3-(3-Cyano­benz­yl)-1-methyl-1H-imidazol-3-ium hexa­fluoro­phosphate

Haque, R.A.; Zetty, Z.H.; Salman, A.W.; Fun, H.-K.; Ooi, C.W.

doi:10.1107/S1600536812001882

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages o489-o490

doi:10.1107/S1600536812001882

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3-(3-Cyanobenzyl)-1-methyl-1H-imidazol-3-ium hexafluorophosphate

Rosenani A. Haque,^a Zulikha H. Zetty,^a Abbas Washeel Salman,^a Hoong-Kun Fun ^b ^*‡ and Chin Wei Ooi ^b

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

(Received 13 January 2012; accepted 16 January 2012; online 21 January 2012)

In the title compound, C₁₂H₁₂N₃⁺·PF₆⁻, the hexafluorophosphate anion is disordered over two orientations with refined site occupancies of 0.8071 (17) and 0.1929 (17). The dihedral angle between the imidazole and benzene rings in the cation is 71.26 (7)°. In the crystal, the cations and anions are linked by C—H⋯F and C—H⋯N hydrogen bonds into a three-dimensional network.

Related literature

For details and applications of N-heterocyclic carbenes, see: Hermann et al. (1997 ); Wanzlick & Kleiner (1961 ); Hermann & Köcher (1997 ); Baker et al. (2007 ); Gade & Laponnaz (2007 ); Özdemir et al. (2005 ); Köcher & Hermann (1997 ); Cetinkaya et al. (1997 ). For a related structure, see: Haque et al. (2011 ). For bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₂H₁₂N₃⁺·F₆P⁻
M_r = 343.22
Triclinic, $[P \overline 1]$
a = 5.9782 (1) Å
b = 8.7920 (1) Å
c = 14.1028 (2) Å
α = 77.975 (1)°
β = 83.279 (1)°
γ = 86.635 (1)°
V = 719.55 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 100 K
0.43 × 0.24 × 0.21 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.897, T_max = 0.949
14376 measured reflections
5233 independent reflections
4485 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.123
S = 1.04
5233 reflections
246 parameters
21 restraints
H-atom parameters constrained
Δρ_max = 0.91 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯F1	0.95	2.46	3.240 (2)	139
C1—H1A⋯F5	0.95	2.27	3.1715 (18)	159
C2—H2A⋯F3ⁱ	0.95	2.46	3.250 (2)	140
C3—H3A⋯N3ⁱⁱ	0.95	2.49	3.3970 (19)	160
C4—H4B⋯F4ⁱⁱⁱ	0.99	2.44	3.177 (2)	131
C6—H6A⋯F4	0.95	2.43	3.361 (2)	167
C10—H10A⋯N3ⁱⁱ	0.95	2.56	3.5019 (17)	170
C11—H11B⋯F6^iv	0.98	2.53	3.400 (2)	148
C11—H11C⋯F1^v	0.98	2.41	3.353 (2)	162
Symmetry codes: (i) x+1, y-1, z; (ii) -x+2, -y, -z+1; (iii) x+1, y, z; (iv) x, y-1, z; (v) -x+1, -y+1, -z.

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/S1600536812001882/hb6605sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812001882/hb6605Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812001882/hb6605Isup3.cml

checkCIF report

Comment top

N-heterocyclic carbenes (NHC) are stable singlet carbenes that are most frequently prepared via deprotonation of azolium salts. Their role as ligands in coordination and modern organometallic synthesis have been widespread, since the investigation of NHC chemistry by Wanzlick in the early 1960s. NHCs have been proven as an alternative to tertiary phosphines in homogeneous catalysis for the past decades, as they have the ability to bond with metals in a variety of oxidation states through their strong σ-donating and negligible π-accepting characters. Furthermore, they are easy to handle and have been shown to be remarkably stable towards air and moisture. NHC complexes with every transition metals have received considerable attention and their diverse applications particularly in the area of catalysis such as olefin metathesis, transfer hydrogenation, hydroformylation, and furan synthesis have been investigated.

