Acta Cryst. (2008). E64, o808 [ doi:10.1107/S1600536808008891 ]
The crystal structure of the title salt, C6H7FN+·C8H5FNO3-, exhibits intramolecular N-H
O and C-HO and intermolecular N-HO and N-HF hydrogen-bond interactions, the intramolecular hydrogen-bond interactions generating S(6) and S(5) ring motifs. The dihedral angles between the aromatic ring and the intramolecular hydrogen-bonded rings in the anion are 2.97 (7) and 6.70 (5)°. The two aromatic rings of the title compound are oriented with a dihedral angle of 77.25 (9)°.
The title compound was prepared according to the method described by Büyükgüngör & Odabaşoǧlu (2006b), using 2-fluoroaniline and oxalic acid as starting materials (yield 90%). Crystals of (I) suitable for x-ray analysis were obtained by slow evaporation of an ethanol (95%) solution at room temperature.
H atom (for NH3) was located in difference synthesis and refined freely. The remaining H atoms were positioned geometrically, with C—H = 0.93 for aromatic H and N—H = 0.86 Å for amine H, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(parent).
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./at2556fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The hydrogen bonds are drawn as dashed lines. |
![[Figure 2]](./at2556fig2thm.gif)
| Fig. 2. A partial packing diagram of (I), showing the formation of R12(5)R42(8)R44(12) motifs. H atoms not involved in hydrogen bonds have been omitted for clarity. [Symmetry codes: (i) 1 - x, 1 - y, z; (ii) x, y - 1, z; (iii) -x, y, -z; (iv) 1 - x, -y, -z; (v) -x, -y, -z]. |
![[Figure 3]](./at2556fig3thm.gif)
| Fig. 3. A partial packing diagram of (I), showing the formation of R22(10) motif. H atoms not involved in hydrogen bonds have been omitted for clarity. [Symmetry code: (i) 1 - x, -y, 1 - z]. |
| C6H7FN+·C8H5FNO3– | Z = 2 |
| Mr = 294.26 | F000 = 304 |
| Triclinic, P1 | Dx = 1.429 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 6.7118 (9) Å | Cell parameters from 9218 reflections |
| b = 9.5998 (14) Å | θ = 1.9–28.1º |
| c = 11.7000 (16) Å | µ = 0.12 mm−1 |
| α = 68.346 (11)º | T = 296 K |
| β = 85.791 (11)º | Plate, colourless |
| γ = 77.375 (11)º | 0.78 × 0.47 × 0.09 mm |
| V = 683.69 (18) Å3 |
| Stoe IPDSII diffractometer | 2684 independent reflections |
| Monochromator: plane graphite | 2023 reflections with I > 2σ(I) |
| Detector resolution: 6.67 pixels mm-1 | Rint = 0.040 |
| T = 296 K | θmax = 26.0º |
| ω rotation method scans | θmin = 1.9º |
| Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | h = −8→8 |
