Bis[μ-P,P′-methylenebis(diisopropyl phosphonate)-κ³O,O′:O]bis[chlorolithium(I)]: a centrosymmetric dimer of lithium chloride with terminal chloride anions

The molecule of the title dimeric compound, [Li₂Cl₂(C₁₃­H₃₀O₆P₂)₂] or [LiCl{[(ⁱPrO)₂P(O)]₂CH₂}]₂, lies about an inversion center and features tetrahedrally coordinated Li atoms. The neutral ligands each chelate to one metal center and bridge to the other center through P=O units. Unusually for lithium chloride complexes, the Cl⁻ ions are in terminal rather than bridging positions. Principal dimensions include Li—O(four-membered ring) = 1.959 (3) and 2.056 (3) Å, Li—O(phosphonate ring) = 1.929 (3) Å, and Li—Cl = 2.293 (3) Å.

S1. Comment

Neutral Lewis base complexes of lithium chloride display a surprisingly wide variety of aggregated forms in the solid state (Chivers et al., 2001). These include monomers (Raston et al., 1988), dimers (Hahn & Rupprecht, 1991), tetramers (Barr et al., 1984a), polymers (Kopp & Neumuller, 1999) and charge-separated compounds (Barr et al., 1984b), with the extent and nature of the aggregation being dependant on the donor ligand. Monomers and charge-separated complexes are generally found when polydentate ligands such as crowns are used, or when sufficient quantities of strong Lewis bases are present. A common feature of the remaining aggregated forms of lithium chloride is the use of Cl⁻ bridges to link the metals. This may either be in a µ² fashion, as seen in the simple dimer [LiCl(THF)₂]₂ (THF is tetrahydrofuran; Hahn & Rupprecht, 1991), or alternatively in a µ³ mode, as found in the tetrameric cubane [LiCl(HMPA)]₄ (HMPA is hexamethylphosphoramide; Barr et al., 1984a). We now add to this collection the structure of the title compound, (I), which, although dimeric, unusually displays terminal Cl⁻ units. \sch

X-ray analysis of (I) revealed a centrosymmetric dimer, with the metal atoms bridged by a pair of P═O units, one from each of the attached phosphonate ligands. The remaining P═O unit of each phosphonate chelates an Li centre to give an overall framework composed of a centrosymmetric four-membered Li₂O₂ ring sandwiched between two six-membered LiOPCPO rings in a step-like configuration (Fig. 1). Tetracoordination of the metal atoms is completed by the terminal Cl⁻ anions. Principal dimensions are given in Table 1.

The closest analogue of (I) is the complex [{LiCl(DMF)}₂·H₂O]_n (DMF is dimethylformamide; Rao et al., 1984), which also contains solvent-bridged Li₂O₂ units. However, in this instance, the attached Cl⁻ anions bridge between dimeric units, as well as binding to water molecules, to form a network assembly. Interestingly, when the closely related monodentate phosphoryl ligand HMPA is used as a Lewis base for LiCl, the tetrameric cubane [LiCl(HMPA)]₄ (Barr et al., 1984a), with µ³-bridging Cl⁻ anions and terminal donor ligands, is formed. Inclusion of water into this system results in the formation of the charge-separated complex [{Li(H₂O)₂(HMPA)₂}²⁺·2Cl⁻] (Barr et al., 1984b), incorporating P═O-bridged dimeric units, as found in (I). Therefore, the formation of (I) can be rationalized by the bidentate phosphonate ligand enabling the preferential bridging of the P═O units, while maintaining tetracoordination at the metal centres.

Rather than considering complex (I) as a traditional dimer, which normally bridges through the anionic groups, it may be better viewed as an associated pair of monomers. This is demonstrated by the short Li—Cl bond length of 2.293 (3) Å in (I), which compares favourably with the value of 2.290 (4) Å found in the monomeric complex [LiCl(12-crown-4)] (Gingl et al., 1991). Finally, the Li—O bond distances within the Li₂O₂ dimer are highly asymmetrical, at 1.959 (3) Å for Li1—O1 and 2.056 (3) Å for Li1—O1ⁱ [symmetry code: (i) −x, −y, 2 − z]. This is an unusual feature compared with similarly P═O-bridged complexes of Li, such as [(RO)₂P(O)CHCNLi·THF]_n (R is?; Henderson et al., 2000), and may be a consequence of chelation of the ligand resulting in a stronger interaction with one metal over the other.

