1-Chloro­methyl-4-aza-1-azoniabi­cyclo­[2.2.2]­octane tetra­fluoro­borate deutero­chloro­form solvate

Batsanov, A.S.; Trmcic, J.; Sandford, G.

doi:10.1107/S1600536805004411

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 3| March 2005| Pages o681-o682

https://doi.org/10.1107/S1600536805004411

1-Chloromethyl-4-aza-1-azoniabicyclo[2.2.2]octane tetrafluoroborate deuterochloroform solvate

Andrei S. Batsanov,^a ^* Jelena Trmcic ^a and Graham Sandford ^a

^aDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, England
^*Correspondence e-mail: a.s.batsanov@durham.ac.uk

(Received 18 January 2005; accepted 8 February 2005; online 19 February 2005)

The title structure, C₇H₁₄ClN₂⁺·BF₄⁻·CDCl₃, comprises 1-chloromethyl-4-aza-1-azoniabicyclo[2.2.2]octane cations, BF₄⁻ anions and CDCl₃ solvent molecules, each having C_s crystallographic symmetry. The cation has a staggered conformation and the anion and solvent molecule are connected via a C—D⋯F interaction.

Comment

In the course of our studies of electrophilic fluorination methodology (Chambers et al., 2004 ), 1-chloromethyl-4-aza-1-azoniabicyclo[2.2.2]octane tetrafluoroborate deuterochloroform solvate, (I), was obtained as a by-product in the reaction of `Selectfluor', (II), with N-ethylpiperidine. Compound (I) was obtained by recrystallization from deuterochloroform. The crystal structure of solvent-free 1-chloromethyl-4-aza-1-azoniabicyclo[2.2.2]octane tetrafluoroborate has been reported previously by Banks et al. (1993 ).

The cation, anion and solvent molecule (Fig. 1 and Table 1) all lie on a crystallographic mirror plane, which passes through atoms Cl1/N1/N2/C1–C3 of the cation (which, therefore, has a staggered conformation around the N1—C1 bond), atoms B, F1 and F2 of the anion, and atoms C6, Cl3 and D of the deuterochloroform molecule. The solvent molecule and the anion are linked by a C6—D⋯F1 hydrogen bond (Table 2) The N—C bonds at quaternized atom N1 are longer by 0.047 (4) Å than at N2.

Figure 1
Twice the asymmetric unit of (I

), showing atomic displacement ellipsoids (at the 50% probability level) and the D—F hydrogen bond (dashed line). Primed atoms are generated by the reflection operation (x, $[1 \over 2]$ − y, z).

Experimental

A mixture comprising (II) (3.5 g, 12.1 mmol) and N-ethylpiperidine (1.0 g, 11.1 mmol) in acetonitrile was heated at reflux temperature 355 K for 18 h. The reaction mixture appeared dark red in colour. On completion of the reaction, the mixture was poured into water and extracted with dichloromethane (3 × 100 ml). The organic phase was dried with magnesium sulfate. After evaporation, the crude product was purified by distillation on a Kugelrohr apparatus. Crystals of X-ray quality were grown from a deuterochloroform solution of the non-volatile residue at room temperature.

Crystal data

C₇H₁₄ClN₂⁺·BF₄⁻·CDCl₃
M_r = 368.84
Orthorhombic, Pnma
a = 22.368 (3) Å
b = 8.4961 (11) Å
c = 7.4726 (10) Å
V = 1420.1 (3) Å³
Z = 4
D_x = 1.725 Mg m⁻³
Mo Kα radiation
Cell parameters from 884 reflections
θ = 12.2–25.4°
μ = 0.86 mm⁻¹
T = 120 (2) K
Plate, colourless
0.50 × 0.20 × 0.06 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.672, T_max = 0.950
16850 measured reflections
2037 independent reflections
1760 reflections with I > 2σ(I)
R_int = 0.045
θ_max = 29.1°
h = −30 → 30
k = −11 → 11
l = −10 → 10

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.095
S = 1.21
2037 reflections
134 parameters
All H-atom parameters refined
w = 1/[σ²(F_o²) + (0.0364P)² + 1.1232P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cl1—C1	1.763 (3)
N1—C1	1.507 (3)
N1—C4	1.507 (2)
N1—C2	1.510 (4)
N2—C3	1.456 (4)
N2—C5	1.464 (2)
F1—B	1.388 (4)
F2—B	1.393 (4)
F3—B	1.381 (2)
Cl2—C6	1.767 (2)
Cl3—C6	1.759 (3)

C1—N1—C4	111.96 (13)
C1—N1—C2	107.0 (2)
C4—N1—C2	108.54 (14)
C3—N2—C5	108.94 (15)
C5—N2—C5ⁱ	108.2 (2)
N1—C1—Cl1	111.99 (18)
N1—C2—C3	108.8 (2)
N2—C3—C2	112.0 (2)
N1—C4—C5	108.63 (17)
N2—C5—C4	111.79 (17)
Symmetry code: (i) $[x,{\script{1\over 2}}-y,z]$ .

