PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o244.
Published online 2007 December 12. doi:  10.1107/S1600536807064896
PMCID: PMC2915302

4-Bromo-2,6-dimethyl­anilinium bromide monohydrate

Abstract

In the title compound, C8H11BrN+·Br·H2O, a network of N—H(...)O, N—H(...)Br and O—H(...)Br hydrogen bonds helps to consolidate the crystal packing.

Related literature

For related literature, see: Hirao & Fukuhara (1998 [triangle]); MacDiamid et al. (1998 [triangle]); Wakayama (1998 [triangle]); Wang et al. (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o244-scheme1.jpg

Experimental

Crystal data

  • C8H11BrN+·Br·H2O
  • M r = 298.99
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o244-efi1.jpg
  • a = 7.1630 (14) Å
  • b = 18.649 (4) Å
  • c = 8.4770 (17) Å
  • β = 109.98 (3)°
  • V = 1064.2 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 7.58 mm−1
  • T = 293 (2) K
  • 0.40 × 0.20 × 0.20 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.152, T max = 0.221
  • 2077 measured reflections
  • 2077 independent reflections
  • 1346 reflections with I > 2σ(I)
  • 3 standard reflections every 200 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.096
  • S = 0.97
  • 2077 reflections
  • 120 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.42 e Å−3
  • Δρmin = −0.52 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807064896/lw2046sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807064896/lw2046Isup2.hkl

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

supplementary crystallographic information

Comment

aniline is a novel,useful intermediate,which can be used in various areas. Some derivatives of aniline have improving anticorrosion ability for metals (Wang et al., 2002). Some show high efficacy as chemical sensors (MacDiamid et al.,1998) and catalitic oxidation (Hirao & Fukuhara, 1998). We report here the crystal structure of the title compound, (I). A network of intermolecular N—H···Br and O—H···Br hydrogen bonds helps to establish the crystal packing, Fig. 1 and Fig. 2.

Experimental

The title compound is synthesized according to the literature(Wakayama et al., 1998). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution.

Refinement

All H atoms bonded to the C atoms were placed geometrically at the distances of 0.93–0.96 Å and included in the refinement in riding motion approximation with Uiso(H) = 1.2 or 1.5Ueq of the carrier atom.

Figures

Fig. 1.
A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level The crystal structure of (I).
Fig. 2.
A packing diagram of the title molecular structure, with dash line indicates intermolecularintermolecular N—H···O, N—H···Br and O—H···Br hydrogen bonds

Crystal data

C8H11BrN+·Br·H2OF000 = 584
Mr = 298.99Dx = 1.866 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 7.1630 (14) Åθ = 9–13º
b = 18.649 (4) ŵ = 7.58 mm1
c = 8.4770 (17) ÅT = 293 (2) K
β = 109.98 (3)ºBlock, colorless
V = 1064.2 (4) Å30.40 × 0.20 × 0.20 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.0000
Radiation source: fine-focus sealed tubeθmax = 26.0º
Monochromator: graphiteθmin = 2.2º
T = 293(2) Kh = −8→8
ω/2θ scansk = 0→22
Absorption correction: ψ scan(North et al., 1968)l = 0→10
Tmin = 0.152, Tmax = 0.2213 standard reflections
2077 measured reflections every 200 reflections
2077 independent reflections intensity decay: none
1346 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096  w = 1/[σ2(Fo2) + (0.0437P)2] where P = (Fo2 + 2Fc2)/3
S = 0.97(Δ/σ)max < 0.001
2077 reflectionsΔρmax = 0.42 e Å3
120 parametersΔρmin = −0.52 e Å3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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
Br10.93285 (11)0.38204 (3)0.77315 (8)0.0490 (2)
Br20.47862 (10)0.69675 (3)0.95867 (8)0.0407 (2)
C10.7335 (8)0.5937 (3)0.4804 (7)0.0276 (13)
C20.6858 (8)0.5297 (3)0.3931 (7)0.0310 (13)
C30.7483 (8)0.4664 (3)0.4828 (7)0.0346 (14)
H30.71950.42240.42820.041*
C40.8528 (9)0.4691 (3)0.6521 (7)0.0368 (15)
C50.9007 (8)0.5334 (3)0.7373 (7)0.0330 (14)
H50.97280.53380.85170.040*
C60.8412 (8)0.5966 (3)0.6519 (6)0.0298 (13)
C70.5756 (9)0.5250 (3)0.2060 (6)0.0410 (16)
H7A0.44690.54660.17990.062*
H7B0.56050.47550.17230.062*
H7C0.64940.54970.14720.062*
C80.8945 (9)0.6665 (3)0.7470 (7)0.0420 (16)
H8A0.77520.69100.74360.063*
H8B0.96820.69600.69640.063*
H8C0.97390.65690.86160.063*
N10.6621 (7)0.6625 (2)0.3935 (5)0.0336 (12)
H1A0.60390.65450.28410.050*
H1B0.76450.69210.40990.050*
H1C0.57490.68220.43430.050*
O10.4192 (8)0.7175 (3)0.5552 (6)0.0494 (12)
H10.442 (3)0.710 (4)0.657 (3)0.05 (2)*
H20.306 (3)0.736 (4)0.518 (3)0.09 (3)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0650 (5)0.0365 (4)0.0427 (4)0.0084 (4)0.0147 (3)0.0129 (3)
Br20.0445 (4)0.0422 (4)0.0337 (3)0.0045 (3)0.0113 (3)0.0053 (3)
C10.030 (3)0.028 (3)0.027 (3)−0.001 (2)0.012 (3)0.000 (2)
C20.035 (3)0.033 (3)0.027 (3)−0.001 (3)0.014 (3)−0.006 (3)
C30.040 (4)0.027 (3)0.034 (3)−0.005 (3)0.011 (3)−0.005 (3)
C40.038 (4)0.039 (4)0.033 (3)−0.001 (3)0.011 (3)0.010 (3)
C50.037 (4)0.034 (3)0.024 (3)0.002 (3)0.006 (3)0.002 (3)
C60.031 (3)0.034 (3)0.023 (3)−0.001 (3)0.008 (3)−0.006 (2)
C70.054 (4)0.038 (4)0.025 (3)−0.006 (3)0.006 (3)−0.009 (3)
C80.045 (4)0.048 (4)0.027 (3)0.003 (3)0.003 (3)−0.004 (3)
N10.037 (3)0.032 (3)0.033 (3)0.002 (2)0.012 (2)0.000 (2)
O10.052 (3)0.069 (4)0.026 (3)0.019 (3)0.012 (2)0.005 (2)