The asymmetric unit of the title compound (Fig. 1) consists a 3-(3-cyanobenzyl)-1-methylimidazolium cation and a hexafluorophosphate anion. The hexafluorophosphate anion is disordered over two orientations with refined site occupancies of 0.8071 (17) and 0.1929 (17). The imidazole ring (N1/N2/C1–C3) is essentially planar with a maximum deviation of 0.003 (1) Å at atom N2. The dihedral angle between the imidazole ring and the benzene ring (C5–C10) is 71.26 (7)°. The bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to the related structure (Haque et al., 2011).

In the crystal structure (Fig. 2), the cations and anions are linked via C1—H1A···F1, C1—H1A···F5, C2—H2A···F3, C3—H3A···N3, C4—H4B···F4, C6—H6A···F4, C10—H10A···N3, C11—H11B···F6, and C11—H11C···F1 hydrogen bonds (Table 1) into a three-dimensional network.

Related literature top

For details and applications of N-heterocyclic carbenes, see: Hermann et al. (1997); Wanzlick & Kleiner (1961); Hermann & Köcher (1997); Baker et al. (2007); Gade & Laponnaz (2007); Özdemir et al. (2005); Köcher & Hermann (1997); Cetinkaya et al. (1997). For a related structure, see: Haque et al. (2011). For bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

To a solution of 1-methylimidazole (0.9 g, 11.0 mmol) in 25 ml of 1,4-dioxane, 3-(bromomethyl)benzonitrile (2.2 g, 11.0 mmol) was added. The mixture was refluxed at 90 °C overnight. The product was isolated by removing the solvent under reduced pressure, and then washed with fresh 1,4-dioxane (2 x 3 ml). The resulting bromide salt was converted quantitatively to its hexafluorophosphate counterpart by metathesis reaction using KPF₆ (1.9 g, 10.3 mmol) in 25 ml of methanol. The white precipitate was collected and washed with distilled water (2 x 3 ml) and then left to dry at ambient temperature. Yield: 1.7 g, (48%); M.p: 104–106 °C. Colourless blocks were obtained by slow evaporation of the salt solution in acetonitrile at ambient 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, showing 50% probability displacement ellipsoids. The minor component is shown by the open bonds.
	Fig. 2. The crystal packing of the title compound, showing the three-dimensional network. Only the major component is shown. H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.

3-(3-Cyanobenzyl)-1-methyl-1H-imidazol-3-ium hexafluorophosphate top

Crystal data top

C₁₂H₁₂N₃⁺·F₆P⁻	Z = 2
M_r = 343.22	F(000) = 348
Triclinic, P1	D_x = 1.584 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.9782 (1) Å	Cell parameters from 6359 reflections
b = 8.7920 (1) Å	θ = 2.5–32.7°
c = 14.1028 (2) Å	µ = 0.26 mm⁻¹
α = 77.975 (1)°	T = 100 K
β = 83.279 (1)°	Block, colourless
γ = 86.635 (1)°	0.43 × 0.24 × 0.21 mm
V = 719.55 (2) Å³

Data collection top

Bruker SMART APEXII CCD diffractometer	5233 independent reflections
Radiation source: fine-focus sealed tube	4485 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 32.7°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
T_min = 0.897, T_max = 0.949	k = −13→13
14376 measured reflections	l = −21→21

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0569P)² + 0.372P] where P = (F_o² + 2F_c²)/3
5233 reflections	(Δ/σ)_max = 0.001
246 parameters	Δρ_max = 0.91 e Å⁻³
21 restraints	Δρ_min = −0.64 e Å⁻³

