4-Eth­oxy­anilinium chloride

Fu, X.

doi:10.1107/S1600536810025973

organic compounds

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Volume 66| Part 8| August 2010| Page o1944

https://doi.org/10.1107/S1600536810025973

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4-Ethoxyanilinium chloride

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 23 June 2010; accepted 1 July 2010; online 7 July 2010)

The title compound, C₈H₁₂NO⁺·Cl⁻, consists of an almost planar protonated 4-ethoxyanilinium cation with the N atom showing the biggest deviation from the plane formed by all non-H atoms of the cation [0.066 (1) Å]. In the crystal, N—H⋯Cl hydrogen bonds link cations and anions into chains along the a axis. Additional C—H⋯π and π–π interactions [centroid–centroid distance = 4.873 (2) Å] stabilize the crystal structure.

Related literature

For background to phase-transition materials, see: Li et al. (2008 ); Ye et al. (2009 ); Zhang et al. (2009 ). For similar structures, see: Fu (2009 ); Jiang et al. (1996 ); Zhao (2009 ).

Experimental

Crystal data

C₈H₁₂NO⁺·Cl⁻
M_r = 173.64
Orthorhombic, P b c a
a = 11.422 (2) Å
b = 7.0890 (14) Å
c = 22.887 (5) Å
V = 1853.2 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.36 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 = 0.879, T_max = 0.931
17046 measured reflections
2116 independent reflections
1655 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.106
S = 1.08
2116 reflections
112 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯Cl1ⁱ	0.94 (2)	2.23 (3)	3.104 (2)	154 (2)
N1—H1C⋯Cl1ⁱⁱ	0.87 (3)	2.27 (3)	3.107 (2)	161 (2)
N1—H1B⋯Cl1	0.90 (3)	2.23 (3)	3.114 (2)	172 (2)
C4—H4A⋯Cg1ⁱⁱⁱ	0.93	2.91	3.654 (2)	138
C7—H7B⋯Cg1^iv	0.97	2.89	3.710 (2)	143
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y-{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x+1, -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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810025973/im2216sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810025973/im2216Isup2.hkl

checkCIF report

Comment top

The crystal structure of 4-ethoxyanilinium perchlorate as well as those of 2- and 4-methoxyanilinium chloride are known (Fu, 2009; Zhao, 2009; Jiang et al., 1996). In this article, the crystal structure of (I) is presented.

The asymmetric unit of the title compound is built by an almost planar protonated 4-ethoxyanilinium cation and a Cl^- anion (Fig. 1). C—H···π interactions with a C4—H4A···Cg1 distance of 3.654 (2) Å and a C7—H7B···Cg1 distance of 3.710 (2) Å, respectively, as well as π-π packing interactions of adjacent benzene rings with a Cg1—Cg1 distance of 4.873 (2) Å, make a great contribution to the observed crystal structure (Cg1 is the centroid of benzene ring). Additional N—H···Cl hydrogen bonding with N—Cl distances of 3.104 (2) Å to 3.114 (2) Å (Table.1) link the cations and anions into chains along a axis (Fig.2).

Related literature top

For background to phase-transition materials, see: Li et al. (2008); Ye et al. (2009); Zhang et al. (2009). For similar structures, see: Fu (2009); Jiang et al. (1996); Zhao (2009).

Experimental top

Single crystals suitable for X-ray diffraction were obtained by slow evaporation at room temperature of an ethanolic solution of equimolar amounts of 4-ethoxyaniline and 6M hydrochloric acid.

Dielectric studies (capacitance and dielectric loss measurements) were performed using an automatic impedance TongHui2828 Analyzer on powder samples that were pressed into tablets on the surfaces of which a conducting carbon glue was deposited. Dielectric permittivity of the compound was tested to systematically to investigate the possibility of ferroelectric phase transitions (Li et al., 2008, Ye et al., 2009; Zhang et al., 2009). Unfortunately, the temperature dependence of the relative permittivity at 1 MHz varied smoothly from 4.0 to 4.3 and there was no distinct anomaly observed from 93 K to 350 K (sublimation higher than 378 K) in the title compound, suggesting that this compound should not be a real ferroelectric or that no distinct phase transition occurred within the measured temperature range.

Structure description top

For background to phase-transition materials, see: Li et al. (2008); Ye et al. (2009); Zhang et al. (2009). For similar structures, see: Fu (2009); Jiang et al. (1996); Zhao (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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.

