3,3'-Dimethyl-1,1'-[(1,3-dihy-droxy-propane-2,2-di-yl)dimethyl-idene]diimidazolium bis-(hexa-fluoro-phosphate).

The title compound, C(13)H(22)N(4)O(2) (2+)·2PF(6) (-), was prepared by the anion exchange of the dibromide ionic liquid with potassium hexa-fluoro-phosphate. The two imidazole rings are each planar (r.m.s. deviations = 0.0016 and 0.0060 Å) and make a dihedral angle of 45.3 (18)°. Intra-molecular O-H⋯F hydrogen bonds occur. Inter-molecular C-H⋯F, O-H⋯O and C-H⋯O hydrogen bonds stabilize the crystal structure.

Related literature

For properties and applications of ionic liquids, see: Welton (1999 ▶). For dicationic ionic liquids, see: Liang et al. (2008 ▶); Geng et al. (2010 ▶). For the synthesis of the title compound, see: Cai et al. (2007 ▶); Cai & Liu, (2009 ▶). For bond-length data, see: Allen et al., (1987 ▶).

Experimental

Crystal data

C13H22N4O2 2+·2PF6 −

M = 556.29

Orthorhombic,

a = 14.622 (3) Å

b = 12.504 (3) Å

c = 12.165 (2) Å

V = 2224.2 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 295 K

0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.940, T max = 0.969

4082 measured reflections

2152 independent reflections

1861 reflections with I > 2σ(I)

R int = 0.067

3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.123

S = 1.00

4082 reflections

298 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.17 e Å−3

Absolute structure: Flack (1983 ▶), 1930 Friedel pairs

Flack parameter: 0.01 (16)

Data collection: CAD-4 (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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/S1600536810047677/rk2245sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047677/rk2245Isup2.hkl

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

C13H22N4O22+·2PF6−	Dx = 1.661 Mg m−3
Mr = 556.29	Melting point = 497–500 K
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 25 reflections
a = 14.622 (3) Å	θ = 9–13°
b = 12.504 (3) Å	µ = 0.31 mm−1
c = 12.165 (2) Å	T = 295 K
V = 2224.2 (8) Å3	Block, colourless
Z = 4	0.20 × 0.10 × 0.10 mm
F(000) = 1128

Enraf–Nonius CAD-4 diffractometer	1861 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.067
graphite	θmax = 25.4°, θmin = 2.1°
ω/2θ–scans	h = 0→17
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
Tmin = 0.940, Tmax = 0.969	l = −14→14
4082 measured reflections	3 standard reflections every 200 reflections
2152 independent reflections	intensity decay: 1%

