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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o677.
Published online 2009 March 6. doi:  10.1107/S1600536809006953
PMCID: PMC2968785

(1S,5R)-1-(4-Fluoro­phen­yl)-3-azonia­bicyclo­[3.1.0]hexane chloride

Abstract

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.

Related literature

For related structures, see: McArdle et al. (2004 [triangle]).

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Object name is e-65-0o677-scheme1.jpg

Experimental

Crystal data

  • C11H13FN+·Cl
  • M r = 213.67
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o677-efi1.jpg
  • a = 6.9146 (10) Å
  • b = 7.8048 (11) Å
  • c = 19.448 (3) Å
  • V = 1049.6 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.34 mm−1
  • T = 296 K
  • 0.50 × 0.36 × 0.25 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.766, T max = 0.919
  • 6726 measured reflections
  • 2292 independent reflections
  • 2244 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.066
  • S = 1.05
  • 2292 reflections
  • 133 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.17 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 934 Friedel pairs
  • Flack parameter: −0.03 (5)

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT-Plus (Bruker, 2007 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809006953/xu2479sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809006953/xu2479Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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).

Experimental

Block-shaped crystals were prepared from an acetonitrile solution by slow evaporation at room temperature.

Refinement

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).

Figures

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.

Crystal data

C11H13FN+·ClDx = 1.352 Mg m3
Mr = 213.67Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 4938 reflections
a = 6.9146 (10) Åθ = 2.1–27.1°
b = 7.8048 (11) ŵ = 0.34 mm1
c = 19.448 (3) ÅT = 296 K
V = 1049.6 (3) Å3Block, colourless
Z = 40.50 × 0.36 × 0.25 mm
F(000) = 448

Data collection

Bruker APEXII CCD diffractometer2292 independent reflections
Radiation source: fine-focus sealed tube2244 reflections with I > 2σ(I)
graphiteRint = 0.028
Detector resolution: 8.3 pixels mm-1θmax = 27.1°, θmin = 2.1°
sets of exposures each taken over 0.5° ω rotation scansh = −8→4
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)k = −9→10
Tmin = 0.766, Tmax = 0.919l = −24→24
6726 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.066w = 1/[σ2(Fo2) + (0.036P)2 + 0.1918P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2292 reflectionsΔρmax = 0.38 e Å3
133 parametersΔρmin = −0.17 e Å3
0 restraintsAbsolute structure: Flack (1983), 934 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.03 (5)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl10.90409 (5)0.57733 (4)0.024884 (16)0.01896 (9)
F1−0.08580 (14)0.45054 (11)0.37784 (4)0.0280 (2)
C60.2562 (2)0.43164 (19)0.20420 (7)0.0184 (3)
C50.3941 (2)0.60246 (17)0.10328 (6)0.0185 (3)
H510.26950.65950.10200.022*
H520.48710.67740.12540.022*
N10.45923 (17)0.55635 (15)0.03221 (6)0.0168 (2)
H10.595 (3)0.557 (2)0.0300 (8)0.020*
H20.422 (3)0.640 (2)0.0035 (8)0.020*
C40.3797 (2)0.43318 (18)0.14105 (6)0.0172 (3)
C70.3340 (2)0.3976 (2)0.26874 (7)0.0225 (3)
H710.46440.37010.27260.027*
C110.0603 (2)0.4731 (2)0.19938 (7)0.0235 (3)
H1110.00670.49720.15660.028*
C90.0279 (2)0.44386 (19)0.32031 (7)0.0217 (3)
C10.3826 (2)0.38066 (16)0.01663 (7)0.0190 (3)
H110.46780.3197−0.01450.023*
H120.25450.3868−0.00360.023*
C80.2196 (2)0.4041 (2)0.32777 (7)0.0248 (3)
H810.27200.38210.37090.030*
C20.3764 (2)0.29489 (18)0.08635 (7)0.0206 (3)
H210.29210.19530.09290.025*
C30.5512 (2)0.31501 (19)0.13212 (7)0.0224 (3)
H310.66770.36240.11190.027*
H320.57300.22850.16710.027*
C10−0.0560 (2)0.4790 (2)0.25780 (8)0.0255 (3)
H101−0.18670.50590.25460.031*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.01835 (16)0.01641 (15)0.02212 (15)−0.00080 (13)−0.00166 (13)0.00305 (12)
F10.0339 (5)0.0273 (5)0.0227 (4)0.0066 (4)0.0116 (4)0.0024 (3)
C60.0212 (7)0.0151 (6)0.0189 (6)−0.0006 (6)0.0024 (5)0.0012 (5)
C50.0235 (7)0.0150 (6)0.0170 (6)−0.0025 (6)0.0013 (6)0.0003 (5)
N10.0187 (6)0.0147 (5)0.0169 (5)0.0003 (5)−0.0001 (4)0.0017 (4)
C40.0182 (6)0.0161 (6)0.0172 (6)0.0000 (6)0.0002 (5)0.0013 (5)
C70.0215 (7)0.0241 (7)0.0217 (6)0.0035 (6)0.0007 (5)0.0037 (6)
C110.0230 (8)0.0292 (7)0.0184 (6)−0.0007 (6)−0.0016 (5)0.0019 (5)
C90.0292 (7)0.0160 (7)0.0198 (6)0.0007 (6)0.0086 (6)0.0005 (5)
C10.0209 (7)0.0162 (6)0.0198 (6)−0.0026 (5)0.0019 (6)−0.0017 (5)
C80.0318 (8)0.0253 (7)0.0174 (6)0.0046 (7)0.0003 (6)0.0049 (6)
C20.0250 (7)0.0137 (6)0.0232 (6)−0.0006 (6)0.0044 (6)0.0004 (5)
C30.0227 (7)0.0230 (7)0.0216 (7)0.0055 (6)0.0024 (5)0.0066 (5)
C100.0204 (7)0.0302 (8)0.0259 (7)0.0024 (6)0.0025 (6)0.0016 (6)

