4-Bromo-2,6-dimethyl­anilinium bromide monohydrate

Tang, J.; Chen, J.; Wang, J.; Lu, A.; Chen, Y.

doi:10.1107/S1600536807064896

organic compounds

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Volume 64| Part 1| January 2008| Page o244

https://doi.org/10.1107/S1600536807064896

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4-Bromo-2,6-dimethylanilinium bromide monohydrate

Jun-jie Tang,^a Jing Chen,^a ^* Jin-tang Wang,^a Ai-hua Lu ^b and You-sheng Chen ^c

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technolgy, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, ^bNanjing Chemzam Pharmaceutical Technology Co. Ltd, Nanjing 210017, People's Republic of China, and ^cDepartment of Pharmacy, Guangdong Vocational and Technical College of Chemical Engineering Pharmaceutics, Guangzhou 510520, People's Republic of China
^*Correspondence e-mail: wjt@njut.edu.cn

(Received 15 November 2007; accepted 1 December 2007; online 12 December 2007)

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 ); MacDiamid et al. (1998 ); Wakayama (1998 ); Wang et al. (2002 ).

Experimental

Crystal data

C₈H₁₁BrN⁺·Br⁻·H₂O
M_r = 298.99
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.045
wR(F²) = 0.096
S = 0.97
2077 reflections
120 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H2⋯Br2ⁱ	0.84 (2)	2.56 (3)	3.380 (5)	169 (3)
O1—H1⋯Br2	0.84 (2)	2.50 (2)	3.322 (5)	174 (3)
N1—H1C⋯O1	0.89	1.87	2.754 (6)	170
N1—H1B⋯Br2ⁱⁱ	0.89	2.53	3.388 (5)	163
N1—H1A⋯Br2ⁱⁱⁱ	0.89	2.71	3.523 (4)	153
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x, y, z-1.

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807064896/lw2046Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

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

Figures top

	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

4-Bromo-2,6-dimethylanilinium bromide monohydrate top

Crystal data top

C₈H₁₁BrN⁺·Br⁻·H₂O	F(000) = 584
M_r = 298.99	D_x = 1.866 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 7.1630 (14) Å	θ = 9–13°
b = 18.649 (4) Å	µ = 7.58 mm⁻¹
c = 8.4770 (17) Å	T = 293 K
β = 109.98 (3)°	Block, colorless
V = 1064.2 (4) Å³	0.40 × 0.20 × 0.20 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1346 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 26.0°, θ_min = 2.2°
ω/2θ scans	h = −8→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→22
T_min = 0.152, T_max = 0.221	l = 0→10
2077 measured reflections	3 standard reflections every 200 reflections
2077 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: difference Fourier map
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ²(F_o²) + (0.0437P)²] where P = (F_o² + 2F_c²)/3
2077 reflections	(Δ/σ)_max < 0.001
120 parameters	Δρ_max = 0.42 e Å⁻³
2 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

C₈H₁₁BrN⁺·Br⁻·H₂O	V = 1064.2 (4) Å³
M_r = 298.99	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.1630 (14) Å	µ = 7.58 mm⁻¹
b = 18.649 (4) Å	T = 293 K
c = 8.4770 (17) Å	0.40 × 0.20 × 0.20 mm
β = 109.98 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1346 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.152, T_max = 0.221	3 standard reflections every 200 reflections
2077 measured reflections	intensity decay: none
2077 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	2 restraints
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	Δρ_max = 0.42 e Å⁻³
2077 reflections	Δρ_min = −0.52 e Å⁻³
120 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.93285 (11)	0.38204 (3)	0.77315 (8)	0.0490 (2)
Br2	0.47862 (10)	0.69675 (3)	0.95867 (8)	0.0407 (2)
C1	0.7335 (8)	0.5937 (3)	0.4804 (7)	0.0276 (13)
C2	0.6858 (8)	0.5297 (3)	0.3931 (7)	0.0310 (13)
C3	0.7483 (8)	0.4664 (3)	0.4828 (7)	0.0346 (14)
H3	0.7195	0.4224	0.4282	0.041*
C4	0.8528 (9)	0.4691 (3)	0.6521 (7)	0.0368 (15)
C5	0.9007 (8)	0.5334 (3)	0.7373 (7)	0.0330 (14)
H5	0.9728	0.5338	0.8517	0.040*
C6	0.8412 (8)	0.5966 (3)	0.6519 (6)	0.0298 (13)
C7	0.5756 (9)	0.5250 (3)	0.2060 (6)	0.0410 (16)
H7A	0.4469	0.5466	0.1799	0.062*
H7B	0.5605	0.4755	0.1723	0.062*
H7C	0.6494	0.5497	0.1472	0.062*
C8	0.8945 (9)	0.6665 (3)	0.7470 (7)	0.0420 (16)
H8A	0.7752	0.6910	0.7436	0.063*
H8B	0.9682	0.6960	0.6964	0.063*
H8C	0.9739	0.6569	0.8616	0.063*
N1	0.6621 (7)	0.6625 (2)	0.3935 (5)	0.0336 (12)
H1A	0.6039	0.6545	0.2841	0.050*
H1B	0.7645	0.6921	0.4099	0.050*
H1C	0.5749	0.6822	0.4343	0.050*
O1	0.4192 (8)	0.7175 (3)	0.5552 (6)	0.0494 (12)
H1	0.442 (3)	0.710 (4)	0.657 (3)	0.05 (2)*
H2	0.306 (3)	0.736 (4)	0.518 (3)	0.09 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0650 (5)	0.0365 (4)	0.0427 (4)	0.0084 (4)	0.0147 (3)	0.0129 (3)
Br2	0.0445 (4)	0.0422 (4)	0.0337 (3)	0.0045 (3)	0.0113 (3)	0.0053 (3)
C1	0.030 (3)	0.028 (3)	0.027 (3)	−0.001 (2)	0.012 (3)	0.000 (2)
C2	0.035 (3)	0.033 (3)	0.027 (3)	−0.001 (3)	0.014 (3)	−0.006 (3)
C3	0.040 (4)	0.027 (3)	0.034 (3)	−0.005 (3)	0.011 (3)	−0.005 (3)
C4	0.038 (4)	0.039 (4)	0.033 (3)	−0.001 (3)	0.011 (3)	0.010 (3)
C5	0.037 (4)	0.034 (3)	0.024 (3)	0.002 (3)	0.006 (3)	0.002 (3)
C6	0.031 (3)	0.034 (3)	0.023 (3)	−0.001 (3)	0.008 (3)	−0.006 (2)
C7	0.054 (4)	0.038 (4)	0.025 (3)	−0.006 (3)	0.006 (3)	−0.009 (3)
C8	0.045 (4)	0.048 (4)	0.027 (3)	0.003 (3)	0.003 (3)	−0.004 (3)
N1	0.037 (3)	0.032 (3)	0.033 (3)	0.002 (2)	0.012 (2)	0.000 (2)
O1	0.052 (3)	0.069 (4)	0.026 (3)	0.019 (3)	0.012 (2)	0.005 (2)

