2-Carbamoyl-3,4,5,6-tetra­fluoro­benzoic acid

Lu, T.; Liao, X.-J.; Liang, Y.-W.; Xu, S.-H.

doi:10.1107/S1600536812036549

organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o2864

https://doi.org/10.1107/S1600536812036549

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2-Carbamoyl-3,4,5,6-tetrafluorobenzoic acid

Tao Lu,^a Xiao-Jian Liao,^a Yuan-Wei Liang ^a and Shi-Hai Xu ^a ^*

^aDepartment of Chemistry, Jinan University, Guangzhou 510632, People's Republic of China
^*Correspondence e-mail: txush@jnu.edu.cn

(Received 8 June 2012; accepted 22 August 2012; online 5 September 2012)

In the title compound, C₈H₃F₄NO₃, the carboxy group lies nearly in the plane of the ring with a C—C—C—O torsion angle of −10.5 (4)°. The carbamoyl group is almost perpendicular to the benzene ring [C—C—C—O torsion angle = 82.2 (4) °]. In the crystal, molecules are linked via O—H⋯O and N—H⋯O hydrogen bonds involving the carbamoyl and carboxy groups.

Related literature

For general background to the title compound and its preparation, see: Xu et al. (2008 ); Li et al. (1999 ); Poshkus & Herweh (1957 ); Cai et al. (1992 ); Lee et al. (2005 ); Guo et al. (2011 ); Liao et al. (2011 ).

Experimental

Crystal data

C₈H₃F₄NO₃
M_r = 237.11
Monoclinic, P 2₁ /c
a = 14.5872 (6) Å
b = 6.9193 (3) Å
c = 8.6129 (4) Å
β = 100.086 (4)°
V = 855.89 (7) Å³
Z = 4
Cu Kα radiation
μ = 1.78 mm⁻¹
T = 268 K
0.42 × 0.31 × 0.17 mm

Data collection

Agilent Xcalibur Gemini ultra Sapphire-3 CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.643, T_max = 1.000
2346 measured reflections
1312 independent reflections
1240 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.091
S = 1.14
1312 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.82	1.78	2.5965 (18)	172
N1—H1A⋯O2ⁱⁱ	0.86	2.11	2.940 (2)	161
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812036549/rk2367sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812036549/rk2367Isup2.hkl

checkCIF report

Comment top

The title compound, C₈H₃F₄NO₃ (Scheme 1, Fig. 1), as an intermediate in the synthesis of coupling reagent (Xu et al., 2008; Li et al., 1999; Poshkus & Herweh, 1957), was prepared by the reaction of 3,4,5,6-tetrafluorophthalic anhydride and ammonia gas at 268 K (Cai et al., 1992; Lee et al., 2005; Guo et al., 2011; Liao et al., 2011) with yield about 90%. The bond lengths and angles in the title molecule are unexceptional. The carboxyl group lies nearly in the plane of phenyl ring - torsion angle C6/C1/C8/O2 = -10.5 (4)°. The aminoacyl group is practically perpendicular to phenyl ring - torsion angle C1/C6/C7/O3 = 82.2 (4)°. In the crystal structure there are some intermolecular hydrogen bonds between the carbonyl- and amino-groups (Table 1) which form a network.

Related literature top

For general background to the title compound and its preparation, see: Xu et al. (2008); Li et al. (1999); Poshkus & Herweh (1957); Cai et al. (1992); Lee et al. (2005); Guo et al. (2011); Liao et al. (2011).

Experimental top

The 44.0 g 3,4,5,6-tetrafluorophthalic anhydride and 700 ml tetrahydrofuran were mixed to form a solution. After stirred solution was cooled to 268 K, ammonia gas was added at the pressure of 0.1 MPa for 1.5 h formed white solid. The white solid residue was dissolved in 350 ml distilled water, tetrahydrofuran was removed in vacuum at room temperature. Hydrochloric acid (2N) was added to adjust solution pH1 at 268 K, after the resulting the title product was obtained by filtration. The crude product was recrystallized from distilled water and methanol to give colourless crystals of the title product.

Structure description top

2-Carbamoyl-3,4,5,6-tetrafluorobenzoic acid

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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 (Dolomanov et al., 2009).

Figures top

Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.

