Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102015135/gg1134sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102015135/gg1134Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102015135/gg1134IIsup3.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270102015135/gg1134sup4.pdf | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270102015135/gg1134sup5.pdf |
CCDC references: 197316; 197317
Preparations were carried out in a dry room (<1% relative humidity). LiCF3SO3 and LiCF3CO2 (ex Aldrich) were dried at 383 K under high vacuum for 12 h. Anhydrous diglyme [bis(2-methoxyethyl) ether; 99.5%, ex Aldrich] was used as received. Compounds (I) and (II) were prepared by the addition of diglyme to the salts, in 1:1 mole ratios. The mixtures were stirred while heating to dissolve the salts. Single crystals grew slowly on standing the solutions at room temperature.
The H atoms were placed geometrically, with C—H = 0.98–0.99 Å, and allowed to refine as riding on the parent C atoms.
For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for (I); SIR92 (Altomare et al., 1993) for (II). For both compounds, 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).
[Li2(CF3SO)2(C6H14O3)] | Z = 2 |
Mr = 446.19 | F(000) = 452 |
Triclinic, P1 | Dx = 1.528 Mg m−3 |
Hall symbol: -P1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.678 (3) Å | Cell parameters from 1639 reflections |
b = 10.815 (3) Å | θ = 1.9–25.1° |
c = 11.899 (4) Å | µ = 0.37 mm−1 |
α = 67.566 (5)° | T = 173 K |
β = 89.831 (5)° | Plate, colourless |
γ = 71.435 (5)° | 0.30 × 0.20 × 0.04 mm |
V = 969.5 (5) Å3 |
Bruker CCD-platform area-detector diffractometer | 3402 independent reflections |
Radiation source: fine-focus sealed tube | 2751 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Blessing, 1995; Sheldrick, 2000) | h = −10→10 |
Tmin = 0.898, Tmax = 0.986 | k = −11→12 |
7068 measured reflections | l = 0→14 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0527P)2 + 0.5304P] where P = (Fo2 + 2Fc2)/3 |
3402 reflections | (Δ/σ)max < 0.001 |
246 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
[Li2(CF3SO)2(C6H14O3)] | γ = 71.435 (5)° |
Mr = 446.19 | V = 969.5 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.678 (3) Å | Mo Kα radiation |
b = 10.815 (3) Å | µ = 0.37 mm−1 |
c = 11.899 (4) Å | T = 173 K |
α = 67.566 (5)° | 0.30 × 0.20 × 0.04 mm |
β = 89.831 (5)° |
Bruker CCD-platform area-detector diffractometer | 3402 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995; Sheldrick, 2000) | 2751 reflections with I > 2σ(I) |
Tmin = 0.898, Tmax = 0.986 | Rint = 0.038 |
7068 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.43 e Å−3 |
3402 reflections | Δρmin = −0.36 e Å−3 |
246 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 | 0.3023 (5) | 0.9632 (5) | 0.1689 (3) | 0.0321 (9) | |
Li2 | 0.2518 (5) | 0.9804 (5) | 0.5497 (3) | 0.0313 (9) | |
C1 | 0.0496 (5) | 1.2477 (4) | −0.0144 (3) | 0.0700 (10) | |
H1A | 0.0633 | 1.3255 | −0.0859 | 0.105* | |
H1B | 0.0544 | 1.2684 | 0.0586 | 0.105* | |
H1C | −0.0568 | 1.2388 | −0.0284 | 0.105* | |
O1 | 0.1770 (2) | 1.1183 (2) | 0.00348 (16) | 0.0446 (5) | |
C2 | 0.1622 (4) | 1.0705 (4) | −0.0909 (2) | 0.0514 (8) | |
H2A | 0.1541 | 1.1469 | −0.1724 | 0.062* | |
H2B | 0.0622 | 1.0446 | −0.0878 | 0.062* | |
C3 | 0.3098 (4) | 0.9447 (4) | −0.0705 (2) | 0.0521 (8) | |
H3A | 0.2943 | 0.8969 | −0.1238 | 0.063* | |
H3B | 0.4067 | 0.9743 | −0.0908 | 0.063* | |
O2 | 0.3341 (2) | 0.8499 (2) | 0.05505 (16) | 0.0426 (5) | |
C4 | 0.4852 (4) | 0.7332 (3) | 0.0901 (3) | 0.0516 (8) | |
H4A | 0.5727 | 0.7646 | 0.0473 | 0.062* | |
H4B | 0.4734 | 0.6566 | 0.0684 | 0.062* | |
C5 | 0.5276 (4) | 0.6803 (3) | 0.2255 (3) | 0.0451 (7) | |
H5A | 0.4453 | 0.6409 | 0.2688 | 0.054* | |
H5B | 0.6368 | 0.6045 | 0.2535 | 0.054* | |
O3 | 0.5283 (2) | 0.79872 (19) | 0.25000 (16) | 0.0364 (4) | |
C6 | 0.5890 (4) | 0.7592 (3) | 0.3750 (3) | 0.0467 (7) | |
H6A | 0.7007 | 0.6898 | 0.3951 | 0.070* | |
H6B | 0.5177 | 0.7168 | 0.4291 | 0.070* | |
H6C | 0.5903 | 0.8440 | 0.3865 | 0.070* | |
S1 | 0.38367 (7) | 1.15752 (6) | 0.30799 (5) | 0.02634 (18) | |
O4 | 0.3395 (2) | 1.11136 (19) | 0.21844 (15) | 0.0362 (4) | |
O5 | 0.3069 (2) | 1.1238 (2) | 0.41657 (16) | 0.0412 (4) | |
O6 | 0.5556 (2) | 1.1329 (2) | 0.32826 (16) | 0.0384 (4) | |
C7 | 0.2935 (4) | 1.3509 (3) | 0.2335 (3) | 0.0451 (7) | |
F1 | 0.1320 (2) | 1.3918 (2) | 0.2090 (2) | 0.0755 (6) | |
F2 | 0.3267 (3) | 1.4108 (2) | 0.30417 (18) | 0.0737 (6) | |
F3 | 0.3508 (3) | 1.4008 (2) | 0.12917 (17) | 0.0744 (6) | |
S2 | 0.08843 (7) | 0.85874 (6) | 0.39104 (5) | 0.02657 (17) | |
O7 | 0.1613 (2) | 0.88230 (19) | 0.28022 (15) | 0.0361 (4) | |
O8 | 0.1731 (2) | 0.8700 (2) | 0.48812 (16) | 0.0414 (5) | |
O9 | −0.0863 (2) | 0.92593 (19) | 0.37151 (15) | 0.0355 (4) | |
C8 | 0.1180 (3) | 0.6696 (3) | 0.4511 (3) | 0.0400 (6) | |
