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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1570–o1571.
Published online 2009 June 13. doi:  10.1107/S160053680902159X
PMCID: PMC2969506

Bis(2-chloro­benz­yl)dimethyl­ammonium bromide

Abstract

In the title compound, C16H18Cl2N+·Br, the dihedral angle between the aromatic ring planes is 57.73 (5)°. In the absence of any strong hydrogen bonds, the structure results from a large number of competing weaker inter­actions including Cl(...)Cl [3.4610 (5) Å] and C—H(...)Cl contacts and both (aryl) C—H(...)Br and N+—Csp 3—H(...)Br cation–anion inter­actions.

Related literature

Routes to quaternary ammonium compounds include the action of hexa­decyl halide on heterocycles such as pyridine (Shelton & Mariemont, 1942 [triangle]); the action of 1-haloalkanes and allied compounds on the higher alkyl esters of p-dimethyl­amino benzoic acid (Piggot & Woolvin, 1940 [triangle]); reaction of a terminal ep­oxy group with tertiary amine followed by the addition of an acid (Horst & Manfred, 1983 [triangle]); reaction of a tertiary amine, an alkyl­ating agent and an ep­oxy compound (Gary & Owen, 1991 [triangle]); reaction of an alkyl halide with pyridine or imidazole at 393 to 623 K (Kimihiko et al., 2002 [triangle]); and reaction of tertiary amines, methanol and a cyclic ester (Walker, 2004 [triangle]). Quaternary ammonium compounds are utilized in many industrial processes, across a wide range of processes from sanitisers in detergent (Peng et al., 2002 [triangle]) to phase transfer catalysis (Stark et al., 2004 [triangle])). For Cl(...)Cl and C—H(...)Cl contacts, see: (López-Duplá, et al. 2003 [triangle]); (Desiraju & Steiner, 1999 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1570-scheme1.jpg

Experimental

Crystal data

  • C16H18Cl2N+·Br
  • M r = 375.12
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1570-efi10.jpg
  • a = 11.9427 (5) Å
  • b = 8.9771 (4) Å
  • c = 15.0759 (6) Å
  • β = 97.411 (2)°
  • V = 1602.80 (12) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.89 mm−1
  • T = 150 K
  • 0.80 × 0.75 × 0.34 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.165, T max = 0.376
  • 13470 measured reflections
  • 3816 independent reflections
  • 3462 reflections with I > 2σ(I)
  • R int = 0.015

Refinement

  • R[F 2 > 2σ(F 2)] = 0.019
  • wR(F 2) = 0.047
  • S = 1.03
  • 3816 reflections
  • 183 parameters
  • H-atom parameters constrained
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902159X/jh2078sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902159X/jh2078Isup2.hkl

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

Acknowledgments

The authors thank the University of the Punjab and the Charles–Wallace Pakistan Trust for financial support, and are also grateful to the Department of Chemistry, Loughborough University, for providing research facilities.

supplementary crystallographic information

Comment

Di(2-chlorobenzyl)dimethylammonium bromide (I, C16H18BrCl2N) was obtained simply and conveniently by reaction of 2-chlorobenzyl bromide with dimethylamine in the presence of triethylamine. It was characterized by IR and NMR spectroscopy and the stucture is shown in Fig. 1. The geometry at the central N atom is close to tetrahedral and the Cl atoms are trans to each other. The ions are linked through both Cl···Cl interactions and H-bonding involving both Cl and Br.

