Poly[bis­(acetonitrile-κN)bis­[μ3-bis(tri­fluoro­methane­sulfonyl)­imido-κ4O,O′:O′′:O′′′]dilithium]

Seo, D.M.; Boyle, P.D.; Henderson, W.A.

doi:10.1107/S1600536811011561

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page m534

doi:10.1107/S1600536811011561

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Poly[bis(acetonitrile-κN)bis[μ₃-bis(trifluoromethanesulfonyl)imido-κ⁴O,O′:O′′:O′′′]dilithium]

Daniel M. Seo,^a Paul D. Boyle ^b and Wesley A. Henderson ^a ^*

^aDepartment of Chemical and Biomolecular Engineering, North Carolina State Univerisity, Raleigh, NC 27695, USA, and ^bDepartment of Chemistry, North Carolina State Univerisity, Raleigh, NC 27695, USA
^*Correspondence e-mail: wesley_henderson@ncsu.edu

(Received 4 March 2011; accepted 28 March 2011; online 7 April 2011)

In the title compound, [Li₂(CF₃SO₂NSO₂CF₃)₂(CH₃CN)₂]_n, two Li⁺ cations reside on crystallographic inversion centers, each coordinated by six O atoms from bis(trifluoromethanesulfonyl)imide (TFSI⁻) anions. The third Li⁺ cation on a general position is four-coordinated by two anion O atoms and two N atoms from acetonitrile molecules in a tetrahedral geometry.

Related literature

For the structure of LiN(SO₂CF₃)₂, see: Nowinski et al. (1994). For a related structure of LiN(SO₂CF₃)₂, see: Henderson et al. (2005 ); Davidson et al. (2003 ); Brouillette et al. (2002 ); Dillon et al. (2001). For the structure of CH₃CN with lithium salts, see: Klapötke et al. (2006 ); Brooks et al. (2002 ); Yokota et al. (1999); Raston et al. (1989 ).

Experimental

Crystal data

[Li₂(C₂F₆NO₄S₂)₂(C₂H₃N)₂]
M_r = 656.29
Monoclinic, P 2₁ /n
a = 10.8654 (2) Å
b = 11.0610 (2) Å
c = 19.1778 (3) Å
β = 90.8483 (10)°
V = 2304.58 (7) Å³
Z = 4
Cu Kα radiation
μ = 5.16 mm⁻¹
T = 110 K
0.40 × 0.20 × 0.15 mm

Data collection

Bruker–Nonius X8 APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.232, T_max = 0.512
9937 measured reflections
3950 independent reflections
3482 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.108
S = 1.07
3950 reflections
348 parameters
H-atom parameters constrained
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: cif2tables.py (Boyle, 2008 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011561/si2342sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011561/si2342Isup2.hkl

checkCIF report

Comment top

The structure contains three symmetry independent Li⁺ cations. Two of these, Li1 and Li2, reside on crystallographic inversion centers and are each are coordinated by six O atoms from TFSI^- anions in a pseudo-octahedral coordination geometry. The third Li⁺ cation, Li3, sits at a general position and is four coordinate: two O atoms and two N atoms from acetonitrile molecules form a pseudo-tetragonal coordination geometry. There are two different TFSI^- anions which ligate the Li⁺ cations Li1 and Li2 by chelating a single lithium as well as bridging the Li1···Li2 sites. These two lithium sites are joined by two TFSI^- anions to form eight membered rings. The rings are formed using atoms {O1, O2} and {O5, O6}, while the axial coordination sites for Li1 and Li2 are occupied by O3 and O7, respectively. These rings form a polymeric chain which propagates along the [0 1 0] direction. Two of the coordination sites for the four coordinate Li3 atom are occupied by O4 and O8, thus providing a link between two TFSI^- ligands. The other two coordination sites are occupied by the N atoms from two different acetonitrile molecules. The methyl tails as well as the CF₃ groups from the TFSI^- anions form the exterior of the polymeric chains.