F4 | 0.2756 (2) | 0.59290 (18) | 0.47376 (18) | 0.0626 (5) | |
F5 | 0.0539 (3) | 0.6299 (2) | 0.55376 (18) | 0.0722 (6) | |
F6 | 0.0480 (2) | 0.63870 (19) | 0.37101 (19) | 0.0657 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Li1 | 0.031 (2) | 0.044 (2) | 0.024 (2) | −0.0169 (19) | 0.0047 (16) | −0.0130 (18) |
Li2 | 0.031 (2) | 0.043 (2) | 0.025 (2) | −0.0155 (18) | 0.0041 (16) | −0.0173 (18) |
C1 | 0.067 (2) | 0.055 (2) | 0.072 (2) | −0.0057 (18) | −0.0257 (18) | −0.0203 (18) |
O1 | 0.0504 (12) | 0.0512 (12) | 0.0301 (9) | −0.0169 (10) | −0.0092 (8) | −0.0143 (8) |
C2 | 0.0586 (19) | 0.080 (2) | 0.0230 (13) | −0.0372 (18) | −0.0005 (12) | −0.0167 (14) |
C3 | 0.067 (2) | 0.078 (2) | 0.0282 (14) | −0.0393 (19) | 0.0146 (13) | −0.0278 (15) |
O2 | 0.0493 (12) | 0.0595 (13) | 0.0315 (10) | −0.0257 (10) | 0.0138 (8) | −0.0257 (9) |
C4 | 0.059 (2) | 0.060 (2) | 0.0550 (18) | −0.0242 (16) | 0.0213 (15) | −0.0401 (16) |
C5 | 0.0492 (17) | 0.0404 (16) | 0.0525 (17) | −0.0145 (13) | 0.0099 (13) | −0.0264 (14) |
O3 | 0.0375 (10) | 0.0350 (10) | 0.0399 (10) | −0.0120 (8) | 0.0024 (8) | −0.0188 (8) |
C6 | 0.0453 (16) | 0.0459 (17) | 0.0448 (16) | −0.0100 (13) | −0.0101 (13) | −0.0183 (14) |
S1 | 0.0279 (3) | 0.0292 (3) | 0.0236 (3) | −0.0102 (2) | 0.0008 (2) | −0.0119 (2) |
O4 | 0.0380 (10) | 0.0398 (10) | 0.0348 (9) | −0.0115 (8) | −0.0034 (7) | −0.0206 (8) |
O5 | 0.0480 (11) | 0.0468 (11) | 0.0326 (10) | −0.0205 (9) | 0.0129 (8) | −0.0166 (8) |
O6 | 0.0274 (9) | 0.0501 (11) | 0.0360 (10) | −0.0127 (8) | −0.0032 (7) | −0.0161 (8) |
C7 | 0.0599 (19) | 0.0351 (15) | 0.0388 (15) | −0.0135 (14) | 0.0062 (13) | −0.0158 (13) |
F1 | 0.0540 (12) | 0.0517 (12) | 0.0890 (15) | 0.0136 (9) | −0.0134 (10) | −0.0209 (10) |
F2 | 0.1162 (18) | 0.0456 (11) | 0.0717 (13) | −0.0280 (11) | 0.0046 (12) | −0.0364 (10) |
F3 | 0.1149 (18) | 0.0443 (11) | 0.0513 (11) | −0.0285 (11) | 0.0232 (11) | −0.0052 (9) |
S2 | 0.0281 (3) | 0.0325 (3) | 0.0251 (3) | −0.0138 (3) | 0.0044 (2) | −0.0150 (3) |
O7 | 0.0362 (10) | 0.0467 (11) | 0.0314 (9) | −0.0207 (8) | 0.0113 (7) | −0.0166 (8) |
O8 | 0.0470 (11) | 0.0506 (12) | 0.0363 (10) | −0.0206 (9) | −0.0024 (8) | −0.0243 (9) |
O9 | 0.0293 (9) | 0.0476 (11) | 0.0348 (9) | −0.0112 (8) | 0.0067 (7) | −0.0235 (8) |
C8 | 0.0437 (16) | 0.0368 (15) | 0.0422 (15) | −0.0175 (13) | 0.0066 (12) | −0.0155 (13) |
F4 | 0.0530 (11) | 0.0385 (10) | 0.0778 (13) | −0.0031 (8) | −0.0008 (9) | −0.0142 (9) |
F5 | 0.0961 (16) | 0.0584 (12) | 0.0605 (12) | −0.0426 (12) | 0.0336 (11) | −0.0092 (10) |
F6 | 0.0808 (14) | 0.0500 (11) | 0.0834 (14) | −0.0323 (10) | −0.0010 (10) | −0.0367 (10) |
Li1—O1 | 2.050 (4) | C5—O3 | 1.420 (3) |
Li1—O2 | 2.113 (4) | C5—H5A | 0.9900 |
Li1—O3 | 2.103 (5) | C5—H5B | 0.9900 |
Li1—O4 | 2.017 (4) | O3—C6 | 1.431 (3) |
Li1—O7 | 1.951 (4) | C6—H6A | 0.9800 |
Li2—O5 | 1.933 (4) | C6—H6B | 0.9800 |
Li2—O8 | 1.901 (4) | C6—H6C | 0.9800 |
Li2—O6i | 1.938 (4) | O9—Li2ii | 1.939 (4) |
Li2—O9ii | 1.939 (4) | O6—Li2i | 1.938 (4) |
C1—O1 | 1.419 (4) | S1—O4 | 1.4358 (17) |
C1—H1A | 0.9800 | S1—O5 | 1.4270 (18) |
C1—H1B | 0.9800 | S1—O6 | 1.4334 (18) |
C1—H1C | 0.9800 | S1—C7 | 1.822 (3) |
O1—C2 | 1.425 (3) | S2—O7 | 1.4301 (18) |
C2—C3 | 1.481 (5) | S2—O8 | 1.4350 (17) |
C2—H2A | 0.9900 | S2—O9 | 1.4329 (18) |
C2—H2B | 0.9900 | S2—C8 | 1.820 (3) |
C3—O2 | 1.422 (3) | C7—F1 | 1.324 (3) |
C3—H3A | 0.9900 | C7—F2 | 1.322 (3) |
C3—H3B | 0.9900 | C7—F3 | 1.317 (3) |
O2—C4 | 1.426 (4) | C8—F4 | 1.319 (3) |
C4—C5 | 1.491 (4) | C8—F5 | 1.316 (3) |
C4—H4A | 0.9900 | C8—F6 | 1.329 (3) |
C4—H4B | 0.9900 | ||
O7—Li1—O4 | 106.5 (2) | O3—C5—C4 | 106.8 (2) |
O7—Li1—O1 | 113.4 (2) | O3—C5—H5A | 110.4 |
O4—Li1—O1 | 90.50 (19) | C4—C5—H5A | 110.4 |
O7—Li1—O3 | 98.91 (19) | O3—C5—H5B | 110.4 |
O4—Li1—O3 | 98.63 (17) | C4—C5—H5B | 110.4 |
O1—Li1—O3 | 142.4 (2) | H5A—C5—H5B | 108.6 |
O7—Li1—O2 | 101.47 (19) | C5—O3—C6 | 112.7 (2) |
O4—Li1—O2 | 152.0 (2) | C5—O3—Li1 | 107.80 (19) |
O1—Li1—O2 | 77.50 (15) | C6—O3—Li1 | 120.03 (19) |
O3—Li1—O2 | 77.61 (16) | O3—C6—H6A | 109.5 |
O8—Li2—O5 | 109.8 (2) | O3—C6—H6B | 109.5 |
O8—Li2—O9ii | 110.7 (2) | H6A—C6—H6B | 109.5 |
O5—Li2—O9ii | 108.7 (2) | O3—C6—H6C | 109.5 |
O8—Li2—O6i | 113.0 (2) | H6A—C6—H6C | 109.5 |
O5—Li2—O6i | 108.2 (2) | H6B—C6—H6C | 109.5 |
O9ii—Li2—O6i | 106.37 (19) | O5—S1—O6 | 114.92 (11) |
O1—C1—H1A | 109.5 | O5—S1—O4 | 115.60 (11) |
O1—C1—H1B | 109.5 | O6—S1—O4 | 114.18 (11) |
H1A—C1—H1B | 109.5 | O5—S1—C7 | 103.05 (12) |
O1—C1—H1C | 109.5 | O6—S1—C7 | 103.32 (13) |
H1A—C1—H1C | 109.5 | O4—S1—C7 | 103.43 (12) |
H1B—C1—H1C | 109.5 | S1—O4—Li1 | 152.27 (16) |
C2—O1—C1 | 112.4 (2) | S1—O5—Li2 | 147.48 (18) |
C2—O1—Li1 | 115.7 (2) | S1—O6—Li2i | 142.17 (17) |
C1—O1—Li1 | 126.1 (2) | F3—C7—F1 | 107.8 (2) |
O1—C2—C3 | 107.8 (2) | F3—C7—F2 | 107.8 (2) |
O1—C2—H2A | 110.2 | F1—C7—F2 | 108.1 (2) |
C3—C2—H2A | 110.2 | F3—C7—S1 | 111.14 (19) |
O1—C2—H2B | 110.2 | F1—C7—S1 | 110.9 (2) |
