N,N,N-Trimethyl-1-[4-(pyridin-2-yl)phen­yl]meth­anaminium hexa­fluorido­phosphate

Ni, B.; Liu, H.; Du, X.; Han, Y.; Li, D.

doi:10.1107/S2414314619012069

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 9| September 2019| x191206

https://doi.org/10.1107/S2414314619012069

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N,N,N-Trimethyl-1-[4-(pyridin-2-yl)phenyl]methanaminium hexafluoridophosphate

Bo Ni,^a Hongping Liu,^a Xizhen Du,^a Yuyang Han ^a and Dandan Li ^a ^*

^aDepartment of Chemistry, Anhui University, Hefei, Anhui 230039, People's Republic of China
^*Correspondence e-mail: chemlidd@163.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 23 July 2019; accepted 31 August 2019; online 6 September 2019)

In the cation of the title molecular salt, C₁₅H₁₉N₂⁺·PF₆⁻, the dihedral angle between the benzene and pyridine rings is 38.21 (10)°. In the crystal, weak C—H⋯F interactions arising from methyl and methylene groups adjacent to the quaternary N atom generate (001) sheets.

Keywords: crystal structure; 2-phenylpyridine; quaternary ammonium salt.

CCDC reference: 1547525

Structure description

Quaternary ammonium derivatives have been investigated as fluorescent probes for biological applications (Choi et al., 2014 ) because of their favourable water solubility (Du et al., 2017 ).

As part of our studies in this area, we now describe the synthesis and structure of the title molecular salt (Fig. 1). The dihedral angle between the C6–C11 benzene ring and its attached C1–C5/N1 pyridine ring is 37.86 (10)° and the C11—C12—N2—C13 torsion angle is 175.60 (15)°. In the crystal, weak C—H⋯F interactions (Table 1) link the components into (001) sheets.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯F4ⁱ	0.97	2.50	3.441 (2)	163
C14—H14A⋯F5ⁱⁱ	0.96	2.55	3.070 (3)	114
C15—H15C⋯F3	0.96	2.54	3.414 (2)	151
Symmetry codes: (i) x, y-1, z; (ii) x-1, y-1, z.

Figure 1
The molecular structure of the title compound showing 50% displacement ellipsoids.

Synthesis and crystallization

Phenylpyridine benzylbromide (2.48 g, 0.1 mol) was dissolved in 20 ml of tetrahydrofuran and 60 ml of trimethylamine (40%) were added and the mixture stirred at 363 K for 12 h. Then, excess NH₄PF₆ was added after the reaction had cooled to room temperature, and the solid product recovered by filtration (1.2 g, 80%). Yellow blocks were recrystallized from ethanol solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₉N₂⁺·F₆P⁻
M_r	372.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	5.9107 (14), 8.5110 (19), 33.155 (8)
β (°)	90.726 (3)
V (Å³)	1667.7 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.23
Crystal size (mm)	0.19 × 0.18 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.615, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	9197, 2929, 2642
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.109, 1.04
No. of reflections	2929
No. of parameters	221
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.32
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1547525

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619012069/hb4310sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619012069/hb4310Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619012069/hb4310Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

N,N,N-Trimethyl-1-[4-(pyridin-2-yl)phenyl]methanaminium hexafluoridophosphate top

Crystal data top

C₁₅H₁₉N₂⁺·F₆P⁻	F(000) = 768
M_r = 372.29	D_x = 1.483 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.9107 (14) Å	Cell parameters from 5626 reflections
b = 8.5110 (19) Å	θ = 2.4–27.5°
c = 33.155 (8) Å	µ = 0.23 mm⁻¹
β = 90.726 (3)°	T = 296 K
V = 1667.7 (7) Å³	Block, yellow
Z = 4	0.19 × 0.18 × 0.17 mm

Data collection top

Bruker APEXII CCD diffractometer	2642 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→5
T_min = 0.615, T_max = 0.746	k = −10→10
9197 measured reflections	l = −39→39
2929 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.041	w = 1/[σ²(F_o²) + (0.0518P)² + 1.2216P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.109	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.50 e Å⁻³
2929 reflections	Δρ_min = −0.32 e Å⁻³
221 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.0052 (9)
Primary atom site location: structure-invariant direct methods

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.