Crystal data top

C₁₂H₁₂N₃⁺·F₆P⁻	γ = 86.635 (1)°
M_r = 343.22	V = 719.55 (2) Å³
Triclinic, P1	Z = 2
a = 5.9782 (1) Å	Mo Kα radiation
b = 8.7920 (1) Å	µ = 0.26 mm⁻¹
c = 14.1028 (2) Å	T = 100 K
α = 77.975 (1)°	0.43 × 0.24 × 0.21 mm
β = 83.279 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	5233 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	4485 reflections with I > 2σ(I)
T_min = 0.897, T_max = 0.949	R_int = 0.019
14376 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	21 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	Δρ_max = 0.91 e Å⁻³
5233 reflections	Δρ_min = −0.64 e Å⁻³
246 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 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	Occ. (<1)
P1	0.0915 (2)	0.73349 (10)	0.16370 (8)	0.0173 (2)	0.8071 (17)
F1	0.3566 (2)	0.7033 (2)	0.15625 (12)	0.0487 (4)	0.8071 (17)
F2	0.1025 (4)	0.8343 (3)	0.05737 (16)	0.0487 (6)	0.8071 (17)
F3	−0.1762 (2)	0.75757 (17)	0.17710 (10)	0.0374 (3)	0.8071 (17)
F4	0.0797 (3)	0.6287 (2)	0.27361 (12)	0.0451 (4)	0.8071 (17)
F5	0.0591 (2)	0.57833 (15)	0.12519 (12)	0.0465 (4)	0.8071 (17)
F6	0.1151 (3)	0.88412 (15)	0.20813 (11)	0.0484 (4)	0.8071 (17)
P1X	0.0958 (11)	0.7363 (8)	0.1577 (5)	0.045 (2)	0.1929 (17)
F1X	0.3348 (10)	0.8099 (9)	0.1558 (4)	0.0486 (16)	0.1929 (17)
F2X	0.0465 (16)	0.8713 (10)	0.0645 (7)	0.0324 (16)	0.1929 (17)
F3X	−0.1326 (12)	0.6656 (11)	0.1492 (5)	0.077 (3)	0.1929 (17)
F4X	0.1509 (10)	0.6010 (6)	0.2425 (4)	0.0288 (12)	0.1929 (17)
F5X	0.2115 (10)	0.6342 (6)	0.0790 (5)	0.0465 (4)	0.1929 (17)
F6X	−0.0153 (13)	0.8381 (7)	0.2262 (5)	0.0484 (4)	0.1929 (17)
N1	0.46336 (19)	0.22118 (13)	0.12431 (7)	0.0216 (2)
N2	0.6288 (2)	0.30531 (13)	0.23067 (8)	0.0233 (2)
N3	0.8071 (2)	−0.08439 (15)	0.65425 (9)	0.0290 (2)
C1	0.4607 (2)	0.33312 (14)	0.17476 (9)	0.0229 (2)
H1A	0.3558	0.4190	0.1715	0.027*
C2	0.6385 (2)	0.11742 (16)	0.14906 (9)	0.0267 (3)
H2A	0.6791	0.0262	0.1240	0.032*
C3	0.7419 (2)	0.16950 (17)	0.21571 (9)	0.0270 (3)
H3A	0.8686	0.1217	0.2465	0.032*
C4	0.6750 (3)	0.39959 (17)	0.30071 (10)	0.0312 (3)
H4A	0.6125	0.5067	0.2803	0.037*
H4B	0.8399	0.4054	0.3004	0.037*
C5	0.5724 (2)	0.33138 (14)	0.40301 (9)	0.0238 (2)
C6	0.3613 (3)	0.38393 (16)	0.43888 (10)	0.0278 (3)
H6A	0.2810	0.4643	0.3991	0.033*
C7	0.2671 (2)	0.31960 (17)	0.53257 (11)	0.0288 (3)
H7A	0.1238	0.3572	0.5565	0.035*
C8	0.3807 (2)	0.20105 (16)	0.59146 (10)	0.0253 (3)
H8A	0.3163	0.1570	0.6554	0.030*
