organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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4-Eth­­oxy­anilinium chloride

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 ππ 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[Li, X. Z., Qu, Z. R. & Xiong, R. G. (2008). Chin. J. Chem. 11, 1959-1962.]); Ye et al. (2009[Ye, H. Y., Fu, D. W., Zhang, Y., Zhang, W., Xiong, R. G. & Huang, S. P. (2009). J. Am. Chem. Soc. 131, 42-43.]); Zhang et al. (2009[Zhang, W., Chen, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. D. (2009). J. Am. Chem. Soc. 131, 12544-12545.]). For similar structures, see: Fu (2009[Fu, X. (2009). Acta Cryst. E65, o2345.]); Jiang et al. (1996[Jiang, Z.-T., Liesegang, J., James, B. D., Skelton, B. W. & White, A. H. (1996). J. Phys. Chem. Solids, 57, 397-404.]); Zhao (2009[Zhao, M. M. (2009). Acta Cryst. E65, o2378.]).

[Scheme 1]

Experimental

Crystal data
  • C8H12NO+·Cl

  • Mr = 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.879, Tmax = 0.931

  • 17046 measured reflections

  • 2116 independent reflections

  • 1655 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.27 e Å−3

  • Δρmin = −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 DA 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—H4ACg1iii 0.93 2.91 3.654 (2) 138
C7—H7BCg1iv 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


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.

Refinement top

Positional parameters of all the H atoms for C atoms were calculated geometrically and were allowed to ride on the C atoms to which they are bonded, with Uiso(H) = 1.2Ueq(C). H atoms bonded to nitrogen atom were found in the difference maps and refined freely.

Structure description 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).

