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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1461.
Published online 2010 May 26. doi:  10.1107/S1600536810018404
PMCID: PMC2979371

4-Ethoxy­anilinium hexa­fluoro­phosphate monohydrate

Abstract

In the crystal of the title compound, C8H12NO+·PF6 ·H2O, inter­molecular N—H(...)F, N—H(...)O and O—H(...)F hydrogen bonds link the mol­ecules into chains along the c axis and C—H(...)π contacts further stabilize the structure. The F atoms of one of the hexa­fluoro­phosphate anions are disordered over two sets of sites with site-occupancy factors of 0.27 (3) and 0.73 (3).

Related literature

For related structures, see: Fu (2009a [triangle],b [triangle]). The title compound was studied as part of our search for ferroelectric compounds, which usually have a phase transition.For background to phase transition materials, see: Li et al. (2008 [triangle]); Zhang et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1461-scheme1.jpg

Experimental

Crystal data

  • C8H12NO+·PF6 ·H2O
  • M r = 301.17
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1461-efi1.jpg
  • a = 17.498 (4) Å
  • b = 5.1236 (10) Å
  • c = 14.793 (3) Å
  • β = 111.68 (3)°
  • V = 1232.4 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.29 mm−1
  • T = 298 K
  • 0.4 × 0.3 × 0.2 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.900, T max = 0.943
  • 12124 measured reflections
  • 2820 independent reflections
  • 1890 reflections with I > 2σ(I)
  • R int = 0.054

Refinement

  • R[F 2 > 2σ(F 2)] = 0.059
  • wR(F 2) = 0.164
  • S = 1.05
  • 2820 reflections
  • 226 parameters
  • 235 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.45 e Å−3
  • Δρmin = −0.48 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536810018404/zq2040sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018404/zq2040Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

As a continuation of our study of dielectric-ferroelectric materials, including organic ligands (Li et al., 2008), metal-organic coordination compounds (Zhang et al., 2009), and organic-inorganic hybrids, we studied the dielectric properties of the title compound. Unfortunately, there was no distinct anomaly observed from 93 to 350 K. In this article, the crystal structure of this compound is presented. The crystal structures of 4-ethoxyanilinium together with other anions are known (Fu, 2009a,b).

The asymmetric unit of the crystal structure consists of one almost coplanar protonated 4-ethoxyanilinium cation with the C2—C1—O1—C7 and C1—O1—C7—C8 torsion angles of 172.9 (3) and 177.4 (3)°, respectively, one hexafluorophosphate anion for which the F atoms are disordered over two sets of positions with site-occupancy factors of 0.27 (3) and 0.73 (3), and one water molecule (Fig.1). In the crystal structure, several intermolecular N—H···F and O—H···F hydrogen bonds link all species to chains along the c axis (Fig.2). In addition, C—H···π interactions further stabilize the crystal structure.

Experimental

1.37 g (10 mmol) of 4-Ethoxybenzenamine was firstly dissolved in 50 ml ethanol, to which hexafluorophosphoric acid (70%, w/w) was then added until the solution becomes acidic under stirring. Single crystals of the title compond were prepared by slow evaporation at room temperature of the acidic solution after 3 days.

Refinement

The water H atoms were found in Fourier difference maps and were refined freely. Positional parameters of all other H atoms were calculated geometrically and allowed to ride on the C and N atoms to which they are bonded, with Uiso(H) = 1.2Ueq(C,N). The F atoms of the hexafluorophosphate anion are disordered in two orientations with site-occupancy factors of 0.73 (3) and 0.27 (3).

Figures

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 c axis. Dashed lines indicate hydrogen bonds.