C9	0.5913 (2)	0.14774 (15)	0.55501 (9)	0.02253 (17)
C10	0.6883 (2)	0.21320 (15)	0.46148 (9)	0.0222 (2)
H10A	0.8329	0.1771	0.4379	0.027*
C11	0.3054 (3)	0.21229 (18)	0.05341 (10)	0.0303 (3)
H11A	0.1951	0.2996	0.0509	0.045*
H11B	0.2269	0.1141	0.0732	0.045*
H11C	0.3889	0.2172	−0.0112	0.045*
C12	0.7105 (2)	0.01965 (15)	0.61205 (9)	0.02253 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0196 (5)	0.0133 (3)	0.0188 (3)	0.0025 (3)	−0.0025 (3)	−0.0035 (3)
F1	0.0187 (5)	0.0593 (9)	0.0658 (10)	−0.0012 (6)	0.0014 (5)	−0.0109 (8)
F2	0.0589 (15)	0.0616 (16)	0.0208 (7)	−0.0189 (10)	−0.0030 (8)	0.0067 (8)
F3	0.0226 (5)	0.0446 (7)	0.0422 (7)	0.0100 (5)	−0.0036 (5)	−0.0058 (6)
F4	0.0442 (9)	0.0523 (10)	0.0318 (8)	−0.0136 (7)	−0.0165 (6)	0.0179 (7)
F5	0.0475 (8)	0.0333 (6)	0.0690 (9)	0.0102 (5)	−0.0183 (7)	−0.0302 (6)
F6	0.0702 (10)	0.0290 (6)	0.0559 (8)	0.0030 (6)	−0.0275 (8)	−0.0211 (6)
P1X	0.019 (3)	0.053 (4)	0.058 (4)	0.001 (2)	−0.007 (2)	0.000 (3)
F1X	0.035 (3)	0.060 (4)	0.047 (3)	−0.026 (3)	−0.014 (2)	0.010 (3)
F2X	0.036 (4)	0.023 (3)	0.028 (3)	0.010 (2)	0.006 (2)	0.008 (2)
F3X	0.047 (4)	0.112 (7)	0.055 (4)	−0.054 (5)	−0.038 (3)	0.056 (5)
F4X	0.039 (3)	0.027 (2)	0.015 (2)	0.012 (2)	−0.0012 (18)	0.0023 (17)
F5X	0.0475 (8)	0.0333 (6)	0.0690 (9)	0.0102 (5)	−0.0183 (7)	−0.0302 (6)
F6X	0.0702 (10)	0.0290 (6)	0.0559 (8)	0.0030 (6)	−0.0275 (8)	−0.0211 (6)
N1	0.0237 (5)	0.0234 (5)	0.0160 (4)	0.0022 (4)	−0.0016 (4)	−0.0014 (4)
N2	0.0265 (5)	0.0237 (5)	0.0181 (4)	−0.0015 (4)	−0.0018 (4)	−0.0006 (4)
N3	0.0273 (6)	0.0320 (6)	0.0274 (5)	0.0024 (5)	−0.0061 (4)	−0.0048 (5)
C1	0.0261 (6)	0.0206 (5)	0.0200 (5)	0.0030 (4)	−0.0013 (4)	−0.0012 (4)
C2	0.0310 (6)	0.0268 (6)	0.0196 (5)	0.0097 (5)	0.0008 (5)	−0.0035 (4)
C3	0.0251 (6)	0.0329 (6)	0.0198 (5)	0.0077 (5)	−0.0013 (4)	−0.0011 (5)
C4	0.0437 (8)	0.0280 (6)	0.0221 (6)	−0.0134 (6)	−0.0048 (5)	−0.0014 (5)
C5	0.0313 (6)	0.0211 (5)	0.0203 (5)	−0.0053 (5)	−0.0054 (5)	−0.0045 (4)
C6	0.0348 (7)	0.0232 (5)	0.0273 (6)	0.0041 (5)	−0.0112 (5)	−0.0068 (5)
C7	0.0285 (6)	0.0296 (6)	0.0297 (6)	0.0070 (5)	−0.0034 (5)	−0.0111 (5)
C8	0.0268 (6)	0.0275 (6)	0.0217 (5)	0.0018 (5)	−0.0006 (5)	−0.0074 (5)
C9	0.0234 (4)	0.0245 (4)	0.0208 (4)	−0.0005 (3)	−0.0034 (3)	−0.0066 (3)
C10	0.0222 (5)	0.0242 (5)	0.0213 (5)	−0.0022 (4)	−0.0029 (4)	−0.0067 (4)
C11	0.0322 (7)	0.0357 (7)	0.0237 (6)	−0.0039 (6)	−0.0067 (5)	−0.0046 (5)
C12	0.0234 (4)	0.0245 (4)	0.0208 (4)	−0.0005 (3)	−0.0034 (3)	−0.0066 (3)