C3—C2—H2B | 110.2 | F2—C7—S1 | 111.0 (2) |
H2A—C2—H2B | 108.5 | O7—S2—O9 | 113.81 (10) |
O2—C3—C2 | 108.0 (2) | O7—S2—O8 | 115.78 (11) |
O2—C3—H3A | 110.1 | O9—S2—O8 | 115.33 (11) |
C2—C3—H3A | 110.1 | O7—S2—C8 | 103.19 (12) |
O2—C3—H3B | 110.1 | O9—S2—C8 | 103.71 (12) |
C2—C3—H3B | 110.1 | O8—S2—C8 | 102.60 (12) |
H3A—C3—H3B | 108.4 | S2—O7—Li1 | 151.12 (16) |
C3—O2—C4 | 113.3 (2) | S2—O8—Li2 | 150.01 (18) |
C3—O2—Li1 | 110.5 (2) | S2—O9—Li2ii | 137.29 (15) |
C4—O2—Li1 | 112.91 (18) | F5—C8—F4 | 108.2 (2) |
O2—C4—C5 | 107.2 (2) | F5—C8—F6 | 108.0 (2) |
O2—C4—H4A | 110.3 | F4—C8—F6 | 107.6 (2) |
C5—C4—H4A | 110.3 | F5—C8—S2 | 111.18 (19) |
O2—C4—H4B | 110.3 | F4—C8—S2 | 110.70 (18) |
C5—C4—H4B | 110.3 | F6—C8—S2 | 110.98 (19) |
H4A—C4—H4B | 108.5 | ||
O7—Li1—O1—C2 | −91.1 (3) | O4—S1—O5—Li2 | 49.4 (3) |
O4—Li1—O1—C2 | 160.6 (2) | C7—S1—O5—Li2 | 161.5 (3) |
O3—Li1—O1—C2 | 55.7 (4) | O8—Li2—O5—S1 | −44.0 (4) |
O2—Li1—O1—C2 | 6.1 (2) | O9ii—Li2—O5—S1 | −165.3 (2) |
O7—Li1—O1—C1 | 59.9 (3) | O6i—Li2—O5—S1 | 79.6 (3) |
O4—Li1—O1—C1 | −48.4 (3) | O5—S1—O6—Li2i | 25.2 (3) |
O3—Li1—O1—C1 | −153.3 (3) | O4—S1—O6—Li2i | −111.8 (3) |
O2—Li1—O1—C1 | 157.1 (3) | C7—S1—O6—Li2i | 136.6 (3) |
C1—O1—C2—C3 | 173.9 (3) | O5—S1—C7—F3 | −179.4 (2) |
Li1—O1—C2—C3 | −31.1 (3) | O6—S1—C7—F3 | 60.6 (2) |
O1—C2—C3—O2 | 48.5 (3) | O4—S1—C7—F3 | −58.7 (2) |
C2—C3—O2—C4 | −172.0 (2) | O5—S1—C7—F1 | −59.6 (2) |
C2—C3—O2—Li1 | −44.2 (3) | O6—S1—C7—F1 | −179.51 (19) |
O7—Li1—O2—C3 | 133.2 (2) | O4—S1—C7—F1 | 61.2 (2) |
O4—Li1—O2—C3 | −45.0 (5) | O5—S1—C7—F2 | 60.6 (2) |
O1—Li1—O2—C3 | 21.5 (2) | O6—S1—C7—F2 | −59.3 (2) |
O3—Li1—O2—C3 | −130.0 (2) | O4—S1—C7—F2 | −178.6 (2) |
O7—Li1—O2—C4 | −98.7 (2) | O9—S2—O7—Li1 | 114.0 (4) |
O4—Li1—O2—C4 | 83.1 (5) | O8—S2—O7—Li1 | −23.1 (4) |
O1—Li1—O2—C4 | 149.6 (2) | C8—S2—O7—Li1 | −134.3 (4) |
O3—Li1—O2—C4 | −2.0 (2) | O4—Li1—O7—S2 | −16.2 (5) |
C3—O2—C4—C5 | 156.8 (2) | O1—Li1—O7—S2 | −114.1 (3) |
Li1—O2—C4—C5 | 30.3 (3) | O3—Li1—O7—S2 | 85.6 (4) |
O2—C4—C5—O3 | −55.0 (3) | O2—Li1—O7—S2 | 164.7 (3) |
C4—C5—O3—C6 | −172.0 (2) | O7—S2—O8—Li2 | 62.8 (4) |
C4—C5—O3—Li1 | 53.2 (3) | O9—S2—O8—Li2 | −73.6 (4) |
O7—Li1—O3—C5 | 71.5 (2) | C8—S2—O8—Li2 | 174.4 (3) |
O4—Li1—O3—C5 | 179.84 (19) | O5—Li2—O8—S2 | −31.4 (5) |
O1—Li1—O3—C5 | −78.0 (4) | O9ii—Li2—O8—S2 | 88.7 (4) |
O2—Li1—O3—C5 | −28.4 (2) | O6i—Li2—O8—S2 | −152.2 (3) |
O7—Li1—O3—C6 | −59.3 (3) | O7—S2—O9—Li2ii | −143.8 (2) |
O4—Li1—O3—C6 | 49.0 (3) | O8—S2—O9—Li2ii | −6.5 (3) |
O1—Li1—O3—C6 | 151.2 (3) | C8—S2—O9—Li2ii | 104.8 (3) |
O2—Li1—O3—C6 | −159.2 (2) | O7—S2—C8—F5 | −178.76 (18) |
O5—S1—O4—Li1 | −48.0 (4) | O9—S2—C8—F5 | −59.8 (2) |
O6—S1—O4—Li1 | 88.7 (4) | O8—S2—C8—F5 | 60.6 (2) |
C7—S1—O4—Li1 | −159.8 (3) | O7—S2—C8—F4 | 61.0 (2) |
O7—Li1—O4—S1 | 50.0 (4) | O9—S2—C8—F4 | 179.91 (18) |
O1—Li1—O4—S1 | 164.6 (3) | O8—S2—C8—F4 | −59.7 (2) |
O3—Li1—O4—S1 | −52.0 (4) | O7—S2—C8—F6 | −58.5 (2) |
O2—Li1—O4—S1 | −131.8 (4) | O9—S2—C8—F6 | 60.4 (2) |
O6—S1—O5—Li2 | −86.9 (3) | O8—S2—C8—F6 | −179.17 (19) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z+1. |
[Li3(C2F3O2)3(C6H14O3)] | F(000) = 992 |
Mr = 494.05 | Dx = 1.592 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2ybc | Cell parameters from 2819 reflections |
a = 9.545 (4) Å | θ = 2.9–24.8° |
b = 13.871 (6) Å | µ = 0.18 mm−1 |
c = 15.589 (7) Å | T = 173 K |
β = 92.974 (8)° | Block, colourless |
V = 2061.2 (15) Å3 | 0.36 × 0.32 × 0.24 mm |
Z = 4 |
Siemens CCD area-detector diffractometer | 3657 independent reflections |
Radiation source: fine-focus sealed tube | 3038 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 25.1°, θmin = 2.0° |
Absorption correction: multi-scan (SABABS; Blessing, 1995; Sheldrick, 2000) | h = −11→11 |
Tmin = 0.878, Tmax = 0.937 | k = −16→16 |
19973 measured reflections | l = −18→18 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.067 | w = 1/[σ2(Fo2) + (0.0309P)2 + 0.5588P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
3657 reflections | Δρmax = 0.17 e Å−3 |
355 parameters | Δρmin = −0.18 e Å−3 |
144 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0022 (6) |
[Li3(C2F3O2)3(C6H14O3)] | V = 2061.2 (15) Å3 |
Mr = 494.05 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.545 (4) Å | µ = 0.18 mm−1 |
b = 13.871 (6) Å | T = 173 K |
c = 15.589 (7) Å | 0.36 × 0.32 × 0.24 mm |
β = 92.974 (8)° |
Siemens CCD area-detector diffractometer | 3657 independent reflections |
Absorption correction: multi-scan (SABABS; Blessing, 1995; Sheldrick, 2000) | 3038 reflections with I > 2σ(I) |
Tmin = 0.878, Tmax = 0.937 | Rint = 0.022 |
19973 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 144 restraints |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.17 e Å−3 |
3657 reflections | Δρmin = −0.18 e Å−3 |
355 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 | Occ. (<1) | |
Li1 | 0.0141 (2) | 0.27923 (16) | 0.57748 (15) | 0.0296 (5) | |
