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

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4-Iodo­anilinium perchlorate 18-crown-6 clathrate

aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
*Correspondence e-mail: yizhang1980@yahoo.com.cn

(Received 21 January 2011; accepted 4 February 2011; online 12 February 2011)

In the title compound, C6H7IN+·ClO4·C12H24O6, the proton­ated 4-iodo­anilinium cation inter­acts with the 18-crown-6 through three N—H⋯O hydrogen bonds, forming a rotator–stator-like structure. The cation, anion and 18-crown-6 mol­ecule all have crystallographically imposed mirror symmetry.

Related literature

For the structure of a related 18-crown-6 clathrate, see: Ge & Zhao (2010[Ge, J.-Z. & Zhao, M.-M. (2010). Acta Cryst. E66, o1478.]). For ferroelectric properties, see: Fu et al. (2007[Fu, D. W., Song, Y. M., Wang, G. X., Ye, Q., Xiong, R. G., Akutagawa, T., Nakamura, T., Chan, P. W. H. & Huang, S. P. (2007). J. Am. Chem. Soc. 129, 5346-5347.]); 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., Cheng, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. P. (2009). J. Am. Chem. Soc. 131, 12544-12545.]).

[Scheme 1]

Experimental

Crystal data
  • C6H7IN+·ClO4·C12H24O6

  • Mr = 583.79

  • Orthorhombic, P n m a

  • a = 15.8805 (11) Å

  • b = 11.3878 (11) Å

  • c = 12.6754 (8) Å

  • V = 2292.3 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.57 mm−1

  • T = 93 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 = 0.575, Tmax = 0.731

  • 24048 measured reflections

  • 2755 independent reflections

  • 2611 reflections with I > 2σ(I)

  • Rint = 0.034

Refinement
  • R[F2 > 2σ(F2)] = 0.024

  • wR(F2) = 0.093

  • S = 1.11

  • 2755 reflections

  • 154 parameters

  • H-atom parameters constrained

  • Δρmax = 0.81 e Å−3

  • Δρmin = −0.65 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2A⋯O4i 0.90 1.96 2.861 (2) 176
N2—H2C⋯O2i 0.90 1.95 2.854 (3) 178
Symmetry code: (i) [-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}].

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: SHELXTL.

Supporting information


Comment top

As a continuation of our studies on the synthesis and characterization of host-guest compounds of 18-crown-6 (Ge & Zhao, 2010), the crystal structure of the title compound is reported herein. The dielectric permittivity of the title compound was tested to investigate the ferroelectric phase transitions materials (Fu et al. 2007; Ye et al. 2009; Zhang et al. 2009). The title compound have no dielectric anomalies under 1M Hz in the temperature range from 90 to 473 K (the compound m. p. > 473 K), suggesting that in the compound no distinct phase transition occurred within the measured temperature range.

The title compound is composed of C6H4INH3+ cations, 18-crown-6 molecules and ClO4- anions (Fig 1). A supramolecular rotator-stator structure is assembled between the protonated 4-iodoanilinium cation and 18-crown-6 molecule by three N—H···O hydrogen bonds (Table 1). The nitrogen atom of the NH3+ group is in the perching position of the crown ring, rather than in the nesting position. The macrocycle adopts a conformation with approximate D3d symmetry, all O—C—C—O torsion angles being gauche and alternating in sign, and all C—O—C—C torsion angles being trans. The C—N bond of the 4-iodoanilinium cation is almost perpendicular to the mean plane of the crown-ether O atoms. The ClO4- anion, the cation and the 18-crown-6 have all crystallographically imposed mirror symmetry. Fig. 2 shows a view of the structure down the b axis. The couples of head-to-head rotator-stator cations almost paralleling and plumbing the (101) direction are alternating arranged. The anions inhabit the cavities formed by the couples of head-to-head rotator-stator cations. In the title compound no intermolecular hydrogen bonds are observed.

Related literature top

For the structure of a related 18-crown-6 clathrate, see: Ge & Zhao (2010). For ferroelectric properties, see: Fu et al. (2007); Ye et al.(2009); Zhang et al. (2009).

