4-Bromo-3-methyl­anilinium hydrogen sulfate

Zhang, L.

doi:10.1107/S160053680903493X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2421

doi:10.1107/S160053680903493X

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4-Bromo-3-methylanilinium hydrogen sulfate

Li Zhang ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical, Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 21 August 2009; accepted 31 August 2009; online 9 September 2009)

In the cation of the title compound, C₇H₉BrN⁺·HSO₄⁻, the amino N atom is protonated. In the crystal, intermolecular O—H⋯O and N—H⋯O hydrogen bonds generate an infinite two-dimensional network parallel to (001).

Related literature

For the structures of amino derivatives, see: Fu et al. (2007 , 2008 ); Fu & Xiong (2008 ). Amino derivatives are used in the construction of metal-organic frameworks. For applications of metal-organic coordination compounds, see: Chen et al. (2001 ); Xiong et al. (1999 ); Xie et al. (2002 ); Zhao et al. (2004 ); Wang et al. (2002 ).

Experimental

Crystal data

C₇H₉BrN⁺·HSO₄⁻
M_r = 284.13
Triclinic, $[P \overline 1]$
a = 4.9448 (10) Å
b = 6.4084 (13) Å
c = 16.674 (3) Å
α = 98.92 (3)°
β = 96.22 (3)°
γ = 100.01 (3)°
V = 509.04 (17) Å³
Z = 2
Mo Kα radiation
μ = 4.23 mm⁻¹
T = 298 K
0.40 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
5279 measured reflections
2323 independent reflections
1804 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.115
S = 1.07
2323 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.89	1.90	2.767 (3)	166
N1—H1B⋯O2ⁱⁱ	0.89	1.91	2.797 (4)	173
O1—H1⋯O4ⁱⁱⁱ	0.82	1.84	2.650 (3)	168
N1—H1C⋯O4	0.89	2.09	2.829 (4)	140
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x, -y, -z+1; (iii) -x+1, -y, -z+1.

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680903493X/pv2203sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680903493X/pv2203Isup2.hkl

checkCIF report

Comment top

The construction of metal-organic coordination compounds has attracted much attention owing to potential functions, such as permittivity, fluorescence, magnetism and optical properties (Wang et al. 2002; Fu et al., 2008; Chen et al., 2001; Xie et al., 2002; Zhao et al.,2004; Xiong et al., 1999). Amino derivatives are a class of excellent ligands for the construction of novel metal-organic frameworks. (Fu et al., 2007; Fu & Xiong 2008). We report here the crystal structure of the title compound, 4-bromo-3-methylanilinium bisulfate.

In the title compound (Fig.1), The amino N atoms are protonated. In the crystal structure, all the amine group H atoms and HSO₄^- H atoms are involved in N—H···O and O—H···O hydrogen bonds (Table 1) with O atoms of HSO₄^- anion. These hydrogen bonds link the ionic units into a two-dimensional network (Fig. 2).

Related literature top

For applications of metal-organic coordination compounds, see: Chen et al. (2001); Xiong et al. (1999); Xie et al. (2002); Zhao et al. (2004); Wang et al. (2002). For the structures of amino derivatives, see: Fu et al. (2007, 2008); Fu & Xiong (2008).

Experimental top

The commercial 4-bromo-3-methylaniline (3 mmol) and H₂SO₄ (0.5 ml) were dissolved in ethanol (20 ml). Colourless block-shaped crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation at room temperature.

Computing details top

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

Figures top

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids have been drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound, viewed along the a axis showing hydrogen bonding (dotted line); H atoms not involved in hydrogen bonding have been omitted for clarity.

