1,3-Bis(6-methyl­pyridin-2-yl)-1H-imidazol-3-ium hexa­fluoro­phosphate

Bae, H.; Yoon, M.; Sun, H.-J.; Lee, D.-H.; Park, G.

doi:10.1107/S1600536813006971

organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page o549

doi:10.1107/S1600536813006971

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1,3-Bis(6-methylpyridin-2-yl)-1H-imidazol-3-ium hexafluorophosphate

Hoyeon Bae,^a Minyoung Yoon,^b Ho-Jung Sun,^c Dong-Heon Lee ^d ^* and Gyungse Park ^e ^*

^aDepartment of Chemistry, Chonbuk National University, Jeonju, Chonbuk 561-756, Republic of Korea, ^bCenter for Smart Supramolecules, Department of Chemistry and Division of Advanced Materials Science, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea, ^cDepartment of Material Science & Engineering, Kunsan National University, Jeonbuk 573-701, Republic of Korea, ^dDepartment of Chemistry and Research Institute of Physics and Chemistry, Chonbuk National University, Jeonju 561-756, Republic of Korea, and ^eDepartment of Chemistry, Kunsan National University, Kunsan, Chonbuk 573-701, Republic of Korea
^*Correspondence e-mail: dhl@jbnu.ac.kr, parkg@kunsan.ac.kr

(Received 25 February 2013; accepted 13 March 2013; online 16 March 2013)

In the title salt, C₁₇H₁₉N₄⁺·PF₆⁻, the two pyridine rings of the cation are inclined to one another by 15.89 (8)°, and inclined to the imidazole ring by 65.05 (10) and 64.07 (10)°. In the crystal, the cations and anions are linked via a series of C—H⋯N and C—H⋯F hydrogen bonds, forming two-dimensional networks lying parallel to (001).

Related literature

For the isolation of an N-heterocyclic carbene, see: Arduengo et al. (1991 ). For related structures, see: Huang et al. (2011 ); Grieco et al. (2011 ); Kim et al. (2009 ). For applications of N-heterocyclic carbenes in catalytic processes, see: Enders et al. (1996 ); Frenzel et al. (1999 ); Scholl et al. (1999 ).

Experimental

Crystal data

C₁₇H₁₉N₄⁺·PF₆⁻
M_r = 424.33
Triclinic, $[P \overline 1]$
a = 6.3839 (3) Å
b = 12.0353 (5) Å
c = 12.8006 (5) Å
α = 108.039 (2)°
β = 96.091 (2)°
γ = 100.593 (2)°
V = 905.12 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 100 K
0.16 × 0.07 × 0.07 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.965, T_max = 0.986
19206 measured reflections
3700 independent reflections
2898 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.133
S = 0.97
3700 reflections
269 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯F3ⁱ	0.95	2.45	3.263 (2)	144
C7—H7A⋯N2ⁱⁱ	0.99	2.59	3.567 (2)	170
C7—H7B⋯F6ⁱⁱⁱ	0.99	2.28	3.264 (2)	172
C10—H10⋯F2^iv	0.95	2.53	3.373 (2)	148
C11—H11B⋯F4^iv	0.99	2.44	3.355 (2)	154
C13—H13⋯F4^iv	0.95	2.34	3.193 (2)	149
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+1, -z+2; (iii) x, y, z+1; (iv) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813006971/ng5317sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813006971/ng5317Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813006971/ng5317Isup3.cml

checkCIF report

Comment top

N,N'-Disubstituted imidazolium salts are of importance because stable and isolable N-heterocyclic carbenes (NHCs) can be easily prepared by deprotonation of the imidazolium salts with a strong base. N-Heterocyclic carbenes (NHCs) have been a topic of extensive research due to their practical applications in many catalytic processes, e.g., Pd–catalysed Heck–, Suzuki–coupling and Ru-based Grubbs catalyses (Frenzel et al., 1999; Enders et al., 1996; Scholl et al., 1999). We previously synthesized an N,N'-disubstituted imidazolium salt, 1,3-bis[(6-methyl-2-pyridinyl)methyl]imidazolium bromide, and reported its crystal structure (Kim et al., 2009)). The title compound was obtained by the anion exchange of the C₁₇H₁₉N₄⁺ Br^- with NH₄PF₆. Here we report the crystal structure of the title compound,1,3-bis[(6-methyl-2-pyridinyl)methyl]imidazolium hexafluorophosphate (Fig. 1).

