Acta Cryst. (2009). E65, o677 [ doi:10.1107/S1600536809006953 ]
The absolute structure of the title compound, C11H13FN+·Cl-, has been determined. The five-membered ring has an envelope conformation with the N atom at the flap position. In the crystal structure, the Cl- anion links with the organic cation via N-H
Cl hydrogen bonding.
Block-shaped crystals were prepared from an acetonitrile solution by slow evaporation at room temperature.
Positional parameters were refined for the two H atoms bonded to N. Other H atoms were positioned with idealized geometry and fixed C—H = 0.93 (aromatic), 0.97 (methylene) or 0.98 Å (methine). Uiso(H) values were 1.2Ueq(C,N).
Data collection: APEX2 (Bruker, 20078); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./xu2479fig1thm.gif)
| Fig. 1. The asymmetric unit of (I). Displacement ellipsoids are shown at the 50% probability level and H atoms are shown as spheres of arbitrary size. |
| C11H13FN+·Cl− | Dx = 1.352 Mg m−3 |
| Mr = 213.67 | Mo Kα radiation, λ = 0.71073 Å |
| Orthorhombic, P212121 | Cell parameters from 4938 reflections |
| a = 6.9146 (10) Å | θ = 2.1–27.1° |
| b = 7.8048 (11) Å | µ = 0.34 mm−1 |
| c = 19.448 (3) Å | T = 296 K |
| V = 1049.6 (3) Å3 | Block, colourless |
| Z = 4 | 0.50 × 0.36 × 0.25 mm |
| F(000) = 448 |
| Bruker APEXII CCD diffractometer | 2292 independent reflections |
| Radiation source: fine-focus sealed tube | 2244 reflections with I > 2σ(I) |
| graphite | Rint = 0.028 |
| Detector resolution: 8.3 pixels mm-1 | θmax = 27.1°, θmin = 2.1° |
| sets of exposures each taken over 0.5° ω rotation scans | h = −8→4 |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −9→10 |
| Tmin = 0.766, Tmax = 0.919 | l = −24→24 |
| 6726 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.036P)2 + 0.1918P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max < 0.001 |
| 2292 reflections | Δρmax = 0.38 e Å−3 |
| 133 parameters | Δρmin = −0.17 e Å−3 |
| 0 restraints | Absolute structure: Flack (1983), 934 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: −0.03 (5) |
| C11H13FN+·Cl− | V = 1049.6 (3) Å3 |
| Mr = 213.67 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 6.9146 (10) Å | µ = 0.34 mm−1 |
| b = 7.8048 (11) Å | T = 296 K |
| c = 19.448 (3) Å | 0.50 × 0.36 × 0.25 mm |
| Bruker APEXII CCD diffractometer | 2292 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2244 reflections with I > 2σ(I) |
| Tmin = 0.766, Tmax = 0.919 | Rint = 0.028 |
| 6726 measured reflections | θmax = 27.1° |
| R[F2 > 2σ(F2)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.066 | Δρmax = 0.38 e Å−3 |
| S = 1.05 | Δρmin = −0.17 e Å−3 |
| 2292 reflections | Absolute structure: Flack (1983), 934 Friedel pairs |
| 133 parameters | Flack parameter: −0.03 (5) |
| 0 restraints |
Experimental. Crystallized from acetonitrile solution |
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. Data were collected by measuring three sets of exposures with the detector set at 2θ = 29°, crystal-to-detector distance 6.00 cm. Refinement of F2 against ALL reflections. |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.90409 (5) | 0.57733 (4) | 0.024884 (16) | 0.01896 (9) | |
| F1 | −0.08580 (14) | 0.45054 (11) | 0.37784 (4) | 0.0280 (2) | |
| C6 | 0.2562 (2) | 0.43164 (19) | 0.20420 (7) | 0.0184 (3) | |
| C5 | 0.3941 (2) | 0.60246 (17) | 0.10328 (6) | 0.0185 (3) | |
| H51 | 0.2695 | 0.6595 | 0.1020 | 0.022* | |
| H52 | 0.4871 | 0.6774 | 0.1254 | 0.022* | |
| N1 | 0.45923 (17) | 0.55635 (15) | 0.03221 (6) | 0.0168 (2) | |
| H1 | 0.595 (3) | 0.557 (2) | 0.0300 (8) | 0.020* | |
| H2 | 0.422 (3) | 0.640 (2) | 0.0035 (8) | 0.020* | |
| C4 | 0.3797 (2) | 0.43318 (18) | 0.14105 (6) | 0.0172 (3) | |
| C7 | 0.3340 (2) | 0.3976 (2) | 0.26874 (7) | 0.0225 (3) | |
| H71 | 0.4644 | 0.3701 | 0.2726 | 0.027* | |
| C11 | 0.0603 (2) | 0.4731 (2) | 0.19938 (7) | 0.0235 (3) | |
| H111 | 0.0067 | 0.4972 | 0.1566 | 0.028* | |
| C9 | 0.0279 (2) | 0.44386 (19) | 0.32031 (7) | 0.0217 (3) | |
| C1 | 0.3826 (2) | 0.38066 (16) | 0.01663 (7) | 0.0190 (3) | |
| H11 | 0.4678 | 0.3197 | −0.0145 | 0.023* | |
| H12 | 0.2545 | 0.3868 | −0.0036 | 0.023* | |
| C8 | 0.2196 (2) | 0.4041 (2) | 0.32777 (7) | 0.0248 (3) | |
| H81 | 0.2720 | 0.3821 | 0.3709 | 0.030* | |
| C2 | 0.3764 (2) | 0.29489 (18) | 0.08635 (7) | 0.0206 (3) | |
| H21 | 0.2921 | 0.1953 | 0.0929 | 0.025* | |
| C3 | 0.5512 (2) | 0.31501 (19) | 0.13212 (7) | 0.0224 (3) | |
| H31 | 0.6677 | 0.3624 | 0.1119 | 0.027* | |
| H32 | 0.5730 | 0.2285 | 0.1671 | 0.027* | |
| C10 | −0.0560 (2) | 0.4790 (2) | 0.25780 (8) | 0.0255 (3) | |
| H101 | −0.1867 | 0.5059 | 0.2546 | 0.031* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.01835 (16) | 0.01641 (15) | 0.02212 (15) | −0.00080 (13) | −0.00166 (13) | 0.00305 (12) |
| F1 | 0.0339 (5) | 0.0273 (5) | 0.0227 (4) | 0.0066 (4) | 0.0116 (4) | 0.0024 (3) |
| C6 | 0.0212 (7) | 0.0151 (6) | 0.0189 (6) | −0.0006 (6) | 0.0024 (5) | 0.0012 (5) |
| C5 | 0.0235 (7) | 0.0150 (6) | 0.0170 (6) | −0.0025 (6) | 0.0013 (6) | 0.0003 (5) |
| N1 | 0.0187 (6) | 0.0147 (5) | 0.0169 (5) | 0.0003 (5) | −0.0001 (4) | 0.0017 (4) |