Related literature top

For the structure of pure LiN(SO₂CF₃)₂, see: Nowinski et al. (1994). For a related structure of LiN(SO₂CF₃)₂, see: Henderson et al. (2005); Davidson et al. (2003); Brouillette et al. (2002); Dillon et al. (2001). For the structure of CH₃CN with lithium salts, see: Klapötke et al. (2006); Brooks et al. (2002); Yokota et al. (1999); Raston et al. (1989).

Experimental top

LiTFSI was purchased from 3M and dried under high-vacuum at 393 K. Anhydrous acetonitrile (Sigma Aldrich, 99.8%) was used as-received. In a vacuum atmospheres (N₂) glove box (< 5 p.p.m. H₂O), LiTFSI (5 mmol) and acetonitrile (6 mmol) were sealed in a vial and the mixture heated on a hot plate to form a homogeneous solution. 2 ml of toluene was then added to the vial to dilute the mixture. Upon standing at 278 K in a refrigerator, colorless plate single crystals formed suitable for analysis.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: cif2tables.py (Boyle, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound. The thermal ellipsoids are shown at a 50% probability level. (Symmetric codes: (i)-x + 2, -y - 1, -z + 1; (ii) -x + 2, -y, -z + 1)
	Fig. 2. Schematic illustration of ion and solvent coordination for the title compound.

Poly[bis(acetonitrile-κN)bis[µ₃- bis(trifluoromethanesulfonyl)imido-κ⁴O,O':O'': O''']dilithium] top

Crystal data top

[Li₂(C₂F₆NO₄S₂)₂(C₂H₃N)₂]	F(000) = 1296
M_r = 656.29	D_x = 1.892 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 315.68 K
Hall symbol: -P 2yn	Cu Kα radiation, λ = 1.54178 Å
a = 10.8654 (2) Å	Cell parameters from 4162 reflections
b = 11.0610 (2) Å	θ = 4.6–65.8°
c = 19.1778 (3) Å	µ = 5.16 mm⁻¹
β = 90.8483 (10)°	T = 110 K
V = 2304.58 (7) Å³	Plate, colourless
Z = 4	0.40 × 0.20 × 0.15 mm

Data collection top

Bruker–Nonius X8 APEXII diffractometer	3950 independent reflections
Radiation source: fine-focus sealed tube	3482 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ω and ϕ scans	θ_max = 66.2°, θ_min = 4.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
T_min = 0.232, T_max = 0.512	k = −13→9
9937 measured reflections	l = −22→22

Refinement top

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) = 0.108	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0689P)² + 0.1796P] where P = (F_o² + 2F_c²)/3
3950 reflections	(Δ/σ)_max = 0.001
348 parameters	Δρ_max = 0.66 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

[Li₂(C₂F₆NO₄S₂)₂(C₂H₃N)₂]	V = 2304.58 (7) Å³
M_r = 656.29	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 10.8654 (2) Å	µ = 5.16 mm⁻¹
b = 11.0610 (2) Å	T = 110 K
c = 19.1778 (3) Å	0.40 × 0.20 × 0.15 mm
β = 90.8483 (10)°

Data collection top

Bruker–Nonius X8 APEXII diffractometer	3950 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3482 reflections with I > 2σ(I)
T_min = 0.232, T_max = 0.512	R_int = 0.041
9937 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.07	Δρ_max = 0.66 e Å⁻³
3950 reflections	Δρ_min = −0.49 e Å⁻³
348 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

