The molecule adopts an E configuration at the C=C double bond. The dihedral angle between the benzene ring and the prop-1-enyl group is 25.4 (3)°. In the crystal, molecules are linked via N—H⋯F hydrogen bonds, forming inversion dimers which are linked into ribbons along the b axis by C—H⋯N hydrogen bonds. The ribbons are linked by N—H⋯π and C—H⋯π interactions, generating a three-dimensional network.
Keywords: crystal structure; 3,3,3-trifluoroprop-1-en; aniline; hydrogen bonding
Abstract
The molecule of the title compound, C9H8F3N, adopts an E configuration with respect to the C=C double bond. The dihedral angle between the benzene ring and the prop-1-enyl group is 25.4 (3)°. In the crystal, molecules are linked via pairs of N—H⋯F hydrogen bonds into inversion dimers with an R 2 2(16) ring motif. The dimers are linked by C—H⋯N hydrogen bonds, forming a ribbon structure along the b-axis direction. The ribbons are linked by N—H⋯π and C—H⋯π interactions, generating a three-dimensional network.
Chemical context
Fluorescein, rhodamine etc. are water-soluble fluorescent reagents. Their derivatives exhibit strong fluorescence in aqueous solution and so can be utilized as ion-probes and in bio-imaging (Aron et al., 2016 ▸; Li et al., 2016 ▸). However, complicated procedures are required to obtain them. It is therefore desirable to develop a new fluorescent reagent with a simple structure that can be obtained by a short-step synthetic process. The title compound has a quite simple structure and is a small molecule, consisting of aniline and 3,3,3-trifluoroprop-1-enyl units, which emits strong fluorescence not only in organic solvents but also in an aqueous medium (H2O/DMSO, 90:10, v/v). Since aniline derivatives with 2,4-bis(3,3,3-trifluoroprop-1-enyl) have been used as fluorogenic substrates for dipepeptidyl peptidase-4 (Ogawa et al., 2017 ▸), the title compound can be treated as a simple but essential component in emitting fluorescence. Hence, it is important to study the relationship between the fluorescent properties and the molecular structure of the title compound. We report here its molecular and crystal structure.
Structural commentary
The molecular structure of the title compound is shown in Fig. 1 ▸. The molecule adopts an E configuration with respect to the C=C double bond. The dihedral angle between the benzene ring and the prop-1-enyl group is 25.4 (3)°. The C5—C10—C11—C12 and C9—C10—C11—C12 torsion angles are −158.9 (3) and 24.6 (4)°, respectively. The bond lengths and angles in the title compound are normal and agree with those in other trifluoropropenylaniline compounds (Shimizu et al., 2009 ▸; Lin et al., 2014 ▸).
Figure 1.
The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
Supramolecular features
In the crystal, two molecules are associated through a pair of intermolecular N—H⋯F hydrogen bonds (Table 1 ▸), forming a centrosymmetric dimer with an 
(16) ring motif (Fig. 2 ▸). The dimers are further linked by C—H⋯N hydrogen bonds (Table 1 ▸), forming a ribbon with a C(6) chain motif along the b-axis direction. The ribbons are linked by N—H⋯π and C—H⋯π interactions (Table 1 ▸), generating a three-dimensional network.
Table 1. Hydrogen-bond geometry (Å, °).
Cg1 is the centroid of the C5–C10 ring.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| N4—H4A⋯F2i | 0.90 (3) | 2.46 (4) | 3.352 (3) | 169 (3) |
| C12—H12⋯N4ii | 0.95 | 2.56 | 3.432 (4) | 152 |
| N4—H4B⋯Cg1iii | 0.88 (3) | 2.59 (4) | 3.315 (2) | 140 (3) |
| C9—H9⋯Cg1iv | 0.95 | 2.73 | 3.480 (3) | 136 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
.
Figure 2.
A packing diagram of the title compound, viewed along the b axis. The N—H⋯F and C—H⋯N hydrogen bonds and N—H⋯π and C—H⋯π interactions are shown as dashed lines.
Database survey
A search of the Cambridge Structural Database (CSD, Version 5.39; May 2018; Groom et al., 2016 ▸) gave 16 hits for 2-(3,3,3-trifluoroprop-1-en-1-yl)azabenzene derivatives, and gave 18 and 45 hits for (E)-3,3,3-trifluoroprop-1-enyl and 2-aminophenyl-1-enyl fragments, respectively. Of these structures, those that resemble the title compound are 4-[2-(3,3,3-trifluoroprop-1-en-1-yl)phenyl]morpholine (Lin et al., 2014 ▸), N-acetyl-N-{2-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]phenyl}acetamide (Niu et al., 2009 ▸) and (E,E)-1,4-dipiperidino-2,5-bis(3,3,3-trifluoroprop-1-enyl)benzene (Shimizu et al., 2009 ▸).
