Revision of the Li13Si4 structure

Zeilinger, M.; Fässler, T.F.

doi:10.1107/S1600536813029759

inorganic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Pages i81-i82

doi:10.1107/S1600536813029759

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Revision of the Li₁₃Si₄ structure

Michael Zeilinger ^a and Thomas F. Fässler ^a ^*

^aDepartment of Chemistry, Technische Universität München, Lichtenbergstrasse 4, 85747 Garching, Germany
^*Correspondence e-mail: thomas.faessler@lrz.tum.de

(Received 14 October 2013; accepted 30 October 2013; online 6 November 2013)

Besides Li₁₇Si₄, Li_16.42Si₄, and Li₁₅Si₄, another lithium-rich representative in the Li–Si system is the phase Li₁₃Si₄ (tridecalithium tetrasilicide), the structure of which has been determined previously [Frank et al. (1975 ). Z. Naturforsch. Teil B, 30, 10–13]. A careful analysis of X-ray diffraction patterns of Li₁₃Si₄ revealed discrepancies between experimentally observed and calculated Bragg positions. Therefore, we redetermined the structure of Li₁₃Si₄ on the basis of single-crystal X-ray diffraction data. Compared to the previous structure report, decisive differences are (i) the introduction of a split position for one Li site [occupancy ratio 0.838 (7):0.162 (7)], (ii) the anisotropic refinement of atomic displacement parameters for all atoms, and (iii) a high accuracy of atom positions and unit-cell parameters. The asymmetric unit of Li₁₃Si₄ contains two Si and seven Li atoms. Except for one Li atom situated on a site with symmetry 2/m, all other atoms are on mirror planes. The structure consists of isolated Si atoms as well as Si–Si dumbbells surrounded by Li atoms. Each Si atom is either 12- or 13-coordinated. The isolated Si atoms are situated in the ab plane at z = 0 and are strictly separated from the Si–Si dumbbells at z = 0.5.

CCDC reference: 969388

Related literature

For details of the structural description of Li₁₃Si₄, see: Frank et al. (1975). For structural data for Li₁₃Si₄ based on computational methods, see: Chevrier et al. (2010 ). For details of the synthesis, thermodynamic properties and crystal structures of Li₁₇Si₄, Li_16.42Si₄ and Li₁₅Si₄, see: Zeilinger & Benson et al. (2013 ); Zeilinger & Kurylyshyn et al. (2013 ); Zeilinger & Baran et al. (2013 ). For further thermodynamic investigations on the Li–Si system, see: Thomas et al. (2013 ); Wang et al. (2013 ). The behavior of silicon as anode material upon lithiation/delithiation is described by Limthongkul et al. (2003 ) and Obrovac & Christensen (2004 ). For in-situ/ex-situ solid state NMR investigations of structural changes in silicon electrodes for lithium-ion batteries, see: Key et al. (2009 , 2011 ).

Experimental

Crystal data

Li₁₃Si₄
M_r = 202.58
Orthorhombic, P b a m
a = 7.9488 (4) Å
b = 15.1248 (8) Å
c = 4.4661 (2) Å
V = 536.93 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 100 K
0.2 × 0.2 × 0.2 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.781, T_max = 0.818
25938 measured reflections
2429 independent reflections
2333 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.015
wR(F²) = 0.044
S = 1.08
2429 reflections
60 parameters
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2012 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 969388

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813029759/wm2778sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813029759/wm2778Isup2.hkl

checkCIF report

Comment top

In the last decade, the demand for high capacity lithium-ion batteries (LIBs) particularly fueled the research on the Li—Si phase system since as anode material, Si theoretically offers a specific capacity of 3579 mA h g^-1 based on the formation of the metastable phase Li₁₅Si₄ (Obrovac & Christensen, 2004). It is well known that Li₁₅Si₄ is the only Li—Si phase that appears in crystalline form during charging and discharging processes in silicon based LIBs at room temperature (Limthongkul et al., 2003; Obrovac & Christensen, 2004). However, in order to understand the lithiation/delithiation mechanism, X-ray diffraction methods only provide sparse information and therefore other techniques such as in-situ / ex-situ solid state NMR are frequently used (Key & Bhattacharyya et al., 2009; Key & Morcrette et al., 2011).

Furthermore, a fundamental understanding of the thermodynamic relation of Li—Si phases, especially in the lithium-rich section of the phase diagram, is of considerable importance. Exemplary work is given by Zeilinger & Baran et al. (2013), Zeilinger & Benson et al. (2013), Zeilinger & Kurylyshyn et al. (2013), Thomas et al. (2013) and Wang et al. (2013). For those studies as well as for NMR investigations it is crucial that all existing Li—Si phases are structurally well characterized since otherwise a phase identification of model compounds can be difficult (Key & Bhattacharyya et al., 2009; Thomas et al., 2013). In the course of our investigations on the thermodynamic properties of Li—Si phases, we identified two new phases, Li₁₇Si₄ (Zeilinger & Benson et al., 2013) and Li_16.42Si₄ (Zeilinger & Kurylyshyn et al., 2013). The latter is assigned a high temperature phase existing in a temperature range of 743–891 K, the former decomposes peritectically at 754–759 K. Li_16.42Si₄ is compositionally embraced by the lithium-richer phase Li₁₇Si₄ and the lithium-poorer phase Li₁₃Si₄. Since the determination of the Li—Si phase diagram in the aforementioned section is carried out by thermal investigations on various samples with different Li concentrations, the structures of the relevant phases have to be ascertained for an unambiguous assignment of phases in X-ray powder diffraction patterns of those samples. However, the calculated X-ray diffraction pattern of Li₁₃Si₄ based on structural data published by Frank et al. (1975) decisively differs from the experimentally observed pattern of a Li₁₃Si₄ sample (Fig. 1). More recent data based on theoretical calculations were reported by Chevrier et al. (2010). Yet, the accordingly calculated pattern is slightly but still distinctly different (Fig. 1).

