4-Meth­oxy­anilinium iodide

Xu, R.

doi:10.1107/S1600536810047549

organic compounds

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https://doi.org/10.1107/S1600536810047549

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4-Methoxyanilinium iodide

Rui-jun Xu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical, Engineering, Southeast UniVersity, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: youyoubanzhen@126.com

(Received 1 July 2010; accepted 16 November 2010; online 27 November 2010)

The crystal structure of the title compound, C₇H₁₀NO⁺·I⁻, displays N—H⋯I hydrogen bonds between the 4-methoxyanilinium cations and the iodide anion together with weaker C—H⋯π contacts.

Related literature

The title compound was invesitgated as a potential candidate for having good dielectric properties. For compounds with dielectric–ferroelectric properties, see: Hang et al. (2009 ); Li et al. (2008 ).

Experimental

Crystal data

C₇H₁₀NO⁺·I⁻
M_r = 251.06
Orthorhombic, P b c a
a = 12.290 (3) Å
b = 7.1302 (14) Å
c = 20.304 (4) Å
V = 1779.2 (6) Å³
Z = 8
Mo Kα radiation
μ = 3.54 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 = 0.291, T_max = 0.493
16921 measured reflections
2040 independent reflections
1803 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.065
S = 1.25
2040 reflections
104 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯I1ⁱ	0.86 (3)	2.67 (2)	3.503 (3)	165 (5)
N1—H1F⋯I1ⁱⁱ	0.86 (1)	2.75 (2)	3.566 (3)	159 (3)
N1—H1E⋯I1	0.86 (4)	2.75 (4)	3.568 (3)	159 (4)
C4—H4⋯Cg1ⁱⁱⁱ	0.93	2.87	3.627 (4)	140
C7—H7⋯Cg1^iv	0.93	2.62	3.483 (4)	155
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810047549/bg2356sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047549/bg2356Isup2.hkl

checkCIF report

Comment top

Dielectric-ferroelectric constitute an interesting class of materials, comprising organic ligands (Li et al., 2008), metal-organic coordination compounds (Hang et al., 2009) and organic-inorganic hybrids. We were interested in the title compound as a potential candidate for having good dielectric properties. Unfortunately, the capacitance and dielectric loss measurements did not show any distinct anomaly when observed from 93 K to 455 K (its sublimation temperaure). Regarding its crystal structure, the asymmetric unit of the title compound contains a (4-methoxyanilinium) cation and a iodide anion (Fig.1). The structure is stabilized by C—H···π interactions (C4—H4···Cg1 3.627 (4) Å and C7—H7···Cg1 3.483 (4) Å) as well as weak N—H···I hydrogen bonds involving the NH₃ group and linking the cations and anions into a 3D structure (Fig. 2 and Tab. 1).

Related literature top

Experimental top

The title compound was obtained by the addition of hydriodic acid (4.12 ml, 0.022 mol) to a solution of 4-methoxyanilin (2.26 g, 0.02 mol) in ethanol, in the stoichiometric ratio 1.1:1. Good quality single crystals were obtained by slow evaporation after two weeks.

Structure description top

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. The molecular structure of the title compound, showing 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-Methoxyanilinium iodide top

Crystal data top

C₇H₁₀NO⁺·I⁻	F(000) = 960
M_r = 251.06	D_x = 1.875 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 7161 reflections
a = 12.290 (3) Å	θ = 3.0–27.7°
b = 7.1302 (14) Å	µ = 3.54 mm⁻¹
c = 20.304 (4) Å	T = 298 K
V = 1779.2 (6) Å³	Prism, colourless
Z = 8	0.40 × 0.30 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	2040 independent reflections
Radiation source: fine-focus sealed tube	1803 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
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 = −9→9
T_min = 0.291, T_max = 0.493	l = −26→26
16921 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)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.065	w = 1/[σ²(F_o²) + (0.0154P)² + 1.2835P] where P = (F_o² + 2F_c²)/3
S = 1.25	(Δ/σ)_max < 0.001
2040 reflections	Δρ_max = 0.51 e Å⁻³
104 parameters	Δρ_min = −0.45 e Å⁻³
3 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: 0.0053 (2)

