4-Eth­oxy­anilinium bromide

Wang, W.

doi:10.1107/S1600536810048713

organic compounds

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Volume 66| Part 12| December 2010| Page o3348

https://doi.org/10.1107/S1600536810048713

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4-Ethoxyanilinium bromide

Wen-zhe Wang ^a ^*

^aCollege of Food Engineering, RiZhao Polytechnic, RiZhao 276826, People's Republic of China
^*Correspondence e-mail: wangwenzhe-11@163.com

(Received 21 November 2010; accepted 22 November 2010; online 27 November 2010)

The title compound, C₈H₁₂NO⁺·Br⁻, is built up from roughly planar (r.m.s. deviation for the non-H atoms = 0.062 Å) protonated 4-ethoxyanilimium cations and Br⁻ anions. In the crystal, the cations and anions are linked by N—H⋯Br and N—H⋯(Br,Br) hydrogen bonds, generating (100) sheets. Very weak C—H⋯π interactions may also help to stabilize the crystal structure.

Related literature

For a related structure containing the same cation, see: Fu (2009 ).

Experimental

Crystal data

C₈H₁₂NO⁺·Br⁻
M_r = 218.09
Monoclinic, P 2₁ /c
a = 11.842 (2) Å
b = 6.5263 (13) Å
c = 12.488 (3) Å
β = 96.44 (3)°
V = 959.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.23 mm⁻¹
T = 298 K
0.40 × 0.30 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.237, T_max = 0.429
9286 measured reflections
2200 independent reflections
1579 reflections with I > 2σ(I)
R_int = 0.073

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.173
S = 1.11
2200 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 1.55 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯Br1	0.89	2.78	3.368 (4)	125
N1—H1B⋯Br1ⁱ	0.89	2.76	3.324 (5)	122
N1—H1C⋯Br1ⁱⁱ	0.89	2.56	3.375 (4)	153
N1—H1D⋯Br1ⁱⁱⁱ	0.89	2.51	3.348 (5)	158
C7—H7A⋯Cg1^iv	0.97	3.01	3.674 (8)	127
C8—H8B⋯Cg1^v	0.96	2.96	3.677 (8)	132
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) -x, -y+1, -z; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) -x+1, -y+1, -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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810048713/hb5753sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810048713/hb5753Isup2.hkl

checkCIF report

Comment top

The crystal structure of 4-ethoxyanilinium together with perchlorate is known (Fu, 2009).

The asymmetric unit of the title compound consists of an almost planar protonated 4-ethoxyanilimium cation with the mean deviation of 0.0618 A from the plane formed by its non-hydrogen atoms and a Br^- anion (Fig.1). The N—H···Br hydrogen bonding with the N—Br distance from 3.324 (5)Å to 3.375 (4) Å, make great contribution to the stability of the crystal structure and link the cations and anions into chains along b axis. The C—H···π interactions with the C···Cg1 distances of C7—H7A···Cg1 3.674 (8)Å and C8—H8B···Cg1 3.677 (8) Å, respectively, (Cg1 is the centroid of benzene ring) also help stable crystal structure.

Related literature top

For a related structure containing the same cation, see: Fu (2009).

Experimental top

Colorless prisms of the title compound were obtained by slow evaporation at room temperature of an ethanol solution of equimolar amounts of 4-ethoxybenzenamine and hydrobromic acid (47% w/w).

Structure description top

The crystal structure of 4-ethoxyanilinium together with perchlorate is known (Fu, 2009).

For a related structure containing the same cation, see: Fu (2009).

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 displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A view of the packing of the title compound, stacking along the c axis. Dashed lines indicate hydrogen bonds.