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

	x	y	z	U_iso*/U_eq
P1	0.90293 (8)	0.73732 (5)	0.07069 (2)	0.02656 (17)
F1	1.1645 (2)	0.72985 (18)	0.07985 (6)	0.0716 (5)
F2	0.9394 (3)	0.63740 (16)	0.03048 (4)	0.0637 (5)
F3	0.6414 (2)	0.74621 (18)	0.05956 (5)	0.0631 (5)
F4	0.8649 (3)	0.83845 (17)	0.10989 (4)	0.0653 (5)
F5	0.9381 (2)	0.89666 (14)	0.04538 (4)	0.0480 (4)
F6	0.8645 (2)	0.57788 (14)	0.09500 (4)	0.0446 (3)
N1	0.0843 (3)	0.2266 (2)	0.26972 (5)	0.0409 (4)
N2	0.5066 (3)	0.24358 (17)	0.05910 (5)	0.0260 (4)
C1	−0.3375 (4)	0.0822 (3)	0.26267 (7)	0.0453 (5)
H1	−0.478424	0.034325	0.260160	0.054*
C2	−0.2701 (4)	0.1496 (3)	0.29865 (7)	0.0421 (5)
H2	−0.364510	0.148830	0.320881	0.051*
C3	−0.0590 (4)	0.2184 (3)	0.30082 (7)	0.0451 (6)
H3	−0.012898	0.261769	0.325324	0.054*
C4	−0.1916 (4)	0.0870 (3)	0.23029 (6)	0.0404 (5)
H4	−0.232793	0.041313	0.205797	0.048*
C5	0.0170 (3)	0.1608 (2)	0.23482 (6)	0.0318 (4)
C6	0.1751 (3)	0.1712 (2)	0.20039 (6)	0.0310 (4)
C7	0.3061 (4)	0.3046 (2)	0.19437 (6)	0.0371 (5)
H7	0.299121	0.387348	0.212637	0.045*
C8	0.4471 (4)	0.3154 (2)	0.16140 (6)	0.0357 (5)
H8	0.529710	0.406868	0.157265	0.043*
C9	0.1968 (4)	0.0460 (2)	0.17366 (6)	0.0344 (5)
H9	0.111937	−0.044679	0.177472	0.041*
C10	0.3437 (4)	0.0551 (2)	0.14138 (6)	0.0333 (5)
H10	0.359911	−0.030722	0.124292	0.040*
C11	0.4664 (3)	0.1911 (2)	0.13441 (6)	0.0292 (4)
C12	0.6243 (3)	0.2045 (2)	0.09932 (5)	0.0282 (4)
H12A	0.704960	0.105971	0.096452	0.034*
H12B	0.735173	0.285529	0.105267	0.034*
C13	0.6872 (4)	0.2653 (2)	0.02812 (6)	0.0336 (5)
H13A	0.617977	0.286957	0.002369	0.050*
H13B	0.776180	0.171279	0.026361	0.050*
H13C	0.782871	0.351684	0.035842	0.050*
C14	0.3537 (4)	0.1130 (2)	0.04599 (6)	0.0336 (5)
H14A	0.232047	0.102903	0.064740	0.050*
H14B	0.437619	0.016475	0.045190	0.050*
H14C	0.293017	0.135565	0.019630	0.050*
C15	0.3718 (3)	0.3917 (2)	0.06230 (6)	0.0344 (5)
H15A	0.254210	0.377693	0.081684	0.052*
H15B	0.305506	0.416454	0.036489	0.052*
H15C	0.469121	0.476111	0.070778	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0267 (3)	0.0212 (3)	0.0319 (3)	−0.00140 (19)	0.0044 (2)	−0.00271 (19)
F1	0.0331 (8)	0.0500 (9)	0.1314 (16)	−0.0012 (6)	−0.0107 (9)	0.0026 (9)
F2	0.1072 (13)	0.0403 (8)	0.0442 (8)	−0.0088 (8)	0.0261 (8)	−0.0127 (6)
F3	0.0327 (8)	0.0586 (9)	0.0977 (12)	−0.0065 (6)	−0.0076 (7)	0.0213 (8)
F4	0.1109 (14)	0.0430 (8)	0.0423 (8)	0.0112 (8)	0.0106 (8)	−0.0130 (6)
F5	0.0593 (9)	0.0290 (7)	0.0557 (8)	−0.0117 (6)	0.0046 (6)	0.0070 (6)
F6	0.0606 (9)	0.0323 (7)	0.0410 (7)	−0.0053 (6)	0.0017 (6)	0.0085 (5)
N1	0.0478 (11)	0.0399 (10)	0.0352 (9)	−0.0055 (8)	0.0093 (7)	−0.0068 (8)
N2	0.0297 (9)	0.0213 (8)	0.0272 (8)	−0.0011 (6)	0.0044 (6)	−0.0004 (6)
C1	0.0378 (12)	0.0524 (14)	0.0458 (12)	−0.0019 (10)	0.0056 (8)	0.0123 (11)
C2	0.0489 (13)	0.0387 (12)	0.0391 (11)	0.0057 (10)	0.0164 (10)	0.0081 (9)
C3	0.0623 (15)	0.0405 (12)	0.0330 (11)	−0.0039 (11)	0.0133 (9)	−0.0059 (9)
C4	0.0416 (11)	0.0472 (13)	0.0323 (10)	−0.0045 (9)	−0.0005 (8)	0.0042 (9)
C5	0.0384 (10)	0.0278 (10)	0.0293 (9)	0.0026 (8)	0.0039 (8)	0.0024 (8)
C6	0.0349 (11)	0.0301 (10)	0.0281 (9)	0.0001 (8)	0.0022 (8)	−0.0001 (8)
C7	0.0453 (13)	0.0309 (11)	0.0354 (11)	−0.0041 (9)	0.0082 (9)	−0.0105 (9)
C8	0.0405 (12)	0.0292 (10)	0.0375 (11)	−0.0090 (9)	0.0087 (9)	−0.0069 (9)
C9	0.0465 (12)	0.0274 (10)	0.0294 (10)	−0.0065 (9)	0.0040 (8)	0.0018 (8)
C10	0.0484 (12)	0.0243 (10)	0.0272 (9)	−0.0001 (9)	0.0040 (8)	−0.0027 (7)
C11	0.0338 (11)	0.0270 (10)	0.0270 (9)	0.0006 (8)	0.0018 (8)	−0.0015 (8)
C12	0.0291 (10)	0.0267 (9)	0.0287 (9)	0.0017 (8)	0.0005 (8)	−0.0012 (7)
C13	0.0364 (11)	0.0338 (11)	0.0308 (10)	−0.0031 (9)	0.0109 (8)	0.0022 (8)
C14	0.0405 (12)	0.0288 (10)	0.0315 (10)	−0.0092 (9)	−0.0006 (8)	−0.0015 (8)
C15	0.0335 (11)	0.0248 (10)	0.0451 (11)	0.0054 (8)	0.0030 (9)	0.0022 (8)