The intermolecular Cl1···Cl2 interaction at 3.4610 (5) Å (under symmetry operation (i), -x + 1/2, y - 1/2, -z + 1/2) is towards the lower end of the range (3.3029 (4) – 3.6759 (4) Å) observed in a related series of di- and trihaloanilinium halides (López-Duplá et al., 2003). This interaction links the cations in zigzag chains running parallel to b (Fig. 2 and Fig. 3). Additionally there is a H-bond linking one of the aromatic carbon atoms (C6) to Cl2 (under symmetry operation (iv), -x, -y + 1, -z), while there are arguably six C—H···Br H-bonds linking each bromide anion to four cations (Table 2). Again these fall within the reported range (3.056 - 3.961 Å) (López-Duplá et al., 2003), but only one involves an aromatic proton (on C16), the other five involve methyl or methylene groups adjacent to the N+ centre (N+— C(sp3)—H···Br-). This type of interaction is reasonably common (Desiraju & Steiner, 1999) and the geometry is as expected for H-bonding; however Desiraju and Steiner have pointed out that the primary interaction in such cases may be electrostatic attraction between the anion and the positive charge with the protons limiting the approach of the anion.

The four closest N+···Br- distances are listed in table 1. The shortest pair are close to the mean value reported for contacts between a quaternary ammonium group and a bromide ion (Desiraju & Steiner, 1999); the remaining two distances are significantly longer and should probably be discounted, despite the fact that one of these molecules (symmetry operation (ii) -x + 1/2, y + 1/2, -z + 1/2) makes two "H-bonds" to Br1, suggesting a genuine N+— C(sp3)—H···Br- attraction. In the absence of any strong H-bonds the structure is, of necessity, held together by a large number of competing weaker interactions between cations and between anions and cations.

Experimental

2-Chlorobenzylbromide (0.65 ml, 1.0 mmol was dissolved in 25 ml dichloromethane and one ml of triethylamine was added, followed by dropwise addition of a solution of 33% dimethylamine (0.20 ml,1.5 mmol) in ethanol. The reaction mixture was stirred for eight hours, then neutralized with 10% sodium bicarbonate solution. The mixture was again stirred and the organic layer was separated, dried over anhydrous magnesium sulfate and filtered before being concentrated on a rotary evaporator. It was then cooled in a refrigerator to give the pure product as colorless needles in 43% yield. The presence of the quaternary ammonium species was established on the basis of the following spectroscopic data:

IR (KBr, cm-1): 3053 (s, νC—H aromatic), 2861 (m, νC—H aliphatic), 1600 (m, νC—C), 776 (m, νC—Cl), 1151 (m νC—N) the latter band is characteristic of CH2—N(CH3)2. Absorption bands due to νC—Br and νN—H of the starting material in the region 690–515 cm-1(m) and 3400–3250 cm-1(m) respectively are absent.

NMR (CDCl3, p.p.m.. 1H): 3.26 (s, 6, CH3), 5.38 (s, 4, CH2), 7.48 – 7.56 (mult., 6, Ar), 8.16 (s, 2, Ar adjacent to Br).

Refinement

H atoms were inserted at calculated positions and refined using a riding model. The constrained C—H distances were 0.95, 0.98 and 0.99 Å for aryl, methyl and methylene respectively. The H atoms of methylene and aryl groups were refined with Uiso(H) = 1.2Ueq(C) and those of the methyl groups with Uiso(H) = 1.5Ueq(C).

Figures

Fig. 1.
Perspective view of compound (I). Displacement elipsoids are drawn at the 50% level and H atoms are shown as spheres of arbitrary radius.
Fig. 2.
C — H···X— C, C — H···Br and Cl···Cl interactions. Symmetry codes: (i) -x + 1/2, y - 1/2, -z + 1/2; (ii) -x + 1/2, y + 1/2, -z + 1/2; (iv) -x, -y + 1, -z; ...
Fig. 3.
Packing diagram viewed down the a axis and showing the Cl···Cl interactions. Cl atoms are shown shaded, Br atoms are shown cross-hatched.

