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Acta Cryst. (2007). E63, o3940    [ doi:10.1107/S1600536807042274 ]

Benzylbutyldimethylammonium bromide

M. Hodorowicz

Abstract top

The crystal structure of the title compound, C13H22N+·Br-, has been determined as part of a study of the relationship between the sorption properties of montmorillonite and the architecture of the hydrophobic layers formed by modifications of the clay mineral by amphiphilic compounds. In the crystal structure, benzylbutyldimethylammonium and bromide ions are linked via weak C-H...Br hydrogen-bonding interactions, with C-H...Br1 = 3.745 (2)-4.016 (2) Å. C-H...[pi] interactions are also observed in the structure. The ammonium cations are packed in a pseudo-tetragonal `parquet'-style pattern, with encapsulated Br- ions.

Comment top

Ammonium halides are widely studied cationic surfactants used in many fields such as micelar catalysis, medicine, detergency. Additionally they are able to change the nature of the surface of clay minerals, such as montmorillonite or bentonite, from hydrophilic to hydrophobic one (Kwolek et al., 2003). The title compound was investigated in the project on relationship between sorption properties of montmorillonite and the architecture of hydrophobic layers which are due to modifications of the clay mineral by, in this case, quaternary alkylammonium salts (Hodorowicz et al., 2003, 2005). The crystal structure analysis of benzyldimethylbutylammonium bromide was performed to find out the influence of molecular geometry on the packing properties of the ammonium cations. The molecular structure of the title compound is shown in Fig. 1. The symmetrically independent part of the unit cell is composed of the ammonium cation, showing pseudosymmetry m, and bromide counterion (N+···Br− = 4.287 (2) Å). The bond lengths and angles indicate the typical tetrahedral arragement of substituents at the N atom. The benzene rings are essentially planar, with a mean deviation of the C atoms from the best plane of 0.006 Å. The molecular dimensions are comparable with the values reported in the literature (Allen et al., 1987). Methyl and methylene groups as well as C—H of C31–C36 benzene ring of the quaternary ammonium cation are involved in weak intermolecular hydrogen interactions of C—H···Br− type (Table 1). This kind of interactions are responsible for self-assembly of ammonium cations in hydrophobic layers (Hodorowicz et al., 2003, 2005). The ammonium cations are packed in a pseudo-tetragonal `parquet'-style pattern, with Br− ions in between (Fig. 2).

Related literature top

For related literature, see: Hodorowicz et al. (2003, 2005); Kwolek et al. (2003); Kruger et al. (2003); Allen et al. (1987).

Experimental top

The title compoud was prepared by dissolving a (1:1) mixture of benzyl bromide [CH3(CH2)3Br] and N,N-dimethylbenzylamine [C6H5CH2N(CH3)2] in acetone at 273 K. The solution was slowly heated to room temperature to give colourless single crystals of the title compound. Recrystallization from acetone afforded crystals suitable for X-ray measurements.