4-Ethoxyanilinium chloride top

Crystal data top

C₈H₁₂NO⁺·Cl⁻	F(000) = 736
M_r = 173.64	D_x = 1.245 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 7266 reflections
a = 11.422 (2) Å	θ = 3.0–27.7°
b = 7.0890 (14) Å	µ = 0.36 mm⁻¹
c = 22.887 (5) Å	T = 298 K
V = 1853.2 (6) Å³	Prism, colourless
Z = 8	0.40 × 0.30 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	2116 independent reflections
Radiation source: fine-focus sealed tube	1655 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.5°
ω scans	h = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
T_min = 0.879, T_max = 0.931	l = −29→29
17046 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0383P)² + 0.7382P] where P = (F_o² + 2F_c²)/3
2116 reflections	(Δ/σ)_max < 0.001
112 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₈H₁₂NO⁺·Cl⁻	V = 1853.2 (6) Å³
M_r = 173.64	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.422 (2) Å	µ = 0.36 mm⁻¹
b = 7.0890 (14) Å	T = 298 K
c = 22.887 (5) Å	0.40 × 0.30 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	2116 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1655 reflections with I > 2σ(I)
T_min = 0.879, T_max = 0.931	R_int = 0.044
17046 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.27 e Å⁻³
2116 reflections	Δρ_min = −0.23 e Å⁻³
112 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
Cl1	0.36897 (4)	0.14153 (8)	0.73645 (2)	0.0565 (2)
C3	0.39597 (14)	0.6120 (3)	0.64180 (8)	0.0382 (4)
O1	0.39659 (12)	0.76724 (19)	0.46863 (5)	0.0495 (4)
C6	0.39549 (15)	0.7056 (3)	0.52510 (8)	0.0384 (4)
N1	0.39087 (15)	0.5668 (3)	0.70418 (7)	0.0456 (4)
H1D	0.323 (2)	0.619 (3)	0.7215 (10)	0.072 (7)*
H1C	0.451 (2)	0.614 (4)	0.7224 (11)	0.081 (8)*
H1B	0.387 (2)	0.442 (5)	0.7096 (12)	0.084 (9)*
C7	0.34271 (19)	0.6523 (3)	0.42485 (8)	0.0509 (5)
H7A	0.2601	0.6365	0.4333	0.061*
H7B	0.3791	0.5287	0.4240	0.061*
C5	0.34210 (18)	0.5419 (3)	0.54364 (9)	0.0511 (5)
H5A	0.3060	0.4626	0.5168	0.061*
C4	0.34242 (17)	0.4958 (3)	0.60251 (9)	0.0507 (5)
H4A	0.3061	0.3858	0.6152	0.061*
C1	0.45119 (17)	0.8200 (3)	0.56533 (8)	0.0468 (5)
H1A	0.4890	0.9289	0.5528	0.056*
C8	0.3583 (2)	0.7490 (4)	0.36708 (9)	0.0651 (6)
H8A	0.3226	0.6748	0.3369	0.098*
H8B	0.4403	0.7631	0.3590	0.098*
H8C	0.3220	0.8711	0.3684	0.098*
C2	0.45113 (17)	0.7739 (3)	0.62369 (8)	0.0456 (5)
H2A	0.4882	0.8517	0.6507	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0385 (3)	0.0715 (4)	0.0596 (3)	−0.0036 (2)	−0.0107 (2)	0.0117 (3)
C3	0.0278 (8)	0.0501 (11)	0.0366 (9)	0.0017 (7)	−0.0005 (7)	0.0041 (8)
O1	0.0676 (9)	0.0474 (8)	0.0334 (7)	−0.0125 (7)	−0.0020 (6)	0.0020 (6)
C6	0.0387 (9)	0.0406 (10)	0.0359 (9)	−0.0017 (8)	0.0015 (7)	0.0015 (8)
N1	0.0329 (9)	0.0653 (13)	0.0387 (9)	0.0010 (8)	−0.0008 (7)	0.0082 (9)
C7	0.0576 (12)	0.0565 (12)	0.0387 (10)	−0.0041 (10)	−0.0017 (8)	−0.0069 (9)
C5	0.0571 (12)	0.0524 (12)	0.0438 (11)	−0.0209 (10)	−0.0067 (9)	0.0004 (9)
C4	0.0510 (11)	0.0532 (12)	0.0477 (11)	−0.0204 (9)	−0.0022 (8)	0.0079 (10)
C1	0.0583 (12)	0.0393 (10)	0.0428 (10)	−0.0122 (9)	0.0003 (9)	0.0029 (8)
C8	0.0884 (17)	0.0686 (15)	0.0382 (11)	0.0068 (13)	−0.0028 (10)	−0.0032 (11)
C2	0.0511 (11)	0.0438 (11)	0.0418 (10)	−0.0087 (9)	−0.0053 (8)	−0.0045 (8)

