4-Bromo-3-methyl-anilinium hydrogen sulfate.

In the cation of the title compound, C(7)H(9)BrN(+)·HSO(4) (-), the amino N atom is protonated. In the crystal, inter-molecular 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 = 284.13

Triclinic,

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[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.115

S = 1.07

2323 reflections

129 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.67 e Å−3

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.

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

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

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

C7H9BrN+·HSO4−	Z = 2
Mr = 284.13	F(000) = 284
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0426P)2 + 0.1536P] where P = (Fo2 + 2Fc2)/3
2323 reflections	(Δ/σ)max < 0.001
129 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.67 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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

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) ; (ii) ; (iii) .