N,N,2,4,6-Penta­methyl­anilinium hexa­fluoro­phosphate

Zhang, Y.

doi:10.1107/S1600536812049379

organic compounds

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Volume 69| Part 1| January 2013| Page o31

https://doi.org/10.1107/S1600536812049379

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N,N,2,4,6-Pentamethylanilinium hexafluorophosphate

Yuan Zhang ^a ^*

^aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
^*Correspondence e-mail: zhangshelley86@Hotmail.com

(Received 30 November 2012; accepted 1 December 2012; online 8 December 2012)

In the crystal structure of the title salt, C₁₁H₁₈N⁺·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.

Related literature

For the background to the title salt, see: Haertling et al. (1999 ); Homes et al. (2001 ).

Experimental

Crystal data

C₁₁H₁₈N⁺·PF₆⁻
M_r = 309.23
Monoclinic, P 2₁ /c
a = 11.466 (2) Å
b = 8.2439 (16) Å
c = 15.559 (3) Å
β = 97.82 (3)°
V = 1457.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.20 × 0.19 × 0.18 mm

Data collection

Rigaku Mercury2 diffractometer
14679 measured reflections
3340 independent reflections
1942 reflections with I > 2σ(I)
R_int = 0.074

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.186
S = 1.03
3340 reflections
177 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: CrystalClear (Rigaku, 2005 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812049379/xu5658sup1.cif

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

checkCIF report

Comment top

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).

Related literature top

For the background to the title salt, see: Haertling et al. (1999); Homes et al. (2001).

Experimental top

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.

Structure description top

For the background to the title salt, see: Haertling et al. (1999); Homes et al. (2001).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: 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).

Figures top

	Fig. 1. Perspective structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along theb axis showing the hydrogen bondings network.

N,N,2,4,6-Pentamethylanilinium hexafluorophosphate top

Crystal data top

C₁₁H₁₈N⁺·PF₆⁻	F(000) = 640
M_r = 309.23	D_x = 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

Data collection top

Rigaku Mercury2 diffractometer	1942 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.074
Graphite monochromator	θ_max = 27.5°, θ_min = 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 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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.186	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0788P)² + 0.4571P] where P = (F_o² + 2F_c²)/3
3340 reflections	(Δ/σ)_max = 0.001
177 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₁H₁₈N⁺·PF₆⁻	V = 1457.0 (5) Å³
M_r = 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)°

Data collection top

Rigaku Mercury2 diffractometer	1942 reflections with I > 2σ(I)
14679 measured reflections	R_int = 0.074
3340 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.186	H-atom parameters constrained
S = 1.03	Δρ_max = 0.21 e Å⁻³
3340 reflections	Δρ_min = −0.27 e Å⁻³
177 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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⁻
M_r	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
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.27

Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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
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Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
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