4-Ethoxy­anilinium perchlorate

Fu, X.

doi:10.1107/S1600536809035041

organic compounds

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Volume 65| Part 10| October 2009| Page o2345

doi:10.1107/S1600536809035041

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4-Ethoxyanilinium perchlorate

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 30 July 2009; accepted 31 August 2009; online 5 September 2009)

In the title compound, C₈H₁₂NO⁺·ClO₄⁻, there are strong hydrogen bonds between the ammonium groups and the perchlorate O atoms.

Related literature

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.

Experimental

Crystal data

C₈H₁₂NO⁺·ClO₄⁻
M_r = 237.64
Monoclinic, P 2₁ /c
a = 5.0663 (10) Å
b = 22.601 (5) Å
c = 9.2091 (18) Å
β = 91.49 (3)°
V = 1054.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.36 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 = 0.928, T_max = 0.93
9440 measured reflections
2415 independent reflections
1795 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.138
S = 1.04
2415 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.89	2.14	3.019 (3)	167
N1—H1B⋯O4ⁱⁱ	0.89	2.13	2.981 (3)	161
N1—H1B⋯Cl1ⁱⁱ	0.89	2.87	3.567 (2)	136
N1—H1F⋯O3ⁱⁱⁱ	0.89	2.29	2.889 (3)	124
N1—H1F⋯O5	0.89	2.29	3.046 (3)	143
Symmetry codes: (i) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x+1, y, 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/S1600536809035041/jh2099sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035041/jh2099Isup2.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 hybrid. 4-Ethoxyanilinium perchlorate has no dielectric disuniform from 80 K to 450 K, (m.p. 459–460 K).

The asymmetric unit of the title compound is composed of cationic (C₂H₅O—C₆H₄—NH₃⁺) and anionic (ClO₄^-)(Fig 1). The average Cl—O bond distances and O—Cl—O bond angles are 1.427 (2)Å and 109.46 (14)°, respectively, confirming a tetrahedral configuration. The strong N—H···O hydrogen bonding (Table 1) (N1—H···O3 2.889 (3) Å) make great contribution to the stability of the crystal structure and link the cations and anions to chains along the a axis (Fig 2).

Related literature top

For background to dielectric–ferroelectric

materials, see: Hang et al. (2009); Li et al. (2008)

Experimental top

Single crystals of 4-ethoxyaniliniumperchlorate are prepared by slow evaporation at room temperature of an ethanol solution of 4-ethoxybenzenamine and perchloric 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 the 30% probability level, and all H atoms have been omitted for clarity.
	Fig. 2. A view of the packing of the title compound, stacking along the a axis. Dashed lines indicate hydrogen bonds.

4-Ethoxyanilinium perchlorate top

Crystal data top

C₈H₁₂NO⁺·ClO₄⁻	F(000) = 496
M_r = 237.64	D_x = 1.497 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4042 reflections
a = 5.0663 (10) Å	θ = 3.5–27.6°
b = 22.601 (5) Å	µ = 0.36 mm⁻¹
c = 9.2091 (18) Å	T = 298 K
β = 91.49 (3)°	Prism, colourless
V = 1054.1 (4) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2415 independent reflections
Radiation source: fine-focus sealed tube	1795 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.5°
ω scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −29→29
T_min = 0.928, T_max = 0.93	l = −11→10
9440 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0663P)² + 0.3412P] where P = (F_o² + 2F_c²)/3
2415 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

C₈H₁₂NO⁺·ClO₄⁻	V = 1054.1 (4) Å³
M_r = 237.64	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.0663 (10) Å	µ = 0.36 mm⁻¹
b = 22.601 (5) Å	T = 298 K
c = 9.2091 (18) Å	0.20 × 0.20 × 0.20 mm
β = 91.49 (3)°

