Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027286/hk2269sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027286/hk2269Isup2.hkl |
CCDC reference: 654912
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.035
- wR factor = 0.090
- Data-to-parameter ratio = 7.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 7.31 PLAT431_ALERT_2_C Short Inter HL..A Contact F3 .. O1 .. 2.97 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O1 .. C7 .. 2.96 Ang.
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.99 From the CIF: _reflns_number_total 1388 Count of symmetry unique reflns 1391 Completeness (_total/calc) 99.78% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound, (I), was prepared by adding tetrachloro-N-phenylphthalimide (100 g, 0.28 mol) to 413 g sulfolane solution of KF (193 g, 3.3 mol) at 433 K (Nowak & Lin, 1991). After stirring for 3 h, the mixture was filtered hot, the product was separated from the sulfolane by the addition of cold water (1900 ml). The yellow solid, was recrystallized by the addition of acetic acid. Then, the crystals of compound (I) were obtained by evaporating the solvent ethyl acetate slowly at room temperature for about 7 d.
H atoms were positioned geometrically, with C—H = 0.93 Å for aromatic H atoms, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C),
The title compound, (I), can be utilized to synthsize 2,3,4,5-tetrafluoro- benzoic acid, it is an important intermediate of fluoroquinolone antibiotics (Cai et al., 2006). We report herein the crystal structure of the title compound, (I).
In the molecule of the title compound, (I), (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angles between the planar rings A (C1—C6), B (N/C7—C10) and C (C9—C14) are A/B = 50.13 (3)°, A/C = 48.34 (3)° and B/C = 3.80 (2)°.
For general backgroud, see: Cai et al. (2006); Allen et al. (1987). For related literature, see: Nowak & Lin (1991).
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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
C14H5F4NO2 | F(000) = 592 |
Mr = 295.19 | Dx = 1.638 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 7.0960 (14) Å | θ = 10–13° |
b = 8.4060 (17) Å | µ = 0.15 mm−1 |
c = 20.068 (4) Å | T = 298 K |
V = 1197.0 (4) Å3 | Block, colorless |
Z = 4 | 0.30 × 0.30 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | 1079 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 26.0°, θmin = 2.0° |
ω/2θ scans | h = −8→8 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→10 |
Tmin = 0.955, Tmax = 0.985 | l = 0→24 |
2348 measured reflections | 3 standard reflections every 120 min |
1388 independent reflections | intensity decay: none |
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) = 0.090 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.05P)2] where P = (Fo2 + 2Fc2)/3 |
1388 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C14H5F4NO2 | V = 1197.0 (4) Å3 |