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—D6⋯F1	0.90 (4)	2.28 (4)	3.123 (4)	156 (3)

All H and D atoms were refined isotropically with C—H bond distances in the range 0.93 (3)–0.99 (3) Å and C—D distances of 0.90 (4) Å.

Data collection: SMART (Bruker, 1999 ); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805004411/tk6209sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805004411/tk6209Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

1-Chloromethyl-4-aza-1-azoniabicyclo[2.2.2]octane tetrafluoroborate deuterochloroform solvate top

Crystal data top

C₇H₁₄ClN₂⁺·BF₄⁻·CDCl₃	F(000) = 744
M_r = 368.84	D_x = 1.725 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 884 reflections
a = 22.368 (3) Å	θ = 12.2–25.4°
b = 8.4961 (11) Å	µ = 0.86 mm⁻¹
c = 7.4726 (10) Å	T = 120 K
V = 1420.1 (3) Å³	Plate, colourless
Z = 4	0.50 × 0.20 × 0.06 mm

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2037 independent reflections
Radiation source: fine-focus sealed tube	1760 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 8 pixels mm^-1	θ_max = 29.1°, θ_min = 1.8°
ω scans	h = −30→30
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −11→11
T_min = 0.672, T_max = 0.950	l = −10→10
16850 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: difference Fourier map
wR(F²) = 0.095	All H-atom parameters refined
S = 1.21	w = 1/[σ²(F_o²) + (0.0364P)² + 1.1232P] where P = (F_o² + 2F_c²)/3
2037 reflections	(Δ/σ)_max = 0.001
134 parameters	Δρ_max = 0.73 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Special details top

Experimental. The data collection nominally covered full sphere of reciprocal space, by a combination of 5 sets of ω scans; each set at different φ and/or 2θ angles and each scan (20 sec exposure) covering 0.3° in ω. Crystal to detector distance 4.41 cm.

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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.25564 (3)	0.2500	0.34874 (9)	0.01955 (16)
N1	0.33556 (10)	0.2500	0.6221 (3)	0.0139 (4)
N2	0.35116 (11)	0.2500	0.9627 (3)	0.0189 (5)
C1	0.33068 (12)	0.2500	0.4210 (4)	0.0180 (5)
H1	0.3499 (9)	0.157 (3)	0.379 (3)	0.014 (5)*
C2	0.40138 (13)	0.2500	0.6669 (4)	0.0305 (8)
H2	0.4162 (12)	0.151 (4)	0.617 (4)	0.046 (9)*
C3	0.40859 (14)	0.2500	0.8711 (4)	0.0254 (6)
H3	0.4297 (10)	0.160 (3)	0.904 (4)	0.027 (7)*
C4	0.30739 (11)	0.1057 (2)	0.7039 (3)	0.0234 (4)
H41	0.2661 (12)	0.113 (3)	0.677 (4)	0.028 (7)*
H42	0.3276 (12)	0.018 (4)	0.651 (4)	0.042 (8)*
C5	0.31737 (10)	0.1104 (2)	0.9081 (3)	0.0218 (4)
H51	0.2774 (11)	0.111 (3)	0.964 (4)	0.027 (7)*
H52	0.3387 (11)	0.022 (3)	0.943 (4)	0.031 (7)*
F1	0.57683 (8)	0.2500	0.6439 (3)	0.0376 (5)
F2	0.65427 (8)	0.2500	0.4503 (3)	0.0317 (4)
F3	0.66116 (7)	0.11659 (19)	0.7124 (2)	0.0437 (4)
B	0.63872 (15)	0.2500	0.6307 (4)	0.0205 (6)
Cl2	0.48099 (2)	0.07856 (6)	0.26682 (7)	0.02478 (14)
Cl3	0.56793 (4)	0.2500	0.05699 (11)	0.0326 (2)
C6	0.52554 (13)	0.2500	0.2552 (4)	0.0216 (5)
D6	0.5509 (15)	0.2500	0.349 (5)	0.019 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0222 (3)	0.0214 (3)	0.0150 (3)	0	−0.0041 (2)	0
N1	0.0171 (10)	0.0161 (10)	0.0086 (9)	0	−0.0007 (8)	0
N2	0.0243 (11)	0.0173 (11)	0.0152 (10)	0	−0.0005 (9)	0
C1	0.0187 (12)	0.0241 (14)	0.0112 (11)	0	0.0005 (10)	0
C2	0.0164 (13)	0.060 (2)	0.0147 (13)	0	−0.0011 (11)	0
C3	0.0239 (14)	0.0385 (18)	0.0140 (13)	0	−0.0032 (11)	0
C4	0.0417 (12)	0.0143 (9)	0.0142 (9)	−0.0067 (9)	−0.0015 (8)	0.0001 (7)
C5	0.0322 (10)	0.0181 (9)	0.0150 (8)	−0.0039 (8)	−0.0018 (8)	0.0046 (7)
F1	0.0254 (9)	0.0646 (15)	0.0228 (9)	0	0.0009 (8)	0
F2	0.0347 (10)	0.0394 (11)	0.0210 (9)	0	0.0080 (8)	0
F3	0.0573 (10)	0.0285 (8)	0.0452 (9)	0.0129 (7)	−0.0061 (7)	0.0111 (7)
B	0.0247 (15)	0.0180 (14)	0.0187 (14)	0	−0.0002 (12)	0
Cl2	0.0308 (3)	0.0220 (2)	0.0216 (2)	0.00027 (19)	0.00304 (19)	0.00215 (19)
Cl3	0.0323 (4)	0.0371 (4)	0.0285 (4)	0.000	0.0129 (3)	0
C6	0.0236 (13)	0.0245 (14)	0.0166 (12)	0	−0.0011 (11)	0

