Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802005895/ac6002sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802005895/ac6002Isup2.hkl |
CCDC reference: 185739
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.002 Å
- R factor = 0.022
- wR factor = 0.061
- Data-to-parameter ratio = 15.6
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Preparations were carried out in a dry room (<1% relative humidity) using anhydrous materials. From a poly(ethylene glycol)dimethyl ether (PEGDME500, Aldrich) and CH3CN solution of LiCF3SO3, crystals of [Li(CF3SO3)(CH3CN)]∞ separated over a period of two weeks.
The crystal is a pseudomerohedral twin with the two components related by the twin law (100/010/001). The twin fraction refines to 67.3 (1)%.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Bruker, 1998); software used to prepare material for publication: SHELXTL/PC and PLATON (Spek, 2001).
[Li(CF3O3S)(C2H3N)] | F(000) = 392 |
Mr = 197.06 | Dx = 1.716 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.4814 (11) Å | Cell parameters from 2977 reflections |
b = 14.790 (3) Å | θ = 2.6–27.5° |
c = 9.409 (2) Å | µ = 0.44 mm−1 |
β = 90.064 (3)° | T = 173 K |
V = 762.8 (3) Å3 | Block, colourless |
Z = 4 | 0.46 × 0.40 × 0.30 mm |
Siemens CCD area-detector diffractometer | 1731 independent reflections |
Radiation source: fine-focus sealed tube | 1693 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Blessing, 1995; Sheldrick, 2000) | h = −7→7 |
Tmin = 0.797, Tmax = 0.893 | k = −19→19 |
6487 measured reflections | l = −12→12 |
Refinement on F2 | Primary atom site location: direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier synthesis |
R[F2 > 2σ(F2)] = 0.022 | Hydrogen site location: placed geometrically |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0351P)2 + 0.139P] where P = (Fo2 + 2Fc2)/3 |
1731 reflections | (Δ/σ)max < 0.001 |
111 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
[Li(CF3O3S)(C2H3N)] | V = 762.8 (3) Å3 |
Mr = 197.06 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.4814 (11) Å | µ = 0.44 mm−1 |
b = 14.790 (3) Å | T = 173 K |
c = 9.409 (2) Å | 0.46 × 0.40 × 0.30 mm |
β = 90.064 (3)° |
Siemens CCD area-detector diffractometer | 1731 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995; Sheldrick, 2000) | 1693 reflections with I > 2σ(I) |
Tmin = 0.797, Tmax = 0.893 | Rint = 0.022 |
6487 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.24 e Å−3 |
1731 reflections | Δρmin = −0.26 e Å−3 |
111 parameters |
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 | ||
Li1 | 0.2780 (5) | 0.56145 (15) | −0.1656 (2) | 0.0235 (4) | |
S1 | 0.22006 (6) | 0.378941 (18) | 0.01485 (4) | 0.01931 (9) | |
O1 | 0.2474 (2) | 0.43582 (6) | −0.10913 (11) | 0.0312 (2) | |
O2 | −0.0251 (2) | 0.37213 (7) | 0.06935 (13) | 0.0317 (3) | |
O3 | 0.4034 (2) | 0.39132 (8) | 0.12214 (12) | 0.0317 (3) | |
C1 | 0.2774 (3) | 0.26604 (9) | −0.05637 (15) | 0.0276 (3) | |
F1 | 0.1151 (2) | 0.24573 (8) | −0.15510 (12) | 0.0476 (3) | |
F2 | 0.4995 (2) | 0.26235 (7) | −0.11398 (13) | 0.0494 (3) | |
F3 | 0.2645 (2) | 0.20396 (6) | 0.04545 (10) | 0.0418 (2) | |
N1 | 0.2498 (3) | 0.56156 (8) | −0.38202 (12) | 0.0298 (3) | |
C2 | 0.2447 (3) | 0.57544 (10) | −0.50076 (15) | 0.0281 (3) | |
C3 | 0.2376 (4) | 0.59454 (16) | −0.65316 (17) | 0.0472 (4) | |
H3A | 0.0835 | 0.5725 | −0.6931 | 0.071* | |
H3B | 0.3743 | 0.5641 | −0.7001 | 0.071* | |
H3C | 0.2502 | 0.6599 | −0.6685 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Li1 | 0.0239 (11) | 0.0253 (10) | 0.0214 (10) | −0.0004 (9) | −0.0019 (9) | 0.0017 (8) |
S1 | 0.01964 (14) | 0.01844 (14) | 0.01987 (15) | −0.00028 (10) | −0.00041 (12) | −0.00057 (11) |
O1 | 0.0439 (6) | 0.0230 (4) | 0.0266 (5) | −0.0016 (5) | −0.0018 (5) | 0.0048 (4) |
O2 | 0.0218 (5) | 0.0324 (6) | 0.0408 (6) | 0.0012 (4) | 0.0044 (5) | −0.0050 (5) |
