Bis(1,3-dimethyl-1H-imidazolium) hexa-fluoro-silicate methanol 0.33-solvate.

The title compound, 6C5H9N2 (+)·3SiF6 (2-)·CH3OH, (I), was prepared by recrystallization of the crude salt from methanol along with solvent-free 2C5H9N2 (+)·SiF6 (2-) (II). Crystals of these solvatomorphs can be separated manually. The solvate (I) crystallizes in a rare hexa-gonal space group P6/mcc. Its asymmetric unit comprises one half of an imidazolium cation bis-ected by the crystallographic m-plane, one-sixth and one-twelfth of two crystallographically independent SiF6 (2-) dianions (Si atoms are located on the 3.2 and 6/m inversion centres), and one-twelfth of a methanol mol-ecule (C atoms are situated on the 622 inversion centres, other atoms are disordered between general positions). In (I), all F atoms of 3.2-located SiF6 (2-) dianions participate in the formation of symmetry-equivalent contacts to the H atoms of imidazolium fragments, thus forming rod-type ensembles positioned on the -6 axes. These 'pillar' rods are, in turn, F⋯H inter-linked through SiF6 (2-) dianions disordered around the 6/m centres. The twelvefold disordered methanol mol-ecules are appended to this array by O-H⋯F hydrogen bonds to the 6/m located SiF6 (2-) dianions. In terms of graph-set notation, the first and second level networks in (I) are N 1 = C 2 (2)(7)[3R 4 (4)(14)]D 2 (2)(4) and N 2 = D 2 (2)(5) (C-H⋯O hydrogen bonds are not considered). After locating all symmetrically independent atoms in the cation and anions, there remained a strong (> 3 e Å(-3)) residual electron density peak located at the 622 inversion centre. Treatment of this pre-refined model with the SQUEEZE procedure in PLATON [Spek (2009). Acta Cryst. D65, 148-155] revealed two voids per unit cell, indicative of the presence of the solvent methanol mol-ecule disordered about the 622 inversion centre.

Related literature

For solvatomorphs of (I), see: Light et al. (2007 ▶); Tian et al. (2013 ▶). For solvatomorphism of (1,3-dimethyl-1H-imidazolium) hexa­fluoro­phosphate, C5H9N2 +·PF6 −, see: Holbrey et al. (2003 ▶). For the practical utility of sterically non-hindered 1,3-dialkyl-1H-imidazolium salts with BF4 − and PF6 − anions for the preparation of Arduengo carbene adducts with BF3 and PF5, see: Tian et al. (2012 ▶). For graph-set notation, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶); Grell et al. (1999 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For the SQUEEZE procedure in PLATON, see: Spek (2009 ▶).

Experimental

Crystal data

6C5H9N2 +·3SiF6 2−·CH4O

M = 1041.10

Hexagonal,

a = 12.6577 (7) Å

c = 16.8174 (18) Å

V = 2333.5 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.22 mm−1

T = 296 K

0.32 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.934, T max = 0.968

11115 measured reflections

804 independent reflections

623 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.098

S = 1.10

804 reflections

75 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.15 e Å−3

Δρmin = −0.41 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: SHELXTL and OLEX2.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813018230/im2435sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813018230/im2435Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813018230/im2435Isup3.cdx

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

6C5H9N2+·3SiF62−·CH4O	Dx = 1.482 Mg m−3
Mr = 1041.10	Melting point: 550 K
Hexagonal, P6/mcc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 6 2c	Cell parameters from 4399 reflections
a = 12.6577 (7) Å	θ = 2.4–28.0°
c = 16.8174 (18) Å	µ = 0.22 mm−1
V = 2333.5 (3) Å3	T = 296 K
Z = 2	Block, yellow
F(000) = 1080	0.32 × 0.20 × 0.15 mm