	x	y	z	U_iso*/U_eq
Li1	1.0000	−0.5000	0.5000	0.0241 (13)
Li2	1.0000	0.0000	0.5000	0.0319 (15)
Li3	1.2401 (4)	−0.2523 (4)	0.7428 (2)	0.0212 (8)
S1	0.86669 (5)	−0.27813 (5)	0.57295 (3)	0.01533 (16)
S2	1.02904 (5)	−0.40779 (5)	0.65910 (3)	0.01465 (16)
O1	0.86025 (16)	−0.38148 (16)	0.52784 (9)	0.0198 (4)
O2	0.88818 (17)	−0.16218 (16)	0.54296 (10)	0.0242 (4)
O3	1.05935 (15)	−0.48372 (15)	0.60138 (9)	0.0189 (4)
O4	1.12685 (17)	−0.37177 (16)	0.70505 (10)	0.0235 (4)
N1	0.9472 (2)	−0.29426 (18)	0.64117 (11)	0.0189 (4)
C1	0.7103 (2)	−0.2650 (3)	0.60816 (15)	0.0259 (6)
F1	0.63021 (15)	−0.26086 (15)	0.55589 (10)	0.0322 (4)
F2	0.70074 (18)	−0.1660 (2)	0.64600 (12)	0.0514 (6)
F3	0.68438 (17)	−0.3600 (2)	0.64704 (11)	0.0514 (6)
C2	0.9349 (3)	−0.5030 (2)	0.71598 (14)	0.0223 (5)
F4	0.83885 (15)	−0.54657 (15)	0.68038 (9)	0.0322 (4)
F5	0.89314 (17)	−0.43864 (16)	0.76878 (8)	0.0338 (4)
F6	1.00206 (18)	−0.59308 (15)	0.74022 (10)	0.0387 (4)
S3	1.17709 (5)	−0.22534 (5)	0.47597 (3)	0.01494 (16)
S4	1.22060 (5)	−0.09504 (5)	0.59873 (3)	0.01427 (16)
O5	1.11998 (18)	−0.34116 (16)	0.46985 (9)	0.0227 (4)
O6	1.11351 (17)	−0.12146 (16)	0.44846 (9)	0.0211 (4)
O7	1.11864 (15)	−0.01780 (16)	0.58177 (9)	0.0194 (4)
O8	1.23617 (17)	−0.13043 (16)	0.66994 (9)	0.0223 (4)
N2	1.23502 (19)	−0.21021 (18)	0.55127 (11)	0.0182 (4)
C3	1.3146 (3)	−0.2392 (2)	0.42186 (15)	0.0237 (5)
F7	1.28089 (18)	−0.24474 (16)	0.35552 (9)	0.0344 (4)
F8	1.38759 (17)	−0.1450 (2)	0.43007 (10)	0.0463 (5)
F9	1.3759 (2)	−0.3386 (2)	0.43789 (11)	0.0532 (6)
C4	1.3576 (2)	−0.0027 (2)	0.58387 (14)	0.0202 (5)
F10	1.36085 (16)	0.08703 (15)	0.62945 (10)	0.0336 (4)
F11	1.35530 (15)	0.04254 (15)	0.52012 (9)	0.0305 (4)
F12	1.45820 (14)	−0.06888 (15)	0.59205 (10)	0.0310 (4)
N3	1.3951 (2)	−0.3487 (2)	0.75516 (13)	0.0278 (5)
C5	1.4711 (2)	−0.4159 (2)	0.76885 (14)	0.0234 (6)
C6	1.5678 (3)	−0.5024 (3)	0.78594 (15)	0.0285 (6)
H61	1.6388	−0.4879	0.7562	0.043*
H62	1.5371	−0.5847	0.7782	0.043*
H63	1.5927	−0.4929	0.8350	0.043*
N4	1.1814 (2)	−0.1550 (2)	0.82413 (12)	0.0289 (5)
C7	1.1632 (3)	−0.0855 (2)	0.86648 (14)	0.0240 (6)
C8	1.1392 (3)	0.0036 (3)	0.92008 (15)	0.0274 (6)
H81	1.1588	0.0844	0.9025	0.041*
H82	1.1904	−0.0138	0.9614	0.041*
H83	1.0521	0.0004	0.9326	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Li1	0.031 (3)	0.027 (3)	0.014 (3)	0.008 (2)	−0.001 (2)	−0.004 (2)
Li2	0.038 (4)	0.036 (4)	0.021 (3)	0.019 (3)	−0.010 (3)	−0.005 (3)
Li3	0.030 (2)	0.0212 (19)	0.0124 (19)	−0.0019 (16)	−0.0045 (17)	0.0002 (16)
S1	0.0196 (3)	0.0144 (3)	0.0120 (3)	0.00129 (19)	0.0004 (2)	−0.0002 (2)