| C4 | 0.0182 (6) | 0.0161 (6) | 0.0172 (6) | 0.0000 (6) | 0.0002 (5) | 0.0013 (5) |
| C7 | 0.0215 (7) | 0.0241 (7) | 0.0217 (6) | 0.0035 (6) | 0.0007 (5) | 0.0037 (6) |
| C11 | 0.0230 (8) | 0.0292 (7) | 0.0184 (6) | −0.0007 (6) | −0.0016 (5) | 0.0019 (5) |
| C9 | 0.0292 (7) | 0.0160 (7) | 0.0198 (6) | 0.0007 (6) | 0.0086 (6) | 0.0005 (5) |
| C1 | 0.0209 (7) | 0.0162 (6) | 0.0198 (6) | −0.0026 (5) | 0.0019 (6) | −0.0017 (5) |
| C8 | 0.0318 (8) | 0.0253 (7) | 0.0174 (6) | 0.0046 (7) | 0.0003 (6) | 0.0049 (6) |
| C2 | 0.0250 (7) | 0.0137 (6) | 0.0232 (6) | −0.0006 (6) | 0.0044 (6) | 0.0004 (5) |
| C3 | 0.0227 (7) | 0.0230 (7) | 0.0216 (7) | 0.0055 (6) | 0.0024 (5) | 0.0066 (5) |
| C10 | 0.0204 (7) | 0.0302 (8) | 0.0259 (7) | 0.0024 (6) | 0.0025 (6) | 0.0016 (6) |
| F1—C9 | 1.3683 (15) | C7—H71 | 0.9300 |
| C6—C7 | 1.3911 (19) | C11—C10 | 1.393 (2) |
| C6—C11 | 1.396 (2) | C11—H111 | 0.9300 |
| C6—C4 | 1.4959 (18) | C9—C8 | 1.369 (2) |
| C5—N1 | 1.4977 (16) | C9—C10 | 1.375 (2) |
| C5—C4 | 1.5149 (18) | C1—C2 | 1.5128 (18) |
| C5—H51 | 0.9700 | C1—H11 | 0.9700 |
| C5—H52 | 0.9700 | C1—H12 | 0.9700 |
| N1—C1 | 1.5011 (16) | C8—H81 | 0.9300 |
| N1—H1 | 0.939 (18) | C2—C3 | 1.509 (2) |
| N1—H2 | 0.899 (17) | C2—H21 | 0.9800 |
| C4—C3 | 1.512 (2) | C3—H31 | 0.9700 |
| C4—C2 | 1.5156 (19) | C3—H32 | 0.9700 |
| C7—C8 | 1.395 (2) | C10—H101 | 0.9300 |
| C7—C6—C11 | 118.70 (12) | F1—C9—C8 | 118.57 (13) |
| C7—C6—C4 | 121.43 (13) | F1—C9—C10 | 118.25 (13) |
| C11—C6—C4 | 119.80 (12) | C8—C9—C10 | 123.18 (13) |
| N1—C5—C4 | 104.93 (10) | N1—C1—C2 | 103.48 (11) |
| N1—C5—H51 | 110.8 | N1—C1—H11 | 111.1 |
| C4—C5—H51 | 110.8 | C2—C1—H11 | 111.1 |
| N1—C5—H52 | 110.8 | N1—C1—H12 | 111.1 |
| C4—C5—H52 | 110.8 | C2—C1—H12 | 111.1 |
| H51—C5—H52 | 108.8 | H11—C1—H12 | 109.0 |
| C5—N1—C1 | 107.42 (10) | C9—C8—C7 | 118.03 (13) |
| C5—N1—H1 | 109.9 (9) | C9—C8—H81 | 121.0 |
| C1—N1—H1 | 110.4 (10) | C7—C8—H81 | 121.0 |
| C5—N1—H2 | 108.2 (11) | C3—C2—C1 | 117.40 (13) |
| C1—N1—H2 | 116.1 (11) | C3—C2—C4 | 59.99 (9) |
| H1—N1—H2 | 104.7 (16) | C1—C2—C4 | 108.28 (11) |
| C3—C4—C2 | 59.78 (10) | C3—C2—H21 | 118.9 |
| C3—C4—C5 | 115.15 (12) | C1—C2—H21 | 118.9 |
| C3—C4—C6 | 122.49 (12) | C4—C2—H21 | 118.9 |
| C6—C4—C5 | 116.26 (12) | C2—C3—C4 | 60.23 (9) |
| C6—C4—C2 | 124.19 (12) | C2—C3—H31 | 117.7 |
| C5—C4—C2 | 106.36 (10) | C4—C3—H31 | 117.7 |
| C6—C7—C8 | 121.09 (14) | C2—C3—H32 | 117.7 |
| C6—C7—H71 | 119.5 | C4—C3—H32 | 117.7 |
| C8—C7—H71 | 119.5 | H31—C3—H32 | 114.9 |