Refinement top

All hydrogen atom positions were observed in difference Fourier map. Nevertheless, in the refinement procedure the hydrogen atoms were positioned geometrically and refined using a riding model (including free rotation about the C—C bond), with C—H = 0.95–0.99 Å (C—H = 0.97 Å for CH2 groups, 0.96 Å for CH3 groups, and 0.93 Å for aromatic CH) and with Uiso(H) = 1.5Ueq(C) for methyl groups and Uiso(H) = 1.2Ueq(C) for all other H atoms.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997) and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. ORTEP-3 (Farrugia, 1999) drawing of the title compound with labels. Displacement ellipsoids of non-H atoms drawn at 30% probabilty level.
[Figure 2] Fig. 2. Mercury (Macrae et al., 2006) drawing of the ammonium cations packed in a pseudo-tetragonal `parquet'-style pattern, with Br− ions in between; viewed along [001].
Benzylbutyldimethylammonium bromide top
Crystal data top
C13H22N+·Br–F000 = 568
Mr = 272.23Dx = 1.313 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4362 reflections
a = 8.924 (2) Åθ = 1.0–32.0º
b = 9.046 (2) ŵ = 2.96 mm−1
c = 17.183 (4) ÅT = 293 (2) K
β = 96.7870 (10)ºPrism, colourless
V = 1377.4 (5) Å30.25 × 0.22 × 0.20 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer		4725 independent reflections
Radiation source: fine-focus sealed tube3058 reflections with I > 2σ(I)
Monochromator: horizontally mounted graphite crystalRint = 0.021
Detector resolution: 9 pixels mm-1θmax = 32.0º
T = 293(2) Kθmin = 3.5º
φ and ω scans to fill the asymmetric unith = 0→13
Absorption correction: multi-scan
(DENZO and SCALEPACK; Otwinowski & Minor, 1997)		k = −13→12
Tmin = 0.493, Tmax = 0.554l = −25→25
7959 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.038  w = 1/[σ2(Fo2) + (0.0084P)2 + 0.6796P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.077(Δ/σ)max < 0.001
S = 1.08Δρmax = 0.36 e Å−3
4725 reflectionsΔρmin = −0.45 e Å−3
137 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0556 (12)
Secondary atom site location: difference Fourier map
Crystal data top
C13H22N+·Br–V = 1377.4 (5) Å3
Mr = 272.23Z = 4
Monoclinic, P21/nMo Kα
a = 8.924 (2) ŵ = 2.96 mm−1
b = 9.046 (2) ÅT = 293 (2) K
c = 17.183 (4) Å0.25 × 0.22 × 0.20 mm
β = 96.7870 (10)º
Data collection top
Nonius KappaCCD area-detector
diffractometer		4725 independent reflections
Absorption correction: multi-scan
(DENZO and SCALEPACK; Otwinowski & Minor, 1997)		3058 reflections with I > 2σ(I)
Tmin = 0.493, Tmax = 0.554Rint = 0.021
7959 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038137 parameters
wR(F2) = 0.077H-atom parameters constrained
S = 1.08Δρmax = 0.36 e Å−3
4725 reflectionsΔρmin = −0.45 e Å−3
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 > 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
xyzUiso*/Ueq
Br10.01487 (2)0.00013 (2)0.241455 (12)0.04883 (9)
N1−0.06917 (17)0.45897 (17)0.19138 (10)0.0387 (3)
C1−0.0634 (2)0.4635 (2)0.28006 (12)0.0433 (4)
H1A−0.16340.48700.29320.052*