S2	0.0209 (3)	0.0143 (3)	0.0088 (3)	−0.0003 (2)	−0.0007 (2)	0.0000 (2)
O1	0.0244 (9)	0.0204 (8)	0.0145 (8)	0.0041 (7)	−0.0042 (7)	−0.0033 (7)
O2	0.0284 (9)	0.0179 (9)	0.0261 (10)	−0.0009 (7)	−0.0054 (7)	0.0072 (7)
O3	0.0248 (9)	0.0192 (8)	0.0126 (8)	0.0044 (6)	0.0010 (7)	−0.0002 (7)
O4	0.0298 (9)	0.0212 (9)	0.0195 (9)	−0.0012 (7)	−0.0070 (7)	0.0025 (7)
N1	0.0288 (11)	0.0145 (9)	0.0133 (10)	0.0030 (8)	−0.0010 (8)	−0.0031 (8)
C1	0.0219 (13)	0.0309 (14)	0.0249 (14)	0.0058 (10)	0.0050 (11)	0.0002 (11)
F1	0.0226 (8)	0.0376 (9)	0.0362 (10)	0.0036 (6)	−0.0033 (7)	0.0029 (7)
F2	0.0379 (10)	0.0616 (13)	0.0549 (12)	0.0145 (9)	0.0075 (9)	−0.0308 (11)
F3	0.0339 (9)	0.0677 (14)	0.0532 (12)	0.0096 (9)	0.0184 (9)	0.0374 (11)
C2	0.0310 (13)	0.0187 (12)	0.0173 (12)	0.0000 (10)	0.0041 (11)	0.0028 (10)
F4	0.0324 (8)	0.0305 (8)	0.0337 (9)	−0.0125 (7)	0.0053 (7)	−0.0030 (7)
F5	0.0455 (10)	0.0399 (9)	0.0165 (8)	−0.0008 (7)	0.0135 (7)	−0.0035 (7)
F6	0.0452 (10)	0.0294 (9)	0.0418 (10)	0.0070 (7)	0.0111 (8)	0.0208 (8)
S3	0.0207 (3)	0.0140 (3)	0.0102 (3)	−0.0003 (2)	0.0020 (2)	−0.0006 (2)
S4	0.0196 (3)	0.0143 (3)	0.0090 (3)	−0.00059 (19)	−0.0006 (2)	0.0010 (2)
O5	0.0367 (10)	0.0172 (8)	0.0141 (8)	−0.0066 (7)	0.0034 (7)	−0.0030 (7)
O6	0.0297 (9)	0.0206 (9)	0.0129 (8)	0.0053 (7)	−0.0016 (7)	−0.0008 (7)
O7	0.0216 (8)	0.0219 (8)	0.0148 (8)	0.0032 (7)	−0.0004 (7)	−0.0040 (7)
O8	0.0336 (9)	0.0208 (8)	0.0123 (8)	−0.0018 (7)	−0.0010 (7)	0.0009 (7)
N2	0.0249 (10)	0.0152 (9)	0.0143 (10)	0.0029 (7)	−0.0021 (8)	0.0006 (8)
C3	0.0274 (13)	0.0244 (12)	0.0195 (13)	−0.0011 (10)	0.0074 (10)	−0.0037 (10)
F7	0.0470 (10)	0.0403 (9)	0.0162 (8)	−0.0102 (7)	0.0124 (7)	−0.0057 (7)
F8	0.0400 (10)	0.0579 (12)	0.0417 (11)	−0.0271 (9)	0.0201 (8)	−0.0218 (9)
F9	0.0543 (12)	0.0562 (13)	0.0499 (12)	0.0327 (10)	0.0257 (10)	0.0126 (10)
C4	0.0225 (12)	0.0198 (12)	0.0182 (12)	−0.0019 (9)	0.0020 (10)	−0.0005 (10)
F10	0.0370 (9)	0.0275 (8)	0.0366 (10)	−0.0109 (7)	0.0078 (7)	−0.0144 (7)
F11	0.0374 (9)	0.0285 (8)	0.0258 (8)	−0.0067 (7)	0.0066 (7)	0.0096 (7)
F12	0.0205 (7)	0.0323 (8)	0.0402 (10)	0.0021 (6)	−0.0004 (7)	0.0014 (7)
N3	0.0307 (12)	0.0214 (11)	0.0311 (13)	−0.0008 (10)	−0.0080 (10)	0.0037 (10)
C5	0.0284 (13)	0.0240 (13)	0.0177 (13)	−0.0068 (11)	−0.0007 (10)	0.0017 (10)
C6	0.0331 (14)	0.0303 (14)	0.0223 (14)	0.0057 (11)	0.0032 (11)	0.0059 (11)
N4	0.0486 (14)	0.0224 (11)	0.0157 (11)	−0.0041 (10)	0.0017 (10)	−0.0001 (10)
C7	0.0328 (14)	0.0217 (13)	0.0174 (13)	−0.0022 (10)	−0.0018 (11)	0.0041 (11)
C8	0.0313 (14)	0.0273 (14)	0.0236 (14)	−0.0007 (10)	0.0019 (11)	−0.0061 (11)