Crystal data

C16H18Cl2N+·BrF(000) = 760
Mr = 375.12Dx = 1.555 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 8351 reflections
a = 11.9427 (5) Åθ = 2.3–28.7°
b = 8.9771 (4) ŵ = 2.89 mm1
c = 15.0759 (6) ÅT = 150 K
β = 97.411 (2)°Block, colourless
V = 1602.80 (12) Å30.80 × 0.75 × 0.34 mm
Z = 4

Data collection

Bruker SMART 1000 CCD diffractometer3816 independent reflections
Radiation source: sealed tube3462 reflections with I > 2σ(I)
graphiteRint = 0.015
ω rotation with narrow frames scansθmax = 28.8°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)h = −15→15
Tmin = 0.165, Tmax = 0.376k = −11→11
13470 measured reflectionsl = −19→20

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.019Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.047H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0215P)2 + 0.7575P] where P = (Fo2 + 2Fc2)/3
3816 reflections(Δ/σ)max = 0.001
183 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = −0.21 e Å3

Special details

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)

xyzUiso*/Ueq
C10.35722 (11)0.30048 (15)0.05726 (9)0.0197 (3)
C20.45188 (11)0.20813 (15)0.06312 (9)0.0215 (3)
Cl10.48415 (3)0.09081 (4)0.15526 (2)0.02628 (8)
C30.52466 (12)0.20869 (18)−0.00141 (10)0.0280 (3)
H30.58860.14490.00420.034*
C40.50319 (14)0.30335 (19)−0.07430 (10)0.0329 (3)
H40.55170.3031−0.11950.039*
C50.41118 (14)0.39814 (19)−0.08124 (10)0.0326 (3)
H50.39670.4632−0.13110.039*
C60.33996 (12)0.39827 (17)−0.01548 (10)0.0259 (3)
H60.27840.4660−0.01990.031*
C70.27893 (11)0.30423 (14)0.12803 (9)0.0184 (3)
H7A0.26040.40930.13970.022*
H7B0.31910.26260.18410.022*
N10.16846 (9)0.21772 (12)0.10372 (7)0.0172 (2)
C80.19294 (12)0.05980 (15)0.08053 (10)0.0231 (3)
H8A0.23670.05850.02980.035*
H8B0.12170.00620.06440.035*
H8C0.23640.01140.13220.035*
C90.09604 (12)0.28868 (16)0.02635 (9)0.0226 (3)
H9A0.02240.23890.01710.034*
H9B0.13300.2791−0.02780.034*
H9C0.08540.39440.03920.034*
C100.10924 (11)0.22455 (16)0.18762 (9)0.0201 (3)
H10A0.15970.18040.23800.024*
H10B0.09750.33040.20240.024*
C11−0.00317 (11)0.14542 (16)0.17982 (9)0.0201 (3)
C12−0.10616 (12)0.22153 (16)0.16489 (9)0.0221 (3)
Cl2−0.10838 (3)0.41433 (4)0.15277 (2)0.02902 (8)
C13−0.20899 (12)0.14761 (19)0.16070 (10)0.0287 (3)
H13−0.27770.20190.15030.034*
C14−0.21075 (13)−0.00522 (19)0.17171 (10)0.0306 (3)
H14−0.2808−0.05650.16790.037*
C15−0.11021 (13)−0.08362 (18)0.18827 (10)0.0288 (3)
H15−0.1113−0.18850.19640.035*
C16−0.00792 (12)−0.00860 (17)0.19297 (9)0.0244 (3)
H160.0605−0.06320.20540.029*
Br10.332790 (12)0.178154 (15)0.376859 (9)0.02633 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0179 (6)0.0197 (6)0.0211 (6)−0.0019 (5)0.0009 (5)−0.0006 (5)
C20.0199 (6)0.0226 (7)0.0212 (6)0.0005 (5)0.0000 (5)−0.0001 (5)
Cl10.02153 (16)0.02815 (18)0.02852 (17)0.00756 (13)0.00083 (13)0.00558 (14)
C30.0215 (7)0.0344 (8)0.0284 (7)0.0010 (6)0.0042 (6)−0.0048 (6)
C40.0314 (8)0.0444 (9)0.0244 (7)−0.0066 (7)0.0096 (6)−0.0029 (7)
C50.0354 (8)0.0375 (9)0.0244 (7)−0.0061 (7)0.0024 (6)0.0081 (6)
C60.0234 (7)0.0258 (7)0.0275 (7)−0.0007 (6)−0.0003 (6)0.0057 (6)
C70.0163 (6)0.0182 (6)0.0200 (6)0.0006 (5)−0.0003 (5)−0.0012 (5)
N10.0153 (5)0.0179 (5)0.0179 (5)0.0021 (4)0.0006 (4)−0.0008 (4)
C80.0222 (7)0.0174 (6)0.0306 (7)0.0005 (5)0.0072 (5)−0.0040 (5)
C90.0206 (7)0.0279 (7)0.0178 (6)0.0025 (5)−0.0032 (5)0.0017 (5)
C100.0163 (6)0.0274 (7)0.0165 (6)0.0027 (5)0.0012 (5)−0.0019 (5)
C110.0174 (6)0.0280 (7)0.0150 (6)0.0026 (5)0.0019 (5)−0.0012 (5)
C120.0200 (7)0.0278 (7)0.0180 (6)0.0038 (5)0.0011 (5)−0.0033 (5)
Cl20.02630 (17)0.02741 (18)0.03270 (19)0.00973 (14)0.00138 (14)−0.00288 (14)
C130.0171 (7)0.0423 (9)0.0265 (7)0.0025 (6)0.0022 (5)−0.0050 (6)
C140.0232 (7)0.0420 (9)0.0272 (7)−0.0083 (6)0.0058 (6)−0.0055 (6)
C150.0348 (8)0.0288 (8)0.0244 (7)−0.0035 (6)0.0098 (6)−0.0008 (6)
C160.0238 (7)0.0289 (7)0.0210 (7)0.0053 (6)0.0056 (5)0.0026 (6)
Br10.02822 (8)0.02006 (7)0.02794 (8)−0.00575 (5)−0.00691 (5)0.00494 (5)