| C10—C11—C6 | 120.85 (13) | C9—C10—C11 | 118.15 (14) |
| C10—C11—H111 | 119.6 | C9—C10—H101 | 120.9 |
| C6—C11—H111 | 119.6 | C11—C10—H101 | 120.9 |
| C1—C2—C4—C5 | −1.68 (16) | C5—N1—C1—C2 | −30.53 (14) |
| N1—C1—C2—C4 | 19.46 (15) | F1—C9—C8—C7 | 179.97 (13) |
| N1—C5—C4—C2 | −16.93 (15) | C10—C9—C8—C7 | −0.6 (3) |
| C5—C4—C6—C11 | 59.81 (19) | C6—C7—C8—C9 | 0.4 (2) |
| C4—C5—N1—C1 | 29.91 (15) | N1—C1—C2—C3 | −45.58 (15) |
| C7—C6—C4—C3 | 34.1 (2) | C6—C4—C2—C3 | −110.84 (15) |
| C11—C6—C4—C3 | −149.04 (14) | C5—C4—C2—C3 | 109.97 (13) |
| C7—C6—C4—C2 | 107.32 (17) | C6—C4—C2—C1 | 137.51 (14) |
| C11—C6—C4—C2 | −75.82 (19) | C3—C4—C2—C1 | −111.65 (14) |
| C7—C6—C4—C5 | −117.04 (15) | C1—C2—C3—C4 | 96.23 (13) |
| N1—C5—C4—C6 | −159.86 (12) | C6—C4—C3—C2 | 113.59 (15) |
| N1—C5—C4—C3 | 46.86 (15) | C5—C4—C3—C2 | −94.97 (12) |
| C11—C6—C7—C8 | 0.2 (2) | F1—C9—C10—C11 | 179.61 (13) |
| C4—C6—C7—C8 | 177.04 (14) | C8—C9—C10—C11 | 0.2 (2) |
| C7—C6—C11—C10 | −0.6 (2) | C6—C11—C10—C9 | 0.4 (2) |
| C4—C6—C11—C10 | −177.53 (14) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···Cl1 | 0.939 (18) | 2.146 (18) | 3.0837 (13) | 176.1 (15) |
| N1—H2···Cl1i | 0.899 (17) | 2.275 (17) | 3.0907 (13) | 150.8 (14) |
| Symmetry codes: (i) x−1/2, −y+3/2, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···Cl1 | 0.939 (18) | 2.146 (18) | 3.0837 (13) | 176.1 (15) |
| N1—H2···Cl1i | 0.899 (17) | 2.275 (17) | 3.0907 (13) | 150.8 (14) |
| Symmetry codes: (i) x−1/2, −y+3/2, −z. |
Bruker (2007). APEX2s and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
McArdle, P., Gilligan, K., Cunningham, D., Dark, R. & Mahon, M. (2004). CrystEngComm, 6, 303–309.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
The title compound was prepared as a potential triple neurotransmittor reuptake inhibitor. Details will be published elsewhere. The molecular structure is shown in Fig. 1. The five-membered ring has an envelope conformation with N1 located 0.454 (2) Å above the plane constituted by C1, C2, C4 and C5, on the same side as C3, giving the six-membered ring N1—C1—C2—C3—C4—C5 a distinct boat conformation.
Two different P21/c polymorphs, with Z' = 1 and 4, respectively, were obtained for the racemate of bicifadine hydrochloride (McArdle et al., 2004), which has a methyl group rather than a F atom in the phenyl ortho position. Ring puckering remains unchanged, but phenyl rotations vary; C5—C4—C6—C11 is thus 59.81 (19)° for the title compound, but 83.9° for polymorph 1 of bicifadine and between -10.1 and -30.8° for polymorph 2 (1S,5R-enatiomers).