organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 69| Part 8| August 2013| Pages o1216-o1217

Bis(1,3-di­methyl-1H-imidazolium) hexa­fluoro­silicate methanol 0.33-solvate

aCollege of Chemistry, Leshan Normal University, Binhe Rd 778, Leshan 614000, Sichuan Province, People's Republic of China
*Correspondence e-mail: maxborzov@mail.ru

(Received 7 June 2013; accepted 1 July 2013; online 6 July 2013)

The title compound, 6C5H9N2+·3SiF62−·CH3OH, (I), was prepared by recrystallization of the crude salt from methanol along with solvent-free 2C5H9N2+·SiF62− (II). Crystals of these solvatomorphs can be separated manually. The solvate (I) crystallizes in a rare hexa­gonal space group P6/mcc. Its asymmetric unit comprises one half of an imidazolium cation bis­ected by the crystallographic m-plane, one-sixth and one-twelfth of two crystallographically independent SiF62– dianions (Si atoms are located on the 3.2 and 6/m inversion centres), and one-twelfth of a methanol mol­ecule (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 SiF62– 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 inter­linked through SiF62– dianions disordered around the 6/m centres. The twelvefold disordered methanol mol­ecules are appended to this array by O—H⋯F hydrogen bonds to the 6/m located SiF62– dianions. In terms of graph-set notation, the first and second level networks in (I) are N1 = C22(7)[3R44(14)]D22(4) and N2 = D22(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 mol­ecule disordered about the 622 inversion centre.

Related literature

For solvatomorphs of (I)[link], see: Light et al. (2007[Light, M. E., Bates, G. W. & Gale, P. A. (2007). Private communication (refcode NIQFAV). CCDC, Cambridge, England.]); Tian et al. (2013[Tian, C., Nie, W. & Borzov, M. V. (2013). Acta Cryst. E69, o1218-o1219.]). For solvatomorphism of (1,3-dimethyl-1H-imidazolium) hexa­fluoro­phosphate, C5H9N2+·PF6, see: Holbrey et al. (2003[Holbrey, J. D., Reichert, W. M. & Nieuwenhuyzen, M. (2003). Chem. Commun. pp. 476-477.]). 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[Tian, C., Nie, W., Borzov, M. V. & Su, P. (2012). Organometallics, 31, 1751-1760.]). For graph-set notation, see: Etter et al. (1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]); Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]); Grell et al. (1999[Grell, J., Bernstein, J. & Tinhofer, G. (1999). Graph Set Analysis of Some Hydrogen Bond Patterns. Some Mathematical Concepts, edited by H. Wähling. München: Fakultät für Mathematik und Informatik, Technische Universität München.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]). For the SQUEEZE procedure in PLATON, see: Spek (2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

[Scheme 1]

Experimental

Crystal data
  • 6C5H9N2+·3SiF62−·CH4O

  • Mr = 1041.10

  • Hexagonal, P 6/m c c

  • 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.934, Tmax = 0.968

  • 11115 measured reflections

  • 804 independent reflections

  • 623 reflections with I > 2σ(I)

  • Rint = 0.045

Refinement
  • R[F2 > 2σ(F2)] = 0.036

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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) -x+1, -y+1, z.

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]); software used to prepare material for publication: SHELXTL and OLEX2.

Supporting information


Comment top

Thermolytic decomposition of sterically non-hindered 1,3-dialkyl-1H-imidazolium salts with [BF4-] and [PF6-] anions present an excellent direct route to Arduengo carbene adducts with BF3 and PF5 (Tian et al., 2012). Being interested in expanding this reaction for the case of [SiF62-], we analysed materials gained by re-crystallization of crude bis(1,3-dimethyl-1H-imidazolium) hexafluorosilicate, [C5H9N2+]2[SiF62–], from either methanol or ethanol media. The material obtained from methanol presented both {[C5H9N2+]2[SiF62–]}3(CH3OH), (I), crystals of which grew at the bottom of a vessel under the layer of the mother liquor and the solvent-free salt, [C5H9N2+]2[SiF62–], (II) (crystals grew on the walls of a vessel above the solution surface during its gradual evaporation into air). Single crystals of (I) and (II) could be easily separated manually. Interestingly, crystallization from ethanol afforded only the solvent-free (II). Identity of the single crystals of (I) prepared from EtOH and MeOH was proved by the unit cell measurements. Details of the structural investigation of (II) can be found in a parallel publication (Tian et al., 2013).