Geometric parameters (Å, °)

C1—C21.3955 (19)C9—H9A0.9800
C1—C61.3990 (19)C9—H9B0.9800
C1—C71.5068 (18)C9—H9C0.9800
C2—C31.386 (2)C10—C111.5100 (18)
C2—Cl11.7463 (14)C10—H10A0.9900
C3—C41.387 (2)C10—H10B0.9900
C3—H30.9500C11—C161.399 (2)
C4—C51.383 (2)C11—C121.3995 (18)
C4—H40.9500C12—C131.390 (2)
C5—C61.387 (2)C12—Cl21.7403 (15)
C5—H50.9500C13—C141.382 (2)
C6—H60.9500C13—H130.9500
C7—N11.5341 (16)C14—C151.386 (2)
C7—H7A0.9900C14—H140.9500
C7—H7B0.9900C15—C161.389 (2)
N1—C81.4979 (16)C15—H150.9500
N1—C91.5014 (16)C16—H160.9500
N1—C101.5279 (16)Br1—N14.3416 (11)
C8—H8A0.9800Br1—N1i4.1439 (11)
C8—H8B0.9800Br1—N1ii4.8527 (11)
C8—H8C0.9800Br1—N1iii5.0105 (11)
C2—C1—C6117.29 (13)N1—C8—H8C109.5
C2—C1—C7122.68 (12)H8A—C8—H8C109.5
C6—C1—C7119.92 (12)H8B—C8—H8C109.5
C3—C2—C1122.00 (13)N1—C9—H9A109.5
C3—C2—Cl1117.81 (11)N1—C9—H9B109.5
C1—C2—Cl1120.17 (10)H9A—C9—H9B109.5
C2—C3—C4119.33 (14)N1—C9—H9C109.5
C2—C3—H3120.3H9A—C9—H9C109.5
C4—C3—H3120.3H9B—C9—H9C109.5
C5—C4—C3120.07 (14)C11—C10—N1114.74 (10)
C5—C4—H4120.0C11—C10—H10A108.6
C3—C4—H4120.0N1—C10—H10A108.6
C4—C5—C6120.05 (14)C11—C10—H10B108.6
C4—C5—H5120.0N1—C10—H10B108.6
C6—C5—H5120.0H10A—C10—H10B107.6
C5—C6—C1121.19 (14)C16—C11—C12117.03 (13)
C5—C6—H6119.4C16—C11—C10120.39 (12)
C1—C6—H6119.4C12—C11—C10122.47 (13)
C1—C7—N1114.37 (10)C13—C12—C11121.81 (14)
C1—C7—H7A108.7C13—C12—Cl2117.94 (11)
N1—C7—H7A108.7C11—C12—Cl2120.24 (11)
C1—C7—H7B108.7C14—C13—C12119.69 (14)
N1—C7—H7B108.7C14—C13—H13120.2
H7A—C7—H7B107.6C12—C13—H13120.2
C8—N1—C9109.29 (10)C13—C14—C15119.95 (14)
C8—N1—C10110.88 (10)C13—C14—H14120.0
C9—N1—C10110.14 (10)C15—C14—H14120.0
C8—N1—C7110.31 (10)C14—C15—C16119.92 (14)
C9—N1—C7111.24 (10)C14—C15—H15120.0
C10—N1—C7104.93 (9)C16—C15—H15120.0
N1—C8—H8A109.5C15—C16—C11121.57 (13)
N1—C8—H8B109.5C15—C16—H16119.2
H8A—C8—H8B109.5C11—C16—H16119.2