Therefore, we redetermined the structure of Li₁₃Si₄ based on single crystal X-ray diffraction data. As can be seen in Fig. 1, the resulting calculated pattern is in very good agreement with the experimental one. Main differences to the previous single-crystal X-ray structure determination by Frank et al. (1975) are i) a significantly more precise determination of atomic positions and unit-cell parameters, respectively (a = 7.99 (2) Å, b = 15.21 (3) Å, c = 4.43 (1) Å compared with a = 7.9488 (4) Å, b = 15.1248 (8) Å, c = 4.4661 (2) Å), ii) an anisotropic refinement of atomic displacement parameters for all atoms and iii) the introduction of a split position for Li6 (occupancy ratio 0.838 (7):0.162 (7)).

Regarding the structure of Li₁₃Si₄ we briefly elaborate on the main structure motifs since this has already been described in detail by Frank et al. (1975). Contrary to the lithium-richer phases Li₁₇Si₄, Li_16.42Si₄ and Li₁₅Si₄ where all Si atoms are isolated, Li₁₃Si₄ contains Si—Si dumbbells beside isolated Si atoms (Fig. 2a). Li—Si distances range from 2.5173 (2) Å to 3.2283 (7) Å and next nearest neighbor distances are clearly separated, starting off from 4.1899 (2) Å. The shortest Li—Li distance is 2.429 (7) Å and comparable to other Li—Si phases (Zeilinger & Benson et al., 2013). The Si—Si distance within the Si—Si dumbbells is 2.3852 (2) Å, further Si atoms are separated by distances larger than 4.4661 (2) Å. Whereas Si1 is coordinated by 12 Li and one Si atom, Si2 is exclusively surrounded by 12 Li atoms. In addition, dumbbells and isolated Si atoms are strictly separated from each other in a layer like fashion as they are located in different ab-planes (Figs. 2 b and c).

Related literature top

For details of the structural description of Li₁₃Si₄, see: Frank et al. (1975). For structural data for Li₁₃Si₄ based on computational methods, see: Chevrier et al. (2010). For details of the synthesis, thermodynamic properties and crystal structures of Li₁₇Si₄, Li_16.42Si₄ and Li₁₅Si₄, see: Zeilinger & Benson et al. (2013); Zeilinger & Kurylyshyn et al. (2013); Zeilinger & Baran et al. (2013). For further thermodynamic investigations on the Li–Si system, see: Thomas et al. (2013); Wang et al. (2013). The behavior of silicon as anode material upon lithiation/delithiation is described by Limthongkul et al. (2003) and Obrovac & Christensen (2004). For in-situ/ex-situ solid state NMR investigations of structural changes in silicon electrodes for lithium-ion batteries, see: Key et al. (2009, 2011).

Experimental top

In our previous work we reported on thermal investigations by differential scanning calorimetry (DSC) means which were targeting the determination of the lithium-rich section of the Li—Si phase diagram (Zeilinger & Kurylyshyn et al. 2013). Various samples with different Li—Si compositions (Li₁₇Si₄, "Li_16.5Si₄", "Li₁₆Si₄" and "Li₁₄Si₄") were synthesized. Crystals of Li₁₃Si₄ could be obtained from a sample with a nominal composition "Li₁₄Si₄". For the synthesis of "Li₁₄Si₄" we refer to Zeilinger & Kurylyshyn et al. (2013). Li₁₃Si₄ crystals were handled inside an Ar-filled glove box, selected under a microscope and sealed inside 0.3 mm glass capillaries for X-ray diffraction experiments.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. (a) Powder X-ray diffraction pattern of a Li₁₃Si₄ sample referenced with the theoretical patterns calculated from (b) single-crystal X-ray data presented herein, previous structural data published by (c) Chevrier et al. (2010) and (d) Frank et al. (1975).

Fig. 2. Structure motifs in Li₁₃Si₄: (a) perspective view along the crystallographic c-axis of the unit cell of Li₁₃Si₄ (atoms of the asymmetric unit are labeled), (b) isolated Si atoms, and (c) Si—Si dumbbells located in different ab-planes (c = 0, 1 and c = 1/2, respectively). Ellipsoids are drawn at a 80% probability level (Li = red, Si = blue; only the major component of Li6 is shown).

Tridecalithium tetrasilicide top

Crystal data top

Li₁₃Si₄	D_x = 1.253 Mg m⁻³
M_r = 202.58	Melting point: 995 K
Orthorhombic, Pbam	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2 2ab	Cell parameters from 9823 reflections
a = 7.9488 (4) Å	θ = 2.9–57.3°
b = 15.1248 (8) Å	µ = 0.47 mm⁻¹
c = 4.4661 (2) Å	T = 100 K
V = 536.93 (5) Å³	Block, metallic silver
Z = 2	0.2 × 0.2 × 0.2 mm
F(000) = 190

Data collection top

Bruker APEXII CCD diffractometer	2429 independent reflections
Radiation source: rotating anode FR591	2333 reflections with I > 2σ(I)
MONTEL optic monochromator	R_int = 0.033
Detector resolution: 16 pixels mm^-1	θ_max = 45.3°, θ_min = 2.7°
ϕ– and ω–rotation scans	h = −13→15
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −28→30
T_min = 0.781, T_max = 0.818	l = −8→8
25938 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.015	Secondary atom site location: difference Fourier map
wR(F²) = 0.044	w = 1/[σ²(F_o²) + (0.0204P)² + 0.0373P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.002
2429 reflections	Δρ_max = 0.68 e Å⁻³
60 parameters	Δρ_min = −0.40 e Å⁻³

Crystal data top

Li₁₃Si₄	V = 536.93 (5) Å³
M_r = 202.58	Z = 2
Orthorhombic, Pbam	Mo Kα radiation
a = 7.9488 (4) Å	µ = 0.47 mm⁻¹
b = 15.1248 (8) Å	T = 100 K
c = 4.4661 (2) Å	0.2 × 0.2 × 0.2 mm