S2. Experimental

All experimental manipulations were performed either under a purified argon atmosphere using standard Schlenk techniques or in an argon-filled glove box. All solvents were distilled from sodium benzophenone ketyl prior to use. Tetraisopropyl methylenediphosphonate was purchased from Lancaster, distilled from CaH₂ and stored over 4 A molecular sieve before use. n-Butyl lithium was purchased from Aldrich and standardized before use. n-Butyl chloride was purchased from Aldrich, distilled from CaH₂ and stored over 4 A molecular sieve prior to use. The NMR spectroscopic data were recorded on a Bruker DPX 400 spectrometer at 298 K. The elemental analysis was carried out on a Perkin-Elmer 2400 elemental analyzer. For the synthesis of (I), n-BuLi (5 mmol as a 1.6 M solution in hexane) was added to a solution of n-BuCl (5 mmol, 0.52 ml) in tetrahydrofuran (THF; 5 ml). The resulting solution was stirred for 2 h before the addition of one equivalent of [(i-PrO)₂P(O)]₂CH₂ (5 mmol, 1.6 ml). After formation of a white precipitate, the THF was removed in vacuo and replaced by toluene (10 ml). Complete dissolution was achieved on strong heating of the mixture. X-ray quality crystals of (I) were produced on slowly cooling the hot solution to 277 K over several hours (yield 0.4 g, 20.1%). Elemental analysis, expected: C 40.38, H 7.82%; found: C 40.62, H 7.87%. ¹H NMR (D₅-pyridine, δ, p.p.m.): 1.34 (d, 12H, ⁱPr CH₃, ³J = 6.2 Hz), 1.36 (d, 12H, ⁱPr CH₃, ³J = 6.2 Hz), 3.09 (t, 2H, P₂CH₂, ²J_PH = 21.2 Hz), 5.04 (sext, 4H, ⁱPr CH, ³J = 6.2 Hz); ¹³C NMR (D₅-pyridine, δ, p.p.m.): 24.55 (ⁱPr CH₃), 24.94 (ⁱPr CH₃), 28.10 (t, CH₂, ¹J_PC = 135.2 Hz), 72.03 (ⁱPr CH).

S3. Refinement

The methyl groups bonded to C11 were each modelled as disordered over two positions, and the occupancy refined to 0.832 (14):0.168 (14). The minor component was treated isotropically, whilst the major component and all other non-H atoms were treated anisotropically. All H atoms were treated as riding, with C—H distances in the range 0.98–1.00 Å. Is this added text OK??

Computing details

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and with 50% probability displacement ellipsoids. The minor occupancy methyl atoms C12A and C13A, and all H atoms, have been omitted for clarity.

Bis[µ-P,P'-methylenebis(diisopropyl phosphonate)-κ³O,O':O]bis[chlorolithium(I)]