Li2 | 0.1466 (2) | 0.06878 (15) | 0.54265 (14) | 0.0273 (5) | |
Li3 | 0.6215 (2) | −0.04229 (17) | 0.54066 (14) | 0.0294 (5) | |
C1 | 0.20271 (18) | 0.23962 (13) | 0.74019 (12) | 0.0512 (4) | |
H1A | 0.2133 | 0.2479 | 0.8026 | 0.077* | |
H1B | 0.2863 | 0.2644 | 0.7137 | 0.077* | |
H1C | 0.1913 | 0.1710 | 0.7266 | 0.077* | |
O1 | 0.08207 (10) | 0.29143 (7) | 0.70768 (6) | 0.0355 (2) | |
C2 | 0.09104 (16) | 0.39181 (11) | 0.72707 (10) | 0.0394 (4) | |
H2A | 0.1739 | 0.4206 | 0.7013 | 0.047* | |
H2B | 0.0997 | 0.4018 | 0.7900 | 0.047* | |
C3 | −0.04118 (16) | 0.43736 (11) | 0.69000 (10) | 0.0386 (4) | |
H3A | −0.1240 | 0.4104 | 0.7172 | 0.046* | |
H3B | −0.0392 | 0.5079 | 0.6994 | 0.046* | |
O2 | −0.04696 (9) | 0.41604 (7) | 0.60055 (6) | 0.0311 (2) | |
C4 | −0.17602 (15) | 0.44079 (11) | 0.55520 (11) | 0.0394 (4) | |
H4A | −0.1867 | 0.5117 | 0.5517 | 0.047* | |
H4B | −0.2566 | 0.4139 | 0.5848 | 0.047* | |
C5 | −0.16924 (16) | 0.39844 (11) | 0.46743 (10) | 0.0397 (4) | |
H5A | −0.2601 | 0.4072 | 0.4347 | 0.048* | |
H5B | −0.0952 | 0.4307 | 0.4358 | 0.048* | |
O3 | −0.13835 (10) | 0.29825 (7) | 0.47727 (6) | 0.0336 (2) | |
C6 | −0.1290 (2) | 0.25071 (13) | 0.39699 (10) | 0.0519 (4) | |
H6A | −0.2182 | 0.2573 | 0.3635 | 0.078* | |
H6B | −0.1087 | 0.1822 | 0.4068 | 0.078* | |
H6C | −0.0536 | 0.2798 | 0.3654 | 0.078* | |
O4 | 0.19297 (10) | 0.30100 (7) | 0.52567 (7) | 0.0380 (3) | |
O5 | 0.28602 (9) | 0.15753 (6) | 0.49780 (6) | 0.0310 (2) | |
C7 | 0.28675 (13) | 0.24706 (9) | 0.50349 (8) | 0.0258 (3) | |
C8 | 0.42327 (15) | 0.29795 (10) | 0.48049 (10) | 0.0382 (4) | |
F1 | 0.4607 (12) | 0.3662 (6) | 0.5374 (6) | 0.080 (3) | 0.33333 |
F2 | 0.4012 (15) | 0.3438 (7) | 0.4070 (5) | 0.079 (3) | 0.33333 |
F3 | 0.5310 (13) | 0.2403 (10) | 0.4737 (8) | 0.076 (4) | 0.33333 |
F1' | 0.3990 (14) | 0.3665 (5) | 0.4238 (5) | 0.048 (3) | 0.33333 |
F2' | 0.5151 (10) | 0.2390 (6) | 0.4479 (6) | 0.043 (2) | 0.33333 |
F3' | 0.4860 (10) | 0.3348 (5) | 0.5507 (5) | 0.051 (2) | 0.33333 |
F1'' | 0.4103 (12) | 0.3876 (4) | 0.4536 (5) | 0.068 (3) | 0.33333 |
F2'' | 0.4861 (10) | 0.2501 (7) | 0.4190 (5) | 0.089 (3) | 0.33333 |
F3'' | 0.5119 (10) | 0.3000 (7) | 0.5481 (5) | 0.093 (3) | 0.33333 |
O6 | 0.23796 (9) | 0.00344 (7) | 0.64218 (6) | 0.0310 (2) | |
O7 | 0.43121 (9) | −0.02165 (7) | 0.57001 (6) | 0.0286 (2) | |
C9 | 0.36146 (13) | −0.02153 (9) | 0.63542 (8) | 0.0255 (3) | |
C10 | 0.43914 (14) | −0.05732 (11) | 0.71812 (9) | 0.0356 (3) | |
F4 | 0.43136 (12) | 0.00515 (9) | 0.78168 (6) | 0.0710 (3) | |
F5 | 0.38624 (10) | −0.14005 (7) | 0.74480 (6) | 0.0576 (3) | |
F6 | 0.57508 (8) | −0.07322 (8) | 0.70751 (6) | 0.0534 (3) | |
O8 | 0.81901 (9) | 0.01497 (6) | 0.55788 (6) | 0.0274 (2) | |
O9 | 0.97841 (9) | 0.13249 (6) | 0.57739 (6) | 0.0257 (2) | |
C11 | 0.86387 (12) | 0.09256 (9) | 0.58820 (8) | 0.0215 (3) | |
C12 | 0.76699 (13) | 0.14297 (9) | 0.65011 (9) | 0.0271 (3) | |
F7 | 0.78961 (11) | 0.10666 (7) | 0.72898 (5) | 0.0515 (3) | |
F8 | 0.63232 (8) | 0.12879 (7) | 0.62815 (6) | 0.0497 (3) | |
F9 | 0.78782 (8) | 0.23701 (5) | 0.65561 (6) | 0.0388 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Li1 | 0.0254 (11) | 0.0266 (12) | 0.0372 (13) | −0.0010 (9) | 0.0044 (9) | −0.0031 (9) |
Li2 | 0.0209 (10) | 0.0256 (11) | 0.0360 (12) | 0.0004 (8) | 0.0059 (9) | −0.0035 (9) |
Li3 | 0.0208 (11) | 0.0355 (13) | 0.0324 (12) | 0.0018 (9) | 0.0051 (9) | −0.0008 (10) |
C1 | 0.0519 (10) | 0.0489 (10) | 0.0509 (10) | 0.0055 (8) | −0.0162 (8) | −0.0036 (8) |
O1 | 0.0381 (6) | 0.0308 (5) | 0.0370 (6) | −0.0031 (4) | −0.0042 (4) | −0.0053 (4) |
C2 | 0.0441 (9) | 0.0351 (8) | 0.0387 (8) | −0.0080 (7) | 0.0008 (7) | −0.0123 (7) |
C3 | 0.0394 (8) | 0.0309 (8) | 0.0465 (9) | −0.0038 (6) | 0.0121 (7) | −0.0134 (7) |
O2 | 0.0251 (5) | 0.0279 (5) | 0.0408 (6) | 0.0006 (4) | 0.0048 (4) | −0.0044 (4) |
C4 | 0.0265 (7) | 0.0281 (8) | 0.0636 (10) | 0.0050 (6) | 0.0020 (7) | 0.0022 (7) |
C5 | 0.0340 (8) | 0.0345 (8) | 0.0498 (9) | −0.0009 (6) | −0.0046 (7) | 0.0121 (7) |
O3 | 0.0365 (5) | 0.0316 (5) | 0.0324 (5) | −0.0014 (4) | −0.0013 (4) | 0.0025 (4) |
C6 | 0.0699 (12) | 0.0527 (11) | 0.0326 (9) | −0.0017 (9) | −0.0027 (8) | −0.0025 (7) |
O4 | 0.0281 (5) | 0.0278 (5) | 0.0594 (7) | 0.0008 (4) | 0.0147 (5) | −0.0022 (5) |
O5 | 0.0270 (5) | 0.0232 (5) | 0.0435 (6) | −0.0020 (4) | 0.0083 (4) | −0.0015 (4) |
C7 | 0.0226 (7) | 0.0265 (7) | 0.0282 (7) | −0.0013 (5) | 0.0012 (5) | 0.0005 (5) |
C8 | 0.0289 (8) | 0.0287 (8) | 0.0578 (10) | −0.0018 (6) | 0.0091 (7) | 0.0021 (7) |
F1 | 0.056 (6) | 0.075 (6) | 0.110 (5) | −0.036 (4) | 0.016 (3) | −0.037 (5) |
F2 | 0.070 (5) | 0.090 (7) | 0.076 (4) | −0.028 (5) | 0.008 (3) | 0.042 (4) |
F3 | 0.027 (3) | 0.058 (4) | 0.144 (10) | 0.001 (3) | 0.018 (5) | 0.018 (5) |
F1' | 0.053 (4) | 0.015 (3) | 0.079 (5) | 0.002 (3) | 0.032 (4) | 0.014 (3) |
F2' | 0.019 (4) | 0.027 (3) | 0.084 (6) | 0.006 (2) | 0.020 (4) | 0.003 (3) |
