4-Methoxy­anilinium chloride

Zhao, M.M.

doi:10.1107/S1600536809035429

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2378

doi:10.1107/S1600536809035429

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4-Methoxyanilinium chloride

Min Min Zhao ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical, Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: zmmzyahfdzg@126.com

(Received 5 August 2009; accepted 2 September 2009; online 9 September 2009)

The crystal structure of the title compound, C₇H₁₀NO⁺·Cl⁻, was synthesized by the reaction of 4-methoxyaniline and hydrochloric acid. In the crystal structure, the ions are involved in intermolecular N—H⋯Cl hydrogen bonds.

Related literature

For a similar organic acid-base product, see: Wu et al. (2006 ). This work is part of a systematic investigation of dielectric–ferroelectric materials, including organic ligands, metal–organic coordination compounds and organic–inorganic hybrid materials; see: Li et al. (2008 ); Hang et al. (2009 ).

Experimental

Crystal data

C₇H₁₀NO⁺·Cl⁻
M_r = 159.61
Orthorhombic, P b c a
a = 8.905 (2) Å
b = 8.489 (2) Å
c = 21.817 (4) Å
V = 1649.3 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.40 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 = 0.924, T_max = 0.924
15436 measured reflections
1886 independent reflections
1452 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.165
S = 1.12
1886 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯Cl1ⁱ	0.89	2.47	3.360 (3)	179
N1—H1E⋯Cl1ⁱⁱ	0.89	2.50	3.209 (2)	137
N1—H1F⋯Cl1ⁱⁱⁱ	0.89	2.38	3.167 (2)	147
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536809035429/im2133sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035429/im2133Isup2.hkl

checkCIF report

Comment top

Acid-base reactions of organic reactands were already widely researched by ancient chemists (Wu et al., 2006). This study is a part of a systematic investigation of dielectric-ferroelectric materials, including organic ligands, metal-organic coordination compounds and organic-inorganic hybrid materials (Li et al., 2008; Hang et al., 2009). Nevertheless, 4-methoxy-anilinium chloride shows no dielectric irregularity in the temperature range of 80 K to 400 K, (m.p. 401 K).

The asymmetric unit of the title compound is composed of cationic (CH₃O–C₆H₄–NH₃⁺) and chloride anions (Fig 1). Intramolecular hydrogen bonds between the ammonium groups of the organic cations and the chloride anions are observed in the crystal structure.

Related literature top

For a similar organic acid-base product, see: Wu et al. (2006). For general background to this research, see: Hang et al. (2009); Li et al. (2008).

Experimental top

Single crystals of 4-methoxy-anilinium chloride are prepared by slow evaporation at room temperature of 20 mL of an ethanolic solution of 4-methoxyphenylamine and an excess of hydrogen chloride (6 mol/L).

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 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. View of the packing of the title compound, stacking along the a axis. Dashed lines indicate hydrogen bonds.

4-Methoxyanilinium chloride top

Crystal data top

C₇H₁₀NO⁺·Cl⁻	F(000) = 672
M_r = 159.61	D_x = 1.286 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6458 reflections
a = 8.905 (2) Å	θ = 3.0–27.6°
b = 8.489 (2) Å	µ = 0.40 mm⁻¹
c = 21.817 (4) Å	T = 298 K
V = 1649.3 (6) Å³	Prism, colourless
Z = 8	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	1886 independent reflections
Radiation source: fine-focus sealed tube	1452 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
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 = −10→11
T_min = 0.924, T_max = 0.924	l = −27→28
15436 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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.165	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0824P)² + 0.5018P] where P = (F_o² + 2F_c²)/3
1886 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