The asymmetric unit of the title compound consists the C₁₇H₉N₄ cation and PF₆ anion. Each of two 6–methylpyridine rings is rotated out of the imidazole plane, with dihedral angle of N1/C2–C6 of 55.83 (9)° and N4/C12–C16 of 11.32 (9)°. The molecular packing is stabilized by four different intermolecular C—H···F hydrogen bonds in the structure. (Table 1 & Fig. 2).

Related literature top

For the isolation of an N-heterocyclic carbene, see: Arduengo et al. (1991). For related structures, see: Huang et al. (2011); Grieco et al. (2011); Kim et al. (2009). For applications of N-heterocyclic carbenes in catalytic processes, see: Enders et al. (1996); Frenzel et al. (1999); Scholl et al. (1999).

Experimental top

Synthesis of 1,3-Bis[(6-methylpyridin-2-yl)-1H-imidazolium hexafluorophosphate: A mixture of 1,3-Bis[(6-methylpyridin-2-yl)-1H-imidazolium bromide (Kim et al., 2009). (2.16 g, 6.01 x 10^–3 mol) and NH₄PF₆ (0.980 g, 6.01 x 10^–3 mol) were dissolved in acetonitrile (35 ml) and the reaction mixture was stirred at room temperature for 19 h. After the solution was filtered the solvent were removed by high-vacuum rotary evaporation. The filtrate was dried under the reduced pressure to afford a brown solid in 95% yield. Single crystals were obtained by Et₂O diffusion into a CHCl₃ solution of the compound.

Spectroscopic analysis: 1H NMR (CDCl₃, 400 MHz): δ8.95 (s, H, CH), 7.62 (t, 2H, J =7.8 Hz, CH), 7.47 (d, 2H, J = 2 Hz, CH), 7.31 (s, 2H, CH), 7.28(d, 2H J = 10 Hz, CH), 7.14 (d, 2H, J = 7.8 Hz, CH), 5.35 (s, 4H, CH₂), 2.50 (s, 6H, CH₃). 13 C NMR (CDCl₃, 100 MHz): δ159.0 (s, C), 150.9 (s, C), 137.9 (s, CH), 136.1 (s, CH), 123.7 (s, CH), 122.4 (s, CH), 120.5 (s, CH), 54.5 (s, CH2), 24.4 (s, CH₃).

Computing details top

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. C—H···F interactions (dotted lines) in the title compound. [Symmetry code: (i) -x, -y + 1, -z + 1; (ii) -x + 1, -y, -z + 1]

1,3-Bis(6-methylpyridin-2-yl)-1H-imidazol-3-ium hexafluorophosphate top

Crystal data top

C₁₇H₁₉N₄⁺·PF₆⁻	Z = 2
M_r = 424.33	F(000) = 436
Triclinic, P1	D_x = 1.557 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3839 (3) Å	Cell parameters from 3700 reflections
b = 12.0353 (5) Å	θ = 1.7–26.5°
c = 12.8006 (5) Å	µ = 0.22 mm⁻¹
α = 108.039 (2)°	T = 100 K
β = 96.091 (2)°	Block, colorless
γ = 100.593 (2)°	0.16 × 0.07 × 0.07 mm
V = 905.12 (7) Å³

Data collection top

Bruker APEXII diffractometer	2898 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.032
Graphite monochromator	θ_max = 26.5°, θ_min = 1.7°
θ/2πhi scans	h = −8→7
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −15→15
T_min = 0.965, T_max = 0.986	l = −16→16
19206 measured reflections	4 standard reflections every 10 min
3700 independent reflections	intensity decay: 0.0%