| Tmin = 0.932, Tmax = 0.988 | k = −11→11 |
| 9218 measured reflections | l = −14→14 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.053 | w = 1/[σ2(Fo2) + (0.1051P)2 + 0.5375P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.168 | (Δ/σ)max < 0.001 |
| S = 0.81 | Δρmax = 0.53 e Å−3 |
| 2684 reflections | Δρmin = −0.30 e Å−3 |
| 203 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.026 (7) |
| Secondary atom site location: difference Fourier map |
| C6H7FN+·C8H5FNO3– | γ = 77.375 (11)º |
| Mr = 294.26 | V = 683.69 (18) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 6.7118 (9) Å | Mo Kα |
| b = 9.5998 (14) Å | µ = 0.12 mm−1 |
| c = 11.7000 (16) Å | T = 296 K |
| α = 68.346 (11)º | 0.78 × 0.47 × 0.09 mm |
| β = 85.791 (11)º |
| Stoe IPDSII diffractometer | 2684 independent reflections |
| Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 2023 reflections with I > 2σ(I) |
| Tmin = 0.932, Tmax = 0.988 | Rint = 0.040 |
| 9218 measured reflections |
| R[F2 > 2σ(F2)] = 0.053 | 203 parameters |
| wR(F2) = 0.168 | H atoms treated by a mixture of independent and constrained refinement |
| S = 0.81 | Δρmax = 0.53 e Å−3 |
| 2684 reflections | Δρmin = −0.30 e Å−3 |
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 | ||
| C1 | 0.0927 (4) | 0.1895 (3) | 0.4566 (2) | 0.0500 (6) | |
| C2 | 0.2329 (5) | 0.2000 (4) | 0.5327 (3) | 0.0662 (7) | |
| C3 | 0.1793 (7) | 0.2559 (5) | 0.6239 (3) | 0.0882 (10) | |
| H3 | 0.2783 | 0.2599 | 0.6735 | 0.106* | |
| C4 | −0.0226 (7) | 0.3060 (5) | 0.6414 (3) | 0.0958 (12) | |
| H4 | −0.0625 | 0.3456 | 0.7030 | 0.115* | |
| C5 | −0.1675 (6) | 0.2980 (4) | 0.5682 (3) | 0.0826 (9) | |
| H5 | −0.3050 | 0.3322 | 0.5809 | 0.099* | |
| C6 | −0.1122 (4) | 0.2399 (3) | 0.4759 (2) | 0.0619 (7) | |
| H6 | −0.2116 | 0.2347 | 0.4272 | 0.074* | |
| C7 | 0.0672 (3) | 0.1176 (3) | 0.2757 (2) | 0.0452 (5) | |
| C8 | 0.2108 (3) | 0.0541 (3) | 0.1899 (2) | 0.0472 (5) | |
| C9 | 0.5179 (4) | 0.6758 (3) | 0.1045 (2) | 0.0592 (7) | |
| C10 | 0.3396 (3) | 0.7306 (3) | 0.0369 (2) | 0.0447 (5) | |
| C11 | 0.2088 (5) | 0.6328 (3) | 0.0524 (3) | 0.0625 (7) | |
| H11 | 0.0855 | 0.6678 | 0.0095 | 0.075* | |
| C12 | 0.2612 (6) | 0.4827 (4) | 0.1318 (3) | 0.0804 (9) | |
| H12 | 0.1723 | 0.4171 | 0.1420 | 0.097* | |
| C13 | 0.4415 (6) | 0.4291 (4) | 0.1955 (3) | 0.0803 (9) | |
| H13 | 0.4763 | 0.3270 | 0.2472 | 0.096* | |
| C14 | 0.5722 (5) | 0.5263 (4) | 0.1834 (3) | 0.0787 (9) | |
| H14 | 0.6942 | 0.4915 | 0.2277 | 0.094* | |