Data collection top

Bruker APEXII CCD diffractometer	2429 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2333 reflections with I > 2σ(I)
T_min = 0.781, T_max = 0.818	R_int = 0.033
25938 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.015	60 parameters
wR(F²) = 0.044	0 restraints
S = 1.08	Δρ_max = 0.68 e Å⁻³
2429 reflections	Δρ_min = −0.40 e Å⁻³

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	Occ. (<1)
Si1	0.426415 (11)	0.431285 (6)	0.5000	0.00704 (2)
Si2	0.415184 (11)	0.160356 (6)	0.0000	0.00617 (2)
Li1	0.15083 (11)	0.02778 (6)	0.0000	0.01635 (13)
Li2	0.0000	0.5000	0.0000	0.01727 (19)
Li3	0.09442 (12)	0.19506 (7)	0.0000	0.0242 (2)
Li4	0.27005 (11)	0.34697 (6)	0.0000	0.01476 (13)
Li5	0.25998 (11)	0.09271 (6)	0.5000	0.01663 (14)
Li6A	0.4138 (3)	0.25535 (7)	0.5000	0.0195 (4)	0.838 (7)
Li6B	0.3327 (12)	0.2487 (4)	0.5000	0.0192 (15)	0.162 (7)
Li7	0.09281 (10)	0.39330 (6)	0.5000	0.01429 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.00650 (4)	0.00658 (4)	0.00803 (4)	−0.00146 (2)	0.000	0.000
Si2	0.00659 (4)	0.00652 (4)	0.00541 (4)	−0.00044 (2)	0.000	0.000
Li1	0.0192 (3)	0.0173 (3)	0.0126 (3)	−0.0052 (3)	0.000	0.000
Li2	0.0249 (5)	0.0097 (4)	0.0172 (5)	−0.0035 (4)	0.000	0.000
Li3	0.0129 (3)	0.0169 (3)	0.0427 (6)	0.0034 (3)	0.000	0.000
Li4	0.0133 (3)	0.0173 (3)	0.0137 (3)	0.0004 (2)	0.000	0.000
Li5	0.0127 (3)	0.0262 (4)	0.0110 (3)	−0.0061 (3)	0.000	0.000
Li6A	0.0374 (11)	0.0107 (4)	0.0104 (4)	0.0041 (4)	0.000	0.000
Li6B	0.019 (4)	0.017 (2)	0.022 (3)	0.003 (2)	0.000	0.000
Li7	0.0105 (3)	0.0204 (3)	0.0119 (3)	−0.0008 (2)	0.000	0.000

Geometric parameters (Å, º) top

Si1—Si1ⁱ	2.3852 (2)	Li3—Li6A^xii	2.7585 (14)
Si1—Li6A	2.6628 (12)	Li3—Li6A^xiii	2.7585 (14)
Si1—Li5ⁱⁱ	2.6762 (8)	Li3—Li5	3.0191 (9)
Si1—Li7	2.7133 (8)	Li3—Li5^viii	3.0191 (9)
Si1—Li1ⁱⁱⁱ	2.7374 (5)	Li3—Li6B	3.038 (7)
Si1—Li1^iv	2.7374 (5)	Li3—Li6B^viii	3.038 (7)
Si1—Li5ⁱⁱⁱ	2.8559 (9)	Li3—Li6B^xii	3.168 (7)
Si1—Li4^v	2.8561 (5)	Li4—Li3ⁱⁱ	2.6556 (13)
Si1—Li4	2.8561 (5)	Li4—Li6B	2.728 (3)
Si1—Li6B	2.860 (7)	Li4—Li6B^viii	2.728 (3)
Si1—Li1^vi	2.9244 (6)	Li4—Li7	2.7317 (7)
Si1—Li1ⁱⁱ	2.9244 (6)	Li4—Li7^viii	2.7318 (7)
Si2—Li2^vii	2.5174 (2)	Li4—Li1^iv	2.8060 (12)
Si2—Li3	2.6031 (9)	Li4—Si2^xiii	2.8229 (9)
Si2—Li3ⁱⁱ	2.6099 (10)	Li4—Si1^viii	2.8562 (5)
Si2—Li6A	2.6554 (6)	Li4—Li6A^viii	2.8659 (11)
Si2—Li6A^viii	2.6554 (6)	Li4—Li6A	2.8659 (11)
Si2—Li6B^viii	2.684 (3)	Li5—Li6B	2.429 (7)
Si2—Li6B	2.684 (3)	Li5—Li1^v	2.5892 (6)
Si2—Li5	2.7487 (5)	Li5—Li7ⁱⁱ	2.6540 (12)
Si2—Li5^viii	2.7487 (5)	Li5—Si1^xiii	2.6762 (8)
Si2—Li7ⁱⁱ	2.7638 (5)	Li5—Li6A	2.7472 (18)
Si2—Li7^ix	2.7638 (5)	Li5—Si2^v	2.7487 (5)
Si2—Li4ⁱⁱ	2.8229 (9)	Li5—Si1^xi	2.8559 (9)
Li1—Li1^x	2.5408 (17)	Li5—Li3^v	3.0191 (9)
Li1—Li3	2.5696 (13)	Li5—Li7^xi	3.2351 (14)
Li1—Li5^viii	2.5892 (6)	Li6A—Si2^v	2.6553 (6)
Li1—Li5	2.5892 (6)	Li6A—Li7ⁱⁱ	2.6605 (16)
Li1—Si1^vii	2.7374 (5)	Li6A—Li3^vi	2.7585 (14)
Li1—Si1^xi	2.7374 (5)	Li6A—Li3ⁱⁱ	2.7585 (14)
Li1—Li4^vii	2.8060 (12)	Li6A—Li4^v	2.8659 (11)
Li1—Li2^vii	2.8071 (9)	Li6A—Li7	3.296 (2)
Li1—Si1^xii	2.9244 (6)	Li6A—Li3^v	3.5021 (19)
Li1—Si1^xiii	2.9244 (6)	Li6B—Si2^v	2.684 (3)
Li2—Si2^xiii	2.5173 (2)	Li6B—Li4^v	2.728 (3)
Li2—Si2^iv	2.5174 (2)	Li6B—Li7	2.902 (7)
Li2—Li1^xiii	2.8071 (9)	Li6B—Li7ⁱⁱ	2.981 (7)
Li2—Li1^iv	2.8071 (9)	Li6B—Li3^v	3.038 (7)
Li2—Li7^viii	2.8522 (6)	Li6B—Li3^vi	3.168 (7)
Li2—Li7^xiv	2.8522 (6)	Li6B—Li3ⁱⁱ	3.168 (7)
Li2—Li7^xv	2.8522 (6)	Li7—Li5^xiii	2.6540 (12)
Li2—Li7	2.8522 (6)	Li7—Li6A^xiii	2.6605 (16)
Li2—Li4^xv	3.1567 (9)	Li7—Li4^v	2.7317 (7)
Li2—Li4	3.1567 (9)	Li7—Si2^xiii	2.7638 (5)
Li2—Li5ⁱⁱⁱ	3.2546 (7)	Li7—Si2^xvi	2.7638 (5)
Li2—Li5^iv	3.2546 (7)	Li7—Li2^v	2.8522 (6)
Li3—Si2^xiii	2.6099 (10)	Li7—Li6B^xiii	2.981 (7)
Li3—Li4^xiii	2.6556 (13)	Li7—Li5ⁱⁱⁱ	3.2351 (14)
Li3—Li4	2.6884 (13)

