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Acta Cryst. (2009). E65, o2345    [ doi:10.1107/S1600536809035041 ]

4-Ethoxyanilinium perchlorate

X. Fu

Abstract top

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

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.

Refinement top

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C atoms to which they are bonded, with Uiso(H) = 1.2Ueq(C).

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
[Figure 1] 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.
[Figure 2] 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
Mr = 237.64Dx = 1.497 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4042 reflections
a = 5.0663 (10) Åθ = 3.5–27.6°
b = 22.601 (5) ŵ = 0.36 mm−1
c = 9.2091 (18) ÅT = 298 K
β = 91.49 (3)°Prism, colourless
V = 1054.1 (4) Å30.20 × 0.20 × 0.20 mm
Z = 4
Data collection top
Rigaku SCXmini
diffractometer		2415 independent reflections
Radiation source: fine-focus sealed tube1795 reflections with I > 2σ(I)
graphiteRint = 0.055
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.5°
ω scansh = −6→6
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −29→29
Tmin = 0.928, Tmax = 0.93l = −11→10
9440 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0663P)2 + 0.3412P]
where P = (Fo2 + 2Fc2)/3
2415 reflections(Δ/σ)max < 0.001
136 parametersΔρmax = 0.25 e Å−3
0 restraintsΔρmin = −0.47 e Å−3
Crystal data top
C8H12NO+·ClO4−V = 1054.1 (4) Å3
Mr = 237.64Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.0663 (10) ŵ = 0.36 mm−1
b = 22.601 (5) ÅT = 298 K
c = 9.2091 (18) Å0.20 × 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)
Tmin = 0.928, Tmax = 0.93Rint = 0.055
9440 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.138Δρmax = 0.25 e Å−3
S = 1.04Δρmin = −0.47 e Å−3
2415 reflectionsAbsolute structure: ?
136 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Cl1−0.00925 (11)0.32367 (2)0.57673 (6)0.0340 (2)
N10.4143 (4)0.28041 (9)0.2574 (2)0.0385 (5)
H1A0.54580.25680.23190.058*
H1B0.26570.25950.26160.058*
H1F0.45170.29610.34410.058*
O50.2716 (4)0.31960 (9)0.5619 (2)0.0524 (5)
C70.5402 (5)0.33118 (11)0.0325 (3)0.0407 (6)
H7A0.67060.30280.02050.049*
O10.2682 (4)0.46533 (8)−0.1381 (2)0.0491 (5)
C60.3806 (5)0.32820 (10)0.1488 (3)0.0343 (5)
C30.3145 (5)0.41839 (11)−0.0489 (3)0.0379 (6)
O4−0.0842 (4)0.28604 (9)0.6953 (2)0.0508 (5)
C80.5097 (5)0.37615 (11)−0.0678 (3)0.0412 (6)
H8A0.61870.3782−0.14730.049*
O3−0.1320 (4)0.30237 (11)0.4463 (2)0.0690 (7)
C40.1528 (5)0.41445 (12)0.0693 (3)0.0481 (7)
H4B0.02100.44250.08140.058*
C50.1838 (5)0.36977 (13)0.1689 (3)0.0477 (7)
H5B0.07490.36740.24850.057*
C20.4325 (7)0.47354 (13)−0.2604 (3)0.0537 (8)
H2A0.42040.4397−0.32490.064*
H2B0.61530.4786−0.22890.064*
O2−0.0857 (5)0.38241 (9)0.6044 (3)0.0738 (7)
C10.3323 (8)0.52830 (15)−0.3361 (4)0.0750 (11)
H1C0.43670.5360−0.41960.112*
H1D0.34470.5613−0.27070.112*
H1E0.15130.5226−0.36640.112*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0336 (4)0.0366 (3)0.0317 (4)−0.0012 (2)0.0009 (2)0.0012 (2)
N10.0387 (13)0.0395 (12)0.0367 (12)−0.0015 (9)−0.0069 (9)0.0010 (9)
