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Acta Cryst. (2007). E63, o3381    [ doi:10.1107/S1600536807031947 ]

Hydrogen bonding in (2-bromobenzyl)dimethylammonium bromide

R. A. Varga and C. Silvestru

Abstract top

Ions of the title compound, C9H13BrN+·Br-, are linked by a strong N-H...Br- hydrogen bond, and this unit is further linked to another three anion-cation units by weak C-H...Br- contacts (H...Br range 2.95-3.09 Å), generating a two-dimensional layer parallel to the bc plane. The layers are stacked along the a axis without any interactions in the third dimension. The Br atom of the cation forms only an intramolecular hydrogen bond (H...Br = 2.76 Å) with one of the methylene H atoms.

Comment top

In solid state, the anion-cation unit of the title compound is held together by a strong N—H···Br− hydrogen bond [H1···Br2 = 2.83 Å] (Fig. 1). Another intramolecular H···Br contact is present between one hydrogen from the methylene group and the bromine bonded to the aromatic ring [H7B···Br1 = 2.76 Å]. The resulting C7—H7B···Br1 angle has a small value due to the rigid skeleton bearing both the donor and the acceptor part of the hydrogen bond-type contact.

The anion-cation unit forms eight weak intermolecular contacts through the two methylene hydrogen atoms, two other H atoms, each from one methyl group bonded to nitrogen, and the bromine anion with three neighboring units (Fig. 2). Four of these interactions are with another anion-cation unit result in zigzag polymers along the c axis and the remaining four contacts with two other units link the one-dimensional arrays, along the b axis, in a two-dimensional supramolecular layer-type arrangement (Varga et al., 2006; Varga & Silvestru, 2007) (Fig. 3). The layers are stacked together, with the aromatic rings intercalated, but with no contacts of any type on the third dimension (Fig. 4).

Related literature top

For similar supramolecular structures formed through H···Br contacts, see: Varga et al. (2006); Varga & Silvestru (2007).

Experimental top

The title compound was obtained unintentionally as the decomposition product from the reaction between dibromo[2-(dimethylaminomethyl)phenyl][2-(dimethylammoniomethyl)phenyl]tin(IV) tetrabromo[2-(dimethylaminomethyl)phenyl]tin(IV) and excess of potassium hydroxide in a CHCl3 / H2O (1:1) mixture. Crystals suitable for single-crystal X-ray diffraction were obtained from a CHCl3-n-hexane (1:4) mixture.

Refinement top

All hydrogen atoms were placed in calculated positions using a riding model, with C—H = 0.93–0.97 Å and with Uiso= 1.5Ueq (C) for methyl H and Uiso= 1.2Ueq (C) for aryl H. The methyl groups were allowed to rotate but not to tip. The hydrogen H1 atom bonded to N1 was found in a difference map and refined with a restrained N—H distance of 0.86 (2) Å

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. View of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bond shown with dashed line.
[Figure 2] Fig. 2. The hydrogen bonding (dashed lines) in structure of the title compound. [Symmetry codes: (i) 2 − x, 2 − y, 2 − z; (ii) 2 − x, 1/2 + y, 1.5 − z; (iii) 2 − x, −1/2 + y, 1.5 − z.]
[Figure 3] Fig. 3. Supramolecular arrangement of the title compound (hydrogen bonds are shown as dashed lines), view along a axis.
[Figure 4] Fig. 4. Crystal packing of the title compound along the c axis.
(2-bromobenzyl)dimethylammonium bromide top
Crystal data top
C9H13BrN+·Br−F(000) = 576
Mr = 295.02Dx = 1.764 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3587 reflections
a = 8.6227 (8) Åθ = 2.5–27.6°
b = 14.6503 (13) ŵ = 7.25 mm−1
c = 9.2118 (8) ÅT = 297 K
β = 107.339 (2)°Block, colourless
V = 1110.80 (17) Å30.23 × 0.21 × 0.10 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		1957 independent reflections
Radiation source: fine-focus sealed tube1700 reflections with I > 2σ(I)
graphiteRint = 0.046
φ and ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan
(SHELXTL; Bruker, 2001)		h = −10→10
Tmin = 0.216, Tmax = 0.491k = −17→17
7866 measured reflectionsl = −10→10
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 1.17 w = 1/[σ2(Fo2) + (0.0392P)2 + 2.3199P]
where P = (Fo2 + 2Fc2)/3
1957 reflections(Δ/σ)max < 0.001
115 parametersΔρmax = 0.70 e Å−3
1 restraintΔρmin = −0.51 e Å−3
Crystal data top
C9H13BrN+·Br−V = 1110.80 (17) Å3
Mr = 295.02Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.6227 (8) ŵ = 7.25 mm−1
b = 14.6503 (13) ÅT = 297 K
c = 9.2118 (8) Å0.23 × 0.21 × 0.10 mm
β = 107.339 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		1957 independent reflections
Absorption correction: multi-scan
(SHELXTL; Bruker, 2001)		1700 reflections with I > 2σ(I)
Tmin = 0.216, Tmax = 0.491Rint = 0.046
7866 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.050H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.110Δρmax = 0.70 e Å−3
S = 1.17Δρmin = −0.51 e Å−3
1957 reflectionsAbsolute structure: ?
115 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