Crystal data

[Li2Cl2(C13H30O6P2)2]	Z = 1
Mr = 773.40	F(000) = 412
Triclinic, P1	Dx = 1.232 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.2172 (2) Å	Cell parameters from 23647 reflections
b = 10.3740 (3) Å	θ = 2.9–30.5°
c = 10.8197 (3) Å	µ = 0.36 mm^−1
α = 84.2355 (12)°	T = 150 K
β = 68.9131 (12)°	Prism, colourless
γ = 76.9692 (10)°	0.25 × 0.25 × 0.20 mm
V = 1042.23 (5) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	4538 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 30.3°, θmin = 3.3°
ϕ and ω scans	h = −13→13
17790 measured reflections	k = −12→13
5337 independent reflections	l = −14→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.116	w = 1/[σ^2(Fo^2) + (0.0536P)^2 + 0.6511P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
5337 reflections	Δρmax = 0.60 e Å^−3
228 parameters	Δρmin = −0.51 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.033 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.15276 (4)	0.08991 (4)	1.18453 (4)	0.02727 (12)
P1	0.14911 (5)	0.17078 (4)	0.82356 (4)	0.02337 (12)
P2	−0.12446 (5)	0.34373 (4)	0.97838 (4)	0.02498 (12)
O1	0.10874 (13)	0.04470 (11)	0.88597 (11)	0.0245 (3)
O2	0.09838 (14)	0.21904 (12)	0.70398 (12)	0.0283 (3)
O3	0.31374 (13)	0.16719 (13)	0.76504 (13)	0.0310 (3)
O4	−0.18598 (13)	0.22961 (12)	0.97284 (13)	0.0280 (3)
O5	−0.14294 (14)	0.46088 (12)	0.87937 (13)	0.0297 (3)
O6	−0.19181 (14)	0.41394 (12)	1.11607 (12)	0.0314 (3)
C1	0.06622 (18)	0.30306 (17)	0.93872 (17)	0.0258 (3)
H1A	0.1068	0.3822	0.9002	0.031*
H1B	0.0879	0.2769	1.0209	0.031*
C2	0.0995 (2)	0.12565 (19)	0.60817 (18)	0.0333 (4)
H2	0.0774	0.0409	0.6552	0.040*
C3	−0.0177 (3)	0.1916 (2)	0.5563 (2)	0.0440 (5)
H3A	−0.1100	0.2044	0.6294	0.066*
H3B	−0.0201	0.1358	0.4895	0.066*
H3C	0.0004	0.2777	0.5160	0.066*
C4	0.2449 (3)	0.0989 (3)	0.5021 (2)	0.0505 (6)
H4A	0.2719	0.1830	0.4642	0.076*
H4B	0.2425	0.0471	0.4323	0.076*
H4C	0.3153	0.0491	0.5404	0.076*
C5	0.41396 (19)	0.12112 (19)	0.8374 (2)	0.0323 (4)
H5	0.3655	0.1470	0.9323	0.039*
C6	0.5358 (2)	0.1934 (2)	0.7719 (2)	0.0444 (5)
H6A	0.5822	0.1690	0.6786	0.067*
H6B	0.6059	0.1688	0.8170	0.067*
H6C	0.4982	0.2891	0.7777	0.067*
C7	0.4618 (2)	−0.0266 (2)	0.8297 (2)	0.0428 (5)
H7A	0.3816	−0.0683	0.8830	0.064*
H7B	0.5408	−0.0551	0.8639	0.064*
H7C	0.4942	−0.0530	0.7373	0.064*
C8	−0.2700 (2)	0.50053 (19)	0.8398 (2)	0.0333 (4)
H8	−0.3150	0.4229	0.8456	0.040*
C9	−0.2160 (3)	0.5498 (3)	0.6987 (2)	0.0586 (7)
H9A	−0.1740	0.6269	0.6947	0.088*
H9B	−0.2958	0.5750	0.6653	0.088*
H9C	−0.1430	0.4796	0.6441	0.088*
C10	−0.3746 (3)	0.6077 (2)	0.9302 (3)	0.0513 (6)
H10A	−0.4004	0.5746	1.0221	0.077*
H10B	−0.4609	0.6339	0.9063	0.077*
H10C	−0.3304	0.6845	0.9210	0.077*