Bruker SMART APEXII diffractometer	804 independent reflections
Radiation source: fine-focus sealed tube	623 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 8.333 pixels mm-1	θmax = 26.0°, θmin = 1.9°
phi and ω scans	h = −15→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→15
Tmin = 0.934, Tmax = 0.968	l = −20→20
11115 measured reflections

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ2(Fo2) + (0.056P)2 + 0.3029P] where P = (Fo2 + 2Fc2)/3
804 reflections	(Δ/σ)max < 0.001
75 parameters	Δρmax = 0.15 e Å−3
0 restraints	Δρmin = −0.41 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	Occ. (<1)
N1	0.32338 (12)	0.39168 (13)	0.06402 (9)	0.0388 (4)
C1	0.2983 (2)	0.3220 (2)	0.0000	0.0404 (6)
H1	0.266 (2)	0.237 (3)	0.0000	0.051 (7)*
C2	0.36659 (17)	0.51001 (18)	0.03979 (11)	0.0430 (4)
H2	0.389 (2)	0.571 (2)	0.0769 (12)	0.056 (6)*
C3	0.3094 (2)	0.3496 (2)	0.14668 (13)	0.0560 (6)
H3BD	0.2418	0.2678	0.1504	0.084*	0.84 (3)
H3BE	0.2946	0.4023	0.1801	0.084*	0.84 (3)
H3BF	0.3825	0.3511	0.1636	0.084*	0.84 (3)
H3AA	0.2256	0.2899	0.1564	0.084*	0.16 (3)
H3AB	0.3337	0.4176	0.1819	0.084*	0.16 (3)
H3AC	0.3597	0.3139	0.1558	0.084*	0.16 (3)
Si1	0.0000	0.0000	0.0000	0.0319 (4)
F1	0.12523 (16)	0.0637 (2)	0.05780 (10)	0.0459 (5)	0.50
Si2	0.6667	0.3333	0.2500	0.0318 (3)
F2	0.55741 (10)	0.33189 (10)	0.19222 (6)	0.0525 (4)
C4	0.0000	0.0000	0.2500	0.115 (4)
H4A	0.0030	0.0004	0.3070	0.138*	0.0833333
H4B	−0.0606	−0.0794	0.2318	0.138*	0.0833333
H4C	−0.0207	0.0595	0.2322	0.138*	0.0833333
O1	0.102 (5)	0.025 (17)	0.2226 (9)	0.115 (19)	0.0833333
H1A	0.1086	0.0345	0.1725	0.138*	0.0833333

	U11	U22	U33	U12	U13	U23
N1	0.0411 (8)	0.0412 (8)	0.0345 (8)	0.0209 (7)	0.0001 (6)	0.0030 (6)
C1	0.0377 (13)	0.0359 (14)	0.0443 (15)	0.0159 (11)	0.000	0.000
C2	0.0544 (11)	0.0407 (10)	0.0386 (9)	0.0273 (9)	−0.0032 (8)	−0.0029 (8)
C3	0.0683 (13)	0.0664 (13)	0.0373 (10)	0.0367 (11)	0.0040 (9)	0.0137 (9)
Si1	0.0316 (5)	0.0316 (5)	0.0324 (8)	0.0158 (3)	0.000	0.000
F1	0.0390 (10)	0.0499 (13)	0.0438 (11)	0.0184 (11)	−0.0091 (9)	−0.0027 (10)
Si2	0.0362 (4)	0.0362 (4)	0.0230 (5)	0.0181 (2)	0.000	0.000
F2	0.0504 (7)	0.0644 (7)	0.0466 (7)	0.0316 (6)	−0.0081 (5)	0.0106 (5)
C4	0.145 (7)	0.145 (7)	0.056 (7)	0.072 (4)	0.000	0.000
O1	0.08 (2)	0.21 (5)	0.048 (10)	0.07 (4)	−0.005 (19)	−0.04 (5)