Synthesis and crystallization
The title compound was prepared by a modification of a reported procedure (Omote et al., 2013 ▸). In a glove box purged with argon gas, iodoaniline (1.0 mmol), (2-methylallyl)palladium(II) chloride dimer (0.1mmol), CuF2 (2.0 mmol) and 2,2′-bipyridyl (2.0 mmol) were placed in a flask. To the flask were added anhydrous DMF (6.0 ml) and (E)-trimethyl-(3,3,3-trifluoroprop-1-enyl)silane (2.0 mmol), and the mixture was stirred at 353 K. After the reaction mixture had been stirred for 4 h, it was poured into ice–water. The mixture was extracted with CH2Cl2, and the organic layer was dried over anhydrous MgSO4. After the solid had been filtered off, the solvent was removed in vacuo, and the residue was purified by silica gel column chromatography to give the product in 68% yield. Colourless single crystals were obtained by recrystallization from an ethyl acetate–hexane (1:10, v/v) solution (m.p. 321–322 K). 1H NMR (CDCl3) δ: 3.81 (2H, s), 6.13 (1H, qd, J = 15.9, 6.5 Hz), 6.72 (1H, dd, J = 8.2, 0.9 Hz), 6.80 (1H, dt, J = 7.5, 0.9 Hz), 7.18 (1H, dt, J = 7.8, 1.4 Hz), 7.24 (1H, qd, J = 15.9, 2.1 Hz), 7.29 (1H, dd, J = 7.8, 1.4 Hz). 13C NMR (CDCl3) δ: 116.6 (q, J = 33.4 Hz), 116.8, 119.2, 119.4, 123.6 (q, J = 269.0 Hz), 127.9, 130.9, 133.3 (q, J = 6.8 Hz), 144.8. 19F NMR (CDCl3) δ: 12.07 (3F, dd, J = 6.5, 2.2 Hz). MS m/z 187 (M +), HRMS calculated for C9H8F3N 187.1617 (M +), found 187.0603.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The amino H atoms were located in a difference Fourier map and refined freely. The C-bound H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined using a riding model with U
iso(H) = 1.2U
eq(C). One outlier (
11) was omitted in the last cycle of refinement.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C9H8F3N |
| M r | 187.16 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 123 |
| a, b, c (Å) | 7.3925 (4), 6.2777 (3), 18.6065 (9) |
| β (°) | 96.243 (7) |
| V (Å3) | 858.37 (8) |
| Z | 4 |
| Radiation type | Cu Kα |
| μ (mm−1) | 1.16 |
| Crystal size (mm) | 0.40 × 0.26 × 0.08 |
| Data collection | |
| Diffractometer | Rigaku R-AXIS RAPID |
| Absorption correction | Multi-scan (ABSCOR; Higashi, 1995 ▸) |
| T min, T max | 0.543, 0.912 |
| No. of measured, independent and observed [F 2 > 2.0σ(F 2)] reflections | 4753, 1566, 1178 |
| R int | 0.049 |
| (sin θ/λ)max (Å−1) | 0.602 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.061, 0.175, 1.03 |
| No. of reflections | 1566 |
| No. of parameters | 126 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.49, −0.39 |
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018012756/is5499sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018012756/is5499Isup2.hkl
CCDC reference: 1866671
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Crystal data
| C9H8F3N | F(000) = 384.00 |
| Mr = 187.16 | Dx = 1.448 Mg m−3 |
| Monoclinic, P21/c | Cu Kα radiation, λ = 1.54187 Å |
| a = 7.3925 (4) Å | Cell parameters from 4006 reflections |
| b = 6.2777 (3) Å | θ = 4.8–68.2° |
| c = 18.6065 (9) Å | µ = 1.16 mm−1 |