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
3700 reflections	(Δ/σ)_max < 0.001
269 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₁₇H₁₉N₄⁺·PF₆⁻	γ = 100.593 (2)°
M_r = 424.33	V = 905.12 (7) Å³
Triclinic, P1	Z = 2
a = 6.3839 (3) Å	Mo Kα radiation
b = 12.0353 (5) Å	µ = 0.22 mm⁻¹
c = 12.8006 (5) Å	T = 100 K
α = 108.039 (2)°	0.16 × 0.07 × 0.07 mm
β = 96.091 (2)°

Data collection top

Bruker APEXII diffractometer	2898 reflections with I > 2σ(I)
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	R_int = 0.032
T_min = 0.965, T_max = 0.986	4 standard reflections every 10 min
19206 measured reflections	intensity decay: 0.0%
3700 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 0.97	Δρ_max = 0.35 e Å⁻³
3700 reflections	Δρ_min = −0.45 e Å⁻³
269 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

	x	y	z	U_iso*/U_eq
P1	0.02678 (7)	0.17116 (4)	0.22243 (4)	0.02100 (17)
F1	−0.20955 (18)	0.16206 (10)	0.25487 (10)	0.0319 (3)
F2	0.26436 (17)	0.18066 (10)	0.18965 (10)	0.0307 (3)
F3	0.09571 (18)	0.30854 (9)	0.30069 (11)	0.0335 (3)
F4	0.1109 (2)	0.13509 (11)	0.32678 (10)	0.0383 (3)
F5	−0.0381 (2)	0.03350 (11)	0.14681 (12)	0.0517 (4)
F6	−0.05468 (19)	0.21073 (14)	0.12030 (11)	0.0472 (4)
N1	0.4837 (2)	0.09220 (12)	0.78766 (12)	0.0161 (3)
N2	0.2781 (2)	0.42854 (12)	0.85867 (12)	0.0172 (3)
N3	0.5463 (2)	0.18196 (13)	0.59095 (12)	0.0178 (3)
N4	0.3855 (2)	0.21935 (12)	0.92229 (12)	0.0159 (3)
C1	0.3009 (3)	0.54548 (17)	0.73429 (16)	0.0246 (4)
H1A	0.3075	0.6315	0.7669	0.037*
H1B	0.2319	0.5167	0.6557	0.037*
H1C	0.4478	0.5319	0.7397	0.037*
C2	0.1717 (3)	0.47883 (15)	0.79610 (14)	0.0181 (4)
C3	−0.0512 (3)	0.46979 (15)	0.78953 (15)	0.0201 (4)
H3	−0.1230	0.5075	0.7462	0.025 (5)*
C4	−0.1665 (3)	0.40628 (16)	0.84576 (16)	0.0218 (4)
H4	−0.3181	0.3993	0.8416	0.027 (5)*
C5	−0.0567 (3)	0.35243 (15)	0.90892 (15)	0.0205 (4)
H5	−0.1320	0.3067	0.9477	0.023 (5)*
C6	0.1643 (3)	0.36706 (15)	0.91398 (14)	0.0173 (4)
C7	0.2937 (3)	0.31832 (16)	0.98693 (14)	0.0199 (4)
H7A	0.4132	0.3841	1.0371	0.032 (6)*
H7B	0.1998	0.2888	1.0340	0.023 (5)*
C8	0.3746 (3)	0.17802 (15)	0.81261 (14)	0.0162 (4)
H8	0.3008	0.2054	0.7604	0.017 (5)*
C9	0.5053 (3)	0.15701 (16)	0.96936 (15)	0.0194 (4)
H9	0.5382	0.1678	1.0465	0.033 (6)*
C10	0.5668 (3)	0.07800 (15)	0.88527 (15)	0.0189 (4)
H10	0.6517	0.0227	0.8920	0.030 (5)*
C11	0.5118 (3)	0.02583 (15)	0.67421 (14)	0.0187 (4)
H11A	0.3680	−0.0104	0.6259	0.028 (5)*
H11B	0.5827	−0.0401	0.6767	0.043 (7)*
C12	0.6464 (3)	0.10626 (15)	0.62463 (14)	0.0164 (4)