| N1 | 0.1682 (3) | 0.1288 (2) | 0.36637 (17) | 0.0496 (5) | |
| H1 | 0.2978 | 0.0935 | 0.3692 | 0.060* | |
| N2 | 0.2905 (3) | 0.8889 (2) | −0.04487 (19) | 0.0447 (5) | |
| O1 | −0.1162 (3) | 0.1563 (2) | 0.25841 (17) | 0.0638 (5) | |
| O2 | 0.1240 (3) | 0.0321 (2) | 0.10956 (16) | 0.0587 (5) | |
| O3 | 0.3972 (3) | 0.0349 (2) | 0.20670 (16) | 0.0651 (5) | |
| F1 | 0.4339 (3) | 0.1515 (3) | 0.51255 (18) | 0.0919 (7) | |
| F2 | 0.6443 (3) | 0.7710 (2) | 0.0900 (2) | 0.1002 (7) | |
| H2A | 0.243 (5) | 0.946 (3) | 0.004 (3) | 0.069 (8)* | |
| H2B | 0.396 (5) | 0.915 (3) | −0.094 (3) | 0.064 (8)* | |
| H2C | 0.187 (5) | 0.898 (3) | −0.092 (3) | 0.073 (9)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0559 (14) | 0.0517 (13) | 0.0407 (12) | −0.0165 (11) | 0.0003 (10) | −0.0118 (10) |
| C2 | 0.0678 (18) | 0.0816 (19) | 0.0546 (15) | −0.0240 (15) | −0.0014 (13) | −0.0257 (14) |
| C3 | 0.107 (3) | 0.115 (3) | 0.0628 (19) | −0.040 (2) | 0.0018 (18) | −0.0461 (19) |
| C4 | 0.134 (4) | 0.105 (3) | 0.068 (2) | −0.035 (2) | 0.020 (2) | −0.051 (2) |
| C5 | 0.086 (2) | 0.090 (2) | 0.075 (2) | −0.0135 (18) | 0.0180 (17) | −0.0395 (18) |
| C6 | 0.0621 (16) | 0.0686 (17) | 0.0554 (15) | −0.0137 (13) | 0.0054 (12) | −0.0239 (13) |
| C7 | 0.0433 (13) | 0.0461 (12) | 0.0438 (12) | −0.0093 (10) | −0.0035 (9) | −0.0128 (10) |
| C8 | 0.0418 (12) | 0.0501 (13) | 0.0448 (12) | −0.0068 (10) | −0.0029 (9) | −0.0124 (10) |
| C9 | 0.0528 (15) | 0.0617 (16) | 0.0590 (15) | −0.0124 (12) | −0.0016 (12) | −0.0166 (12) |
| C10 | 0.0465 (12) | 0.0475 (12) | 0.0420 (11) | −0.0057 (10) | 0.0015 (9) | −0.0211 (10) |
| C11 | 0.0719 (18) | 0.0591 (16) | 0.0633 (16) | −0.0226 (13) | −0.0022 (13) | −0.0243 (13) |
| C12 | 0.102 (3) | 0.0582 (18) | 0.083 (2) | −0.0320 (17) | 0.0009 (19) | −0.0194 (16) |
| C13 | 0.102 (3) | 0.0503 (16) | 0.0728 (19) | −0.0055 (16) | 0.0036 (18) | −0.0103 (14) |
| C14 | 0.0662 (19) | 0.078 (2) | 0.0695 (19) | 0.0046 (16) | −0.0092 (15) | −0.0104 (16) |
| N1 | 0.0409 (10) | 0.0623 (12) | 0.0463 (11) | −0.0105 (9) | −0.0033 (8) | −0.0198 (9) |
| N2 | 0.0391 (11) | 0.0510 (11) | 0.0458 (11) | −0.0096 (8) | −0.0009 (9) | −0.0192 (9) |
| O1 | 0.0404 (10) | 0.0909 (14) | 0.0671 (11) | −0.0012 (9) | −0.0080 (8) | −0.0420 (10) |
| O2 | 0.0498 (10) | 0.0734 (12) | 0.0605 (10) | −0.0046 (8) | −0.0034 (8) | −0.0369 (9) |
| O3 | 0.0402 (10) | 0.0987 (15) | 0.0522 (10) | −0.0088 (9) | −0.0004 (7) | −0.0254 (10) |
| F1 | 0.0653 (11) | 0.1443 (18) | 0.0815 (12) | −0.0250 (11) | −0.0134 (9) | −0.0540 (12) |
