4-Bromo-3-methyl­anilinium perchlorate

Zhang, L.

doi:10.1107/S160053680903520X

organic compounds

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Volume 65| Part 10| October 2009| Page o2422

doi:10.1107/S160053680903520X

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4-Bromo-3-methylanilinium perchlorate

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 26 August 2009; accepted 1 September 2009; online 9 September 2009)

In the title compound, C₇H₉BrN⁺·ClO₄⁻, the cations and anions are linked by intermolecular N—H⋯O hydrogen bonds, forming a two-dimensional network parallel to the ab plane.

Related literature

For the use of amine derivatives in the construction of metal-organic frameworks, see: Fu et al. (2007 , 2008 ); Fu & Xiong (2008 ); Wang et al. (2002 ). For applications of metal-organic coordination compounds, see: Chen et al. (2001 ); Xiong et al. (1999 ); Xie et al. (2003 ); Zhao et al. (2004 ).

Experimental

Crystal data

C₇H₉BrN⁺·ClO₄⁻
M_r = 286.51
Triclinic, $[P \overline 1]$
a = 4.9455 (10) Å
b = 6.9647 (14) Å
c = 15.714 (3) Å
α = 95.78 (3)°
β = 94.40 (3)°
γ = 102.62 (3)°
V = 522.8 (2) Å³
Z = 2
Mo Kα radiation
μ = 4.18 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
5411 measured reflections
2382 independent reflections
1584 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.127
S = 1.03
2382 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.89	2.04	2.909 (4)	166
N1—H1B⋯O1ⁱⁱ	0.89	2.03	2.875 (4)	159
N1—H1C⋯O3	0.89	2.02	2.857 (4)	156
Symmetry codes: (i) -x+2, -y, -z+1; (ii) -x+2, -y+1, -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/S160053680903520X/ci2895sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680903520X/ci2895Isup2.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 (Chen et al., 2001; Xie et al., 2003; Zhao et al., 2004; Xiong et al., 1999). Amine derivatives are a class of excellent ligands for the construction of novel metal-organic frameworks (Fu et al., 2007, 2008; Wang et al. 2002; Fu & Xiong 2008). We report here the crystal structure of the title compound, 4-bromo-3-methylanilinium perchlorate.

In the title compound (Fig.1), the amino N atom is protonated. In the crystal structure, all the amine group H atoms are involved in N—H···O hydrogen bonding (Table 1) with O atoms of ClO₄^- anion. These hydrogen bonds link the ionic units into a two-dimensional network parallel to the ab plane (Fig. 2).

Related literature top

For applications of metal-organic coordination compounds, see: Chen et al. (2001); Xiong et al. (1999); Xie et al. (2003); Zhao et al. (2004). For amine derivatives, see: Fu et al. (2007, 2008); Fu & Xiong (2008); Wang et al. (2002).

Experimental top

The commercial 4-bromo-3-methylbenzenamine (3 mmol, 0.75 g) and HClO₄ (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. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound, viewed along the c axis, showing the N—H···O hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.

4-Bromo-3-methylanilinium perchlorate top

Crystal data top

C₇H₉BrN⁺·ClO₄⁻	Z = 2
M_r = 286.51	F(000) = 284
Triclinic, P1	D_x = 1.820 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.9455 (10) Å	Cell parameters from 1584 reflections
b = 6.9647 (14) Å	θ = 3.0–27.5°
c = 15.714 (3) Å	µ = 4.18 mm⁻¹
α = 95.78 (3)°	T = 298 K
β = 94.40 (3)°	Needle, colourless
γ = 102.62 (3)°	0.40 × 0.05 × 0.05 mm
V = 522.8 (2) Å³

Data collection top

Rigaku Mercury2 diffractometer	2382 independent reflections
Radiation source: fine-focus sealed tube	1584 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD profile fitting scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
T_min = 0.910, T_max = 1.000	l = −20→20
5411 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0535P)² + 0.0338P] where P = (F_o² + 2F_c²)/3
2382 reflections	(Δ/σ)_max = 0.001
129 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