F3' | 0.028 (4) | 0.039 (5) | 0.085 (4) | −0.009 (3) | −0.007 (2) | −0.020 (4) |
F1'' | 0.042 (3) | 0.029 (3) | 0.135 (7) | 0.000 (3) | 0.030 (5) | 0.023 (4) |
F2'' | 0.062 (5) | 0.080 (6) | 0.132 (6) | −0.019 (3) | 0.069 (5) | −0.031 (5) |
F3'' | 0.045 (4) | 0.107 (8) | 0.124 (6) | −0.032 (5) | −0.039 (4) | 0.036 (5) |
O6 | 0.0227 (5) | 0.0382 (6) | 0.0328 (5) | 0.0051 (4) | 0.0086 (4) | 0.0035 (4) |
O7 | 0.0212 (4) | 0.0357 (5) | 0.0297 (5) | 0.0019 (4) | 0.0082 (4) | 0.0017 (4) |
C9 | 0.0221 (7) | 0.0241 (7) | 0.0306 (7) | −0.0021 (5) | 0.0056 (5) | 0.0004 (5) |
C10 | 0.0279 (7) | 0.0441 (9) | 0.0352 (8) | 0.0000 (6) | 0.0044 (6) | 0.0046 (7) |
F4 | 0.0866 (8) | 0.0873 (8) | 0.0374 (6) | 0.0185 (6) | −0.0141 (5) | −0.0168 (5) |
F5 | 0.0464 (5) | 0.0644 (7) | 0.0618 (6) | −0.0078 (5) | 0.0002 (5) | 0.0364 (5) |
F6 | 0.0248 (4) | 0.0775 (7) | 0.0573 (6) | 0.0053 (4) | −0.0020 (4) | 0.0238 (5) |
O8 | 0.0246 (5) | 0.0250 (5) | 0.0326 (5) | −0.0022 (4) | 0.0033 (4) | −0.0062 (4) |
O9 | 0.0194 (4) | 0.0242 (5) | 0.0337 (5) | −0.0001 (4) | 0.0036 (4) | −0.0022 (4) |
C11 | 0.0205 (6) | 0.0221 (6) | 0.0216 (6) | 0.0016 (5) | −0.0018 (5) | 0.0015 (5) |
C12 | 0.0250 (7) | 0.0239 (7) | 0.0325 (7) | −0.0022 (5) | 0.0029 (5) | −0.0019 (5) |
F7 | 0.0786 (7) | 0.0488 (6) | 0.0285 (5) | 0.0125 (5) | 0.0163 (4) | 0.0032 (4) |
F8 | 0.0220 (4) | 0.0574 (6) | 0.0708 (6) | −0.0037 (4) | 0.0115 (4) | −0.0241 (5) |
F9 | 0.0388 (5) | 0.0241 (4) | 0.0550 (5) | −0.0012 (3) | 0.0178 (4) | −0.0092 (4) |
Li1—O1 | 2.105 (3) | C5—H5B | 0.9900 |
Li1—O2 | 2.023 (2) | O3—C6 | 1.4216 (19) |
Li1—O3 | 2.096 (3) | C6—H6A | 0.9800 |
Li1—O4 | 1.950 (2) | C6—H6B | 0.9800 |
Li1—O9i | 2.064 (3) | C6—H6C | 0.9800 |
Li1—F9i | 2.601 (2) | O4—C7 | 1.2299 (16) |
Li2—O5 | 1.967 (2) | O5—C7 | 1.2450 (16) |
Li2—O6 | 1.962 (2) | O5—Li3ii | 1.936 (2) |
Li2—O8ii | 1.991 (2) | C7—C8 | 1.5405 (19) |
Li2—O9i | 1.935 (2) | C8—F1' | 1.311 (6) |
Li2—C9 | 2.749 (3) | C8—F3 | 1.311 (6) |
Li3—O5ii | 1.936 (2) | C8—F1'' | 1.316 (6) |
Li3—O7 | 1.917 (2) | C8—F2 | 1.317 (6) |
Li3—O7ii | 1.981 (3) | C8—F3'' | 1.317 (6) |
Li3—O8 | 2.051 (2) | C8—F2' | 1.320 (5) |
Li1—Li2 | 3.238 (3) | C8—F3' | 1.323 (5) |
Li2—Li3ii | 2.649 (3) | C8—F2'' | 1.333 (6) |
Li3—Li2ii | 2.649 (3) | C8—F1 | 1.334 (6) |
Li3—Li3ii | 2.838 (4) | O6—C9 | 1.2384 (16) |
C1—O1 | 1.4278 (19) | O7—C9 | 1.2464 (16) |
C1—H1A | 0.9800 | O7—Li3ii | 1.981 (3) |
C1—H1B | 0.9800 | C9—C10 | 1.536 (2) |
C1—H1C | 0.9800 | C10—F4 | 1.3212 (18) |
O1—C2 | 1.4264 (18) | C10—F5 | 1.3291 (18) |
C2—C3 | 1.500 (2) | C10—F6 | 1.3348 (17) |
C2—H2A | 0.9900 | O8—C11 | 1.2426 (15) |
C2—H2B | 0.9900 | O8—Li2ii | 1.991 (2) |
C3—O2 | 1.4237 (19) | O9—C11 | 1.2449 (15) |
C3—H3A | 0.9900 | O9—Li2iii | 1.935 (2) |
C3—H3B | 0.9900 | O9—Li1iii | 2.064 (3) |
O2—C4 | 1.4300 (17) | C11—C12 | 1.5389 (18) |
C4—C5 | 1.494 (2) | C12—F9 | 1.3215 (16) |
C4—H4A | 0.9900 | C12—F8 | 1.3276 (16) |
C4—H4B | 0.9900 | C12—F7 | 1.3359 (17) |
C5—O3 | 1.4273 (18) | F9—Li1iii | 2.601 (2) |
C5—H5A | 0.9900 | ||
O4—Li1—O2 | 101.25 (11) | C6—O3—C5 | 112.28 (12) |
O4—Li1—O9i | 107.49 (11) | C6—O3—Li1 | 121.65 (11) |
O2—Li1—O9i | 151.19 (12) | C5—O3—Li1 | 109.53 (10) |
O4—Li1—O3 | 105.12 (11) | O3—C6—H6A | 109.5 |
O2—Li1—O3 | 79.57 (9) | O3—C6—H6B | 109.5 |
O9i—Li1—O3 | 90.88 (9) | H6A—C6—H6B | 109.5 |
O4—Li1—O1 | 98.88 (10) | O3—C6—H6C | 109.5 |
O2—Li1—O1 | 80.24 (9) | H6A—C6—H6C | 109.5 |
O9i—Li1—O1 | 97.04 (10) | H6B—C6—H6C | 109.5 |
O3—Li1—O1 | 151.14 (12) | C7—O4—Li1 | 133.47 (11) |
O4—Li1—F9i | 174.37 (12) | C7—O5—Li3ii | 147.62 (11) |
O2—Li1—F9i | 82.76 (8) | C7—O5—Li2 | 126.89 (10) |
O9i—Li1—F9i | 68.72 (7) | Li3ii—O5—Li2 | 85.47 (10) |
O3—Li1—F9i | 79.39 (8) | O4—C7—O5 | 128.70 (12) |
O1—Li1—F9i | 77.79 (8) | O4—C7—C8 | 115.06 (12) |
O4—Li1—Li2 | 73.27 (8) | O5—C7—C8 | 116.24 (11) |
O2—Li1—Li2 | 173.77 (11) | F1'—C8—F3 | 120.0 (9) |
O9i—Li1—Li2 | 34.59 (6) | F1'—C8—F1'' | 24.4 (5) |
O3—Li1—Li2 | 104.52 (9) | F3—C8—F1'' | 127.7 (9) |
O1—Li1—Li2 | 97.51 (9) | F1'—C8—F2 | 18.0 (6) |
F9i—Li1—Li2 | 102.51 (8) | F3—C8—F2 | 108.3 (7) |
O9i—Li2—O6 | 109.32 (11) | F1''—C8—F2 | 42.2 (7) |
O9i—Li2—O5 | 113.58 (11) | F1'—C8—F3'' | 127.4 (7) |
O6—Li2—O5 | 106.81 (11) | F3—C8—F3'' | 66.7 (7) |
O9i—Li2—O8ii | 131.27 (12) | F1''—C8—F3'' | 106.3 (5) |
O6—Li2—O8ii | 105.57 (11) | F2—C8—F3'' | 138.8 (8) |
O5—Li2—O8ii | 86.75 (9) | F1'—C8—F2' | 106.7 (6) |
O9i—Li2—Li3ii | 158.01 (12) | F3—C8—F2' | 18.5 (9) |
O6—Li2—Li3ii | 88.59 (9) | F1''—C8—F2' | 121.1 (7) |
O5—Li2—Li3ii | 46.77 (7) | F2—C8—F2' | 92.5 (7) |
O8ii—Li2—Li3ii | 50.02 (7) | F3''—C8—F2' | 84.8 (6) |
O9i—Li2—C9 | 131.92 (11) | F1'—C8—F3' | 109.5 (5) |
O6—Li2—C9 | 23.75 (4) | F3—C8—F3' | 88.8 (7) |
O5—Li2—C9 | 88.42 (9) | F1''—C8—F3' | 86.0 (5) |
O8ii—Li2—C9 | 89.97 (9) | F2—C8—F3' | 125.3 (7) |
Li3ii—Li2—C9 | 64.87 (8) | F3''—C8—F3' | 23.8 (4) |