Geometric parameters (Å, º) top

C3—C4	1.364 (3)	C7—H7A	0.9700
C3—C2	1.373 (3)	C7—H7B	0.9700
C3—N1	1.464 (2)	C5—C4	1.386 (3)
O1—C6	1.364 (2)	C5—H5A	0.9300
O1—C7	1.431 (2)	C4—H4A	0.9300
C6—C5	1.378 (3)	C1—C2	1.375 (3)
C6—C1	1.382 (3)	C1—H1A	0.9300
N1—H1D	0.94 (2)	C8—H8A	0.9600
N1—H1C	0.87 (3)	C8—H8B	0.9600
N1—H1B	0.90 (3)	C8—H8C	0.9600
C7—C8	1.500 (3)	C2—H2A	0.9300

C4—C3—C2	120.75 (17)	C6—C5—C4	119.76 (18)
C4—C3—N1	119.51 (18)	C6—C5—H5A	120.1
C2—C3—N1	119.70 (17)	C4—C5—H5A	120.1
C6—O1—C7	118.49 (15)	C3—C4—C5	119.98 (18)
O1—C6—C5	124.45 (17)	C3—C4—H4A	120.0
O1—C6—C1	116.03 (16)	C5—C4—H4A	120.0
C5—C6—C1	119.51 (17)	C2—C1—C6	120.50 (17)
C3—N1—H1D	110.9 (14)	C2—C1—H1A	119.7
C3—N1—H1C	110.6 (17)	C6—C1—H1A	119.7
H1D—N1—H1C	107 (2)	C7—C8—H8A	109.5
C3—N1—H1B	110.7 (18)	C7—C8—H8B	109.5
H1D—N1—H1B	107 (2)	H8A—C8—H8B	109.5
H1C—N1—H1B	111 (2)	C7—C8—H8C	109.5
O1—C7—C8	107.79 (18)	H8A—C8—H8C	109.5
O1—C7—H7A	110.1	H8B—C8—H8C	109.5
C8—C7—H7A	110.1	C3—C2—C1	119.47 (17)
O1—C7—H7B	110.1	C3—C2—H2A	120.3
C8—C7—H7B	110.1	C1—C2—H2A	120.3
H7A—C7—H7B	108.5

C7—O1—C6—C5	−2.4 (3)	C6—C5—C4—C3	−0.3 (3)
C7—O1—C6—C1	178.51 (17)	O1—C6—C1—C2	177.53 (18)
C6—O1—C7—C8	−178.74 (17)	C5—C6—C1—C2	−1.6 (3)
O1—C6—C5—C4	−177.57 (19)	C4—C3—C2—C1	0.7 (3)
C1—C6—C5—C4	1.5 (3)	N1—C3—C2—C1	−177.14 (18)
C2—C3—C4—C5	−0.8 (3)	C6—C1—C2—C3	0.5 (3)
N1—C3—C4—C5	177.04 (18)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···Cl1ⁱ	0.94 (2)	2.23 (3)	3.104 (2)	154 (2)
N1—H1C···Cl1ⁱⁱ	0.87 (3)	2.27 (3)	3.107 (2)	161 (2)
N1—H1B···Cl1	0.90 (3)	2.23 (3)	3.114 (2)	172 (2)
C4—H4A···Cg1ⁱⁱⁱ	0.93	2.91	3.654 (2)	138
C7—H7B···Cg1^iv	0.97	2.89	3.710 (2)	143

Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) −x+1, y+1/2, −z+3/2; (iii) x, −y−3/2, z−1/2; (iv) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₈H₁₂NO⁺·Cl⁻
M_r	173.64
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	11.422 (2), 7.0890 (14), 22.887 (5)
V (Å³)	1853.2 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.879, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	17046, 2116, 1655
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.106, 1.08
No. of reflections	2116
No. of parameters	112
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.23

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 C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···Cl1ⁱ	0.94 (2)	2.23 (3)	3.104 (2)	154 (2)
N1—H1C···Cl1ⁱⁱ	0.87 (3)	2.27 (3)	3.107 (2)	161 (2)
N1—H1B···Cl1	0.90 (3)	2.23 (3)	3.114 (2)	172 (2)
C4—H4A···Cg1ⁱⁱⁱ	0.93	2.91	3.654 (2)	137.90
C7—H7B···Cg1^iv	0.97	2.89	3.710 (2)	142.66

Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) −x+1, y+1/2, −z+3/2; (iii) x, −y−3/2, z−1/2; (iv) −x+1, −y+1, −z+1.

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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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o1944

https://doi.org/10.1107/S1600536810025973

Open

access