Geometric parameters (Å, º) top

P1—F2	1.571 (2)	C2—C3	1.351 (2)
P1—F1	1.5860 (17)	C2—H2A	0.9500
P1—F3	1.5964 (17)	C3—H3A	0.9500
P1—F6	1.5983 (15)	C4—C5	1.5141 (19)
P1—F5	1.5993 (14)	C4—H4A	0.9900
P1—F4	1.6257 (18)	C4—H4B	0.9900
P1X—F6X	1.523 (8)	C5—C10	1.3899 (18)
P1X—F4X	1.552 (8)	C5—C6	1.394 (2)
P1X—F3X	1.560 (8)	C6—C7	1.391 (2)
P1X—F1X	1.598 (8)	C6—H6A	0.9500
P1X—F2X	1.619 (10)	C7—C8	1.3875 (19)
P1X—F5X	1.637 (8)	C7—H7A	0.9500
N1—C1	1.3275 (17)	C8—C9	1.3959 (18)
N1—C2	1.3751 (17)	C8—H8A	0.9500
N1—C11	1.4695 (18)	C9—C10	1.3970 (18)
N2—C1	1.3298 (17)	C9—C12	1.4444 (18)
N2—C3	1.3799 (17)	C10—H10A	0.9500
N2—C4	1.4733 (18)	C11—H11A	0.9800
N3—C12	1.1471 (18)	C11—H11B	0.9800
C1—H1A	0.9500	C11—H11C	0.9800

F2—P1—F1	92.46 (13)	N2—C1—H1A	125.6
F2—P1—F3	90.74 (12)	C3—C2—N1	107.16 (12)
F1—P1—F3	176.79 (11)	C3—C2—H2A	126.4
F2—P1—F6	91.41 (12)	N1—C2—H2A	126.4
F1—P1—F6	90.49 (11)	C2—C3—N2	107.07 (12)
F3—P1—F6	89.64 (10)	C2—C3—H3A	126.5
F2—P1—F5	91.54 (13)	N2—C3—H3A	126.5
F1—P1—F5	91.14 (10)	N2—C4—C5	111.59 (11)
F3—P1—F5	88.56 (10)	N2—C4—H4A	109.3
F6—P1—F5	176.57 (12)	C5—C4—H4A	109.3
F2—P1—F4	179.81 (15)	N2—C4—H4B	109.3
F1—P1—F4	87.62 (10)	C5—C4—H4B	109.3
F3—P1—F4	89.18 (10)	H4A—C4—H4B	108.0
F6—P1—F4	88.76 (10)	C10—C5—C6	119.47 (12)
F5—P1—F4	88.29 (10)	C10—C5—C4	119.72 (13)
F6X—P1X—F4X	93.3 (5)	C6—C5—C4	120.81 (13)
F6X—P1X—F3X	92.6 (6)	C7—C6—C5	120.48 (12)
F4X—P1X—F3X	92.2 (5)	C7—C6—H6A	119.8
F6X—P1X—F1X	91.3 (5)	C5—C6—H6A	119.8
F4X—P1X—F1X	91.2 (5)	C8—C7—C6	120.60 (13)
F3X—P1X—F1X	174.7 (6)	C8—C7—H7A	119.7
F6X—P1X—F2X	90.2 (5)	C6—C7—H7A	119.7
F4X—P1X—F2X	176.5 (6)	C7—C8—C9	118.78 (12)
F3X—P1X—F2X	87.9 (6)	C7—C8—H8A	120.6
F1X—P1X—F2X	88.5 (6)	C9—C8—H8A	120.6
F6X—P1X—F5X	176.9 (6)	C8—C9—C10	120.97 (12)
F4X—P1X—F5X	89.9 (4)	C8—C9—C12	120.61 (12)
F3X—P1X—F5X	87.1 (6)	C10—C9—C12	118.39 (12)
F1X—P1X—F5X	88.8 (5)	C5—C10—C9	119.70 (12)
F2X—P1X—F5X	86.6 (5)	C5—C10—H10A	120.2
C1—N1—C2	108.59 (11)	C9—C10—H10A	120.2
C1—N1—C11	125.08 (11)	N1—C11—H11A	109.5
C2—N1—C11	126.33 (12)	N1—C11—H11B	109.5
C1—N2—C3	108.33 (11)	H11A—C11—H11B	109.5
C1—N2—C4	125.08 (12)	N1—C11—H11C	109.5
C3—N2—C4	126.49 (12)	H11A—C11—H11C	109.5
N1—C1—N2	108.85 (11)	H11B—C11—H11C	109.5
N1—C1—H1A	125.6	N3—C12—C9	177.42 (14)