Adduct (I), crystallizes in a rare hexagonal space group P6/mcc. Analysis of the Cambridge Structural Database [CSD; version 5.32, release May 2013 (Allen, 2002)] reveals only 75 entries and 68 different compounds related to this space group. The asymmetric unit of (I) is depicted in Fig. 1. It comprises one half of the cationic moiety, a one-sixth of a [SiF62–] dianion (Si2 atom at the 3.2 inversion centre), a one-twelfth of another [SiF62–] dianion (Si1 atom at the 6/m inversion centre; the F1 atom site occupancy factor 1/2), and a solvent methanol molecule (C-atom at the 622 inversion centre, each of the other atoms is disordered over 12 general positions). A unit cell of (I) contains 12 [C5H9N2+], 6 [SiF62–], and 2 CH3OH moieties. The cation [C5H9N2+] adopts C2v point group symmetry and is bisected with the m-plane of the crystal lattice. The methyl group of the cation exhibits a slight disorder between two positions [the site occupancy factor of the minor component 0.16 (3)].

In crystal lattice of (I), O—H···F hydrogen bonds and an extended three-dimensional-network of C—H···F contacts are both present (see Table 1). All F-atoms of a 3.2-located [SiF62–] dianion participate in C2—H2···F2xxii and symmetry-related contacts [symmetry code: (xxii) –x + 1, –y + 1, z]. These contacts are responsible for formation of rod-type ensembles positioned on the 6 axes which present the "pillar" elements of the entire lattice (see Fig. 2a). In their turn, these rods are F···H interlinked through [SiF62–] dianions disordered around the 6/m centres. Each 6/m located dianion links six different rod-type structures (see Fig. 2 b). The vacancies at the 622 inversion centres are occupied by twelve-fold disordered methanol molecules which are appended to the entire array by O1—H1A···F1 H-bonds (see Fig. 2c). The entire packing diagram is provided in Fig. 3.

Among the closest analogues of (I) and (II), solvatomorphism was observed for (1,3-dimethyl-1H-imidazolium) hexafluorophosphate, [C5H9N2+][PF6-], (III), and its semisolvate with benzene (IV) (Holbrey et al., 2003). In that case, inclusion of the solvent molecule resulted not in an increase, but in a decrease of the crystal symmetry [from Pbca for (III) down to P21/c for (IV)]. Interestingly, measurements of the single-crystal of (III) at different temperatures did not reveal any polymorphs (Holbrey et al., 2003).

Crystals of (I) exhibit remarkable stability in air. They do not loose methanol even if evacuated at ambient temperature during a prolonged time (296 K, 0.133 Pa, 5 h). However, when gradually heated in air in a microscopic melting point apparatus, crystals of (I) behave themselves unlike crystals of solvent-free (II) do [m.p. 550 K for (II); Tian et al. (2013)]. Within the temperature range of 463–466 K, crystals of (I) start to break down to a powder material which further melts at the same temperature as compound (II) does. These empirical observations explicitly point out the fact that interconversions between the solvatomorphs (I) and (II) are impossible without complete destruction of their crystal lattices.

Related literature top

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 use of the SQUEEZE procedure in PLATON, see: Spek (2009).