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. 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
xyzUiso*/Ueq
Br21.01040 (8)1.09349 (4)0.77395 (7)0.0421 (2)
Br10.55425 (9)0.75580 (5)0.50628 (9)0.0672 (3)
C10.5417 (7)0.8600 (4)0.6257 (7)0.0390 (13)
C20.6691 (6)0.8827 (3)0.7517 (6)0.0301 (12)
C30.6466 (8)0.9588 (4)0.8348 (7)0.0458 (15)
H30.72950.97600.92090.055*
C40.5061 (9)1.0087 (5)0.7931 (9)0.0605 (19)
H40.49411.05890.85050.073*
C50.3849 (8)0.9846 (5)0.6678 (9)0.0558 (18)
H50.28981.01880.63940.067*
C60.4001 (7)0.9102 (5)0.5814 (8)0.0509 (16)
H60.31660.89410.49500.061*
C70.8256 (6)0.8306 (4)0.8117 (6)0.0353 (13)
H7A0.85180.82560.92140.042*
H7B0.81100.76940.76970.042*
C81.1244 (7)0.8408 (4)0.8720 (7)0.0432 (14)
H8A1.13170.77630.85680.065*
H8B1.13270.85250.97660.065*
H8C1.21110.87140.84630.065*
C90.9548 (7)0.8636 (4)0.6101 (6)0.0437 (14)
H9A1.03880.89870.58760.066*
H9B0.85060.88410.54740.066*
H9C0.96830.80020.59010.066*
N10.9650 (5)0.8755 (3)0.7728 (5)0.0311 (10)
H10.964 (8)0.9336 (15)0.783 (8)0.06 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br20.0564 (4)0.0284 (3)0.0410 (3)−0.0039 (3)0.0136 (3)−0.0004 (2)
Br10.0509 (5)0.0714 (5)0.0772 (6)−0.0147 (4)0.0156 (4)−0.0333 (4)
C10.036 (3)0.041 (3)0.042 (3)−0.004 (3)0.014 (3)0.003 (3)
C20.031 (3)0.027 (3)0.034 (3)0.001 (2)0.013 (2)0.004 (2)
C30.047 (4)0.052 (4)0.040 (3)0.001 (3)0.016 (3)0.001 (3)
C40.072 (5)0.046 (4)0.075 (5)0.017 (4)0.041 (4)0.004 (3)
C50.039 (4)0.060 (4)0.076 (5)0.020 (3)0.029 (4)0.027 (4)
C60.025 (3)0.072 (5)0.055 (4)0.002 (3)0.010 (3)0.015 (3)
C70.035 (3)0.033 (3)0.039 (3)0.001 (2)0.011 (3)0.004 (2)
C80.035 (3)0.042 (3)0.049 (4)0.007 (3)0.008 (3)0.003 (3)
C90.041 (3)0.055 (4)0.037 (3)−0.008 (3)0.014 (3)−0.004 (3)
N10.030 (2)0.026 (2)0.038 (3)−0.0002 (19)0.011 (2)0.0012 (19)
Geometric parameters (Å, °) top
Br2—H12.38 (3)C7—N11.503 (7)
Br1—C11.904 (6)C7—H7A0.9700
C1—C61.378 (8)C7—H7B0.9700
C1—C21.380 (8)C8—N11.494 (7)
C2—C31.398 (8)C8—H8A0.9600
C2—C71.504 (7)C8—H8B0.9600
C3—C41.368 (9)C8—H8C0.9600
C3—H30.9300C9—N11.485 (7)
C4—C51.353 (10)C9—H9A0.9600
C4—H40.9300C9—H9B0.9600
C5—C61.379 (10)C9—H9C0.9600
C5—H50.9300N1—H10.86 (2)
C6—H60.9300
C6—C1—C2122.3 (6)N1—C7—H7B109.1
C6—C1—Br1117.0 (5)C2—C7—H7B109.1
C2—C1—Br1120.7 (4)H7A—C7—H7B107.8