(I) top

Crystal data top

C₈H₃F₄NO₃	F(000) = 472
M_r = 237.11	D_x = 1.840 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.5418 Å
a = 14.5872 (6) Å	Cell parameters from 1702 reflections
b = 6.9193 (3) Å	θ = 5.2–62.6°
c = 8.6129 (4) Å	µ = 1.78 mm⁻¹
β = 100.086 (4)°	T = 268 K
V = 855.89 (7) Å³	Block, colourless
Z = 4	0.42 × 0.31 × 0.17 mm

Data collection top

Agilent Xcalibur Gemini ultra Sapphire-3 CCD diffractometer	1312 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1240 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.013
Detector resolution: 16.0288 pixels mm^-1	θ_max = 62.7°, θ_min = 7.1°
ω scans	h = −15→16
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −4→7
T_min = 0.643, T_max = 1.000	l = −9→9
2346 measured reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0432P)² + 0.5536P] where P = (F_o² + 2F_c²)/3
1312 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₈H₃F₄NO₃	V = 855.89 (7) Å³
M_r = 237.11	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 14.5872 (6) Å	µ = 1.78 mm⁻¹
b = 6.9193 (3) Å	T = 268 K
c = 8.6129 (4) Å	0.42 × 0.31 × 0.17 mm
β = 100.086 (4)°

Data collection top

Agilent Xcalibur Gemini ultra Sapphire-3 CCD diffractometer	1312 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1240 reflections with I > 2σ(I)
T_min = 0.643, T_max = 1.000	R_int = 0.013
2346 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.14	Δρ_max = 0.23 e Å⁻³
1312 reflections	Δρ_min = −0.17 e Å⁻³
146 parameters

Special details top

Experimental. Absorption correction: CrysAlisPro (Agilent Technologies, 2011); Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.27285 (8)	0.04074 (16)	0.69216 (13)	0.0293 (3)
F4	0.11543 (8)	0.66145 (18)	0.36824 (14)	0.0328 (3)
F2	0.09507 (9)	0.02888 (19)	0.54379 (17)	0.0416 (4)
O3	0.39455 (9)	0.41810 (19)	0.84775 (14)	0.0219 (3)
F3	0.01714 (8)	0.3444 (2)	0.38240 (16)	0.0394 (4)
O1	0.27710 (9)	0.8186 (2)	0.40108 (15)	0.0253 (4)
H1	0.3157	0.9023	0.3929	0.038*
O2	0.39129 (9)	0.7021 (2)	0.58320 (16)	0.0280 (4)
N1	0.45248 (11)	0.2650 (2)	0.65574 (18)	0.0234 (4)
H1A	0.5059	0.2493	0.7150	0.028*
H1B	0.4431	0.2227	0.5604	0.028*
C1	0.25134 (12)	0.5238 (3)	0.5229 (2)	0.0182 (4)
C5	0.23637 (13)	0.1978 (3)	0.6119 (2)	0.0213 (4)
C6	0.29012 (12)	0.3598 (3)	0.6086 (2)	0.0173 (4)
C4	0.14478 (14)	0.1886 (3)	0.5367 (2)	0.0266 (5)
C3	0.10574 (13)	0.3486 (3)	0.4559 (2)	0.0259 (5)
C8	0.31341 (12)	0.6916 (3)	0.5074 (2)	0.0182 (4)
C2	0.15862 (13)	0.5134 (3)	0.4498 (2)	0.0223 (4)
C7	0.38555 (12)	0.3533 (3)	0.7106 (2)	0.0174 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0368 (7)	0.0204 (6)	0.0312 (6)	0.0008 (5)	0.0074 (5)	0.0066 (5)
F4	0.0216 (6)	0.0325 (7)	0.0399 (7)	0.0031 (5)	−0.0069 (5)	0.0090 (5)
F2	0.0326 (7)	0.0308 (7)	0.0608 (9)	−0.0166 (6)	0.0066 (6)	0.0017 (6)
O3	0.0257 (7)	0.0245 (7)	0.0145 (7)	0.0056 (6)	0.0007 (5)	−0.0019 (5)
F3	0.0163 (6)	0.0463 (8)	0.0514 (8)	−0.0076 (5)	−0.0056 (5)	−0.0016 (6)
O1	0.0235 (7)	0.0248 (8)	0.0254 (7)	−0.0043 (6)	−0.0017 (6)	0.0084 (6)
O2	0.0205 (7)	0.0282 (8)	0.0318 (8)	−0.0053 (6)	−0.0053 (6)	0.0070 (6)
N1	0.0191 (8)	0.0329 (10)	0.0168 (8)	0.0069 (7)	−0.0009 (6)	−0.0051 (7)
C1	0.0191 (9)	0.0204 (10)	0.0153 (9)	0.0009 (7)	0.0036 (7)	−0.0015 (7)
C5	0.0257 (10)	0.0190 (10)	0.0203 (9)	0.0030 (8)	0.0068 (8)	0.0016 (7)
C6	0.0186 (9)	0.0200 (10)	0.0140 (8)	0.0013 (7)	0.0052 (7)	−0.0020 (7)
C4	0.0237 (10)	0.0265 (11)	0.0312 (11)	−0.0084 (8)	0.0090 (8)	−0.0043 (9)
C3	0.0153 (9)	0.0326 (12)	0.0288 (10)	−0.0020 (8)	0.0013 (8)	−0.0046 (9)
C8	0.0191 (9)	0.0198 (10)	0.0150 (9)	0.0012 (7)	0.0015 (7)	−0.0004 (7)
C2	0.0187 (9)	0.0262 (11)	0.0208 (9)	0.0036 (8)	0.0004 (7)	0.0014 (8)
C7	0.0213 (9)	0.0157 (9)	0.0153 (9)	0.0004 (7)	0.0032 (7)	0.0023 (7)

