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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o1920.
Published online 2010 July 3. doi:  10.1107/S1600536810025365
PMCID: PMC3007241

4-Hy­droxy­anilinium perchlorate dihydrate

Abstract

In the crystal structure of the title compound, C6H8NO+·ClO4 ·2H2O, inter­molecular N—H(...)O and O—H(...)O hydrogen bonds occur. The protonated amine cations and the perchlorate anions are linked through the water mol­ecules, and the hy­droxy groups of the cations and the anions are linked through the water mol­ecules. The cations are connected to the perchlorate anions via inter­molecular N—H(...)O hydrogen bonds. In addition, the crystal structure exhibits weak inter­molecular C—H(...)π inter­actions.

Related literature

For background to phase transition materials, see: Li et al. (2008 [triangle]); Zhang et al. (2009 [triangle])

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Object name is e-66-o1920-scheme1.jpg

Experimental

Crystal data

  • C6H8NO+·ClO4 ·2H2O
  • M r = 245.62
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1920-efi3.jpg
  • a = 24.341 (5) Å
  • b = 5.253 (1) Å
  • c = 7.824 (2) Å
  • V = 1000.4 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.40 mm−1
  • T = 298 K
  • 0.40 × 0.30 × 0.20 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.866, T max = 0.923
  • 9517 measured reflections
  • 2275 independent reflections
  • 1986 reflections with I > 2σ(I)
  • R int = 0.052

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.097
  • S = 1.11
  • 2275 reflections
  • 168 parameters
  • 8 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.53 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1049 Friedel pairs
  • Flack parameter: 0.00 (7)

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: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810025365/lx2151sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025365/lx2151Isup2.hkl

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

Acknowledgments

The authors are grateful to the starter fund of Southeast University for financial support to purchase the diffractometer.

supplementary crystallographic information

Comment

As a continuation of our study of phase transition materials, including organic ligands (Li et al., 2008), metal-organic coordination compounds (Zhang et al., 2009), organic–inorganic hybrids, we studied the dielectric properties of the title compound, unfortunately, there was no distinct anomaly observed from 93 K to 350 K, suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range. Here, we report the crystal structure of the title compound (Fig. 1).

The asymmetric unit of the title compound is made up of a 4–hydroxyanilinium cation cation wherein the non-hydrogen atoms are practically co-planar with a mean deviation of 0.015 (2) Å, a perchlorate anion and two solvent molecules of water (Fig. 1). The crystal packing (Fig. 2) is stabilized by intermolecular N—H···O , O—H···O hydrogen bonds and weak intermolecular C—H···π interactions. (Table 1). Both the protonated amine cations and the perchlorate anions are linked through the water molecules, and the hydroxy groups of the cations and the anions are linked through the water molecules. Additionally, the cations are connected to the perchlorate anions via intermolecular N—H···O hydrogen bonds.

Experimental

1.09g (10 mmol) 4–aminophenol was firstly dissolved in 10ml ethanol, to which perchloric acid aqueous solution (70% w/w) was then added under stirring until the PH of the solution was ca. 6. Ethanol was added until the precipitated substrates disappeared. Colorless prism single crystal for X–ray was obtained by the acid solution slow evaporated at room temperature after two days.

Refinement

Aryl H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å. Uiso(H) = 1.2Ueq(C). The other H atoms attached to N and O atoms were found difference maps using restraints for O—H bond distances (O—H = 0.85 (5) Å) and H—O—H angles (H···H =1.35 (10) Å). Their displacement parameters were freely refined.

Figures

Fig. 1.
The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small cycles of arbitrary radius.
Fig. 2.
N—H···O, O—H···O and C—H···π interactions (dotted lines) in the crystal structure of the title compound. Cg denotes the ring centroid. [Symmetry codes: ...