Experimental top

Crude 1,3-dimethyl-1H-imidazolium hexafluorosilicate was prepared by a reaction of 1,3-dimethyl-1H-imidazolium iodide and disilver hexafluorosilicate (molar ratio 2:1) in distilled water. Concentrating of the filtrate till dryness followed by re-crystallization from methanol gave both (I) and (II) in an over-all almost quantitative yield. If ethanol is used for re-crystallization, only crystals of (II) are formed. A single crystal of (I) suitable for X-ray diffraction analysis was picked up directly from the material from the bottom of the crystallization vessel. Identity of the single crystals of (II) grown from EtOH and MeOH was proved by unit cell measurements. Melting point measurements were performed with a Microscopic Melting Point X4 apparatus (Beijing MAISIQI High-Tech Co., Ltd.)

Refinement top

The straightforward solution of the structure of (I) in an actual centrosymmetric space group P6/mcc suggested by XPREP failed. The structure was initially solved in a related chiral space group P6cc and then transferred to P6/mcc by a corresponding shift along the c-axis. After locating all symmetrically independent atoms in the cation and anions [C1, H1 (sof-s 1/2), C2, H2, N1, C3, H3A—C, Si1 (sof 0.08333), F1 (sof 0.5; disordered over the 6/m centre, assigned to PART -1), Si2 (sof 0.16667), and F2 (sof 1); all sof-s fixed], there still remained a strong (> 3 e Å-3) residual electron density peak (Q-peak) located at the 622 inversion centre. Treatment of this pre-refined model with the SQUEEZE procedure of the PLATON program package (Spek, 2009) revealed two voids per unit cell at (0, 0, 1/4) and (0, 0, 3/4) (each of 65 Å3 and 19 e; total electron count per unit cell 38 e) that was indicative of the presence of the solvent methanol molecule disordered around the 622 inversion centre. Thus, the strongest Q-peak was assigned a C-type (C4; fixed sof 0.08333). The next refinement cycle retrieved a weaker Q-peak at a general position approximately 1.2 Å away from C4 which was further treated as an O-atom disordered between 12 symmetry equivalent positions (O1; fixed sof 0.08333). A Q-peak nearly located on the 6-fold inversion axis approximately 1.0 Å away from C4 was used as a basis for the calculation of the methanol molecule H-atoms positions (treated further as riding atoms with all sof-s fixed to 0.08333). Position of the remaining hydroxyl group H-atom was not evident from the difference Fourier synthesis (a disorder between 12 positions). However, a comparatively short O1···F1 distance [2.80 (3) Å] suggested a presence of an H-bond connecting these two atoms. This way, H-atom (H1A) was put 0.85 Å away from O1 on the line connecting O1 and F1 atoms and treated as a riding atom (AFIX 3 instruction) with sof fixed to 0.08333. Disordered O1, H4A—C, and H1A atoms were all assigned to PART -2. At the final step of the refinement, a noticeable disorder of the methyl group in the imidazolium moiety [minor component sof 0.16 (3)] was also taken into account. All non-H atoms were refined anisotropically. Atoms H1 and H2 were found from the difference Fourier synthesis and refined isotropically. The methyl groups H atoms were treated as riding atoms with distance C—H = 0.96 and Uiso(H) = 1.5 Ueq(C). Hydroxyl group H-atom was treated as a riding atom with distance O—H = 0.85 and Uiso(H) = 1.2 Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Sheldrick, 2008) and OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. Asymmetric unit of (I) along with equivalent atoms with labelling and thermal ellipsoids at the 50% probability