O9i—Li2—Li1 | 37.27 (6) | F2'—C8—F3' | 106.1 (5) |
O6—Li2—Li1 | 116.44 (10) | F1'—C8—F2'' | 87.0 (6) |
O5—Li2—Li1 | 76.86 (8) | F3—C8—F2'' | 41.8 (8) |
O8ii—Li2—Li1 | 137.68 (11) | F1''—C8—F2'' | 106.2 (6) |
Li3ii—Li2—Li1 | 123.42 (10) | F2—C8—F2'' | 70.9 (6) |
C9—Li2—Li1 | 127.57 (9) | F3''—C8—F2'' | 106.9 (5) |
O7—Li3—O5ii | 130.54 (13) | F2'—C8—F2'' | 23.4 (5) |
O7—Li3—O7ii | 86.57 (9) | F3'—C8—F2'' | 125.8 (6) |
O5ii—Li3—O7ii | 101.49 (11) | F1'—C8—F1 | 88.0 (6) |
O7—Li3—O8 | 141.89 (13) | F3—C8—F1 | 107.6 (7) |
O5ii—Li3—O8 | 85.94 (9) | F1''—C8—F1 | 63.8 (6) |
O7ii—Li3—O8 | 97.51 (10) | F2—C8—F1 | 105.2 (6) |
O7—Li3—Li2ii | 164.48 (13) | F3''—C8—F1 | 46.6 (5) |
O5ii—Li3—Li2ii | 47.76 (7) | F2'—C8—F1 | 122.4 (7) |
O7ii—Li3—Li2ii | 79.40 (9) | F3'—C8—F1 | 23.2 (5) |
O8—Li3—Li2ii | 48.09 (7) | F2''—C8—F1 | 135.7 (8) |
O7—Li3—Li3ii | 44.17 (7) | F1'—C8—C7 | 111.6 (6) |
O5ii—Li3—Li3ii | 125.32 (14) | F3—C8—C7 | 114.6 (8) |
O7ii—Li3—Li3ii | 42.40 (7) | F1''—C8—C7 | 116.1 (5) |
O8—Li3—Li3ii | 128.51 (15) | F2—C8—C7 | 108.9 (6) |
Li2ii—Li3—Li3ii | 121.49 (13) | F3''—C8—C7 | 109.8 (5) |
O1—C1—H1A | 109.5 | F2'—C8—C7 | 113.1 (5) |
O1—C1—H1B | 109.5 | F3'—C8—C7 | 109.7 (5) |
H1A—C1—H1B | 109.5 | F2''—C8—C7 | 110.9 (5) |
O1—C1—H1C | 109.5 | F1—C8—C7 | 111.8 (6) |
H1A—C1—H1C | 109.5 | C9—O6—Li2 | 116.60 (10) |
H1B—C1—H1C | 109.5 | C9—O7—Li3 | 138.43 (11) |
C2—O1—C1 | 112.19 (11) | C9—O7—Li3ii | 126.13 (11) |
C2—O1—Li1 | 107.15 (10) | Li3—O7—Li3ii | 93.43 (9) |
C1—O1—Li1 | 120.27 (11) | O6—C9—O7 | 128.40 (13) |
O1—C2—C3 | 106.83 (11) | O6—C9—C10 | 116.05 (11) |
O1—C2—H2A | 110.4 | O7—C9—C10 | 115.54 (11) |
C3—C2—H2A | 110.4 | O6—C9—Li2 | 39.65 (8) |
O1—C2—H2B | 110.4 | O7—C9—Li2 | 89.18 (9) |
C3—C2—H2B | 110.4 | C10—C9—Li2 | 154.59 (10) |
H2A—C2—H2B | 108.6 | F4—C10—F5 | 107.13 (13) |
O2—C3—C2 | 106.20 (11) | F4—C10—F6 | 107.10 (12) |
O2—C3—H3A | 110.5 | F5—C10—F6 | 106.47 (12) |
C2—C3—H3A | 110.5 | F4—C10—C9 | 111.96 (12) |
O2—C3—H3B | 110.5 | F5—C10—C9 | 111.53 (12) |
C2—C3—H3B | 110.5 | F6—C10—C9 | 112.30 (11) |
H3A—C3—H3B | 108.7 | C11—O8—Li2ii | 137.48 (10) |
C3—O2—C4 | 115.03 (11) | C11—O8—Li3 | 132.97 (10) |
C3—O2—Li1 | 111.84 (11) | Li2ii—O8—Li3 | 81.89 (9) |
C4—O2—Li1 | 112.72 (10) | C11—O9—Li2iii | 125.60 (11) |
O2—C4—C5 | 106.34 (12) | C11—O9—Li1iii | 125.80 (10) |
O2—C4—H4A | 110.5 | Li2iii—O9—Li1iii | 108.14 (10) |
C5—C4—H4A | 110.5 | O8—C11—O9 | 128.43 (12) |
O2—C4—H4B | 110.5 | O8—C11—C12 | 115.20 (11) |
C5—C4—H4B | 110.5 | O9—C11—C12 | 116.31 (11) |
H4A—C4—H4B | 108.7 | F9—C12—F8 | 107.66 (11) |
O3—C5—C4 | 107.64 (12) | F9—C12—F7 | 107.21 (11) |
O3—C5—H5A | 110.2 | F8—C12—F7 | 106.83 (11) |
C4—C5—H5A | 110.2 | F9—C12—C11 | 113.32 (10) |
O3—C5—H5B | 110.2 | F8—C12—C11 | 112.10 (11) |
C4—C5—H5B | 110.2 | F7—C12—C11 | 109.40 (11) |
H5A—C5—H5B | 108.5 | C12—F9—Li1iii | 108.52 (8) |
O4—Li1—Li2—O9i | −171.41 (14) | Li2—O5—C7—C8 | 167.26 (12) |
O3—Li1—Li2—O9i | −69.66 (11) | O4—C7—C8—F1' | −52.5 (4) |
O1—Li1—Li2—O9i | 91.53 (12) | O5—C7—C8—F1' | 128.0 (4) |
F9i—Li1—Li2—O9i | 12.44 (8) | O4—C7—C8—F3 | 167.0 (6) |
O4—Li1—Li2—O6 | 101.07 (12) | O5—C7—C8—F3 | −12.5 (7) |
O9i—Li1—Li2—O6 | −87.52 (13) | O4—C7—C8—F1'' | −26.3 (5) |
O3—Li1—Li2—O6 | −157.19 (10) | O5—C7—C8—F1'' | 154.2 (4) |
O1—Li1—Li2—O6 | 4.01 (13) | O4—C7—C8—F2 | −71.4 (5) |
F9i—Li1—Li2—O6 | −75.08 (12) | O5—C7—C8—F2 | 109.0 (5) |
O4—Li1—Li2—O5 | −1.38 (8) | O4—C7—C8—F3'' | 94.4 (4) |
O9i—Li1—Li2—O5 | 170.02 (14) | O5—C7—C8—F3'' | −85.2 (4) |
O3—Li1—Li2—O5 | 100.36 (10) | O4—C7—C8—F2' | −172.8 (5) |
O1—Li1—Li2—O5 | −98.45 (10) | O5—C7—C8—F2' | 7.6 (5) |
F9i—Li1—Li2—O5 | −177.53 (9) | O4—C7—C8—F3' | 69.0 (4) |
O4—Li1—Li2—O8ii | −71.34 (16) | O5—C7—C8—F3' | −110.5 (3) |
O9i—Li1—Li2—O8ii | 100.06 (17) | O4—C7—C8—F2'' | −147.6 (4) |
O3—Li1—Li2—O8ii | 30.40 (18) | O5—C7—C8—F2'' | 32.8 (5) |
O1—Li1—Li2—O8ii | −168.41 (13) | O4—C7—C8—F1 | 44.3 (5) |
F9i—Li1—Li2—O8ii | 112.51 (15) | O5—C7—C8—F1 | −135.3 (5) |
O4—Li1—Li2—Li3ii | −6.09 (13) | O9i—Li2—O6—C9 | −163.97 (11) |
O9i—Li1—Li2—Li3ii | 165.31 (16) | O5—Li2—O6—C9 | −40.70 (15) |
O3—Li1—Li2—Li3ii | 95.65 (13) | O8ii—Li2—O6—C9 | 50.61 (14) |
O1—Li1—Li2—Li3ii | −103.16 (13) | Li3ii—Li2—O6—C9 | 2.98 (13) |
F9i—Li1—Li2—Li3ii | 177.76 (10) | Li1—Li2—O6—C9 | −124.10 (11) |
O4—Li1—Li2—C9 | 76.19 (12) | O5ii—Li3—O7—C9 | 94.5 (2) |
O9i—Li1—Li2—C9 | −112.41 (14) | O7ii—Li3—O7—C9 | −163.31 (16) |
O3—Li1—Li2—C9 | 177.93 (9) | O8—Li3—O7—C9 | −65.5 (3) |
O1—Li1—Li2—C9 | −20.88 (13) | Li2ii—Li3—O7—C9 | 171.4 (4) |
F9i—Li1—Li2—C9 | −99.96 (11) | Li3ii—Li3—O7—C9 | −163.31 (16) |
O4—Li1—O1—C2 | 80.67 (12) | O5ii—Li3—O7—Li3ii | −102.20 (18) |
O2—Li1—O1—C2 | −19.32 (11) | O7ii—Li3—O7—Li3ii | 0.0 |
O9i—Li1—O1—C2 | −170.32 (10) | O8—Li3—O7—Li3ii | 97.8 (2) |
O3—Li1—O1—C2 | −65.5 (3) | Li2ii—Li3—O7—Li3ii | −25.3 (4) |
F9i—Li1—O1—C2 | −103.95 (9) | Li2—O6—C9—O7 | −9.8 (2) |
Li2—Li1—O1—C2 | 154.81 (9) | Li2—O6—C9—C10 | 170.34 (11) |
