3,5-Bis(3-methyl­imidazolium-1-ylmeth­yl)toluene bis­(hexa­fluoro­phosphate)

Washeel, A.; Haque, R.A.; Teoh, S.G.; Yeap, C.S.; Fun, H.-K.

doi:10.1107/S1600536810003739

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o556

doi:10.1107/S1600536810003739

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3,5-Bis(3-methylimidazolium-1-ylmethyl)toluene bis(hexafluorophosphate)

Abbas Washeel,^a Rosenani A. Haque,^a Siang Guan Teoh,^a Chin Sing Yeap ^b ‡ and Hoong-Kun Fun ^b ^*§

^aSchool of Chemical Science, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 21 January 2010; accepted 30 January 2010; online 6 February 2010)

The asymmetric unit of the title N-heterocyclic carbene compound, C₁₇H₂₂N₄²⁺·2PF₆⁻, consists of one N-heterocyclic carbene dication and two hexafluorophosphate anions. The two imidazole rings are twisted away from but to the same side of the central toluene ring, making dihedral angles of 76.69 (7) and 78.03 (7)° with the central ring. In the crystal, the components are linked by C—H⋯F interactions, generating a three-dimensional network.

Related literature

For background to N-heterocyclic carbenes, see: Wanzlick & Schönherr (1968 ); Öfele (1968 ); Arduengo et al. (1991 ). For applications of N-heterocyclic carbene derivatives, see: Meyer et al. (2009 ); Ray et al. (2007 ); Medvetz et al. (2008 ). For a related structure, see: Jiang (2009 ). For the synthesis, see; Dias & Jin (1994 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₇H₂₂N₄²⁺·2PF₆⁻
M_r = 572.33
Monoclinic, P 2₁ /c
a = 6.1289 (1) Å
b = 19.0139 (4) Å
c = 20.1770 (4) Å
β = 97.390 (1)°
V = 2331.78 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 100 K
0.53 × 0.28 × 0.20 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.858, T_max = 0.942
42881 measured reflections
11275 independent reflections
7988 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.149
S = 1.03
11275 reflections
319 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯F2ⁱ	0.93	2.47	3.3431 (16)	157
C5—H5A⋯F8ⁱⁱ	0.93	2.39	3.2686 (16)	157
C8—H8A⋯F12ⁱⁱ	0.93	2.40	3.2808 (16)	158
C9—H9A⋯F4ⁱ	0.93	2.41	3.2513 (19)	151
C10—H10A⋯F4ⁱⁱⁱ	0.93	2.38	3.2967 (17)	169
C12—H12B⋯F5^iv	0.97	2.42	3.3040 (18)	150
C14—H14A⋯F8ⁱⁱⁱ	0.93	2.55	3.283 (2)	136
C14—H14A⋯F10ⁱⁱⁱ	0.93	2.53	3.3050 (19)	141
C15—H15A⋯F7^v	0.93	2.50	3.2568 (19)	139
C16—H16B⋯F9^vi	0.96	2.48	3.135 (2)	125
C16—H16C⋯F2	0.96	2.48	3.314 (2)	146
C17—H17C⋯F11	0.96	2.42	3.3563 (18)	166
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) x+1, y, z; (v) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810003739/tk2620sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810003739/tk2620Isup2.hkl

checkCIF report

Comment top

N-Heterocyclic carbenes (NHCs) were first pioneered by Wanzlick and Öfele in 1968 (Wanzlick & Schönherr, 1968; Öfele, 1968). After the isolation of the first stable crystalline carbene by Arduengo in 1991, the research area of NHCs has continued to grow (Arduengo et al., 1991). NHCs are an important class of ligands and their metal complexes are important in homogeneous catalysis for a wide range of reactions including C–C coupling reactions, olefin metathesis, hydroformylation, and polymerization reactions (Meyer et al., 2009). The biological activities of many of these complexes were confirmed (Ray et al., 2007) and the silver complexes derived from 4,5-dichloro-1H-imidazole were found to be active against human cancer cell lines (Medvetz et al., 2008).