Geometric parameters (Å, º) top

Li1—O3	2.0473 (17)	S3—O5	1.4275 (18)
Li1—O1	2.0817 (17)	S3—O6	1.4370 (18)
Li1—O5	2.2678 (17)	S3—N2	1.576 (2)
Li2—O7	2.0247 (17)	S3—C3	1.838 (3)
Li2—O6	2.0831 (17)	S4—O8	1.4284 (18)
Li2—O2	2.3243 (18)	S4—O7	1.4326 (18)
Li3—O4	1.940 (5)	S4—N2	1.575 (2)
Li3—O8	1.942 (5)	S4—C4	1.831 (3)
Li3—N3	2.004 (5)	C3—F8	1.317 (3)
Li3—N4	2.006 (5)	C3—F9	1.319 (3)
S1—O2	1.4263 (18)	C3—F7	1.320 (3)
S1—O1	1.4347 (18)	C4—F11	1.321 (3)
S1—N1	1.573 (2)	C4—F10	1.323 (3)
S1—C1	1.844 (3)	C4—F12	1.323 (3)
S2—O4	1.4272 (19)	N3—C5	1.139 (4)
S2—O3	1.4317 (18)	C5—C6	1.455 (4)
S2—N1	1.574 (2)	C6—H61	0.9800
S2—C2	1.838 (3)	C6—H62	0.9800
C1—F1	1.318 (4)	C6—H63	0.9800
C1—F2	1.318 (4)	N4—C7	1.138 (4)
C1—F3	1.322 (3)	C7—C8	1.450 (4)
C2—F6	1.316 (3)	C8—H81	0.9800
C2—F5	1.323 (3)	C8—H82	0.9800
C2—F4	1.329 (3)	C8—H83	0.9800