Crystal data

C6H8NO+·ClO4·2H2OF(000) = 512
Mr = 245.62Dx = 1.631 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 4523 reflections
a = 24.341 (5) Åθ = 3.1–55.2°
b = 5.253 (1) ŵ = 0.40 mm1
c = 7.824 (2) ÅT = 298 K
V = 1000.4 (4) Å3Prism, colourless
Z = 40.40 × 0.30 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer2275 independent reflections
Radiation source: fine-focus sealed tube1986 reflections with I > 2σ(I)
graphiteRint = 0.052
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = −31→31
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −6→6
Tmin = 0.866, Tmax = 0.923l = −10→10
9517 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.097w = 1/[σ2(Fo2) + (0.0423P)2] where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.001
2275 reflectionsΔρmax = 0.21 e Å3
168 parametersΔρmin = −0.53 e Å3
8 restraintsAbsolute structure: Flack (1983), 1049 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.00 (7)

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 > 2sigma(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*/Ueq
Cl10.70519 (2)0.26502 (10)0.38081 (9)0.03119 (16)
O10.41921 (9)0.7270 (4)0.6125 (3)0.0418 (5)
H1O0.4080 (14)0.855 (5)0.638 (4)0.041 (10)*
O20.65704 (9)0.1268 (4)0.4283 (3)0.0543 (6)
O30.72121 (12)0.1930 (5)0.2130 (3)0.0615 (7)
O40.69370 (9)0.5318 (3)0.3859 (3)0.0490 (5)
O50.74825 (10)0.2072 (4)0.4975 (4)0.0633 (7)
N10.64637 (12)0.7547 (5)0.7092 (4)0.0383 (6)
H1N0.6637 (19)0.763 (7)0.624 (7)0.067 (14)*
H2N0.6575 (16)0.911 (8)0.768 (6)0.082 (13)*
H3N0.6580 (18)0.587 (9)0.759 (6)0.102 (16)*
C10.47480 (12)0.7447 (5)0.6368 (3)0.0303 (6)
C20.50729 (12)0.5551 (5)0.5650 (4)0.0323 (6)
H20.49110.42560.50140.039*
C30.56328 (12)0.5591 (5)0.5878 (4)0.0347 (6)
H30.58520.43260.54040.042*
C40.58649 (11)0.7533 (4)0.6821 (3)0.0308 (6)
C50.55500 (11)0.9431 (5)0.7512 (4)0.0320 (6)
H50.57141.07440.81240.038*
C60.49832 (11)0.9382 (5)0.7292 (4)0.0324 (6)
H60.47651.06510.77680.039*
O1W0.68473 (10)0.2523 (4)0.8370 (3)0.0461 (6)
H1AW0.680 (3)0.245 (11)0.937 (6)0.19 (4)*
H1BW0.7155 (18)0.270 (10)0.793 (8)0.13 (2)*
O2W0.62796 (12)0.7872 (5)0.0985 (4)0.0514 (6)
H2AW0.6577 (16)0.773 (8)0.172 (5)0.079 (15)*
H2BW0.6131 (18)0.658 (6)0.103 (6)0.070 (14)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0311 (3)0.0332 (3)0.0292 (3)0.0050 (2)0.0005 (3)−0.0030 (3)
O10.0300 (11)0.0394 (11)0.0560 (14)0.0019 (10)−0.0011 (10)−0.0022 (11)
O20.0455 (12)0.0505 (11)0.0667 (15)−0.0075 (10)0.0107 (11)0.0084 (11)
O30.0783 (17)0.0697 (15)0.0365 (14)0.0053 (14)0.0176 (13)−0.0112 (11)
O40.0573 (13)0.0358 (9)0.0541 (12)0.0082 (9)−0.0003 (13)0.0001 (11)
O50.0484 (15)0.0774 (16)0.0640 (17)0.0242 (13)−0.0244 (13)−0.0038 (13)
N10.0317 (14)0.0414 (15)0.0419 (17)0.0010 (12)0.0015 (12)0.0017 (13)
C10.0319 (14)0.0327 (13)0.0262 (14)−0.0010 (12)−0.0009 (12)0.0064 (11)
C20.0337 (15)0.0293 (13)0.0341 (14)−0.0031 (12)−0.0005 (12)−0.0067 (11)
C30.0357 (16)0.0277 (12)0.0405 (16)0.0041 (11)0.0070 (13)−0.0073 (11)
C40.0292 (13)0.0301 (13)0.0331 (14)0.0011 (12)0.0000 (11)0.0044 (11)
C50.0383 (15)0.0287 (11)0.0290 (13)−0.0009 (11)−0.0045 (12)−0.0015 (11)
C60.0358 (14)0.0295 (13)0.0320 (15)0.0087 (11)−0.0014 (11)−0.0040 (12)
O1W0.0394 (12)0.0513 (12)0.0477 (18)−0.0040 (12)−0.0053 (10)0.0005 (11)
O2W0.0401 (15)0.0486 (14)0.0654 (17)0.0015 (12)−0.0133 (12)0.0038 (13)