Geometric parameters (Å, º) top

P1—F1	1.5729 (15)	C6—C9	1.392 (3)
P1—F2	1.5982 (14)	C7—H7	0.9300
P1—F3	1.5865 (15)	C7—C8	1.386 (3)
P1—F4	1.5774 (14)	C8—H8	0.9300
P1—F5	1.6096 (13)	C8—C11	1.391 (3)
P1—F6	1.5960 (13)	C9—H9	0.9300
N1—C3	1.345 (3)	C9—C10	1.389 (3)
N1—C5	1.341 (3)	C10—H10	0.9300
N2—C12	1.532 (2)	C10—C11	1.387 (3)
N2—C13	1.502 (2)	C11—C12	1.505 (3)
N2—C14	1.494 (2)	C12—H12A	0.9700
N2—C15	1.496 (2)	C12—H12B	0.9700
C1—H1	0.9300	C13—H13A	0.9600
C1—C2	1.378 (3)	C13—H13B	0.9600
C1—C4	1.386 (3)	C13—H13C	0.9600
C2—H2	0.9300	C14—H14A	0.9600
C2—C3	1.379 (3)	C14—H14B	0.9600
C3—H3	0.9300	C14—H14C	0.9600
C4—H4	0.9300	C15—H15A	0.9600
C4—C5	1.390 (3)	C15—H15B	0.9600
C5—C6	1.487 (3)	C15—H15C	0.9600
C6—C7	1.391 (3)