The asymmetric unit of the title compound consists of one N-heterocyclic carbene dication and two hexafluorophosphate anions (Fig. 1). The geometric parameters are comparable to those of a related structure (Jiang, 2009). Each of the imidazole rings (N1–C8–N2–C10–C9 and N3–C13–N4–C15–C14) is planar with a maximum deviation of 0.003 (1) Å (for N1) and 0.002 (2) Å (for C14 & C15), respectively. The two imidazole rings are twisted away from the central toluene ring but are orientated to the same side of the ring, making dihedral angles of 76.69 (7) and 78.03 (7)° with the central ring, respectively. The two hexafluorophosphate anions link the ions into a three-dimensional network via intermolecular C—H···F hydrogen bonds (Fig. 2, Table 1).

Related literature top

For background to N-heterocyclic carbenes, see: Wanzlick & Schönherr (1968); Öfele (1968); Arduengo et al. (1991). For applications of N-heterocyclic carbene derivatives, see: Meyer et al. (2009); Ray et al. (2007); Medvetz et al. (2008). For a related structure, see: Jiang (2009). For the synthesis, see; Dias & Jin (1994). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Experimental top

The title compound was prepared following the procedure of Dias & Jin (1994). To a stirred solution of 3,5-bis(bromomethyl)toluene (1.0 g, 3.6 mmol) in 1,4-dioxane (20 ml), 1-methylimidazole (0.9 g, 7.2 mmol) was added. The mixture was refluxed at 373 K for 24 h. The sticky product was isolated by decantation, then washed with diethyl ether (2x3 ml). KPF₆ (1.3 g, 7.2 mmol) in methanol (20 ml) was added with stirring for 1 h. Then the mixture left standing overnight. The beige precipitate was collected and washed with distilled water and recrystallised from hot methanol. The yield was 1.5 g (72.88 %), m.pt.: 467-469 K. Crystals were obtained by slow evaporation of the salt solution in acetonitrile at low temperature.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with 50% probability ellipsoids for non-H atoms.
	Fig. 2. The crystal packing of the title compound, viewed down the a axis, showing the molecules are linked a 3-D network. Intermolecular hydrogen bonds are shown as dashed lines.

3,5-Bis(3-methylimidazolium-1-ylmethyl)toluene bis(hexafluorophosphate) top

Crystal data top

C₁₇H₂₂N₄²⁺·2PF₆⁻	F(000) = 1160
M_r = 572.33	D_x = 1.630 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9980 reflections
a = 6.1289 (1) Å	θ = 2.3–33.1°
b = 19.0139 (4) Å	µ = 0.30 mm⁻¹
c = 20.1770 (4) Å	T = 100 K
β = 97.390 (1)°	Block, colourless
V = 2331.78 (8) Å³	0.53 × 0.28 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	11275 independent reflections
Radiation source: fine-focus sealed tube	7988 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 36.4°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→10
T_min = 0.858, T_max = 0.942	k = −31→31
42881 measured reflections	l = −33→33

