organic compounds
N,N,2,4,6-Pentamethylanilinium hexafluorophosphate
aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
*Correspondence e-mail: zhangshelley86@Hotmail.com
In the 11H18N+·PF6−, the cation and anion are connected via an N—H⋯F hydrogen bond; weak C—H⋯F hydrogen bonding also occurs between the cations and anions.
of the title salt, CRelated literature
For the background to the title salt, see: Haertling et al. (1999); Homes et al. (2001).
Experimental
Crystal data
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Data collection
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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: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536812049379/xu5658sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049379/xu5658Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812049379/xu5658Isup3.cml
A mix of N,N,2,4,6-pentamethylbenzenamine (1.36 g, 0.01 mol) and hexafluorophosphoric acid (1.90 g, 0.01 mol) in methanol (20 ml) was stirred until clear. After several days, the title compound was formed and recrystallized from methanol solution to afford colourless prismatic crystals suitable for X-ray analysis.
H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.96 and N—H = 0.91 Å and Uiso(H) = 1.2eq(C,N).
At present, much attention in ferroelectric material field is focused on developing ferroelectric pure organic or inorganic compounds (Haertling et al. 1999; Homes et al. 2001). In order to find more dielectric ferroelectric materials, we investigate the physical properties of the title compound (Fig. 1). The
of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent (dielectric constant equaling to 3.7 to 5.2), suggesting that this compound should be not a real or there may be no distinct occurred within the measured temperature range. Similarly, below the melting point (453 K) of the compound, the as a function of temperature also goes smoothly, and there is no dielectric anomaly observed (dielectric constant equaling to 3.7 to 5.2). Herein, we report the synthesis and of the title compound.Molecules of the title compound have normal geometric parameters. The bond lengths and angles are within their normal ranges. In the crystal, the cation and anion are connected via N—H···F and weak C—H···F hydrogen bonds (Table 1).
For the background to the title salt, see: Haertling et al. (1999); Homes et al. (2001).
Data collection: CrystalClear (Rigaku, 2005); cell
CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C11H18N+·PF6− | F(000) = 640 |
Mr = 309.23 | Dx = 1.410 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3340 reflections |
a = 11.466 (2) Å | θ = 2.7–27.5° |
b = 8.2439 (16) Å | µ = 0.24 mm−1 |
c = 15.559 (3) Å | T = 293 K |
β = 97.82 (3)° | Prism, colorless |
V = 1457.0 (5) Å3 | 0.20 × 0.19 × 0.18 mm |
Z = 4 |
Rigaku Mercury2 diffractometer | 1942 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.074 |
Graphite monochromator | θmax = 27.5°, θmin = 3.1° |
Detector resolution: 13.6612 pixels mm-1 | h = −14→14 |
