1-(2-Bromo­ethyl)-1,4-diazo­niabicyclo­[2.2.2]octane bromide tetra­fluoro­borate

Xiao, J.

doi:10.1107/S1600536810017204

organic compounds

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Volume 66| Part 6| June 2010| Page o1344

https://doi.org/10.1107/S1600536810017204

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1-(2-Bromoethyl)-1,4-diazoniabicyclo[2.2.2]octane bromide tetrafluoroborate

Jing-mei Xiao ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: xjm_cool@163.com

(Received 21 April 2010; accepted 11 May 2010; online 15 May 2010)

In the crystal of the title compound, C₈H₁₇BrN₂²⁺·Br⁻·BF₄⁻, a weak intermolecular N—H⋯Br hydrogen bond is observed between the cation and the bromide anion. A two-part disorder model was applied to the BF₄⁻ anion with a refined major–minor occupancy ratio of 0.837 (14):0.163 (14).

Related literature

For the crystal structures and properties of related compounds, see: Chen et al.(2009 ); Fu et al. (2009 ); Zhao et al. (2008 ).

Experimental

Crystal data

C₈H₁₇BrN₂²⁺·BF₄⁻·Br⁻
M_r = 387.87
Orthorhombic, P b c a
a = 11.972 (2) Å
b = 10.782 (2) Å
c = 21.165 (4) Å
V = 2732.0 (10) Å³
Z = 8
Mo Kα radiation
μ = 5.96 mm⁻¹
T = 293 K
0.3 × 0.25 × 0.2 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.191, T_max = 0.303
26313 measured reflections
3124 independent reflections
1881 reflections with I > 2σ(I)
R_int = 0.109

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.108
S = 1.04
3124 reflections
198 parameters
34 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Br2	0.91 (7)	2.23 (7)	3.141 (5)	176 (6)

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: https://doi.org/10.1107/S1600536810017204/nk2032sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810017204/nk2032Isup2.hkl

checkCIF report

Comment top

The variable-temperature dielectric response, especially in relatively high frequency range, is very useful for searching phase transitions, in which there is a dielectric anomaly at the transition temperature. Unluckily, the title compound has no dielectric disuniform from 93 K to 453 K( m.p. > 473 K ) and report here.

In this report we have established unambiguously the structure at 293 K of the title compound in the solid state by X-ray diffraction analysis. As shown in Fig. 1. Single crystal X-ray analysis reveals that there are weak hydrogen bonds between 1-(2-bromoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium cation and bromide anion.

For the crystal structures and properties of related compounds, see: Chen et al. (2009); Fu et al. (2009); Zhao et al. (2008).

Related literature top

For the crystal structures and properties of related compounds, see: Chen et al.(2009); Fu et al. (2009); Zhao et al. (2008).

Experimental top

1,4-Diazabicyclo [2.2.2]octane (5.6 g, 0.05 mol) was dissolved in 20 ml of chloroform. To this solution 0.048 mol of 1,2-dibromoethane was added at once and the mixture was refluxed for 8 hours. On standing for 16 hours at room temperature, colorless crystals were obtained in large quantity. The crude product was collected and dissolved in 20 ml methanol, and 10ml HBF₄ (1 mol/L) in methanol was added slowly with stirring, while white precipitate formed at once.The suspension was filtered, and dissolved in H₂O, After a few weeks, colorless crystals were obtained by slow evaporation.

Structure description top

For the crystal structures and properties of related compounds, see: Chen et al. (2009); Fu et al. (2009); Zhao et al. (2008).

For the crystal structures and properties of related compounds, see: Chen et al.(2009); Fu et al. (2009); Zhao et al. (2008).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and the minor disorder component is omitted.

1-(2-Bromoethyl)-1,4-diazoniabicyclo[2.2.2]octane bromide tetrafluoroborate top

Crystal data top

C₈H₁₇BrN₂²⁺·BF₄⁻·Br⁻	F(000) = 1520
M_r = 387.87	D_x = 1.886 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5732 reflections
a = 11.972 (2) Å	θ = 3.7–27.5°
b = 10.782 (2) Å	µ = 5.96 mm⁻¹
c = 21.165 (4) Å	T = 293 K
V = 2732.0 (10) Å³	Prism, colourless
Z = 8	0.3 × 0.25 × 0.2 mm

Data collection top

Rigaku Mercury2 diffractometer	3124 independent reflections
Radiation source: fine-focus sealed tube	1881 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.109
CCD_Profile_fitting scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −15→15
T_min = 0.191, T_max = 0.303	k = −14→14
26313 measured reflections	l = −27→27