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.066	w = 1/[σ2(Fo2) + (0.034P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.123	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 0.20 e Å−3
4082 reflections	Δρmin = −0.17 e Å−3
298 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
1 restraint	Extinction coefficient: 0.105 (11)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1930 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.01 (16)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
O1	0.8641 (3)	0.5204 (5)	0.2865 (3)	0.119 (2)
H1A	0.8104	0.5362	0.2756	0.179*
N1	1.0848 (6)	0.8302 (5)	0.4610 (6)	0.103 (2)
C1	1.1347 (5)	0.9027 (6)	0.5270 (7)	0.123 (3)
H1B	1.1127	0.9740	0.5144	0.185*
H1C	1.1983	0.8989	0.5082	0.185*
H1D	1.1268	0.8845	0.6030	0.185*
O2	1.0931 (3)	0.4708 (3)	0.5634 (3)	0.0826 (14)
H2A	1.1025	0.4740	0.6298	0.124*
N2	1.0515 (4)	0.6773 (4)	0.3942 (5)	0.0724 (16)
C2	1.1092 (6)	0.7153 (6)	0.4672 (6)	0.092 (3)
H2B	1.1525	0.6804	0.5101	0.111*
N3	0.9585 (3)	0.2977 (4)	0.4254 (4)	0.0595 (13)
C3	1.0013 (6)	0.7562 (7)	0.3474 (7)	0.101 (2)
H3A	0.9577	0.7467	0.2927	0.121*
N4	0.8598 (4)	0.1738 (4)	0.4570 (4)	0.0708 (15)
C4	1.0258 (6)	0.8556 (7)	0.3952 (8)	0.098 (3)
H4A	1.0027	0.9233	0.3801	0.117*
C5	1.0500 (4)	0.5689 (4)	0.3557 (5)	0.0593 (15)
H5A	1.1108	0.5385	0.3631	0.071*
H5B	1.0342	0.5684	0.2783	0.071*
C6	0.9823 (3)	0.4998 (4)	0.4183 (4)	0.0402 (12)
C7	1.0003 (4)	0.4992 (5)	0.5411 (4)	0.0649 (16)
H7A	0.9877	0.5695	0.5712	0.078*
H7B	0.9598	0.4484	0.5765	0.078*
C8	0.8832 (3)	0.5271 (5)	0.3995 (4)	0.0580 (15)
H8A	0.8445	0.4778	0.4398	0.070*
H8B	0.8709	0.5990	0.4257	0.070*
C9	1.0043 (4)	0.3873 (4)	0.3704 (5)	0.0637 (15)
H9A	0.9872	0.3866	0.2934	0.076*
H9B	1.0698	0.3760	0.3744	0.076*
C10	0.9922 (5)	0.2325 (5)	0.5067 (5)	0.0652 (19)
H10A	1.0493	0.2387	0.5397	0.078*
C11	0.9291 (5)	0.1587 (6)	0.5303 (6)	0.081 (2)
H11A	0.9320	0.1074	0.5855	0.098*
C12	0.8786 (4)	0.2570 (4)	0.3921 (5)	0.0599 (16)
H12A	0.8428	0.2821	0.3344	0.072*
C13	0.7815 (5)	0.1020 (6)	0.4552 (6)	0.109 (3)
H13A	0.7397	0.1243	0.3988	0.164*
H13B	0.7513	0.1040	0.5252	0.164*
H13C	0.8019	0.0305	0.4404	0.164*
P1	0.72571 (13)	0.35606 (18)	0.68464 (19)	0.0911 (6)
F1	0.7669 (3)	0.4744 (3)	0.6875 (5)	0.1535 (18)
F2	0.6868 (3)	0.2424 (3)	0.6720 (5)	0.1459 (18)
F3	0.6246 (3)	0.4001 (4)	0.6840 (4)	0.1420 (16)
F4	0.7290 (3)	0.3498 (5)	0.8136 (3)	0.151 (2)
F5	0.7254 (4)	0.3651 (4)	0.5546 (4)	0.140 (2)
F6	0.8266 (2)	0.3132 (4)	0.6825 (5)	0.1478 (18)
P2	0.64385 (14)	0.33975 (18)	0.1878 (2)	0.0992 (7)
F7	0.7457 (4)	0.3277 (4)	0.1659 (6)	0.179 (2)
F8	0.6282 (7)	0.3840 (8)	0.0811 (7)	0.355 (7)
F9	0.6598 (5)	0.3032 (5)	0.3039 (4)	0.220 (3)
F10	0.6708 (5)	0.4574 (5)	0.2350 (7)	0.238 (4)
F11	0.6079 (10)	0.2399 (7)	0.1625 (8)	0.390 (8)
F12	0.5486 (5)	0.3672 (9)	0.2204 (9)	0.314 (6)

