organic compounds
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
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
of related 4-methylanilinium tetrafluoroborate 18-crown-6 clathrate has been reported by Ge & Zhao (2010Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku, 2005); cell 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
10.1107/S1600536811053992/cv5196sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811053992/cv5196Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811053992/cv5196Isup3.cml
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 ε = C/(T–T0)), suggesting that this compound is not ferroelectric or there may be no distinct occurring within the measured temperature range between 128 K and 378 K.
of the compound as a function of temperature indicates that the permittivity is basically temperature-independent (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.
Data collection: CrystalClear (Rigaku, 2005); cell
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).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]. |
C7H10N+·ClO4−·C12H24O6 | F(000) = 1008 |
Mr = 471.92 | Dx = 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 |
Rigaku Mercury2 diffractometer | 2843 independent reflections |
Radiation source: fine-focus sealed tube | 2051 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
CCD_Profile_fitting scans | h = −20→19 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −15→15 |
Tmin = 0.944, Tmax = 0.952 | l = −16→16 |
23471 measured reflections |
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(Fo2) + (0.0508P)2 + 0.9055P] where P = (Fo2 + 2Fc2)/3 |
2843 reflections | (Δ/σ)max < 0.001 |
156 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C7H10N+·ClO4−·C12H24O6 | V = 2365.0 (8) Å3 |
Mr = 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 |
Rigaku Mercury2 diffractometer | 2843 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 2051 reflections with I > 2σ(I) |
Tmin = 0.944, Tmax = 0.952 | Rint = 0.056 |
23471 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.23 e Å−3 |
2843 reflections | Δρmin = −0.29 e Å−3 |
156 parameters |
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. |
x | y | z | Uiso*/Ueq | 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 |
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 |
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. |
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 |
Mr | 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) |
Tmin, Tmax | 0.944, 0.952 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23471, 2843, 2051 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.23, −0.29 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
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
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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.