| β = 96.243 (7)° | T = 123 K |
| V = 858.37 (8) Å3 | Platelet, colourless |
| Z = 4 | 0.40 × 0.26 × 0.08 mm |
Data collection
| Rigaku R-AXIS RAPID diffractometer | 1178 reflections with F2 > 2.0σ(F2) |
| Detector resolution: 10.000 pixels mm-1 | Rint = 0.049 |
| ω scans | θmax = 68.2°, θmin = 4.8° |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −8→8 |
| Tmin = 0.543, Tmax = 0.912 | k = −6→7 |
| 4753 measured reflections | l = −22→22 |
| 1566 independent reflections |
Refinement
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.175 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.1029P)2 + 0.1188P] where P = (Fo2 + 2Fc2)/3 |
| 1566 reflections | (Δ/σ)max < 0.001 |
| 126 parameters | Δρmax = 0.49 e Å−3 |
| 0 restraints | Δρmin = −0.39 e Å−3 |
| Primary atom site location: structure-invariant direct methods |
Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
| Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 sigma(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| F1 | 0.2762 (3) | −0.0078 (3) | 0.52691 (8) | 0.0597 (7) | |
| F2 | 0.3860 (2) | −0.3171 (3) | 0.51696 (8) | 0.0569 (6) | |
| F3 | 0.0979 (2) | −0.2730 (4) | 0.50888 (9) | 0.0661 (7) | |
| N4 | 0.3895 (3) | 0.4055 (4) | 0.31939 (13) | 0.0343 (6) | |
| C5 | 0.3078 (3) | 0.2521 (4) | 0.27331 (13) | 0.0272 (6) | |
| C6 | 0.2853 (3) | 0.2886 (4) | 0.19799 (12) | 0.0293 (6) | |
| H6 | 0.3289 | 0.4171 | 0.1791 | 0.035* | |
| C7 | 0.2009 (3) | 0.1398 (4) | 0.15202 (13) | 0.0311 (6) | |
| H7 | 0.1863 | 0.1670 | 0.1015 | 0.037* | |
| C8 | 0.1362 (4) | −0.0502 (4) | 0.17775 (12) | 0.0311 (6) | |
| H8 | 0.0788 | −0.1528 | 0.1453 | 0.037* | |
| C9 | 0.1567 (3) | −0.0871 (4) | 0.25119 (12) | 0.0276 (6) | |
| H9 | 0.1123 | −0.2164 | 0.2691 | 0.033* | |
| C10 | 0.2413 (3) | 0.0608 (4) | 0.30004 (11) | 0.0220 (6) | |
| C11 | 0.2527 (3) | 0.0253 (4) | 0.37877 (12) | 0.0276 (6) | |
| H11 | 0.2651 | 0.1475 | 0.4090 | 0.033* | |
| C12 | 0.2471 (3) | −0.1615 (4) | 0.41076 (12) | 0.0310 (6) | |
| H12 | 0.2410 | −0.2856 | 0.3814 | 0.037* | |
| C13 | 0.2497 (4) | −0.1887 (4) | 0.48945 (13) | 0.0346 (7) | |
| H4A | 0.448 (4) | 0.362 (6) | 0.3618 (18) | 0.070 (11)* | |
| H4B | 0.448 (5) | 0.497 (5) | 0.2944 (18) | 0.067 (11)* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| F1 | 0.1045 (18) | 0.0494 (12) | 0.0245 (8) | 0.0050 (11) | 0.0032 (10) | −0.0071 (8) |
| F2 | 0.0673 (13) | 0.0635 (13) | 0.0370 (10) | 0.0222 (10) | −0.0073 (9) | 0.0154 (8) |
| F3 | 0.0571 (12) | 0.1073 (17) | 0.0329 (9) | −0.0274 (11) | −0.0002 (8) | 0.0251 (10) |
| N4 | 0.0379 (14) | 0.0297 (13) | 0.0346 (13) | −0.0050 (11) | 0.0003 (11) | −0.0022 (11) |
| C5 | 0.0267 (13) | 0.0255 (13) | 0.0292 (13) | 0.0036 (11) | 0.0021 (10) | −0.0008 (11) |
| C6 | 0.0319 (14) | 0.0290 (14) | 0.0271 (13) | 0.0045 (12) | 0.0035 (10) | 0.0050 (11) |
| C7 | 0.0310 (14) | 0.0389 (16) | 0.0236 (12) | 0.0041 (12) | 0.0035 (10) | 0.0037 (11) |
| C8 | 0.0332 (15) | 0.0355 (15) | 0.0239 (13) | −0.0023 (12) | 0.0000 (11) | −0.0043 (11) |
| C9 | 0.0295 (13) | 0.0276 (14) | 0.0254 (12) | 0.0026 (12) | 0.0009 (10) | 0.0004 (11) |