4-Ethoxyanilinium bromide top

Crystal data top

C₈H₁₂NO⁺·Br⁻	F(000) = 440
M_r = 218.09	D_x = 1.510 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3858 reflections
a = 11.842 (2) Å	θ = 3.1–27.7°
b = 6.5263 (13) Å	µ = 4.23 mm⁻¹
c = 12.488 (3) Å	T = 298 K
β = 96.44 (3)°	Prism, colourless
V = 959.0 (3) Å³	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2200 independent reflections
Radiation source: fine-focus sealed tube	1579 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.073
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −15→15
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→8
T_min = 0.237, T_max = 0.429	l = −16→16
9286 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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0748P)² + 1.0824P] where P = (F_o² + 2F_c²)/3
2200 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 1.55 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₈H₁₂NO⁺·Br⁻	V = 959.0 (3) Å³
M_r = 218.09	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.842 (2) Å	µ = 4.23 mm⁻¹
b = 6.5263 (13) Å	T = 298 K
c = 12.488 (3) Å	0.40 × 0.30 × 0.20 mm
β = 96.44 (3)°

Data collection top

Rigaku SCXmini diffractometer	2200 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1579 reflections with I > 2σ(I)
T_min = 0.237, T_max = 0.429	R_int = 0.073
9286 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 1.11	Δρ_max = 1.55 e Å⁻³
2200 reflections	Δρ_min = −0.42 e Å⁻³
100 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	0.01352 (5)	0.76484 (8)	0.12594 (4)	0.0493 (3)
O1	0.5504 (4)	0.2634 (6)	0.0985 (5)	0.0665 (14)
N1	0.0856 (4)	0.2654 (7)	0.1354 (4)	0.0514 (12)
H1B	0.0671	0.3613	0.1810	0.077*
H1C	0.0632	0.1434	0.1568	0.077*
H1D	0.0516	0.2921	0.0697	0.077*
C6	0.4385 (6)	0.2722 (9)	0.1145 (6)	0.0575 (16)
C4	0.2549 (5)	0.1252 (9)	0.0666 (5)	0.0551 (15)
H4A	0.2087	0.0301	0.0274	0.066*
C3	0.2087 (5)	0.2643 (7)	0.1331 (5)	0.0458 (13)
C5	0.3688 (5)	0.1288 (10)	0.0589 (5)	0.0608 (17)
H5A	0.4001	0.0332	0.0156	0.073*
C1	0.3918 (6)	0.4084 (9)	0.1824 (6)	0.0640 (18)
H1A	0.4380	0.5023	0.2225	0.077*
C8	0.7385 (6)	0.3844 (11)	0.1062 (6)	0.073 (2)
H8A	0.7906	0.4880	0.1355	0.109*
H8B	0.7315	0.3907	0.0289	0.109*
H8C	0.7665	0.2519	0.1296	0.109*
C2	0.2756 (6)	0.4042 (10)	0.1902 (5)	0.0630 (17)
H2A	0.2438	0.4972	0.2346	0.076*
C7	0.6253 (6)	0.4193 (11)	0.1441 (6)	0.075 (2)
H7A	0.6314	0.4131	0.2221	0.089*
H7B	0.5965	0.5534	0.1213	0.089*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0600 (4)	0.0431 (4)	0.0460 (4)	−0.0070 (3)	0.0119 (3)	−0.0002 (2)
O1	0.046 (2)	0.064 (3)	0.090 (4)	−0.0075 (19)	0.010 (2)	−0.017 (2)
N1	0.043 (3)	0.061 (3)	0.050 (3)	−0.007 (2)	0.009 (2)	0.000 (2)
C6	0.050 (4)	0.056 (4)	0.068 (4)	−0.004 (3)	0.012 (3)	−0.002 (3)
C4	0.045 (3)	0.055 (3)	0.067 (4)	−0.011 (3)	0.016 (3)	−0.019 (3)
C3	0.045 (3)	0.044 (3)	0.049 (3)	0.002 (2)	0.010 (2)	−0.002 (2)
C5	0.048 (4)	0.059 (4)	0.077 (5)	−0.007 (3)	0.016 (3)	−0.025 (3)
C1	0.052 (4)	0.064 (4)	0.077 (5)	−0.010 (3)	0.009 (3)	−0.027 (3)
C8	0.053 (4)	0.083 (5)	0.082 (5)	−0.014 (4)	0.006 (4)	0.013 (4)
C2	0.061 (4)	0.061 (4)	0.068 (4)	0.002 (3)	0.011 (3)	−0.021 (3)
C7	0.060 (5)	0.074 (5)	0.088 (6)	−0.021 (4)	−0.001 (4)	0.002 (4)