Si1ⁱ—Si1—Li6A	152.78 (5)	Li3ⁱⁱ—Li4—Li7	124.20 (2)
Si1ⁱ—Si1—Li5ⁱⁱ	68.43 (2)	Li3—Li4—Li7	87.21 (3)
Li6A—Si1—Li5ⁱⁱ	84.35 (5)	Li6B—Li4—Li7	64.21 (14)
Si1ⁱ—Si1—Li7	131.60 (2)	Li6B^viii—Li4—Li7	154.5 (2)
Li6A—Si1—Li7	75.63 (5)	Li3ⁱⁱ—Li4—Li7^viii	124.20 (2)
Li5ⁱⁱ—Si1—Li7	159.98 (3)	Li3—Li4—Li7^viii	87.21 (3)
Si1ⁱ—Si1—Li1ⁱⁱⁱ	69.231 (19)	Li6B—Li4—Li7^viii	154.5 (2)
Li6A—Si1—Li1ⁱⁱⁱ	121.62 (2)	Li6B^viii—Li4—Li7^viii	64.21 (14)
Li5ⁱⁱ—Si1—Li1ⁱⁱⁱ	107.13 (2)	Li7—Li4—Li7^viii	109.66 (4)
Li7—Si1—Li1ⁱⁱⁱ	83.90 (2)	Li3ⁱⁱ—Li4—Li1^iv	90.90 (4)
Si1ⁱ—Si1—Li1^iv	69.231 (19)	Li3—Li4—Li1^iv	161.67 (4)
Li6A—Si1—Li1^iv	121.62 (2)	Li6B—Li4—Li1^iv	119.34 (14)
Li5ⁱⁱ—Si1—Li1^iv	107.13 (2)	Li6B^viii—Li4—Li1^iv	119.34 (14)
Li7—Si1—Li1^iv	83.90 (2)	Li7—Li4—Li1^iv	82.28 (3)
Li1ⁱⁱⁱ—Si1—Li1^iv	109.32 (3)	Li7^viii—Li4—Li1^iv	82.28 (3)
Si1ⁱ—Si1—Li5ⁱⁱⁱ	60.62 (2)	Li3ⁱⁱ—Li4—Si2^xiii	163.90 (4)
Li6A—Si1—Li5ⁱⁱⁱ	146.60 (5)	Li3—Li4—Si2^xiii	56.47 (3)
Li5ⁱⁱ—Si1—Li5ⁱⁱⁱ	129.047 (16)	Li6B—Li4—Si2^xiii	99.3 (2)
Li7—Si1—Li5ⁱⁱⁱ	70.97 (3)	Li6B^viii—Li4—Si2^xiii	99.3 (2)
Li1ⁱⁱⁱ—Si1—Li5ⁱⁱⁱ	55.100 (14)	Li7—Li4—Si2^xiii	59.65 (2)
Li1^iv—Si1—Li5ⁱⁱⁱ	55.100 (14)	Li7^viii—Li4—Si2^xiii	59.65 (2)
Si1ⁱ—Si1—Li4^v	127.050 (14)	Li1^iv—Li4—Si2^xiii	105.20 (3)
Li6A—Si1—Li4^v	62.45 (3)	Li3ⁱⁱ—Li4—Si1	71.60 (2)
Li5ⁱⁱ—Si1—Li4^v	111.752 (19)	Li3—Li4—Si1	127.412 (15)
Li7—Si1—Li4^v	58.678 (17)	Li6B—Li4—Si1	61.57 (14)
Li1ⁱⁱⁱ—Si1—Li4^v	60.17 (2)	Li6B^viii—Li4—Si1	143.5 (2)
Li1^iv—Si1—Li4^v	141.10 (3)	Li7—Li4—Si1	58.048 (18)
Li5ⁱⁱⁱ—Si1—Li4^v	98.97 (2)	Li7^viii—Li4—Si1	138.51 (4)
Si1ⁱ—Si1—Li4	127.051 (14)	Li1^iv—Li4—Si1	57.815 (16)
Li6A—Si1—Li4	62.45 (3)	Si2^xiii—Li4—Si1	116.896 (19)
Li5ⁱⁱ—Si1—Li4	111.752 (19)	Li3ⁱⁱ—Li4—Si1^viii	71.60 (2)
Li7—Si1—Li4	58.678 (17)	Li3—Li4—Si1^viii	127.413 (15)
Li1ⁱⁱⁱ—Si1—Li4	141.10 (3)	Li6B—Li4—Si1^viii	143.5 (2)
Li1^iv—Si1—Li4	60.17 (2)	Li6B^viii—Li4—Si1^viii	61.57 (14)
Li5ⁱⁱⁱ—Si1—Li4	98.97 (2)	Li7—Li4—Si1^viii	138.51 (4)
Li4^v—Si1—Li4	102.86 (3)	Li7^viii—Li4—Si1^viii	58.048 (18)
Si1ⁱ—Si1—Li6B	165.72 (19)	Li1^iv—Li4—Si1^viii	57.814 (16)
Li6A—Si1—Li6B	12.94 (15)	Si2^xiii—Li4—Si1^viii	116.896 (19)
Li5ⁱⁱ—Si1—Li6B	97.30 (19)	Si1—Li4—Si1^viii	102.86 (3)
Li7—Si1—Li6B	62.68 (19)	Li3ⁱⁱ—Li4—Li6A^viii	59.80 (4)
Li1ⁱⁱⁱ—Si1—Li6B	117.15 (8)	Li3—Li4—Li6A^viii	78.11 (4)
Li1^iv—Si1—Li6B	117.15 (8)	Li6B—Li4—Li6A^viii	107.55 (12)
Li5ⁱⁱⁱ—Si1—Li6B	133.66 (19)	Li6B^viii—Li4—Li6A^viii	13.10 (18)
Li4^v—Si1—Li6B	57.02 (7)	Li7—Li4—Li6A^viii	165.17 (5)
