PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2376.
Published online 2009 September 9. doi:  10.1107/S1600536809034497
PMCID: PMC2970227

2,4,6-Trimethyl­anilinium bromide

Abstract

In the title compound, C9H14N+·Br, an intra­molecular N—H(...)Br inter­action links the anion to the cation. In the crystal structure, inter­molecular N—H(...)Br inter­actions link the mol­ecules into a three-dimensional network.

Related literature

For related structures, see: Lemmerer & Billing (2007 [triangle]); Long et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2376-scheme1.jpg

Experimental

Crystal data

  • C9H14N+·Br
  • M r = 216.11
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2376-efi1.jpg
  • a = 10.399 (2) Å
  • b = 18.720 (4) Å
  • c = 10.282 (2) Å
  • V = 2001.6 (7) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 4.05 mm−1
  • T = 294 K
  • 0.2 × 0.2 × 0.2 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.88, T max = 1.000
  • 18944 measured reflections
  • 2292 independent reflections
  • 1627 reflections with I > 2σ(I)
  • R int = 0.099

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.122
  • S = 1.00
  • 2292 reflections
  • 113 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.41 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809034497/hk2763sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034497/hk2763Isup2.hkl

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

supplementary crystallographic information

Comment

The crystal structure of the title compound is reported herein as part of a study of 2,4,6-trimethylanilinium halide salts. The other halide salts have been reported, previously (Lemmerer & Billing, 2007; Long et al., 2007).

The asymmetric unit of the title compound, (Fig. 1), contains one 2,4,6 -trimethylbenzenaminium cation and one bromide anion. The intramolecular N-H···Br interaction (Table 1) links the anion to the cation.

In the crystal structure, intra- and intermolecular N-H···Br interactions (Table 1) link the molecules into a three-dimensional network.

Experimental

For the preparation of the title compound, 2,4,6-trimethylaniline (3 mmol) was dissolved in ethanol (6 ml), and concentrated hydrobromic acid was added dropwise to dissolve the solid phase persisting in a mixture of bismuth tricbromide (3 mmol) and water (5 ml). The two solutions were then mixed and stirred for 15 min. The resulting precipitate was filtered off and dissolved in hydrobromic acid. Colorless crystals suitable for X-ray analysis were formed after several weeks by slow evaporation of the solvent at room temperature.

Refinement

Atoms H1A, H1B and H1C (for NH3) are located in a difference Fourier map and refined isotropically. The remaining H atoms were positioned geometrically with C-H = 0.93 and 0.96 Å for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for aromatic H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bond is shown as dashed line.

Crystal data

C9H14N+·BrF(000) = 880
Mr = 216.11Dx = 1.434 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1647 reflections
a = 10.399 (2) Åθ = 3.0–27.6°
b = 18.720 (4) ŵ = 4.05 mm1
c = 10.282 (2) ÅT = 294 K
V = 2001.6 (7) Å3Prism, colorless
Z = 80.2 × 0.2 × 0.2 mm

Data collection

Rigaku SCXmini diffractometer2292 independent reflections
Radiation source: fine-focus sealed tube1627 reflections with I > 2σ(I)
graphiteRint = 0.099
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω scansh = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −24→24
Tmin = 0.88, Tmax = 1.000l = −13→13
18944 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.122w = 1/[σ2(Fo2) + (0.0437P)2 + 2.8318P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2292 reflectionsΔρmax = 0.37 e Å3
113 parametersΔρmin = −0.41 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0097 (8)