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0703P)² + 0.7107P] where P = (F_o² + 2F_c²)/3
11275 reflections	(Δ/σ)_max = 0.001
319 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₁₇H₂₂N₄²⁺·2PF₆⁻	V = 2331.78 (8) Å³
M_r = 572.33	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.1289 (1) Å	µ = 0.30 mm⁻¹
b = 19.0139 (4) Å	T = 100 K
c = 20.1770 (4) Å	0.53 × 0.28 × 0.20 mm
β = 97.390 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	11275 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	7988 reflections with I > 2σ(I)
T_min = 0.858, T_max = 0.942	R_int = 0.034
42881 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.03	Δρ_max = 0.62 e Å⁻³
11275 reflections	Δρ_min = −0.44 e Å⁻³
319 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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 > 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
N1	1.09705 (19)	0.13322 (5)	0.47609 (5)	0.02147 (19)
N2	1.01744 (18)	0.14740 (6)	0.57634 (5)	0.02158 (19)
N3	1.07523 (19)	0.45850 (6)	0.36551 (5)	0.0224 (2)
N4	0.89594 (19)	0.55547 (6)	0.34480 (6)	0.0241 (2)
C1	0.8951 (2)	0.20094 (7)	0.33537 (6)	0.0244 (2)
H1A	0.8258	0.1574	0.3299	0.029*
C2	0.7957 (2)	0.25985 (7)	0.30300 (6)	0.0229 (2)
C3	0.9031 (2)	0.32451 (7)	0.31150 (6)	0.0220 (2)
H3A	0.8388	0.3642	0.2904	0.026*
C4	1.1060 (2)	0.33027 (7)	0.35138 (6)	0.0224 (2)
C5	1.2019 (2)	0.27104 (7)	0.38343 (6)	0.0230 (2)
H5A	1.3370	0.2747	0.4101	0.028*
C6	1.0960 (2)	0.20638 (7)	0.37567 (6)	0.0229 (2)
C7	1.1966 (3)	0.14348 (7)	0.41401 (7)	0.0284 (3)
H7A	1.1736	0.1017	0.3864	0.034*
H7B	1.3539	0.1506	0.4249	0.034*
C8	1.1522 (2)	0.16744 (6)	0.53334 (6)	0.0216 (2)
H8A	1.2659	0.1999	0.5418	0.026*
C9	0.9202 (3)	0.09042 (7)	0.48282 (7)	0.0287 (3)
H9A	0.8481	0.0610	0.4503	0.034*
C10	0.8715 (2)	0.09935 (8)	0.54570 (7)	0.0293 (3)
H10A	0.7596	0.0770	0.5647	0.035*
C11	1.0210 (3)	0.17284 (9)	0.64499 (7)	0.0326 (3)
H11A	1.1495	0.2013	0.6568	0.049*
H11B	1.0243	0.1335	0.6749	0.049*
H11C	0.8917	0.2004	0.6483	0.049*
C12	1.2268 (2)	0.39980 (7)	0.36005 (8)	0.0286 (3)
H12A	1.3332	0.3979	0.4000	0.034*
H12B	1.3064	0.4076	0.3221	0.034*
C13	1.0490 (2)	0.51400 (7)	0.32521 (6)	0.0215 (2)
H13A	1.1257	0.5224	0.2891	0.026*
C14	0.9316 (3)	0.46493 (8)	0.41259 (7)	0.0310 (3)
H14A	0.9148	0.4333	0.4467	0.037*
C15	0.8204 (3)	0.52554 (8)	0.39983 (8)	0.0316 (3)
H15A	0.7131	0.5438	0.4236	0.038*
C16	0.8185 (3)	0.62160 (8)	0.31312 (8)	0.0360 (3)
H16A	0.9219	0.6376	0.2845	0.054*
H16B	0.8050	0.6563	0.3469	0.054*
H16C	0.6778	0.6143	0.2871	0.054*
C17	0.5767 (2)	0.25388 (8)	0.26001 (7)	0.0307 (3)
H17A	0.5086	0.2994	0.2553	0.046*
H17B	0.4836	0.2222	0.2806	0.046*
H17C	0.5982	0.2362	0.2168	0.046*
P1	0.48424 (5)	0.488905 (18)	0.175041 (16)	0.02100 (7)
F1	0.74701 (13)	0.49029 (5)	0.18064 (5)	0.03038 (18)
F2	0.48256 (17)	0.57311 (5)	0.17898 (5)	0.0381 (2)
F3	0.22094 (15)	0.48912 (6)	0.16927 (6)	0.0434 (2)
F4	0.46926 (17)	0.49406 (6)	0.09530 (4)	0.0407 (2)
F5	0.50201 (18)	0.48512 (7)	0.25471 (5)	0.0442 (3)
