4-Methoxy­anilinium bromide

Fu, X.

doi:10.1107/S160053680903503X

organic compounds

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Volume 65| Part 10| October 2009| Page o2344

doi:10.1107/S160053680903503X

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4-Methoxyanilinium bromide

Xue-qun Fu ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fuxuequn222@163.com

(Received 5 August 2009; accepted 31 August 2009; online 5 September 2009)

The title compound, C₇H₁₀NO⁺·Br⁻, consists of almost planar 4-methoxyanilinium cations, wherein the O atom lies 0.049 (3) Å out of the plane formed by the non-H atoms, and a Br⁻ anion. Strong N—H⋯Br and N—H⋯(Br,Br) hydrogen bonding contributes to the stability of the crystal structure and links the cations and anions into a three-dimensional network.

Related literature

For background to dielectric–ferroelectric materials, see: Hang et al. (2009 ); Li et al. (2008 ). For related structures, see: Tan et al. (2006 ); Soumhi et al. (2006 ); Ben Amor et al. (1995 ).

Experimental

Crystal data

C₇H₁₀NO⁺·Br⁻
M_r = 204.07
Orthorhombic, P b c a
a = 8.9779 (18) Å
b = 8.6978 (17) Å
c = 22.132 (4) Å
V = 1728.2 (6) Å³
Z = 8
Mo Kα radiation
μ = 4.69 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.391, T_max = 0.391
16334 measured reflections
1985 independent reflections
1276 reflections with I > 2σ(I)
R_int = 0.075

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.100
S = 1.12
1985 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1	0.89	2.52	3.409 (3)	177
N1—H1B⋯Br1ⁱ	0.89	2.55	3.314 (3)	145
N1—H1B⋯Br1ⁱⁱ	0.89	3.00	3.430 (3)	112
N1—H1C⋯Br1ⁱⁱⁱ	0.89	2.57	3.300 (3)	140
Symmetry codes: (i) -x, -y+1, -z; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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: PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680903503X/pv2194sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680903503X/pv2194Isup2.hkl

checkCIF report

Comment top

This study is a part of systematic investigation of dielectric-ferroelectric materials, including organic ligands (Li et al., 2008), metal-organic coordination compounds (Hang et al., 2009) and organic-inorganic hybrids. The title compound, 4-methoxyanilinium bromide, (I), has no dielectric disuniform from 80 K to 450 K, (m.p. 458–459 K). In this article, the crystal structure of (I) has been presented.

The asymmetric unit of the title compound is built up from an almost planar 4-methoxybenzenamine cation wherein O1 lies 0.049 (3) Å out of the plane formed by its non-hydrogen atoms and a Br^- anion (Fig. 1). The strong N—H···Br hydrogen bonding (N···Br distances 3.300 (3)–3.430 (3) Å) contribute to the stability of the crystal structure and lead the cations and anions to tridimensional network (Fig 2). The crystal structures containing 4-methoxybenzenamine cation have been reported (Tan et al., 2006; Soumhi et al., 2006; Ben Amor et al., 1995).

Related literature top

For background to dielectric–ferroelectric

materials, see: Hang et al. (2009); Li et al. (2008). For related structures, see: Tan et al. (2006); Soumhi et al. (2006); Ben Amor et al. (1995).

Experimental top

Single crystals of 4-methoxyanilinium bromide were prepared by slow evaporation at room temperature of an ethanol solution of 4-methoxybenzenamine and hydrobromic acid.

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: PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at 30% probability level.
	Fig. 2. A view of the packing of the title compound; dashed lines indicate hydrogen bonds.

4-Methoxyanilinium bromide top

Crystal data top

C₇H₁₀NO⁺·Br⁻	F(000) = 816
M_r = 204.07	D_x = 1.569 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6139 reflections
a = 8.9779 (18) Å	θ = 3.3–27.7°
b = 8.6978 (17) Å	µ = 4.69 mm⁻¹
c = 22.132 (4) Å	T = 298 K
V = 1728.2 (6) Å³	Prism, colourless
Z = 8	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	1985 independent reflections
Radiation source: fine-focus sealed tube	1276 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.075
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.391, T_max = 0.391	l = −28→28
16334 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0263P)² + 1.3429P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max = 0.001
1985 reflections	Δρ_max = 0.39 e Å⁻³
93 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0232 (9)