	U11	U22	U33	U12	U13	U23
O1	0.069 (3)	0.240 (6)	0.049 (2)	0.047 (4)	0.006 (2)	0.014 (3)
N1	0.109 (6)	0.068 (5)	0.131 (6)	−0.036 (5)	0.018 (5)	−0.028 (4)
C1	0.117 (7)	0.105 (6)	0.147 (8)	−0.006 (6)	0.008 (7)	0.006 (6)
O2	0.054 (3)	0.125 (4)	0.069 (3)	0.022 (3)	−0.011 (2)	−0.016 (3)
N2	0.065 (4)	0.067 (4)	0.086 (4)	−0.006 (3)	0.021 (3)	−0.005 (3)
C2	0.090 (6)	0.085 (6)	0.102 (6)	−0.023 (5)	0.021 (5)	−0.031 (5)
N3	0.063 (3)	0.050 (3)	0.066 (3)	−0.011 (3)	−0.019 (3)	−0.010 (3)
C3	0.085 (6)	0.110 (6)	0.108 (6)	−0.009 (6)	0.028 (5)	−0.005 (6)
N4	0.061 (3)	0.087 (4)	0.065 (3)	−0.029 (3)	−0.006 (3)	0.009 (3)
C4	0.077 (6)	0.100 (7)	0.116 (8)	0.008 (5)	0.038 (5)	0.012 (6)
C5	0.053 (3)	0.053 (3)	0.071 (4)	0.004 (3)	0.009 (3)	0.004 (3)
C6	0.047 (3)	0.036 (2)	0.037 (3)	−0.012 (3)	−0.006 (3)	0.005 (2)
C7	0.061 (4)	0.092 (4)	0.042 (3)	0.000 (3)	−0.003 (3)	−0.020 (3)
C8	0.047 (3)	0.087 (4)	0.041 (3)	0.021 (3)	0.004 (3)	0.015 (3)
C9	0.068 (4)	0.075 (4)	0.048 (3)	−0.007 (4)	0.005 (3)	−0.002 (3)
C10	0.071 (5)	0.052 (4)	0.072 (5)	−0.003 (4)	−0.016 (4)	0.005 (3)
C11	0.087 (5)	0.089 (5)	0.069 (5)	0.014 (5)	−0.003 (4)	0.004 (4)
C12	0.067 (4)	0.025 (2)	0.088 (4)	−0.004 (3)	−0.020 (4)	0.001 (3)
C13	0.077 (5)	0.133 (7)	0.118 (6)	−0.067 (5)	−0.007 (4)	−0.008 (5)
P1	0.0748 (13)	0.1251 (16)	0.0734 (12)	−0.0271 (12)	−0.0068 (14)	−0.0219 (14)
F1	0.166 (4)	0.136 (3)	0.159 (4)	−0.059 (3)	−0.010 (4)	−0.044 (4)
F2	0.170 (4)	0.120 (3)	0.148 (4)	−0.072 (3)	−0.012 (4)	−0.026 (4)
F3	0.077 (3)	0.234 (5)	0.116 (3)	−0.002 (3)	−0.004 (3)	0.021 (4)
F4	0.117 (4)	0.264 (7)	0.073 (3)	0.014 (4)	0.002 (3)	−0.007 (4)
F5	0.135 (5)	0.198 (6)	0.087 (4)	−0.029 (4)	0.016 (3)	0.012 (3)
F6	0.067 (3)	0.206 (5)	0.170 (4)	0.001 (3)	−0.014 (4)	−0.073 (4)
P2	0.0872 (16)	0.1174 (17)	0.0929 (15)	−0.0272 (13)	−0.0190 (16)	0.0416 (15)
F7	0.130 (5)	0.235 (6)	0.171 (5)	−0.026 (4)	0.038 (5)	−0.041 (6)
F8	0.375 (14)	0.489 (14)	0.201 (8)	−0.219 (11)	−0.182 (9)	0.238 (9)
F9	0.263 (8)	0.293 (8)	0.104 (5)	−0.080 (7)	−0.052 (5)	0.083 (5)
F10	0.206 (7)	0.153 (5)	0.355 (12)	−0.041 (5)	0.034 (7)	0.001 (7)
F11	0.70 (2)	0.233 (7)	0.241 (9)	−0.308 (11)	0.025 (13)	−0.029 (8)
F12	0.111 (5)	0.491 (15)	0.340 (14)	0.080 (7)	−0.002 (6)	0.009 (12)