CCD_Profile_fitting scans | k = −10→10 |
14679 measured reflections | l = −20→20 |
3340 independent 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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.186 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0788P)2 + 0.4571P] where P = (Fo2 + 2Fc2)/3 |
3340 reflections | (Δ/σ)max = 0.001 |
177 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C11H18N+·PF6− | V = 1457.0 (5) Å3 |
Mr = 309.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.466 (2) Å | µ = 0.24 mm−1 |
b = 8.2439 (16) Å | T = 293 K |
c = 15.559 (3) Å | 0.20 × 0.19 × 0.18 mm |
β = 97.82 (3)° |
Rigaku Mercury2 diffractometer | 1942 reflections with I > 2σ(I) |
14679 measured reflections | Rint = 0.074 |
3340 independent reflections |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.186 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.21 e Å−3 |
3340 reflections | Δρmin = −0.27 e Å−3 |
177 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
P1 | 0.32971 (7) | 0.80605 (11) | 0.35021 (6) | 0.0588 (3) | |
N1 | 0.68536 (19) | 0.8547 (3) | 0.37739 (14) | 0.0466 (6) | |
H1 | 0.6213 | 0.8201 | 0.4009 | 0.056* | |
F1 | 0.43410 (18) | 0.9123 (3) | 0.39786 (18) | 0.1138 (9) | |
F2 | 0.2284 (2) | 0.6948 (3) | 0.30436 (15) | 0.0956 (8) | |
F3 | 0.3564 (2) | 0.8663 (3) | 0.25858 (15) | 0.1075 (8) | |
F4 | 0.3043 (2) | 0.7382 (4) | 0.44062 (14) | 0.1104 (9) | |
F5 | 0.4216 (2) | 0.6632 (3) | 0.34402 (15) | 0.0948 (7) | |
F6 | 0.2418 (2) | 0.9486 (3) | 0.3564 (2) | 0.1270 (11) | |
C1 | 0.7884 (2) | 0.7941 (3) | 0.43803 (17) | 0.0432 (6) | |
C2 | 0.7626 (2) | 0.7091 (3) | 0.51013 (18) | 0.0482 (7) | |
C3 | 0.8564 (3) | 0.6512 (4) | 0.56766 (19) | 0.0559 (8) | |
H3 | 0.8409 | 0.5922 | 0.6158 | 0.067* | |
C4 | 0.9722 (3) | 0.6782 (4) | 0.5560 (2) | 0.0560 (8) | |
C5 | 0.9930 (3) | 0.7638 (4) | 0.4838 (2) | 0.0568 (8) | |
H5 | 1.0706 | 0.7832 | 0.4757 | 0.068* | |
C6 | 0.9034 (2) | 0.8228 (3) | 0.42212 (18) | 0.0487 (7) | |
C7 | 1.0726 (3) | 0.6148 (4) | 0.6206 (2) | 0.0763 (11) | |
H7A | 1.1392 | 0.5919 | 0.5912 | 0.114* | |
H7B | 1.0484 | 0.5172 | 0.6468 | 0.114* | |
H7C | 1.0940 | 0.6949 | 0.6647 | 0.114* | |
C8 | 0.6383 (3) | 0.6771 (5) | 0.5279 (2) | 0.0735 (10) | |
H8A | 0.6403 | 0.6149 | 0.5802 | 0.110* | |
H8B | 0.5964 | 0.6177 | 0.4803 | 0.110* | |
H8C | 0.5991 | 0.7784 | 0.5344 | 0.110* | |
C9 | 0.9394 (3) | 0.9078 (5) | 0.3437 (2) | 0.0707 (10) | |
H9A | 0.9402 | 0.8312 | 0.2973 | 0.106* | |
H9B | 1.0166 | 0.9534 | 0.3584 | 0.106* | |
H9C | 0.8842 | 0.9928 | 0.3256 | 0.106* | |
C10 | 0.6719 (3) | 0.7799 (5) | 0.2888 (2) | 0.0751 (10) | |
H10A | 0.7327 | 0.8200 | 0.2576 | 0.113* | |
H10B | 0.5963 | 0.8079 | 0.2580 | 0.113* | |
H10C | 0.6783 | 0.6642 | 0.2940 | 0.113* | |
C11 | 0.6748 (3) | 1.0353 (4) | 0.3754 (2) | 0.0693 (9) | |
H11A | 0.6797 | 1.0758 | 0.4336 | 0.104* | |
H11B | 0.6005 | 1.0656 | 0.3434 | 0.104* | |
H11C | 0.7375 | 1.0806 | 0.3480 | 0.104* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0438 (5) | 0.0666 (6) | 0.0658 (6) | −0.0018 (4) | 0.0060 (4) | −0.0077 (4) |