Crystal data top

C₇H₁₀NO⁺·I⁻	V = 1779.2 (6) Å³
M_r = 251.06	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.290 (3) Å	µ = 3.54 mm⁻¹
b = 7.1302 (14) Å	T = 298 K
c = 20.304 (4) Å	0.40 × 0.30 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	2040 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1803 reflections with I > 2σ(I)
T_min = 0.291, T_max = 0.493	R_int = 0.052
16921 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	3 restraints
wR(F²) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 1.25	Δρ_max = 0.51 e Å⁻³
2040 reflections	Δρ_min = −0.45 e Å⁻³
104 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
I1	0.613461 (19)	0.22260 (3)	0.471872 (12)	0.04311 (12)
C1	0.3182 (4)	0.1321 (6)	0.88673 (18)	0.0580 (11)
H1A	0.3321	0.0724	0.9283	0.087*
H1B	0.2444	0.1083	0.8736	0.087*
H1C	0.3293	0.2648	0.8909	0.087*
C2	0.3836 (3)	0.1268 (4)	0.77653 (15)	0.0332 (7)
C3	0.3010 (3)	0.2400 (4)	0.75290 (18)	0.0347 (7)
H3	0.2448	0.2778	0.7806	0.042*
C4	0.3024 (3)	0.2967 (4)	0.68761 (16)	0.0327 (7)
H4	0.2472	0.3728	0.6713	0.039*
C5	0.3856 (2)	0.2399 (4)	0.64723 (16)	0.0303 (7)
C6	0.4686 (3)	0.1275 (5)	0.67025 (17)	0.0377 (8)
H6	0.5244	0.0896	0.6423	0.045*
C7	0.4676 (3)	0.0724 (5)	0.73515 (18)	0.0425 (8)
H7	0.5237	−0.0019	0.7514	0.051*
N1	0.3861 (3)	0.2978 (5)	0.57794 (16)	0.0402 (7)
H1F	0.400 (3)	0.4157 (18)	0.5742 (18)	0.041 (10)*
H1E	0.438 (3)	0.248 (5)	0.5554 (19)	0.059 (13)*
H1D	0.324 (2)	0.281 (6)	0.559 (2)	0.077 (16)*
O1	0.3897 (2)	0.0598 (4)	0.83889 (12)	0.0517 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.04084 (17)	0.04212 (17)	0.04635 (17)	−0.00309 (9)	0.01153 (9)	−0.00348 (10)
C1	0.078 (3)	0.064 (3)	0.032 (2)	0.008 (2)	0.0061 (19)	0.0060 (18)
C2	0.041 (2)	0.0286 (17)	0.0296 (17)	−0.0015 (14)	−0.0032 (13)	0.0018 (12)
C3	0.0360 (17)	0.0326 (17)	0.0354 (18)	0.0031 (13)	0.0052 (14)	−0.0018 (13)
C4	0.0299 (16)	0.0293 (16)	0.0388 (18)	0.0051 (13)	−0.0023 (13)	0.0015 (13)
C5	0.0321 (17)	0.0284 (16)	0.0303 (16)	−0.0021 (12)	0.0010 (12)	0.0009 (12)
C6	0.0309 (17)	0.042 (2)	0.0404 (19)	0.0093 (14)	0.0065 (14)	0.0018 (15)
C7	0.040 (2)	0.043 (2)	0.044 (2)	0.0164 (16)	−0.0033 (15)	0.0045 (16)
N1	0.0400 (18)	0.0456 (19)	0.0352 (16)	0.0018 (15)	0.0045 (13)	0.0085 (14)
O1	0.0712 (19)	0.0532 (16)	0.0307 (13)	0.0172 (13)	0.0012 (12)	0.0097 (11)