Geometric parameters (Å, º) top

F1—C5	1.346 (2)	N1—C7	1.308 (2)
F4—C2	1.336 (2)	C1—C6	1.416 (3)
F2—C4	1.329 (2)	C1—C8	1.493 (3)
O3—C7	1.249 (2)	C1—C2	1.390 (3)
F3—C3	1.336 (2)	C5—C6	1.371 (3)
O1—H1	0.8200	C5—C4	1.380 (3)
O1—C8	1.312 (2)	C6—C7	1.511 (2)
O2—C8	1.209 (2)	C4—C3	1.377 (3)
N1—H1A	0.8600	C3—C2	1.383 (3)
N1—H1B	0.8600

C8—O1—H1	109.5	F2—C4—C3	120.74 (17)
H1A—N1—H1B	120.0	C3—C4—C5	118.76 (18)
C7—N1—H1A	120.0	F3—C3—C4	120.14 (18)
C7—N1—H1B	120.0	F3—C3—C2	119.97 (18)
C6—C1—C8	118.48 (16)	C4—C3—C2	119.88 (17)
C2—C1—C6	117.56 (17)	O1—C8—C1	113.98 (15)
C2—C1—C8	123.83 (17)	O2—C8—O1	124.27 (17)
F1—C5—C6	119.64 (16)	O2—C8—C1	121.69 (16)
F1—C5—C4	117.84 (17)	F4—C2—C1	122.02 (17)
C6—C5—C4	122.52 (18)	F4—C2—C3	115.95 (16)
C1—C6—C7	124.76 (16)	C3—C2—C1	122.02 (18)
C5—C6—C1	119.22 (16)	O3—C7—N1	123.22 (17)
C5—C6—C7	115.81 (16)	O3—C7—C6	118.21 (15)
F2—C4—C5	120.50 (18)	N1—C7—C6	118.29 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.82	1.78	2.5965 (18)	172
N1—H1A···O3ⁱⁱ	0.86	2.82	3.281 (2)	116
N1—H1A···O2ⁱⁱ	0.86	2.11	2.940 (2)	161

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₃F₄NO₃
M_r	237.11
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	268
a, b, c (Å)	14.5872 (6), 6.9193 (3), 8.6129 (4)
β (°)	100.086 (4)
V (Å³)	855.89 (7)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.78
Crystal size (mm)	0.42 × 0.31 × 0.17

Data collection
Diffractometer	Agilent Xcalibur Gemini ultra Sapphire-3 CCD
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.643, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2346, 1312, 1240
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.576

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.091, 1.14
No. of reflections	1312
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.17

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.82	1.78	2.5965 (18)	172.4
N1—H1A···O3ⁱⁱ	0.86	2.82	3.281 (2)	115.6
N1—H1A···O2ⁱⁱ	0.86	2.11	2.940 (2)	161.2

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y−1/2, −z+3/2.

Acknowledgements

This work was supported by grants from the National Natural Science Fund (Nos. 21172094 and 20772048), Guangdong Science and Technology Plan projects (No. 2011 A080504007) and Tianhe Science and Technology Plan projects (No. 104ZH134).

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