1-Bromo-methyl-4-aza-1-azoniabicyclo-[2.2.2]octane bromide.

The title compound, C(7)H(14)BrN(2) (+)·Br(-), was prepared by nucleophilic substitution of DABCO (systematic name: 1,4-diaza-bicyclo-[2.2.2]octa-ne) with dibromo-methane in acetone. The structure features Br⋯H close contacts (2.79 and 2.90 Å) as well as a weak bromine-bromide inter-action [3.6625 (6) Å].

Related literature

For use of DABCO as an organocatalyst, see Basaviah et al. (2003 ▶). For related haloalkyl­ations of DABCO, see: Almarzoqi et al. (1986 ▶); Fronczek et al. (1990 ▶); Gustafsson et al. (2005 ▶); Banks et al. (1993 ▶); Batsanov et al. (2005 ▶); Fletcher Claville et al. (2007 ▶). For inversion twinning, see: Flack & Bernardinelli (2000 ▶).

Experimental

Crystal data

C7H14BrN2 +·Br−

M = 286.02

Orthorhombic,

a = 7.1100 (3) Å

b = 11.8085 (5) Å

c = 11.7702 (5) Å

V = 988.21 (7) Å3

Z = 4

Mo Kα radiation

μ = 8.15 mm−1

T = 193 K

0.36 × 0.35 × 0.06 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: integration [SHELXTL (Sheldrick, 2008 ▶) and XPREP (Bruker, 2005 ▶)] T min = 0.151, T max = 0.744

7347 measured reflections

991 independent reflections

954 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.052

S = 1.10

991 reflections

61 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.44 e Å−3

Absolute structure: Flack (1983 ▶), 468 Friedel pairs

Flack parameter: −0.004 (17)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT and XPREP (Bruker, 2005 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and CrystalMaker (CrystalMaker, 1994 ▶); software used to prepare material for publication: XCIF (Bruker, 2005 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810000292/pk2223sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810000292/pk2223Isup2.hkl

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

C7H14BrN2+·Br−	F(000) = 560
Mr = 286.02	Dx = 1.922 Mg m−3
Orthorhombic, Cmc21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c -2	Cell parameters from 3160 reflections
a = 7.1100 (3) Å	θ = 3.3–26.3°
b = 11.8085 (5) Å	µ = 8.15 mm−1
c = 11.7702 (5) Å	T = 193 K
V = 988.21 (7) Å3	Plate, colourless
Z = 4	0.36 × 0.35 × 0.06 mm

Bruker Kappa APEXII CCD diffractometer	991 independent reflections
Radiation source: fine-focus sealed tube	954 reflections with I > 2σ(I)
graphite	Rint = 0.050
φ and ω scans	θmax = 25.4°, θmin = 3.3°
Absorption correction: integration (SHELXTL and XPREP; Bruker, 2005)	h = −8→8
Tmin = 0.151, Tmax = 0.744	k = −14→14
7347 measured reflections	l = −14→14

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)] = 0.022	H-atom parameters constrained
wR(F2) = 0.052	w = 1/[σ2(Fo2) + (0.0248P)2] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
991 reflections	Δρmax = 0.42 e Å−3
61 parameters	Δρmin = −0.44 e Å−3
1 restraint	Absolute structure: Flack (1983), 468 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.004 (17)

Experimental. One distinct cell was identified using APEX2 (Bruker, 2004). Seven frame series were integrated and filtered for statistical outliers using SAINT (Bruker, 2005) then corrected for absorption by integration using SHELXTL/XPREP V2005/2 (Bruker, 2005) before using SAINT/SADABS (Bruker, 2005) to sort, merge, and scale the combined data. No decay correction was applied.

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. Structure was phased by direct methods (Sheldrick, 2008). Systematic conditions suggested the ambiguous space group. The space group choice was confirmed by successful convergence of the full-matrix least-squares refinement on F2. The highest peaks in the final difference Fourier map were in the vicinity of atoms Br1 and Br2; the final map had no other significant features. A final analysis of variance between observed and calculated structure factors showed some dependence on amplitude and resolution.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.5000	0.14054 (4)	−0.05638 (4)	0.03174 (19)
Br2	0.0000	0.65245 (4)	0.34152 (3)	0.02920 (17)
N1	0.5000	0.5040 (4)	0.1977 (4)	0.0281 (9)
N2	0.5000	0.3707 (3)	0.0253 (3)	0.0188 (8)
C1	0.5000	0.5692 (5)	0.0917 (5)	0.0360 (13)
H1A	0.6126	0.6185	0.0898	0.043*	0.50
H1B	0.3874	0.6185	0.0898	0.043*	0.50
C2	0.5000	0.4932 (4)	−0.0128 (4)	0.0291 (12)
H2A	0.3871	0.5086	−0.0595	0.035*	0.50
H2B	0.6129	0.5086	−0.0595	0.035*	0.50
C3	0.3326 (5)	0.4320 (3)	0.1979 (3)	0.0369 (9)
H3A	0.2189	0.4804	0.1960	0.044*
H3B	0.3294	0.3875	0.2691	0.044*
C4	0.3283 (5)	0.3507 (3)	0.0964 (3)	0.0264 (8)
H4A	0.3263	0.2714	0.1236	0.032*
H4B	0.2137	0.3640	0.0506	0.032*
C5	0.5000	0.3026 (4)	−0.0825 (4)	0.0234 (10)
H5A	0.6125	0.3229	−0.1278	0.028*	0.50
H5B	0.3875	0.3229	−0.1278	0.028*	0.50