Geometric parameters (Å, º) top

C1—O1	1.407 (4)	C4—H4	0.9300
C1—H1A	0.9600	C5—C6	1.380 (4)
C1—H1B	0.9600	C5—N1	1.466 (4)
C1—H1C	0.9600	C6—C7	1.375 (5)
C2—O1	1.355 (4)	C6—H6	0.9300
C2—C3	1.383 (5)	C7—H7	0.9300
C2—C7	1.386 (5)	N1—H1F	0.860 (10)
C3—C4	1.386 (5)	N1—H1E	0.86 (4)
C3—H3	0.9300	N1—H1D	0.86 (3)
C4—C5	1.371 (4)

O1—C1—H1A	109.5	C4—C5—N1	119.6 (3)
O1—C1—H1B	109.5	C6—C5—N1	119.0 (3)
H1A—C1—H1B	109.5	C7—C6—C5	119.0 (3)
O1—C1—H1C	109.5	C7—C6—H6	120.5
H1A—C1—H1C	109.5	C5—C6—H6	120.5
H1B—C1—H1C	109.5	C6—C7—C2	120.5 (3)
O1—C2—C3	124.8 (3)	C6—C7—H7	119.8
O1—C2—C7	115.2 (3)	C2—C7—H7	119.8
C3—C2—C7	120.0 (3)	C5—N1—H1F	111 (3)
C2—C3—C4	119.5 (3)	C5—N1—H1E	113 (3)
C2—C3—H3	120.3	H1F—N1—H1E	102 (3)
C4—C3—H3	120.3	C5—N1—H1D	113 (4)
C5—C4—C3	119.7 (3)	H1F—N1—H1D	105 (4)
C5—C4—H4	120.1	H1E—N1—H1D	111 (5)
C3—C4—H4	120.1	C2—O1—C1	118.8 (3)
C4—C5—C6	121.3 (3)

O1—C2—C3—C4	−178.6 (3)	N1—C5—C6—C7	−179.6 (3)
C7—C2—C3—C4	0.6 (5)	C5—C6—C7—C2	0.9 (5)
C2—C3—C4—C5	0.0 (5)	O1—C2—C7—C6	178.2 (3)
C3—C4—C5—C6	−0.2 (5)	C3—C2—C7—C6	−1.1 (5)
C3—C4—C5—N1	179.1 (3)	C3—C2—O1—C1	−10.9 (5)
C4—C5—C6—C7	−0.3 (5)	C7—C2—O1—C1	169.8 (4)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···I1ⁱ	0.86 (3)	2.67 (2)	3.503 (3)	165 (5)
N1—H1F···I1ⁱⁱ	0.86 (1)	2.75 (2)	3.566 (3)	159 (3)
N1—H1E···I1	0.86 (4)	2.75 (4)	3.568 (3)	159 (4)
C4—H4···Cg1ⁱⁱⁱ	0.93	2.87	3.627 (4)	140
C7—H7···Cg1^iv	0.93	2.62	3.483 (4)	155

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

Experimental details

Crystal data
Chemical formula	C₇H₁₀NO⁺·I⁻
M_r	251.06
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	12.290 (3), 7.1302 (14), 20.304 (4)
V (Å³)	1779.2 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.54
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	0.291, 0.493
No. of measured, independent and observed [I > 2σ(I)] reflections	16921, 2040, 1803
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.065, 1.25
No. of reflections	2040
No. of parameters	104
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.45

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 C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···I1ⁱ	0.86 (3)	2.665 (17)	3.503 (3)	165 (5)
N1—H1F···I1ⁱⁱ	0.860 (10)	2.748 (16)	3.566 (3)	159 (3)
N1—H1E···I1	0.86 (4)	2.75 (4)	3.568 (3)	159 (4)
C4—H4···Cg1ⁱⁱⁱ	0.93	2.87	3.627 (4)	140
C7—H7···Cg1^iv	0.93	2.62	3.483 (4)	155

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

Acknowledgements

The author thanks Southeast University for financial support of this research and is very grateful for the guidance of Professor Wen Zhang.

References

Hang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des. 5, 2026–2029. Web of Science CSD CrossRef Google Scholar
Li, X. Z., Qu, Z. R. & Xiong, R. G. (2008). Chin. J. Chem. 11, 1959–1962. Web of Science CSD CrossRef 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

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3316

https://doi.org/10.1107/S1600536810047549

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