O50.0312 (11)0.0653 (13)0.0610 (14)−0.0010 (8)0.0053 (9)0.0067 (10)
C70.0417 (15)0.0362 (14)0.0441 (15)0.0104 (11)0.0001 (12)−0.0050 (11)
O10.0579 (13)0.0459 (11)0.0442 (12)0.0144 (9)0.0143 (9)0.0122 (8)
C60.0343 (14)0.0338 (12)0.0344 (14)−0.0023 (10)−0.0052 (10)0.0007 (10)
C30.0384 (15)0.0376 (13)0.0379 (15)0.0027 (10)0.0016 (11)0.0014 (10)
O40.0505 (13)0.0586 (12)0.0437 (11)−0.0009 (9)0.0078 (9)0.0163 (9)
C80.0474 (17)0.0410 (14)0.0357 (15)0.0051 (11)0.0103 (12)−0.0004 (11)
O30.0636 (16)0.1054 (19)0.0375 (12)−0.0328 (13)−0.0096 (10)−0.0041 (11)
C40.0420 (17)0.0505 (16)0.0523 (18)0.0139 (12)0.0129 (13)0.0090 (13)
C50.0413 (17)0.0547 (17)0.0477 (17)0.0079 (12)0.0135 (13)0.0097 (13)
C20.074 (2)0.0434 (16)0.0442 (17)0.0078 (13)0.0200 (15)0.0042 (12)
O20.0894 (18)0.0380 (12)0.0948 (18)0.0172 (11)0.0180 (14)0.0021 (11)
C10.113 (3)0.059 (2)0.055 (2)0.0190 (19)0.026 (2)0.0138 (16)
Geometric parameters (Å, °) top
Cl1—O21.408 (2)C6—C51.386 (4)
Cl1—O31.422 (2)C3—C41.382 (4)
Cl1—O51.4358 (19)C3—C81.389 (3)
Cl1—O41.4426 (19)C8—H8A0.9300
N1—C61.479 (3)C4—C51.371 (4)
N1—H1A0.8900C4—H4B0.9300
N1—H1B0.8900C5—H5B0.9300
N1—H1F0.8900C2—C11.502 (4)
C7—C61.361 (4)C2—H2A0.9700
C7—C81.379 (4)C2—H2B0.9700
C7—H7A0.9300C1—H1C0.9600
O1—C31.358 (3)C1—H1D0.9600
O1—C21.430 (3)C1—H1E0.9600
O2—Cl1—O3110.83 (16)C7—C8—C3119.4 (2)
O2—Cl1—O5110.84 (14)C7—C8—H8A120.3
O3—Cl1—O5108.09 (13)C3—C8—H8A120.3
O2—Cl1—O4109.88 (14)C5—C4—C3121.0 (2)
O3—Cl1—O4108.77 (13)C5—C4—H4B119.5
O5—Cl1—O4108.36 (12)C3—C4—H4B119.5
C6—N1—H1A109.5C4—C5—C6118.7 (3)
C6—N1—H1B109.5C4—C5—H5B120.7
H1A—N1—H1B109.5C6—C5—H5B120.7
C6—N1—H1F109.5O1—C2—C1106.0 (2)
H1A—N1—H1F109.5O1—C2—H2A110.5
H1B—N1—H1F109.5C1—C2—H2A110.5
C6—C7—C8120.3 (2)O1—C2—H2B110.5
C6—C7—H7A119.8C1—C2—H2B110.5
C8—C7—H7A119.8H2A—C2—H2B108.7
C3—O1—C2118.9 (2)C2—C1—H1C109.5
C7—C6—C5121.1 (2)C2—C1—H1D109.5
C7—C6—N1120.5 (2)H1C—C1—H1D109.5
C5—C6—N1118.4 (2)C2—C1—H1E109.5
O1—C3—C4115.5 (2)H1C—C1—H1E109.5
O1—C3—C8125.0 (2)H1D—C1—H1E109.5
C4—C3—C8119.5 (2)
C8—C7—C6—C50.4 (4)O1—C3—C4—C5−178.6 (2)
C8—C7—C6—N1−179.4 (2)C8—C3—C4—C50.6 (4)
C2—O1—C3—C4178.1 (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—C30.0 (4)N1—C6—C5—C4179.5 (2)
O1—C3—C8—C7178.6 (2)C3—O1—C2—C1179.9 (3)
C4—C3—C8—C7−0.5 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O4i0.892.143.019 (3)167
N1—H1B···O4ii0.892.132.981 (3)161
N1—H1B···Cl1ii0.892.873.567 (2)136
N1—H1F···O3iii0.892.292.889 (3)124
N1—H1F···O50.892.293.046 (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.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O4i0.892.143.019 (3)167
N1—H1B···O4ii0.892.132.981 (3)161
N1—H1B···Cl1ii0.892.873.567 (2)136
N1—H1F···O3iii0.892.292.889 (3)124
N1—H1F···O50.892.293.046 (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.
Acknowledgements top

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

references
References top

Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.

Hang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des. 9, 2026–2029

Li, X. Z., Qu, Z. R. & Xiong, R. G. (2008). Chin. J. Chem. 11, 1959–1962

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.