F6	0.48927 (19)	0.40533 (5)	0.16983 (6)	0.0488 (3)
P2	0.66006 (5)	0.168232 (18)	0.043019 (17)	0.02251 (8)
F7	0.39775 (14)	0.15921 (5)	0.03209 (5)	0.0366 (2)
F8	0.66196 (17)	0.16954 (6)	−0.03614 (5)	0.0412 (2)
F9	0.92024 (15)	0.17795 (6)	0.05369 (6)	0.0421 (2)
F10	0.69001 (18)	0.08453 (5)	0.04230 (6)	0.0420 (2)
F11	0.6604 (2)	0.16457 (8)	0.12203 (5)	0.0575 (4)
F12	0.62782 (18)	0.25150 (5)	0.04312 (7)	0.0552 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0274 (5)	0.0155 (4)	0.0224 (4)	0.0010 (4)	0.0065 (4)	0.0017 (4)
N2	0.0240 (5)	0.0208 (5)	0.0200 (4)	0.0028 (4)	0.0029 (4)	0.0019 (4)
N3	0.0262 (5)	0.0190 (5)	0.0223 (4)	−0.0057 (4)	0.0044 (4)	0.0003 (4)
N4	0.0248 (5)	0.0214 (5)	0.0254 (5)	−0.0017 (4)	0.0010 (4)	−0.0041 (4)
C1	0.0336 (7)	0.0184 (5)	0.0230 (5)	−0.0047 (5)	0.0101 (5)	−0.0033 (4)
C2	0.0285 (6)	0.0220 (5)	0.0192 (5)	−0.0055 (4)	0.0072 (4)	−0.0028 (4)
C3	0.0268 (6)	0.0202 (5)	0.0195 (5)	−0.0020 (4)	0.0050 (4)	0.0006 (4)
C4	0.0265 (6)	0.0191 (5)	0.0223 (5)	−0.0025 (4)	0.0060 (4)	0.0007 (4)
C5	0.0251 (6)	0.0225 (5)	0.0220 (5)	0.0006 (4)	0.0060 (4)	0.0007 (4)
C6	0.0317 (6)	0.0186 (5)	0.0205 (5)	0.0023 (4)	0.0115 (4)	0.0002 (4)
C7	0.0401 (7)	0.0207 (6)	0.0275 (6)	0.0084 (5)	0.0158 (5)	0.0025 (5)
C8	0.0209 (5)	0.0187 (5)	0.0253 (5)	−0.0008 (4)	0.0034 (4)	−0.0007 (4)
C9	0.0364 (7)	0.0223 (6)	0.0268 (6)	−0.0105 (5)	0.0013 (5)	0.0016 (5)
C10	0.0290 (6)	0.0300 (7)	0.0292 (6)	−0.0090 (5)	0.0053 (5)	0.0062 (5)
C11	0.0418 (8)	0.0350 (7)	0.0211 (5)	0.0130 (6)	0.0048 (5)	−0.0007 (5)
C12	0.0238 (6)	0.0216 (6)	0.0402 (7)	−0.0035 (4)	0.0031 (5)	0.0041 (5)
C13	0.0232 (5)	0.0215 (5)	0.0201 (5)	−0.0031 (4)	0.0037 (4)	0.0003 (4)
C14	0.0437 (8)	0.0272 (6)	0.0247 (6)	−0.0118 (6)	0.0145 (5)	−0.0026 (5)
C15	0.0350 (7)	0.0304 (7)	0.0320 (6)	−0.0078 (5)	0.0146 (6)	−0.0107 (5)
C16	0.0386 (8)	0.0261 (7)	0.0395 (8)	0.0054 (6)	−0.0089 (6)	−0.0022 (6)
C17	0.0309 (7)	0.0333 (7)	0.0275 (6)	−0.0074 (5)	0.0022 (5)	−0.0039 (5)
P1	0.01773 (14)	0.02285 (15)	0.02274 (14)	0.00107 (10)	0.00376 (11)	0.00061 (11)
F1	0.0179 (3)	0.0379 (5)	0.0356 (4)	0.0027 (3)	0.0042 (3)	0.0001 (4)
F2	0.0392 (5)	0.0242 (4)	0.0517 (6)	0.0057 (4)	0.0091 (4)	−0.0031 (4)
F3	0.0176 (4)	0.0592 (7)	0.0538 (6)	−0.0036 (4)	0.0061 (4)	−0.0061 (5)
F4	0.0399 (5)	0.0593 (6)	0.0223 (4)	0.0208 (5)	0.0018 (4)	−0.0017 (4)
F5	0.0407 (5)	0.0687 (8)	0.0247 (4)	−0.0091 (5)	0.0100 (4)	0.0080 (4)
F6	0.0449 (6)	0.0229 (4)	0.0752 (8)	−0.0043 (4)	−0.0051 (5)	0.0019 (5)
P2	0.01778 (14)	0.02462 (16)	0.02537 (15)	0.00125 (11)	0.00367 (11)	−0.00180 (12)
F7	0.0190 (4)	0.0468 (5)	0.0443 (5)	−0.0040 (4)	0.0055 (3)	0.0089 (4)
F8	0.0350 (5)	0.0598 (7)	0.0299 (4)	0.0093 (4)	0.0084 (4)	0.0100 (4)
F9	0.0178 (4)	0.0478 (6)	0.0593 (6)	0.0006 (4)	−0.0010 (4)	0.0095 (5)
F10	0.0447 (6)	0.0269 (4)	0.0538 (6)	0.0047 (4)	0.0039 (5)	0.0042 (4)
F11	0.0468 (6)	0.1009 (11)	0.0251 (4)	0.0206 (6)	0.0064 (4)	−0.0085 (5)
F12	0.0356 (5)	0.0249 (5)	0.1015 (10)	0.0045 (4)	−0.0052 (6)	−0.0120 (5)