Data collection top

Rigaku SCXmini diffractometer	2415 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1795 reflections with I > 2σ(I)
T_min = 0.928, T_max = 0.93	R_int = 0.055
9440 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 1.04	Δρ_max = 0.25 e Å⁻³
2415 reflections	Δρ_min = −0.47 e Å⁻³
136 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	−0.00925 (11)	0.32367 (2)	0.57673 (6)	0.0340 (2)
N1	0.4143 (4)	0.28041 (9)	0.2574 (2)	0.0385 (5)
H1A	0.5458	0.2568	0.2319	0.058*
H1B	0.2657	0.2595	0.2616	0.058*
H1F	0.4517	0.2961	0.3441	0.058*
O5	0.2716 (4)	0.31960 (9)	0.5619 (2)	0.0524 (5)
C7	0.5402 (5)	0.33118 (11)	0.0325 (3)	0.0407 (6)
H7A	0.6706	0.3028	0.0205	0.049*
O1	0.2682 (4)	0.46533 (8)	−0.1381 (2)	0.0491 (5)
C6	0.3806 (5)	0.32820 (10)	0.1488 (3)	0.0343 (5)
C3	0.3145 (5)	0.41839 (11)	−0.0489 (3)	0.0379 (6)
O4	−0.0842 (4)	0.28604 (9)	0.6953 (2)	0.0508 (5)
C8	0.5097 (5)	0.37615 (11)	−0.0678 (3)	0.0412 (6)
H8A	0.6187	0.3782	−0.1473	0.049*
O3	−0.1320 (4)	0.30237 (11)	0.4463 (2)	0.0690 (7)
C4	0.1528 (5)	0.41445 (12)	0.0693 (3)	0.0481 (7)
H4B	0.0210	0.4425	0.0814	0.058*
C5	0.1838 (5)	0.36977 (13)	0.1689 (3)	0.0477 (7)
H5B	0.0749	0.3674	0.2485	0.057*
C2	0.4325 (7)	0.47354 (13)	−0.2604 (3)	0.0537 (8)
H2A	0.4204	0.4397	−0.3249	0.064*
H2B	0.6153	0.4786	−0.2289	0.064*
O2	−0.0857 (5)	0.38241 (9)	0.6044 (3)	0.0738 (7)
C1	0.3323 (8)	0.52830 (15)	−0.3361 (4)	0.0750 (11)
H1C	0.4367	0.5360	−0.4196	0.112*
H1D	0.3447	0.5613	−0.2707	0.112*
H1E	0.1513	0.5226	−0.3664	0.112*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0336 (4)	0.0366 (3)	0.0317 (4)	−0.0012 (2)	0.0009 (2)	0.0012 (2)
N1	0.0387 (13)	0.0395 (12)	0.0367 (12)	−0.0015 (9)	−0.0069 (9)	0.0010 (9)
O5	0.0312 (11)	0.0653 (13)	0.0610 (14)	−0.0010 (8)	0.0053 (9)	0.0067 (10)
C7	0.0417 (15)	0.0362 (14)	0.0441 (15)	0.0104 (11)	0.0001 (12)	−0.0050 (11)
O1	0.0579 (13)	0.0459 (11)	0.0442 (12)	0.0144 (9)	0.0143 (9)	0.0122 (8)
C6	0.0343 (14)	0.0338 (12)	0.0344 (14)	−0.0023 (10)	−0.0052 (10)	0.0007 (10)
C3	0.0384 (15)	0.0376 (13)	0.0379 (15)	0.0027 (10)	0.0016 (11)	0.0014 (10)
O4	0.0505 (13)	0.0586 (12)	0.0437 (11)	−0.0009 (9)	0.0078 (9)	0.0163 (9)
C8	0.0474 (17)	0.0410 (14)	0.0357 (15)	0.0051 (11)	0.0103 (12)	−0.0004 (11)
O3	0.0636 (16)	0.1054 (19)	0.0375 (12)	−0.0328 (13)	−0.0096 (10)	−0.0041 (11)
C4	0.0420 (17)	0.0505 (16)	0.0523 (18)	0.0139 (12)	0.0129 (13)	0.0090 (13)
C5	0.0413 (17)	0.0547 (17)	0.0477 (17)	0.0079 (12)	0.0135 (13)	0.0097 (13)
C2	0.074 (2)	0.0434 (16)	0.0442 (17)	0.0078 (13)	0.0200 (15)	0.0042 (12)
O2	0.0894 (18)	0.0380 (12)	0.0948 (18)	0.0172 (11)	0.0180 (14)	0.0021 (11)
C1	0.113 (3)	0.059 (2)	0.055 (2)	0.0190 (19)	0.026 (2)	0.0138 (16)