Crystal data

C8H12NO+·PF6·H2OF(000) = 616
Mr = 301.17Dx = 1.623 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4774 reflections
a = 17.498 (4) Åθ = 3.1–27.7°
b = 5.1236 (10) ŵ = 0.29 mm1
c = 14.793 (3) ÅT = 298 K
β = 111.68 (3)°Prism, colourless
V = 1232.4 (4) Å30.4 × 0.3 × 0.2 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer2820 independent reflections
Radiation source: fine-focus sealed tube1890 reflections with I > 2σ(I)
graphiteRint = 0.054
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = −22→22
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −6→6
Tmin = 0.900, Tmax = 0.943l = −19→19
12124 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164H atoms treated by a mixture of independent and constrained refinement
S = 1.05w = 1/[σ2(Fo2) + (0.0764P)2 + 0.6523P] where P = (Fo2 + 2Fc2)/3
2820 reflections(Δ/σ)max = 0.003
226 parametersΔρmax = 0.45 e Å3
235 restraintsΔρmin = −0.48 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/UeqOcc. (<1)
N10.15275 (14)0.3564 (5)0.42609 (17)0.0414 (6)
H1A0.14270.48600.38320.050*
H1B0.13040.39360.46970.050*
H1C0.13110.20920.39530.050*
O10.49349 (12)0.2376 (5)0.60339 (18)0.0624 (7)
C10.40946 (18)0.2556 (6)0.5644 (2)0.0458 (7)
C40.24232 (16)0.3242 (5)0.47587 (19)0.0366 (6)
C30.29478 (19)0.4801 (6)0.4497 (2)0.0515 (8)
H3A0.27390.60740.40210.062*
C50.27196 (18)0.1368 (7)0.5450 (2)0.0497 (8)
H5A0.23600.03330.56250.060*
C60.35635 (19)0.1007 (7)0.5895 (2)0.0558 (9)
H6A0.3769−0.02860.63640.067*
C20.37808 (19)0.4465 (7)0.4943 (3)0.0561 (9)
H2A0.41370.55270.47730.067*
C80.6217 (2)0.0478 (10)0.6954 (3)0.0783 (12)
H8A0.6483−0.09350.73800.117*
H8B0.64050.21080.72790.117*
H8C0.63470.03960.63780.117*
C70.5304 (2)0.0266 (8)0.6678 (3)0.0632 (10)
H7A0.5107−0.13900.63590.076*
H7B0.51640.03720.72540.076*
O1W0.08195 (12)0.8613 (5)0.44539 (16)0.0473 (5)
H1WB0.0467 (16)0.843 (9)0.3908 (11)0.086 (15)*
H1WA0.071 (2)0.856 (9)0.4948 (14)0.086 (15)*
P10.11668 (4)0.96937 (15)0.18642 (5)0.0396 (3)
F30.0519 (7)1.103 (3)0.2240 (8)0.064 (2)0.73 (3)
F50.1765 (9)0.833 (3)0.1430 (10)0.065 (2)0.73 (3)
F40.0451 (7)0.782 (2)0.1246 (9)0.072 (2)0.73 (3)
F10.0911 (6)1.1714 (17)0.0948 (6)0.0618 (15)0.73 (3)
F20.1410 (8)0.783 (2)0.2777 (7)0.086 (2)0.73 (3)
F60.1869 (6)1.169 (2)0.2477 (7)0.0704 (18)0.73 (3)
F6'0.1908 (13)1.081 (6)0.2715 (16)0.066 (4)0.27 (3)
F4'0.0396 (15)0.830 (6)0.1040 (17)0.053 (4)0.27 (3)
F2'0.1153 (17)0.730 (5)0.256 (2)0.070 (4)0.27 (3)
F3'0.0594 (18)1.160 (7)0.2229 (19)0.056 (4)0.27 (3)
F5'0.184 (3)0.796 (8)0.164 (3)0.062 (4)0.27 (3)
F1'0.1166 (18)1.168 (5)0.1154 (19)0.075 (4)0.27 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0383 (13)0.0429 (13)0.0428 (13)−0.0011 (11)0.0147 (11)−0.0042 (11)
O10.0333 (11)0.0710 (15)0.0758 (16)0.0024 (11)0.0119 (11)0.0209 (13)
C10.0335 (14)0.0500 (17)0.0516 (17)0.0022 (13)0.0128 (13)0.0029 (14)
C40.0337 (14)0.0378 (15)0.0383 (14)−0.0002 (12)0.0132 (12)−0.0041 (12)
C30.0425 (16)0.0509 (18)0.0603 (19)0.0031 (14)0.0181 (15)0.0191 (16)
C50.0406 (17)0.0564 (19)0.0508 (17)−0.0050 (15)0.0153 (14)0.0124 (15)
C60.0443 (18)0.060 (2)0.0577 (19)0.0035 (16)0.0128 (15)0.0216 (17)
C20.0425 (17)0.0553 (19)0.073 (2)−0.0024 (15)0.0237 (16)0.0172 (17)
C80.045 (2)0.108 (3)0.071 (3)0.018 (2)0.0099 (19)0.020 (2)
C70.0450 (18)0.073 (2)0.064 (2)0.0094 (18)0.0113 (16)0.0147 (19)
O1W0.0395 (12)0.0532 (13)0.0448 (13)−0.0011 (10)0.0105 (11)0.0014 (11)
P10.0366 (4)0.0479 (5)0.0323 (4)0.0065 (3)0.0103 (3)−0.0011 (3)
F30.055 (3)0.082 (6)0.065 (3)0.018 (3)0.034 (2)−0.005 (3)
F50.055 (3)0.086 (4)0.054 (5)0.022 (2)0.019 (4)−0.012 (3)
F40.068 (3)0.074 (4)0.071 (5)−0.032 (3)0.022 (3)−0.011 (3)
F10.054 (4)0.073 (2)0.054 (3)0.014 (3)0.014 (2)0.026 (2)
F20.092 (6)0.101 (5)0.054 (3)0.027 (4)0.015 (3)0.036 (3)
F60.057 (2)0.078 (4)0.066 (4)−0.013 (3)0.011 (2)−0.025 (3)
F6'0.042 (4)0.089 (9)0.054 (7)0.011 (6)0.004 (5)−0.032 (6)
F4'0.044 (5)0.075 (8)0.040 (6)−0.004 (5)0.015 (4)−0.013 (6)
F2'0.074 (10)0.075 (7)0.060 (8)0.017 (6)0.025 (6)0.029 (6)
F3'0.048 (6)0.066 (9)0.042 (6)0.022 (6)0.003 (5)−0.007 (5)
F5'0.050 (6)0.087 (10)0.049 (10)0.018 (6)0.018 (7)−0.017 (7)
F1'0.065 (10)0.081 (6)0.066 (7)−0.007 (7)0.010 (6)0.035 (6)

