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

Görbitz, C.H.; Hansen, T.; Vestli, K.

doi:10.1107/S1600536809006953

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o677

doi:10.1107/S1600536809006953

Open

access

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

Carl Henrik Görbitz,^a ^* Tore Hansen ^a and Kristian Vestli ^a

^aDepartment of Chemistry, University of Oslo, PO Box 1033 Blindern, N-0315 Oslo, Norway
^*Correspondence e-mail: c.h.gorbitz@kjemi.uio.no

(Received 30 January 2009; accepted 25 February 2009; online 6 March 2009)

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 ).

Experimental

Crystal data

C₁₁H₁₃FN⁺·Cl⁻
M_r = 213.67
Orthorhombic, P 2₁ 2₁ 2₁
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 ) 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[F² > 2σ(F²)] = 0.025
wR(F²) = 0.066
S = 1.05
2292 reflections
133 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 934 Friedel pairs
Flack parameter: −0.03 (5)

Table 1
Hydrogen-bond geometry (Å, °)

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 code: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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

Computing details top

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).

Figures top

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.

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

Crystal data top

C₁₁H₁₃FN⁺·Cl⁻	D_x = 1.352 Mg m⁻³
M_r = 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

Data collection top

Bruker APEXII CCD diffractometer	2292 independent reflections
Radiation source: fine-focus sealed tube	2244 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 8.3 pixels mm^-1	θ_max = 27.1°, θ_min = 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
T_min = 0.766, T_max = 0.919	l = −24→24
6726 measured reflections

Refinement top

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(F_o²) + (0.036P)² + 0.1918P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2292 reflections	Δρ_max = 0.38 e Å⁻³
133 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 934 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (5)

Crystal data top

C₁₁H₁₃FN⁺·Cl⁻	V = 1049.6 (3) Å³
M_r = 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

Data collection top

Bruker APEXII CCD diffractometer	2292 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2244 reflections with I > 2σ(I)
T_min = 0.766, T_max = 0.919	R_int = 0.028
6726 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.066	Δρ_max = 0.38 e Å⁻³
S = 1.05	Δρ_min = −0.17 e Å⁻³
2292 reflections	Absolute structure: Flack (1983), 934 Friedel pairs
133 parameters	Absolute structure parameter: −0.03 (5)
0 restraints

Special details top

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) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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 code: (i) x−1/2, −y+3/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃FN⁺·Cl⁻
M_r	213.67
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	6.9146 (10), 7.8048 (11), 19.448 (3)
V (Å³)	1049.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.50 × 0.36 × 0.25

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.766, 0.919
No. of measured, independent and observed [I > 2σ(I)] reflections	6726, 2292, 2244
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.066, 1.05
No. of reflections	2292
No. of parameters	133
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.17
Absolute structure	Flack (1983), 934 Friedel pairs
Absolute structure parameter	−0.03 (5)

Computer programs: APEX2 (Bruker, 20078), SAINT-Plus (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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 code: (i) x−1/2, −y+3/2, −z.

References

Bruker (2007). APEX2 and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
McArdle, P., Gilligan, K., Cunningham, D., Dark, R. & Mahon, M. (2004). CrystEngComm, 6, 303–309. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o677

doi:10.1107/S1600536809006953

Open

access