C13	0.8589 (3)	0.10113 (16)	0.61417 (15)	0.0198 (4)
H13	0.9250	0.0475	0.6396	0.021 (5)*
C14	0.9729 (3)	0.17597 (16)	0.56576 (15)	0.0210 (4)
H14	1.1185	0.1743	0.5573	0.020 (5)*
C15	0.8716 (3)	0.25257 (16)	0.53018 (15)	0.0199 (4)
H15	0.9460	0.3038	0.4960	0.022 (5)*
C16	0.6582 (3)	0.25440 (15)	0.54479 (14)	0.0185 (4)
C17	0.5434 (3)	0.33675 (18)	0.50650 (18)	0.0277 (4)
H17A	0.5198	0.3113	0.4248	0.042*
H17B	0.6318	0.4190	0.5378	0.042*
H17C	0.4035	0.3337	0.5319	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0187 (3)	0.0230 (3)	0.0248 (3)	0.0041 (2)	0.0065 (2)	0.0125 (2)
F1	0.0232 (6)	0.0308 (6)	0.0450 (7)	0.0050 (5)	0.0158 (5)	0.0147 (5)
F2	0.0196 (6)	0.0401 (7)	0.0371 (7)	0.0072 (5)	0.0100 (5)	0.0176 (5)
F3	0.0274 (6)	0.0206 (6)	0.0519 (8)	0.0073 (5)	0.0026 (5)	0.0117 (5)
F4	0.0493 (8)	0.0459 (8)	0.0417 (8)	0.0283 (6)	0.0193 (6)	0.0317 (6)
F5	0.0393 (8)	0.0334 (8)	0.0601 (10)	−0.0049 (6)	0.0220 (7)	−0.0123 (6)
F6	0.0257 (7)	0.0908 (11)	0.0386 (8)	0.0116 (7)	0.0034 (6)	0.0427 (8)
N1	0.0154 (7)	0.0146 (7)	0.0194 (8)	0.0032 (6)	0.0042 (6)	0.0073 (6)
N2	0.0157 (8)	0.0177 (7)	0.0187 (8)	0.0043 (6)	0.0038 (6)	0.0062 (6)
N3	0.0169 (8)	0.0183 (8)	0.0181 (8)	0.0037 (6)	0.0024 (6)	0.0062 (6)
N4	0.0135 (7)	0.0172 (7)	0.0188 (7)	0.0036 (6)	0.0030 (6)	0.0086 (6)
C1	0.0240 (10)	0.0272 (10)	0.0275 (10)	0.0082 (8)	0.0058 (8)	0.0142 (8)
C2	0.0203 (9)	0.0157 (8)	0.0171 (9)	0.0050 (7)	0.0031 (7)	0.0035 (7)
C3	0.0178 (9)	0.0170 (9)	0.0239 (9)	0.0054 (7)	0.0004 (7)	0.0047 (7)
C4	0.0139 (9)	0.0185 (9)	0.0292 (10)	0.0027 (7)	0.0031 (7)	0.0036 (8)
C5	0.0192 (9)	0.0164 (9)	0.0249 (10)	0.0027 (7)	0.0070 (7)	0.0052 (7)
C6	0.0185 (9)	0.0151 (8)	0.0182 (9)	0.0049 (7)	0.0044 (7)	0.0041 (7)
C7	0.0225 (10)	0.0211 (9)	0.0177 (9)	0.0076 (7)	0.0061 (7)	0.0066 (7)
C8	0.0133 (8)	0.0170 (8)	0.0190 (9)	0.0024 (7)	0.0016 (7)	0.0081 (7)
C9	0.0172 (9)	0.0235 (9)	0.0207 (9)	0.0045 (7)	0.0021 (7)	0.0124 (7)
C10	0.0158 (9)	0.0203 (9)	0.0246 (10)	0.0046 (7)	0.0032 (7)	0.0130 (8)
C11	0.0193 (9)	0.0177 (9)	0.0197 (9)	0.0062 (7)	0.0064 (7)	0.0048 (7)
C12	0.0169 (9)	0.0158 (8)	0.0141 (8)	0.0041 (7)	0.0007 (7)	0.0025 (7)
C13	0.0172 (9)	0.0211 (9)	0.0213 (9)	0.0054 (7)	0.0021 (7)	0.0075 (7)
C14	0.0147 (9)	0.0239 (9)	0.0229 (10)	0.0047 (7)	0.0037 (7)	0.0055 (8)
C15	0.0190 (9)	0.0220 (9)	0.0178 (9)	0.0013 (7)	0.0052 (7)	0.0067 (7)
C16	0.0188 (9)	0.0204 (9)	0.0151 (9)	0.0040 (7)	0.0024 (7)	0.0051 (7)
C17	0.0272 (11)	0.0284 (10)	0.0345 (11)	0.0087 (8)	0.0067 (9)	0.0186 (9)