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0229P)² + 7.8245P] where P = (F_o² + 2F_c²)/3
3124 reflections	(Δ/σ)_max < 0.001
198 parameters	Δρ_max = 0.47 e Å⁻³
34 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

C₈H₁₇BrN₂²⁺·BF₄⁻·Br⁻	V = 2732.0 (10) Å³
M_r = 387.87	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.972 (2) Å	µ = 5.96 mm⁻¹
b = 10.782 (2) Å	T = 293 K
c = 21.165 (4) Å	0.3 × 0.25 × 0.2 mm

Data collection top

Rigaku Mercury2 diffractometer	3124 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1881 reflections with I > 2σ(I)
T_min = 0.191, T_max = 0.303	R_int = 0.109
26313 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	34 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.47 e Å⁻³
3124 reflections	Δρ_min = −0.47 e Å⁻³
198 parameters

Special details top

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 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 > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.71717 (5)	0.02659 (6)	0.01789 (3)	0.0522 (2)
Br2	1.27841 (5)	0.46079 (6)	0.27319 (3)	0.0510 (2)
C1	0.7924 (4)	0.1425 (6)	0.0745 (3)	0.0471 (15)
H1A	0.7844	0.2268	0.0592	0.057*
H1B	0.7609	0.1375	0.1167	0.057*
C2	0.9138 (4)	0.1047 (5)	0.0752 (3)	0.0411 (14)
H2A	0.9423	0.1082	0.0324	0.049*
H2B	0.9189	0.0193	0.0893	0.049*
C3	0.9635 (5)	0.1612 (6)	0.1856 (2)	0.0523 (17)
H3A	0.9787	0.0751	0.1957	0.063*
H3B	0.8853	0.1774	0.1942	0.063*
C4	1.0354 (5)	0.2443 (6)	0.2262 (2)	0.0464 (15)
H4A	0.9891	0.3048	0.2478	0.056*
H4B	1.0741	0.1953	0.2578	0.056*
C5	0.9738 (5)	0.3202 (5)	0.1038 (3)	0.0402 (14)
H5A	0.9839	0.3358	0.0590	0.048*
H5B	0.8991	0.3465	0.1154	0.048*
C6	1.0584 (5)	0.3924 (5)	0.1409 (3)	0.0466 (15)
H6A	1.1116	0.4305	0.1124	0.056*
H6B	1.0213	0.4578	0.1644	0.056*
C7	1.1075 (4)	0.1500 (6)	0.1040 (3)	0.0512 (16)
H7A	1.1266	0.1717	0.0609	0.061*
H7B	1.1174	0.0612	0.1090	0.061*
C8	1.1838 (4)	0.2187 (6)	0.1496 (3)	0.0491 (16)
H8A	1.2188	0.1603	0.1783	0.059*
H8B	1.2422	0.2612	0.1263	0.059*
N1	0.9874 (3)	0.1842 (4)	0.11705 (17)	0.0266 (10)
N2	1.1176 (4)	0.3085 (5)	0.1852 (2)	0.0397 (12)
H2	1.165 (6)	0.349 (6)	0.212 (3)	0.09 (2)*