4-Bromo-3-methylanilinium hydrogen sulfate top

Crystal data top

C₇H₉BrN⁺·HSO₄⁻	Z = 2
M_r = 284.13	F(000) = 284
Triclinic, P1	D_x = 1.854 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.9448 (10) Å	Cell parameters from 1804 reflections
b = 6.4084 (13) Å	θ = 3.3–27.5°
c = 16.674 (3) Å	µ = 4.23 mm⁻¹
α = 98.92 (3)°	T = 298 K
β = 96.22 (3)°	Block, colorless
γ = 100.01 (3)°	0.40 × 0.05 × 0.05 mm
V = 509.04 (17) Å³

Data collection top

Rigaku Mercury2 diffractometer	2323 independent reflections
Radiation source: fine-focus sealed tube	1804 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
CCD profile fitting scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→8
T_min = 0.910, T_max = 1.000	l = −21→21
5279 measured reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0426P)² + 0.1536P] where P = (F_o² + 2F_c²)/3
2323 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.67 e Å⁻³

Crystal data top

C₇H₉BrN⁺·HSO₄⁻	γ = 100.01 (3)°
M_r = 284.13	V = 509.04 (17) Å³
Triclinic, P1	Z = 2
a = 4.9448 (10) Å	Mo Kα radiation
b = 6.4084 (13) Å	µ = 4.23 mm⁻¹
c = 16.674 (3) Å	T = 298 K
α = 98.92 (3)°	0.40 × 0.05 × 0.05 mm
β = 96.22 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2323 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1804 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.053
5279 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.07	Δρ_max = 0.40 e Å⁻³
2323 reflections	Δρ_min = −0.67 e Å⁻³
129 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	0.74330 (10)	0.74731 (8)	0.96412 (3)	0.0635 (2)
N1	0.0682 (6)	0.3866 (4)	0.63055 (17)	0.0278 (6)
H1A	−0.0452	0.4741	0.6182	0.042*
H1B	−0.0308	0.2561	0.6299	0.042*
H1C	0.1857	0.3782	0.5939	0.042*
C1	0.5271 (7)	0.6260 (6)	0.8613 (2)	0.0355 (8)
C4	0.2233 (7)	0.4704 (5)	0.7120 (2)	0.0273 (7)
C5	0.4016 (7)	0.3520 (5)	0.7448 (2)	0.0290 (7)
H5	0.4154	0.2193	0.7156	0.035*
C3	0.1915 (7)	0.6643 (5)	0.7535 (2)	0.0329 (8)
H3	0.0696	0.7418	0.7309	0.039*
C6	0.5593 (7)	0.4282 (6)	0.8206 (2)	0.0309 (8)
C2	0.3444 (8)	0.7420 (6)	0.8295 (2)	0.0404 (9)
H2	0.3247	0.8723	0.8594	0.049*
C7	0.7547 (8)	0.2971 (7)	0.8549 (3)	0.0458 (10)
H7A	0.9411	0.3782	0.8635	0.069*
H7B	0.7431	0.1659	0.8169	0.069*
H7C	0.7043	0.2638	0.9061	0.069*
S1	0.37322 (15)	0.18764 (12)	0.42345 (5)	0.0231 (2)
O1	0.6927 (5)	0.1969 (4)	0.43590 (16)	0.0379 (6)
H1	0.7257	0.0932	0.4558	0.057*
O2	0.2512 (6)	0.0108 (4)	0.35840 (16)	0.0433 (7)
O3	0.3537 (5)	0.3945 (3)	0.40391 (16)	0.0328 (6)
O4	0.2770 (5)	0.1540 (4)	0.50052 (14)	0.0305 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0640 (3)	0.0704 (4)	0.0396 (3)	−0.0081 (2)	−0.0124 (2)	−0.0034 (2)
N1	0.0312 (15)	0.0272 (15)	0.0268 (14)	0.0091 (11)	0.0038 (11)	0.0062 (12)
C1	0.0342 (19)	0.038 (2)	0.0290 (18)	−0.0039 (15)	0.0024 (15)	0.0041 (16)
C4	0.0278 (17)	0.0235 (17)	0.0296 (18)	0.0015 (13)	0.0040 (13)	0.0058 (14)
C5	0.0307 (17)	0.0267 (17)	0.0319 (18)	0.0076 (14)	0.0071 (14)	0.0080 (15)
C3	0.0350 (19)	0.0261 (18)	0.038 (2)	0.0064 (14)	0.0067 (15)	0.0066 (16)
C6	0.0254 (17)	0.0352 (19)	0.0342 (19)	0.0017 (14)	0.0067 (14)	0.0156 (16)
C2	0.050 (2)	0.0265 (19)	0.041 (2)	0.0040 (16)	0.0063 (18)	−0.0014 (17)
C7	0.044 (2)	0.055 (3)	0.043 (2)	0.0132 (18)	−0.0031 (18)	0.023 (2)
S1	0.0207 (4)	0.0192 (4)	0.0313 (4)	0.0042 (3)	0.0043 (3)	0.0091 (3)
O1	0.0225 (12)	0.0427 (15)	0.0590 (17)	0.0108 (10)	0.0136 (11)	0.0304 (13)
O2	0.0570 (17)	0.0272 (13)	0.0392 (15)	−0.0020 (11)	0.0044 (13)	−0.0009 (12)
O3	0.0303 (13)	0.0235 (12)	0.0486 (15)	0.0056 (10)	0.0055 (11)	0.0181 (11)
O4	0.0318 (13)	0.0285 (13)	0.0369 (14)	0.0092 (10)	0.0122 (10)	0.0145 (11)