C1—C2—C3116.5 (5)N1—C8—H8A109.5
C1—C2—C7126.1 (5)N1—C8—H8B109.5
C3—C2—C7117.3 (5)H8A—C8—H8B109.5
C4—C3—C2121.9 (6)N1—C8—H8C109.5
C4—C3—H3119.1H8A—C8—H8C109.5
C2—C3—H3119.1H8B—C8—H8C109.5
C5—C4—C3119.6 (7)N1—C9—H9A109.5
C5—C4—H4120.2N1—C9—H9B109.5
C3—C4—H4120.2H9A—C9—H9B109.5
C4—C5—C6121.1 (6)N1—C9—H9C109.5
C4—C5—H5119.4H9A—C9—H9C109.5
C6—C5—H5119.4H9B—C9—H9C109.5
C1—C6—C5118.6 (6)C9—N1—C8110.1 (4)
C1—C6—H6120.7C9—N1—C7112.2 (4)
C5—C6—H6120.7C8—N1—C7111.2 (4)
N1—C7—C2112.6 (4)C9—N1—H1103 (5)
N1—C7—H7A109.1C8—N1—H1108 (5)
C2—C7—H7A109.1C7—N1—H1112 (5)
C6—C1—C2—C31.0 (8)C2—C1—C6—C5−1.0 (9)
Br1—C1—C2—C3−178.2 (4)Br1—C1—C6—C5178.2 (5)
C6—C1—C2—C7178.0 (5)C4—C5—C6—C10.4 (10)
Br1—C1—C2—C7−1.2 (8)C1—C2—C7—N1103.2 (6)
C1—C2—C3—C4−0.4 (8)C3—C2—C7—N1−79.9 (6)
C7—C2—C3—C4−177.6 (5)C2—C7—N1—C9−74.2 (6)
C2—C3—C4—C5−0.2 (10)C2—C7—N1—C8162.0 (5)
C3—C4—C5—C60.2 (10)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br20.86 (2)2.38 (2)3.217 (4)165 (6)
C7—H7B···Br10.972.763.266 (5)113
C8—H8A···Br2i0.963.043.916 (6)153
C7—H7B···Br2i0.973.093.918 (6)144
C7—H7A···Br2ii0.972.953.819 (5)150
C8—H8B···Br2ii0.963.023.895 (7)152
Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+2, −y+2, −z+2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br20.86 (2)2.38 (2)3.217 (4)165 (6)
C7—H7B···Br10.972.763.266 (5)113
C8—H8A···Br2i0.963.043.916 (6)153
C7—H7B···Br2i0.973.093.918 (6)144
C7—H7A···Br2ii0.972.953.819 (5)150
C8—H8B···Br2ii0.963.023.895 (7)152
Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+2, −y+2, −z+2.
Acknowledgements top

We thank the National Center for X-ray Diffraction (`Babes-Bolyai' University, Cluj-Napoca) for performing the single-crystal X-ray diffraction study.

references
References top

Brandenburg, K. & Putz, H. (2006). DIAMOND. Version 3. Crystal Impact GbR, Bonn, Germany.

Bruker (2000). SMART (Version 5.625) and SAINT-Plus (Version 6.29). Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2001). SHELXTL. Version 6.10.12. Bruker AXS Inc., Madison, Wisconsin, USA.

Varga, R. A., Rotar, A., Schuermann, M., Jurkschat, K. & Silvestru, C. (2006). Eur. J. Inorg. Chem. 7, 1475–1486.

Varga, R. A. & Silvestru, C. (2007). Acta Cryst. C63, m48–m50.

Westrip, S. P. (2007). publCIF. In preparation.