level. F1i-iii,v,vi,ix-atoms (sof 1/2) correspond to the second component of the disordered dianion and are depicted as small spheres surrounded with thermal ellipsoids as rims. Symmetry equivalents of the methanol molecule (disordered between 12 positions) are not depicted for clarity. Symmetry codes: (i) x, y, –z; (ii) –x + y, –x, –z; (iii) xy, x, z; (iv) –x, –y, –z; (v) –y, xy, –z; (vi) y, –x + y, z; (vii) –y, xy, z; (viii) y, –x + y, –z; (ix) –x, –y, z; (x) –x + y, –x, z; (xi) xy, x, –z; (xii) –x + y+1, y, –z + 1/2; (xiii) –y + 1, xy, z; (xiv) x, xy, –z + 1/2; (xv) –x + y+1, –x + 1, z; (xvi) –y + 1, –x + 1, –z + 1/2.
[Figure 2] Fig. 2. Different motives of C—H···F contacts and O—H···F H-bonds in (I) with labeling. H-atoms of methyl groups are omitted for clarity. C—H···F contacts and H-bonds are depicted as dotted lines. Symmetry codes: (iv) –x, –y, –z; (vii) –y, xy, z; (viii) y, –x + y, –z; (x) –x + y, –x, z; (xi) xy, x, –z; (xxii) –x + 1, –y + 1, z; (xxiii) xy, x, z; (xxiv) –x + 1, –x + y+1, –z + 1/2; (xxv) x, xy + 1, –z–1/2; (xxvi) x, xy + 1, z–1/2. (a) The rod-type assembling of the imidazolium cations and the [SiF62–] dianions located at the 3.2 inversion centres. A view along the a-axis. H···F contacts motif C22(7)[3R44(14)]. (b) Linking of the rod ensembles by the [SiF62–] dianions located at the 6/m inversion centres. A view along the c-axis. Methanol molecules are omitted for clarity. Only one of two disordered [SiF62–] dianions is depicted. All shown imidazolium cations belong to different rod-type aggregates. H···F contacts motif D22(4). (c) H-bonding between the twofold disordered [SiF62–] dianions located at the 6/m inversion centres and the 12-fold disordered methanol molecules. A view along the (3, 1, 0) direction. Only crystallographically independent atoms are labeled. H-bonds motif either D22(4) or D.
[Figure 3] Fig. 3. Packing diagram for (II) viewed along the c-axis. H-atoms of methyl groups are omitted for clarity. H···F contacts are depicted as dotted lines. O—H···F H-bonds are eclipsed. The first and second level networks: N1=C22(7)[3R44(14)]D22(4) and N2=D22(5) (C—H···O H-bonds are not considered).
Bis(1,3-dimethyl-1H-imidazolium) hexafluorosilicate methanol 0.33-solvate top
Crystal data top
6C5H9N2+·3SiF62·CH4ODx = 1.482 Mg m3
Mr = 1041.10Melting point: 550 K
Hexagonal, P6/mccMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 6 2cCell parameters from 4399 reflections
a = 12.6577 (7) Åθ = 2.4–28.0°
c = 16.8174 (18) ŵ = 0.22 mm1
V = 2333.5 (3) Å3T = 296 K
Z = 2Block, yellow
F(000) = 10800.32 × 0.20 × 0.15 mm
Data collection top
Bruker SMART APEXII
diffractometer
804 independent reflections
Radiation source: fine-focus sealed tube623 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
Detector resolution: 8.333 pixels mm-1θmax = 26.0°, θmin = 1.9°
phi and ω scansh = 1511
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 1215
Tmin = 0.934, Tmax = 0.968l = 2020
11115 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H 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 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = 0.41 e Å3
Crystal data top
6C5H9N2+·3SiF62·CH4OZ = 2
Mr = 1041.10Mo Kα radiation
Hexagonal, P6/mccµ = 0.22 mm1
a = 12.6577 (7) ÅT = 296 K
c = 16.8174 (18) Å0.32 × 0.20 × 0.15 mm
V = 2333.5 (3) Å3
Data collection top
Bruker SMART APEXII
diffractometer
804 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
623 reflections with I > 2σ(I)
Tmin = 0.934, Tmax = 0.968Rint = 0.045
11115 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.15 e Å3
804 reflectionsΔρmin = 0.41 e Å3
75 parameters
Special details top

