organic compounds
2-Carbamoyl-3,4,5,6-tetrafluorobenzoic acid
aDepartment of Chemistry, Jinan University, Guangzhou 510632, People's Republic of China
*Correspondence e-mail: txush@jnu.edu.cn
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
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2011); cell 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
https://doi.org/10.1107/S1600536812036549/rk2367sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812036549/rk2367Isup2.hkl
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.
All H atoms were positioned geometrically and were included in the
in the riding-model approximation, with distances: 0.86Å (NH2), 0.82Å (OH) with Uiso(H) = 1.2Ueq(N) and Uiso(H) = 1.5Ueq(O) .Data collection: CrysAlis PRO (Agilent, 2011); cell
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).C8H3F4NO3 | F(000) = 472 |
Mr = 237.11 | Dx = 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 |
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 | Rint = 0.013 |
Detector resolution: 16.0288 pixels mm-1 | θmax = 62.7°, θmin = 7.1° |
ω scans | h = −15→16 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −4→7 |
Tmin = 0.643, Tmax = 1.000 | l = −9→9 |
2346 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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0432P)2 + 0.5536P] where P = (Fo2 + 2Fc2)/3 |
1312 reflections | (Δ/σ)max < 0.001 |
146 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C8H3F4NO3 | V = 855.89 (7) Å3 |
Mr = 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)° |
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) |
Tmin = 0.643, Tmax = 1.000 | Rint = 0.013 |
2346 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.23 e Å−3 |
1312 reflections | Δρmin = −0.17 e Å−3 |
146 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.643, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2346, 1312, 1240 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.23, −0.17 |
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).
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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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.