O3ⁱ—Li1—O3	180.00 (3)	F2—C1—F3	109.3 (3)
O3ⁱ—Li1—O1	94.49 (7)	F1—C1—S1	109.02 (19)
O3—Li1—O1	85.51 (7)	F2—C1—S1	110.3 (2)
O3ⁱ—Li1—O1ⁱ	85.51 (7)	F3—C1—S1	110.43 (18)
O3—Li1—O1ⁱ	94.49 (7)	F6—C2—F5	109.4 (2)
O1—Li1—O1ⁱ	180.00 (9)	F6—C2—F4	109.5 (2)
O3ⁱ—Li1—O5ⁱ	89.99 (7)	F5—C2—F4	108.2 (2)
O3—Li1—O5ⁱ	90.01 (7)	F6—C2—S2	109.43 (18)
O1—Li1—O5ⁱ	89.90 (7)	F5—C2—S2	110.27 (18)
O1ⁱ—Li1—O5ⁱ	90.10 (7)	F4—C2—S2	110.04 (18)
O3ⁱ—Li1—O5	90.01 (7)	O5—S3—O6	118.77 (12)
O3—Li1—O5	89.99 (7)	O5—S3—N2	109.75 (11)
O1—Li1—O5	90.10 (7)	O6—S3—N2	115.79 (11)
O1ⁱ—Li1—O5	89.90 (7)	O5—S3—C3	103.57 (11)
O5ⁱ—Li1—O5	180.00 (8)	O6—S3—C3	104.46 (12)
O7ⁱⁱ—Li2—O7	180.00 (6)	N2—S3—C3	102.08 (12)
O7ⁱⁱ—Li2—O6ⁱⁱ	86.00 (7)	O8—S4—O7	117.44 (11)
O7—Li2—O6ⁱⁱ	94.00 (7)	O8—S4—N2	108.63 (11)
O7ⁱⁱ—Li2—O6	94.00 (7)	O7—S4—N2	115.75 (11)
O7—Li2—O6	86.00 (7)	O8—S4—C4	102.51 (12)
O6ⁱⁱ—Li2—O6	180.00 (8)	O7—S4—C4	105.05 (11)
O7ⁱⁱ—Li2—O2	91.11 (7)	N2—S4—C4	105.86 (11)
O7—Li2—O2	88.89 (7)	S3—O5—Li1	157.68 (11)
O6ⁱⁱ—Li2—O2	90.76 (7)	S3—O6—Li2	128.77 (11)
O6—Li2—O2	89.24 (7)	S4—O7—Li2	135.66 (11)
O7ⁱⁱ—Li2—O2ⁱⁱ	88.89 (7)	S4—O8—Li3	151.60 (18)
O7—Li2—O2ⁱⁱ	91.11 (7)	S4—N2—S3	125.01 (13)
O6ⁱⁱ—Li2—O2ⁱⁱ	89.24 (7)	F8—C3—F9	109.2 (3)
O6—Li2—O2ⁱⁱ	90.76 (7)	F8—C3—F7	108.1 (2)
O2—Li2—O2ⁱⁱ	180.00 (6)	F9—C3—F7	108.5 (2)
O4—Li3—O8	101.3 (2)	F8—C3—S3	111.08 (18)
O4—Li3—N3	102.0 (2)	F9—C3—S3	110.49 (19)
O8—Li3—N3	117.6 (2)	F7—C3—S3	109.38 (19)
O4—Li3—N4	116.6 (2)	F11—C4—F10	109.1 (2)
O8—Li3—N4	100.6 (2)	F11—C4—F12	108.9 (2)
N3—Li3—N4	118.1 (2)	F10—C4—F12	108.8 (2)
O2—S1—O1	118.69 (11)	F11—C4—S4	110.56 (18)
O2—S1—N1	110.18 (11)	F10—C4—S4	109.24 (17)
O1—S1—N1	115.64 (11)	F12—C4—S4	110.19 (17)
O2—S1—C1	103.54 (12)	C5—N3—Li3	168.4 (3)
O1—S1—C1	104.28 (12)	N3—C5—C6	179.6 (3)
N1—S1—C1	102.06 (12)	C5—C6—H61	109.5
O4—S2—O3	117.61 (11)	C5—C6—H62	109.5
O4—S2—N1	108.98 (11)	H61—C6—H62	109.5
O3—S2—N1	115.77 (11)	C5—C6—H63	109.5
O4—S2—C2	102.09 (12)	H61—C6—H63	109.5
O3—S2—C2	105.03 (11)	H62—C6—H63	109.5
N1—S2—C2	105.62 (12)	C7—N4—Li3	167.9 (3)
S1—O1—Li1	128.84 (11)	N4—C7—C8	179.5 (3)
S1—O2—Li2	157.89 (12)	C7—C8—H81	109.5
S2—O3—Li1	135.48 (11)	C7—C8—H82	109.5
S2—O4—Li3	152.09 (18)	H81—C8—H82	109.5
S1—N1—S2	125.29 (13)	C7—C8—H83	109.5
F1—C1—F2	109.5 (2)	H81—C8—H83	109.5
F1—C1—F3	108.2 (2)	H82—C8—H83	109.5

O2—S1—O1—Li1	93.14 (15)	O3ⁱ—Li1—O5—S3	139.2 (3)
N1—S1—O1—Li1	−41.19 (18)	O3—Li1—O5—S3	−40.8 (3)
C1—S1—O1—Li1	−152.37 (14)	O1—Li1—O5—S3	44.7 (3)
O3ⁱ—Li1—O1—S1	−141.25 (14)	O1ⁱ—Li1—O5—S3	−135.3 (3)
O3—Li1—O1—S1	38.75 (14)	O5—S3—O6—Li2	94.77 (15)
O5ⁱ—Li1—O1—S1	128.77 (14)	N2—S3—O6—Li2	−39.14 (18)
O5—Li1—O1—S1	−51.23 (14)	C3—S3—O6—Li2	−150.52 (14)
O1—S1—O2—Li2	−86.1 (3)	O7ⁱⁱ—Li2—O6—S3	−142.32 (14)
N1—S1—O2—Li2	50.5 (4)	O7—Li2—O6—S3	37.68 (14)
C1—S1—O2—Li2	159.0 (3)	O2—Li2—O6—S3	−51.26 (14)
O7ⁱⁱ—Li2—O2—S1	137.1 (3)	O2ⁱⁱ—Li2—O6—S3	128.74 (14)
O7—Li2—O2—S1	−42.9 (3)	O8—S4—O7—Li2	−144.13 (14)
O6ⁱⁱ—Li2—O2—S1	−136.9 (3)	N2—S4—O7—Li2	−13.6 (2)
O6—Li2—O2—S1	43.1 (3)	C4—S4—O7—Li2	102.77 (16)
O4—S2—O3—Li1	−143.85 (14)	O6ⁱⁱ—Li2—O7—S4	170.77 (16)
N1—S2—O3—Li1	−12.6 (2)	O6—Li2—O7—S4	−9.23 (16)
C2—S2—O3—Li1	103.50 (17)	O2—Li2—O7—S4	80.09 (16)
O1—Li1—O3—S2	−9.75 (15)	O2ⁱⁱ—Li2—O7—S4	−99.91 (16)
O1ⁱ—Li1—O3—S2	170.25 (15)	O7—S4—O8—Li3	115.4 (4)
O5ⁱ—Li1—O3—S2	−99.65 (16)	N2—S4—O8—Li3	−18.4 (4)
O5—Li1—O3—S2	80.35 (16)	C4—S4—O8—Li3	−130.1 (4)
O3—S2—O4—Li3	107.9 (4)	O4—Li3—O8—S4	−28.7 (5)
N1—S2—O4—Li3	−26.5 (4)	N3—Li3—O8—S4	81.5 (5)
C2—S2—O4—Li3	−137.8 (4)	N4—Li3—O8—S4	−148.9 (3)
O8—Li3—O4—S2	−19.3 (5)	O8—S4—N2—S3	155.10 (15)
N3—Li3—O4—S2	−141.1 (3)	O7—S4—N2—S3	20.5 (2)
N4—Li3—O4—S2	88.7 (4)	C4—S4—N2—S3	−95.43 (17)
O2—S1—N1—S2	−131.85 (16)	O5—S3—N2—S4	−133.72 (15)
O1—S1—N1—S2	6.2 (2)	O6—S3—N2—S4	4.1 (2)
C1—S1—N1—S2	118.67 (17)	C3—S3—N2—S4	116.90 (17)
O4—S2—N1—S1	154.01 (15)	O5—S3—C3—F8	−170.8 (2)
O3—S2—N1—S1	18.8 (2)	O6—S3—C3—F8	64.2 (2)
C2—S2—N1—S1	−96.96 (17)	N2—S3—C3—F8	−56.7 (2)
O2—S1—C1—F1	70.7 (2)	O5—S3—C3—F9	−49.4 (2)
O1—S1—C1—F1	−54.1 (2)	O6—S3—C3—F9	−174.4 (2)
N1—S1—C1—F1	−174.84 (18)	N2—S3—C3—F9	64.7 (2)
O2—S1—C1—F2	−49.6 (2)	O5—S3—C3—F7	70.1 (2)
O1—S1—C1—F2	−174.4 (2)	O6—S3—C3—F7	−54.9 (2)
N1—S1—C1—F2	64.9 (2)	N2—S3—C3—F7	−175.92 (17)
O2—S1—C1—F3	−170.5 (2)	O8—S4—C4—F11	−177.28 (17)