N1—C1	1.326 (2)	C3—H3AA	0.9600
N1—C2	1.375 (2)	C3—H3AB	0.9600
N1—C3	1.467 (2)	C3—H3AC	0.9600
C1—N1i	1.326 (2)	Si1—F1	1.6821 (17)
C1—H1	0.94 (3)	Si2—F2	1.6829 (10)
C2—C2i	1.338 (4)	C4—O1	1.25 (2)
C2—H2	0.92 (2)	C4—H4A	0.9600
C3—H3BD	0.9600	C4—H4B	0.9600
C3—H3BE	0.9600	C4—H4C	0.9600
C3—H3BF	0.9600	O1—H1A	0.8498
C1—N1—C2	108.46 (16)	O1x—C4—O1ix	55.4 (3)
C1—N1—C3	125.63 (17)	O1xiv—C4—O1xvii	55.4 (3)
C2—N1—C3	125.90 (16)	O1x—C4—O1xvii	150 (10)
N1i—C1—N1	108.6 (2)	O1ix—C4—O1xvii	96 (10)
N1i—C1—H1	125.69 (12)	O1xiv—C4—O1xviii	136.8 (15)
N1—C1—H1	125.69 (12)	O1x—C4—O1xviii	51 (10)
C2i—C2—N1	107.25 (10)	O1ix—C4—O1xviii	53 (10)
C2i—C2—H2	132.8 (13)	O1xvii—C4—O1xviii	107.3 (8)
N1—C2—H2	120.0 (13)	O1xiv—C4—O1iii	51 (10)
N1—C3—H3BD	109.5	O1x—C4—O1iii	136.8 (15)
N1—C3—H3BE	109.5	O1ix—C4—O1iii	107.3 (8)
H3BD—C3—H3BE	109.5	O1xvii—C4—O1iii	53 (10)
N1—C3—H3BF	109.5	O1xviii—C4—O1iii	154 (10)
H3BD—C3—H3BF	109.5	O1xiv—C4—O1vi	100 (10)
H3BE—C3—H3BF	109.5	O1x—C4—O1vi	55.4 (3)
N1—C3—H3AA	109.5	O1ix—C4—O1vi	107.3 (8)
N1—C3—H3AB	109.5	O1xvii—C4—O1vi	154 (10)
H3AA—C3—H3AB	109.5	O1xviii—C4—O1vi	96 (10)
N1—C3—H3AC	109.5	O1iii—C4—O1vi	107.3 (8)
H3AA—C3—H3AC	109.5	O1xiv—C4—O1xix	55.4 (3)
H3AB—C3—H3AC	109.5	O1x—C4—O1xix	100 (10)
F1ii—Si1—F1iii	180.00 (19)	O1ix—C4—O1xix	154 (10)
F1ii—Si1—F1iv	48.16 (4)	O1xvii—C4—O1xix	107.3 (8)
F1iii—Si1—F1iv	131.84 (4)	O1xviii—C4—O1xix	107.3 (8)
F1ii—Si1—F1v	89.94 (9)	O1iii—C4—O1xix	96 (10)
F1iii—Si1—F1v	90.06 (9)	O1vi—C4—O1xix	53 (10)
F1iv—Si1—F1v	48.16 (4)	O1xiv—C4—O1xx	107.3 (8)
F1ii—Si1—F1vi	90.06 (9)	O1x—C4—O1xx	53 (10)
F1iii—Si1—F1vi	89.94 (9)	O1ix—C4—O1xx	100 (10)
F1iv—Si1—F1vi	131.84 (4)	O1xvii—C4—O1xx	136.8 (15)
F1v—Si1—F1vi	180.00 (13)	O1xviii—C4—O1xx	55.4 (3)
F1ii—Si1—F1vii	131.84 (4)	O1iii—C4—O1xx	150 (10)
F1iii—Si1—F1vii	48.16 (4)	O1vi—C4—O1xx	51 (10)
F1iv—Si1—F1vii	90.06 (9)	O1xix—C4—O1xx	55.4 (3)
F1v—Si1—F1vii	70.61 (12)	O1xiv—C4—O1xxi	107.3 (8)