| F2 | 0.0742 (12) | 0.0985 (15) | 0.1081 (15) | −0.0317 (10) | −0.0328 (11) | −0.0010 (12) |
| C1—C6 | 1.386 (4) | C9—F2 | 1.337 (3) |
| C1—C2 | 1.385 (4) | C9—C14 | 1.374 (4) |
| C1—N1 | 1.399 (3) | C9—C10 | 1.375 (3) |
| C2—C3 | 1.356 (5) | C10—C11 | 1.377 (3) |
| C2—F1 | 1.361 (4) | C10—N2 | 1.445 (3) |
| C3—C4 | 1.363 (5) | C11—C12 | 1.378 (4) |
| C3—H3 | 0.9300 | C11—H11 | 0.9300 |
| C4—C5 | 1.375 (5) | C12—C13 | 1.365 (5) |
| C4—H4 | 0.9300 | C12—H12 | 0.9300 |
| C5—C6 | 1.381 (4) | C13—C14 | 1.379 (5) |
| C5—H5 | 0.9300 | C13—H13 | 0.9300 |
| C6—H6 | 0.9300 | C14—H14 | 0.9300 |
| C7—O1 | 1.214 (3) | N1—H1 | 0.8600 |
| C7—N1 | 1.349 (3) | N2—H2A | 0.93 (3) |
| C7—C8 | 1.536 (3) | N2—H2B | 0.90 (3) |
| C8—O3 | 1.244 (3) | N2—H2C | 0.89 (3) |
| C8—O2 | 1.244 (3) | ||
| C6—C1—C2 | 117.3 (2) | C14—C9—C10 | 122.3 (3) |
| C6—C1—N1 | 125.0 (2) | C9—C10—C11 | 118.4 (2) |
| C2—C1—N1 | 117.7 (2) | C9—C10—N2 | 119.9 (2) |
| C3—C2—F1 | 119.5 (3) | C11—C10—N2 | 121.7 (2) |
| C3—C2—C1 | 123.4 (3) | C12—C11—C10 | 119.8 (3) |
| F1—C2—C1 | 117.0 (2) | C12—C11—H11 | 120.1 |
| C2—C3—C4 | 118.7 (3) | C10—C11—H11 | 120.1 |
| C2—C3—H3 | 120.7 | C13—C12—C11 | 120.9 (3) |
| C4—C3—H3 | 120.7 | C13—C12—H12 | 119.5 |
| C3—C4—C5 | 120.0 (3) | C11—C12—H12 | 119.5 |
| C3—C4—H4 | 120.0 | C12—C13—C14 | 120.1 (3) |
| C5—C4—H4 | 120.0 | C12—C13—H13 | 120.0 |
| C6—C5—C4 | 121.1 (3) | C14—C13—H13 | 120.0 |
| C6—C5—H5 | 119.5 | C9—C14—C13 | 118.5 (3) |
| C4—C5—H5 | 119.5 | C9—C14—H14 | 120.8 |
| C5—C6—C1 | 119.5 (3) | C13—C14—H14 | 120.8 |
| C5—C6—H6 | 120.3 | C7—N1—C1 | 129.4 (2) |
| C1—C6—H6 | 120.3 | C7—N1—H1 | 115.3 |
| O1—C7—N1 | 125.5 (2) | C1—N1—H1 | 115.3 |
| O1—C7—C8 | 121.8 (2) | C10—N2—H2A | 106.5 (18) |
| N1—C7—C8 | 112.65 (19) | C10—N2—H2B | 111.4 (18) |
| O3—C8—O2 | 128.1 (2) | H2A—N2—H2B | 116 (3) |
| O3—C8—C7 | 116.8 (2) | C10—N2—H2C | 106.7 (19) |
| O2—C8—C7 | 115.1 (2) | H2A—N2—H2C | 108 (3) |
| F2—C9—C14 | 119.3 (3) | H2B—N2—H2C | 108 (3) |
| F2—C9—C10 | 118.4 (2) | ||
| C6—C1—C2—C3 | 0.2 (4) | F2—C9—C10—C11 | −179.6 (2) |
| N1—C1—C2—C3 | −179.6 (3) | C14—C9—C10—C11 | 2.2 (4) |
| C6—C1—C2—F1 | −179.5 (2) | F2—C9—C10—N2 | −1.7 (4) |
| N1—C1—C2—F1 | 0.7 (4) | C14—C9—C10—N2 | −179.9 (3) |
| F1—C2—C3—C4 | 179.0 (3) | C9—C10—C11—C12 | −1.8 (4) |
| C1—C2—C3—C4 | −0.7 (5) | N2—C10—C11—C12 | −179.7 (3) |
| C2—C3—C4—C5 | 0.6 (6) | C10—C11—C12—C13 | 0.0 (5) |
| C3—C4—C5—C6 | −0.2 (6) | C11—C12—C13—C14 | 1.6 (5) |
| C4—C5—C6—C1 | −0.3 (5) | F2—C9—C14—C13 | −178.8 (3) |
| C2—C1—C6—C5 | 0.2 (4) | C10—C9—C14—C13 | −0.6 (5) |