O1—C8	1.406 (6)	C6—C7	1.518 (7)
O1—H1A	0.8200	C6—C9	1.556 (8)
N1—C4	1.219 (9)	C7—H7A	0.9700
N1—C1	1.413 (9)	C7—H7B	0.9700
N1—C2	1.482 (10)	C8—H8A	0.9700
C1—H1B	0.9600	C8—H8B	0.9700
C1—H1C	0.9600	C9—H9A	0.9700
C1—H1D	0.9600	C9—H9B	0.9700
O2—C7	1.428 (7)	C10—C11	1.336 (8)
O2—H2A	0.8200	C10—H10A	0.9300
N2—C2	1.314 (8)	C11—H11A	0.9300
N2—C3	1.354 (9)	C12—H12A	0.9300
N2—C5	1.434 (6)	C13—H13A	0.9600
C2—H2B	0.9300	C13—H13B	0.9600
N3—C12	1.338 (6)	C13—H13C	0.9600
N3—C10	1.372 (7)	P1—F2	1.538 (4)
N3—C9	1.467 (7)	P1—F6	1.570 (4)
C3—C4	1.419 (11)	P1—F4	1.572 (4)
C3—H3A	0.9300	P1—F3	1.578 (4)
N4—C12	1.335 (7)	P1—F5	1.586 (5)
N4—C11	1.363 (8)	P1—F1	1.598 (4)
N4—C13	1.454 (7)	P2—F11	1.390 (6)
C4—H4A	0.9300	P2—F8	1.429 (6)
C5—C6	1.519 (6)	P2—F12	1.489 (7)
C5—H5A	0.9700	P2—F9	1.503 (5)
C5—H5B	0.9700	P2—F7	1.521 (6)
C6—C8	1.506 (6)	P2—F10	1.628 (6)
C8—O1—H1A	109.5	H8A—C8—H8B	108.3
C4—N1—C1	124.8 (9)	N3—C9—C6	115.2 (4)
C4—N1—C2	117.1 (8)	N3—C9—H9A	108.5
C1—N1—C2	118.0 (8)	C6—C9—H9A	108.5
N1—C1—H1B	109.5	N3—C9—H9B	108.5
N1—C1—H1C	109.5	C6—C9—H9B	108.5
H1B—C1—H1C	109.5	H9A—C9—H9B	107.5
N1—C1—H1D	109.5	C11—C10—N3	108.5 (6)
H1B—C1—H1D	109.5	C11—C10—H10A	125.8
H1C—C1—H1D	109.5	N3—C10—H10A	125.8
C7—O2—H2A	109.5	C10—C11—N4	106.1 (6)
C2—N2—C3	111.6 (7)	C10—C11—H11A	126.9
C2—N2—C5	124.9 (6)	N4—C11—H11A	126.9
C3—N2—C5	122.9 (7)	N4—C12—N3	107.3 (5)
N2—C2—N1	99.3 (7)	N4—C12—H12A	126.4
N2—C2—H2B	130.3	N3—C12—H12A	126.4
N1—C2—H2B	130.3	N4—C13—H13A	109.5
C12—N3—C10	107.8 (5)	N4—C13—H13B	109.5
C12—N3—C9	123.4 (5)	H13A—C13—H13B	109.5
C10—N3—C9	128.2 (5)	N4—C13—H13C	109.5
N2—C3—C4	109.2 (8)	H13A—C13—H13C	109.5
N2—C3—H3A	125.4	H13B—C13—H13C	109.5
C4—C3—H3A	125.4	F2—P1—F6	91.8 (3)
C12—N4—C11	109.9 (6)	F2—P1—F4	93.7 (3)
C12—N4—C13	129.4 (6)	F6—P1—F4	88.3 (3)
C11—N4—C13	120.7 (6)	F2—P1—F3	88.6 (3)
N1—C4—C3	102.7 (9)	F6—P1—F3	178.7 (4)
N1—C4—H4A	128.7	F4—P1—F3	92.9 (3)
C3—C4—H4A	128.7	F2—P1—F5	88.0 (3)
N2—C5—C6	112.6 (4)	F6—P1—F5	90.6 (3)
N2—C5—H5A	109.1	F4—P1—F5	178.0 (3)
C6—C5—H5A	109.1	F3—P1—F5	88.1 (3)