B1	0.4770 (8)	0.2507 (9)	0.0910 (4)	0.0421 (19)	0.837 (14)
F1	0.5239 (8)	0.1669 (6)	0.1311 (3)	0.086 (2)	0.837 (14)
F2	0.4322 (7)	0.3475 (6)	0.1246 (4)	0.074 (2)	0.837 (14)
F3	0.3930 (7)	0.1935 (9)	0.0574 (5)	0.090 (3)	0.837 (14)
F4	0.5562 (5)	0.2945 (7)	0.0483 (3)	0.0681 (19)	0.837 (14)
B1'	0.460 (3)	0.244 (3)	0.0923 (13)	0.0421 (19)	0.163 (14)
F1'	0.454 (3)	0.186 (2)	0.1488 (12)	0.067 (7)	0.163 (14)
F2'	0.401 (3)	0.353 (3)	0.0918 (18)	0.065 (8)	0.163 (14)
F3'	0.419 (4)	0.168 (5)	0.0460 (19)	0.082 (9)	0.163 (14)
F4'	0.569 (2)	0.276 (4)	0.078 (2)	0.084 (9)	0.163 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0483 (4)	0.0598 (4)	0.0485 (4)	−0.0138 (3)	−0.0101 (3)	−0.0049 (3)
Br2	0.0442 (4)	0.0533 (4)	0.0555 (4)	0.0022 (3)	−0.0125 (3)	−0.0125 (3)
C1	0.039 (3)	0.056 (4)	0.046 (4)	−0.010 (3)	−0.010 (3)	−0.010 (3)
C2	0.036 (3)	0.039 (3)	0.048 (4)	−0.005 (3)	−0.004 (3)	−0.006 (3)
C3	0.051 (4)	0.072 (4)	0.033 (3)	−0.020 (3)	0.002 (3)	0.015 (3)
C4	0.047 (3)	0.067 (4)	0.025 (3)	0.003 (3)	0.000 (3)	0.001 (3)
C5	0.048 (3)	0.027 (3)	0.045 (3)	0.006 (3)	−0.016 (3)	−0.003 (3)
C6	0.064 (4)	0.029 (3)	0.047 (4)	−0.006 (3)	−0.007 (3)	0.002 (3)
C7	0.034 (3)	0.052 (4)	0.067 (4)	0.009 (3)	0.008 (3)	−0.017 (3)
C8	0.028 (3)	0.062 (4)	0.057 (4)	0.001 (3)	0.002 (3)	−0.006 (3)
N1	0.026 (2)	0.026 (2)	0.028 (2)	−0.0026 (19)	0.0001 (18)	−0.0006 (18)
N2	0.036 (3)	0.049 (3)	0.034 (3)	−0.011 (2)	−0.004 (2)	−0.002 (2)
B1	0.043 (5)	0.041 (4)	0.043 (5)	−0.004 (4)	−0.009 (4)	0.000 (3)
F1	0.125 (7)	0.079 (4)	0.055 (4)	0.022 (4)	−0.005 (4)	0.019 (3)
F2	0.087 (5)	0.054 (3)	0.080 (5)	0.002 (3)	0.021 (4)	−0.022 (4)
F3	0.079 (5)	0.118 (6)	0.073 (5)	−0.021 (4)	−0.002 (4)	−0.040 (4)
F4	0.063 (3)	0.090 (4)	0.051 (4)	0.003 (3)	0.012 (3)	0.017 (3)
B1'	0.043 (5)	0.041 (4)	0.043 (5)	−0.004 (4)	−0.009 (4)	0.000 (3)
F1'	0.092 (17)	0.063 (13)	0.047 (13)	0.037 (13)	0.009 (12)	−0.001 (11)
F2'	0.064 (15)	0.048 (12)	0.082 (18)	−0.007 (12)	0.028 (14)	0.004 (14)
F3'	0.096 (18)	0.097 (17)	0.052 (15)	−0.041 (16)	0.000 (15)	−0.040 (13)
F4'	0.053 (14)	0.099 (16)	0.101 (19)	−0.009 (13)	0.001 (15)	0.015 (17)