Geometric parameters (Å, º) top

P1—F5	1.5883 (13)	C4—H4	0.9500
P1—F6	1.5933 (12)	C5—C6	1.381 (2)
P1—F3	1.5951 (12)	C5—H5	0.9500
P1—F4	1.5980 (12)	C6—C7	1.501 (2)
P1—F1	1.6003 (12)	C7—H7A	0.9900
P1—F2	1.6095 (12)	C7—H7B	0.9900
N1—C8	1.327 (2)	C8—H8	0.9500
N1—C10	1.377 (2)	C9—C10	1.345 (3)
N1—C11	1.473 (2)	C9—H9	0.9500
N2—C2	1.343 (2)	C10—H10	0.9500
N2—C6	1.346 (2)	C11—C12	1.506 (3)
N3—C16	1.341 (2)	C11—H11A	0.9900
N3—C12	1.350 (2)	C11—H11B	0.9900
N4—C8	1.326 (2)	C12—C13	1.388 (2)
N4—C9	1.380 (2)	C13—C14	1.388 (3)
N4—C7	1.482 (2)	C13—H13	0.9500
C1—C2	1.496 (3)	C14—C15	1.376 (2)
C1—H1A	0.9800	C14—H14	0.9500
C1—H1B	0.9800	C15—C16	1.398 (2)
C1—H1C	0.9800	C15—H15	0.9500
C2—C3	1.399 (2)	C16—C17	1.501 (2)
C3—C4	1.375 (3)	C17—H17A	0.9800
C3—H3	0.9500	C17—H17B	0.9800
C4—C5	1.391 (2)	C17—H17C	0.9800