Geometric parameters (Å, º) top

Cl1—C1	1.763 (3)	C4—H42	0.96 (3)
N1—C1	1.507 (3)	C4—C5	1.543 (3)
N1—C4	1.507 (2)	C5—H52	0.93 (3)
N1—C2	1.510 (4)	C5—H51	0.99 (3)
N2—C3	1.456 (4)	F1—B	1.388 (4)
N2—C5	1.464 (2)	F2—B	1.393 (4)
C1—H1	0.95 (2)	F3—B	1.381 (2)
C2—H2	0.98 (3)	Cl2—C6	1.767 (2)
C2—C3	1.535 (4)	Cl3—C6	1.759 (3)
C3—H3	0.93 (3)	C6—D6	0.90 (4)
C4—H41	0.95 (3)

C1—N1—C4	111.96 (13)	H41—C4—N1	105.3 (17)
C4ⁱ—N1—C4	108.8 (2)	H42—C4—N1	105.6 (18)
C1—N1—C2	107.0 (2)	H41—C4—C5	110.6 (17)
C4—N1—C2	108.54 (14)	H42—C4—C5	111.1 (19)
C3—N2—C5	108.94 (15)	N1—C4—C5	108.63 (17)
C5—N2—C5ⁱ	108.2 (2)	H52—C5—H51	110 (2)
H1ⁱ—C1—H1	112 (3)	H52—C5—N2	108.0 (17)
H1—C1—N1	107.2 (14)	H51—C5—N2	110.3 (16)
H1—C1—Cl1	109.3 (13)	H52—C5—C4	109.5 (17)
N1—C1—Cl1	111.99 (18)	H51—C5—C4	106.8 (15)
H2ⁱ—C2—H2	119 (4)	N2—C5—C4	111.79 (17)
H2—C2—N1	104.2 (17)	F3ⁱ—B—F3	110.3 (3)
H2—C2—C3	110.2 (19)	F3—B—F1	109.34 (18)
N1—C2—C3	108.8 (2)	F3—B—F2	109.68 (18)
H3ⁱ—C3—H3	110 (3)	F1—B—F2	108.5 (2)
H3—C3—N2	108.8 (15)	Cl3—C6—Cl2	110.21 (11)
H3—C3—C2	108.5 (16)	Cl2ⁱ—C6—Cl2	111.04 (16)
N2—C3—C2	112.0 (2)	Cl3—C6—D6	109 (2)
H41—C4—H42	115 (2)	Cl2—C6—D6	108.4 (11)

C2—N1—C1—Cl1	180.0

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—D6···F1	0.90 (4)	2.28 (4)	3.123 (4)	156 (3)

Acknowledgements

We thank the Asahi Glass Co. (Japan) for funding (studentship to JT).

References

Banks, R. E., Sharif, I. & Pritchard, R. G. (1993). Acta Cryst. C49, 492–495. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
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Chambers, R. D., Holling, D., Sandford, G., Batsanov, A. S. & Howard, J. A. K. (2004). J. Fluorine Chem. 125, 661–671. Web of Science CSD CrossRef CAS Google Scholar
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