C6—C1—C2—C3−2.0 (2)C8—N1—C10—C11−60.79 (14)
C7—C1—C2—C3−178.34 (13)C9—N1—C10—C1160.32 (15)
C6—C1—C2—Cl1176.20 (11)C7—N1—C10—C11−179.87 (11)
C7—C1—C2—Cl1−0.19 (18)N1—C10—C11—C1682.49 (15)
C1—C2—C3—C4−0.1 (2)N1—C10—C11—C12−101.51 (15)
Cl1—C2—C3—C4−178.34 (12)C16—C11—C12—C13−1.8 (2)
C2—C3—C4—C51.3 (2)C10—C11—C12—C13−177.91 (13)
C3—C4—C5—C6−0.3 (2)C16—C11—C12—Cl2177.16 (10)
C4—C5—C6—C1−2.0 (2)C10—C11—C12—Cl21.03 (18)
C2—C1—C6—C53.0 (2)C11—C12—C13—C140.2 (2)
C7—C1—C6—C5179.49 (13)Cl2—C12—C13—C14−178.79 (12)
C2—C1—C7—N1−101.76 (14)C12—C13—C14—C151.0 (2)
C6—C1—C7—N181.94 (15)C13—C14—C15—C16−0.6 (2)
C1—C7—N1—C855.23 (14)C14—C15—C16—C11−1.1 (2)
C1—C7—N1—C9−66.23 (14)C12—C11—C16—C152.2 (2)
C1—C7—N1—C10174.70 (11)C10—C11—C16—C15178.46 (12)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x+1/2, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6···Cl2iv0.952.873.6451 (15)140
C9—H9A···Br1v0.982.993.6365 (13)125
C9—H9C···Br1ii0.982.953.8414 (15)151
C7—H7A···Br1ii0.992.663.6095 (13)162
C7—H7B···Br10.992.993.8916 (13)152
C10—H10A···Br10.992.753.6709 (13)156
C16—H16···Br1i0.952.993.7361 (14)136

Symmetry codes: (iv) −x, −y+1, −z; (v) x−1/2, −y+1/2, z−1/2; (ii) −x+1/2, y+1/2, −z+1/2; (i) −x+1/2, y−1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: JH2078).

References

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  • Piggot, H. A. & Woolvin, C. S. (1940). US Patent No. 2 202 864.
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  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shelton, R. S. & Mariemont, O. (1942). US Patent No. 2 295 504–5.
  • Stark, C. M., Liotta, C. L. & Halpern, M. (2004). Phase Transfer Catalysis: Fundamentals, Applications and Industrial Perspectives. New York: Chapman & Hall.
  • Walker, L. E. (2004). US Patent No. 6 74 307.

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