Geometric parameters (Å, º) top

Br1—C1	1.952 (5)	C6—H6A	0.9700
C1—C2	1.509 (7)	C6—H6B	0.9700
C1—H1A	0.9700	C7—N1	1.510 (6)
C1—H1B	0.9700	C7—C8	1.521 (8)
C2—N1	1.515 (6)	C7—H7A	0.9700
C2—H2A	0.9700	C7—H7B	0.9700
C2—H2B	0.9700	C8—N2	1.461 (7)
C3—N1	1.499 (6)	C8—H8A	0.9700
C3—C4	1.511 (7)	C8—H8B	0.9700
C3—H3A	0.9700	N2—H2	0.91 (7)
C3—H3B	0.9700	B1—F1	1.361 (9)
C4—N2	1.483 (7)	B1—F2	1.371 (9)
C4—H4A	0.9700	B1—F3	1.377 (9)
C4—H4B	0.9700	B1—F4	1.393 (9)
C5—C6	1.500 (7)	B1'—F1'	1.354 (19)
C5—N1	1.502 (6)	B1'—F2'	1.364 (19)
C5—H5A	0.9700	B1'—F3'	1.370 (19)
C5—H5B	0.9700	B1'—F4'	1.388 (19)
C6—N2	1.484 (7)

C2—C1—Br1	106.1 (4)	N1—C7—C8	109.7 (4)
C2—C1—H1A	110.5	N1—C7—H7A	109.7
Br1—C1—H1A	110.5	C8—C7—H7A	109.7
C2—C1—H1B	110.5	N1—C7—H7B	109.7
Br1—C1—H1B	110.5	C8—C7—H7B	109.7
H1A—C1—H1B	108.7	H7A—C7—H7B	108.2
C1—C2—N1	114.4 (4)	N2—C8—C7	108.9 (4)
C1—C2—H2A	108.7	N2—C8—H8A	109.9
N1—C2—H2A	108.7	C7—C8—H8A	109.9
C1—C2—H2B	108.7	N2—C8—H8B	109.9
N1—C2—H2B	108.7	C7—C8—H8B	109.9
H2A—C2—H2B	107.6	H8A—C8—H8B	108.3
N1—C3—C4	110.1 (4)	C3—N1—C5	108.8 (4)
N1—C3—H3A	109.6	C3—N1—C7	108.5 (4)
C4—C3—H3A	109.6	C5—N1—C7	107.9 (4)
N1—C3—H3B	109.6	C3—N1—C2	111.2 (4)
C4—C3—H3B	109.6	C5—N1—C2	112.3 (4)
H3A—C3—H3B	108.2	C7—N1—C2	108.0 (4)
N2—C4—C3	108.8 (4)	C8—N2—C4	110.7 (5)
N2—C4—H4A	109.9	C8—N2—C6	109.7 (5)
C3—C4—H4A	109.9	C4—N2—C6	109.7 (4)
N2—C4—H4B	109.9	C8—N2—H2	108 (4)
C3—C4—H4B	109.9	C4—N2—H2	106 (4)
H4A—C4—H4B	108.3	C6—N2—H2	113 (4)
C6—C5—N1	109.6 (4)	F1—B1—F2	110.1 (7)
C6—C5—H5A	109.8	F1—B1—F3	109.0 (7)
N1—C5—H5A	109.8	F2—B1—F3	108.8 (7)
C6—C5—H5B	109.8	F1—B1—F4	110.4 (7)
N1—C5—H5B	109.8	F2—B1—F4	110.1 (7)
H5A—C5—H5B	108.2	F3—B1—F4	108.3 (7)
N2—C6—C5	109.7 (4)	F1'—B1'—F2'	112 (2)
N2—C6—H6A	109.7	F1'—B1'—F3'	109 (2)
C5—C6—H6A	109.7	F2'—B1'—F3'	109 (2)
N2—C6—H6B	109.7	F1'—B1'—F4'	111 (2)
C5—C6—H6B	109.7	F2'—B1'—F4'	106 (2)
H6A—C6—H6B	108.2	F3'—B1'—F4'	109 (2)

Br1—C1—C2—N1	−179.9 (4)	C8—C7—N1—C5	63.8 (6)
N1—C3—C4—N2	−8.1 (7)	C8—C7—N1—C2	−174.6 (5)
N1—C5—C6—N2	−7.7 (6)	C1—C2—N1—C3	70.8 (6)
N1—C7—C8—N2	−7.9 (7)	C1—C2—N1—C5	−51.3 (6)
C4—C3—N1—C5	−54.1 (6)	C1—C2—N1—C7	−170.2 (5)
C4—C3—N1—C7	63.1 (6)	C7—C8—N2—C4	65.3 (6)
C4—C3—N1—C2	−178.3 (5)	C7—C8—N2—C6	−55.8 (6)
C6—C5—N1—C3	63.3 (6)	C3—C4—N2—C8	−56.3 (6)
C6—C5—N1—C7	−54.3 (6)	C3—C4—N2—C6	64.9 (6)
C6—C5—N1—C2	−173.2 (4)	C5—C6—N2—C8	65.9 (6)
C8—C7—N1—C3	−53.9 (6)	C5—C6—N2—C4	−55.9 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Br2	0.91 (7)	2.23 (7)	3.141 (5)	176 (6)

Experimental details

Crystal data
Chemical formula	C₈H₁₇BrN₂²⁺·BF₄⁻·Br⁻
M_r	387.87
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	11.972 (2), 10.782 (2), 21.165 (4)
V (Å³)	2732.0 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	5.96
Crystal size (mm)	0.3 × 0.25 × 0.2

Data collection
Diffractometer	Rigaku Mercury2
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.191, 0.303
No. of measured, independent and observed [I > 2σ(I)] reflections	26313, 3124, 1881
R_int	0.109
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.108, 1.04
No. of reflections	3124
No. of parameters	198
No. of restraints	34
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.47

Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Br2	0.91 (7)	2.23 (7)	3.141 (5)	176 (6)

Acknowledgements

This work was supported by a start-up grant from Southeast University.

References

Chen, L.-Z., Zhao, H., Ge, J.-Z., Wu, D.-H. & Xiong, R.-G. (2009). Cryst. Growth Des. 9, 3828–3831. Web of Science CSD CrossRef CAS Google Scholar
Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994–997. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, H., Qu, Z.-R., Ye, H.-Y. & Xiong, R.-G. (2008). Chem. Soc. Rev. 37, 84–100. Web of Science CrossRef PubMed Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1-(2-Bromo­ethyl)-1,4-diazo­niabi­cyclo­[2.2.2]octane bromide tetra­fluoro­borate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1-(2-Bromoethyl)-1,4-diazoniabicyclo[2.2.2]octane bromide tetrafluoroborate