Experimental top

4-Iodoaniline (2 mmol) and excess perchloric acid (4 mmol) were dissolved in methanol, then 18-crown-6 (2 mmol) was added to the mixture. The precipitate was filtered and washed with a small amount of methanol. Single crystals suitable for X-ray diffraction analysis were obtained from slow evaporation of the methanol solution at room temperature after two days.

Refinement top

All hydrogen atoms were calculated geometrically allowed to ride, with C—H = 0.93-0.97 Å, N—H = 0.90 Å, and with Uiso(H) = 1.2 Uiso(C, N).

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: SHELXTL (Sheldrick, 2008).

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. Symmetry codes: (A) x, 1/2-y, z; (B) 3/2-x, 1-y, 1/2+z; (C) 3/2-x, -1/2+y, 1/2+z; (D) x, 3/2-y, z.
[Figure 2] Fig. 2. Packing diagram of the title compound viewed along the b axis. Dashed lines indicate hydrogen bonds. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.
4-iodoanilinium perchlorate–18-crown-6 (1/1) top
Crystal data top
C6H7IN+·ClO4·C12H24O6F(000) = 1184
Mr = 583.79Dx = 1.692 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 17071 reflections
a = 15.8805 (11) Åθ = 3.2–27.8°
b = 11.3878 (11) ŵ = 1.57 mm1
c = 12.6754 (8) ÅT = 93 K
V = 2292.3 (3) Å3Prism, colourless
Z = 40.40 × 0.30 × 0.20 mm
Data collection top
Rigaku SCXmini
diffractometer
2755 independent reflections
Radiation source: fine-focus sealed tube2611 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 2.1°
CCD_Profile_fitting scansh = 2020
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1414
Tmin = 0.575, Tmax = 0.731l = 1616
24048 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)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0591P)2 + 1.2714P]
where P = (Fo2 + 2Fc2)/3
2755 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 0.81 e Å3
0 restraintsΔρmin = 0.65 e Å3
Crystal data top
C6H7IN+·ClO4·C12H24O6V = 2292.3 (3) Å3
Mr = 583.79Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 15.8805 (11) ŵ = 1.57 mm1
b = 11.3878 (11) ÅT = 93 K
c = 12.6754 (8) Å0.40 × 0.30 × 0.20 mm
Data collection top
Rigaku SCXmini
diffractometer
2755 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
2611 reflections with I > 2σ(I)
Tmin = 0.575, Tmax = 0.731Rint = 0.034
24048 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.093H-atom parameters constrained
S = 1.11Δρmax = 0.81 e Å3
2755 reflectionsΔρmin = 0.65 e Å3
154 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
I11.020717 (13)0.75000.497027 (14)0.01781 (10)
N20.69020 (16)0.75000.21864 (19)0.0118 (5)
H2A0.69190.68500.17820.018*
H2C0.64400.75000.25990.018*
C250.87428 (14)0.6439 (2)0.37576 (16)0.0155 (4)
H25A0.89940.57110.39750.019*
C260.80150 (13)0.64394 (18)0.31502 (16)0.0141 (4)
H26A0.77570.57130.29410.017*
C270.76611 (18)0.75000.2846 (2)0.0116 (5)
C300.91063 (18)0.75000.4050 (2)0.0146 (6)
O40.79657 (9)0.45595 (13)0.59043 (12)0.0152 (3)
O50.70915 (15)0.25000.52965 (18)0.0158 (4)
C60.81605 (14)0.56511 (19)0.64275 (17)0.0160 (4)
H6A0.77300.58300.69470.019*
H6B0.81770.62860.59170.019*
C70.71692 (14)0.4594 (2)0.53731 (19)0.0176 (5)
H7A0.71240.53090.49610.021*
H7B0.67150.45840.58850.021*
C80.71071 (15)0.3540 (2)0.46600 (18)0.0182 (5)
H8A0.65980.35870.42390.022*
H8B0.75860.35180.41860.022*
O10.89363 (9)0.46966 (13)0.78008 (12)0.0141 (3)
O20.95815 (15)0.25000.84574 (18)0.0137 (4)
C10.97204 (13)0.4574 (2)0.83409 (18)0.0155 (4)
H1A0.98410.52820.87390.019*
H1B1.01710.44560.78350.019*
C20.96711 (14)0.35433 (19)0.90738 (17)0.0150 (4)