Geometric parameters (Å, °)

Br1—C41.901 (6)C7—H7A0.9600
C1—C21.384 (7)C7—H7B0.9600
C1—C61.395 (7)C7—H7C0.9600
C1—N11.481 (6)C8—H8A0.9600
C2—C31.393 (7)C8—H8B0.9600
C2—C71.513 (7)C8—H8C0.9600
C3—C41.374 (7)N1—H1A0.8900
C3—H30.9300N1—H1B0.8900
C4—C51.381 (8)N1—H1C0.8900
C5—C61.373 (7)O1—H10.84 (2)
C5—H50.9300O1—H20.84 (2)
C6—C81.511 (7)
C2—C1—C6122.6 (5)C2—C7—H7B109.5
C2—C1—N1120.0 (5)H7A—C7—H7B109.5
C6—C1—N1117.3 (5)C2—C7—H7C109.5
C1—C2—C3117.6 (5)H7A—C7—H7C109.5
C1—C2—C7123.8 (5)H7B—C7—H7C109.5
C3—C2—C7118.5 (5)C6—C8—H8A109.5
C4—C3—C2119.9 (5)C6—C8—H8B109.5
C4—C3—H3120.1H8A—C8—H8B109.5
C2—C3—H3120.1C6—C8—H8C109.5
C3—C4—C5121.8 (5)H8A—C8—H8C109.5
C3—C4—Br1119.3 (5)H8B—C8—H8C109.5
C5—C4—Br1118.9 (4)C1—N1—H1A109.5
C6—C5—C4119.5 (5)C1—N1—H1B109.5
C6—C5—H5120.2H1A—N1—H1B109.5
C4—C5—H5120.2C1—N1—H1C109.5
C5—C6—C1118.5 (5)H1A—N1—H1C109.5
C5—C6—C8118.9 (5)H1B—N1—H1C109.5
C1—C6—C8122.6 (5)H1—O1—H2106 (3)
C2—C7—H7A109.5
C6—C1—C2—C30.4 (8)C3—C4—C5—C60.7 (9)
N1—C1—C2—C3−176.9 (5)Br1—C4—C5—C6−179.0 (4)
C6—C1—C2—C7−177.7 (5)C4—C5—C6—C10.0 (8)
N1—C1—C2—C75.0 (8)C4—C5—C6—C8179.9 (5)
C1—C2—C3—C40.2 (9)C2—C1—C6—C5−0.6 (8)
C7—C2—C3—C4178.5 (5)N1—C1—C6—C5176.8 (5)
C2—C3—C4—C5−0.8 (9)C2—C1—C6—C8179.5 (6)
C2—C3—C4—Br1178.9 (4)N1—C1—C6—C8−3.1 (8)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H2···Br2i0.84 (2)2.56 (3)3.380 (5)169 (3)
O1—H1···Br20.84 (2)2.50 (2)3.322 (5)174 (3)
N1—H1C···O10.891.872.754 (6)170
N1—H1B···Br2ii0.892.533.388 (5)163
N1—H1A···Br2iii0.892.713.523 (4)153

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x+1/2, −y+3/2, z−1/2; (iii) x, y, z−1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LW2046).

References

  • Enraf–Nonius (1989). CAD-4 Software Version 5.0. Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Hirao, T. & Fukuhara, S. (1998). J. Org. Chem.63, 7534–7535. [PubMed]
  • MacDiamid, A. G., Zhang, W. J., Feng, J., Huang, F. & Hsieh, B. (1998). Polym. Prepr. (Am. Chem. Soc. Div. Polym. Chem.),39, 80–81.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (1997). SHELXL97 and SHELXS97 University of Göttingen, Germany.
  • Wakayama, D. K. K. (1998). Shizen Kagaku, 48, 9–15.
  • Wang, C., Gao, J. B. & Chen, C. H. (2002). Polym. Prepr. (Am. Chem. Soc. Div. Polym. Chem.), 40, 1746–1747.

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