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
xyzUiso*/UeqOcc. (<1)
N10.32338 (12)0.39168 (13)0.06402 (9)0.0388 (4)
C10.2983 (2)0.3220 (2)0.00000.0404 (6)
H10.266 (2)0.237 (3)0.00000.051 (7)*
C20.36659 (17)0.51001 (18)0.03979 (11)0.0430 (4)
H20.389 (2)0.571 (2)0.0769 (12)0.056 (6)*
C30.3094 (2)0.3496 (2)0.14668 (13)0.0560 (6)
H3BD0.24180.26780.15040.084*0.84 (3)
H3BE0.29460.40230.18010.084*0.84 (3)
H3BF0.38250.35110.16360.084*0.84 (3)
H3AA0.22560.28990.15640.084*0.16 (3)
H3AB0.33370.41760.18190.084*0.16 (3)
H3AC0.35970.31390.15580.084*0.16 (3)
Si10.00000.00000.00000.0319 (4)
F10.12523 (16)0.0637 (2)0.05780 (10)0.0459 (5)0.50
Si20.66670.33330.25000.0318 (3)
F20.55741 (10)0.33189 (10)0.19222 (6)0.0525 (4)
C40.00000.00000.25000.115 (4)
H4A0.00300.00040.30700.138*0.0833333
H4B0.06060.07940.23180.138*0.0833333
H4C0.02070.05950.23220.138*0.0833333
O10.102 (5)0.025 (17)0.2226 (9)0.115 (19)0.0833333
H1A0.10860.03450.17250.138*0.0833333
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0411 (8)0.0412 (8)0.0345 (8)0.0209 (7)0.0001 (6)0.0030 (6)
C10.0377 (13)0.0359 (14)0.0443 (15)0.0159 (11)0.0000.000
C20.0544 (11)0.0407 (10)0.0386 (9)0.0273 (9)0.0032 (8)0.0029 (8)
C30.0683 (13)0.0664 (13)0.0373 (10)0.0367 (11)0.0040 (9)0.0137 (9)
Si10.0316 (5)0.0316 (5)0.0324 (8)0.0158 (3)0.0000.000
F10.0390 (10)0.0499 (13)0.0438 (11)0.0184 (11)0.0091 (9)0.0027 (10)
Si20.0362 (4)0.0362 (4)0.0230 (5)0.0181 (2)0.0000.000
F20.0504 (7)0.0644 (7)0.0466 (7)0.0316 (6)0.0081 (5)0.0106 (5)
C40.145 (7)0.145 (7)0.056 (7)0.072 (4)0.0000.000
O10.08 (2)0.21 (5)0.048 (10)0.07 (4)0.005 (19)0.04 (5)
Geometric parameters (Å, º) top
N1—C11.326 (2)C3—H3AA0.9600
N1—C21.375 (2)C3—H3AB0.9600
N1—C31.467 (2)C3—H3AC0.9600
C1—N1i1.326 (2)Si1—F11.6821 (17)
C1—H10.94 (3)Si2—F21.6829 (10)
C2—C2i1.338 (4)C4—O11.25 (2)
C2—H20.92 (2)C4—H4A0.9600
C3—H3BD0.9600C4—H4B0.9600
C3—H3BE0.9600C4—H4C0.9600
C3—H3BF0.9600O1—H1A0.8498
C1—N1—C2108.46 (16)O1x—C4—O1ix55.4 (3)
C1—N1—C3125.63 (17)O1xiv—C4—O1xvii55.4 (3)
C2—N1—C3125.90 (16)O1x—C4—O1xvii150 (10)
N1i—C1—N1108.6 (2)O1ix—C4—O1xvii96 (10)
N1i—C1—H1125.69 (12)O1xiv—C4—O1xviii136.8 (15)
N1—C1—H1125.69 (12)O1x—C4—O1xviii51 (10)
C2i—C2—N1107.25 (10)O1ix—C4—O1xviii53 (10)
C2i—C2—H2132.8 (13)O1xvii—C4—O1xviii107.3 (8)
N1—C2—H2120.0 (13)O1xiv—C4—O1iii51 (10)
N1—C3—H3BD109.5O1x—C4—O1iii136.8 (15)
N1—C3—H3BE109.5O1ix—C4—O1iii107.3 (8)
H3BD—C3—H3BE109.5O1xvii—C4—O1iii53 (10)
N1—C3—H3BF109.5O1xviii—C4—O1iii154 (10)
H3BD—C3—H3BF109.5O1xiv—C4—O1vi100 (10)
H3BE—C3—H3BF109.5O1x—C4—O1vi55.4 (3)