Geometric parameters (Å, º) top

O1—C6	1.363 (9)	C3—C2	1.358 (8)
O1—C7	1.426 (7)	C5—H5A	0.9300
N1—C3	1.461 (8)	C1—C2	1.390 (9)
N1—H1B	0.8900	C1—H1A	0.9300
N1—H1C	0.8900	C8—C7	1.489 (9)
N1—H1D	0.8900	C8—H8A	0.9600
C6—C5	1.382 (9)	C8—H8B	0.9600
C6—C1	1.385 (9)	C8—H8C	0.9600
C4—C5	1.362 (8)	C2—H2A	0.9300
C4—C3	1.384 (7)	C7—H7A	0.9700
C4—H4A	0.9300	C7—H7B	0.9700

C6—O1—C7	118.9 (5)	C6—C1—C2	119.8 (6)
C3—N1—H1B	109.5	C6—C1—H1A	120.1
C3—N1—H1C	109.5	C2—C1—H1A	120.1
H1B—N1—H1C	109.5	C7—C8—H8A	109.5
C3—N1—H1D	109.5	C7—C8—H8B	109.5
H1B—N1—H1D	109.5	H8A—C8—H8B	109.5
H1C—N1—H1D	109.5	C7—C8—H8C	109.5
O1—C6—C5	115.7 (6)	H8A—C8—H8C	109.5
O1—C6—C1	125.3 (6)	H8B—C8—H8C	109.5
C5—C6—C1	119.0 (6)	C3—C2—C1	120.0 (6)
C5—C4—C3	119.5 (5)	C3—C2—H2A	120.0
C5—C4—H4A	120.3	C1—C2—H2A	120.0
C3—C4—H4A	120.3	O1—C7—C8	107.8 (6)
C2—C3—C4	120.6 (6)	O1—C7—H7A	110.1
C2—C3—N1	120.8 (5)	C8—C7—H7A	110.1
C4—C3—N1	118.5 (5)	O1—C7—H7B	110.1
C4—C5—C6	121.1 (6)	C8—C7—H7B	110.1
C4—C5—H5A	119.5	H7A—C7—H7B	108.5
C6—C5—H5A	119.5

C7—O1—C6—C5	173.5 (6)	O1—C6—C1—C2	178.9 (7)
C7—O1—C6—C1	−7.8 (10)	C5—C6—C1—C2	−2.6 (11)
C5—C4—C3—C2	0.3 (10)	C4—C3—C2—C1	−0.1 (10)
C5—C4—C3—N1	176.6 (6)	N1—C3—C2—C1	−176.3 (6)
C3—C4—C5—C6	−1.6 (10)	C6—C1—C2—C3	1.3 (11)
O1—C6—C5—C4	−178.6 (6)	C6—O1—C7—C8	−174.7 (6)
C1—C6—C5—C4	2.7 (11)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Br1	0.89	2.78	3.368 (4)	125
N1—H1B···Br1ⁱ	0.89	2.76	3.324 (5)	122
N1—H1C···Br1ⁱⁱ	0.89	2.56	3.375 (4)	153
N1—H1D···Br1ⁱⁱⁱ	0.89	2.51	3.348 (5)	158
C7—H7A···Cg1^iv	0.97	3.01	3.674 (8)	127
C8—H8B···Cg1^v	0.96	2.96	3.677 (8)	132

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂NO⁺·Br⁻
M_r	218.09
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.842 (2), 6.5263 (13), 12.488 (3)
β (°)	96.44 (3)
V (Å³)	959.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.23
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.237, 0.429
No. of measured, independent and observed [I > 2σ(I)] reflections	9286, 2200, 1579
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.173, 1.11
No. of reflections	2200
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.55, −0.42

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Br1	0.89	2.78	3.368 (4)	125
N1—H1B···Br1ⁱ	0.89	2.76	3.324 (5)	122
N1—H1C···Br1ⁱⁱ	0.89	2.56	3.375 (4)	153
N1—H1D···Br1ⁱⁱⁱ	0.89	2.51	3.348 (5)	158
C7—H7A···Cg1^iv	0.97	3.01	3.674 (8)	127
C8—H8B···Cg1^v	0.96	2.96	3.677 (8)	132

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

Acknowledgements

The author is grateful for financial support from RiZhao Polytechnic.

References

Fu, X. (2009). Acta Cryst. E65, o2345. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3348

https://doi.org/10.1107/S1600536810048713

Open

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