O3 | 0.0270 (6) | 0.0400 (6) | 0.0279 (6) | −0.0082 (5) | −0.0065 (5) | −0.0001 (4) |
C1 | 0.0362 (7) | 0.0199 (6) | 0.0266 (7) | 0.0018 (6) | 0.0051 (6) | 0.0012 (5) |
F1 | 0.0698 (7) | 0.0361 (5) | 0.0367 (5) | −0.0055 (5) | −0.0102 (5) | −0.0135 (4) |
F2 | 0.0501 (6) | 0.0358 (5) | 0.0622 (7) | 0.0123 (5) | 0.0301 (6) | 0.0004 (5) |
F3 | 0.0605 (7) | 0.0231 (4) | 0.0417 (5) | 0.0041 (4) | 0.0077 (5) | 0.0102 (4) |
N1 | 0.0328 (7) | 0.0331 (6) | 0.0236 (6) | −0.0026 (5) | −0.0033 (6) | 0.0009 (4) |
C2 | 0.0257 (6) | 0.0355 (7) | 0.0232 (6) | −0.0031 (5) | −0.0026 (7) | 0.0018 (5) |
C3 | 0.0381 (10) | 0.0822 (13) | 0.0213 (7) | −0.0047 (10) | −0.0024 (7) | 0.0103 (8) |
Li1—O1 | 1.940 (2) | O3—Li1ii | 1.925 (3) |
Li1—O2i | 1.926 (3) | C1—F1 | 1.3202 (19) |
Li1—O3ii | 1.925 (3) | C1—F3 | 1.3290 (16) |
Li1—N1 | 2.042 (3) | C1—F2 | 1.3343 (18) |
S1—O3 | 1.4353 (12) | N1—C2 | 1.1362 (19) |
S1—O2 | 1.4424 (12) | C2—C3 | 1.4620 (19) |
S1—O1 | 1.4461 (10) | C3—H3A | 0.9800 |
S1—C1 | 1.8266 (14) | C3—H3B | 0.9800 |
O2—Li1i | 1.926 (3) | C3—H3C | 0.9800 |
N1—Li1—O1 | 105.52 (11) | F1—C1—F3 | 108.28 (13) |
N1—Li1—O2i | 114.53 (13) | F1—C1—F2 | 108.62 (13) |
N1—Li1—O3ii | 106.22 (12) | F3—C1—F2 | 108.29 (13) |
O1—Li1—O2i | 107.28 (12) | F1—C1—S1 | 110.49 (10) |
O1—Li1—O3ii | 111.60 (13) | F3—C1—S1 | 110.97 (9) |
O2i—Li1—O3ii | 111.61 (12) | F2—C1—S1 | 110.12 (10) |
O3—S1—O2 | 114.25 (8) | C2—N1—Li1 | 169.24 (14) |
O3—S1—O1 | 114.85 (7) | N1—C2—C3 | 179.26 (18) |
O2—S1—O1 | 115.13 (7) | C2—C3—H3A | 109.5 |
O3—S1—C1 | 104.71 (7) | C2—C3—H3B | 109.5 |
O2—S1—C1 | 103.15 (7) | H3A—C3—H3B | 109.5 |
O1—S1—C1 | 102.58 (6) | C2—C3—H3C | 109.5 |
S1—O1—Li1 | 141.93 (9) | H3A—C3—H3C | 109.5 |
S1—O2—Li1i | 143.40 (10) | H3B—C3—H3C | 109.5 |
S1—O3—Li1ii | 146.13 (10) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Li(CF3O3S)(C2H3N)] |
Mr | 197.06 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 5.4814 (11), 14.790 (3), 9.409 (2) |
β (°) | 90.064 (3) |
V (Å3) | 762.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.44 |
Crystal size (mm) | 0.46 × 0.40 × 0.30 |
Data collection | |
Diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Blessing, 1995; Sheldrick, 2000) |
Tmin, Tmax | 0.797, 0.893 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6487, 1731, 1693 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.061, 1.11 |
No. of reflections | 1731 |
No. of parameters | 111 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.26 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Bruker, 1998), SHELXTL/PC and PLATON (Spek, 2001).
Li1—O1 | 1.940 (2) | Li1—O3ii | 1.925 (3) |
Li1—O2i | 1.926 (3) | Li1—N1 | 2.042 (3) |
N1—Li1—O1 | 105.52 (11) | O1—Li1—O2i | 107.28 (12) |
N1—Li1—O2i | 114.53 (13) | O1—Li1—O3ii | 111.60 (13) |
N1—Li1—O3ii | 106.22 (12) | O2i—Li1—O3ii | 111.61 (12) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z. |
In the course of studies on the reactions of LiCF3SO3 with various short- and long-chain ethylene oxide compounds, it has been found that addition of CH3CN can result in the formation of crystals of [Li(CF3SO3)(CH3CN)]∞. The crystals for this study were grown from a solution of LiCF3SO3 in poly(ethylene glycol) dimethyl ether (PEGDME500, Aldrich) and CH3CN. The structure has been determined to be that of one-dimensional polymers that propagate along the a axis. Partial details of this structure have previously been reported (Huang, 1994).
Each Li atom is tetrahedrally coordinated by three oxygen donors from three different CF3SO3 anions [Li—O = 1.925 (3), 1.926 (3) and 1.940 (2) Å] and one CH3CN nitrogen donor [Li—N = 2.042 (3) Å; Fig. 1]. In turn, each CF3SO3- anion is coordinated to three different Li atoms. The arrangement of the two three-connecting units is such that centrosymmetric eight-atom [LiOSOLiOSO] rings are formed (Fig. 2). These eight-atom rings are fused on opposite edges with like rings creating the one-dimensional polymer.