Methyl 2-{[2,8-bis­(trifluoro­meth­yl)quinolin-4-yl]­oxy}acetate

Feng, Z.-Q.; Yang, X.-L.; Ye, Y.-F.; Wang, H.-Q.; Dong, T.

doi:10.1107/S1600536811000328

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o321

doi:10.1107/S1600536811000328

Open

access

Methyl 2-{[2,8-bis(trifluoromethyl)quinolin-4-yl]oxy}acetate

Zhi-Qiang Feng,^a ^* Xiao-Li Yang,^a Yuan-Feng Ye,^a Huai-Qing Wang ^a and Tao Dong ^a

^aSchool of Material Engineering, Jinling Institute of Technology, Nanjing 211169, People's Republic of China
^*Correspondence e-mail: fzq@jit.edu.cn

(Received 23 December 2010; accepted 5 January 2011; online 12 January 2011)

In the crystal structure of the title compound, C₁₄H₉F₆NO₃, molecules are connected by intermolecular C—H⋯O hydrogen bonds. The best planes through the benzene and pyridyl rings make a dihedral angle of 1.59 (12)°.

Related literature

The title compound is an important organic synthesis intermediate. For the synthetic procedure, see: Lilienkampf et al. (2009 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₉F₆NO₃
M_r = 353.22
Monoclinic, P 2₁ /c
a = 4.6980 (9) Å
b = 20.549 (4) Å
c = 15.176 (3) Å
β = 95.74 (3)°
V = 1457.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.953, T_max = 0.984
3017 measured reflections
2676 independent reflections
1747 reflections with I > 2σ(I)
R_int = 0.019
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.146
S = 1.01
2676 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12B⋯O2ⁱ	0.97	2.54	3.448 (4)	156
Symmetry code: (i) x+1, y, z.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811000328/vm2070sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811000328/vm2070Isup2.hkl

checkCIF report

Comment top

The title compound, methyl 2-((2,8-bis(trifluoromethyl)quinolin-4-yl)oxy)acetate is an important intermediate for the synthesis of drugs (Lilienkampf et al., 2009). Here we report the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1. The bond lengths and angles are within normal ranges (Allen et al., 1987).

The phenyl ring and pyridyl ring are nearly coplanar as indicated by the dihedral angle of 1.59 (12) ° between the best planes through both rings.

The molecules show C—H···O and C—H···F intermolecular and intramolecular hydrogen bonds (Table 1) resulting in a three dimensional network, which seems to be very effective in the stabilization of the crystal structure (Fig. 2).

Related literature top

The title compound is an important organic synthesis intermediate. For the synthetic procedure, see: Lilienkampf et al. (2009). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I) was prepared by a method reported in literature (Lilienkampf et al., 2009). The crystals were obtained by dissolving (I) (0.5 g, 1.42 mmol) in ethanol (25 ml) and evaporating the solvent slowly at room temperature for about 5 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of title compound (I) with atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Hydrogen bonds are shown by dashed lines.
	Fig. 2. A packing diagram for (I). C—H···O and C—H···F hydrogen bonds are shown by dashed lines.

Methyl 2-{[2,8-bis(trifluoromethyl)quinolin-4-yl]oxy}acetate top

Crystal data top

C₁₄H₉F₆NO₃	F(000) = 712
M_r = 353.22	D_x = 1.609 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 4.6980 (9) Å	θ = 9–13°
b = 20.549 (4) Å	µ = 0.16 mm⁻¹
c = 15.176 (3) Å	T = 293 K
β = 95.74 (3)°	Block, colourless
V = 1457.7 (5) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1747 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 25.3°, θ_min = 1.7°
ω/2θ scans	h = 0→5
Absorption correction: ψ scan (North et al., 1968)	k = 0→24
T_min = 0.953, T_max = 0.984	l = −18→18
3017 measured reflections	3 standard reflections every 200 reflections
2676 independent reflections	intensity decay: 1%