Geometric parameters (Å, º) top

Br1—C1	1.894 (4)	C3—H3	0.9300
N1—C4	1.458 (4)	C6—C7	1.509 (5)
N1—H1A	0.8900	C2—H2	0.9300
N1—H1B	0.8900	C7—H7A	0.9600
N1—H1C	0.8900	C7—H7B	0.9600
C1—C2	1.379 (6)	C7—H7C	0.9600
C1—C6	1.386 (5)	S1—O3	1.430 (2)
C4—C3	1.369 (5)	S1—O2	1.437 (3)
C4—C5	1.382 (5)	S1—O4	1.452 (2)
C5—C6	1.380 (5)	S1—O1	1.560 (2)
C5—H5	0.9300	O1—H1	0.8200
C3—C2	1.376 (5)

C4—N1—H1A	109.5	C5—C6—C7	119.9 (3)
C4—N1—H1B	109.5	C1—C6—C7	123.4 (3)
H1A—N1—H1B	109.5	C3—C2—C1	119.8 (3)
C4—N1—H1C	109.5	C3—C2—H2	120.1
H1A—N1—H1C	109.5	C1—C2—H2	120.1
H1B—N1—H1C	109.5	C6—C7—H7A	109.5
C2—C1—C6	122.6 (3)	C6—C7—H7B	109.5
C2—C1—Br1	117.8 (3)	H7A—C7—H7B	109.5
C6—C1—Br1	119.6 (3)	C6—C7—H7C	109.5
C3—C4—C5	121.7 (3)	H7A—C7—H7C	109.5
C3—C4—N1	119.5 (3)	H7B—C7—H7C	109.5
C5—C4—N1	118.8 (3)	O3—S1—O2	114.06 (16)
C6—C5—C4	120.8 (3)	O3—S1—O4	113.59 (14)
C6—C5—H5	119.6	O2—S1—O4	111.41 (15)
C4—C5—H5	119.6	O3—S1—O1	102.60 (13)
C4—C3—C2	118.4 (3)	O2—S1—O1	107.73 (16)
C4—C3—H3	120.8	O4—S1—O1	106.61 (14)
C2—C3—H3	120.8	S1—O1—H1	109.5
C5—C6—C1	116.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.89	1.90	2.767 (3)	166
N1—H1B···O2ⁱⁱ	0.89	1.91	2.797 (4)	173
O1—H1···O4ⁱⁱⁱ	0.82	1.84	2.650 (3)	168
N1—H1C···O4	0.89	2.09	2.829 (4)	140

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

Experimental details

Crystal data
Chemical formula	C₇H₉BrN⁺·HSO₄⁻
M_r	284.13
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	4.9448 (10), 6.4084 (13), 16.674 (3)
α, β, γ (°)	98.92 (3), 96.22 (3), 100.01 (3)
V (Å³)	509.04 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.23
Crystal size (mm)	0.40 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5279, 2323, 1804
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.115, 1.07
No. of reflections	2323
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.67

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.89	1.90	2.767 (3)	166.0
N1—H1B···O2ⁱⁱ	0.89	1.91	2.797 (4)	173.0
O1—H1···O4ⁱⁱⁱ	0.82	1.84	2.650 (3)	168.3
N1—H1C···O4	0.89	2.09	2.829 (4)	139.7

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

Acknowledgements

This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.

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