Geometric parameters (Å, °)

Cl1—O31.421 (2)C2—C31.375 (4)
Cl1—O51.423 (2)C2—H20.9300
Cl1—O21.428 (2)C3—C41.379 (4)
Cl1—O41.4297 (18)C3—H30.9300
O1—C11.370 (3)C4—C51.369 (4)
O1—H1O0.75 (3)C5—C61.391 (4)
N1—C41.473 (4)C5—H50.9300
N1—H1N0.79 (5)C6—H60.9300
N1—H2N0.98 (4)O1W—H1AW0.79 (5)
N1—H3N1.00 (5)O1W—H1BW0.83 (4)
C1—C61.372 (4)O2W—H2AW0.93 (4)
C1—C21.391 (4)O2W—H2BW0.77 (3)
O3—Cl1—O5109.51 (18)C3—C2—H2120.0
O3—Cl1—O2109.27 (17)C1—C2—H2120.0
O5—Cl1—O2109.22 (16)C2—C3—C4119.1 (2)
O3—Cl1—O4109.90 (17)C2—C3—H3120.4
O5—Cl1—O4109.61 (14)C4—C3—H3120.4
O2—Cl1—O4109.31 (13)C5—C4—C3121.4 (2)
C1—O1—H1O105 (3)C5—C4—N1119.6 (2)
C4—N1—H1N114 (3)C3—C4—N1119.1 (2)
C4—N1—H2N110 (2)C4—C5—C6119.6 (2)
H1N—N1—H2N102 (4)C4—C5—H5120.2
C4—N1—H3N109 (3)C6—C5—H5120.2
H1N—N1—H3N103 (4)C1—C6—C5119.5 (2)
H2N—N1—H3N119 (4)C1—C6—H6120.2
O1—C1—C6122.4 (3)C5—C6—H6120.2
O1—C1—C2117.2 (2)H1AW—O1W—H1BW124 (7)
C6—C1—C2120.4 (3)H2AW—O2W—H2BW106 (4)
C3—C2—C1120.0 (3)
O1—C1—C2—C3−178.6 (2)C3—C4—C5—C61.3 (4)
C6—C1—C2—C30.7 (4)N1—C4—C5—C6−178.4 (3)
C1—C2—C3—C4−0.2 (4)O1—C1—C6—C5179.1 (2)
C2—C3—C4—C5−0.8 (4)C2—C1—C6—C5−0.2 (4)
C2—C3—C4—N1178.9 (3)C4—C5—C6—C1−0.8 (4)

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 benzene ring.
D—H···AD—HH···AD···AD—H···A
O1—H1O···O2Wi0.75 (3)2.10 (3)2.801 (3)156 (4)
N1—H1N···O40.79 (5)2.34 (5)3.016 (4)144 (4)
N1—H2N···O1Wii0.98 (4)1.98 (5)2.951 (4)168 (4)
N1—H3N···O1W1.00 (5)1.97 (5)2.972 (4)175 (4)
O1W—H1AW···O3iii0.79 (5)2.40 (7)3.089 (3)146 (8)
O1W—H1BW···O50.83 (4)2.47 (6)3.083 (4)132 (5)
O2W—H2AW···O40.93 (4)2.28 (4)3.068 (4)143 (4)
O2W—H2BW···O1iv0.77 (3)2.17 (3)2.937 (3)173 (5)
C2—H2···Cg1iv0.932.883.677 (3)144

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LX2151).

References

  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • 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]

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