| N1—C1—C6—C5 | −179.9 (3) | C12—C13—C14—C9 | −1.3 (5) |
| O1—C7—C8—O3 | 171.7 (2) | O1—C7—N1—C1 | −2.4 (4) |
| N1—C7—C8—O3 | −6.3 (3) | C8—C7—N1—C1 | 175.6 (2) |
| O1—C7—C8—O2 | −6.5 (3) | C6—C1—N1—C7 | 6.0 (4) |
| N1—C7—C8—O2 | 175.5 (2) | C2—C1—N1—C7 | −174.2 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O3 | 0.86 | 2.19 | 2.623 (3) | 111 |
| N1—H1···F1i | 0.86 | 2.61 | 3.313 (3) | 140 |
| N2—H2A···O2ii | 0.93 (3) | 1.77 (3) | 2.696 (3) | 170 (3) |
| N2—H2B···O3iii | 0.90 (3) | 1.86 (3) | 2.753 (3) | 174 (3) |
| N2—H2C···O2iv | 0.89 (3) | 2.05 (3) | 2.802 (3) | 142 (3) |
| N2—H2C···O1iv | 0.89 (3) | 2.30 (3) | 3.041 (3) | 141 (3) |
| C6—H6···O1 | 0.93 | 2.36 | 2.941 (3) | 120 |
| Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y+1, z; (iii) −x+1, −y+1, −z; (iv) −x, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O3 | 0.86 | 2.19 | 2.623 (3) | 111 |
| N1—H1···F1i | 0.86 | 2.61 | 3.313 (3) | 140 |
| N2—H2A···O2ii | 0.93 (3) | 1.77 (3) | 2.696 (3) | 170 (3) |
| N2—H2B···O3iii | 0.90 (3) | 1.86 (3) | 2.753 (3) | 174 (3) |
| N2—H2C···O2iv | 0.89 (3) | 2.05 (3) | 2.802 (3) | 142 (3) |
| N2—H2C···O1iv | 0.89 (3) | 2.30 (3) | 3.041 (3) | 141 (3) |
| C6—H6···O1 | 0.93 | 2.36 | 2.941 (3) | 120 |
| Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y+1, z; (iii) −x+1, −y+1, −z; (iv) −x, −y+1, −z. |
The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDSII diffractometer (purchased under grant F. 279 of the University Research Fund).
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The present work is part of a structural study of compounds of anillinium carboxylates and we report here the structure of 2-fluoroanilinium 2-(2-fluorophenylamino)-2-oxoacetate, (I).
The title compound (I) is built up from a 2-fluoroanilinium cation and 2-(2-fluorophenylamino)-2-oxoacetate anion (Fig. 1). There are two intramolecular hydrogen bonds which generate S(6)and S(5) motifs (Bernstein et al., 1995; Etter, 1990), and the anions and cations of (I) are linked to each other by five intermolecular hydrogen bond interactions (Table 1.). The intermolecular hydrogen interactions, except N—H···F, generate R12(5)R42(8)R44(12) motifs (Fig. 2) and these motifs link N—H···F hydrogen bonded R22(10) rings (Fig. 3) forming a three dimensional network. The dihedral angles between the aromatic ring and intramolecular hydrogen bonded rings in the anion are 2.97 (7)° and 6.70 (5)°. The two aromatic rings of the title compound are oriented with a dihedral angle of 77.25 (9)°.