Geometric parameters (Å, º) top

N1—C8	1.3310 (16)	C10—H10A	0.9300
N1—C9	1.3759 (18)	C11—H11A	0.9600
N1—C7	1.4752 (17)	C11—H11B	0.9600
N2—C8	1.3284 (17)	C11—H11C	0.9600
N2—C10	1.3691 (18)	C12—H12A	0.9700
N2—C11	1.4647 (17)	C12—H12B	0.9700
N3—C13	1.3294 (16)	C13—H13A	0.9300
N3—C14	1.3810 (18)	C14—C15	1.347 (2)
N3—C12	1.4652 (18)	C14—H14A	0.9300
N4—C13	1.3242 (17)	C15—H15A	0.9300
N4—C15	1.3795 (19)	C16—H16A	0.9600
N4—C16	1.4618 (19)	C16—H16B	0.9600
C1—C6	1.389 (2)	C16—H16C	0.9600
C1—C2	1.3965 (19)	C17—H17A	0.9600
C1—H1A	0.9300	C17—H17B	0.9600
C2—C3	1.3945 (17)	C17—H17C	0.9600
C2—C17	1.5059 (19)	P1—F6	1.5932 (10)
C3—C4	1.3959 (18)	P1—F5	1.5988 (10)
C3—H3A	0.9300	P1—F1	1.6001 (9)
C4—C5	1.3907 (18)	P1—F4	1.6027 (9)
C4—C12	1.5143 (18)	P1—F3	1.6029 (10)
C5—C6	1.3897 (18)	P1—F2	1.6031 (10)
C5—H5A	0.9300	P2—F9	1.5921 (10)
C6—C7	1.5123 (18)	P2—F11	1.5955 (11)
C7—H7A	0.9700	P2—F12	1.5957 (11)
C7—H7B	0.9700	P2—F8	1.5989 (10)
C8—H8A	0.9300	P2—F10	1.6024 (10)
C9—C10	1.351 (2)	P2—F7	1.6036 (9)
C9—H9A	0.9300

