4-Methyl­anilinium perchlorate 18-crown-6 clathrate

Wang, Y.-F.

doi:10.1107/S1600536811053992

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o185

doi:10.1107/S1600536811053992

Open

access

4-Methylanilinium perchlorate 18-crown-6 clathrate

Yu-Feng Wang ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: wangyufeng0924@163.com

(Received 5 November 2011; accepted 15 December 2011; online 21 December 2011)

In the title compound, C₇H₁₀N⁺·ClO₄⁻·C₁₂H₂₄O₆, the 4-methylanilinium cation interacts with an 18-crown-6 molecule forming a rotator–stator-like structure through bifurcated N—H⋯(O,O) hydrogen bonds between the ammonium group of the cation and the O atoms of the crown ether molecule. All three components of the structure possess mirror symmetry. The benzene ring is inclined to the mean plane of the crown ether molecule by 86.84 (8)°.

Related literature

The crystal structure of related 4-methylanilinium tetrafluoroborate 18-crown-6 clathrate has been reported by Ge & Zhao (2010 ).

Experimental

Crystal data

C₇H₁₀N⁺·ClO₄⁻·C₁₂H₂₄O₆
M_r = 471.92
Orthorhombic, P n m a
a = 15.510 (3) Å
b = 11.717 (2) Å
c = 13.014 (3) Å
V = 2365.0 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 293 K
0.27 × 0.26 × 0.23 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.944, T_max = 0.952
23471 measured reflections
2843 independent reflections
2051 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.131
S = 1.04
2843 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2ⁱ	0.89	2.23	2.9477 (19)	138
N1—H1B⋯O3ⁱ	0.89	2.19	2.9511 (18)	143
N1—H1C⋯O4	0.89	2.20	2.924 (3)	138
N1—H1C⋯O3	0.89	2.20	2.9511 (18)	142
N1—H1A⋯O2	0.89	2.22	2.9477 (19)	139
N1—H1A⋯O1	0.89	2.15	2.888 (3)	140
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z]$ .

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/S1600536811053992/cv5196sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053992/cv5196Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811053992/cv5196Isup3.cml

checkCIF report

Comment top

Recently, the crystal structure of 4-methylanilinium tetrafluoroborate 18-crown-6 clathrate (I), obtained in our laboratory, has been reported (Ge & Zhao, 2010). In continuation of our studies of compounds containing 18-crown-6 macrocycles and ammonium cations RNH₃⁺, we present here the title compound (II) (Fig. 1), which is isostructural with (I).

In (II), the methyl and the protonated –NH₃ groups of the 4-methylanilinium lie on a dual axis of rotation, and perchlorate anion lie on a mirror plane. All bond length and angles are normal and correspond to those reported for (I) (Ge & Zhao, 2010). The 4-methylanilinium cation interacts with 18-crown-6 molecule forming a rotator–stator structure through bifurcated N—H···(O,O) hydrogen bonds (Table 1) between the ammonium group of the cation and the O atoms of the crown ether molecule.

Related literature top

The crystal structure of related 4-methylanilinium tetrafluoroborate 18-crown-6 clathrate has been reported by Ge & Zhao (2010).

Experimental top

In room temperature p-tolylanmine (5 mmol, 0.535 g) was dissolved in 20 ml Me thanol, then HClO₄ was added into the previous solution slowly with properly sirring until the solution become neutral.At last 18-crown-6 (5 mmol,1.65 g) were dissolved in the solution above, strring. Quite a quantity of white deposit are obtained,methanol are added into the solution again until deposit are dissolved. A great quantity of colorless block crystasls were obtained by filtrating after several hours in air. Block colorless single crystals suitable for X-ray structure analysis were obtained by the slow evaporation of the above solution after a week in air.

The dielectric constant of the compound as a function of temperature indicates that the permittivity is basically temperature-independent (ε = C/(T–T₀)), suggesting that this compound is not ferroelectric or there may be no distinct phase transition occurring within the measured temperature range between 128 K and 378 K.

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, showing the atomic numbering scheme with 30% probability displacement ellipsoids [symmetry code: (A) x, 1/2-y, z].