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.080P)²] where P = (F_o² + 2F_c²)/3
2676 reflections	(Δ/σ)_max < 0.001
217 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₄H₉F₆NO₃	V = 1457.7 (5) Å³
M_r = 353.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.6980 (9) Å	µ = 0.16 mm⁻¹
b = 20.549 (4) Å	T = 293 K
c = 15.176 (3) Å	0.30 × 0.20 × 0.10 mm
β = 95.74 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1747 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.019
T_min = 0.953, T_max = 0.984	3 standard reflections every 200 reflections
3017 measured reflections	intensity decay: 1%
2676 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.01	Δρ_max = 0.30 e Å⁻³
2676 reflections	Δρ_min = −0.24 e Å⁻³
217 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
N	0.6586 (4)	0.29913 (10)	0.42412 (14)	0.0383 (5)
O1	0.5803 (5)	0.19700 (9)	0.65680 (13)	0.0594 (6)
C1	0.2049 (6)	0.40690 (14)	0.5400 (2)	0.0526 (7)
H1A	0.1174	0.4474	0.5322	0.063*
C2	0.1686 (6)	0.37110 (15)	0.61581 (19)	0.0589 (8)
H2A	0.0538	0.3874	0.6572	0.071*
O2	0.3296 (6)	0.08697 (12)	0.58771 (19)	0.0863 (8)
C3	0.2985 (6)	0.31288 (14)	0.62992 (19)	0.0504 (7)
H3A	0.2751	0.2896	0.6813	0.060*
O3	0.6519 (6)	0.02604 (12)	0.66729 (19)	0.0956 (9)
C4	0.4696 (5)	0.28728 (13)	0.56703 (17)	0.0397 (6)
F4	0.7603 (4)	0.18242 (10)	0.30737 (13)	0.0839 (7)
F5	1.1459 (4)	0.17660 (9)	0.39252 (12)	0.0840 (7)
C5	0.5037 (5)	0.32214 (11)	0.48869 (16)	0.0367 (6)
F6	1.0470 (4)	0.26159 (9)	0.31789 (13)	0.0773 (6)
C6	0.3659 (5)	0.38388 (11)	0.47696 (17)	0.0398 (6)
C7	0.6128 (6)	0.22650 (13)	0.57896 (17)	0.0436 (6)
C8	0.7689 (6)	0.20394 (12)	0.51395 (17)	0.0445 (7)
H8A	0.8646	0.1643	0.5198	0.053*
C9	0.7797 (5)	0.24217 (12)	0.43878 (16)	0.0390 (6)
C10	0.9331 (6)	0.21592 (13)	0.36447 (18)	0.0453 (7)
C11	0.3985 (6)	0.42315 (13)	0.39586 (19)	0.0462 (7)
C12	0.7187 (7)	0.13683 (16)	0.6768 (2)	0.0603 (8)
H12A	0.7505	0.1314	0.7406	0.072*
H12B	0.9034	0.1365	0.6534	0.072*
C13	0.5397 (8)	0.08173 (16)	0.6375 (2)	0.0637 (9)
C14	0.4960 (10)	−0.0321 (2)	0.6392 (3)	0.1169 (16)
H14A	0.5940	−0.0695	0.6652	0.175*