C8—N1—C9	108.59 (11)	N3—C12—H12B	109.3
C8—N1—C7	125.85 (12)	C4—C12—H12B	109.3
C9—N1—C7	125.40 (12)	H12A—C12—H12B	108.0
C8—N2—C10	108.76 (11)	N4—C13—N3	108.95 (11)
C8—N2—C11	126.01 (12)	N4—C13—H13A	125.5
C10—N2—C11	125.23 (12)	N3—C13—H13A	125.5
C13—N3—C14	108.23 (12)	C15—C14—N3	107.21 (12)
C13—N3—C12	125.92 (12)	C15—C14—H14A	126.4
C14—N3—C12	125.84 (12)	N3—C14—H14A	126.4
C13—N4—C15	108.57 (12)	C14—C15—N4	107.04 (13)
C13—N4—C16	125.75 (13)	C14—C15—H15A	126.5
C15—N4—C16	125.68 (13)	N4—C15—H15A	126.5
C6—C1—C2	120.95 (12)	N4—C16—H16A	109.5
C6—C1—H1A	119.5	N4—C16—H16B	109.5
C2—C1—H1A	119.5	H16A—C16—H16B	109.5
C3—C2—C1	118.63 (12)	N4—C16—H16C	109.5
C3—C2—C17	120.59 (12)	H16A—C16—H16C	109.5
C1—C2—C17	120.78 (12)	H16B—C16—H16C	109.5
C2—C3—C4	120.75 (12)	C2—C17—H17A	109.5
C2—C3—H3A	119.6	C2—C17—H17B	109.5
C4—C3—H3A	119.6	H17A—C17—H17B	109.5
C5—C4—C3	119.76 (12)	C2—C17—H17C	109.5
C5—C4—C12	118.82 (12)	H17A—C17—H17C	109.5
C3—C4—C12	121.41 (12)	H17B—C17—H17C	109.5
C6—C5—C4	120.04 (12)	F6—P1—F5	91.26 (7)
C6—C5—H5A	120.0	F6—P1—F1	89.61 (6)
C4—C5—H5A	120.0	F5—P1—F1	89.54 (5)
C1—C6—C5	119.86 (12)	F6—P1—F4	89.65 (6)
C1—C6—C7	120.87 (12)	F5—P1—F4	178.89 (7)
C5—C6—C7	119.21 (13)	F1—P1—F4	89.83 (5)
N1—C7—C6	110.66 (10)	F6—P1—F3	91.47 (6)
N1—C7—H7A	109.5	F5—P1—F3	90.62 (6)
C6—C7—H7A	109.5	F1—P1—F3	178.90 (6)
N1—C7—H7B	109.5	F4—P1—F3	89.99 (6)
C6—C7—H7B	109.5	F6—P1—F2	178.73 (7)
H7A—C7—H7B	108.1	F5—P1—F2	89.72 (6)
N2—C8—N1	108.46 (11)	F1—P1—F2	89.59 (5)
N2—C8—H8A	125.8	F4—P1—F2	89.36 (6)
N1—C8—H8A	125.8	F3—P1—F2	89.32 (6)
C10—C9—N1	106.89 (12)	F9—P2—F11	89.85 (6)
C10—C9—H9A	126.6	F9—P2—F12	90.39 (6)
N1—C9—H9A	126.6	F11—P2—F12	91.50 (8)
C9—C10—N2	107.30 (12)	F9—P2—F8	89.86 (6)
C9—C10—H10A	126.4	F11—P2—F8	178.32 (7)
N2—C10—H10A	126.4	F12—P2—F8	90.15 (7)
N2—C11—H11A	109.5	F9—P2—F10	90.15 (6)
N2—C11—H11B	109.5	F11—P2—F10	88.87 (7)
H11A—C11—H11B	109.5	F12—P2—F10	179.35 (7)
N2—C11—H11C	109.5	F8—P2—F10	89.47 (6)
H11A—C11—H11C	109.5	F9—P2—F7	179.46 (6)
H11B—C11—H11C	109.5	F11—P2—F7	90.30 (6)
N3—C12—C4	111.62 (11)	F12—P2—F7	89.09 (6)
N3—C12—H12A	109.3	F8—P2—F7	90.02 (6)
C4—C12—H12A	109.3	F10—P2—F7	90.37 (6)