Li4—Si1—Li6B	57.02 (7)	Li7^viii—Li4—Li6A^viii	72.11 (3)
Si1ⁱ—Si1—Li1^vi	61.073 (16)	Li1^iv—Li4—Li6A^viii	112.45 (4)
Li6A—Si1—Li1^vi	103.56 (3)	Si2^xiii—Li4—Li6A^viii	112.31 (5)
Li5ⁱⁱ—Si1—Li1^vi	54.856 (16)	Si1—Li4—Li6A^viii	130.66 (5)
Li7—Si1—Li1^vi	129.866 (14)	Si1^viii—Li4—Li6A^viii	55.47 (3)
Li1ⁱⁱⁱ—Si1—Li1^vi	53.20 (3)	Li3ⁱⁱ—Li4—Li6A	59.80 (4)
Li1^iv—Si1—Li1^vi	130.304 (9)	Li3—Li4—Li6A	78.10 (4)
Li5ⁱⁱⁱ—Si1—Li1^vi	97.78 (2)	Li6B—Li4—Li6A	13.10 (18)
Li4^v—Si1—Li1^vi	76.29 (2)	Li6B^viii—Li4—Li6A	107.55 (12)
Li4—Si1—Li1^vi	163.14 (2)	Li7—Li4—Li6A	72.11 (3)
Li6B—Si1—Li1^vi	111.30 (11)	Li7^viii—Li4—Li6A	165.17 (5)
Si1ⁱ—Si1—Li1ⁱⁱ	61.073 (16)	Li1^iv—Li4—Li6A	112.45 (4)
Li6A—Si1—Li1ⁱⁱ	103.56 (3)	Si2^xiii—Li4—Li6A	112.31 (5)
Li5ⁱⁱ—Si1—Li1ⁱⁱ	54.856 (16)	Si1—Li4—Li6A	55.47 (3)
Li7—Si1—Li1ⁱⁱ	129.866 (14)	Si1^viii—Li4—Li6A	130.66 (5)
Li1ⁱⁱⁱ—Si1—Li1ⁱⁱ	130.304 (9)	Li6A^viii—Li4—Li6A	102.37 (5)
Li1^iv—Si1—Li1ⁱⁱ	53.20 (3)	Li6B—Li5—Li1	116.63 (6)
Li5ⁱⁱⁱ—Si1—Li1ⁱⁱ	97.78 (2)	Li6B—Li5—Li1^v	116.63 (6)
Li4^v—Si1—Li1ⁱⁱ	163.14 (2)	Li1—Li5—Li1^v	119.19 (5)
Li4—Si1—Li1ⁱⁱ	76.29 (2)	Li6B—Li5—Li7ⁱⁱ	71.7 (2)
Li6B—Si1—Li1ⁱⁱ	111.30 (11)	Li1—Li5—Li7ⁱⁱ	111.36 (3)
Li1^vi—Si1—Li1ⁱⁱ	99.56 (3)	Li1^v—Li5—Li7ⁱⁱ	111.36 (3)
Li2^vii—Si2—Li3	117.17 (2)	Li6B—Li5—Si1^xiii	111.6 (2)
Li2^vii—Si2—Li3ⁱⁱ	131.38 (2)	Li1—Li5—Si1^xiii	67.45 (3)
Li3—Si2—Li3ⁱⁱ	111.451 (16)	Li1^v—Li5—Si1^xiii	67.45 (3)
Li2^vii—Si2—Li6A	121.49 (2)	Li7ⁱⁱ—Li5—Si1^xiii	176.78 (5)
Li3—Si2—Li6A	83.51 (5)	Li6B—Li5—Li6A	12.67 (19)
Li3ⁱⁱ—Si2—Li6A	63.18 (4)	Li1—Li5—Li6A	119.26 (3)
Li2^vii—Si2—Li6A^viii	121.49 (2)	Li1^v—Li5—Li6A	119.26 (3)
Li3—Si2—Li6A^viii	83.51 (5)	Li7ⁱⁱ—Li5—Li6A	58.99 (5)
Li3ⁱⁱ—Si2—Li6A^viii	63.18 (4)	Si1^xiii—Li5—Li6A	124.23 (6)
Li6A—Si2—Li6A^viii	114.48 (4)	Li6B—Li5—Si2	62.07 (9)
Li2^vii—Si2—Li6B^viii	123.03 (10)	Li1—Li5—Si2	65.853 (16)
Li3—Si2—Li6B^viii	70.1 (2)	Li1^v—Li5—Si2	172.86 (4)
Li3ⁱⁱ—Si2—Li6B^viii	73.51 (18)	Li7ⁱⁱ—Li5—Si2	61.506 (17)
Li6A—Si2—Li6B^viii	115.43 (10)	Si1^xiii—Li5—Si2	119.680 (19)
Li6A^viii—Si2—Li6B^viii	14.03 (17)	Li6A—Li5—Si2	57.78 (2)
Li2^vii—Si2—Li6B	123.03 (10)	Li6B—Li5—Si2^v	62.07 (9)
Li3—Si2—Li6B	70.1 (2)	Li1—Li5—Si2^v	172.86 (4)
Li3ⁱⁱ—Si2—Li6B	73.51 (18)	Li1^v—Li5—Si2^v	65.854 (16)
Li6A—Si2—Li6B	14.03 (17)	Li7ⁱⁱ—Li5—Si2^v	61.506 (17)
Li6A^viii—Si2—Li6B	115.43 (10)	Si1^xiii—Li5—Si2^v	119.680 (19)
Li6B^viii—Si2—Li6B	112.6 (2)	Li6A—Li5—Si2^v	57.78 (2)
Li2^vii—Si2—Li5	76.21 (2)	Si2—Li5—Si2^v	108.66 (3)
Li3—Si2—Li5	68.62 (2)	Li6B—Li5—Si1^xi	162.5 (2)