H14B	0.4832	−0.0354	0.5759	0.175*
H14C	0.3070	−0.0301	0.6580	0.175*
F1	0.2699 (4)	0.48154 (8)	0.39902 (12)	0.0684 (5)
F2	0.6694 (3)	0.43562 (7)	0.38446 (11)	0.0572 (5)
F3	0.2832 (3)	0.39444 (8)	0.32177 (11)	0.0619 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.0317 (11)	0.0390 (12)	0.0447 (12)	−0.0009 (9)	0.0068 (9)	−0.0036 (10)
O1	0.0794 (15)	0.0544 (12)	0.0462 (11)	0.0071 (11)	0.0160 (10)	0.0103 (9)
C1	0.0458 (16)	0.0528 (17)	0.0594 (19)	0.0093 (13)	0.0070 (14)	−0.0120 (14)
C2	0.0570 (19)	0.068 (2)	0.0536 (18)	0.0110 (16)	0.0174 (15)	−0.0152 (16)
O2	0.0896 (19)	0.0781 (17)	0.0894 (18)	−0.0053 (15)	−0.0004 (16)	−0.0006 (14)
C3	0.0475 (16)	0.0623 (19)	0.0426 (15)	−0.0016 (14)	0.0108 (13)	−0.0029 (13)
O3	0.120 (2)	0.0559 (15)	0.113 (2)	0.0237 (15)	0.0212 (18)	0.0158 (14)
C4	0.0316 (13)	0.0459 (14)	0.0418 (14)	−0.0052 (11)	0.0050 (11)	−0.0066 (12)
F4	0.0720 (12)	0.1071 (16)	0.0741 (13)	−0.0201 (11)	0.0146 (10)	−0.0478 (11)
F5	0.0813 (14)	0.0987 (15)	0.0746 (13)	0.0501 (12)	0.0215 (11)	0.0041 (11)
C5	0.0287 (12)	0.0400 (13)	0.0419 (14)	−0.0010 (11)	0.0061 (11)	−0.0073 (11)
F6	0.0927 (14)	0.0688 (12)	0.0784 (13)	0.0018 (10)	0.0485 (11)	0.0007 (10)
C6	0.0294 (13)	0.0383 (14)	0.0508 (15)	−0.0013 (11)	−0.0004 (11)	−0.0063 (12)
C7	0.0433 (15)	0.0463 (15)	0.0405 (15)	−0.0025 (12)	0.0014 (12)	0.0038 (12)
C8	0.0471 (15)	0.0401 (14)	0.0461 (16)	0.0037 (12)	0.0040 (12)	−0.0003 (12)
C9	0.0324 (13)	0.0417 (14)	0.0429 (15)	−0.0031 (11)	0.0041 (11)	−0.0037 (12)
C10	0.0442 (15)	0.0437 (15)	0.0483 (16)	0.0059 (13)	0.0072 (13)	−0.0044 (13)
C11	0.0364 (14)	0.0446 (15)	0.0579 (18)	0.0025 (12)	0.0062 (13)	−0.0012 (13)
C12	0.0614 (19)	0.066 (2)	0.0537 (18)	0.0093 (16)	0.0076 (15)	0.0166 (16)
C13	0.078 (2)	0.061 (2)	0.055 (2)	0.0157 (18)	0.0226 (19)	0.0079 (16)
C14	0.138 (4)	0.072 (3)	0.142 (4)	0.001 (3)	0.021 (3)	−0.003 (3)
F1	0.0688 (12)	0.0480 (10)	0.0911 (13)	0.0169 (8)	0.0205 (10)	0.0105 (9)
F2	0.0416 (9)	0.0577 (10)	0.0730 (11)	−0.0068 (7)	0.0090 (8)	0.0047 (8)
F3	0.0648 (11)	0.0651 (11)	0.0537 (10)	−0.0066 (9)	−0.0046 (9)	0.0042 (8)