O4—Li1—O1—C1 | −48.96 (15) | Li3—O7—C9—O6 | 172.08 (14) |
O2—Li1—O1—C1 | −148.95 (12) | Li3ii—O7—C9—O6 | 12.9 (2) |
O9i—Li1—O1—C1 | 60.06 (14) | Li3—O7—C9—C10 | −8.1 (2) |
O3—Li1—O1—C1 | 164.9 (2) | Li3ii—O7—C9—C10 | −167.31 (12) |
F9i—Li1—O1—C1 | 126.43 (12) | Li3—O7—C9—Li2 | 165.82 (15) |
Li2—Li1—O1—C1 | 25.18 (14) | Li3ii—O7—C9—Li2 | 6.61 (13) |
C1—O1—C2—C3 | −179.79 (13) | O9i—Li2—C9—O6 | 20.50 (14) |
Li1—O1—C2—C3 | 46.13 (14) | O5—Li2—C9—O6 | 141.36 (14) |
O1—C2—C3—O2 | −57.80 (14) | O8ii—Li2—C9—O6 | −131.89 (14) |
C2—C3—O2—C4 | 171.05 (11) | Li3ii—Li2—C9—O6 | −176.70 (14) |
C2—C3—O2—Li1 | 40.78 (14) | Li1—Li2—C9—O6 | 69.30 (14) |
O4—Li1—O2—C3 | −109.96 (12) | O9i—Li2—C9—O7 | −167.20 (14) |
O9i—Li1—O2—C3 | 74.1 (3) | O6—Li2—C9—O7 | 172.30 (15) |
O3—Li1—O2—C3 | 146.52 (9) | O5—Li2—C9—O7 | −46.34 (10) |
O1—Li1—O2—C3 | −12.75 (11) | O8ii—Li2—C9—O7 | 40.42 (10) |
F9i—Li1—O2—C3 | 66.04 (10) | Li3ii—Li2—C9—O7 | −4.40 (9) |
O4—Li1—O2—C4 | 118.60 (12) | Li1—Li2—C9—O7 | −118.40 (12) |
O9i—Li1—O2—C4 | −57.3 (3) | O9i—Li2—C9—C10 | −0.1 (3) |
O3—Li1—O2—C4 | 15.08 (12) | O6—Li2—C9—C10 | −20.6 (2) |
O1—Li1—O2—C4 | −144.19 (10) | O5—Li2—C9—C10 | 120.8 (2) |
F9i—Li1—O2—C4 | −65.41 (11) | O8ii—Li2—C9—C10 | −152.5 (2) |
C3—O2—C4—C5 | −170.93 (11) | Li3ii—Li2—C9—C10 | 162.7 (2) |
Li1—O2—C4—C5 | −41.09 (15) | Li1—Li2—C9—C10 | 48.7 (3) |
O2—C4—C5—O3 | 53.80 (14) | O6—C9—C10—F4 | −52.92 (17) |
C4—C5—O3—C6 | −179.79 (12) | O7—C9—C10—F4 | 127.24 (13) |
C4—C5—O3—Li1 | −41.44 (14) | Li2—C9—C10—F4 | −38.5 (3) |
O4—Li1—O3—C6 | 50.18 (16) | O6—C9—C10—F5 | 67.11 (16) |
O2—Li1—O3—C6 | 149.14 (12) | O7—C9—C10—F5 | −112.73 (14) |
O9i—Li1—O3—C6 | −58.22 (14) | Li2—C9—C10—F5 | 81.6 (3) |
O1—Li1—O3—C6 | −164.6 (2) | O6—C9—C10—F6 | −173.46 (12) |
F9i—Li1—O3—C6 | −126.37 (12) | O7—C9—C10—F6 | 6.69 (18) |
Li2—Li1—O3—C6 | −26.05 (15) | Li2—C9—C10—F6 | −159.01 (19) |
O4—Li1—O3—C5 | −83.56 (13) | O7—Li3—O8—C11 | −10.3 (3) |
O2—Li1—O3—C5 | 15.40 (11) | O5ii—Li3—O8—C11 | −175.15 (11) |
O9i—Li1—O3—C5 | 168.05 (10) | O7ii—Li3—O8—C11 | 83.77 (15) |
O1—Li1—O3—C5 | 61.7 (3) | Li2ii—Li3—O8—C11 | 152.20 (15) |
F9i—Li1—O3—C5 | 99.89 (10) | Li3ii—Li3—O8—C11 | 51.7 (2) |
Li2—Li1—O3—C5 | −159.79 (10) | O7—Li3—O8—Li2ii | −162.5 (2) |
O2—Li1—O4—C7 | 173.44 (13) | O5ii—Li3—O8—Li2ii | 32.65 (9) |
O9i—Li1—O4—C7 | −8.6 (2) | O7ii—Li3—O8—Li2ii | −68.42 (11) |
O3—Li1—O4—C7 | −104.46 (16) | Li3ii—Li3—O8—Li2ii | −100.53 (18) |
O1—Li1—O4—C7 | 91.71 (16) | Li2ii—O8—C11—O9 | −23.2 (2) |
Li2—Li1—O4—C7 | −3.51 (15) | Li3—O8—C11—O9 | −160.09 (13) |
O9i—Li2—O5—C7 | 13.10 (19) | Li2ii—O8—C11—C12 | 159.71 (13) |
O6—Li2—O5—C7 | −107.49 (14) | Li3—O8—C11—C12 | 22.80 (18) |
O8ii—Li2—O5—C7 | 147.22 (11) | Li2iii—O9—C11—O8 | −22.3 (2) |
Li3ii—Li2—O5—C7 | −178.87 (15) | Li1iii—O9—C11—O8 | 148.99 (13) |
C9—Li2—O5—C7 | −122.73 (12) | Li2iii—O9—C11—C12 | 154.82 (11) |
Li1—Li2—O5—C7 | 6.52 (13) | Li1iii—O9—C11—C12 | −33.92 (17) |
O9i—Li2—O5—Li3ii | −168.03 (13) | O8—C11—C12—F9 | −155.94 (11) |
O6—Li2—O5—Li3ii | 71.38 (11) | O9—C11—C12—F9 | 26.58 (16) |
O8ii—Li2—O5—Li3ii | −33.91 (9) | O8—C11—C12—F8 | −33.82 (15) |
C9—Li2—O5—Li3ii | 56.14 (9) | O9—C11—C12—F8 | 148.70 (11) |
Li1—Li2—O5—Li3ii | −174.60 (9) | O8—C11—C12—F7 | 84.50 (13) |
Li1—O4—C7—O5 | 10.5 (2) | O9—C11—C12—F7 | −92.98 (13) |
Li1—O4—C7—C8 | −169.04 (13) | F8—C12—F9—Li1iii | −134.45 (10) |
Li3ii—O5—C7—O4 | 169.88 (17) | F7—C12—F9—Li1iii | 110.92 (11) |
Li2—O5—C7—O4 | −12.2 (2) | C11—C12—F9—Li1iii | −9.89 (13) |
Li3ii—O5—C7—C8 | −10.6 (3) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z+1; (iii) x+1, y, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Li2(CF3SO)2(C6H14O3)] | [Li3(C2F3O2)3(C6H14O3)] |
Mr | 446.19 | 494.05 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 8.678 (3), 10.815 (3), 11.899 (4) | 9.545 (4), 13.871 (6), 15.589 (7) |
α, β, γ (°) | 67.566 (5), 89.831 (5), 71.435 (5) | 90, 92.974 (8), 90 |
V (Å3) | 969.5 (5) | 2061.2 (15) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.37 | 0.18 |
Crystal size (mm) | 0.30 × 0.20 × 0.04 | 0.36 × 0.32 × 0.24 |
Data collection | ||
Diffractometer | Bruker CCD-platform area-detector diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Blessing, 1995; Sheldrick, 2000) | Multi-scan (SABABS; Blessing, 1995; Sheldrick, 2000) |
Tmin, Tmax | 0.898, 0.986 | 0.878, 0.937 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7068, 3402, 2751 | 19973, 3657, 3038 |
Rint | 0.038 | 0.022 |
(sin θ/λ)max (Å−1) | 0.596 | 0.596 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.116, 1.02 | 0.026, 0.067, 1.03 |
No. of reflections | 3402 | 3657 |
No. of parameters | 246 | 355 |
No. of restraints | 0 | 144 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.36 | 0.17, −0.18 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1990), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Bruker, 1998), SHELXTL/PC and PLATON (Spek, 2001).