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
[Figure 1] Fig. 1. Molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] 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+·ClF(000) = 736
Mr = 173.64Dx = 1.245 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 7266 reflections
a = 11.422 (2) Åθ = 3.0–27.7°
b = 7.0890 (14) ŵ = 0.36 mm1
c = 22.887 (5) ÅT = 298 K
V = 1853.2 (6) Å3Prism, colourless
Z = 80.40 × 0.30 × 0.20 mm
Data collection top
Rigaku SCXmini
diffractometer
2116 independent reflections
Radiation source: fine-focus sealed tube1655 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.5°
ω scansh = 1414
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 99
Tmin = 0.879, Tmax = 0.931l = 2929
17046 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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0383P)2 + 0.7382P]
where P = (Fo2 + 2Fc2)/3
2116 reflections(Δ/σ)max < 0.001
112 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C8H12NO+·ClV = 1853.2 (6) Å3
Mr = 173.64Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 11.422 (2) ŵ = 0.36 mm1
b = 7.0890 (14) ÅT = 298 K
c = 22.887 (5) Å0.40 × 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)
Tmin = 0.879, Tmax = 0.931Rint = 0.044
17046 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.27 e Å3
2116 reflectionsΔρmin = 0.23 e Å3
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
xyzUiso*/Ueq
Cl10.36897 (4)0.14153 (8)0.73645 (2)0.0565 (2)
C30.39597 (14)0.6120 (3)0.64180 (8)0.0382 (4)
O10.39659 (12)0.76724 (19)0.46863 (5)0.0495 (4)
C60.39549 (15)0.7056 (3)0.52510 (8)0.0384 (4)
N10.39087 (15)0.5668 (3)0.70418 (7)0.0456 (4)
H1D0.323 (2)0.619 (3)0.7215 (10)0.072 (7)*
H1C0.451 (2)0.614 (4)0.7224 (11)0.081 (8)*
H1B0.387 (2)0.442 (5)0.7096 (12)0.084 (9)*
C70.34271 (19)0.6523 (3)0.42485 (8)0.0509 (5)
H7A0.26010.63650.43330.061*
H7B0.37910.52870.42400.061*
C50.34210 (18)0.5419 (3)0.54364 (9)0.0511 (5)
H5A0.30600.46260.51680.061*
C40.34242 (17)0.4958 (3)0.60251 (9)0.0507 (5)
H4A0.30610.38580.61520.061*
C10.45119 (17)0.8200 (3)0.56533 (8)0.0468 (5)
H1A0.48900.92890.55280.056*
C80.3583 (2)0.7490 (4)0.36708 (9)0.0651 (6)
H8A0.32260.67480.33690.098*
H8B0.44030.76310.35900.098*
H8C0.32200.87110.36840.098*
C20.45113 (17)0.7739 (3)0.62369 (8)0.0456 (5)
H2A0.48820.85170.65070.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0385 (3)0.0715 (4)0.0596 (3)0.0036 (2)0.0107 (2)0.0117 (3)
C30.0278 (8)0.0501 (11)0.0366 (9)0.0017 (7)0.0005 (7)0.0041 (8)
O10.0676 (9)0.0474 (8)0.0334 (7)0.0125 (7)0.0020 (6)0.0020 (6)
C60.0387 (9)0.0406 (10)0.0359 (9)0.0017 (8)0.0015 (7)0.0015 (8)
N10.0329 (9)0.0653 (13)0.0387 (9)0.0010 (8)0.0008 (7)0.0082 (9)
C70.0576 (12)0.0565 (12)0.0387 (10)0.0041 (10)0.0017 (8)0.0069 (9)
C50.0571 (12)0.0524 (12)0.0438 (11)0.0209 (10)0.0067 (9)0.0004 (9)
C40.0510 (11)0.0532 (12)0.0477 (11)0.0204 (9)0.0022 (8)0.0079 (10)
C10.0583 (12)0.0393 (10)0.0428 (10)0.0122 (9)0.0003 (9)0.0029 (8)
C80.0884 (17)0.0686 (15)0.0382 (11)0.0068 (13)0.0028 (10)0.0032 (11)
C20.0511 (11)0.0438 (11)0.0418 (10)0.0087 (9)0.0053 (8)0.0045 (8)
Geometric parameters (Å, º) top
C3—C41.364 (3)C7—H7A0.9700
C3—C21.373 (3)C7—H7B0.9700
C3—N11.464 (2)C5—C41.386 (3)
O1—C61.364 (2)C5—H5A0.9300
O1—C71.431 (2)C4—H4A0.9300
C6—C51.378 (3)C1—C21.375 (3)
C6—C11.382 (3)C1—H1A0.9300
N1—H1D0.94 (2)C8—H8A0.9600
N1—H1C0.87 (3)C8—H8B0.9600
N1—H1B0.90 (3)C8—H8C0.9600
C7—C81.500 (3)C2—H2A0.9300
C4—C3—C2120.75 (17)C6—C5—C4119.76 (18)
C4—C3—N1119.51 (18)C6—C5—H5A120.1
C2—C3—N1119.70 (17)C4—C5—H5A120.1
C6—O1—C7118.49 (15)C3—C4—C5119.98 (18)
O1—C6—C5124.45 (17)C3—C4—H4A120.0
O1—C6—C1116.03 (16)C5—C4—H4A120.0
C5—C6—C1119.51 (17)C2—C1—C6120.50 (17)
C3—N1—H1D110.9 (14)C2—C1—H1A119.7
C3—N1—H1C110.6 (17)C6—C1—H1A119.7
H1D—N1—H1C107 (2)C7—C8—H8A109.5
C3—N1—H1B110.7 (18)C7—C8—H8B109.5
H1D—N1—H1B107 (2)H8A—C8—H8B109.5
H1C—N1—H1B111 (2)C7—C8—H8C109.5
O1—C7—C8107.79 (18)H8A—C8—H8C109.5
O1—C7—H7A110.1H8B—C8—H8C109.5
C8—C7—H7A110.1C3—C2—C1119.47 (17)
O1—C7—H7B110.1C3—C2—H2A120.3
C8—C7—H7B110.1C1—C2—H2A120.3
H7A—C7—H7B108.5
C7—O1—C6—C52.4 (3)C6—C5—C4—C30.3 (3)
C7—O1—C6—C1178.51 (17)O1—C6—C1—C2177.53 (18)
C6—O1—C7—C8178.74 (17)C5—C6—C1—C21.6 (3)
O1—C6—C5—C4177.57 (19)C4—C3—C2—C10.7 (3)
C1—C6—C5—C41.5 (3)N1—C3—C2—C1177.14 (18)
C2—C3—C4—C50.8 (3)C6—C1—C2—C30.5 (3)
N1—C3—C4—C5177.04 (18)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1D···Cl1i0.94 (2)2.23 (3)3.104 (2)154 (2)
N1—H1C···Cl1ii0.87 (3)2.27 (3)3.107 (2)161 (2)
N1—H1B···Cl10.90 (3)2.23 (3)3.114 (2)172 (2)
C4—H4A···Cg1iii0.932.913.654 (2)138
C7—H7B···Cg1iv0.972.893.710 (2)143
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x+1, y+1/2, z+3/2; (iii) x, y3/2, z1/2; (iv) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC8H12NO+·Cl
Mr173.64
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)298
a, b, c (Å)11.422 (2), 7.0890 (14), 22.887 (5)
V3)1853.2 (6)
Z8
Radiation typeMo Kα
µ (mm1)0.36
Crystal size (mm)0.40 × 0.30 × 0.20
Data collection
DiffractometerRigaku SCXmini
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.879, 0.931
No. of measured, independent and
observed [I > 2σ(I)] reflections
17046, 2116, 1655
Rint0.044
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.106, 1.08
No. of reflections2116
No. of parameters112
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1D···Cl1i0.94 (2)2.23 (3)3.104 (2)154 (2)
N1—H1C···Cl1ii0.87 (3)2.27 (3)3.107 (2)161 (2)
N1—H1B···Cl10.90 (3)2.23 (3)3.114 (2)172 (2)
C4—H4A···Cg1iii0.932.913.654 (2)137.90
C7—H7B···Cg1iv0.972.893.710 (2)142.66
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x+1, y+1/2, z+3/2; (iii) x, y3/2, z1/2; (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

First citationFu, X. (2009). Acta Cryst. E65, o2345.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationJiang, Z.-T., Liesegang, J., James, B. D., Skelton, B. W. & White, A. H. (1996). J. Phys. Chem. Solids, 57, 397–404.  Google Scholar
First citationLi, X. Z., Qu, Z. R. & Xiong, R. G. (2008). Chin. J. Chem. 11, 1959–1962.  Web of Science CSD CrossRef Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationYe, H. Y., Fu, D. W., Zhang, Y., Zhang, W., Xiong, R. G. & Huang, S. P. (2009). J. Am. Chem. Soc. 131, 42–43.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationZhang, W., Chen, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. D. (2009). J. Am. Chem. Soc. 131, 12544–12545.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationZhao, M. M. (2009). Acta Cryst. E65, o2378.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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