C6—C1—C2—C3	0.45 (19)	C7—N1—C8—N2	175.98 (11)
C6—C1—C2—C17	−179.27 (12)	C8—N1—C9—C10	−0.46 (16)
C1—C2—C3—C4	0.19 (19)	C7—N1—C9—C10	−175.99 (12)
C17—C2—C3—C4	179.91 (12)	N1—C9—C10—N2	0.27 (17)
C2—C3—C4—C5	−0.45 (19)	C8—N2—C10—C9	0.01 (16)
C2—C3—C4—C12	178.79 (12)	C11—N2—C10—C9	179.28 (13)
C3—C4—C5—C6	0.08 (19)	C13—N3—C12—C4	−120.97 (14)
C12—C4—C5—C6	−179.19 (12)	C14—N3—C12—C4	57.56 (18)
C2—C1—C6—C5	−0.83 (19)	C5—C4—C12—N3	−141.60 (12)
C2—C1—C6—C7	176.25 (11)	C3—C4—C12—N3	39.15 (18)
C4—C5—C6—C1	0.56 (19)	C15—N4—C13—N3	−0.04 (15)
C4—C5—C6—C7	−176.57 (11)	C16—N4—C13—N3	−179.56 (12)
C8—N1—C7—C6	−81.82 (17)	C14—N3—C13—N4	0.27 (14)
C9—N1—C7—C6	92.95 (16)	C12—N3—C13—N4	179.02 (11)
C1—C6—C7—N1	−80.96 (15)	C13—N3—C14—C15	−0.40 (16)
C5—C6—C7—N1	96.14 (15)	C12—N3—C14—C15	−179.15 (12)
C10—N2—C8—N1	−0.30 (15)	N3—C14—C15—N4	0.37 (16)
C11—N2—C8—N1	−179.56 (12)	C13—N4—C15—C14	−0.21 (16)
C9—N1—C8—N2	0.47 (15)	C16—N4—C15—C14	179.31 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···F2ⁱ	0.93	2.47	3.3431 (16)	157
C5—H5A···F8ⁱⁱ	0.93	2.39	3.2686 (16)	157
C8—H8A···F12ⁱⁱ	0.93	2.40	3.2808 (16)	158
C9—H9A···F4ⁱ	0.93	2.41	3.2513 (19)	151
C10—H10A···F4ⁱⁱⁱ	0.93	2.38	3.2967 (17)	169
C12—H12B···F5^iv	0.97	2.42	3.3040 (18)	150
C14—H14A···F8ⁱⁱⁱ	0.93	2.55	3.283 (2)	136
C14—H14A···F10ⁱⁱⁱ	0.93	2.53	3.3050 (19)	141
C15—H15A···F7^v	0.93	2.50	3.2568 (19)	139
C16—H16B···F9^vi	0.96	2.48	3.135 (2)	125
C16—H16C···F2	0.96	2.48	3.314 (2)	146
C17—H17C···F11	0.96	2.42	3.3563 (18)	166

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

Experimental details

Crystal data
Chemical formula	C₁₇H₂₂N₄²⁺·2PF₆⁻
M_r	572.33
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	6.1289 (1), 19.0139 (4), 20.1770 (4)
β (°)	97.390 (1)
V (Å³)	2331.78 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.53 × 0.28 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.858, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	42881, 11275, 7988
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.834

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.149, 1.03
No. of reflections	11275
No. of parameters	319
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.44

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···F2ⁱ	0.9300	2.4700	3.3431 (16)	157.00
C5—H5A···F8ⁱⁱ	0.9300	2.3900	3.2686 (16)	157.00
C8—H8A···F12ⁱⁱ	0.9300	2.4000	3.2808 (16)	158.00
C9—H9A···F4ⁱ	0.9300	2.4100	3.2513 (19)	151.00
C10—H10A···F4ⁱⁱⁱ	0.9300	2.3800	3.2967 (17)	169.00
C12—H12B···F5^iv	0.9700	2.4200	3.3040 (18)	150.00
C14—H14A···F8ⁱⁱⁱ	0.9300	2.5500	3.283 (2)	136.00
C14—H14A···F10ⁱⁱⁱ	0.9300	2.5300	3.3050 (19)	141.00
C15—H15A···F7^v	0.9300	2.5000	3.2568 (19)	139.00
C16—H16B···F9^vi	0.9600	2.4800	3.135 (2)	125.00
C16—H16C···F2	0.9600	2.4800	3.314 (2)	146.00
C17—H17C···F11	0.9600	2.4200	3.3563 (18)	166.00

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

Footnotes

‡Thomson Reuters ResearcherID: A-5523-2009.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

AW, RAH and SGT thank Universiti Sains Malaysia (USM) for the FRGS fund (203/PKIMIA/671115). HKF and CSY thank USM for the Research University Golden Goose grant (1001/PFIZIK/811012). CSY thanks USM for the award of a USM Fellowship.

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