4-Methylanilinium perchlorate–1,4,7,10,13,16-hexaoxacyclooctadecane (1/1) top

Crystal data top

C₇H₁₀N⁺·ClO₄⁻·C₁₂H₂₄O₆	F(000) = 1008
M_r = 471.92	D_x = 1.325 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	θ = 3.1–27.8°
a = 15.510 (3) Å	µ = 0.21 mm⁻¹
b = 11.717 (2) Å	T = 293 K
c = 13.014 (3) Å	Block, colourless
V = 2365.0 (8) Å³	0.27 × 0.26 × 0.23 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	2843 independent reflections
Radiation source: fine-focus sealed tube	2051 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
CCD_Profile_fitting scans	h = −20→19
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
T_min = 0.944, T_max = 0.952	l = −16→16
23471 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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0508P)² + 0.9055P] where P = (F_o² + 2F_c²)/3
2843 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₇H₁₀N⁺·ClO₄⁻·C₁₂H₂₄O₆	V = 2365.0 (8) Å³
M_r = 471.92	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 15.510 (3) Å	µ = 0.21 mm⁻¹
b = 11.717 (2) Å	T = 293 K
c = 13.014 (3) Å	0.27 × 0.26 × 0.23 mm

Data collection top

Rigaku Mercury2 diffractometer	2843 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2051 reflections with I > 2σ(I)
T_min = 0.944, T_max = 0.952	R_int = 0.056
23471 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.04	Δρ_max = 0.23 e Å⁻³
2843 reflections	Δρ_min = −0.29 e Å⁻³
156 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	Occ. (<1)
Cl1	0.39923 (4)	0.2500	0.29294 (6)	0.0499 (2)
O9	0.48479 (14)	0.2500	0.33632 (19)	0.0668 (6)
O10	0.38749 (12)	0.14964 (16)	0.23197 (15)	0.0872 (6)
O8	0.33818 (15)	0.2500	0.37618 (19)	0.0764 (7)
O3	0.39105 (9)	0.03863 (11)	0.71904 (11)	0.0521 (4)
O4	0.45688 (13)	0.2500	0.65171 (14)	0.0500 (5)
N1	0.29743 (14)	0.2500	0.77156 (16)	0.0419 (5)
H1A	0.2845	0.2166	0.8310	0.063*	0.50
H1B	0.3141	0.3216	0.7830	0.063*	0.50
H1C	0.3400	0.2118	0.7412	0.063*	0.50
O2	0.29941 (9)	0.04793 (12)	0.90648 (11)	0.0584 (4)
O1	0.21558 (14)	0.2500	0.97086 (15)	0.0608 (6)
C13	0.22121 (16)	0.2500	0.70472 (18)	0.0392 (6)
C9	0.39753 (15)	−0.04759 (18)	0.79645 (17)	0.0588 (6)
H9A	0.4433	−0.0283	0.8442	0.071*
H9B	0.4114	−0.1203	0.7649	0.071*
C8	0.46909 (14)	0.04990 (18)	0.66202 (17)	0.0564 (5)
H8A	0.4795	−0.0190	0.6227	0.068*
H8B	0.5171	0.0608	0.7087	0.068*
C14	0.18536 (14)	0.14842 (18)	0.67484 (15)	0.0533 (5)
H14	0.2097	0.0797	0.6956	0.064*
C7	0.46218 (15)	0.14939 (18)	0.59148 (15)	0.0545 (5)
H7A	0.5123	0.1528	0.5470	0.065*
H7B	0.4112	0.1421	0.5488	0.065*
C10	0.31436 (15)	−0.05658 (18)	0.85247 (18)	0.0611 (6)
H10A	0.2678	−0.0705	0.8043	0.073*
H10B	0.3165	−0.1197	0.9006	0.073*
C11	0.22117 (15)	0.0464 (2)	0.9626 (2)	0.0705 (7)
H11A	0.2175	−0.0228	1.0032	0.085*
H11B	0.1726	0.0482	0.9158	0.085*
C12	0.21869 (16)	0.1486 (2)	1.03166 (17)	0.0720 (7)
H12A	0.1683	0.1448	1.0757	0.086*
H12B	0.2696	0.1497	1.0750	0.086*
C17	0.07397 (19)	0.2500	0.5819 (2)	0.0558 (8)
C18	0.11245 (14)	0.1491 (2)	0.61334 (16)	0.0598 (6)
H18	0.0887	0.0799	0.5926	0.072*
C19	−0.0071 (2)	0.2500	0.5175 (3)	0.0878 (12)
H19A	−0.0486	0.1992	0.5474	0.132*	0.50
H19B	0.0064	0.2250	0.4491	0.132*	0.50
H19C	−0.0305	0.3258	0.5150	0.132*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0481 (4)	0.0428 (4)	0.0587 (4)	0.000	0.0021 (3)	0.000
O9	0.0551 (13)	0.0592 (13)	0.0862 (16)	0.000	−0.0069 (12)	0.000
O10	0.0857 (13)	0.0753 (12)	0.1007 (13)	−0.0023 (10)	−0.0109 (11)	−0.0348 (11)
O8	0.0657 (15)	0.0856 (17)	0.0778 (16)	0.000	0.0166 (13)	0.000
O3	0.0547 (8)	0.0424 (7)	0.0593 (9)	0.0062 (6)	0.0008 (7)	0.0064 (6)
O4	0.0629 (12)	0.0435 (11)	0.0437 (10)	0.000	0.0081 (9)	0.000
N1	0.0443 (12)	0.0426 (12)	0.0388 (12)	0.000	0.0047 (10)	0.000
O2	0.0560 (9)	0.0527 (9)	0.0664 (9)	−0.0097 (7)	0.0087 (7)	0.0088 (7)
O1	0.0650 (13)	0.0781 (15)	0.0393 (11)	0.000	0.0077 (10)	0.000
C13	0.0397 (13)	0.0461 (14)	0.0319 (12)	0.000	0.0051 (11)	0.000
C9	0.0688 (14)	0.0412 (11)	0.0665 (14)	0.0059 (10)	−0.0085 (12)	0.0068 (10)
C8	0.0589 (12)	0.0497 (12)	0.0605 (13)	0.0122 (10)	0.0065 (11)	−0.0074 (10)
C14	0.0597 (12)	0.0468 (12)	0.0534 (12)	−0.0010 (10)	−0.0048 (10)	0.0000 (9)
C7	0.0610 (12)	0.0549 (13)	0.0477 (11)	0.0044 (10)	0.0069 (10)	−0.0079 (10)
C10	0.0699 (14)	0.0433 (12)	0.0700 (14)	−0.0104 (10)	−0.0115 (12)	0.0142 (10)
C11	0.0611 (14)	0.0783 (17)	0.0721 (16)	−0.0125 (12)	0.0103 (12)	0.0237 (14)
C12	0.0649 (14)	0.106 (2)	0.0453 (12)	−0.0048 (14)	0.0128 (11)	0.0184 (14)
C17	0.0428 (15)	0.082 (2)	0.0421 (15)	0.000	0.0020 (13)	0.000
C18	0.0607 (13)	0.0635 (14)	0.0550 (12)	−0.0145 (11)	−0.0021 (11)	−0.0045 (11)
C19	0.060 (2)	0.126 (4)	0.077 (3)	0.000	−0.016 (2)	0.000