Li3ⁱⁱ—Si2—Li5	123.840 (16)	Li1—Li5—Si1^xi	60.12 (2)
Li6A—Si2—Li5	61.08 (4)	Li1^v—Li5—Si1^xi	60.12 (2)
Li6A^viii—Si2—Li5	151.98 (5)	Li7ⁱⁱ—Li5—Si1^xi	125.82 (4)
Li6B^viii—Si2—Li5	138.7 (2)	Si1^xiii—Li5—Si1^xi	50.954 (16)
Li6B—Si2—Li5	53.11 (15)	Li6A—Li5—Si1^xi	175.18 (6)
Li2^vii—Si2—Li5^viii	76.21 (2)	Si2—Li5—Si1^xi	123.439 (18)
Li3—Si2—Li5^viii	68.62 (2)	Si2^v—Li5—Si1^xi	123.440 (18)
Li3ⁱⁱ—Si2—Li5^viii	123.840 (16)	Li6B—Li5—Li3	66.78 (13)
Li6A—Si2—Li5^viii	151.98 (5)	Li1—Li5—Li3	53.88 (3)
Li6A^viii—Si2—Li5^viii	61.08 (4)	Li1^v—Li5—Li3	133.34 (4)
Li6B^viii—Si2—Li5^viii	53.11 (15)	Li7ⁱⁱ—Li5—Li3	113.18 (3)
Li6B—Si2—Li5^viii	138.7 (2)	Si1^xiii—Li5—Li3	68.76 (2)
Li5—Si2—Li5^viii	108.66 (3)	Li6A—Li5—Li3	74.63 (4)
Li2^vii—Si2—Li7ⁱⁱ	65.184 (19)	Si2—Li5—Li3	53.408 (19)
Li3—Si2—Li7ⁱⁱ	124.026 (15)	Si2^v—Li5—Li3	127.28 (4)
Li3ⁱⁱ—Si2—Li7ⁱⁱ	88.12 (3)	Si1^xi—Li5—Li3	102.25 (3)
Li6A—Si2—Li7ⁱⁱ	58.76 (3)	Li6B—Li5—Li3^v	66.78 (13)
Li6A^viii—Si2—Li7ⁱⁱ	147.18 (5)	Li1—Li5—Li3^v	133.34 (4)
Li6B^viii—Si2—Li7ⁱⁱ	160.6 (2)	Li1^v—Li5—Li3^v	53.88 (3)
Li6B—Si2—Li7ⁱⁱ	66.34 (14)	Li7ⁱⁱ—Li5—Li3^v	113.18 (3)
Li5—Si2—Li7ⁱⁱ	57.56 (2)	Si1^xiii—Li5—Li3^v	68.76 (2)
Li5^viii—Si2—Li7ⁱⁱ	140.93 (3)	Li6A—Li5—Li3^v	74.63 (4)
Li2^vii—Si2—Li7^ix	65.184 (18)	Si2—Li5—Li3^v	127.28 (4)
Li3—Si2—Li7^ix	124.026 (15)	Si2^v—Li5—Li3^v	53.408 (19)
Li3ⁱⁱ—Si2—Li7^ix	88.12 (3)	Si1^xi—Li5—Li3^v	102.25 (3)
Li6A—Si2—Li7^ix	147.18 (5)	Li3—Li5—Li3^v	95.40 (4)
Li6A^viii—Si2—Li7^ix	58.77 (3)	Li6B—Li5—Li7^xi	145.0 (2)
Li6B^viii—Si2—Li7^ix	66.34 (14)	Li1—Li5—Li7^xi	76.56 (3)
Li6B—Si2—Li7^ix	160.6 (2)	Li1^v—Li5—Li7^xi	76.56 (3)
Li5—Si2—Li7^ix	140.93 (3)	Li7ⁱⁱ—Li5—Li7^xi	73.37 (4)
Li5^viii—Si2—Li7^ix	57.56 (2)	Si1^xiii—Li5—Li7^xi	103.41 (3)
Li7ⁱⁱ—Si2—Li7^ix	107.80 (3)	Li6A—Li5—Li7^xi	132.36 (5)
Li2^vii—Si2—Li4ⁱⁱ	72.216 (17)	Si2—Li5—Li7^xi	100.64 (2)
Li3—Si2—Li4ⁱⁱ	170.62 (3)	Si2^v—Li5—Li7^xi	100.64 (2)
Li3ⁱⁱ—Si2—Li4ⁱⁱ	59.16 (3)	Si1^xi—Li5—Li7^xi	52.46 (2)
Li6A—Si2—Li4ⁱⁱ	91.45 (5)	Li3—Li5—Li7^xi	129.47 (2)
Li6A^viii—Si2—Li4ⁱⁱ	91.45 (5)	Li3^v—Li5—Li7^xi	129.47 (2)
Li6B^viii—Si2—Li4ⁱⁱ	105.3 (2)	Si2^v—Li6A—Si2	114.48 (4)
Li6B—Si2—Li4ⁱⁱ	105.3 (2)	Si2^v—Li6A—Li7ⁱⁱ	62.65 (2)
Li5—Si2—Li4ⁱⁱ	115.713 (19)	Si2—Li6A—Li7ⁱⁱ	62.65 (2)
Li5^viii—Si2—Li4ⁱⁱ	115.713 (19)	Si2^v—Li6A—Si1	122.72 (2)
Li7ⁱⁱ—Si2—Li4ⁱⁱ	58.534 (15)	Si2—Li6A—Si1	122.72 (2)
Li7^ix—Si2—Li4ⁱⁱ	58.534 (15)	Li7ⁱⁱ—Li6A—Si1	145.53 (10)
Li1^x—Li1—Li3	99.26 (5)	Si2^v—Li6A—Li5	61.14 (3)
