4-Iodo­anilinium perchlorate 18-crown-6 clathrate

Zhang, Y.; Zhao, M.-M.

doi:10.1107/S1600536811004260

organic compounds

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Volume 67| Part 3| March 2011| Page o596

doi:10.1107/S1600536811004260

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4-Iodoanilinium perchlorate 18-crown-6 clathrate

Yi Zhang ^a ^* and Min-Min Zhao ^a

^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 ). For ferroelectric properties, see: Fu et al. (2007 ); Ye et al.(2009 ); Zhang et al. (2009 ).

Experimental

Crystal data

C₆H₇IN⁺·ClO₄⁻·C₁₂H₂₄O₆
M_r = 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 ) T_min = 0.575, T_max = 0.731
24048 measured reflections
2755 independent reflections
2611 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.093
S = 1.11
2755 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811004260/rz2549sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811004260/rz2549Isup2.hkl

checkCIF report

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 D_3d 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.

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

	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.
	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⁻·C₁₂H₂₄O₆	F(000) = 1184
M_r = 583.79	D_x = 1.692 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 17071 reflections
a = 15.8805 (11) Å	θ = 3.2–27.8°
b = 11.3878 (11) Å	µ = 1.57 mm⁻¹
c = 12.6754 (8) Å	T = 93 K
V = 2292.3 (3) Å³	Prism, colourless
Z = 4	0.40 × 0.30 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	2755 independent reflections
Radiation source: fine-focus sealed tube	2611 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.1°
CCD_Profile_fitting scans	h = −20→20
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
T_min = 0.575, T_max = 0.731	l = −16→16
24048 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0591P)² + 1.2714P] where P = (F_o² + 2F_c²)/3
2755 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

C₆H₇IN⁺·ClO₄⁻·C₁₂H₂₄O₆	V = 2292.3 (3) Å³
M_r = 583.79	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 15.8805 (11) Å	µ = 1.57 mm⁻¹
b = 11.3878 (11) Å	T = 93 K
c = 12.6754 (8) Å	0.40 × 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)
T_min = 0.575, T_max = 0.731	R_int = 0.034
24048 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.11	Δρ_max = 0.81 e Å⁻³
2755 reflections	Δρ_min = −0.65 e Å⁻³
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