F1vi—Si1—F1vii	109.39 (12)	O1x—C4—O1xxi	96 (10)
F1ii—Si1—F1viii	48.16 (4)	O1ix—C4—O1xxi	51 (10)
F1iii—Si1—F1viii	131.84 (4)	O1xvii—C4—O1xxi	55.4 (3)
F1iv—Si1—F1viii	89.94 (9)	O1xviii—C4—O1xxi	55.4 (3)
F1v—Si1—F1viii	109.39 (12)	O1iii—C4—O1xxi	100 (10)
F1vi—Si1—F1viii	70.61 (12)	O1vi—C4—O1xxi	150 (10)
F1vii—Si1—F1viii	180.00 (13)	O1xix—C4—O1xxi	136.8 (15)
F1ii—Si1—F1ix	90.06 (9)	O1xx—C4—O1xxi	107.3 (8)
F1iii—Si1—F1ix	89.94 (9)	O1xiv—C4—O1vii	96 (10)
F1iv—Si1—F1ix	70.61 (12)	O1x—C4—O1vii	107.3 (8)
F1v—Si1—F1ix	90.06 (9)	O1ix—C4—O1vii	55.4 (3)
F1vi—Si1—F1ix	89.94 (9)	O1xvii—C4—O1vii	51 (10)
F1vii—Si1—F1ix	48.16 (4)	O1xviii—C4—O1vii	100 (10)
F1viii—Si1—F1ix	131.84 (4)	O1iii—C4—O1vii	55.4 (3)
F1ii—Si1—F1i	89.94 (9)	O1vi—C4—O1vii	136.8 (15)
F1iii—Si1—F1i	90.06 (9)	O1xix—C4—O1vii	150 (10)
F1iv—Si1—F1i	109.39 (12)	O1xx—C4—O1vii	154 (10)
F1v—Si1—F1i	89.94 (9)	O1xxi—C4—O1vii	53 (10)
F1vi—Si1—F1i	90.06 (9)	O1xiv—C4—O1	53 (10)
F1vii—Si1—F1i	131.84 (4)	O1x—C4—O1	107.3 (8)
F1viii—Si1—F1i	48.16 (4)	O1ix—C4—O1	136.8 (15)
F1ix—Si1—F1i	180.00 (14)	O1xvii—C4—O1	100 (10)
F1ii—Si1—F1x	70.61 (12)	O1xviii—C4—O1	150 (10)
F1iii—Si1—F1x	109.39 (12)	O1iii—C4—O1	55.4 (3)
F1iv—Si1—F1x	90.06 (9)	O1vi—C4—O1	55.4 (3)
F1v—Si1—F1x	131.84 (4)	O1xix—C4—O1	51 (10)
F1vi—Si1—F1x	48.16 (4)	O1xx—C4—O1	96 (10)
F1vii—Si1—F1x	89.94 (9)	O1xxi—C4—O1	154 (10)
F1viii—Si1—F1x	90.06 (9)	O1vii—C4—O1	107.3 (8)
F1ix—Si1—F1x	48.16 (4)	O1xiv—C4—H4A	66.7
F1i—Si1—F1x	131.84 (4)	O1x—C4—H4A	112.4
F1ii—Si1—F1xi	109.39 (12)	O1ix—C4—H4A	113.7
F1iii—Si1—F1xi	70.61 (12)	O1xvii—C4—H4A	68.7
F1iv—Si1—F1xi	89.94 (9)	O1xviii—C4—H4A	70.1
F1v—Si1—F1xi	48.16 (4)	O1iii—C4—H4A	110.7
F1vi—Si1—F1xi	131.84 (4)	O1vi—C4—H4A	110.3
F1vii—Si1—F1xi	90.06 (9)	O1xix—C4—H4A	66.4
F1viii—Si1—F1xi	89.94 (9)	O1xx—C4—H4A	68.1
F1ix—Si1—F1xi	131.84 (4)	O1xxi—C4—H4A	70.4
F1i—Si1—F1xi	48.16 (4)	O1vii—C4—H4A	112.9