H2D1.01780.34980.94990.018*
H2E0.91930.36290.95430.018*
Cl10.60734 (4)0.75000.70231 (5)0.01306 (16)
O170.62206 (10)0.64643 (15)0.76547 (13)0.0230 (4)
O210.52124 (13)0.75000.6644 (2)0.0173 (5)
O220.66395 (14)0.75000.61313 (17)0.0179 (5)
C50.90019 (14)0.55317 (19)0.69569 (17)0.0157 (4)
H5A0.94190.52690.64500.019*
H5B0.91790.62870.72330.019*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.01152 (15)0.02558 (16)0.01632 (15)0.0000.00231 (6)0.000
N20.0115 (11)0.0107 (11)0.0132 (11)0.0000.0000 (10)0.000
C250.0162 (10)0.0170 (10)0.0135 (9)0.0027 (8)0.0001 (8)0.0020 (8)
C260.0154 (10)0.0123 (10)0.0145 (10)0.0008 (8)0.0009 (8)0.0015 (8)
C270.0095 (13)0.0148 (14)0.0104 (13)0.0000.0009 (11)0.000
C300.0101 (13)0.0228 (15)0.0108 (13)0.0000.0019 (11)0.000
O40.0136 (7)0.0131 (7)0.0189 (7)0.0020 (6)0.0022 (6)0.0007 (6)
O50.0195 (11)0.0148 (11)0.0131 (10)0.0000.0012 (9)0.000
C60.0195 (10)0.0107 (10)0.0177 (10)0.0017 (8)0.0015 (9)0.0025 (8)
C70.0152 (10)0.0195 (11)0.0180 (11)0.0027 (8)0.0034 (9)0.0037 (9)
C80.0181 (11)0.0235 (12)0.0128 (10)0.0002 (9)0.0026 (9)0.0047 (9)
O10.0130 (7)0.0137 (7)0.0156 (7)0.0019 (5)0.0003 (6)0.0031 (6)
O20.0184 (10)0.0099 (10)0.0128 (10)0.0000.0013 (9)0.000
C10.0137 (10)0.0138 (11)0.0189 (11)0.0020 (8)0.0009 (8)0.0013 (8)
C20.0158 (10)0.0142 (10)0.0151 (10)0.0002 (8)0.0015 (8)0.0027 (8)
Cl10.0118 (3)0.0126 (3)0.0148 (3)0.0000.0005 (3)0.000
O170.0210 (8)0.0224 (9)0.0257 (9)0.0028 (7)0.0004 (7)0.0111 (7)
O210.0116 (11)0.0177 (12)0.0225 (13)0.0000.0016 (8)0.000
O220.0154 (11)0.0215 (11)0.0169 (11)0.0000.0053 (9)0.000
C50.0188 (10)0.0120 (10)0.0163 (10)0.0030 (8)0.0027 (8)0.0021 (8)
Geometric parameters (Å, º) top
I1—C302.102 (3)C7—H7A0.9700
N2—C271.467 (4)C7—H7B0.9702
N2—H2A0.9002C8—H8A0.9700
N2—H2C0.9006C8—H8B0.9700
C25—C261.389 (3)O1—C11.428 (3)
C25—C301.390 (3)O1—C51.435 (2)
C25—H25A0.9599O2—C21.429 (2)
C26—C271.387 (3)O2—C2ii1.429 (2)
C26—H26A0.9601C1—C21.499 (3)
C27—C26i1.387 (3)C1—H1A0.9699
C30—C25i1.390 (3)C1—H1B0.9700
O4—C71.433 (3)C2—H2D0.9701
O4—C61.443 (3)C2—H2E0.9701
O5—C8ii1.433 (3)Cl1—O221.444 (2)
O5—C81.433 (3)Cl1—O17i1.4445 (16)
C6—C51.501 (3)Cl1—O171.4445 (16)
C6—H6A0.9700Cl1—O211.449 (2)
C6—H6B0.9701C5—H5A0.9701
C7—C81.506 (3)C5—H5B0.9700
C27—N2—H2A107.4C7—C8—H8A110.0
C27—N2—H2C109.7O5—C8—H8B109.9
H2A—N2—H2C110.8C7—C8—H8B109.9
C26—C25—C30119.5 (2)H8A—C8—H8B108.3
C26—C25—H25A120.4C1—O1—C5111.03 (16)
C30—C25—H25A120.1C2—O2—C2ii112.5 (2)
C27—C26—C25119.5 (2)O1—C1—C2109.15 (17)
C27—C26—H26A120.0O1—C1—H1A109.9
C25—C26—H26A120.5C2—C1—H1A109.8
C26i—C27—C26121.1 (3)O1—C1—H1B109.9
C26i—C27—N2119.44 (13)C2—C1—H1B109.8
C26—C27—N2119.44 (14)H1A—C1—H1B108.3
C25—C30—C25i120.9 (3)O2—C2—C1108.51 (18)
C25—C30—I1119.56 (14)O2—C2—H2D110.0
C25i—C30—I1119.56 (14)C1—C2—H2D110.0
C7—O4—C6112.42 (16)O2—C2—H2E110.0
C8ii—O5—C8111.4 (2)C1—C2—H2E110.0
O4—C6—C5108.56 (17)H2D—C2—H2E108.4
O4—C6—H6A110.0O22—Cl1—O17i109.46 (9)
C5—C6—H6A110.0O22—Cl1—O17109.46 (9)
O4—C6—H6B110.0O17i—Cl1—O17109.47 (15)
C5—C6—H6B110.0O22—Cl1—O21109.14 (14)
H6A—C6—H6B108.4O17i—Cl1—O21109.65 (9)
O4—C7—C8108.52 (18)O17—Cl1—O21109.65 (9)
O4—C7—H7A110.0O1—C5—C6109.19 (17)
C8—C7—H7A109.9O1—C5—H5A109.8
O4—C7—H7B110.0C6—C5—H5A109.9
C8—C7—H7B110.0O1—C5—H5B109.9
H7A—C7—H7B108.4C6—C5—H5B109.8
O5—C8—C7108.78 (18)H5A—C5—H5B108.3
O5—C8—H8A109.9
Symmetry codes: (i) x, y+3/2, z; (ii) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O4iii0.901.962.861 (2)176
N2—H2C···O2iii0.901.952.854 (3)178
Symmetry code: (iii) x+3/2, y+1, z1/2.