Mr = 295.19 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.0960 (14) Å | µ = 0.15 mm−1 |
b = 8.4060 (17) Å | T = 298 K |
c = 20.068 (4) Å | 0.30 × 0.30 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | 1079 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.032 |
Tmin = 0.955, Tmax = 0.985 | 3 standard reflections every 120 min |
2348 measured reflections | intensity decay: none |
1388 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.15 e Å−3 |
1388 reflections | Δρmin = −0.16 e Å−3 |
190 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.7900 (3) | 1.1852 (2) | −0.18876 (8) | 0.0824 (6) | |
F2 | 0.4777 (3) | 1.2338 (2) | −0.11603 (10) | 0.0814 (7) | |
F3 | 0.4567 (2) | 1.1333 (2) | 0.01142 (9) | 0.0673 (5) | |
F4 | 1.0865 (3) | 1.0230 (2) | −0.13876 (8) | 0.0734 (6) | |
O1 | 1.2119 (3) | 0.8510 (2) | −0.01010 (9) | 0.0576 (5) | |
O2 | 0.6970 (3) | 0.9697 (3) | 0.11857 (9) | 0.0606 (5) | |
N | 0.9795 (3) | 0.8960 (3) | 0.06903 (10) | 0.0454 (5) | |
C1 | 1.0590 (6) | 0.6500 (4) | 0.21979 (15) | 0.0730 (10) | |
H1A | 0.9942 | 0.5770 | 0.2460 | 0.088* | |
C2 | 0.9740 (5) | 0.7132 (4) | 0.16367 (15) | 0.0605 (8) | |
H2A | 0.8535 | 0.6809 | 0.1514 | 0.073* | |
C3 | 1.0692 (4) | 0.8240 (3) | 0.12618 (12) | 0.0470 (6) | |
C4 | 1.2493 (4) | 0.8701 (4) | 0.14324 (14) | 0.0566 (8) | |
H4A | 1.3134 | 0.9445 | 0.1175 | 0.068* | |
C5 | 1.3328 (5) | 0.8057 (4) | 0.19844 (14) | 0.0682 (9) | |
H5A | 1.4542 | 0.8366 | 0.2102 | 0.082* | |
C6 | 1.2381 (6) | 0.6949 (5) | 0.23682 (15) | 0.0754 (10) | |
H6A | 1.2959 | 0.6509 | 0.2741 | 0.090* | |
C7 | 0.7977 (4) | 0.9623 (3) | 0.07029 (13) | 0.0478 (6) | |
C8 | 1.0603 (4) | 0.9040 (3) | 0.00558 (13) | 0.0461 (6) | |
C9 | 0.9221 (4) | 0.9915 (3) | −0.03620 (13) | 0.0450 (6) | |
C10 | 0.7641 (4) | 1.0220 (3) | 0.00212 (12) | 0.0457 (6) | |
C11 | 0.6128 (4) | 1.1016 (3) | −0.02440 (15) | 0.0511 (7) | |
C12 | 0.6241 (4) | 1.1549 (3) | −0.08918 (15) | 0.0574 (8) | |
C13 | 0.7831 (5) | 1.1282 (4) | −0.12682 (14) | 0.0582 (8) | |
C14 | 0.9322 (4) | 1.0455 (3) | −0.10040 (14) | 0.0536 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0990 (15) | 0.0909 (13) | 0.0573 (10) | 0.0218 (13) | −0.0001 (11) | 0.0167 (10) |
F2 | 0.0773 (14) | 0.0777 (12) | 0.0893 (14) | 0.0330 (12) | −0.0168 (11) | 0.0018 (11) |
F3 | 0.0498 (9) | 0.0643 (11) | 0.0878 (12) | 0.0148 (9) | 0.0115 (9) | −0.0076 (9) |
F4 | 0.0708 (11) | 0.0915 (13) | 0.0578 (9) | 0.0197 (12) | 0.0179 (9) | 0.0110 (9) |
O1 | 0.0524 (11) | 0.0644 (12) | 0.0560 (11) | 0.0151 (11) | 0.0074 (10) | −0.0006 (10) |
O2 | 0.0502 (11) | 0.0740 (14) | 0.0576 (11) | −0.0024 (12) | 0.0118 (10) | −0.0086 (10) |
N | 0.0443 (12) | 0.0505 (12) | 0.0413 (10) | −0.0034 (11) | 0.0016 (10) | −0.0022 (10) |
C1 | 0.088 (3) | 0.075 (2) | 0.0565 (18) | −0.005 (2) | 0.0140 (17) | 0.0132 (16) |
C2 | 0.0644 (19) | 0.0591 (17) | 0.0579 (16) | −0.0104 (17) | 0.0043 (16) | 0.0007 (15) |