Li1—O1 | 2.050 (4) | Li2—O5 | 1.933 (4) |
Li1—O2 | 2.113 (4) | Li2—O8 | 1.901 (4) |
Li1—O3 | 2.103 (5) | Li2—O6i | 1.938 (4) |
Li1—O4 | 2.017 (4) | Li2—O9ii | 1.939 (4) |
Li1—O7 | 1.951 (4) | ||
C1—O1—C2—C3 | 173.9 (3) | C3—O2—C4—C5 | 156.8 (2) |
O1—C2—C3—O2 | 48.5 (3) | O2—C4—C5—O3 | −55.0 (3) |
C2—C3—O2—C4 | −172.0 (2) | C4—C5—O3—C6 | −172.0 (2) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z+1. |
Li1—O1 | 2.105 (3) | Li2—O8ii | 1.991 (2) |
Li1—O2 | 2.023 (2) | Li2—O9i | 1.935 (2) |
Li1—O3 | 2.096 (3) | Li3—O5ii | 1.936 (2) |
Li1—O4 | 1.950 (2) | Li3—O7 | 1.917 (2) |
Li1—O9i | 2.064 (3) | Li3—O7ii | 1.981 (3) |
Li2—O5 | 1.967 (2) | Li3—O8 | 2.051 (2) |
Li2—O6 | 1.962 (2) | ||
C1—O1—C2—C3 | −179.79 (13) | C3—O2—C4—C5 | −170.93 (11) |
O1—C2—C3—O2 | −57.80 (14) | O2—C4—C5—O3 | 53.80 (14) |
C2—C3—O2—C4 | 171.05 (11) | C4—C5—O3—C6 | −179.79 (12) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z+1. |
The structural characterization of [Li2(CF3SO3)2(C6H14O3)]n, (I), and [Li3(C2F3O2)3(C6H14O3)]n, (II), was performed as part of a comprehensive study of lithium salt phase behaviour with glyme ligands (Henderson, 2002). Single crystals of (I) and (II) were obtained during the preparation of samples for the determination of diglyme-LiCF3SO3 and diglyme-LiCF3CO2 phase diagrams. The exploration of such solvate structures provides insight into the properties of liquid electrolytes, as well as the poorly understood conductivity mechanisms in poly(ethylene oxide)-lithium salt solid electrolytes (Rhodes & Frech, 2001). \sch
The structure of (I) contains two Li+ cations, two CF3SO3- anions and one diglyme molecule in the asymmetric unit, all in general positions (Fig. 1). Atom Li1 is five-coordinate, coordinated by three ether O atoms from the diglyme and two O atoms from different CF3SO3- anions. Atom Li2 is four-coordinate, with four different CF3SO3- anions coordinated to the cation through O atoms. Both of the CF3SO3- anions in the asymmetric unit are tridentate, coordinated to three different Li+ cations (Fig. 3).
The structure of (II) contains three Li+ cations, three CF3CO2- anions and one diglyme molecule in the asymmetric unit, all in general positions (Fig. 2). Atom Li1 is five-coordinate, coordinated by three ether O atoms from the diglyme and two O atoms from different CF3CO2- anions. Atoms Li2 and Li3 are four-coordinated, by four O atoms from different CF3CO2- anions. The CF3CO2- anion containing atom C7 and that containing atom C9 are both tridentate, with one O atom coordinated to two Li+ cations and the other to only one cation. The CF3CO2- anion containing atom C11 has tetradentate coordination, with both O atoms coordinated to two Li+ cations (Fig. 4).
One-dimensional polymeric chains are formed from the aggregation of the Li+ cations and the anions in the two structures. The crystal structure of (I) contains an inversion centre in the centroid of an –Li—O—S—O—Li—O—S—O– eight-atom ring. This connects two [Li(diglyme)] fragments together. The crystal structure of (II) contains two inversion centres, one in the centroid of an –Li—O—C—O—Li—O—C—O– eight-atom ring and one in the centroid of an –Li—O—Li—O– four-atom ring. The former connects two [Li(diglyme)] fragments together, while the latter also connects the [Li(diglyme)] fragments, but has other cations and anions linking the four-atom ring to the fragments, as outlined above.
Despite the highly aggregated nature of the ions, the coordination in (I) still differs markedly from that found in crystalline LiCF3SO3 (Tremayne et al., 1992), in which four-coordinate Li+ cations are each coordinated by three CF3SO3- anions. The anions are tetradentate in the crystalline LiCF3SO3 salt, coordinated to three cations with two O atoms coordinated to the same cation.
The Li+ cations coordinated to the diglyme molecules in (I) and (II) have the same form of cationic coordination as that found in the structures of poly(ethylene oxide)3-LiCF3SO3 (Lightfoot et al., 1993) and (diglyme)-LiCF3SO3 (Rhodes & Frech, 2001). In the structure of (diglyme)-LiCF3SO3, the asymmetric unit contains two independent halves of two (diglyme)Li(CF3SO3)2Li(diglyme) dimers, which have the same connectivity but slightly different geometrical parameters. Each dimer has a crystallographic inversion centre at the centroid between two S atoms of the CF3SO3- anions. The dimers contain two five-coordinate Li+ cations, coordinated by three ether O atoms from a diglyme molecule and two O atoms from two separate CF3SO3- anions. The anions are bidentate coordinated to both Li+ cations in each dimer through two O atoms. In contrast, the CF3SO3- anions in (I) are tridentate coordinated to three different Li+ cations. In (II), the CF3CO2- anions are either tri- or tetradentate coordinated to three or four different Li+ cations.
The Li1—O bond lengths and angles in (I) and (II) (Tables 1 and 2) are similar to those found in both poly(ethylene oxide)3-LiCF3SO3 and (diglyme)1-LiCF3SO3. The remaining four-coordinate Li+ cations in (I) and (II) are coordinated by four separate anions. The O—Li—O angles at Li2 in (I) are within 4° of 109.5° [106.4 (2)–113.0 (2)°], indicating a regular tetrahedral geometry. However, the O—Li—O angles at Li2 [86.8 (1)–131.2 (1)°] and Li3 [86.6 (1)–141.9 (1)°] in (II) indicate a highly distorted tetrahedral geometry (Figs. 1 and 2). The difference in anion coordination accounts for the different stoichiometries of (I) and (II). The phase diagram of the diglyme-LiCF3CO2 system indicates that a (diglyme)1-LiCF3CO2 compound also forms (Henderson, 2002).
Note that although 1:1 mole ratio mixtures were used to prepare (I) and (II), the (diglyme)1-LiX (X is CF3SO3- or CF3CO2-) phases did not crystallize at 295 K, despite having melting temperatures of 320 and 302 K, respectively; single crystals of (I) and (II) formed slowly instead. The probable explanation for this is the considerable hysteresis between the crystallization and melting temperatures (Henderson, 2002) of many glyme-lithium salt phases. Some of the Li+ cations in the amorphous mixture which is formed after melting and cooling to room temperature are likely to be aggregated into solvate structures similar to those found in the reported compounds. This facilitates nucleation of (I) and (II) rather than the structures predicted thermodynamically from the phase diagrams.