F5—P1—F6	91.57 (8)	C5—C6—C7	120.87 (16)
F5—P1—F3	178.51 (7)	N4—C7—C6	112.82 (14)
F6—P1—F3	89.86 (7)	N4—C7—H7A	109.0
F5—P1—F4	89.92 (8)	C6—C7—H7A	109.0
F6—P1—F4	178.50 (8)	N4—C7—H7B	109.0
F3—P1—F4	88.65 (7)	C6—C7—H7B	109.0
F5—P1—F1	90.45 (7)	H7A—C7—H7B	107.8
F6—P1—F1	89.57 (6)	N4—C8—N1	108.81 (14)
F3—P1—F1	89.98 (6)	N4—C8—H8	125.6
F4—P1—F1	90.59 (7)	N1—C8—H8	125.6
F5—P1—F2	89.65 (7)	C10—C9—N4	106.99 (15)
F6—P1—F2	90.28 (6)	C10—C9—H9	126.5
F3—P1—F2	89.92 (6)	N4—C9—H9	126.5
F4—P1—F2	89.57 (6)	C9—C10—N1	107.26 (15)
F1—P1—F2	179.82 (6)	C9—C10—H10	126.4
C8—N1—C10	108.43 (15)	N1—C10—H10	126.4
C8—N1—C11	124.97 (14)	N1—C11—C12	111.69 (14)
C10—N1—C11	126.59 (14)	N1—C11—H11A	109.3
C2—N2—C6	118.40 (15)	C12—C11—H11A	109.3
C16—N3—C12	118.01 (15)	N1—C11—H11B	109.3
C8—N4—C9	108.50 (14)	C12—C11—H11B	109.3
C8—N4—C7	127.20 (14)	H11A—C11—H11B	107.9
C9—N4—C7	124.26 (15)	N3—C12—C13	122.89 (16)
C2—C1—H1A	109.5	N3—C12—C11	115.65 (15)
C2—C1—H1B	109.5	C13—C12—C11	121.46 (15)
H1A—C1—H1B	109.5	C14—C13—C12	118.66 (16)
C2—C1—H1C	109.5	C14—C13—H13	120.7
H1A—C1—H1C	109.5	C12—C13—H13	120.7
H1B—C1—H1C	109.5	C15—C14—C13	118.86 (17)
N2—C2—C3	121.23 (17)	C15—C14—H14	120.6
N2—C2—C1	117.52 (16)	C13—C14—H14	120.6
C3—C2—C1	121.25 (16)	C14—C15—C16	119.50 (17)
C4—C3—C2	120.01 (17)	C14—C15—H15	120.2
C4—C3—H3	120.0	C16—C15—H15	120.2
C2—C3—H3	120.0	N3—C16—C15	122.06 (16)
C3—C4—C5	118.67 (17)	N3—C16—C17	117.27 (16)
C3—C4—H4	120.7	C15—C16—C17	120.66 (16)
C5—C4—H4	120.7	C16—C17—H17A	109.5
C6—C5—C4	118.44 (17)	C16—C17—H17B	109.5
C6—C5—H5	120.8	H17A—C17—H17B	109.5
C4—C5—H5	120.8	C16—C17—H17C	109.5
N2—C6—C5	123.21 (16)	H17A—C17—H17C	109.5
N2—C6—C7	115.87 (15)	H17B—C17—H17C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F3ⁱ	0.95	2.45	3.263 (2)	144
C7—H7A···N2ⁱⁱ	0.99	2.59	3.567 (2)	170
C7—H7B···F6ⁱⁱⁱ	0.99	2.28	3.264 (2)	172
C10—H10···F2^iv	0.95	2.53	3.373 (2)	148
C11—H11B···F4^iv	0.99	2.44	3.355 (2)	154
C13—H13···F4^iv	0.95	2.34	3.193 (2)	149

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+2; (iii) x, y, z+1; (iv) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₉N₄⁺·PF₆⁻
M_r	424.33
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.3839 (3), 12.0353 (5), 12.8006 (5)
α, β, γ (°)	108.039 (2), 96.091 (2), 100.593 (2)
V (Å³)	905.12 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.16 × 0.07 × 0.07

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.965, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	19206, 3700, 2898
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.133, 0.97
No. of reflections	3700
No. of parameters	269
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.45

Computer programs: APEX2 (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F3ⁱ	0.95	2.45	3.263 (2)	144
C7—H7A···N2ⁱⁱ	0.99	2.59	3.567 (2)	170
C7—H7B···F6ⁱⁱⁱ	0.99	2.28	3.264 (2)	172
C10—H10···F2^iv	0.95	2.53	3.373 (2)	148
C11—H11B···F4^iv	0.99	2.44	3.355 (2)	154
C13—H13···F4^iv	0.95	2.34	3.193 (2)	149

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+2; (iii) x, y, z+1; (iv) −x+1, −y, −z+1.

Acknowledgements

This work was supported by the "Human Resource Development (project name: Advanced track for Si-based solar cell materials and devices, project No. 201040100660)" of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korean Government Ministry of Knowledge Economy.

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