H1B−0.03770.36560.30050.052*
C110.0478 (2)0.5733 (2)0.32121 (13)0.0505 (5)
H11A0.14940.54700.31160.061*
H11B0.02610.67140.30000.061*
C120.0385 (2)0.5749 (2)0.40864 (13)0.0510 (5)
H12A0.05830.47630.42960.061*
H12B−0.06280.60270.41810.061*
C130.1511 (3)0.6825 (3)0.45093 (16)0.0700 (7)
H13A0.14210.68070.50600.084*
H13B0.13060.78040.43100.084*
H13C0.25150.65420.44250.084*
C2−0.1167 (3)0.6065 (2)0.15765 (13)0.0539 (5)
H2A−0.21390.63180.17240.065*
H2B−0.12230.60250.10160.065*
H2C−0.04440.68000.17730.065*
C3−0.1856 (2)0.3414 (2)0.16165 (11)0.0418 (4)
H3A−0.15790.24880.18800.050*
H3B−0.28310.37050.17620.050*
C31−0.2008 (2)0.3157 (2)0.07474 (12)0.0412 (4)
C32−0.3044 (2)0.3941 (2)0.02355 (13)0.0513 (5)
H32−0.36410.46610.04320.062*
C33−0.3195 (3)0.3662 (3)−0.05597 (14)0.0580 (6)
H33−0.38890.4196−0.08950.070*
C34−0.2324 (3)0.2596 (3)−0.08580 (14)0.0581 (6)
H34−0.24240.2415−0.13940.070*
C35−0.1303 (3)0.1797 (2)−0.03612 (14)0.0568 (5)
H35−0.07120.1078−0.05630.068*
C36−0.1154 (2)0.2061 (2)0.04369 (13)0.0488 (5)
H36−0.04770.15030.07700.059*
C40.0826 (2)0.4170 (3)0.16919 (13)0.0513 (5)
H4A0.11140.32220.19130.062*
H4B0.15570.48970.18890.062*
H4C0.07800.41210.11320.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.04368 (12)0.04684 (12)0.05522 (14)−0.00025 (9)0.00274 (8)0.00673 (10)
N10.0350 (7)0.0334 (7)0.0490 (9)−0.0011 (6)0.0100 (7)0.0040 (6)
C10.0405 (9)0.0443 (11)0.0461 (10)0.0012 (8)0.0094 (8)0.0048 (8)
C110.0519 (12)0.0452 (11)0.0550 (12)−0.0024 (9)0.0091 (10)0.0024 (10)
C120.0480 (11)0.0482 (12)0.0582 (13)0.0042 (9)0.0113 (10)−0.0054 (10)
C130.0710 (16)0.0664 (16)0.0727 (17)−0.0093 (13)0.0084 (13)−0.0159 (14)
C20.0680 (14)0.0359 (10)0.0570 (13)−0.0008 (10)0.0050 (11)0.0069 (9)
C30.0368 (9)0.0366 (9)0.0537 (11)−0.0034 (7)0.0123 (8)0.0048 (8)
C310.0357 (9)0.0374 (9)0.0513 (11)−0.0043 (7)0.0086 (8)0.0027 (8)
C320.0413 (10)0.0487 (12)0.0637 (14)0.0025 (9)0.0055 (10)0.0053 (10)
C330.0528 (12)0.0591 (14)0.0598 (14)−0.0068 (10)−0.0037 (10)0.0109 (11)
C340.0647 (14)0.0581 (14)0.0523 (13)−0.0205 (11)0.0101 (11)−0.0015 (11)
C350.0617 (13)0.0462 (12)0.0647 (14)−0.0051 (10)0.0165 (11)−0.0089 (11)
C360.0493 (11)0.0384 (10)0.0590 (13)0.0021 (8)0.0079 (9)0.0001 (9)
C40.0375 (10)0.0581 (13)0.0610 (13)−0.0043 (9)0.0174 (9)−0.0032 (11)
Geometric parameters (Å, °) top
N1—C21.496 (2)C2—H2C0.9600
N1—C41.499 (2)C3—C311.501 (3)
N1—C11.519 (2)C3—H3A0.9700
N1—C31.532 (2)C3—H3B0.9700
N1—Br14.287 (2)C31—C321.392 (3)
C1—C111.518 (3)C31—C361.395 (3)
C1—H1A0.9700C32—C331.380 (3)
C1—H1B0.9700C32—H320.9300
C11—C121.515 (3)C33—C341.375 (3)
C11—H11A0.9700C33—H330.9300
C11—H11B0.9700C34—C351.378 (3)
C12—C131.520 (3)C34—H340.9300
C12—H12A0.9700C35—C361.383 (3)
C12—H12B0.9700C35—H350.9300
C13—H13A0.9600C36—H360.9300
C13—H13B0.9600C4—H4A0.9600
C13—H13C0.9600C4—H4B0.9600
C2—H2A0.9600C4—H4C0.9600
C2—H2B0.9600
C2—N1—C4110.54 (16)N1—C2—H2B109.5
C2—N1—C1109.82 (15)H2A—C2—H2B109.5
C4—N1—C1109.70 (15)N1—C2—H2C109.5
C2—N1—C3109.90 (15)H2A—C2—H2C109.5
C4—N1—C3109.68 (15)H2B—C2—H2C109.5
C1—N1—C3107.14 (14)C31—C3—N1114.67 (14)
C2—N1—Br1167.48 (12)C31—C3—H3A108.6
C4—N1—Br170.35 (10)N1—C3—H3A108.6
C1—N1—Br180.81 (9)C31—C3—H3B108.6
C3—N1—Br159.34 (9)N1—C3—H3B108.6
C11—C1—N1115.32 (16)H3A—C3—H3B107.6
C11—C1—H1A108.4C32—C31—C36118.2 (2)
N1—C1—H1A108.4C32—C31—C3121.68 (18)
C11—C1—H1B108.4C36—C31—C3120.06 (18)
N1—C1—H1B108.4C33—C32—C31120.8 (2)
H1A—C1—H1B107.5C33—C32—H32119.6
C12—C11—C1111.03 (17)C31—C32—H32119.6
C12—C11—H11A109.4C34—C33—C32120.2 (2)
C1—C11—H11A109.4C34—C33—H33119.9
C12—C11—H11B109.4C32—C33—H33119.9
C1—C11—H11B109.4C33—C34—C35119.9 (2)
H11A—C11—H11B108.0C33—C34—H34120.0
C11—C12—C13111.7 (2)C35—C34—H34120.0
C11—C12—H12A109.3C34—C35—C36120.2 (2)
C13—C12—H12A109.3C34—C35—H35119.9
C11—C12—H12B109.3C36—C35—H35119.9
C13—C12—H12B109.3C35—C36—C31120.6 (2)
H12A—C12—H12B107.9C35—C36—H36119.7
C12—C13—H13A109.5C31—C36—H36119.7
C12—C13—H13B109.5N1—C4—H4A109.5
H13A—C13—H13B109.5N1—C4—H4B109.5
C12—C13—H13C109.5H4A—C4—H4B109.5
H13A—C13—H13C109.5N1—C4—H4C109.5
H13B—C13—H13C109.5H4A—C4—H4C109.5
N1—C2—H2A109.5H4B—C4—H4C109.5
C2—N1—C1—C11−61.3 (2)N1—C3—C31—C32−90.8 (2)
C4—N1—C1—C1160.4 (2)N1—C3—C31—C3692.4 (2)
C3—N1—C1—C11179.40 (16)C36—C31—C32—C33−1.4 (3)
Br1—N1—C1—C11125.59 (16)C3—C31—C32—C33−178.28 (19)
N1—C1—C11—C12176.89 (17)C31—C32—C33—C340.2 (3)
C1—C11—C12—C13179.01 (19)C32—C33—C34—C350.4 (3)
C2—N1—C3—C3163.8 (2)C33—C34—C35—C360.1 (3)
C4—N1—C3—C31−58.0 (2)C34—C35—C36—C31−1.4 (3)
C1—N1—C3—C31−176.96 (15)C32—C31—C36—C352.0 (3)
Br1—N1—C3—C31−109.11 (16)C3—C31—C36—C35178.89 (18)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···Br10.972.823.745 (2)160
C3—H3B···Br1i0.972.893.825 (2)162
C33—H33···Br1ii0.933.023.814 (2)145
C36—H36···Br10.933.133.929 (2)146
C2—H2C···Br1iii0.963.123.966 (2)148
C4—H4B···Br1iv0.963.043.811 (2)138
C4—H4A···Br10.963.194.038 (2)149
C11—H11B···Br1iii0.973.144.096 (2)170
C1—H1A···Br1i0.973.134.016 (2)153
C11—H11A···Br1iv0.973.264.222 (2)171
C35—H35···Br1v0.933.424.125 (2)134
C2—H2A···Br1i0.963.434.244 (2)144
C12—H12A···Cg1vi0.973.234.111152
C12—H12B···Cg1vii0.973.103.980151
Symmetry codes: (i) −x−1/2, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x, y+1, z; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x, −y, −z; (vi) x−1/2, −y−1/2, z−1/2; (vii) −x+3/2, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···Br10.972.823.745 (2)160
C3—H3B···Br1i0.972.893.825 (2)162
C33—H33···Br1ii0.933.023.814 (2)145
C36—H36···Br10.933.133.929 (2)146
C2—H2C···Br1iii0.963.123.966 (2)148
C4—H4B···Br1iv0.963.043.811 (2)138
C1—H1A···Br1i0.973.134.016 (2)153
C12—H12B···Cg1v0.973.103.980151
Symmetry codes: (i) −x−1/2, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x, y+1, z; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+3/2, y+1/2, −z+1/2.
Acknowledgements top

The author thanks the Joint X-ray Laboratory, Faculty of Chemistry, and SLAFiBS, Jagiellonian University, for making the Nonius KappaCCD diffractometer available.

references
References top

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