	x	y	z	U_iso*/U_eq
I1	1.020717 (13)	0.7500	0.497027 (14)	0.01781 (10)
N2	0.69020 (16)	0.7500	0.21864 (19)	0.0118 (5)
H2A	0.6919	0.6850	0.1782	0.018*
H2C	0.6440	0.7500	0.2599	0.018*
C25	0.87428 (14)	0.6439 (2)	0.37576 (16)	0.0155 (4)
H25A	0.8994	0.5711	0.3975	0.019*
C26	0.80150 (13)	0.64394 (18)	0.31502 (16)	0.0141 (4)
H26A	0.7757	0.5713	0.2941	0.017*
C27	0.76611 (18)	0.7500	0.2846 (2)	0.0116 (5)
C30	0.91063 (18)	0.7500	0.4050 (2)	0.0146 (6)
O4	0.79657 (9)	0.45595 (13)	0.59043 (12)	0.0152 (3)
O5	0.70915 (15)	0.2500	0.52965 (18)	0.0158 (4)
C6	0.81605 (14)	0.56511 (19)	0.64275 (17)	0.0160 (4)
H6A	0.7730	0.5830	0.6947	0.019*
H6B	0.8177	0.6286	0.5917	0.019*
C7	0.71692 (14)	0.4594 (2)	0.53731 (19)	0.0176 (5)
H7A	0.7124	0.5309	0.4961	0.021*
H7B	0.6715	0.4584	0.5885	0.021*
C8	0.71071 (15)	0.3540 (2)	0.46600 (18)	0.0182 (5)
H8A	0.6598	0.3587	0.4239	0.022*
H8B	0.7586	0.3518	0.4186	0.022*
O1	0.89363 (9)	0.46966 (13)	0.78008 (12)	0.0141 (3)
O2	0.95815 (15)	0.2500	0.84574 (18)	0.0137 (4)
C1	0.97204 (13)	0.4574 (2)	0.83409 (18)	0.0155 (4)
H1A	0.9841	0.5282	0.8739	0.019*
H1B	1.0171	0.4456	0.7835	0.019*
C2	0.96711 (14)	0.35433 (19)	0.90738 (17)	0.0150 (4)
H2D	1.0178	0.3498	0.9499	0.018*
H2E	0.9193	0.3629	0.9543	0.018*
Cl1	0.60734 (4)	0.7500	0.70231 (5)	0.01306 (16)
O17	0.62206 (10)	0.64643 (15)	0.76547 (13)	0.0230 (4)
O21	0.52124 (13)	0.7500	0.6644 (2)	0.0173 (5)
O22	0.66395 (14)	0.7500	0.61313 (17)	0.0179 (5)
C5	0.90019 (14)	0.55317 (19)	0.69569 (17)	0.0157 (4)
H5A	0.9419	0.5269	0.6450	0.019*
H5B	0.9179	0.6287	0.7233	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01152 (15)	0.02558 (16)	0.01632 (15)	0.000	−0.00231 (6)	0.000
N2	0.0115 (11)	0.0107 (11)	0.0132 (11)	0.000	0.0000 (10)	0.000
C25	0.0162 (10)	0.0170 (10)	0.0135 (9)	0.0027 (8)	0.0001 (8)	0.0020 (8)
C26	0.0154 (10)	0.0123 (10)	0.0145 (10)	−0.0008 (8)	0.0009 (8)	−0.0015 (8)
C27	0.0095 (13)	0.0148 (14)	0.0104 (13)	0.000	0.0009 (11)	0.000
C30	0.0101 (13)	0.0228 (15)	0.0108 (13)	0.000	0.0019 (11)	0.000
O4	0.0136 (7)	0.0131 (7)	0.0189 (7)	0.0020 (6)	−0.0022 (6)	0.0007 (6)
O5	0.0195 (11)	0.0148 (11)	0.0131 (10)	0.000	−0.0012 (9)	0.000
C6	0.0195 (10)	0.0107 (10)	0.0177 (10)	0.0017 (8)	0.0015 (9)	0.0025 (8)
C7	0.0152 (10)	0.0195 (11)	0.0180 (11)	0.0027 (8)	−0.0034 (9)	0.0037 (9)
C8	0.0181 (11)	0.0235 (12)	0.0128 (10)	0.0002 (9)	−0.0026 (9)	0.0047 (9)
O1	0.0130 (7)	0.0137 (7)	0.0156 (7)	−0.0019 (5)	−0.0003 (6)	0.0031 (6)
O2	0.0184 (10)	0.0099 (10)	0.0128 (10)	0.000	−0.0013 (9)	0.000
C1	0.0137 (10)	0.0138 (11)	0.0189 (11)	−0.0020 (8)	−0.0009 (8)	−0.0013 (8)
C2	0.0158 (10)	0.0142 (10)	0.0151 (10)	0.0002 (8)	−0.0015 (8)	−0.0027 (8)
Cl1	0.0118 (3)	0.0126 (3)	0.0148 (3)	0.000	0.0005 (3)	0.000
O17	0.0210 (8)	0.0224 (9)	0.0257 (9)	0.0028 (7)	0.0004 (7)	0.0111 (7)
O21	0.0116 (11)	0.0177 (12)	0.0225 (13)	0.000	−0.0016 (8)	0.000
O22	0.0154 (11)	0.0215 (11)	0.0169 (11)	0.000	0.0053 (9)	0.000
C5	0.0188 (10)	0.0120 (10)	0.0163 (10)	−0.0030 (8)	0.0027 (8)	0.0021 (8)