C3 | 0.0492 (15) | 0.0501 (15) | 0.0415 (13) | −0.0017 (14) | 0.0028 (12) | −0.0029 (12) |
C4 | 0.0528 (17) | 0.068 (2) | 0.0487 (15) | −0.0076 (16) | 0.0000 (13) | 0.0009 (14) |
C5 | 0.0546 (18) | 0.097 (2) | 0.0527 (16) | −0.0034 (19) | −0.0084 (15) | 0.0002 (18) |
C6 | 0.083 (2) | 0.095 (3) | 0.0487 (16) | 0.013 (2) | 0.0006 (17) | 0.0082 (18) |
C7 | 0.0450 (14) | 0.0479 (15) | 0.0507 (14) | −0.0069 (14) | 0.0029 (13) | −0.0112 (12) |
C8 | 0.0462 (14) | 0.0445 (14) | 0.0477 (14) | 0.0008 (13) | 0.0036 (13) | −0.0069 (12) |
C9 | 0.0450 (14) | 0.0401 (13) | 0.0498 (14) | 0.0021 (12) | 0.0018 (12) | −0.0047 (11) |
C10 | 0.0468 (14) | 0.0376 (13) | 0.0525 (14) | −0.0007 (12) | 0.0042 (12) | −0.0081 (12) |
C11 | 0.0446 (14) | 0.0431 (14) | 0.0656 (17) | 0.0031 (14) | 0.0037 (14) | −0.0120 (13) |
C12 | 0.0617 (18) | 0.0432 (16) | 0.0672 (18) | 0.0119 (15) | −0.0094 (15) | −0.0059 (14) |
C13 | 0.070 (2) | 0.0550 (17) | 0.0494 (14) | 0.0080 (17) | 0.0001 (15) | −0.0001 (14) |
C14 | 0.0577 (17) | 0.0534 (16) | 0.0497 (14) | 0.0091 (15) | 0.0065 (14) | −0.0033 (13) |
F1—C13 | 1.333 (3) | C3—C4 | 1.379 (4) |
F2—C12 | 1.345 (3) | C4—C5 | 1.368 (4) |
F3—C11 | 1.347 (3) | C4—H4A | 0.9300 |
F4—C14 | 1.352 (3) | C5—C6 | 1.383 (5) |
O1—C8 | 1.206 (3) | C5—H5A | 0.9300 |
O2—C7 | 1.206 (3) | C6—H6A | 0.9300 |
N—C8 | 1.398 (3) | C7—C10 | 1.477 (4) |
N—C7 | 1.405 (4) | C8—C9 | 1.485 (4) |
N—C3 | 1.445 (3) | C9—C14 | 1.368 (4) |
C1—C6 | 1.369 (5) | C9—C10 | 1.384 (3) |
C1—C2 | 1.383 (5) | C10—C11 | 1.373 (4) |
C1—H1A | 0.9300 | C11—C12 | 1.377 (4) |
C2—C3 | 1.375 (4) | C12—C13 | 1.376 (4) |
C2—H2A | 0.9300 | C13—C14 | 1.373 (4) |
C8—N—C7 | 112.0 (2) | N—C7—C10 | 105.5 (2) |
C8—N—C3 | 124.2 (2) | O1—C8—N | 125.9 (3) |
C7—N—C3 | 123.8 (2) | O1—C8—C9 | 128.6 (3) |
C6—C1—C2 | 120.1 (3) | N—C8—C9 | 105.5 (2) |
C6—C1—H1A | 119.9 | C14—C9—C10 | 120.3 (3) |
C2—C1—H1A | 119.9 | C14—C9—C8 | 131.4 (3) |
C3—C2—C1 | 119.4 (3) | C10—C9—C8 | 108.2 (2) |
C3—C2—H2A | 120.3 | C11—C10—C9 | 120.6 (2) |
C1—C2—H2A | 120.3 | C11—C10—C7 | 130.6 (2) |
C2—C3—C4 | 120.7 (3) | C9—C10—C7 | 108.7 (2) |
C2—C3—N | 120.1 (3) | F3—C11—C10 | 122.2 (3) |
C4—C3—N | 119.2 (3) | F3—C11—C12 | 119.2 (3) |
C5—C4—C3 | 119.4 (3) | C10—C11—C12 | 118.6 (3) |
C5—C4—H4A | 120.3 | F2—C12—C13 | 119.6 (3) |
C3—C4—H4A | 120.3 | F2—C12—C11 | 119.6 (3) |
C4—C5—C6 | 120.5 (3) | C13—C12—C11 | 120.9 (3) |
C4—C5—H5A | 119.8 | F1—C13—C14 | 120.9 (3) |
C6—C5—H5A | 119.8 | F1—C13—C12 | 118.9 (3) |
C1—C6—C5 | 119.9 (3) | C14—C13—C12 | 120.2 (3) |
C1—C6—H6A | 120.1 | F4—C14—C9 | 122.2 (3) |
C5—C6—H6A | 120.1 | F4—C14—C13 | 118.4 (2) |
O2—C7—N | 125.4 (3) | C9—C14—C13 | 119.4 (3) |
O2—C7—C10 | 129.1 (3) | ||
C6—C1—C2—C3 | −1.6 (5) | C14—C9—C10—C7 | −175.3 (2) |
C1—C2—C3—C4 | 1.3 (4) | C8—C9—C10—C7 | 2.5 (3) |
C1—C2—C3—N | −177.4 (3) | O2—C7—C10—C11 | 0.5 (5) |
C8—N—C3—C2 | −129.0 (3) | N—C7—C10—C11 | −177.8 (3) |
