)	C6—C7—C9—C10	−69.67 (18)
C14—O1—C4—C3	172.94 (18)	C11—O4—C10—O3	7.0 (3)
C2—C3—C4—O1	−177.34 (18)	C11—O4—C10—C9	−171.67 (15)
C2—C3—C4—C5	2.8 (3)	O2—C9—C10—O3	8.1 (2)
O1—C4—C5—C6	178.83 (16)	C7—C9—C10—O3	127.84 (17)
C3—C4—C5—C6	−1.3 (3)	C13—C9—C10—O3	−106.54 (18)
N1—C1—C6—C5	−178.63 (14)	O2—C9—C10—O4	−173.15 (13)
C2—C1—C6—C5	3.1 (2)	C7—C9—C10—O4	−53.40 (18)
N1—C1—C6—C7	0.41 (17)	C13—C9—C10—O4	72.22 (17)
C2—C1—C6—C7	−177.88 (14)	C10—O4—C11—C12	83.2 (2)
C4—C5—C6—C1	−1.5 (2)	O2—C9—C13—F1	54.98 (18)
C4—C5—C6—C7	179.74 (16)	C7—C9—C13—F1	−64.61 (19)
C1—C6—C7—C8	−0.69 (17)	C10—C9—C13—F1	170.92 (14)
C5—C6—C7—C8	178.15 (17)	O2—C9—C13—F3	176.06 (15)
C1—C6—C7—C9	176.89 (13)	C7—C9—C13—F3	56.5 (2)
C5—C6—C7—C9	−4.3 (3)	C10—C9—C13—F3	−67.99 (19)
C1—N1—C8—C7	−0.48 (19)	O2—C9—C13—F2	−64.04 (18)
C6—C7—C8—N1	0.73 (18)	C7—C9—C13—F2	176.37 (13)
C9—C7—C8—N1	−176.66 (14)	C10—C9—C13—F2	51.91 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86 (2)	2.11 (2)	2.9166 (18)	156.8 (18)
O2—H2B···O3ⁱⁱ	0.80 (2)	2.03 (2)	2.7798 (17)	156 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄F₃NO₄
M_r	317.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.6277 (4), 15.9760 (6), 9.9738 (4)
β (°)	109.314 (5)
V (Å³)	1447.75 (10)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.15
Crystal size (mm)	0.55 × 0.45 × 0.40

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby CCD diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.782, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5738, 2911, 2319
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.116, 1.06
No. of reflections	2911
No. of parameters	234
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.14

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86 (2)	2.11 (2)	2.9166 (18)	156.8 (18)
O2—H2B···O3ⁱⁱ	0.80 (2)	2.03 (2)	2.7798 (17)	156 (2)

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

Acknowledgements

This work was supported by the Grant of Fundamental Research of the Center of Science and Technology, Republic of Uzbekistan (grant No. F3-142).

References

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