Geometric parameters (Å, °)

N1—C41.474 (4)C8—H8B0.9600
N1—H1A0.8900C8—H8C0.9600
N1—H1B0.8900C7—H7A0.9700
N1—H1C0.8900C7—H7B0.9700
O1—C11.370 (4)O1W—H1WB0.821 (10)
O1—C71.428 (4)O1W—H1WA0.82 (3)
C1—C61.373 (4)P1—F1'1.46 (2)
C1—C21.384 (4)P1—F6'1.546 (18)
C4—C51.358 (4)P1—F41.575 (10)
C4—C31.376 (4)P1—F51.578 (13)
C3—C21.371 (4)P1—F21.580 (8)
C3—H3A0.9300P1—F31.590 (11)
C5—C61.389 (4)P1—F61.598 (7)
C5—H5A0.9300P1—F5'1.60 (4)
C6—H6A0.9300P1—F2'1.61 (2)
C2—H2A0.9300P1—F4'1.61 (3)
C8—C71.500 (5)P1—F3'1.63 (3)
C8—H8A0.9600P1—F11.632 (7)
C4—N1—H1A109.5F6'—P1—F392.8 (9)
C4—N1—H1B109.4F4—P1—F387.1 (6)
H1A—N1—H1B109.5F5—P1—F3176.5 (7)
C4—N1—H1C109.5F2—P1—F387.9 (6)
H1A—N1—H1C109.5F1'—P1—F676.1 (9)
H1B—N1—H1C109.5F4—P1—F6177.8 (5)
C1—O1—C7118.8 (3)F5—P1—F691.6 (8)
O1—C1—C6125.2 (3)F2—P1—F689.7 (3)
O1—C1—C2115.5 (3)F3—P1—F691.4 (6)
C6—C1—C2119.4 (3)F1'—P1—F5'92.5 (15)
C5—C4—C3120.9 (3)F6'—P1—F5'85.2 (18)
C5—C4—N1119.7 (3)F4—P1—F5'91.5 (18)
C3—C4—N1119.4 (3)F2—P1—F5'81.6 (13)
C2—C3—C4119.5 (3)F3—P1—F5'169.4 (13)
C2—C3—H3A120.2F6—P1—F5'90.3 (18)
C4—C3—H3A120.2F1'—P1—F2'174.5 (15)
C4—C5—C6119.6 (3)F6'—P1—F2'88.1 (9)
C4—C5—H5A120.2F4—P1—F2'73.3 (9)
C6—C5—H5A120.2F5—P1—F2'95.5 (12)
C1—C6—C5120.1 (3)F3—P1—F2'85.4 (12)
C1—C6—H6A119.9F6—P1—F2'108.2 (8)
C5—C6—H6A119.9F5'—P1—F2'84.1 (17)
C3—C2—C1120.4 (3)F1'—P1—F4'89.3 (11)
C3—C2—H2A119.8F6'—P1—F4'174.7 (12)
C1—C2—H2A119.8F5—P1—F4'89.5 (10)
C7—C8—H8A109.5F2—P1—F4'105.3 (9)
C7—C8—H8B109.5F3—P1—F4'87.1 (10)
H8A—C8—H8B109.5F6—P1—F4'164.9 (9)
C7—C8—H8C109.5F5'—P1—F4'94.0 (19)
H8A—C8—H8C109.5F2'—P1—F4'86.7 (10)
H8B—C8—H8C109.5F1'—P1—F3'89.0 (15)
O1—C7—C8107.4 (3)F6'—P1—F3'86.7 (13)
O1—C7—H7A110.2F4—P1—F3'96.0 (12)
C8—C7—H7A110.2F5—P1—F3'169.1 (14)
O1—C7—H7B110.2F2—P1—F3'94.9 (12)
C8—C7—H7B110.2F6—P1—F3'82.3 (12)
H7A—C7—H7B108.5F5'—P1—F3'171.8 (19)