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
Br10.10008 (4)0.00542 (2)0.69604 (4)0.0471 (2)
N10.1859 (4)0.0634 (2)0.3959 (4)0.0420 (9)
H1A0.113 (4)0.058 (2)0.361 (5)0.053 (14)*
H1B0.171 (5)0.042 (3)0.477 (6)0.085 (18)*
H1C0.249 (4)0.033 (3)0.346 (4)0.052 (12)*
C10.2218 (4)0.1388 (2)0.4055 (4)0.0364 (9)
C20.3168 (4)0.1578 (2)0.4945 (4)0.0466 (11)
C30.3457 (4)0.2299 (3)0.5046 (4)0.0563 (13)
H3A0.40630.24400.56590.068*
C40.2896 (5)0.2813 (3)0.4289 (5)0.0545 (12)
C50.2005 (4)0.2595 (2)0.3376 (5)0.0523 (11)
H5A0.16300.29350.28370.063*
C60.1650 (4)0.1883 (2)0.3237 (4)0.0416 (10)
C70.3892 (4)0.1028 (3)0.5721 (5)0.0747 (17)
H7A0.35650.05610.55250.112*
H7B0.37860.11230.66330.112*
H7C0.47890.10500.55030.112*
C80.3257 (6)0.3597 (3)0.4419 (6)0.0892 (19)
H8A0.27660.38740.38110.134*
H8B0.41570.36550.42400.134*
H8C0.30770.37560.52870.134*
C90.0696 (5)0.1680 (3)0.2198 (5)0.0656 (14)
H9A0.04220.21020.17440.098*
H9B−0.00350.14540.25920.098*
H9C0.10930.13560.15960.098*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0419 (3)0.0519 (3)0.0473 (3)−0.00391 (19)−0.00179 (18)0.0025 (2)
N10.035 (2)0.048 (2)0.043 (2)−0.0016 (17)−0.0005 (18)0.0009 (18)
C10.033 (2)0.041 (2)0.035 (2)−0.0008 (17)0.0048 (17)0.0004 (18)
C20.037 (2)0.065 (3)0.038 (2)−0.011 (2)−0.0016 (19)0.005 (2)
C30.052 (3)0.078 (3)0.039 (3)−0.027 (3)0.001 (2)−0.012 (2)
C40.061 (3)0.050 (3)0.053 (3)−0.016 (2)0.012 (2)−0.006 (2)
C50.050 (2)0.049 (3)0.058 (3)0.001 (2)0.002 (2)0.010 (2)
C60.035 (2)0.050 (2)0.040 (2)−0.0016 (19)−0.0005 (18)0.0021 (19)
C70.050 (3)0.100 (4)0.074 (4)−0.025 (3)−0.024 (3)0.037 (3)
C80.108 (5)0.059 (3)0.101 (5)−0.031 (3)0.005 (4)−0.016 (3)
C90.060 (3)0.078 (3)0.058 (3)−0.018 (3)−0.024 (2)0.018 (3)

Geometric parameters (Å, °)

N1—C11.464 (5)C6—C11.383 (5)
N1—H1A0.84 (5)C6—C51.391 (6)
N1—H1B0.94 (6)C6—C91.507 (6)
N1—H1C1.01 (5)C7—H7A0.9600
C2—C31.387 (6)C7—H7B0.9600
C2—C11.393 (5)C7—H7C0.9600
C2—C71.504 (6)C8—H8A0.9600
C3—H3A0.9300C8—H8B0.9600
C4—C31.368 (6)C8—H8C0.9600
C4—C81.521 (7)C9—H9A0.9600
C5—C41.380 (6)C9—H9B0.9600
C5—H5A0.9300C9—H9C0.9600
C1—N1—H1A112 (3)C1—C6—C5117.8 (4)
C1—N1—H1B114 (3)C1—C6—C9122.9 (4)
C1—N1—H1C114 (3)C5—C6—C9119.3 (4)
H1A—N1—H1B100 (4)C2—C7—H7A109.5
H1A—N1—H1C108 (4)C2—C7—H7B109.5
H1B—N1—H1C108 (4)C2—C7—H7C109.5
C2—C1—N1118.1 (4)H7A—C7—H7B109.5
C6—C1—N1119.7 (4)H7A—C7—H7C109.5
C6—C1—C2122.1 (4)H7B—C7—H7C109.5
C1—C2—C7122.0 (4)C4—C8—H8A109.5
C3—C2—C1116.8 (4)C4—C8—H8B109.5
C3—C2—C7121.1 (4)C4—C8—H8C109.5
C2—C3—H3A118.3H8A—C8—H8B109.5
C4—C3—C2123.3 (4)H8A—C8—H8C109.5
C4—C3—H3A118.3H8B—C8—H8C109.5
C3—C4—C5117.8 (4)C6—C9—H9A109.5
C3—C4—C8121.5 (5)C6—C9—H9B109.5
C5—C4—C8120.7 (5)C6—C9—H9C109.5
C4—C5—C6122.0 (4)H9A—C9—H9B109.5
C4—C5—H5A119.0H9A—C9—H9C109.5
C6—C5—H5A119.0H9B—C9—H9C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···Br1i0.84 (5)2.58 (5)3.376 (4)157 (4)
N1—H1B···Br10.94 (6)2.47 (6)3.391 (4)168 (4)
N1—H1C···Br1ii1.01 (5)2.32 (5)3.292 (4)162 (4)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2763).

References

  • Lemmerer, A. & Billing, D. G. (2007). Acta Cryst. E63, o929–o931.
  • Long, S., Siegler, M. & Li, T. (2007). Acta Cryst. E63, o3080.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography