1-Benzyl-3-phenyl-imidazolium hexa-fluoro-phosphate.

in the title compound, C(16)H(15)N(2) (+)·PF(6) (-), a precursor of N-heterocyclic carbene, the phenyl and benzyl rings are twisted away from the central imidazolium ring system, making dihedral angles of 70.30 (8) and 32.03 (10)°, respectively. The crystal structure is stabilized by C-H⋯F hydrogen bonds. Furthermore, P-F⋯π inter-actions involving imidazolium rings are observed [F⋯π = 2.9857 (16), P⋯π = 4.1630 (16) Å, P-F⋯π = 127.92 (6)°].

Related literature

The first stable N-heterocyclic carbene was isolated by Arduengo et al. (1991 ▶). For the synthesis, see: Liu et al. (2003 ▶). For related structures, see: Wan et al. (2008 ▶). For related structures, see: Newman et al. (2007 ▶); Herrmann (2002 ▶); Yang et al. (2009 ▶).

Experimental

Crystal data

C16H15N2 +·PF6 −

M = 380.27

Triclinic,

a = 9.221 (2) Å

b = 10.046 (3) Å

c = 10.108 (2) Å

α = 110.733 (2)°

β = 91.969 (2)°

γ = 110.315 (2)°

V = 807.9 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.24 mm−1

T = 93 K

0.43 × 0.40 × 0.37 mm

Data collection

Rigaku SPIDER diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.905, T max = 0.919

4739 measured reflections

2902 independent reflections

2361 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.084

S = 1.00

2902 reflections

226 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.28 e Å−3

Data collection: RAPID-AUTO (Rigaku/MSC, 2004 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031584/at2854sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031584/at2854Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H15N2+·PF6−	Z = 2
Mr = 380.27	F(000) = 388
Triclinic, P1	Dx = 1.563 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.221 (2) Å	Cell parameters from 2516 reflections
b = 10.046 (3) Å	θ = 3.1–27.5°
c = 10.108 (2) Å	µ = 0.24 mm−1
α = 110.733 (2)°	T = 93 K
β = 91.969 (2)°	Block, colourless
γ = 110.315 (2)°	0.43 × 0.40 × 0.37 mm
V = 807.9 (3) Å3

Rigaku SPIDER diffractometer	2902 independent reflections
Radiation source: Rotating Anode	2361 reflections with I > 2σ(I)
graphite	Rint = 0.017
ω scans	θmax = 25.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→7
Tmin = 0.905, Tmax = 0.919	k = −11→12
4739 measured reflections	l = −12→11

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.043P)2 + 0.066P] where P = (Fo2 + 2Fc2)/3
2902 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

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.

	x	y	z	Uiso*/Ueq
P1	1.23197 (5)	1.00569 (5)	0.79232 (5)	0.02127 (14)
F1	1.38948 (11)	1.06413 (12)	0.73171 (11)	0.0297 (3)
F2	1.07593 (13)	0.94747 (15)	0.85307 (13)	0.0444 (3)
F3	1.16399 (13)	1.10464 (14)	0.73467 (12)	0.0380 (3)
F4	1.30246 (13)	0.90834 (14)	0.85235 (12)	0.0381 (3)
F5	1.30920 (14)	1.15038 (13)	0.94289 (11)	0.0427 (3)
F6	1.15883 (14)	0.86186 (13)	0.64242 (12)	0.0433 (3)
N1	0.47043 (15)	0.20046 (16)	0.35708 (14)	0.0188 (3)
N2	0.28468 (15)	−0.02584 (16)	0.25378 (14)	0.0192 (3)
C1	0.5504 (2)	0.4242 (2)	0.29382 (18)	0.0235 (4)
H1	0.4593	0.3740	0.2211	0.028*
C2	0.6550 (2)	0.5713 (2)	0.31694 (19)	0.0255 (4)
H2	0.6367	0.6216	0.2581	0.031*
C3	0.7858 (2)	0.6454 (2)	0.42503 (18)	0.0241 (4)
H3	0.8553	0.7475	0.4422	0.029*
C4	0.8153 (2)	0.5709 (2)	0.50786 (19)	0.0270 (4)
H4	0.9061	0.6213	0.5810	0.032*
C5	0.7131 (2)	0.4229 (2)	0.48495 (19)	0.0243 (4)
H5	0.7337	0.3714	0.5416	0.029*
C6	0.58132 (19)	0.3514 (2)	0.37897 (18)	0.0191 (4)
C7	0.4319 (2)	0.1417 (2)	0.46130 (18)	0.0218 (4)
H7	0.4787	0.1912	0.5602	0.026*
C8	0.3160 (2)	0.0014 (2)	0.39716 (18)	0.0223 (4)
H8	0.2652	−0.0662	0.4423	0.027*
C9	0.37939 (19)	0.0950 (2)	0.23205 (18)	0.0194 (4)
H9	0.3822	0.1051	0.1421	0.023*
C10	0.1627 (2)	−0.1631 (2)	0.14214 (19)	0.0233 (4)
H10A	0.1772	−0.1595	0.0467	0.028*
H10B	0.0580	−0.1612	0.1581	0.028*
C11	0.16757 (19)	−0.3114 (2)	0.14213 (17)	0.0197 (4)
C12	0.28553 (19)	−0.3616 (2)	0.08983 (18)	0.0224 (4)
H12	0.3691	−0.2983	0.0598	0.027*
C13	0.2811 (2)	−0.5030 (2)	0.08160 (18)	0.0254 (4)
H13	0.3614	−0.5368	0.0453	0.030*
C14	0.1600 (2)	−0.5965 (2)	0.12598 (18)	0.0255 (4)
H14	0.1569	−0.6941	0.1195	0.031*
C15	0.0439 (2)	−0.5460 (2)	0.17967 (18)	0.0248 (4)
H15	−0.0385	−0.6087	0.2113	0.030*
C16	0.04776 (19)	−0.4049 (2)	0.18733 (17)	0.0219 (4)
H16	−0.0325	−0.3713	0.2240	0.026*

	U11	U22	U33	U12	U13	U23
P1	0.0232 (3)	0.0215 (3)	0.0217 (3)	0.0089 (2)	0.0073 (2)	0.0108 (2)
F1	0.0233 (5)	0.0358 (7)	0.0297 (6)	0.0075 (5)	0.0084 (5)	0.0159 (5)
F2	0.0366 (7)	0.0571 (9)	0.0629 (8)	0.0237 (6)	0.0301 (6)	0.0422 (7)
F3	0.0390 (7)	0.0481 (8)	0.0470 (7)	0.0250 (6)	0.0148 (6)	0.0323 (7)
F4	0.0498 (7)	0.0469 (8)	0.0437 (7)	0.0330 (6)	0.0230 (6)	0.0315 (6)
F5	0.0644 (8)	0.0339 (7)	0.0229 (6)	0.0196 (6)	0.0073 (6)	0.0029 (6)
F6	0.0445 (7)	0.0274 (7)	0.0348 (7)	−0.0020 (6)	−0.0008 (5)	0.0025 (6)
N1	0.0206 (7)	0.0181 (8)	0.0174 (8)	0.0075 (6)	0.0029 (6)	0.0066 (7)
N2	0.0197 (7)	0.0187 (8)	0.0184 (8)	0.0076 (6)	0.0021 (6)	0.0063 (7)
C1	0.0236 (9)	0.0251 (10)	0.0214 (10)	0.0088 (8)	0.0026 (8)	0.0094 (8)
C2	0.0305 (10)	0.0247 (10)	0.0259 (10)	0.0122 (8)	0.0077 (8)	0.0134 (9)
C3	0.0251 (9)	0.0209 (10)	0.0239 (10)	0.0065 (8)	0.0083 (8)	0.0081 (8)
C4	0.0244 (9)	0.0275 (11)	0.0228 (10)	0.0061 (8)	−0.0002 (8)	0.0070 (9)
C5	0.0264 (9)	0.0238 (10)	0.0227 (10)	0.0086 (8)	0.0015 (8)	0.0103 (9)
C6	0.0211 (9)	0.0178 (9)	0.0177 (9)	0.0081 (7)	0.0058 (7)	0.0053 (8)
C7	0.0308 (10)	0.0232 (10)	0.0148 (9)	0.0128 (8)	0.0059 (7)	0.0086 (8)
C8	0.0292 (10)	0.0234 (10)	0.0174 (9)	0.0121 (8)	0.0070 (8)	0.0093 (8)
C9	0.0203 (8)	0.0216 (10)	0.0164 (9)	0.0088 (7)	0.0023 (7)	0.0068 (8)
C10	0.0210 (9)	0.0238 (10)	0.0216 (10)	0.0059 (8)	−0.0007 (7)	0.0078 (8)
C11	0.0202 (8)	0.0204 (10)	0.0146 (9)	0.0059 (7)	−0.0017 (7)	0.0049 (8)
C12	0.0187 (9)	0.0248 (10)	0.0218 (10)	0.0060 (8)	0.0038 (7)	0.0092 (8)
C13	0.0233 (9)	0.0292 (11)	0.0229 (10)	0.0120 (8)	−0.0007 (8)	0.0079 (9)
C14	0.0293 (10)	0.0209 (10)	0.0218 (10)	0.0065 (8)	−0.0052 (8)	0.0073 (8)
C15	0.0225 (9)	0.0265 (11)	0.0205 (10)	0.0019 (8)	−0.0006 (8)	0.0116 (9)
C16	0.0200 (9)	0.0264 (10)	0.0147 (9)	0.0063 (8)	0.0007 (7)	0.0057 (8)