Geometric parameters (Å, º) top

N—C9	1.311 (3)	F5—C10	1.322 (3)
N—C5	1.362 (3)	C5—C6	1.428 (3)
O1—C7	1.350 (3)	F6—C10	1.320 (3)
O1—C12	1.416 (4)	C6—C11	1.492 (4)
C1—C6	1.362 (4)	C7—C8	1.368 (4)
C1—C2	1.391 (4)	C8—C9	1.390 (3)
C1—H1A	0.9300	C8—H8A	0.9300
C2—C3	1.350 (4)	C9—C10	1.498 (3)
C2—H2A	0.9300	C11—F2	1.327 (3)
O2—C13	1.186 (4)	C11—F3	1.336 (3)
C3—C4	1.410 (4)	C11—F1	1.346 (3)
C3—H3A	0.9300	C12—C13	1.498 (5)
O3—C13	1.321 (4)	C12—H12A	0.9700
O3—C14	1.443 (5)	C12—H12B	0.9700
C4—C5	1.411 (4)	C14—H14A	0.9600
C4—C7	1.421 (4)	C14—H14B	0.9600
F4—C10	1.320 (3)	C14—H14C	0.9600

C9—N—C5	116.2 (2)	C8—C9—C10	118.3 (2)
C7—O1—C12	119.4 (2)	F6—C10—F4	106.0 (2)
C6—C1—C2	121.3 (3)	F6—C10—F5	105.8 (2)
C6—C1—H1A	119.3	F4—C10—F5	106.7 (2)
C2—C1—H1A	119.3	F6—C10—C9	113.5 (2)
C3—C2—C1	120.6 (3)	F4—C10—C9	111.8 (2)
C3—C2—H2A	119.7	F5—C10—C9	112.5 (2)
C1—C2—H2A	119.7	F2—C11—F3	106.8 (2)
C2—C3—C4	120.2 (3)	F2—C11—F1	105.8 (2)
C2—C3—H3A	119.9	F3—C11—F1	106.1 (2)
C4—C3—H3A	119.9	F2—C11—C6	113.0 (2)
C13—O3—C14	116.3 (3)	F3—C11—C6	112.9 (2)
C3—C4—C5	120.1 (2)	F1—C11—C6	111.7 (2)
C3—C4—C7	122.4 (2)	O1—C12—C13	110.3 (2)
C5—C4—C7	117.5 (2)	O1—C12—H12A	109.6
N—C5—C4	122.9 (2)	C13—C12—H12A	109.6
N—C5—C6	119.1 (2)	O1—C12—H12B	109.6
C4—C5—C6	117.9 (2)	C13—C12—H12B	109.6
C1—C6—C5	119.9 (3)	H12A—C12—H12B	108.1
C1—C6—C11	120.1 (2)	O2—C13—O3	125.1 (4)
C5—C6—C11	120.0 (2)	O2—C13—C12	125.7 (3)
O1—C7—C8	126.5 (2)	O3—C13—C12	109.2 (3)
O1—C7—C4	114.4 (2)	O3—C14—H14A	109.5
C8—C7—C4	119.1 (2)	O3—C14—H14B	109.5
C7—C8—C9	117.8 (2)	H14A—C14—H14B	109.5
C7—C8—H8A	121.1	O3—C14—H14C	109.5
C9—C8—H8A	121.1	H14A—C14—H14C	109.5
N—C9—C8	126.4 (2)	H14B—C14—H14C	109.5
N—C9—C10	115.3 (2)

C6—C1—C2—C3	1.6 (5)	C4—C7—C8—C9	0.1 (4)
C1—C2—C3—C4	−0.9 (4)	C5—N—C9—C8	−1.1 (4)
C2—C3—C4—C5	−0.6 (4)	C5—N—C9—C10	176.2 (2)
C2—C3—C4—C7	179.5 (3)	C7—C8—C9—N	1.4 (4)
C9—N—C5—C4	−0.7 (3)	C7—C8—C9—C10	−175.9 (2)
C9—N—C5—C6	−180.0 (2)	N—C9—C10—F6	32.0 (3)
C3—C4—C5—N	−177.9 (2)	C8—C9—C10—F6	−150.4 (2)
C7—C4—C5—N	2.1 (3)	N—C9—C10—F4	−87.8 (3)
C3—C4—C5—C6	1.4 (3)	C8—C9—C10—F4	89.8 (3)
C7—C4—C5—C6	−178.7 (2)	N—C9—C10—F5	152.1 (2)
C2—C1—C6—C5	−0.7 (4)	C8—C9—C10—F5	−30.3 (3)
C2—C1—C6—C11	179.4 (2)	C1—C6—C11—F2	123.2 (3)
N—C5—C6—C1	178.5 (2)	C5—C6—C11—F2	−56.7 (3)
C4—C5—C6—C1	−0.8 (3)	C1—C6—C11—F3	−115.5 (3)
N—C5—C6—C11	−1.6 (3)	C5—C6—C11—F3	64.6 (3)
C4—C5—C6—C11	179.1 (2)	C1—C6—C11—F1	4.0 (3)
C12—O1—C7—C8	0.5 (4)	C5—C6—C11—F1	−175.9 (2)
C12—O1—C7—C4	−178.6 (2)	C7—O1—C12—C13	−85.0 (3)
C3—C4—C7—O1	−2.6 (4)	C14—O3—C13—O2	−2.8 (5)
C5—C4—C7—O1	177.5 (2)	C14—O3—C13—C12	176.8 (3)
C3—C4—C7—C8	178.2 (2)	O1—C12—C13—O2	8.6 (4)
C5—C4—C7—C8	−1.7 (4)	O1—C12—C13—O3	−171.1 (3)
O1—C7—C8—C9	−179.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···F1	0.93	2.32	2.675 (3)	102
C12—H12B···O2ⁱ	0.97	2.54	3.448 (4)	156

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₉F₆NO₃
M_r	353.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	4.6980 (9), 20.549 (4), 15.176 (3)
β (°)	95.74 (3)
V (Å³)	1457.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.953, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	3017, 2676, 1747
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.146, 1.01
No. of reflections	2676
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.24

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···O2ⁱ	0.97	2.54	3.448 (4)	156

Symmetry code: (i) x+1, y, z.

Acknowledgements

This work was supported by the Natural Science Fund for Colleges and Universities in Jiangsu Province (09kjd150011). The authors thank the Center of Testing and Analysis, Nanjing University, for help with the data collection.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Lilienkampf, A., Mao, J. L., Wan, B. J., Wang, Y. H., Franzblau, S. J. & Kozikowski, A. P. (2009). J. Med. Chem. 52, 2109–2118. Web of Science CrossRef PubMed CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar