Methyl 2-amino-3,4,5,6-tetra-fluoro-benzoate.

In the title compound, C(8)H(5)F(4)NO(2), synthesized by esterification of 2,3,4,5-tetra-fluoro-anthranilic acid with methanol, an intra-molecular amine N-H⋯O(carbon-yl) hydrogen bond is present, while inter-molecular N-H⋯O hydrogen bonds produce chains in the crystal, which extend along the b-axis direction.

Related literature

For general background to this compound and its synthesis, see: Cai et al. (1992 ▶); Liao et al. (2007 ▶); Xu et al. (2008 ▶); Li et al. (1999 ▶).

Experimental

Crystal data

C8H5F4NO2

M = 223.0

Monoclinic,

a = 4.5246 (2) Å

b = 9.6484 (4) Å

c = 19.3133 (9) Å

β = 91.324 (4)°

V = 842.90 (6) Å3

Z = 4

Cu Kα radiation

μ = 1.66 mm−1

T = 295 K

0.62 × 0.22 × 0.17 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 Gemini Ultra CCD diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.622, T max = 1.000

2513 measured reflections

1332 independent reflections

1185 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.140

S = 1.03

1332 reflections

145 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.17 e Å−3

Δρmin = −0.20 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); 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: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015182/zs2108sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015182/zs2108Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811015182/zs2108Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C8H5F4NO2	F(000) = 448
Mr = 223.0	Dx = 1.758 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.5418 Å
a = 4.5246 (2) Å	Cell parameters from 1857 reflections
b = 9.6484 (4) Å	θ = 4.6–63.3°
c = 19.3133 (9) Å	µ = 1.66 mm−1
β = 91.324 (4)°	T = 295 K
V = 842.90 (6) Å3	Prism, colourless
Z = 4	0.62 × 0.22 × 0.17 mm

Oxford Diffraction Xcalibur Sapphire3 Gemini Ultra CCD diffractometer	1332 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1185 reflections with I > 2σ(I)
mirror	Rint = 0.018
Detector resolution: 16.0288 pixels mm-1	θmax = 63.4°, θmin = 4.6°
ω scans	h = −5→4
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −10→10
Tmin = 0.622, Tmax = 1.000	l = −22→21
2513 measured reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0959P)2 + 0.1931P] where P = (Fo2 + 2Fc2)/3
1332 reflections	(Δ/σ)max = 0.001
145 parameters	Δρmax = 0.17 e Å−3
4 restraints	Δρmin = −0.20 e Å−3

Geometry. 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 esds 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.

	x	y	z	Uiso*/Ueq
F1	−0.0308 (3)	0.34475 (14)	0.54384 (7)	0.0577 (5)
F2	0.3821 (3)	−0.06985 (13)	0.70892 (7)	0.0608 (5)
F4	−0.2509 (3)	0.09206 (15)	0.52989 (7)	0.0614 (5)
F7	−0.0460 (3)	−0.11671 (14)	0.61192 (8)	0.0691 (6)
O3	0.6161 (4)	0.44489 (16)	0.68851 (8)	0.0594 (6)
O5	0.3628 (4)	0.50208 (16)	0.59299 (9)	0.0614 (6)
N12	0.6013 (4)	0.1837 (2)	0.73274 (10)	0.0507 (7)
C6	0.3985 (4)	0.1679 (2)	0.68073 (10)	0.0394 (6)
C8	0.3010 (4)	0.2775 (2)	0.63623 (9)	0.0380 (6)
C9	0.0669 (5)	0.0104 (2)	0.61966 (11)	0.0474 (7)
C10	0.4398 (4)	0.4146 (2)	0.64304 (10)	0.0408 (6)
C11	0.0806 (4)	0.2464 (2)	0.58597 (9)	0.0404 (6)
C13	0.2801 (5)	0.0359 (2)	0.66907 (10)	0.0434 (6)
C14	−0.0354 (5)	0.1169 (2)	0.57774 (11)	0.0458 (6)
C15	0.5115 (7)	0.6350 (3)	0.59424 (16)	0.0759 (10)
H12A	0.661 (7)	0.115 (3)	0.7566 (16)	0.075 (9)*
H12B	0.678 (6)	0.267 (3)	0.7397 (14)	0.070 (8)*
H15A	0.44700	0.68880	0.55490	0.1140*
H15B	0.72120	0.62090	0.59260	0.1140*
H15C	0.46470	0.68340	0.63600	0.1140*

	U11	U22	U33	U12	U13	U23
F1	0.0617 (8)	0.0530 (8)	0.0572 (8)	−0.0006 (6)	−0.0233 (6)	0.0059 (6)
F2	0.0727 (9)	0.0404 (7)	0.0690 (9)	0.0027 (6)	−0.0032 (7)	0.0116 (6)
F4	0.0540 (8)	0.0700 (9)	0.0594 (8)	−0.0116 (6)	−0.0146 (6)	−0.0162 (6)
F7	0.0748 (10)	0.0441 (8)	0.0882 (11)	−0.0209 (6)	−0.0010 (8)	−0.0080 (7)
O3	0.0744 (11)	0.0454 (9)	0.0571 (10)	−0.0116 (7)	−0.0273 (8)	0.0005 (7)
O5	0.0716 (11)	0.0408 (9)	0.0704 (10)	−0.0096 (7)	−0.0279 (8)	0.0127 (7)
N12	0.0606 (12)	0.0402 (11)	0.0505 (11)	0.0041 (9)	−0.0178 (9)	0.0033 (8)
C6	0.0413 (10)	0.0378 (10)	0.0392 (10)	0.0040 (8)	0.0008 (8)	−0.0016 (8)
C8	0.0397 (10)	0.0356 (10)	0.0385 (10)	0.0021 (8)	−0.0039 (8)	−0.0026 (8)
C9	0.0493 (12)	0.0379 (11)	0.0553 (12)	−0.0065 (9)	0.0079 (10)	−0.0071 (9)
C10	0.0433 (11)	0.0354 (10)	0.0433 (11)	0.0041 (8)	−0.0049 (8)	−0.0013 (8)
C11	0.0414 (10)	0.0402 (11)	0.0395 (10)	0.0040 (8)	−0.0039 (8)	−0.0015 (8)
C13	0.0487 (11)	0.0341 (10)	0.0476 (11)	0.0025 (8)	0.0036 (9)	0.0022 (8)
C14	0.0409 (10)	0.0520 (12)	0.0442 (11)	−0.0050 (9)	−0.0038 (8)	−0.0104 (9)
C15	0.095 (2)	0.0390 (13)	0.092 (2)	−0.0168 (13)	−0.0328 (16)	0.0158 (12)

F1—C11	1.341 (2)	C6—C13	1.398 (3)
F2—C13	1.353 (2)	C6—C8	1.426 (3)
F4—C14	1.349 (3)	C8—C11	1.408 (3)
F7—C9	1.336 (2)	C8—C10	1.469 (3)
O3—C10	1.209 (3)	C9—C13	1.364 (3)
O5—C10	1.324 (3)	C9—C14	1.381 (3)
O5—C15	1.448 (3)	C11—C14	1.363 (3)
N12—C6	1.353 (3)	C15—H15A	0.9600
N12—H12A	0.85 (3)	C15—H15B	0.9600
N12—H12B	0.88 (3)	C15—H15C	0.9600
C10—O5—C15	115.98 (19)	F1—C11—C8	121.20 (17)
C6—N12—H12B	118.2 (18)	F1—C11—C14	116.08 (17)
H12A—N12—H12B	121 (3)	C8—C11—C14	122.72 (18)
C6—N12—H12A	121 (2)	C6—C13—C9	122.65 (18)
C8—C6—C13	117.80 (17)	F2—C13—C6	118.11 (18)
N12—C6—C8	123.97 (18)	F2—C13—C9	119.25 (17)
N12—C6—C13	118.22 (18)	F4—C14—C9	119.76 (18)
C6—C8—C10	119.22 (16)	F4—C14—C11	120.86 (18)
C6—C8—C11	117.50 (17)	C9—C14—C11	119.4 (2)
C10—C8—C11	123.25 (17)	O5—C15—H15A	109.00
C13—C9—C14	119.87 (19)	O5—C15—H15B	109.00
F7—C9—C13	120.44 (18)	O5—C15—H15C	109.00
F7—C9—C14	119.69 (19)	H15A—C15—H15B	109.00
O3—C10—C8	123.81 (18)	H15A—C15—H15C	109.00
O3—C10—O5	122.31 (18)	H15B—C15—H15C	110.00
O5—C10—C8	113.83 (16)
C15—O5—C10—O3	2.4 (3)	C6—C8—C11—C14	−1.4 (3)
C15—O5—C10—C8	−175.26 (19)	C10—C8—C11—F1	−4.7 (3)
N12—C6—C8—C10	4.4 (3)	C10—C8—C11—C14	176.41 (19)
N12—C6—C8—C11	−177.73 (18)	F7—C9—C13—F2	1.8 (3)
C13—C6—C8—C10	−174.65 (17)	F7—C9—C13—C6	−177.89 (19)
C13—C6—C8—C11	3.3 (3)	C14—C9—C13—F2	−178.81 (19)
N12—C6—C13—F2	−2.2 (3)	C14—C9—C13—C6	1.5 (3)
N12—C6—C13—C9	177.5 (2)	F7—C9—C14—F4	0.8 (3)
C8—C6—C13—F2	176.87 (17)	F7—C9—C14—C11	179.94 (19)
C8—C6—C13—C9	−3.4 (3)	C13—C9—C14—F4	−178.57 (19)
C6—C8—C10—O3	−6.8 (3)	C13—C9—C14—C11	0.6 (3)
C6—C8—C10—O5	170.78 (17)	F1—C11—C14—F4	−0.4 (3)
C11—C8—C10—O3	175.38 (19)	F1—C11—C14—C9	−179.53 (18)
C11—C8—C10—O5	−7.0 (3)	C8—C11—C14—F4	178.59 (18)
C6—C8—C11—F1	177.52 (16)	C8—C11—C14—C9	−0.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12A···O3i	0.85 (3)	2.19 (3)	3.028 (2)	171 (3)
N12—H12B···O3	0.88 (3)	2.00 (3)	2.662 (2)	131 (2)
N12—H12A···F2	0.85 (3)	2.36 (3)	2.676 (2)	103 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N12—H12A⋯O3i	0.85 (3)	2.19 (3)	3.028 (2)	171 (3)
N12—H12B⋯O3	0.88 (3)	2.00 (3)	2.662 (2)	131 (2)

Symmetry code: (i) .