N1 | 0.0410 (12) | 0.0534 (14) | 0.0461 (13) | −0.0011 (10) | 0.0077 (10) | 0.0047 (10) |
F1 | 0.0631 (13) | 0.121 (2) | 0.154 (2) | −0.0277 (14) | 0.0021 (14) | −0.0462 (17) |
F2 | 0.0882 (15) | 0.1006 (17) | 0.0926 (16) | −0.0308 (13) | −0.0073 (12) | −0.0137 (12) |
F3 | 0.126 (2) | 0.1015 (18) | 0.0994 (18) | 0.0058 (15) | 0.0303 (15) | 0.0358 (14) |
F4 | 0.1209 (19) | 0.148 (2) | 0.0674 (15) | −0.0243 (18) | 0.0314 (13) | −0.0149 (14) |
F5 | 0.0918 (15) | 0.0934 (16) | 0.1004 (17) | 0.0358 (13) | 0.0172 (13) | 0.0080 (12) |
F6 | 0.0688 (14) | 0.0922 (18) | 0.222 (3) | 0.0201 (13) | 0.0262 (16) | −0.0326 (19) |
C1 | 0.0427 (14) | 0.0416 (15) | 0.0451 (15) | 0.0000 (12) | 0.0057 (11) | −0.0008 (12) |
C2 | 0.0487 (15) | 0.0503 (17) | 0.0466 (16) | 0.0005 (13) | 0.0096 (12) | 0.0003 (13) |
C3 | 0.064 (2) | 0.0586 (19) | 0.0435 (16) | 0.0016 (15) | 0.0034 (14) | 0.0015 (13) |
C4 | 0.0576 (18) | 0.0516 (18) | 0.0548 (18) | 0.0065 (14) | −0.0069 (14) | −0.0121 (14) |
C5 | 0.0431 (15) | 0.0622 (19) | 0.065 (2) | −0.0031 (14) | 0.0062 (14) | −0.0076 (16) |
C6 | 0.0448 (15) | 0.0517 (17) | 0.0504 (17) | −0.0029 (13) | 0.0092 (12) | −0.0023 (13) |
C7 | 0.076 (2) | 0.074 (2) | 0.070 (2) | 0.0143 (19) | −0.0217 (18) | −0.0071 (18) |
C8 | 0.059 (2) | 0.096 (3) | 0.068 (2) | −0.0054 (18) | 0.0193 (16) | 0.0252 (19) |
C9 | 0.0540 (18) | 0.086 (2) | 0.076 (2) | −0.0051 (18) | 0.0245 (16) | 0.0151 (19) |
C10 | 0.067 (2) | 0.105 (3) | 0.051 (2) | −0.005 (2) | −0.0001 (15) | −0.0204 (18) |
C11 | 0.069 (2) | 0.060 (2) | 0.079 (2) | 0.0075 (17) | 0.0088 (17) | 0.0133 (17) |
P1—F6 | 1.560 (2) | C5—C6 | 1.394 (4) |
P1—F2 | 1.573 (2) | C5—H5 | 0.9300 |
P1—F3 | 1.579 (2) | C6—C9 | 1.512 (4) |
P1—F4 | 1.577 (3) | C7—H7A | 0.9600 |
P1—F1 | 1.584 (2) | C7—H7B | 0.9600 |
P1—F5 | 1.591 (2) | C7—H7C | 0.9600 |
N1—C11 | 1.494 (4) | C8—H8A | 0.9600 |
N1—C1 | 1.494 (3) | C8—H8B | 0.9600 |
N1—C10 | 1.499 (4) | C8—H8C | 0.9600 |
N1—H1 | 0.9100 | C9—H9A | 0.9600 |
C1—C2 | 1.388 (4) | C9—H9B | 0.9600 |
C1—C6 | 1.394 (4) | C9—H9C | 0.9600 |
C2—C3 | 1.387 (4) | C10—H10A | 0.9600 |
C2—C8 | 1.512 (4) | C10—H10B | 0.9600 |
C3—C4 | 1.382 (4) | C10—H10C | 0.9600 |
C3—H3 | 0.9300 | C11—H11A | 0.9600 |
C4—C5 | 1.374 (4) | C11—H11B | 0.9600 |
C4—C7 | 1.515 (4) | C11—H11C | 0.9600 |
F6—P1—F2 | 91.36 (14) | C6—C5—H5 | 118.4 |
F6—P1—F3 | 91.42 (16) | C1—C6—C5 | 116.4 (3) |
F2—P1—F3 | 89.77 (14) | C1—C6—C9 | 126.2 (3) |
F6—P1—F4 | 90.74 (17) | C5—C6—C9 | 117.4 (3) |
F2—P1—F4 | 89.02 (14) | C4—C7—H7A | 109.5 |
F3—P1—F4 | 177.55 (15) | C4—C7—H7B | 109.5 |
F6—P1—F1 | 90.47 (14) | H7A—C7—H7B | 109.5 |
F2—P1—F1 | 177.89 (15) | C4—C7—H7C | 109.5 |
F3—P1—F1 | 91.24 (15) | H7A—C7—H7C | 109.5 |
F4—P1—F1 | 89.91 (15) | H7B—C7—H7C | 109.5 |
F6—P1—F5 | 178.83 (14) | C2—C8—H8A | 109.5 |
F2—P1—F5 | 89.71 (14) | C2—C8—H8B | 109.5 |
F3—P1—F5 | 88.11 (13) | H8A—C8—H8B | 109.5 |
F4—P1—F5 | 89.76 (15) | C2—C8—H8C | 109.5 |
F1—P1—F5 | 88.47 (13) | H8A—C8—H8C | 109.5 |
C11—N1—C1 | 113.6 (2) | H8B—C8—H8C | 109.5 |
C11—N1—C10 | 113.1 (3) | C6—C9—H9A | 109.5 |