F1—P1—F2	89.82 (10)	C6—C7—H7	119.7
F1—P1—F3	177.64 (10)	C8—C7—C6	120.58 (18)
F1—P1—F4	90.74 (10)	C8—C7—H7	119.7
F1—P1—F5	90.10 (8)	C7—C8—H8	119.6
F1—P1—F6	90.81 (8)	C7—C8—C11	120.80 (19)
F2—P1—F5	89.64 (8)	C11—C8—H8	119.6
F3—P1—F2	88.43 (10)	C6—C9—H9	119.6
F3—P1—F5	88.30 (8)	C10—C9—C6	120.75 (18)
F3—P1—F6	90.77 (8)	C10—C9—H9	119.6
F4—P1—F2	178.94 (9)	C9—C10—H10	119.7
F4—P1—F3	90.98 (10)	C11—C10—C9	120.55 (18)
F4—P1—F5	89.46 (8)	C11—C10—H10	119.7
F4—P1—F6	91.44 (8)	C8—C11—C12	119.77 (18)
F6—P1—F2	89.45 (7)	C10—C11—C8	118.68 (18)
F6—P1—F5	178.71 (7)	C10—C11—C12	121.51 (17)
C5—N1—C3	117.2 (2)	N2—C12—H12A	108.7
C13—N2—C12	107.65 (15)	N2—C12—H12B	108.7
C14—N2—C12	110.97 (14)	C11—C12—N2	114.22 (15)
C14—N2—C13	108.99 (14)	C11—C12—H12A	108.7
C14—N2—C15	109.06 (15)	C11—C12—H12B	108.7
C15—N2—C12	110.95 (14)	H12A—C12—H12B	107.6
C15—N2—C13	109.17 (14)	N2—C13—H13A	109.5
C2—C1—H1	120.6	N2—C13—H13B	109.5
C2—C1—C4	118.8 (2)	N2—C13—H13C	109.5
C4—C1—H1	120.6	H13A—C13—H13B	109.5
C1—C2—H2	120.9	H13A—C13—H13C	109.5
C1—C2—C3	118.2 (2)	H13B—C13—H13C	109.5
C3—C2—H2	120.9	N2—C14—H14A	109.5
N1—C3—C2	124.1 (2)	N2—C14—H14B	109.5
N1—C3—H3	118.0	N2—C14—H14C	109.5
C2—C3—H3	118.0	H14A—C14—H14B	109.5
C1—C4—H4	120.4	H14A—C14—H14C	109.5
C1—C4—C5	119.3 (2)	H14B—C14—H14C	109.5
C5—C4—H4	120.4	N2—C15—H15A	109.5
N1—C5—C4	122.33 (19)	N2—C15—H15B	109.5
N1—C5—C6	117.06 (18)	N2—C15—H15C	109.5
C4—C5—C6	120.60 (18)	H15A—C15—H15B	109.5
C7—C6—C5	121.02 (18)	H15A—C15—H15C	109.5
C7—C6—C9	118.53 (18)	H15B—C15—H15C	109.5
C9—C6—C5	120.44 (18)

N1—C5—C6—C7	−36.7 (3)	C6—C7—C8—C11	−2.2 (3)
N1—C5—C6—C9	142.5 (2)	C6—C9—C10—C11	−2.0 (3)
C1—C2—C3—N1	1.4 (4)	C7—C6—C9—C10	−0.9 (3)
C1—C4—C5—N1	0.7 (3)	C7—C8—C11—C10	−0.7 (3)
C1—C4—C5—C6	−178.6 (2)	C7—C8—C11—C12	−178.75 (19)
C2—C1—C4—C5	−0.7 (3)	C8—C11—C12—N2	−101.0 (2)
C3—N1—C5—C4	0.2 (3)	C9—C6—C7—C8	3.0 (3)
C3—N1—C5—C6	179.52 (19)	C9—C10—C11—C8	2.8 (3)
C4—C1—C2—C3	−0.3 (3)	C9—C10—C11—C12	−179.17 (18)
C4—C5—C6—C7	142.6 (2)	C10—C11—C12—N2	81.1 (2)
C4—C5—C6—C9	−38.2 (3)	C13—N2—C12—C11	175.60 (15)
C5—N1—C3—C2	−1.3 (3)	C14—N2—C12—C11	−65.2 (2)
C5—C6—C7—C8	−177.7 (2)	C15—N2—C12—C11	56.2 (2)
C5—C6—C9—C10	179.84 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···F4ⁱ	0.97	2.50	3.441 (2)	163
C14—H14A···F5ⁱⁱ	0.96	2.55	3.070 (3)	114
C15—H15C···F3	0.96	2.54	3.414 (2)	151

Symmetry codes: (i) x, y−1, z; (ii) x−1, y−1, z.

Funding information

The authors thank the National Nature Science Foundation of China (award No. 21701160) and Anhui University (Start-up Grant No. S020118002/026) for financial support of this project.

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