Geometric parameters (Å, º) top

Cl1—O2	1.408 (2)	C6—C5	1.386 (4)
Cl1—O3	1.422 (2)	C3—C4	1.382 (4)
Cl1—O5	1.4358 (19)	C3—C8	1.389 (3)
Cl1—O4	1.4426 (19)	C8—H8A	0.9300
N1—C6	1.479 (3)	C4—C5	1.371 (4)
N1—H1A	0.8900	C4—H4B	0.9300
N1—H1B	0.8900	C5—H5B	0.9300
N1—H1F	0.8900	C2—C1	1.502 (4)
C7—C6	1.361 (4)	C2—H2A	0.9700
C7—C8	1.379 (4)	C2—H2B	0.9700
C7—H7A	0.9300	C1—H1C	0.9600
O1—C3	1.358 (3)	C1—H1D	0.9600
O1—C2	1.430 (3)	C1—H1E	0.9600

O2—Cl1—O3	110.83 (16)	C7—C8—C3	119.4 (2)
O2—Cl1—O5	110.84 (14)	C7—C8—H8A	120.3
O3—Cl1—O5	108.09 (13)	C3—C8—H8A	120.3
O2—Cl1—O4	109.88 (14)	C5—C4—C3	121.0 (2)
O3—Cl1—O4	108.77 (13)	C5—C4—H4B	119.5
O5—Cl1—O4	108.36 (12)	C3—C4—H4B	119.5
C6—N1—H1A	109.5	C4—C5—C6	118.7 (3)
C6—N1—H1B	109.5	C4—C5—H5B	120.7
H1A—N1—H1B	109.5	C6—C5—H5B	120.7
C6—N1—H1F	109.5	O1—C2—C1	106.0 (2)
H1A—N1—H1F	109.5	O1—C2—H2A	110.5
H1B—N1—H1F	109.5	C1—C2—H2A	110.5
C6—C7—C8	120.3 (2)	O1—C2—H2B	110.5
C6—C7—H7A	119.8	C1—C2—H2B	110.5
C8—C7—H7A	119.8	H2A—C2—H2B	108.7
C3—O1—C2	118.9 (2)	C2—C1—H1C	109.5
C7—C6—C5	121.1 (2)	C2—C1—H1D	109.5
C7—C6—N1	120.5 (2)	H1C—C1—H1D	109.5
C5—C6—N1	118.4 (2)	C2—C1—H1E	109.5
O1—C3—C4	115.5 (2)	H1C—C1—H1E	109.5
O1—C3—C8	125.0 (2)	H1D—C1—H1E	109.5
C4—C3—C8	119.5 (2)

C8—C7—C6—C5	0.4 (4)	O1—C3—C4—C5	−178.6 (2)
C8—C7—C6—N1	−179.4 (2)	C8—C3—C4—C5	0.6 (4)
C2—O1—C3—C4	178.1 (3)	C3—C4—C5—C6	−0.2 (4)
C2—O1—C3—C8	−1.1 (4)	C7—C6—C5—C4	−0.3 (4)
C6—C7—C8—C3	0.0 (4)	N1—C6—C5—C4	179.5 (2)
O1—C3—C8—C7	178.6 (2)	C3—O1—C2—C1	179.9 (3)
C4—C3—C8—C7	−0.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.89	2.14	3.019 (3)	167
N1—H1B···O4ⁱⁱ	0.89	2.13	2.981 (3)	161
N1—H1B···Cl1ⁱⁱ	0.89	2.87	3.567 (2)	136
N1—H1F···O3ⁱⁱⁱ	0.89	2.29	2.889 (3)	124
N1—H1F···O5	0.89	2.29	3.046 (3)	143

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂NO⁺·ClO₄⁻
M_r	237.64
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	5.0663 (10), 22.601 (5), 9.2091 (18)
β (°)	91.49 (3)
V (Å³)	1054.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
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	0.928, 0.93
No. of measured, independent and observed [I > 2σ(I)] reflections	9440, 2415, 1795
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.138, 1.04
No. of reflections	2415
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.47

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···O4ⁱ	0.89	2.14	3.019 (3)	167.3
N1—H1B···O4ⁱⁱ	0.89	2.13	2.981 (3)	160.8
N1—H1B···Cl1ⁱⁱ	0.89	2.87	3.567 (2)	136.0
N1—H1F···O3ⁱⁱⁱ	0.89	2.29	2.889 (3)	124.4
N1—H1F···O5	0.89	2.29	3.046 (3)	143.0

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

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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