Geometric parameters (Å, °)

F1—C91.3683 (15)C7—H710.9300
C6—C71.3911 (19)C11—C101.393 (2)
C6—C111.396 (2)C11—H1110.9300
C6—C41.4959 (18)C9—C81.369 (2)
C5—N11.4977 (16)C9—C101.375 (2)
C5—C41.5149 (18)C1—C21.5128 (18)
C5—H510.9700C1—H110.9700
C5—H520.9700C1—H120.9700
N1—C11.5011 (16)C8—H810.9300
N1—H10.939 (18)C2—C31.509 (2)
N1—H20.899 (17)C2—H210.9800
C4—C31.512 (2)C3—H310.9700
C4—C21.5156 (19)C3—H320.9700
C7—C81.395 (2)C10—H1010.9300
C7—C6—C11118.70 (12)F1—C9—C8118.57 (13)
C7—C6—C4121.43 (13)F1—C9—C10118.25 (13)
C11—C6—C4119.80 (12)C8—C9—C10123.18 (13)
N1—C5—C4104.93 (10)N1—C1—C2103.48 (11)
N1—C5—H51110.8N1—C1—H11111.1
C4—C5—H51110.8C2—C1—H11111.1
N1—C5—H52110.8N1—C1—H12111.1
C4—C5—H52110.8C2—C1—H12111.1
H51—C5—H52108.8H11—C1—H12109.0
C5—N1—C1107.42 (10)C9—C8—C7118.03 (13)
C5—N1—H1109.9 (9)C9—C8—H81121.0
C1—N1—H1110.4 (10)C7—C8—H81121.0
C5—N1—H2108.2 (11)C3—C2—C1117.40 (13)
C1—N1—H2116.1 (11)C3—C2—C459.99 (9)
H1—N1—H2104.7 (16)C1—C2—C4108.28 (11)
C3—C4—C259.78 (10)C3—C2—H21118.9
C3—C4—C5115.15 (12)C1—C2—H21118.9
C3—C4—C6122.49 (12)C4—C2—H21118.9
C6—C4—C5116.26 (12)C2—C3—C460.23 (9)
C6—C4—C2124.19 (12)C2—C3—H31117.7
C5—C4—C2106.36 (10)C4—C3—H31117.7
C6—C7—C8121.09 (14)C2—C3—H32117.7
C6—C7—H71119.5C4—C3—H32117.7
C8—C7—H71119.5H31—C3—H32114.9
C10—C11—C6120.85 (13)C9—C10—C11118.15 (14)
C10—C11—H111119.6C9—C10—H101120.9
C6—C11—H111119.6C11—C10—H101120.9
C1—C2—C4—C5−1.68 (16)C5—N1—C1—C2−30.53 (14)
N1—C1—C2—C419.46 (15)F1—C9—C8—C7179.97 (13)
N1—C5—C4—C2−16.93 (15)C10—C9—C8—C7−0.6 (3)
C5—C4—C6—C1159.81 (19)C6—C7—C8—C90.4 (2)
C4—C5—N1—C129.91 (15)N1—C1—C2—C3−45.58 (15)
C7—C6—C4—C334.1 (2)C6—C4—C2—C3−110.84 (15)
C11—C6—C4—C3−149.04 (14)C5—C4—C2—C3109.97 (13)
C7—C6—C4—C2107.32 (17)C6—C4—C2—C1137.51 (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—C496.23 (13)
N1—C5—C4—C6−159.86 (12)C6—C4—C3—C2113.59 (15)
N1—C5—C4—C346.86 (15)C5—C4—C3—C2−94.97 (12)
C11—C6—C7—C80.2 (2)F1—C9—C10—C11179.61 (13)
C4—C6—C7—C8177.04 (14)C8—C9—C10—C110.2 (2)
C7—C6—C11—C10−0.6 (2)C6—C11—C10—C90.4 (2)
C4—C6—C11—C10−177.53 (14)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.939 (18)2.146 (18)3.0837 (13)176.1 (15)
N1—H2···Cl1i0.899 (17)2.275 (17)3.0907 (13)150.8 (14)

Symmetry codes: (i) x−1/2, −y+3/2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2479).

References

  • Bruker (2007). APEX2 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. [PubMed]

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