Li1^x—Li1—Li5^viii	116.21 (3)	Si2—Li6A—Li5	61.14 (3)
Li3—Li1—Li5^viii	71.64 (3)	Li7ⁱⁱ—Li6A—Li5	58.76 (3)
Li1^x—Li1—Li5	116.21 (3)	Si1—Li6A—Li5	155.71 (9)
Li3—Li1—Li5	71.64 (3)	Si2^v—Li6A—Li3^vi	57.60 (2)
Li5^viii—Li1—Li5	119.19 (5)	Si2—Li6A—Li3^vi	145.67 (8)
Li1^x—Li1—Si1^vii	67.17 (2)	Li7ⁱⁱ—Li6A—Li3^vi	87.22 (5)
Li3—Li1—Si1^vii	119.07 (2)	Si1—Li6A—Li3^vi	73.07 (4)
Li5^viii—Li1—Si1^vii	64.776 (18)	Li5—Li6A—Li3^vi	118.37 (3)
Li5—Li1—Si1^vii	168.80 (4)	Si2^v—Li6A—Li3ⁱⁱ	145.67 (8)
Li1^x—Li1—Si1^xi	67.17 (2)	Si2—Li6A—Li3ⁱⁱ	57.61 (2)
Li3—Li1—Si1^xi	119.07 (2)	Li7ⁱⁱ—Li6A—Li3ⁱⁱ	87.22 (5)
Li5^viii—Li1—Si1^xi	168.80 (4)	Si1—Li6A—Li3ⁱⁱ	73.07 (4)
Li5—Li1—Si1^xi	64.776 (18)	Li5—Li6A—Li3ⁱⁱ	118.37 (3)
Si1^vii—Li1—Si1^xi	109.32 (3)	Li3^vi—Li6A—Li3ⁱⁱ	108.10 (8)
Li1^x—Li1—Li4^vii	83.64 (4)	Si2^v—Li6A—Li4	156.71 (9)
Li3—Li1—Li4^vii	177.10 (5)	Si2—Li6A—Li4	66.92 (2)
Li5^viii—Li1—Li4^vii	107.13 (3)	Li7ⁱⁱ—Li6A—Li4	128.45 (2)
Li5—Li1—Li4^vii	107.13 (3)	Si1—Li6A—Li4	62.08 (3)
Si1^vii—Li1—Li4^vii	62.011 (17)	Li5—Li6A—Li4	104.80 (6)
Si1^xi—Li1—Li4^vii	62.012 (18)	Li3^vi—Li6A—Li4	134.98 (5)
Li1^x—Li1—Li2^vii	152.08 (6)	Li3ⁱⁱ—Li6A—Li4	56.31 (3)
Li3—Li1—Li2^vii	108.66 (4)	Si2^v—Li6A—Li4^v	66.92 (2)
Li5^viii—Li1—Li2^vii	74.07 (3)	Si2—Li6A—Li4^v	156.71 (9)
Li5—Li1—Li2^vii	74.07 (3)	Li7ⁱⁱ—Li6A—Li4^v	128.45 (2)
Si1^vii—Li1—Li2^vii	98.16 (2)	Si1—Li6A—Li4^v	62.08 (3)
Si1^xi—Li1—Li2^vii	98.16 (2)	Li5—Li6A—Li4^v	104.80 (6)
Li4^vii—Li1—Li2^vii	68.44 (3)	Li3^vi—Li6A—Li4^v	56.31 (3)
Li1^x—Li1—Si2	155.65 (6)	Li3ⁱⁱ—Li6A—Li4^v	134.98 (5)
Li3—Li1—Si2	56.39 (3)	Li4—Li6A—Li4^v	102.37 (5)
Li5^viii—Li1—Si2	59.72 (2)	Si2^v—Li6A—Li7	110.22 (5)
Li5—Li1—Si2	59.72 (2)	Si2—Li6A—Li7	110.22 (5)
Si1^vii—Li1—Si2	122.029 (17)	Li7ⁱⁱ—Li6A—Li7	161.59 (8)
Si1^xi—Li1—Si2	122.029 (17)	Si1—Li6A—Li7	52.88 (3)
Li4^vii—Li1—Si2	120.71 (4)	Li5—Li6A—Li7	102.83 (7)
Li2^vii—Li1—Si2	52.269 (16)	Li3^vi—Li6A—Li7	103.34 (4)
Li1^x—Li1—Si1^xii	59.63 (2)	Li3ⁱⁱ—Li6A—Li7	103.34 (4)
Li3—Li1—Si1^xii	71.64 (2)	Li4—Li6A—Li7	52.06 (3)
Li5^viii—Li1—Si1^xii	57.691 (19)	Li4^v—Li6A—Li7	52.06 (3)
Li5—Li1—Si1^xii	141.50 (4)	Si2^v—Li6A—Li3	113.47 (6)
Si1^vii—Li1—Si1^xii	49.695 (9)	Si2—Li6A—Li3	47.61 (3)
Si1^xi—Li1—Si1^xii	126.80 (3)	Li7ⁱⁱ—Li6A—Li3	99.65 (4)
Li4^vii—Li1—Si1^xii	110.06 (2)	Si1—Li6A—Li3	106.70 (5)
Li2^vii—Li1—Si1^xii	129.406 (14)	Li5—Li6A—Li3	56.23 (4)
Si2—Li1—Si1^xii	107.16 (2)	Li3^vi—Li6A—Li3	164.63 (7)
Li1^x—Li1—Si1^xiii	59.63 (2)	Li3ⁱⁱ—Li6A—Li3	86.09 (2)
Li3—Li1—Si1^xiii	71.64 (2)	Li4—Li6A—Li3	48.69 (3)