N1—C3—H3AA109.5O1ix—C4—O1vi107.3 (8)
N1—C3—H3AB109.5O1xvii—C4—O1vi154 (10)
H3AA—C3—H3AB109.5O1xviii—C4—O1vi96 (10)
N1—C3—H3AC109.5O1iii—C4—O1vi107.3 (8)
H3AA—C3—H3AC109.5O1xiv—C4—O1xix55.4 (3)
H3AB—C3—H3AC109.5O1x—C4—O1xix100 (10)
F1ii—Si1—F1iii180.00 (19)O1ix—C4—O1xix154 (10)
F1ii—Si1—F1iv48.16 (4)O1xvii—C4—O1xix107.3 (8)
F1iii—Si1—F1iv131.84 (4)O1xviii—C4—O1xix107.3 (8)
F1ii—Si1—F1v89.94 (9)O1iii—C4—O1xix96 (10)
F1iii—Si1—F1v90.06 (9)O1vi—C4—O1xix53 (10)
F1iv—Si1—F1v48.16 (4)O1xiv—C4—O1xx107.3 (8)
F1ii—Si1—F1vi90.06 (9)O1x—C4—O1xx53 (10)
F1iii—Si1—F1vi89.94 (9)O1ix—C4—O1xx100 (10)
F1iv—Si1—F1vi131.84 (4)O1xvii—C4—O1xx136.8 (15)
F1v—Si1—F1vi180.00 (13)O1xviii—C4—O1xx55.4 (3)
F1ii—Si1—F1vii131.84 (4)O1iii—C4—O1xx150 (10)
F1iii—Si1—F1vii48.16 (4)O1vi—C4—O1xx51 (10)
F1iv—Si1—F1vii90.06 (9)O1xix—C4—O1xx55.4 (3)
F1v—Si1—F1vii70.61 (12)O1xiv—C4—O1xxi107.3 (8)
F1vi—Si1—F1vii109.39 (12)O1x—C4—O1xxi96 (10)
F1ii—Si1—F1viii48.16 (4)O1ix—C4—O1xxi51 (10)
F1iii—Si1—F1viii131.84 (4)O1xvii—C4—O1xxi55.4 (3)
F1iv—Si1—F1viii89.94 (9)O1xviii—C4—O1xxi55.4 (3)
F1v—Si1—F1viii109.39 (12)O1iii—C4—O1xxi100 (10)
F1vi—Si1—F1viii70.61 (12)O1vi—C4—O1xxi150 (10)
F1vii—Si1—F1viii180.00 (13)O1xix—C4—O1xxi136.8 (15)
F1ii—Si1—F1ix90.06 (9)O1xx—C4—O1xxi107.3 (8)
F1iii—Si1—F1ix89.94 (9)O1xiv—C4—O1vii96 (10)
F1iv—Si1—F1ix70.61 (12)O1x—C4—O1vii107.3 (8)
F1v—Si1—F1ix90.06 (9)O1ix—C4—O1vii55.4 (3)
F1vi—Si1—F1ix89.94 (9)O1xvii—C4—O1vii51 (10)
F1vii—Si1—F1ix48.16 (4)O1xviii—C4—O1vii100 (10)
F1viii—Si1—F1ix131.84 (4)O1iii—C4—O1vii55.4 (3)
F1ii—Si1—F1i89.94 (9)O1vi—C4—O1vii136.8 (15)
F1iii—Si1—F1i90.06 (9)O1xix—C4—O1vii150 (10)
F1iv—Si1—F1i109.39 (12)O1xx—C4—O1vii154 (10)
F1v—Si1—F1i89.94 (9)O1xxi—C4—O1vii53 (10)
F1vi—Si1—F1i90.06 (9)O1xiv—C4—O153 (10)
F1vii—Si1—F1i131.84 (4)O1x—C4—O1107.3 (8)
F1viii—Si1—F1i48.16 (4)O1ix—C4—O1136.8 (15)
F1ix—Si1—F1i180.00 (14)O1xvii—C4—O1100 (10)
F1ii—Si1—F1x70.61 (12)O1xviii—C4—O1150 (10)
F1iii—Si1—F1x109.39 (12)O1iii—C4—O155.4 (3)
F1iv—Si1—F1x90.06 (9)O1vi—C4—O155.4 (3)
F1v—Si1—F1x131.84 (4)O1xix—C4—O151 (10)
F1vi—Si1—F1x48.16 (4)O1xx—C4—O196 (10)
F1vii—Si1—F1x89.94 (9)O1xxi—C4—O1154 (10)
F1viii—Si1—F1x90.06 (9)O1vii—C4—O1107.3 (8)
F1ix—Si1—F1x48.16 (4)O1xiv—C4—H4A66.7
F1i—Si1—F1x131.84 (4)O1x—C4—H4A112.4
F1ii—Si1—F1xi109.39 (12)O1ix—C4—H4A113.7
F1iii—Si1—F1xi70.61 (12)O1xvii—C4—H4A68.7
F1iv—Si1—F1xi89.94 (9)O1xviii—C4—H4A70.1
F1v—Si1—F1xi48.16 (4)O1iii—C4—H4A110.7
F1vi—Si1—F1xi131.84 (4)O1vi—C4—H4A110.3
F1vii—Si1—F1xi90.06 (9)O1xix—C4—H4A66.4
F1viii—Si1—F1xi89.94 (9)O1xx—C4—H4A68.1