P1—F2	1.5875 (11)	C5—C6	1.378 (2)
P1—F3	1.5933 (11)	C5—H5	0.9500
P1—F6	1.5942 (12)	C7—C8	1.345 (2)
P1—F1	1.5978 (11)	C7—H7	0.9500
P1—F5	1.6052 (12)	C8—H8	0.9500
P1—F4	1.6066 (11)	C9—H9	0.9500
N1—C9	1.336 (2)	C10—C11	1.505 (2)
N1—C7	1.380 (2)	C10—H10A	0.9900
N1—C6	1.437 (2)	C10—H10B	0.9900
N2—C9	1.323 (2)	C11—C16	1.389 (2)
N2—C8	1.376 (2)	C11—C12	1.396 (2)
N2—C10	1.474 (2)	C12—C13	1.379 (2)
C1—C2	1.385 (2)	C12—H12	0.9500
C1—C6	1.389 (2)	C13—C14	1.391 (2)
C1—H1	0.9500	C13—H13	0.9500
C2—C3	1.383 (2)	C14—C15	1.386 (2)
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.380 (2)	C15—C16	1.380 (2)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.386 (2)	C16—H16	0.9500
C4—H4	0.9500
F2—P1—F3	90.46 (6)	C5—C6—C1	121.20 (17)
F2—P1—F6	90.77 (7)	C5—C6—N1	120.21 (15)
F3—P1—F6	90.53 (7)	C1—C6—N1	118.58 (15)
F2—P1—F1	179.73 (6)	C8—C7—N1	107.46 (15)
F3—P1—F1	89.79 (6)	C8—C7—H7	126.3
F6—P1—F1	89.34 (6)	N1—C7—H7	126.3
F2—P1—F5	90.23 (7)	C7—C8—N2	107.13 (15)
F3—P1—F5	90.14 (7)	C7—C8—H8	126.4
F6—P1—F5	178.80 (7)	N2—C8—H8	126.4
F1—P1—F5	89.66 (6)	N2—C9—N1	108.96 (14)
F2—P1—F4	89.83 (6)	N2—C9—H9	125.5
F3—P1—F4	179.11 (7)	N1—C9—H9	125.5
F6—P1—F4	90.31 (7)	N2—C10—C11	112.54 (14)
F1—P1—F4	89.92 (6)	N2—C10—H10A	109.1
F5—P1—F4	89.02 (7)	C11—C10—H10A	109.1
C9—N1—C7	107.81 (14)	N2—C10—H10B	109.1
C9—N1—C6	125.48 (14)	C11—C10—H10B	109.1
C7—N1—C6	126.60 (15)	H10A—C10—H10B	107.8
C9—N2—C8	108.63 (14)	C16—C11—C12	118.95 (16)
C9—N2—C10	124.79 (14)	C16—C11—C10	119.61 (15)
C8—N2—C10	126.53 (14)	C12—C11—C10	121.34 (15)
C2—C1—C6	118.79 (17)	C13—C12—C11	120.18 (16)
C2—C1—H1	120.6	C13—C12—H12	119.9
C6—C1—H1	120.6	C11—C12—H12	119.9
C3—C2—C1	120.50 (17)	C12—C13—C14	120.50 (17)
C3—C2—H2	119.8	C12—C13—H13	119.8
C1—C2—H2	119.8	C14—C13—H13	119.8
C4—C3—C2	119.89 (17)	C15—C14—C13	119.44 (17)
C4—C3—H3	120.1	C15—C14—H14	120.3
C2—C3—H3	120.1	C13—C14—H14	120.3
C3—C4—C5	120.38 (17)	C16—C15—C14	120.11 (16)
C3—C4—H4	119.8	C16—C15—H15	119.9
C5—C4—H4	119.8	C14—C15—H15	119.9
C6—C5—C4	119.21 (17)	C15—C16—C11	120.81 (16)
C6—C5—H5	120.4	C15—C16—H16	119.6
C4—C5—H5	120.4	C11—C16—H16	119.6
C6—C1—C2—C3	−1.4 (3)	C8—N2—C9—N1	−0.49 (18)
C1—C2—C3—C4	1.9 (3)	C10—N2—C9—N1	177.44 (14)
C2—C3—C4—C5	−1.0 (3)	C7—N1—C9—N2	0.77 (18)
C3—C4—C5—C6	−0.3 (3)	C6—N1—C9—N2	−175.77 (14)
C4—C5—C6—C1	0.8 (3)	C9—N2—C10—C11	132.27 (16)
C4—C5—C6—N1	−177.50 (15)	C8—N2—C10—C11	−50.2 (2)
C2—C1—C6—C5	0.0 (3)	N2—C10—C11—C16	109.96 (17)
C2—C1—C6—N1	178.40 (15)	N2—C10—C11—C12	−73.7 (2)
C9—N1—C6—C5	−151.02 (16)	C16—C11—C12—C13	0.9 (2)
C7—N1—C6—C5	33.1 (2)	C10—C11—C12—C13	−175.41 (16)
C9—N1—C6—C1	30.6 (2)	C11—C12—C13—C14	−0.4 (3)
C7—N1—C6—C1	−145.30 (16)	C12—C13—C14—C15	−0.4 (3)
C9—N1—C7—C8	−0.76 (18)	C13—C14—C15—C16	0.7 (2)
C6—N1—C7—C8	175.73 (15)	C14—C15—C16—C11	−0.2 (2)
N1—C7—C8—N2	0.46 (18)	C12—C11—C16—C15	−0.6 (2)
C9—N2—C8—C7	0.01 (18)	C10—C11—C16—C15	175.78 (15)
C10—N2—C8—C7	−177.88 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···F1i	0.95	2.50	3.099 (2)	121
C8—H8···F6i	0.95	2.50	3.392 (2)	156
C9—H9···F5ii	0.95	2.34	3.247 (2)	159
C10—H10A···F4ii	0.99	2.49	3.444 (2)	161
C10—H10B···F3iii	0.99	2.49	3.455 (3)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯F1i	0.95	2.50	3.099 (2)	121
C8—H8⋯F6i	0.95	2.50	3.392 (2)	156
C9—H9⋯F5ii	0.95	2.34	3.247 (2)	159
C10—H10A⋯F4ii	0.99	2.49	3.444 (2)	161
C10—H10B⋯F3iii	0.99	2.49	3.455 (3)	164

Symmetry codes: (i) ; (ii) ; (iii) .