| C10 | 0.0211 (13) | 0.0241 (13) | 0.0201 (11) | 0.0020 (10) | −0.0010 (9) | −0.0007 (10) |
| C11 | 0.0295 (15) | 0.0293 (14) | 0.0232 (12) | 0.0010 (11) | −0.0008 (10) | −0.0024 (10) |
| C12 | 0.0388 (15) | 0.0315 (15) | 0.0218 (12) | 0.0012 (12) | −0.0008 (11) | 0.0002 (11) |
| C13 | 0.0400 (16) | 0.0373 (16) | 0.0254 (13) | 0.0004 (13) | −0.0013 (11) | 0.0035 (11) |
Geometric parameters (Å, º)
| F1—C13 | 1.336 (3) | C7—H7 | 0.9500 |
| F2—C13 | 1.348 (3) | C8—C9 | 1.378 (3) |
| F3—C13 | 1.326 (3) | C8—H8 | 0.9500 |
| N4—C5 | 1.383 (3) | C9—C10 | 1.398 (3) |
| N4—H4A | 0.90 (3) | C9—H9 | 0.9500 |
| N4—H4B | 0.88 (3) | C10—C11 | 1.475 (3) |
| C5—C10 | 1.409 (3) | C11—C12 | 1.318 (3) |
| C5—C6 | 1.412 (3) | C11—H11 | 0.9500 |
| C6—C7 | 1.371 (3) | C12—C13 | 1.472 (3) |
| C6—H6 | 0.9500 | C12—H12 | 0.9500 |
| C7—C8 | 1.389 (4) | ||
| C5—N4—H4A | 118 (2) | C10—C9—H9 | 119.1 |
| C5—N4—H4B | 109 (2) | C9—C10—C5 | 119.0 (2) |
| H4A—N4—H4B | 116 (3) | C9—C10—C11 | 121.2 (2) |
| N4—C5—C10 | 121.3 (2) | C5—C10—C11 | 119.7 (2) |
| N4—C5—C6 | 119.9 (2) | C12—C11—C10 | 125.6 (2) |
| C10—C5—C6 | 118.7 (2) | C12—C11—H11 | 117.2 |
| C7—C6—C5 | 120.3 (2) | C10—C11—H11 | 117.2 |
| C7—C6—H6 | 119.8 | C11—C12—C13 | 123.7 (2) |
| C5—C6—H6 | 119.8 | C11—C12—H12 | 118.1 |
| C6—C7—C8 | 121.4 (2) | C13—C12—H12 | 118.1 |
| C6—C7—H7 | 119.3 | F3—C13—F1 | 106.1 (2) |
| C8—C7—H7 | 119.3 | F3—C13—F2 | 106.1 (2) |
| C9—C8—C7 | 118.7 (2) | F1—C13—F2 | 104.4 (2) |
| C9—C8—H8 | 120.6 | F3—C13—C12 | 113.4 (2) |
| C7—C8—H8 | 120.6 | F1—C13—C12 | 113.9 (2) |
| C8—C9—C10 | 121.8 (2) | F2—C13—C12 | 112.1 (2) |
| C8—C9—H9 | 119.1 | ||
| N4—C5—C6—C7 | −178.5 (2) | N4—C5—C10—C11 | 2.2 (4) |
| C10—C5—C6—C7 | −0.3 (4) | C6—C5—C10—C11 | −176.1 (2) |
| C5—C6—C7—C8 | −0.3 (4) | C9—C10—C11—C12 | 24.6 (4) |
| C6—C7—C8—C9 | 0.5 (4) | C5—C10—C11—C12 | −158.9 (3) |
| C7—C8—C9—C10 | −0.3 (4) | C10—C11—C12—C13 | −176.8 (2) |
| C8—C9—C10—C5 | −0.2 (4) | C11—C12—C13—F3 | 115.4 (3) |
| C8—C9—C10—C11 | 176.3 (2) | C11—C12—C13—F1 | −6.2 (4) |
| N4—C5—C10—C9 | 178.7 (2) | C11—C12—C13—F2 | −124.5 (3) |
| C6—C5—C10—C9 | 0.5 (3) |
Hydrogen-bond geometry (Å, º)
Cg1 is the centroid of the C5–C10 ring.
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4A···F2i | 0.90 (3) | 2.46 (4) | 3.352 (3) | 169 (3) |
| C12—H12···N4ii | 0.95 | 2.56 | 3.432 (4) | 152 |
| N4—H4B···Cg1iii | 0.88 (3) | 2.59 (4) | 3.315 (2) | 140 (3) |
| C9—H9···Cg1iv | 0.95 | 2.73 | 3.480 (3) | 136 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y−1, z; (iii) −x+1, y+1/2, −z+1/2; (iv) −x, y−1/2, −z+1/2.
Funding Statement
This work was funded by the Cooperative Research Program of Network Joint Reserarch Center for Materials and Devices (Institute for Materials Chemistry and Engineering, Kyushu University) (No. 20181296) grant .
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018012756/is5499sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018012756/is5499Isup2.hkl
CCDC reference: 1866671
Additional supporting information: crystallographic information; 3D view; checkCIF report