C₇H₉BrN⁺·ClO₄⁻	γ = 102.62 (3)°
M_r = 286.51	V = 522.8 (2) Å³
Triclinic, P1	Z = 2
a = 4.9455 (10) Å	Mo Kα radiation
b = 6.9647 (14) Å	µ = 4.18 mm⁻¹
c = 15.714 (3) Å	T = 298 K
α = 95.78 (3)°	0.40 × 0.05 × 0.05 mm
β = 94.40 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2382 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1584 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.053
5411 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.03	Δρ_max = 0.44 e Å⁻³
2382 reflections	Δρ_min = −0.57 e Å⁻³
129 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.71423 (12)	0.24442 (9)	0.97211 (3)	0.0819 (3)
N1	1.0957 (6)	0.2471 (5)	0.6136 (2)	0.0392 (7)
H1A	1.1784	0.1471	0.6028	0.059*
H1B	1.2142	0.3609	0.6090	0.059*
H1C	0.9465	0.2317	0.5759	0.059*
C1	0.8397 (8)	0.2542 (6)	0.8609 (3)	0.0470 (10)
C2	0.9780 (10)	0.1151 (6)	0.8326 (3)	0.0548 (12)
H2	1.0127	0.0226	0.8682	0.066*
C3	1.0671 (9)	0.1102 (6)	0.7516 (3)	0.0461 (10)
H3	1.1623	0.0160	0.7319	0.055*
C4	1.0104 (8)	0.2496 (5)	0.7008 (2)	0.0351 (8)
C5	0.8762 (7)	0.3934 (5)	0.7301 (2)	0.0357 (8)
H5	0.8456	0.4876	0.6948	0.043*
C6	0.7862 (8)	0.3996 (6)	0.8114 (3)	0.0412 (9)
C7	0.6377 (9)	0.5534 (7)	0.8433 (3)	0.0582 (12)
H7A	0.6417	0.6485	0.8029	0.087*
H7B	0.7280	0.6191	0.8980	0.087*
H7C	0.4479	0.4913	0.8493	0.087*
Cl1	0.49638 (17)	0.22738 (12)	0.42344 (6)	0.0330 (2)
O1	0.5691 (7)	0.3547 (4)	0.3590 (2)	0.0653 (9)
O2	0.5586 (6)	0.0410 (4)	0.3998 (2)	0.0556 (8)
O3	0.6498 (6)	0.3195 (4)	0.50396 (19)	0.0547 (8)
O4	0.2066 (5)	0.1974 (4)	0.4320 (2)	0.0575 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0920 (5)	0.1064 (5)	0.0435 (4)	0.0025 (4)	0.0248 (3)	0.0218 (3)
N1	0.0411 (17)	0.0467 (18)	0.0321 (18)	0.0158 (15)	0.0029 (14)	0.0044 (15)
C1	0.046 (2)	0.055 (2)	0.034 (2)	−0.002 (2)	0.0072 (18)	0.006 (2)
C2	0.068 (3)	0.051 (2)	0.044 (3)	0.006 (2)	0.003 (2)	0.023 (2)
C3	0.056 (3)	0.044 (2)	0.041 (3)	0.018 (2)	0.004 (2)	0.0060 (19)
C4	0.0342 (18)	0.0356 (19)	0.032 (2)	0.0021 (16)	−0.0007 (16)	0.0044 (16)
C5	0.0339 (19)	0.039 (2)	0.036 (2)	0.0094 (16)	0.0042 (16)	0.0087 (17)
C6	0.038 (2)	0.045 (2)	0.036 (2)	0.0029 (18)	0.0026 (18)	0.0000 (18)
C7	0.059 (3)	0.071 (3)	0.048 (3)	0.022 (2)	0.011 (2)	−0.002 (2)
Cl1	0.0322 (4)	0.0332 (4)	0.0357 (5)	0.0104 (4)	0.0041 (4)	0.0074 (4)
O1	0.087 (2)	0.0574 (18)	0.055 (2)	0.0112 (18)	0.0140 (18)	0.0289 (16)
O2	0.0624 (19)	0.0415 (15)	0.068 (2)	0.0236 (15)	0.0084 (16)	0.0015 (14)
O3	0.0547 (18)	0.0522 (17)	0.0515 (19)	0.0132 (14)	−0.0179 (14)	−0.0049 (14)
O4	0.0305 (14)	0.072 (2)	0.068 (2)	0.0109 (14)	0.0101 (14)	−0.0056 (17)