Experimental details

Crystal data
Chemical formulaC6H7IN+·ClO4·C12H24O6
Mr583.79
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)93
a, b, c (Å)15.8805 (11), 11.3878 (11), 12.6754 (8)
V3)2292.3 (3)
Z4
Radiation typeMo Kα
µ (mm1)1.57
Crystal size (mm)0.40 × 0.30 × 0.20
Data collection
DiffractometerRigaku SCXmini
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.575, 0.731
No. of measured, independent and
observed [I > 2σ(I)] reflections
24048, 2755, 2611
Rint0.034
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.093, 1.11
No. of reflections2755
No. of parameters154
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.81, 0.65

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O4i0.901.962.861 (2)176
N2—H2C···O2i0.901.952.854 (3)178
Symmetry code: (i) x+3/2, y+1, z1/2.
 

Acknowledgements

This work was supported by the Start-up Projects for Postdoctoral Research Funds (1112000064) and the Major Postdoctoral Research Funds (3212000602) of Southeast University.

References

First citationFu, D. W., Song, Y. M., Wang, G. X., Ye, Q., Xiong, R. G., Akutagawa, T., Nakamura, T., Chan, P. W. H. & Huang, S. P. (2007). J. Am. Chem. Soc. 129, 5346–5347.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationGe, J.-Z. & Zhao, M.-M. (2010). Acta Cryst. E66, o1478.  Web of Science CSD CrossRef IUCr Journals 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., Cheng, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. P. (2009). J. Am. Chem. Soc. 131, 12544–12545.  Web of Science CSD CrossRef PubMed CAS Google Scholar

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