	U11	U22	U33	U12	U13	U23
Br1	0.0285 (4)	0.0282 (3)	0.0385 (4)	0.000	0.000	−0.0120 (3)
Br2	0.0230 (3)	0.0325 (3)	0.0321 (4)	0.000	0.000	0.0042 (3)
N1	0.037 (2)	0.027 (2)	0.021 (2)	0.000	0.000	−0.0071 (18)
N2	0.021 (2)	0.023 (2)	0.013 (2)	0.000	0.000	−0.0006 (16)
C1	0.046 (3)	0.024 (3)	0.038 (3)	0.000	0.000	−0.005 (2)
C2	0.042 (3)	0.023 (3)	0.022 (3)	0.000	0.000	0.006 (2)
C3	0.039 (2)	0.037 (2)	0.034 (2)	−0.0058 (18)	0.0135 (16)	−0.0103 (18)
C4	0.0189 (18)	0.035 (2)	0.0254 (17)	−0.0029 (15)	0.0062 (12)	−0.0040 (13)
C5	0.032 (3)	0.025 (2)	0.013 (2)	0.000	0.000	−0.0048 (18)

Br1—C5	1.938 (5)	C3—C4	1.532 (4)
N1—C3i	1.463 (4)	C3—H3A	0.9900
N1—C3	1.464 (4)	C3—H3B	0.9900
N1—C1	1.466 (6)	C4—H4A	0.9900
N2—C4	1.499 (4)	C4—H4B	0.9900
N2—C4i	1.499 (4)	C5—H5A	0.9900
N2—C5	1.502 (6)	C5—H5B	0.9900
N2—C2	1.514 (6)	Br1—Br2ii	3.6625 (6)
C1—C2	1.522 (7)	Br2—H5Aiii	2.79
C1—H1A	0.9900	Br2—H5Biv	2.79
C1—H1B	0.9900	Br2—H4Bv	2.90
C2—H2A	0.9900	Br2—H4Biv	2.90
C2—H2B	0.9900
C3i—N1—C3	108.9 (4)	H2A—C2—H2B	108.3
C3i—N1—C1	107.8 (3)	N1—C3—C4	112.3 (3)
C3—N1—C1	107.8 (3)	N1—C3—H3A	109.1
C4—N2—C4i	109.1 (4)	C4—C3—H3A	109.1
C4—N2—C5	112.8 (2)	N1—C3—H3B	109.1
C4i—N2—C5	112.8 (2)	C4—C3—H3B	109.1
C4—N2—C2	108.4 (2)	H3A—C3—H3B	107.9
C4i—N2—C2	108.4 (2)	N2—C4—C3	108.7 (3)
C5—N2—C2	105.2 (3)	N2—C4—H4A	109.9
N1—C1—C2	112.2 (4)	C3—C4—H4A	109.9
N1—C1—H1A	109.2	N2—C4—H4B	109.9
C2—C1—H1A	109.2	C3—C4—H4B	109.9
N1—C1—H1B	109.2	H4A—C4—H4B	108.3
C2—C1—H1B	109.2	N2—C5—Br1	113.2 (3)
H1A—C1—H1B	107.9	N2—C5—H5A	108.9
N2—C2—C1	108.9 (4)	Br1—C5—H5A	108.9
N2—C2—H2A	109.9	N2—C5—H5B	108.9
C1—C2—H2A	109.9	Br1—C5—H5B	108.9
N2—C2—H2B	109.9	H5A—C5—H5B	107.7
C1—C2—H2B	109.9
C3i—N1—C1—C2	58.7 (2)	C4i—N2—C4—C3	59.3 (4)
C3—N1—C1—C2	−58.7 (2)	C5—N2—C4—C3	−174.6 (3)
C4—N2—C2—C1	59.1 (2)	C2—N2—C4—C3	−58.6 (3)
C4i—N2—C2—C1	−59.1 (2)	N1—C3—C4—N2	−0.5 (4)
C5—N2—C2—C1	180.0	C4—N2—C5—Br1	−62.1 (2)
N1—C1—C2—N2	0.0	C4i—N2—C5—Br1	62.1 (2)
C3i—N1—C3—C4	−57.5 (5)	C2—N2—C5—Br1	180.0
C1—N1—C3—C4	59.2 (4)