O1—S1—C1—F3	64.7 (2)	O7—S4—C4—F11	−54.0 (2)
N1—S1—C1—F3	−56.1 (2)	N2—S4—C4—F11	68.9 (2)
O4—S2—C2—F6	−58.6 (2)	O8—S4—C4—F10	−57.2 (2)
O3—S2—C2—F6	64.6 (2)	O7—S4—C4—F10	66.1 (2)
N1—S2—C2—F6	−172.51 (19)	N2—S4—C4—F10	−170.98 (17)
O4—S2—C2—F5	61.7 (2)	O8—S4—C4—F12	62.3 (2)
O3—S2—C2—F5	−175.04 (18)	O7—S4—C4—F12	−174.42 (17)
N1—S2—C2—F5	−52.2 (2)	N2—S4—C4—F12	−51.5 (2)
O4—S2—C2—F4	−178.96 (17)	O4—Li3—N3—C5	−56.2 (14)
O3—S2—C2—F4	−55.7 (2)	O8—Li3—N3—C5	−166.0 (12)
N1—S2—C2—F4	67.1 (2)	N4—Li3—N3—C5	73.1 (14)
O6—S3—O5—Li1	−88.8 (3)	O4—Li3—N4—C7	−157.1 (12)
N2—S3—O5—Li1	47.7 (4)	O8—Li3—N4—C7	−48.6 (14)
C3—S3—O5—Li1	156.1 (3)	N3—Li3—N4—C7	80.8 (13)

Symmetry codes: (i) −x+2, −y−1, −z+1; (ii) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Li₂(C₂F₆NO₄S₂)₂(C₂H₃N)₂]
M_r	656.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	110
a, b, c (Å)	10.8654 (2), 11.0610 (2), 19.1778 (3)
β (°)	90.8483 (10)
V (Å³)	2304.58 (7)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	5.16
Crystal size (mm)	0.40 × 0.20 × 0.15

Data collection
Diffractometer	Bruker–Nonius X8 APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.232, 0.512
No. of measured, independent and observed [I > 2σ(I)] reflections	9937, 3950, 3482
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.593

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.108, 1.07
No. of reflections	3950
No. of parameters	348
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.49

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), cif2tables.py (Boyle, 2008).

Acknowledgements

The authors wish to thank Dr Peter S. White and the Department of Chemistry at the University of North Carolina at Chapel Hill for use of their diffractometer. They also wish to express their gratitude to the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, which fully supported this research (Award DE-SC0002169).

References

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