C2—N1—C1—N2	0.34 (14)	N2—C4—C5—C6	−95.13 (16)
C11—N1—C1—N2	−179.13 (12)	C10—C5—C6—C7	0.3 (2)
C3—N2—C1—N1	−0.48 (14)	C4—C5—C6—C7	179.33 (13)
C4—N2—C1—N1	−177.01 (11)	C5—C6—C7—C8	−0.7 (2)
C1—N1—C2—C3	−0.07 (15)	C6—C7—C8—C9	0.1 (2)
C11—N1—C2—C3	179.40 (12)	C7—C8—C9—C10	0.8 (2)
N1—C2—C3—N2	−0.22 (15)	C7—C8—C9—C12	−177.06 (13)
C1—N2—C3—C2	0.43 (15)	C6—C5—C10—C9	0.52 (19)
C4—N2—C3—C2	176.90 (12)	C4—C5—C10—C9	−178.47 (12)
C1—N2—C4—C5	95.87 (16)	C8—C9—C10—C5	−1.09 (19)
C3—N2—C4—C5	−80.04 (18)	C12—C9—C10—C5	176.79 (12)
N2—C4—C5—C10	83.85 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···F1	0.95	2.46	3.240 (2)	139
C1—H1A···F5	0.95	2.27	3.1715 (18)	159
C2—H2A···F3ⁱ	0.95	2.46	3.250 (2)	140
C3—H3A···N3ⁱⁱ	0.95	2.49	3.3970 (19)	160
C4—H4B···F4ⁱⁱⁱ	0.99	2.44	3.177 (2)	131
C6—H6A···F4	0.95	2.43	3.361 (2)	167
C10—H10A···N3ⁱⁱ	0.95	2.56	3.5019 (17)	170
C11—H11B···F6^iv	0.98	2.53	3.400 (2)	148
C11—H11C···F1^v	0.98	2.41	3.353 (2)	162

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₃⁺·F₆P⁻
M_r	343.22
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	5.9782 (1), 8.7920 (1), 14.1028 (2)
α, β, γ (°)	77.975 (1), 83.279 (1), 86.635 (1)
V (Å³)	719.55 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.43 × 0.24 × 0.21

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.897, 0.949
No. of measured, independent and observed [I > 2σ(I)] reflections	14376, 5233, 4485
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.760

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.123, 1.04
No. of reflections	5233
No. of parameters	246
No. of restraints	21
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.91, −0.64

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···F1	0.95	2.46	3.240 (2)	139
C1—H1A···F5	0.95	2.27	3.1715 (18)	159
C2—H2A···F3ⁱ	0.95	2.46	3.250 (2)	140
C3—H3A···N3ⁱⁱ	0.95	2.49	3.3970 (19)	160
C4—H4B···F4ⁱⁱⁱ	0.99	2.44	3.177 (2)	131
C6—H6A···F4	0.95	2.43	3.361 (2)	167
C10—H10A···N3ⁱⁱ	0.95	2.56	3.5019 (17)	170
C11—H11B···F6^iv	0.98	2.53	3.400 (2)	148
C11—H11C···F1^v	0.98	2.41	3.353 (2)	162

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

Footnotes

‡Visiting Professor, College of Pharmacy, King Saud University, Riyadh, Saudi Arabia. Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

HKF and CWO thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). CWO thanks the Malaysian Government and USM for the award of the post of research assistant under the Research University (RU) grant (1001/PFIZIK/811151). RAH and ZZH thank USM for the FRGS fund (203/PKIMIA/671115), short term grant (304/PKIMIA/639001) and RU grant (1001/PKIMIA/813023). AWS thanks USM for the RU grant (1001/PKIMIA/843090).

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