C11	−0.2053 (3)	0.3398 (2)	1.2422 (2)	0.0424 (5)
H11	−0.1311	0.2561	1.2300	0.051*
Li1	0.1061 (3)	−0.0434 (3)	1.0554 (3)	0.0272 (6)
C12	−0.3586 (6)	0.3124 (7)	1.2967 (3)	0.0670 (18)	0.832 (14)
H12A	−0.4283	0.3966	1.3119	0.100*	0.832 (14)
H12B	−0.3727	0.2619	1.3804	0.100*	0.832 (14)
H12C	−0.3722	0.2613	1.2324	0.100*	0.832 (14)
C13	−0.1891 (6)	0.4361 (7)	1.3325 (4)	0.0540 (11)	0.832 (14)
H13A	−0.0962	0.4622	1.2911	0.081*	0.832 (14)
H13B	−0.1946	0.3926	1.4184	0.081*	0.832 (14)
H13C	−0.2661	0.5149	1.3456	0.081*	0.832 (14)
C12A	−0.290 (2)	0.2603 (16)	1.2968 (15)	0.040 (4)*	0.168 (14)
H12D	−0.2746	0.1915	1.2343	0.060*	0.168 (14)
H12E	−0.3897	0.3094	1.3221	0.060*	0.168 (14)
H12F	−0.2716	0.2191	1.3760	0.060*	0.168 (14)
C13A	−0.167 (2)	0.389 (2)	1.319 (2)	0.041 (5)*	0.168 (14)
H13D	−0.2194	0.4811	1.3351	0.062*	0.168 (14)
H13E	−0.0641	0.3872	1.2800	0.062*	0.168 (14)
H13F	−0.1878	0.3387	1.4029	0.062*	0.168 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0302 (2)	0.0317 (2)	0.0248 (2)	−0.00894 (16)	−0.01391 (16)	−0.00028 (15)
P1	0.0235 (2)	0.0248 (2)	0.0215 (2)	−0.00558 (16)	−0.00750 (16)	0.00129 (16)
P2	0.0268 (2)	0.0224 (2)	0.0248 (2)	−0.00456 (16)	−0.00838 (17)	0.00014 (16)
O1	0.0258 (6)	0.0249 (6)	0.0233 (6)	−0.0059 (4)	−0.0090 (5)	0.0009 (4)
O2	0.0338 (7)	0.0284 (6)	0.0239 (6)	−0.0061 (5)	−0.0121 (5)	0.0016 (5)
O3	0.0251 (6)	0.0372 (7)	0.0293 (6)	−0.0084 (5)	−0.0074 (5)	0.0031 (5)
O4	0.0282 (6)	0.0241 (6)	0.0323 (7)	−0.0060 (5)	−0.0113 (5)	0.0010 (5)
O5	0.0305 (6)	0.0272 (6)	0.0317 (7)	−0.0060 (5)	−0.0127 (5)	0.0049 (5)
O6	0.0374 (7)	0.0272 (6)	0.0255 (6)	−0.0032 (5)	−0.0079 (5)	−0.0013 (5)
C1	0.0278 (8)	0.0255 (8)	0.0254 (8)	−0.0071 (6)	−0.0094 (7)	−0.0019 (6)
C2	0.0444 (11)	0.0341 (10)	0.0226 (8)	−0.0079 (8)	−0.0128 (8)	−0.0016 (7)
C3	0.0456 (12)	0.0564 (13)	0.0356 (11)	−0.0084 (10)	−0.0212 (9)	−0.0035 (9)
C4	0.0477 (13)	0.0632 (15)	0.0314 (11)	0.0057 (11)	−0.0106 (9)	−0.0107 (10)
C5	0.0240 (8)	0.0389 (10)	0.0347 (10)	−0.0068 (7)	−0.0108 (7)	−0.0018 (8)
C6	0.0320 (10)	0.0491 (12)	0.0535 (13)	−0.0159 (9)	−0.0117 (9)	−0.0018 (10)
C7	0.0292 (10)	0.0383 (11)	0.0552 (13)	−0.0044 (8)	−0.0104 (9)	0.0027 (9)
C8	0.0355 (10)	0.0295 (9)	0.0391 (10)	−0.0046 (7)	−0.0197 (8)	0.0020 (7)
C9	0.0623 (16)	0.0685 (17)	0.0408 (13)	0.0020 (13)	−0.0249 (12)	0.0091 (12)
C10	0.0415 (12)	0.0465 (13)	0.0607 (15)	0.0051 (10)	−0.0183 (11)	−0.0080 (11)
C11	0.0516 (13)	0.0363 (11)	0.0261 (9)	0.0014 (9)	−0.0051 (9)	0.0038 (8)
Li1	0.0294 (15)	0.0271 (14)	0.0267 (14)	−0.0064 (11)	−0.0120 (12)	0.0026 (11)
C12	0.072 (4)	0.102 (4)	0.0369 (16)	−0.057 (3)	−0.0103 (16)	0.0061 (17)
C13	0.069 (3)	0.072 (3)	0.0349 (17)	−0.031 (2)	−0.0274 (17)	0.005 (2)

Geometric parameters (Å, º)

Li1—Cl1	2.293 (3)	C6—H6B	0.9800
Li1—O1	1.959 (3)	C6—H6C	0.9800
Li1—O1^i	2.056 (3)	C7—H7A	0.9800
Li1—O4^i	1.928 (3)	C7—H7B	0.9800
P1—O1	1.4840 (12)	C7—H7C	0.9800
P1—O2	1.5584 (12)	C8—C9	1.504 (3)
P1—O3	1.5626 (13)	C8—C10	1.505 (3)
P1—C1	1.7924 (17)	C8—H8	1.0000
P1—Li1^i	3.001 (3)	C9—H9A	0.9800
P2—O4	1.4756 (13)	C9—H9B	0.9800
P2—O5	1.5623 (13)	C9—H9C	0.9800
P2—O6	1.5741 (13)	C10—H10A	0.9800
P2—C1	1.7950 (18)	C10—H10B	0.9800
O2—C2	1.484 (2)	C10—H10C	0.9800
O3—C5	1.474 (2)	C11—C13A	1.23 (2)
O5—C8	1.470 (2)	C11—C12A	1.281 (16)
O6—C11	1.475 (2)	C11—C13	1.539 (6)
C1—H1A	0.9900	C11—C12	1.544 (5)
C1—H1B	0.9900	C11—H11	1.0000
C2—C4	1.501 (3)	Li1—Li1^i	2.779 (6)
C2—C3	1.502 (3)	C12—H12A	0.9800
C2—H2	1.0000	C12—H12B	0.9800
C3—H3A	0.9800	C12—H12C	0.9800
C3—H3B	0.9800	C13—H13A	0.9800
C3—H3C	0.9800	C13—H13B	0.9800
C4—H4A	0.9800	C13—H13C	0.9800
C4—H4B	0.9800	C12A—H12D	0.9800
C4—H4C	0.9800	C12A—H12E	0.9800
C5—C7	1.501 (3)	C12A—H12F	0.9800
C5—C6	1.515 (3)	C13A—H13D	0.9800
C5—H5	1.0000	C13A—H13E	0.9800
C6—H6A	0.9800	C13A—H13F	0.9800
P1—O1—Li1	132.30 (11)	H6B—C6—H6C	109.5
Li1—O1—Li1^i	87.55 (13)	C5—C7—H7A	109.5
O1—Li1—Cl1	110.93 (14)	C5—C7—H7B	109.5
O1^i—Li1—Cl1	112.10 (14)	H7A—C7—H7B	109.5
O4^i—Li1—O1	109.16 (15)	C5—C7—H7C	109.5
O4^i—Li1—O1^i	100.19 (14)	H7A—C7—H7C	109.5
O1—P1—O2	113.94 (7)	H7B—C7—H7C	109.5
O1—P1—O3	115.05 (7)	O5—C8—C9	105.52 (17)
O2—P1—O3	103.51 (7)	O5—C8—C10	108.47 (17)
O1—P1—C1	110.77 (8)	C9—C8—C10	111.74 (19)
O2—P1—C1	104.43 (8)	O5—C8—H8	110.3
O3—P1—C1	108.36 (8)	C9—C8—H8	110.3
O4—P2—O5	116.02 (7)	C10—C8—H8	110.3
O4—P2—O6	113.93 (7)	C8—C9—H9A	109.5
O5—P2—O6	102.51 (7)	C8—C9—H9B	109.5
O4—P2—C1	113.38 (8)	H9A—C9—H9B	109.5
O5—P2—C1	102.31 (8)	C8—C9—H9C	109.5
O6—P2—C1	107.42 (8)	H9A—C9—H9C	109.5
P1—O1—Li1^i	114.96 (11)	H9B—C9—H9C	109.5
C2—O2—P1	122.03 (11)	C8—C10—H10A	109.5
C5—O3—P1	125.05 (11)	C8—C10—H10B	109.5
P2—O4—Li1^i	133.18 (12)	H10A—C10—H10B	109.5
C8—O5—P2	123.36 (11)	C8—C10—H10C	109.5
C11—O6—P2	122.21 (12)	H10A—C10—H10C	109.5
P1—C1—P2	111.67 (9)	H10B—C10—H10C	109.5
P1—C1—H1A	109.3	C13A—C11—C12A	114.7 (13)
P2—C1—H1A	109.3	C13A—C11—O6	114.7 (11)
P1—C1—H1B	109.3	C12A—C11—O6	126.5 (8)
P2—C1—H1B	109.3	C12A—C11—C13	117.5 (7)