Crystal data top

C₇H₁₀NO⁺·Br⁻	V = 1728.2 (6) Å³
M_r = 204.07	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.9779 (18) Å	µ = 4.69 mm⁻¹
b = 8.6978 (17) Å	T = 298 K
c = 22.132 (4) Å	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	1985 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1276 reflections with I > 2σ(I)
T_min = 0.391, T_max = 0.391	R_int = 0.075
16334 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.12	Δρ_max = 0.39 e Å⁻³
1985 reflections	Δρ_min = −0.33 e Å⁻³
93 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 > 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
O1	0.1517 (3)	0.3060 (4)	0.29591 (13)	0.0721 (9)
N1	0.0282 (4)	0.2527 (4)	0.05037 (14)	0.0548 (9)
H1A	0.0842	0.3201	0.0305	0.066*
H1B	−0.0676	0.2748	0.0447	0.066*
H1C	0.0469	0.1583	0.0369	0.066*
C1	0.1170 (5)	0.2823 (5)	0.23712 (18)	0.0497 (10)
C2	0.1934 (5)	0.3727 (5)	0.1965 (2)	0.0650 (12)
H2A	0.2650	0.4412	0.2105	0.078*
C3	0.1653 (5)	0.3630 (5)	0.13576 (18)	0.0596 (11)
H3A	0.2166	0.4258	0.1088	0.071*
C4	0.0621 (4)	0.2612 (4)	0.11502 (17)	0.0427 (9)
C5	−0.0123 (4)	0.1673 (5)	0.15443 (17)	0.0538 (10)
H5A	−0.0808	0.0958	0.1401	0.065*
C6	0.0153 (5)	0.1797 (5)	0.21591 (17)	0.0533 (11)
H6A	−0.0363	0.1173	0.2429	0.064*
C7	0.0851 (7)	0.2069 (6)	0.3394 (2)	0.0914 (17)
H7A	0.1184	0.2351	0.3791	0.137*
H7B	0.1134	0.1025	0.3312	0.137*
H7C	−0.0213	0.2162	0.3373	0.137*
Br1	0.25218 (4)	0.51025 (4)	−0.021898 (16)	0.0495 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.084 (2)	0.088 (2)	0.0449 (17)	0.0026 (19)	−0.0164 (17)	−0.0048 (17)
N1	0.057 (2)	0.059 (2)	0.0480 (19)	0.0099 (16)	−0.0074 (17)	−0.0047 (15)
C1	0.048 (2)	0.053 (2)	0.048 (2)	0.011 (2)	−0.0035 (19)	−0.006 (2)
C2	0.067 (3)	0.068 (3)	0.060 (3)	−0.021 (2)	−0.008 (2)	−0.009 (2)
C3	0.063 (3)	0.066 (3)	0.050 (3)	−0.017 (2)	−0.001 (2)	−0.001 (2)
C4	0.042 (2)	0.045 (2)	0.041 (2)	0.0082 (17)	−0.0029 (17)	−0.0057 (17)
C5	0.049 (2)	0.054 (3)	0.058 (3)	−0.005 (2)	−0.007 (2)	−0.006 (2)
C6	0.051 (3)	0.061 (3)	0.048 (2)	−0.004 (2)	0.001 (2)	0.0055 (19)
C7	0.107 (4)	0.120 (5)	0.047 (3)	0.011 (4)	−0.007 (3)	0.012 (3)
Br1	0.0493 (3)	0.0461 (3)	0.0531 (3)	0.00163 (19)	−0.0010 (2)	−0.00423 (18)

Geometric parameters (Å, º) top

O1—C1	1.354 (5)	C3—C4	1.361 (5)
O1—C7	1.424 (6)	C3—H3A	0.9300
N1—C4	1.465 (5)	C4—C5	1.369 (5)
N1—H1A	0.8893	C5—C6	1.387 (5)
N1—H1B	0.8903	C5—H5A	0.9300
N1—H1C	0.8899	C6—H6A	0.9300
C1—C6	1.360 (6)	C7—H7A	0.9600
C1—C2	1.377 (6)	C7—H7B	0.9600
C2—C3	1.370 (5)	C7—H7C	0.9600
C2—H2A	0.9300

C1—O1—C7	117.5 (4)	C3—C4—C5	120.4 (4)
C4—N1—H1A	109.5	C3—C4—N1	120.3 (4)
C4—N1—H1B	109.2	C5—C4—N1	119.4 (3)
H1A—N1—H1B	109.5	C4—C5—C6	119.4 (4)
C4—N1—H1C	109.6	C4—C5—H5A	120.3
H1A—N1—H1C	109.6	C6—C5—H5A	120.3
H1B—N1—H1C	109.5	C1—C6—C5	120.6 (4)
O1—C1—C6	125.9 (4)	C1—C6—H6A	119.7
O1—C1—C2	115.2 (4)	C5—C6—H6A	119.7
C6—C1—C2	118.9 (4)	O1—C7—H7A	109.5
C3—C2—C1	120.9 (4)	O1—C7—H7B	109.5
C3—C2—H2A	119.5	H7A—C7—H7B	109.5
C1—C2—H2A	119.5	O1—C7—H7C	109.5
C4—C3—C2	119.7 (4)	H7A—C7—H7C	109.5
C4—C3—H3A	120.1	H7B—C7—H7C	109.5
C2—C3—H3A	120.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1	0.89	2.52	3.409 (3)	177
N1—H1B···Br1ⁱ	0.89	2.55	3.314 (3)	145
N1—H1B···Br1ⁱⁱ	0.89	3.00	3.430 (3)	112
N1—H1C···Br1ⁱⁱⁱ	0.89	2.57	3.300 (3)	140

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

Experimental details

Crystal data
Chemical formula	C₇H₁₀NO⁺·Br⁻
M_r	204.07
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	8.9779 (18), 8.6978 (17), 22.132 (4)
V (Å³)	1728.2 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.69
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.391, 0.391
No. of measured, independent and observed [I > 2σ(I)] reflections	16334, 1985, 1276
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.100, 1.12
No. of reflections	1985
No. of parameters	93
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.33

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1	0.89	2.52	3.409 (3)	177
N1—H1B···Br1ⁱ	0.89	2.55	3.314 (3)	145
N1—H1B···Br1ⁱⁱ	0.89	3.00	3.430 (3)	112
N1—H1C···Br1ⁱⁱⁱ	0.89	2.57	3.300 (3)	140

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

Acknowledgements

The author is grateful to the starter fund of Southeast University for financial support to buy the X-ray diffractometer.

References

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