C7—N—C3—C2 | 49.0 (4) | O2—C7—C10—C9 | 177.9 (3) |
C8—N—C3—C4 | 52.3 (4) | N—C7—C10—C9 | −0.4 (3) |
C7—N—C3—C4 | −129.7 (3) | C9—C10—C11—F3 | 180.0 (2) |
C2—C3—C4—C5 | −0.6 (4) | C7—C10—C11—F3 | −2.9 (5) |
N—C3—C4—C5 | 178.1 (3) | C9—C10—C11—C12 | −2.1 (4) |
C3—C4—C5—C6 | 0.2 (5) | C7—C10—C11—C12 | 175.1 (3) |
C2—C1—C6—C5 | 1.2 (6) | F3—C11—C12—F2 | −1.7 (4) |
C4—C5—C6—C1 | −0.5 (5) | C10—C11—C12—F2 | −179.7 (3) |
C8—N—C7—O2 | 179.6 (3) | F3—C11—C12—C13 | 178.4 (3) |
C3—N—C7—O2 | 1.4 (4) | C10—C11—C12—C13 | 0.4 (4) |
C8—N—C7—C10 | −2.1 (3) | F2—C12—C13—F1 | 1.8 (4) |
C3—N—C7—C10 | 179.7 (2) | C11—C12—C13—F1 | −178.4 (3) |
C7—N—C8—O1 | −177.2 (3) | F2—C12—C13—C14 | −178.9 (3) |
C3—N—C8—O1 | 1.0 (5) | C11—C12—C13—C14 | 1.0 (5) |
C7—N—C8—C9 | 3.5 (3) | C10—C9—C14—F4 | 177.7 (3) |
C3—N—C8—C9 | −178.3 (2) | C8—C9—C14—F4 | 0.5 (5) |
O1—C8—C9—C14 | −5.5 (5) | C10—C9—C14—C13 | −1.0 (4) |
N—C8—C9—C14 | 173.8 (3) | C8—C9—C14—C13 | −178.2 (3) |
O1—C8—C9—C10 | 177.0 (3) | F1—C13—C14—F4 | −0.1 (5) |
N—C8—C9—C10 | −3.7 (3) | C12—C13—C14—F4 | −179.4 (3) |
C14—C9—C10—C11 | 2.4 (4) | F1—C13—C14—C9 | 178.6 (3) |
C8—C9—C10—C11 | −179.8 (2) | C12—C13—C14—C9 | −0.7 (5) |
Experimental details
Crystal data | |
Chemical formula | C14H5F4NO2 |
Mr | 295.19 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 7.0960 (14), 8.4060 (17), 20.068 (4) |
V (Å3) | 1197.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.30 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.955, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2348, 1388, 1079 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.090, 1.03 |
No. of reflections | 1388 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.16 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1985), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
F1—C13 | 1.333 (3) | O2—C7 | 1.206 (3) |
F2—C12 | 1.345 (3) | N—C8 | 1.398 (3) |
F3—C11 | 1.347 (3) | N—C7 | 1.405 (4) |
F4—C14 | 1.352 (3) | N—C3 | 1.445 (3) |
O1—C8 | 1.206 (3) | ||
C8—N—C7 | 112.0 (2) | N—C8—C9 | 105.5 (2) |
C8—N—C3 | 124.2 (2) | F3—C11—C10 | 122.2 (3) |
C7—N—C3 | 123.8 (2) | F3—C11—C12 | 119.2 (3) |
C2—C3—N | 120.1 (3) | F2—C12—C13 | 119.6 (3) |
C4—C3—N | 119.2 (3) | F2—C12—C11 | 119.6 (3) |
O2—C7—N | 125.4 (3) | F1—C13—C14 | 120.9 (3) |
O2—C7—C10 | 129.1 (3) | F1—C13—C12 | 118.9 (3) |
N—C7—C10 | 105.5 (2) | F4—C14—C9 | 122.2 (3) |
O1—C8—N | 125.9 (3) | F4—C14—C13 | 118.4 (2) |
O1—C8—C9 | 128.6 (3) |
The title compound, (I), can be utilized to synthsize 2,3,4,5-tetrafluoro- benzoic acid, it is an important intermediate of fluoroquinolone antibiotics (Cai et al., 2006). We report herein the crystal structure of the title compound, (I).
In the molecule of the title compound, (I), (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angles between the planar rings A (C1—C6), B (N/C7—C10) and C (C9—C14) are A/B = 50.13 (3)°, A/C = 48.34 (3)° and B/C = 3.80 (2)°.