F1ix—Si1—F1xi131.84 (4)O1xxi—C4—H4A70.4
F1i—Si1—F1xi48.16 (4)O1vii—C4—H4A112.9
F1x—Si1—F1xi180.00 (19)O1—C4—H4A109.5
F1ii—Si1—F1131.84 (4)O1xiv—C4—H4B154.5
F1iii—Si1—F148.16 (4)O1x—C4—H4B3.1
F1iv—Si1—F1180.0O1ix—C4—H4B55.4
F1v—Si1—F1131.83 (4)O1xvii—C4—H4B148.9
F1vi—Si1—F148.17 (4)O1xviii—C4—H4B48.1
F1vii—Si1—F189.94 (9)O1iii—C4—H4B139.8
F1viii—Si1—F190.06 (9)O1vi—C4—H4B56.8
F1ix—Si1—F1109.39 (12)O1xix—C4—H4B99.4
F1i—Si1—F170.61 (12)O1xx—C4—H4B51.6
F1x—Si1—F189.95 (9)O1xxi—C4—H4B94.1
F1xi—Si1—F190.05 (9)O1vii—C4—H4B108.2
F2xii—Si2—F2xiii89.25 (7)O1—C4—H4B109.5
F2xii—Si2—F2xiv89.99 (6)H4A—C4—H4B109.5
F2xiii—Si2—F2xiv90.77 (8)O1xiv—C4—H4C95.1
F2xii—Si2—F2xv90.77 (8)O1x—C4—H4C108.7
F2xiii—Si2—F2xv89.99 (6)O1ix—C4—H4C55.7
F2xiv—Si2—F2xv178.93 (8)O1xvii—C4—H4C48.5
F2xii—Si2—F2xvi89.99 (6)O1xviii—C4—H4C98.1
F2xiii—Si2—F2xvi178.93 (8)O1iii—C4—H4C56.6
F2xiv—Si2—F2xvi89.99 (6)O1vi—C4—H4C140.2
F2xv—Si2—F2xvi89.25 (7)O1xix—C4—H4C150.0
F2xii—Si2—F2178.93 (8)O1xx—C4—H4C153.2
F2xiii—Si2—F289.99 (6)O1xxi—C4—H4C50.5
F2xiv—Si2—F289.25 (7)O1vii—C4—H4C3.4
F2xv—Si2—F289.99 (6)O1—C4—H4C109.5
F2xvi—Si2—F290.77 (8)H4A—C4—H4C109.5
O1xiv—C4—O1x154 (10)H4B—C4—H4C109.5
O1xiv—C4—O1ix150 (10)C4—O1—H1A114.9
C2—N1—C1—N1i0.3 (3)C1—N1—C2—C2i0.18 (16)
C3—N1—C1—N1i179.32 (13)C3—N1—C2—C2i179.20 (14)
Symmetry codes: (i) x, y, z; (ii) x+y, x, z; (iii) xy, x, z; (iv) x, y, z; (v) y, xy, z; (vi) y, x+y, z; (vii) y, xy, z; (viii) y, x+y, z; (ix) x, y, z; (x) x+y, x, z; (xi) xy, x, z; (xii) x+y+1, y, z+1/2; (xiii) y+1, xy, z; (xiv) x, xy, z+1/2; (xv) x+y+1, x+1, z; (xvi) y+1, x+1, z+1/2; (xvii) y, x, z+1/2; (xviii) x, x+y, z+1/2; (xix) xy, y, z+1/2; (xx) y, x, z+1/2; (xxi) x+y, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···F10.851.96 (1)2.80 (3)177 (13)
C1—H1···F10.94 (3)2.24 (3)3.044 (3)143 (2)
C2—H2···F2xxii0.92 (2)2.21 (2)3.095 (2)160.3 (17)
Symmetry code: (xxii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula6C5H9N2+·3SiF62·CH4O
Mr1041.10
Crystal system, space groupHexagonal, P6/mcc
Temperature (K)296
a, c (Å)12.6577 (7), 16.8174 (18)
V3)2333.5 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.22
Crystal size (mm)0.32 × 0.20 × 0.15
Data collection
DiffractometerBruker SMART APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.934, 0.968
No. of measured, independent and
observed [I > 2σ(I)] reflections
11115, 804, 623
Rint0.045
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.098, 1.10
No. of reflections804
No. of parameters75
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.15, 0.41