Geometric parameters (Å, º) top

Cl1—O10	1.4302 (17)	C8—C7	1.488 (3)
Cl1—O10ⁱ	1.4302 (17)	C8—H8A	0.9700
Cl1—O8	1.439 (2)	C8—H8B	0.9700
Cl1—O9	1.442 (2)	C14—C18	1.385 (3)
O3—C8	1.426 (2)	C14—H14	0.9300
O3—C9	1.430 (2)	C7—H7A	0.9700
O4—C7ⁱ	1.418 (2)	C7—H7B	0.9700
O4—C7	1.418 (2)	C10—H10A	0.9700
N1—C13	1.468 (3)	C10—H10B	0.9700
N1—H1A	0.8900	C11—C12	1.497 (3)
N1—H1B	0.8900	C11—H11A	0.9700
N1—H1C	0.8900	C11—H11B	0.9700
O2—C11	1.417 (3)	C12—H12A	0.9700
O2—C10	1.431 (3)	C12—H12B	0.9700
O1—C12ⁱ	1.428 (3)	C17—C18ⁱ	1.386 (3)
O1—C12	1.428 (3)	C17—C18	1.386 (3)
C13—C14	1.370 (2)	C17—C19	1.511 (4)
C13—C14ⁱ	1.370 (2)	C18—H18	0.9300
C9—C10	1.485 (3)	C19—H19A	0.9600
C9—H9A	0.9700	C19—H19B	0.9600
C9—H9B	0.9700	C19—H19C	0.9600