F1x—Si1—F1xi	180.00 (19)	O1—C4—H4A	109.5
F1ii—Si1—F1	131.84 (4)	O1xiv—C4—H4B	154.5
F1iii—Si1—F1	48.16 (4)	O1x—C4—H4B	3.1
F1iv—Si1—F1	180.0	O1ix—C4—H4B	55.4
F1v—Si1—F1	131.83 (4)	O1xvii—C4—H4B	148.9
F1vi—Si1—F1	48.17 (4)	O1xviii—C4—H4B	48.1
F1vii—Si1—F1	89.94 (9)	O1iii—C4—H4B	139.8
F1viii—Si1—F1	90.06 (9)	O1vi—C4—H4B	56.8
F1ix—Si1—F1	109.39 (12)	O1xix—C4—H4B	99.4
F1i—Si1—F1	70.61 (12)	O1xx—C4—H4B	51.6
F1x—Si1—F1	89.95 (9)	O1xxi—C4—H4B	94.1
F1xi—Si1—F1	90.05 (9)	O1vii—C4—H4B	108.2
F2xii—Si2—F2xiii	89.25 (7)	O1—C4—H4B	109.5
F2xii—Si2—F2xiv	89.99 (6)	H4A—C4—H4B	109.5
F2xiii—Si2—F2xiv	90.77 (8)	O1xiv—C4—H4C	95.1
F2xii—Si2—F2xv	90.77 (8)	O1x—C4—H4C	108.7
F2xiii—Si2—F2xv	89.99 (6)	O1ix—C4—H4C	55.7
F2xiv—Si2—F2xv	178.93 (8)	O1xvii—C4—H4C	48.5
F2xii—Si2—F2xvi	89.99 (6)	O1xviii—C4—H4C	98.1
F2xiii—Si2—F2xvi	178.93 (8)	O1iii—C4—H4C	56.6
F2xiv—Si2—F2xvi	89.99 (6)	O1vi—C4—H4C	140.2
F2xv—Si2—F2xvi	89.25 (7)	O1xix—C4—H4C	150.0
F2xii—Si2—F2	178.93 (8)	O1xx—C4—H4C	153.2
F2xiii—Si2—F2	89.99 (6)	O1xxi—C4—H4C	50.5
F2xiv—Si2—F2	89.25 (7)	O1vii—C4—H4C	3.4
F2xv—Si2—F2	89.99 (6)	O1—C4—H4C	109.5
F2xvi—Si2—F2	90.77 (8)	H4A—C4—H4C	109.5
O1xiv—C4—O1x	154 (10)	H4B—C4—H4C	109.5
O1xiv—C4—O1ix	150 (10)	C4—O1—H1A	114.9
C2—N1—C1—N1i	−0.3 (3)	C1—N1—C2—C2i	0.18 (16)
C3—N1—C1—N1i	−179.32 (13)	C3—N1—C2—C2i	179.20 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···F1	0.85	1.96 (1)	2.80 (3)	177 (13)
C1—H1···F1	0.94 (3)	2.24 (3)	3.044 (3)	143 (2)
C2—H2···F2xxii	0.92 (2)	2.21 (2)	3.095 (2)	160.3 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···F1	0.85	1.955 (2)	2.80 (3)	177 (13)
C1—H1···F1	0.94 (3)	2.24 (3)	3.044 (3)	143 (2)
C2—H2···F2xxii	0.92 (2)	2.21 (2)	3.095 (2)	160 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯F1	0.85	1.96 (1)	2.80 (3)	177 (13)
C1—H1⋯F1	0.94 (3)	2.24 (3)	3.044 (3)	143 (2)
C2—H2⋯F2i	0.92 (2)	2.21 (2)	3.095 (2)	160.3 (17)

Symmetry code: (i) .