Geometric parameters (Å, º) top

I1—C30	2.102 (3)	C7—H7A	0.9700
N2—C27	1.467 (4)	C7—H7B	0.9702
N2—H2A	0.9002	C8—H8A	0.9700
N2—H2C	0.9006	C8—H8B	0.9700
C25—C26	1.389 (3)	O1—C1	1.428 (3)
C25—C30	1.390 (3)	O1—C5	1.435 (2)
C25—H25A	0.9599	O2—C2	1.429 (2)
C26—C27	1.387 (3)	O2—C2ⁱⁱ	1.429 (2)
C26—H26A	0.9601	C1—C2	1.499 (3)
C27—C26ⁱ	1.387 (3)	C1—H1A	0.9699
C30—C25ⁱ	1.390 (3)	C1—H1B	0.9700
O4—C7	1.433 (3)	C2—H2D	0.9701
O4—C6	1.443 (3)	C2—H2E	0.9701
O5—C8ⁱⁱ	1.433 (3)	Cl1—O22	1.444 (2)
O5—C8	1.433 (3)	Cl1—O17ⁱ	1.4445 (16)
C6—C5	1.501 (3)	Cl1—O17	1.4445 (16)
C6—H6A	0.9700	Cl1—O21	1.449 (2)
C6—H6B	0.9701	C5—H5A	0.9701
C7—C8	1.506 (3)	C5—H5B	0.9700

C27—N2—H2A	107.4	C7—C8—H8A	110.0
C27—N2—H2C	109.7	O5—C8—H8B	109.9
H2A—N2—H2C	110.8	C7—C8—H8B	109.9
C26—C25—C30	119.5 (2)	H8A—C8—H8B	108.3
C26—C25—H25A	120.4	C1—O1—C5	111.03 (16)
C30—C25—H25A	120.1	C2—O2—C2ⁱⁱ	112.5 (2)
C27—C26—C25	119.5 (2)	O1—C1—C2	109.15 (17)
C27—C26—H26A	120.0	O1—C1—H1A	109.9
C25—C26—H26A	120.5	C2—C1—H1A	109.8
C26ⁱ—C27—C26	121.1 (3)	O1—C1—H1B	109.9
C26ⁱ—C27—N2	119.44 (13)	C2—C1—H1B	109.8
C26—C27—N2	119.44 (14)	H1A—C1—H1B	108.3
C25—C30—C25ⁱ	120.9 (3)	O2—C2—C1	108.51 (18)
C25—C30—I1	119.56 (14)	O2—C2—H2D	110.0
C25ⁱ—C30—I1	119.56 (14)	C1—C2—H2D	110.0
C7—O4—C6	112.42 (16)	O2—C2—H2E	110.0
C8ⁱⁱ—O5—C8	111.4 (2)	C1—C2—H2E	110.0
O4—C6—C5	108.56 (17)	H2D—C2—H2E	108.4
O4—C6—H6A	110.0	O22—Cl1—O17ⁱ	109.46 (9)
C5—C6—H6A	110.0	O22—Cl1—O17	109.46 (9)
O4—C6—H6B	110.0	O17ⁱ—Cl1—O17	109.47 (15)
C5—C6—H6B	110.0	O22—Cl1—O21	109.14 (14)
H6A—C6—H6B	108.4	O17ⁱ—Cl1—O21	109.65 (9)
O4—C7—C8	108.52 (18)	O17—Cl1—O21	109.65 (9)
O4—C7—H7A	110.0	O1—C5—C6	109.19 (17)
C8—C7—H7A	109.9	O1—C5—H5A	109.8
O4—C7—H7B	110.0	C6—C5—H5A	109.9
C8—C7—H7B	110.0	O1—C5—H5B	109.9
H7A—C7—H7B	108.4	C6—C5—H5B	109.8
O5—C8—C7	108.78 (18)	H5A—C5—H5B	108.3
O5—C8—H8A	109.9

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4ⁱⁱⁱ	0.90	1.96	2.861 (2)	176
N2—H2C···O2ⁱⁱⁱ	0.90	1.95	2.854 (3)	178

Symmetry code: (iii) −x+3/2, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₆H₇IN⁺·ClO₄⁻·C₁₂H₂₄O₆
M_r	583.79
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	93
a, b, c (Å)	15.8805 (11), 11.3878 (11), 12.6754 (8)
V (Å³)	2292.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.57
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.575, 0.731
No. of measured, independent and observed [I > 2σ(I)] reflections	24048, 2755, 2611
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.093, 1.11
No. of reflections	2755
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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+3/2, −y+1, z−1/2.

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

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