O10—Cl1—O10ⁱ	110.61 (17)	O4—C7—H7A	110.0
O10—Cl1—O8	109.50 (10)	C8—C7—H7A	110.0
O10ⁱ—Cl1—O8	109.50 (10)	O4—C7—H7B	110.0
O10—Cl1—O9	109.54 (9)	C8—C7—H7B	110.0
O10ⁱ—Cl1—O9	109.54 (9)	H7A—C7—H7B	108.4
O8—Cl1—O9	108.11 (15)	O2—C10—C9	108.74 (17)
C8—O3—C9	111.86 (15)	O2—C10—H10A	109.9
C7ⁱ—O4—C7	112.5 (2)	C9—C10—H10A	109.9
C13—N1—H1A	109.5	O2—C10—H10B	109.9
C13—N1—H1B	109.5	C9—C10—H10B	109.9
H1A—N1—H1B	109.5	H10A—C10—H10B	108.3
C13—N1—H1C	109.5	O2—C11—C12	108.77 (19)
H1A—N1—H1C	109.5	O2—C11—H11A	109.9
H1B—N1—H1C	109.5	C12—C11—H11A	109.9
C11—O2—C10	112.44 (17)	O2—C11—H11B	109.9
C12ⁱ—O1—C12	112.6 (2)	C12—C11—H11B	109.9
C14—C13—C14ⁱ	120.6 (3)	H11A—C11—H11B	108.3
C14—C13—N1	119.68 (13)	O1—C12—C11	109.48 (17)
C14ⁱ—C13—N1	119.68 (13)	O1—C12—H12A	109.8
O3—C9—C10	109.56 (17)	C11—C12—H12A	109.8
O3—C9—H9A	109.8	O1—C12—H12B	109.8
C10—C9—H9A	109.8	C11—C12—H12B	109.8
O3—C9—H9B	109.8	H12A—C12—H12B	108.2
C10—C9—H9B	109.8	C18ⁱ—C17—C18	117.1 (3)
H9A—C9—H9B	108.2	C18ⁱ—C17—C19	121.45 (14)
O3—C8—C7	109.42 (16)	C18—C17—C19	121.45 (14)
O3—C8—H8A	109.8	C14—C18—C17	121.8 (2)
C7—C8—H8A	109.8	C14—C18—H18	119.1
O3—C8—H8B	109.8	C17—C18—H18	119.1
C7—C8—H8B	109.8	C17—C19—H19A	109.5
H8A—C8—H8B	108.2	C17—C19—H19B	109.5
C13—C14—C18	119.4 (2)	H19A—C19—H19B	109.5
C13—C14—H14	120.3	C17—C19—H19C	109.5
C18—C14—H14	120.3	H19A—C19—H19C	109.5
O4—C7—C8	108.33 (16)	H19B—C19—H19C	109.5

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2ⁱ	0.89	2.23	2.9477 (19)	138
N1—H1B···O3ⁱ	0.89	2.19	2.9511 (18)	143
N1—H1C···O4	0.89	2.20	2.924 (3)	138
N1—H1C···O3	0.89	2.20	2.9511 (18)	142
N1—H1A···O2	0.89	2.22	2.9477 (19)	139
N1—H1A···O1	0.89	2.15	2.888 (3)	140

Symmetry code: (i) x, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₇H₁₀N⁺·ClO₄⁻·C₁₂H₂₄O₆
M_r	471.92
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	15.510 (3), 11.717 (2), 13.014 (3)
V (Å³)	2365.0 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.27 × 0.26 × 0.23

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.944, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	23471, 2843, 2051
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.131, 1.04
No. of reflections	2843
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.29

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
N1—H1B···O2ⁱ	0.89	2.23	2.9477 (19)	137.5
N1—H1B···O3ⁱ	0.89	2.19	2.9511 (18)	143.0
N1—H1C···O4	0.89	2.20	2.924 (3)	138.0
N1—H1C···O3	0.89	2.20	2.9511 (18)	142.2
N1—H1A···O2	0.89	2.22	2.9477 (19)	138.8
N1—H1A···O1	0.89	2.15	2.888 (3)	140.3

Symmetry code: (i) x, −y+1/2, z.

Acknowledgements

The author thanks the SEU research start-up capital of new teachers for support.

References

Ge, J.-Z. & Zhao, M.-M. (2010). Acta Cryst. E66, m739. Web of Science CrossRef IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o185

doi:10.1107/S1600536811053992

Open

access