Geometric parameters (Å, º) top

Br1—C1	1.902 (4)	C4—C5	1.379 (5)
N1—C4	1.464 (5)	C5—C6	1.384 (5)
N1—H1A	0.89	C5—H5	0.93
N1—H1B	0.89	C6—C7	1.493 (6)
N1—H1C	0.89	C7—H7A	0.96
C1—C2	1.362 (6)	C7—H7B	0.96
C1—C6	1.394 (6)	C7—H7C	0.96
C2—C3	1.377 (6)	Cl1—O2	1.419 (3)
C2—H2	0.93	Cl1—O4	1.421 (3)
C3—C4	1.378 (5)	Cl1—O1	1.428 (3)
C3—H3	0.93	Cl1—O3	1.437 (3)

C4—N1—H1A	109.5	C4—C5—C6	120.9 (4)
C4—N1—H1B	109.5	C4—C5—H5	119.5
H1A—N1—H1B	109.5	C6—C5—H5	119.5
C4—N1—H1C	109.5	C5—C6—C1	116.4 (4)
H1A—N1—H1C	109.5	C5—C6—C7	121.3 (4)
H1B—N1—H1C	109.5	C1—C6—C7	122.3 (4)
C2—C1—C6	122.6 (4)	C6—C7—H7A	109.5
C2—C1—Br1	117.7 (3)	C6—C7—H7B	109.5
C6—C1—Br1	119.7 (3)	H7A—C7—H7B	109.5
C1—C2—C3	120.6 (4)	C6—C7—H7C	109.5
C1—C2—H2	119.7	H7A—C7—H7C	109.5
C3—C2—H2	119.7	H7B—C7—H7C	109.5
C2—C3—C4	117.8 (4)	O2—Cl1—O4	108.72 (18)
C2—C3—H3	121.1	O2—Cl1—O1	109.8 (2)
C4—C3—H3	121.1	O4—Cl1—O1	109.9 (2)
C3—C4—C5	121.6 (4)	O2—Cl1—O3	110.55 (17)
C3—C4—N1	119.6 (3)	O4—Cl1—O3	109.01 (19)
C5—C4—N1	118.7 (3)	O1—Cl1—O3	108.79 (18)

C6—C1—C2—C3	−1.4 (7)	C4—C5—C6—C1	0.2 (5)
Br1—C1—C2—C3	178.0 (3)	C4—C5—C6—C7	−179.3 (4)
C1—C2—C3—C4	−0.2 (6)	C2—C1—C6—C5	1.4 (6)
C2—C3—C4—C5	1.8 (6)	Br1—C1—C6—C5	−178.0 (3)
C2—C3—C4—N1	−178.6 (3)	C2—C1—C6—C7	−179.2 (4)
C3—C4—C5—C6	−1.8 (6)	Br1—C1—C6—C7	1.4 (5)
N1—C4—C5—C6	178.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.89	2.04	2.909 (4)	166
N1—H1B···O1ⁱⁱ	0.89	2.03	2.875 (4)	159
N1—H1C···O3	0.89	2.02	2.857 (4)	156

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

Experimental details

Crystal data
Chemical formula	C₇H₉BrN⁺·ClO₄⁻
M_r	286.51
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	4.9455 (10), 6.9647 (14), 15.714 (3)
α, β, γ (°)	95.78 (3), 94.40 (3), 102.62 (3)
V (Å³)	522.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.18
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	5411, 2382, 1584
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.127, 1.03
No. of reflections	2382
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.57

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···O2ⁱ	0.89	2.04	2.909 (4)	166
N1—H1B···O1ⁱⁱ	0.89	2.03	2.875 (4)	159
N1—H1C···O3	0.89	2.02	2.857 (4)	156

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

Acknowledgements

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

References

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