Geometric parameters (Å, º) top

Br1—C4	1.901 (6)	C7—H7A	0.9600
C1—C2	1.384 (7)	C7—H7B	0.9600
C1—C6	1.395 (7)	C7—H7C	0.9600
C1—N1	1.481 (6)	C8—H8A	0.9600
C2—C3	1.393 (7)	C8—H8B	0.9600
C2—C7	1.513 (7)	C8—H8C	0.9600
C3—C4	1.374 (7)	N1—H1A	0.8900
C3—H3	0.9300	N1—H1B	0.8900
C4—C5	1.381 (8)	N1—H1C	0.8900
C5—C6	1.373 (7)	O1—H1	0.84 (2)
C5—H5	0.9300	O1—H2	0.84 (2)
C6—C8	1.511 (7)

C2—C1—C6	122.6 (5)	C2—C7—H7B	109.5
C2—C1—N1	120.0 (5)	H7A—C7—H7B	109.5
C6—C1—N1	117.3 (5)	C2—C7—H7C	109.5
C1—C2—C3	117.6 (5)	H7A—C7—H7C	109.5
C1—C2—C7	123.8 (5)	H7B—C7—H7C	109.5
C3—C2—C7	118.5 (5)	C6—C8—H8A	109.5
C4—C3—C2	119.9 (5)	C6—C8—H8B	109.5
C4—C3—H3	120.1	H8A—C8—H8B	109.5
C2—C3—H3	120.1	C6—C8—H8C	109.5
C3—C4—C5	121.8 (5)	H8A—C8—H8C	109.5
C3—C4—Br1	119.3 (5)	H8B—C8—H8C	109.5
C5—C4—Br1	118.9 (4)	C1—N1—H1A	109.5
C6—C5—C4	119.5 (5)	C1—N1—H1B	109.5
C6—C5—H5	120.2	H1A—N1—H1B	109.5
C4—C5—H5	120.2	C1—N1—H1C	109.5
C5—C6—C1	118.5 (5)	H1A—N1—H1C	109.5
C5—C6—C8	118.9 (5)	H1B—N1—H1C	109.5
C1—C6—C8	122.6 (5)	H1—O1—H2	106 (3)
C2—C7—H7A	109.5

C6—C1—C2—C3	0.4 (8)	C3—C4—C5—C6	0.7 (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—C1	0.0 (8)
N1—C1—C2—C7	5.0 (8)	C4—C5—C6—C8	179.9 (5)
C1—C2—C3—C4	0.2 (9)	C2—C1—C6—C5	−0.6 (8)
C7—C2—C3—C4	178.5 (5)	N1—C1—C6—C5	176.8 (5)
C2—C3—C4—C5	−0.8 (9)	C2—C1—C6—C8	179.5 (6)
C2—C3—C4—Br1	178.9 (4)	N1—C1—C6—C8	−3.1 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2···Br2ⁱ	0.84 (2)	2.56 (3)	3.380 (5)	169 (3)
O1—H1···Br2	0.84 (2)	2.50 (2)	3.322 (5)	174 (3)
N1—H1C···O1	0.89	1.87	2.754 (6)	170
N1—H1B···Br2ⁱⁱ	0.89	2.53	3.388 (5)	163
N1—H1A···Br2ⁱⁱⁱ	0.89	2.71	3.523 (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.

Experimental details

Crystal data
Chemical formula	C₈H₁₁BrN⁺·Br⁻·H₂O
M_r	298.99
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.1630 (14), 18.649 (4), 8.4770 (17)
β (°)	109.98 (3)
V (Å³)	1064.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.58
Crystal size (mm)	0.40 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.152, 0.221
No. of measured, independent and observed [I > 2σ(I)] reflections	2077, 2077, 1346
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.096, 0.97
No. of reflections	2077
No. of parameters	120
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.52

Computer programs: CAD-4 Software (Enraf–Nonius,1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2···Br2ⁱ	0.84 (2)	2.56 (3)	3.380 (5)	169 (3)
O1—H1···Br2	0.84 (2)	2.50 (2)	3.322 (5)	174 (3)
N1—H1C···O1	0.89	1.87	2.754 (6)	170
N1—H1B···Br2ⁱⁱ	0.89	2.53	3.388 (5)	163
N1—H1A···Br2ⁱⁱⁱ	0.89	2.71	3.523 (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.

References

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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o244

https://doi.org/10.1107/S1600536807064896

Open

access