C1—N1—C10 | 114.6 (2) | C6—C9—H9B | 109.5 |
C11—N1—H1 | 104.7 | H9A—C9—H9B | 109.5 |
C1—N1—H1 | 104.7 | C6—C9—H9C | 109.5 |
C10—N1—H1 | 104.7 | H9A—C9—H9C | 109.5 |
C2—C1—C6 | 122.7 (2) | H9B—C9—H9C | 109.5 |
C2—C1—N1 | 116.2 (2) | N1—C10—H10A | 109.5 |
C6—C1—N1 | 121.1 (2) | N1—C10—H10B | 109.5 |
C1—C2—C3 | 117.6 (3) | H10A—C10—H10B | 109.5 |
C1—C2—C8 | 123.0 (3) | N1—C10—H10C | 109.5 |
C3—C2—C8 | 119.3 (3) | H10A—C10—H10C | 109.5 |
C4—C3—C2 | 122.3 (3) | H10B—C10—H10C | 109.5 |
C4—C3—H3 | 118.9 | N1—C11—H11A | 109.5 |
C2—C3—H3 | 118.9 | N1—C11—H11B | 109.5 |
C5—C4—C3 | 117.8 (3) | H11A—C11—H11B | 109.5 |
C5—C4—C7 | 121.3 (3) | N1—C11—H11C | 109.5 |
C3—C4—C7 | 120.9 (3) | H11A—C11—H11C | 109.5 |
C4—C5—C6 | 123.2 (3) | H11B—C11—H11C | 109.5 |
C4—C5—H5 | 118.4 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F1 | 0.91 | 2.27 | 2.979 (3) | 134 |
C11—H11A···F4i | 0.96 | 2.47 | 3.399 (4) | 162 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C11H18N+·PF6− |
Mr | 309.23 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.466 (2), 8.2439 (16), 15.559 (3) |
β (°) | 97.82 (3) |
V (Å3) | 1457.0 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.20 × 0.19 × 0.18 |
Data collection | |
Diffractometer | Rigaku Mercury2 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14679, 3340, 1942 |
Rint | 0.074 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.186, 1.03 |
No. of reflections | 3340 |
No. of parameters | 177 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.27 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F1 | 0.91 | 2.27 | 2.979 (3) | 134 |
C11—H11A···F4i | 0.96 | 2.47 | 3.399 (4) | 162 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Acknowledgements
The author is grateful to the starter fund of Nanjing College of Chemical Technology for financial support.
References
Haertling, G. H. (1999). J. Am. Ceram. Soc. A82, 797–810. CrossRef Google Scholar
Homes, C. C., Vogt, T., Shapiro, S. M., Wakimoto, S. & Ramirez, A. P. (2001). Science, 293, 673–676. Web of Science CrossRef PubMed CAS 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.
At present, much attention in ferroelectric material field is focused on developing ferroelectric pure organic or inorganic compounds (Haertling et al. 1999; Homes et al. 2001). In order to find more dielectric ferroelectric materials, we investigate the physical properties of the title compound (Fig. 1). The dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent (dielectric constant equaling to 3.7 to 5.2), suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range. Similarly, below the melting point (453 K) of the compound, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed (dielectric constant equaling to 3.7 to 5.2). Herein, we report the synthesis and crystal structure of the title compound.
Molecules of the title compound have normal geometric parameters. The bond lengths and angles are within their normal ranges. In the crystal, the cation and anion are connected via N—H···F and weak C—H···F hydrogen bonds (Table 1).