H1WB—O1W—H1WA122 (2)F2'—P1—F3'94.9 (17)
F1'—P1—F6'96.0 (11)F4'—P1—F3'94.1 (14)
F1'—P1—F4102.6 (9)F6'—P1—F1109.3 (11)
F6'—P1—F4161.3 (10)F4—P1—F189.4 (4)
F1'—P1—F580.8 (12)F5—P1—F187.8 (5)
F6'—P1—F590.7 (10)F2—P1—F1177.8 (5)
F4—P1—F589.9 (8)F3—P1—F190.3 (5)
F1'—P1—F2164.6 (8)F6—P1—F189.0 (3)
F6'—P1—F269.4 (10)F5'—P1—F1100.2 (13)
F4—P1—F291.9 (4)F2'—P1—F1162.3 (8)
F5—P1—F294.0 (6)F4'—P1—F175.9 (10)
F1'—P1—F398.1 (12)F3'—P1—F183.1 (11)
C7—O1—C1—C66.9 (5)C2—C1—C6—C5−0.3 (5)
C7—O1—C1—C2−172.9 (3)C4—C5—C6—C10.7 (5)
C5—C4—C3—C2−0.2 (5)C4—C3—C2—C10.7 (5)
N1—C4—C3—C2−178.5 (3)O1—C1—C2—C3179.3 (3)
C3—C4—C5—C6−0.5 (5)C6—C1—C2—C3−0.4 (5)
N1—C4—C5—C6177.8 (3)C1—O1—C7—C8177.4 (3)
O1—C1—C6—C5180.0 (3)

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1A···F2'0.892.163.03 (2)167
N1—H1A···F20.892.173.049 (10)169
N1—H1B···F1i0.892.223.066 (8)158
N1—H1B···F1'i0.892.283.09 (3)152
N1—H1C···O1Wii0.892.222.883 (3)131
N1—H1C···F3ii0.892.463.137 (12)133
N1—H1C···F3'ii0.892.403.01 (3)126
N1—H1C···F6'ii0.892.512.96 (2)112
O1W—H1WB···F3'iii0.82 (1)2.20 (3)2.97 (3)156 (4)
O1W—H1WB···F3iii0.82 (1)2.28 (3)3.030 (12)152 (4)
O1W—H1WA···F4i0.82 (3)2.24 (2)3.040 (12)164 (4)
O1W—H1WA···F4'i0.82 (3)2.11 (3)2.88 (2)155 (4)
O1W—H1WA···F5i0.82 (3)2.48 (4)2.951 (16)117 (3)
C8—H8C···Cg1iv0.963.164.023 (5)150

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZQ2040).

References

  • Ferguson, G. (1999). PRPKAPPA University of Guelph, Canada.
  • Fu, X. (2009a). Acta Cryst. E65, o2345. [PMC free article] [PubMed]
  • Fu, X. (2009b). Acta Cryst. E65, o2520. [PMC free article] [PubMed]
  • 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. [PubMed]
  • Zhang, W., Chen, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. D. (2009). J. Am. Chem. Soc.131, 12544–12545. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography