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

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ISSN: 2056-9890

4-Methyl­anilinium perchlorate 18-crown-6 clathrate

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[Ge, J.-Z. & Zhao, M.-M. (2010). Acta Cryst. E66, m739.]).

[Scheme 1]

Experimental

Crystal data
  • C7H10N+·ClO4·C12H24O6

  • Mr = 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.944, Tmax = 0.952

  • 23471 measured reflections

  • 2843 independent reflections

  • 2051 reflections with I > 2σ(I)

  • Rint = 0.056

Refinement
  • R[F2 > 2σ(F2)] = 0.052

  • wR(F2) = 0.131

  • S = 1.04

  • 2843 reflections

  • 156 parameters

  • H-atom parameters constrained

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.29 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[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

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.

Refinement top

H atoms were placed in calculated positions (C—H = 0.93–0.97 Å; N—H = 0.89 Å) and refined as riding, with Uiso = 1.2-1.5 Ueq of the parent atom.

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, 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·C12H24O6F(000) = 1008
Mr = 471.92Dx = 1.325 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nθ = 3.1–27.8°
a = 15.510 (3) ŵ = 0.21 mm1
b = 11.717 (2) ÅT = 293 K
c = 13.014 (3) ÅBlock, colourless
V = 2365.0 (8) Å30.27 × 0.26 × 0.23 mm
Z = 4
Data collection top
Rigaku Mercury2
diffractometer
2843 independent reflections
Radiation source: fine-focus sealed tube2051 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.056
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
CCD_Profile_fitting scansh = 2019
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1515
Tmin = 0.944, Tmax = 0.952l = 1616
23471 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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0508P)2 + 0.9055P]
where P = (Fo2 + 2Fc2)/3
2843 reflections(Δ/σ)max < 0.001
156 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C7H10N+·ClO4·C12H24O6V = 2365.0 (8) Å3
Mr = 471.92Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 15.510 (3) ŵ = 0.21 mm1
b = 11.717 (2) ÅT = 293 K
c = 13.014 (3) Å0.27 × 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)
Tmin = 0.944, Tmax = 0.952Rint = 0.056
23471 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.131H-atom parameters constrained
S = 1.04Δρmax = 0.23 e Å3
2843 reflectionsΔρmin = 0.29 e Å3
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
xyzUiso*/UeqOcc. (<1)
Cl10.39923 (4)0.25000.29294 (6)0.0499 (2)
O90.48479 (14)0.25000.33632 (19)0.0668 (6)
O100.38749 (12)0.14964 (16)0.23197 (15)0.0872 (6)
O80.33818 (15)0.25000.37618 (19)0.0764 (7)
O30.39105 (9)0.03863 (11)0.71904 (11)0.0521 (4)
O40.45688 (13)0.25000.65171 (14)0.0500 (5)
N10.29743 (14)0.25000.77156 (16)0.0419 (5)
H1A0.28450.21660.83100.063*0.50
H1B0.31410.32160.78300.063*0.50
H1C0.34000.21180.74120.063*0.50
O20.29941 (9)0.04793 (12)0.90648 (11)0.0584 (4)
O10.21558 (14)0.25000.97086 (15)0.0608 (6)
C130.22121 (16)0.25000.70472 (18)0.0392 (6)
C90.39753 (15)0.04759 (18)0.79645 (17)0.0588 (6)
H9A0.44330.02830.84420.071*
H9B0.41140.12030.76490.071*
C80.46909 (14)0.04990 (18)0.66202 (17)0.0564 (5)
H8A0.47950.01900.62270.068*
H8B0.51710.06080.70870.068*
C140.18536 (14)0.14842 (18)0.67484 (15)0.0533 (5)
H140.20970.07970.69560.064*
C70.46218 (15)0.14939 (18)0.59148 (15)0.0545 (5)
H7A0.51230.15280.54700.065*
H7B0.41120.14210.54880.065*
C100.31436 (15)0.05658 (18)0.85247 (18)0.0611 (6)
H10A0.26780.07050.80430.073*
H10B0.31650.11970.90060.073*
C110.22117 (15)0.0464 (2)0.9626 (2)0.0705 (7)
H11A0.21750.02281.00320.085*
H11B0.17260.04820.91580.085*
C120.21869 (16)0.1486 (2)1.03166 (17)0.0720 (7)
H12A0.16830.14481.07570.086*
H12B0.26960.14971.07500.086*
C170.07397 (19)0.25000.5819 (2)0.0558 (8)
C180.11245 (14)0.1491 (2)0.61334 (16)0.0598 (6)
H180.08870.07990.59260.072*
C190.0071 (2)0.25000.5175 (3)0.0878 (12)
H19A0.04860.19920.54740.132*0.50
H19B0.00640.22500.44910.132*0.50
H19C0.03050.32580.51500.132*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0481 (4)0.0428 (4)0.0587 (4)0.0000.0021 (3)0.000
O90.0551 (13)0.0592 (13)0.0862 (16)0.0000.0069 (12)0.000
O100.0857 (13)0.0753 (12)0.1007 (13)0.0023 (10)0.0109 (11)0.0348 (11)
O80.0657 (15)0.0856 (17)0.0778 (16)0.0000.0166 (13)0.000
O30.0547 (8)0.0424 (7)0.0593 (9)0.0062 (6)0.0008 (7)0.0064 (6)
O40.0629 (12)0.0435 (11)0.0437 (10)0.0000.0081 (9)0.000
N10.0443 (12)0.0426 (12)0.0388 (12)0.0000.0047 (10)0.000
O20.0560 (9)0.0527 (9)0.0664 (9)0.0097 (7)0.0087 (7)0.0088 (7)
O10.0650 (13)0.0781 (15)0.0393 (11)0.0000.0077 (10)0.000
C130.0397 (13)0.0461 (14)0.0319 (12)0.0000.0051 (11)0.000
C90.0688 (14)0.0412 (11)0.0665 (14)0.0059 (10)0.0085 (12)0.0068 (10)
C80.0589 (12)0.0497 (12)0.0605 (13)0.0122 (10)0.0065 (11)0.0074 (10)
C140.0597 (12)0.0468 (12)0.0534 (12)0.0010 (10)0.0048 (10)0.0000 (9)
C70.0610 (12)0.0549 (13)0.0477 (11)0.0044 (10)0.0069 (10)0.0079 (10)
C100.0699 (14)0.0433 (12)0.0700 (14)0.0104 (10)0.0115 (12)0.0142 (10)
C110.0611 (14)0.0783 (17)0.0721 (16)0.0125 (12)0.0103 (12)0.0237 (14)
C120.0649 (14)0.106 (2)0.0453 (12)0.0048 (14)0.0128 (11)0.0184 (14)
C170.0428 (15)0.082 (2)0.0421 (15)0.0000.0020 (13)0.000
C180.0607 (13)0.0635 (14)0.0550 (12)0.0145 (11)0.0021 (11)0.0045 (11)
C190.060 (2)0.126 (4)0.077 (3)0.0000.016 (2)0.000
Geometric parameters (Å, º) top
Cl1—O101.4302 (17)C8—C71.488 (3)
Cl1—O10i1.4302 (17)C8—H8A0.9700
Cl1—O81.439 (2)C8—H8B0.9700
Cl1—O91.442 (2)C14—C181.385 (3)
O3—C81.426 (2)C14—H140.9300
O3—C91.430 (2)C7—H7A0.9700
O4—C7i1.418 (2)C7—H7B0.9700
O4—C71.418 (2)C10—H10A0.9700
N1—C131.468 (3)C10—H10B0.9700
N1—H1A0.8900C11—C121.497 (3)
N1—H1B0.8900C11—H11A0.9700
N1—H1C0.8900C11—H11B0.9700
O2—C111.417 (3)C12—H12A0.9700
O2—C101.431 (3)C12—H12B0.9700
O1—C12i1.428 (3)C17—C18i1.386 (3)
O1—C121.428 (3)C17—C181.386 (3)
C13—C141.370 (2)C17—C191.511 (4)
C13—C14i1.370 (2)C18—H180.9300
C9—C101.485 (3)C19—H19A0.9600
C9—H9A0.9700C19—H19B0.9600
C9—H9B0.9700C19—H19C0.9600
O10—Cl1—O10i110.61 (17)O4—C7—H7A110.0
O10—Cl1—O8109.50 (10)C8—C7—H7A110.0
O10i—Cl1—O8109.50 (10)O4—C7—H7B110.0
O10—Cl1—O9109.54 (9)C8—C7—H7B110.0
O10i—Cl1—O9109.54 (9)H7A—C7—H7B108.4
O8—Cl1—O9108.11 (15)O2—C10—C9108.74 (17)
C8—O3—C9111.86 (15)O2—C10—H10A109.9
C7i—O4—C7112.5 (2)C9—C10—H10A109.9
C13—N1—H1A109.5O2—C10—H10B109.9
C13—N1—H1B109.5C9—C10—H10B109.9
H1A—N1—H1B109.5H10A—C10—H10B108.3
C13—N1—H1C109.5O2—C11—C12108.77 (19)
H1A—N1—H1C109.5O2—C11—H11A109.9
H1B—N1—H1C109.5C12—C11—H11A109.9
C11—O2—C10112.44 (17)O2—C11—H11B109.9
C12i—O1—C12112.6 (2)C12—C11—H11B109.9
C14—C13—C14i120.6 (3)H11A—C11—H11B108.3
C14—C13—N1119.68 (13)O1—C12—C11109.48 (17)
C14i—C13—N1119.68 (13)O1—C12—H12A109.8
O3—C9—C10109.56 (17)C11—C12—H12A109.8
O3—C9—H9A109.8O1—C12—H12B109.8
C10—C9—H9A109.8C11—C12—H12B109.8
O3—C9—H9B109.8H12A—C12—H12B108.2
C10—C9—H9B109.8C18i—C17—C18117.1 (3)
H9A—C9—H9B108.2C18i—C17—C19121.45 (14)
O3—C8—C7109.42 (16)C18—C17—C19121.45 (14)
O3—C8—H8A109.8C14—C18—C17121.8 (2)
C7—C8—H8A109.8C14—C18—H18119.1
O3—C8—H8B109.8C17—C18—H18119.1
C7—C8—H8B109.8C17—C19—H19A109.5
H8A—C8—H8B108.2C17—C19—H19B109.5
C13—C14—C18119.4 (2)H19A—C19—H19B109.5
C13—C14—H14120.3C17—C19—H19C109.5
C18—C14—H14120.3H19A—C19—H19C109.5
O4—C7—C8108.33 (16)H19B—C19—H19C109.5
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O2i0.892.232.9477 (19)138
N1—H1B···O3i0.892.192.9511 (18)143
N1—H1C···O40.892.202.924 (3)138
N1—H1C···O30.892.202.9511 (18)142
N1—H1A···O20.892.222.9477 (19)139
N1—H1A···O10.892.152.888 (3)140
Symmetry code: (i) x, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC7H10N+·ClO4·C12H24O6
Mr471.92
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)293
a, b, c (Å)15.510 (3), 11.717 (2), 13.014 (3)
V3)2365.0 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.21
Crystal size (mm)0.27 × 0.26 × 0.23
Data collection
DiffractometerRigaku Mercury2
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.944, 0.952
No. of measured, independent and
observed [I > 2σ(I)] reflections
23471, 2843, 2051
Rint0.056
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.131, 1.04
No. of reflections2843
No. of parameters156
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1B···O2i0.892.232.9477 (19)137.5
N1—H1B···O3i0.892.192.9511 (18)143.0
N1—H1C···O40.892.202.924 (3)138.0
N1—H1C···O30.892.202.9511 (18)142.2
N1—H1A···O20.892.222.9477 (19)138.8
N1—H1A···O10.892.152.888 (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

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

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