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···F10.851.9550 (17)2.80 (3)177 (13)
C1—H1···F10.94 (3)2.24 (3)3.044 (3)143.2 (16)
C2—H2···F2i0.92 (2)2.21 (2)3.095 (2)160.3 (17)
Symmetry code: (i) x+1, y+1, z.
Table 2. C—H···F contacts and O—H···F H-bond geometry (Å, °) in (II). top
D—H···AD—HH···AD···AD—H···A
O1—H1A···F10.851.955 (2)2.80 (3)177 (13)
C1—H1···F10.94 (3)2.24 (3)3.044 (3)143 (2)
C2—H2···F2xxii0.92 (2)2.21 (2)3.095 (2)160 (2)
Symmetry code: (xxii): –x+1, –y+1, z.
 

Footnotes

Previous address: Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education, College of Chemistry and Material Science, the North-West University of Xi'an, Taibai Bei Avenue 229, Xi'an 710069, Province, People's Republic of China

§Previous address: Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education, College of Chemistry and Material Science, the North-West University of Xi'an, Taibai Bei Avenue 229, Xi'an 710069, Province, People's Republic of China.

Acknowledgements

Financial support from the National Natural Science Foundation of China (project Nos. 20702041 and 21072157) and the Shaanxi Province Administration of Foreign Experts Bureau Foundation (grant No. 20106100079) is gratefully acknowledged. The authors are thankful to Mr Su Pengfei (Xi'an Modern Chemistry Research Institute) for his help in carrying out X-ray diffraction measurements.

References

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Volume 69| Part 8| August 2013| Pages o1216-o1217
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