H1A—C1—H1B	107.9	O6—C11—C13	104.7 (2)
O2—C2—C4	109.21 (17)	C13A—C11—C12	116.6 (11)
O2—C2—C3	105.53 (16)	O6—C11—C12	106.2 (3)
C4—C2—C3	113.23 (17)	C13—C11—C12	110.1 (3)
O2—C2—H2	109.6	C13A—C11—H11	95.6
C4—C2—H2	109.6	C12A—C11—H11	82.4
C3—C2—H2	109.6	O6—C11—H11	111.8
C2—C3—H3A	109.5	C13—C11—H11	111.8
C2—C3—H3B	109.5	C12—C11—H11	111.8
H3A—C3—H3B	109.5	O1—Li1—O1^i	92.45 (13)
C2—C3—H3C	109.5	O4^i—Li1—Cl1	126.31 (15)
H3A—C3—H3C	109.5	C11—C12—H12A	109.5
H3B—C3—H3C	109.5	C11—C12—H12B	109.5
C2—C4—H4A	109.5	C11—C12—H12C	109.5
C2—C4—H4B	109.5	C11—C13—H13A	109.5
H4A—C4—H4B	109.5	C11—C13—H13B	109.5
C2—C4—H4C	109.5	C11—C13—H13C	109.5
H4A—C4—H4C	109.5	C11—C12A—H12D	109.5
H4B—C4—H4C	109.5	C11—C12A—H12E	109.5
O3—C5—C7	109.85 (16)	H12D—C12A—H12E	109.5
O3—C5—C6	105.13 (16)	C11—C12A—H12F	109.5
C7—C5—C6	113.00 (17)	H12D—C12A—H12F	109.5
O3—C5—H5	109.6	H12E—C12A—H12F	109.5
C7—C5—H5	109.6	C11—C13A—H13D	109.5
C6—C5—H5	109.6	C11—C13A—H13E	109.5
C5—C6—H6A	109.5	H13D—C13A—H13E	109.5
C5—C6—H6B	109.5	C11—C13A—H13F	109.5
H6A—C6—H6B	109.5	H13D—C13A—H13F	109.5
C5—C6—H6C	109.5	H13E—C13A—H13F	109.5
H6A—C6—H6C	109.5
O2—P1—O1—Li1	−165.37 (15)	O2—P1—C1—P2	54.90 (10)
O3—P1—O1—Li1	75.31 (16)	O3—P1—C1—P2	164.75 (8)
C1—P1—O1—Li1	−47.99 (17)	O4—P2—C1—P1	30.55 (12)
O2—P1—O1—Li1^i	−54.29 (13)	O5—P2—C1—P1	−95.15 (10)
O3—P1—O1—Li1^i	−173.60 (11)	O6—P2—C1—P1	157.34 (8)
C1—P1—O1—Li1^i	63.09 (13)	P1—O2—C2—C4	−86.00 (18)
O1—P1—O2—C2	−37.69 (15)	P1—O2—C2—C3	151.97 (14)
O3—P1—O2—C2	87.98 (14)	P1—O3—C5—C7	84.45 (18)
C1—P1—O2—C2	−158.68 (13)	P1—O3—C5—C6	−153.69 (14)
O1—P1—O3—C5	−51.79 (16)	P2—O5—C8—C9	−147.02 (16)
O2—P1—O3—C5	−176.75 (13)	P2—O5—C8—C10	93.10 (18)
C1—P1—O3—C5	72.79 (15)	P2—O6—C11—C13A	134.1 (11)
O5—P2—O4—Li1^i	123.40 (16)	P2—O6—C11—C12A	−70.0 (11)
O6—P2—O4—Li1^i	−117.88 (16)	P2—O6—C11—C13	148.0 (3)
C1—P2—O4—Li1^i	5.39 (19)	P2—O6—C11—C12	−95.5 (3)
O4—P2—O5—C8	34.63 (16)	P1—O1—Li1—O4^i	−136.18 (13)
O6—P2—O5—C8	−90.17 (14)	Li1^i—O1—Li1—O4^i	101.67 (17)
C1—P2—O5—C8	158.59 (14)	P1—O1—Li1—O1^i	122.15 (14)
O4—P2—O6—C11	50.58 (17)	Li1^i—O1—Li1—O1^i	0.0
O5—P2—O6—C11	176.75 (15)	P1—O1—Li1—Cl1	7.3 (2)
C1—P2—O6—C11	−75.88 (17)	Li1^i—O1—Li1—Cl1	−114.81 (17)
O1—P1—C1—P2	−68.16 (11)

Symmetry code: (i) −x, −y, −z+2.