N2—C5—H5B	109.1	F2—P1—F1	175.5 (4)
C6—C5—H5B	109.1	F6—P1—F1	87.8 (3)
H5A—C5—H5B	107.8	F4—P1—F1	90.8 (3)
C8—C6—C7	108.5 (4)	F3—P1—F1	91.7 (3)
C8—C6—C5	114.9 (4)	F5—P1—F1	87.5 (3)
C7—C6—C5	112.5 (4)	F11—P2—F8	95.0 (6)
C8—C6—C9	110.3 (4)	F11—P2—F12	84.9 (6)
C7—C6—C9	109.2 (4)	F8—P2—F12	90.2 (6)
C5—C6—C9	101.1 (4)	F11—P2—F9	89.6 (5)
O2—C7—C6	110.6 (4)	F8—P2—F9	174.9 (6)
O2—C7—H7A	109.5	F12—P2—F9	88.0 (5)
C6—C7—H7A	109.5	F11—P2—F7	104.1 (7)
O2—C7—H7B	109.5	F8—P2—F7	92.1 (5)
C6—C7—H7B	109.5	F12—P2—F7	170.5 (5)
H7A—C7—H7B	108.1	F9—P2—F7	88.9 (4)
O1—C8—C6	109.0 (4)	F11—P2—F10	169.1 (6)
O1—C8—H8A	109.9	F8—P2—F10	90.5 (5)
C6—C8—H8A	109.9	F12—P2—F10	85.6 (5)
O1—C8—H8B	109.9	F9—P2—F10	84.6 (4)
C6—C8—H8B	109.9	F7—P2—F10	85.1 (3)
C3—N2—C2—N1	1.7 (7)	C7—C6—C8—O1	−175.8 (5)
C5—N2—C2—N1	173.0 (5)	C5—C6—C8—O1	57.2 (7)
C4—N1—C2—N2	−1.5 (9)	C9—C6—C8—O1	−56.3 (6)
C1—N1—C2—N2	−178.1 (6)	C12—N3—C9—C6	93.2 (6)
C2—N2—C3—C4	−1.6 (9)	C10—N3—C9—C6	−96.3 (7)
C5—N2—C3—C4	−173.1 (6)	C8—C6—C9—N3	−66.1 (6)
C1—N1—C4—C3	177.0 (7)	C7—C6—C9—N3	53.0 (6)
C2—N1—C4—C3	0.6 (10)	C5—C6—C9—N3	171.8 (5)
N2—C3—C4—N1	0.5 (9)	C12—N3—C10—C11	−6.0 (7)
C2—N2—C5—C6	95.0 (7)	C9—N3—C10—C11	−177.7 (6)
C3—N2—C5—C6	−94.7 (7)	N3—C10—C11—N4	4.7 (8)
N2—C5—C6—C8	68.1 (6)	C12—N4—C11—C10	−1.8 (8)
N2—C5—C6—C7	−56.8 (6)	C13—N4—C11—C10	176.3 (6)
N2—C5—C6—C9	−173.2 (5)	C11—N4—C12—N3	−1.8 (7)
C8—C6—C7—O2	178.5 (5)	C13—N4—C12—N3	−179.7 (6)
C5—C6—C7—O2	−53.2 (6)	C10—N3—C12—N4	4.7 (7)
C9—C6—C7—O2	58.2 (6)	C9—N3—C12—N4	176.9 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···O1	0.97	2.56	2.910 (7)	101
C9—H9A···O1	0.97	2.46	2.831 (8)	102
O1—H1A···F10	0.82	2.32	3.001 (8)	141
O2—H2A···O1i	0.82	1.97	2.787 (6)	175
C2—H2B···F7i	0.93	2.41	3.261 (11)	152
C13—H13B···O2ii	0.96	2.54	3.186 (7)	125

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯F10	0.82	2.32	3.001 (8)	141
O2—H2A⋯O1i	0.82	1.97	2.787 (6)	175
C2—H2B⋯F7i	0.93	2.41	3.261 (11)	152
C13—H13B⋯O2ii	0.96	2.54	3.186 (7)	125

Symmetry codes: (i) ; (ii) .