C₇H₁₀NO⁺·Cl⁻	V = 1649.3 (6) Å³
M_r = 159.61	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.905 (2) Å	µ = 0.40 mm⁻¹
b = 8.489 (2) Å	T = 298 K
c = 21.817 (4) Å	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	1886 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1452 reflections with I > 2σ(I)
T_min = 0.924, T_max = 0.924	R_int = 0.058
15436 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.165	H-atom parameters constrained
S = 1.12	Δρ_max = 0.25 e Å⁻³
1886 reflections	Δρ_min = −0.54 e Å⁻³
91 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	0.75138 (6)	0.98509 (7)	0.52111 (3)	0.0470 (3)
O1	0.1534 (2)	0.1996 (2)	0.29469 (8)	0.0623 (6)
N1	0.0252 (3)	0.2494 (3)	0.04478 (10)	0.0617 (7)
H1D	−0.0468	0.3203	0.0383	0.093*
H1E	−0.0059	0.1553	0.0320	0.093*
H1F	0.1073	0.2770	0.0242	0.093*
C2	0.1175 (3)	0.2222 (3)	0.23454 (10)	0.0438 (6)
C5	0.0595 (3)	0.2423 (3)	0.11049 (11)	0.0441 (6)
C4	0.1677 (3)	0.1392 (3)	0.13138 (12)	0.0561 (7)
H4A	0.2203	0.0762	0.1039	0.067*
C6	−0.0179 (3)	0.3363 (3)	0.15081 (12)	0.0492 (6)
H6A	−0.0895	0.4069	0.1363	0.059*
C7	0.0108 (3)	0.3259 (3)	0.21326 (11)	0.0472 (6)
H7A	−0.0420	0.3890	0.2407	0.057*
C3	0.1970 (3)	0.1303 (4)	0.19295 (13)	0.0575 (7)
H3A	0.2710	0.0621	0.2071	0.069*
C1	0.0870 (4)	0.3025 (4)	0.33900 (13)	0.0761 (10)
H1A	0.1211	0.2740	0.3792	0.114*
H1B	−0.0203	0.2934	0.3371	0.114*
H1C	0.1157	0.4092	0.3304	0.114*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0461 (4)	0.0472 (4)	0.0478 (4)	−0.0017 (2)	0.0013 (3)	−0.0042 (2)
O1	0.0691 (13)	0.0735 (13)	0.0442 (10)	−0.0047 (11)	−0.0113 (9)	0.0042 (9)
N1	0.0690 (16)	0.0723 (16)	0.0439 (12)	−0.0200 (12)	−0.0091 (11)	0.0082 (11)
C2	0.0435 (14)	0.0466 (12)	0.0414 (13)	−0.0109 (11)	−0.0051 (10)	0.0065 (10)
C5	0.0440 (13)	0.0496 (13)	0.0388 (12)	−0.0143 (11)	−0.0040 (10)	0.0055 (10)
C4	0.0598 (16)	0.0597 (16)	0.0488 (15)	0.0083 (13)	0.0060 (12)	−0.0031 (12)
C6	0.0421 (13)	0.0499 (14)	0.0554 (14)	0.0024 (11)	−0.0056 (11)	0.0060 (12)
C7	0.0404 (13)	0.0526 (15)	0.0486 (13)	−0.0008 (11)	0.0000 (11)	−0.0056 (11)
C3	0.0570 (16)	0.0592 (16)	0.0564 (16)	0.0167 (14)	−0.0053 (13)	0.0062 (13)
C1	0.075 (2)	0.109 (3)	0.0448 (15)	−0.011 (2)	−0.0045 (14)	−0.0147 (16)

Geometric parameters (Å, º) top

O1—C2	1.364 (3)	C4—C3	1.370 (4)
O1—C1	1.431 (4)	C4—H4A	0.9300
N1—C5	1.467 (3)	C6—C7	1.389 (4)
N1—H1D	0.8900	C6—H6A	0.9300
N1—H1E	0.8900	C7—H7A	0.9300
N1—H1F	0.8900	C3—H3A	0.9300
C2—C7	1.376 (4)	C1—H1A	0.9600
C2—C3	1.390 (4)	C1—H1B	0.9600
C5—C6	1.373 (4)	C1—H1C	0.9600
C5—C4	1.380 (4)

C2—O1—C1	117.9 (2)	C5—C6—C7	119.9 (2)
C5—N1—H1D	109.5	C5—C6—H6A	120.0
C5—N1—H1E	109.5	C7—C6—H6A	120.0
H1D—N1—H1E	109.5	C2—C7—C6	119.9 (2)
C5—N1—H1F	109.5	C2—C7—H7A	120.0
H1D—N1—H1F	109.5	C6—C7—H7A	120.0
H1E—N1—H1F	109.5	C4—C3—C2	120.8 (2)
O1—C2—C7	125.2 (2)	C4—C3—H3A	119.6
O1—C2—C3	115.4 (2)	C2—C3—H3A	119.6
C7—C2—C3	119.4 (2)	O1—C1—H1A	109.5
C6—C5—C4	120.5 (2)	O1—C1—H1B	109.5
C6—C5—N1	119.8 (2)	H1A—C1—H1B	109.5
C4—C5—N1	119.6 (2)	O1—C1—H1C	109.5
C3—C4—C5	119.5 (2)	H1A—C1—H1C	109.5
C3—C4—H4A	120.3	H1B—C1—H1C	109.5
C5—C4—H4A	120.3

C1—O1—C2—C7	−6.9 (4)	O1—C2—C7—C6	−178.8 (2)
C1—O1—C2—C3	173.4 (3)	C3—C2—C7—C6	0.9 (4)
C6—C5—C4—C3	0.4 (4)	C5—C6—C7—C2	0.4 (4)
N1—C5—C4—C3	−178.5 (2)	C5—C4—C3—C2	1.0 (4)
C4—C5—C6—C7	−1.1 (4)	O1—C2—C3—C4	178.1 (3)
N1—C5—C6—C7	177.8 (2)	C7—C2—C3—C4	−1.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···Cl1ⁱ	0.89	2.47	3.360 (3)	179
N1—H1E···Cl1ⁱⁱ	0.89	2.50	3.209 (2)	137
N1—H1F···Cl1ⁱⁱⁱ	0.89	2.38	3.167 (2)	147

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

Experimental details

Crystal data
Chemical formula	C₇H₁₀NO⁺·Cl⁻
M_r	159.61
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	8.905 (2), 8.489 (2), 21.817 (4)
V (Å³)	1649.3 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
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	0.924, 0.924
No. of measured, independent and observed [I > 2σ(I)] reflections	15436, 1886, 1452
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.165, 1.12
No. of reflections	1886
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.54

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—H1D···Cl1ⁱ	0.89	2.47	3.360 (3)	179.3
N1—H1E···Cl1ⁱⁱ	0.89	2.50	3.209 (2)	136.8
N1—H1F···Cl1ⁱⁱⁱ	0.89	2.38	3.167 (2)	147.0

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

Acknowledgements

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

References

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