Li5^viii—Li1—Si1^xiii	141.50 (4)	Li4^v—Li6A—Li3	109.49 (7)
Li5—Li1—Si1^xiii	57.691 (19)	Li7—Li6A—Li3	66.64 (4)
Si1^vii—Li1—Si1^xiii	126.80 (3)	Si2^v—Li6A—Li3^v	47.61 (3)
Si1^xi—Li1—Si1^xiii	49.695 (9)	Si2—Li6A—Li3^v	113.47 (6)
Li4^vii—Li1—Si1^xiii	110.06 (2)	Li7ⁱⁱ—Li6A—Li3^v	99.65 (4)
Li2^vii—Li1—Si1^xiii	129.406 (14)	Si1—Li6A—Li3^v	106.70 (5)
Si2—Li1—Si1^xiii	107.16 (2)	Li5—Li6A—Li3^v	56.23 (4)
Si1^xii—Li1—Si1^xiii	99.56 (3)	Li3^vi—Li6A—Li3^v	86.09 (2)
Si2^xiii—Li2—Si2^iv	180.000 (4)	Li3ⁱⁱ—Li6A—Li3^v	164.63 (7)
Si2^xiii—Li2—Li1^xiii	65.859 (17)	Li4—Li6A—Li3^v	109.48 (7)
Si2^iv—Li2—Li1^xiii	114.141 (17)	Li4^v—Li6A—Li3^v	48.69 (3)
Si2^xiii—Li2—Li1^iv	114.142 (17)	Li7—Li6A—Li3^v	66.64 (4)
Si2^iv—Li2—Li1^iv	65.859 (17)	Li3—Li6A—Li3^v	79.23 (5)
Li1^xiii—Li2—Li1^iv	180.0	Li5—Li6B—Si2^v	64.82 (11)
Si2^xiii—Li2—Li7^viii	61.584 (16)	Li5—Li6B—Si2	64.82 (11)
Si2^iv—Li2—Li7^viii	118.416 (16)	Si2^v—Li6B—Si2	112.6 (2)
Li1^xiii—Li2—Li7^viii	99.849 (19)	Li5—Li6B—Li4	119.1 (2)
Li1^iv—Li2—Li7^viii	80.151 (19)	Si2^v—Li6B—Li4	175.5 (4)
Si2^xiii—Li2—Li7^xiv	118.417 (16)	Si2—Li6B—Li4	68.579 (18)
Si2^iv—Li2—Li7^xiv	61.583 (16)	Li5—Li6B—Li4^v	119.1 (2)
Li1^xiii—Li2—Li7^xiv	80.151 (19)	Si2^v—Li6B—Li4^v	68.579 (19)
Li1^iv—Li2—Li7^xiv	99.849 (19)	Si2—Li6B—Li4^v	175.5 (4)
Li7^viii—Li2—Li7^xiv	180.0	Li4—Li6B—Li4^v	109.86 (19)
Si2^xiii—Li2—Li7^xv	118.417 (16)	Li5—Li6B—Si1	178.7 (4)
Si2^iv—Li2—Li7^xv	61.583 (16)	Si2^v—Li6B—Si1	114.7 (2)
Li1^xiii—Li2—Li7^xv	80.151 (19)	Si2—Li6B—Si1	114.7 (2)
Li1^iv—Li2—Li7^xv	99.849 (19)	Li4—Li6B—Si1	61.41 (11)
Li7^viii—Li2—Li7^xv	76.94 (3)	Li4^v—Li6B—Si1	61.41 (11)
Li7^xiv—Li2—Li7^xv	103.06 (3)	Li5—Li6B—Li7	125.1 (4)
Si2^xiii—Li2—Li7	61.584 (16)	Si2^v—Li6B—Li7	122.40 (15)
Si2^iv—Li2—Li7	118.417 (16)	Si2—Li6B—Li7	122.40 (15)
Li1^xiii—Li2—Li7	99.850 (19)	Li4—Li6B—Li7	57.95 (11)
Li1^iv—Li2—Li7	80.151 (19)	Li4^v—Li6B—Li7	57.95 (11)
Li7^viii—Li2—Li7	103.06 (3)	Si1—Li6B—Li7	56.18 (10)
Li7^xiv—Li2—Li7	76.94 (3)	Li5—Li6B—Li7ⁱⁱ	57.68 (13)
Li7^xv—Li2—Li7	180.0	Si2^v—Li6B—Li7ⁱⁱ	58.12 (12)
Si2^xiii—Li2—Li4^xv	121.622 (16)	Si2—Li6B—Li7ⁱⁱ	58.12 (12)
Si2^iv—Li2—Li4^xv	58.378 (16)	Li4—Li6B—Li7ⁱⁱ	121.27 (18)
Li1^xiii—Li2—Li4^xv	55.76 (2)	Li4^v—Li6B—Li7ⁱⁱ	121.27 (18)
Li1^iv—Li2—Li4^xv	124.24 (2)	Si1—Li6B—Li7ⁱⁱ	121.0 (3)
Li7^viii—Li2—Li4^xv	126.209 (14)	Li7—Li6B—Li7ⁱⁱ	177.2 (4)
Li7^xiv—Li2—Li4^xv	53.791 (15)	Li5—Li6B—Li3	65.94 (17)
Li7^xv—Li2—Li4^xv	53.791 (15)	Si2^v—Li6B—Li3	129.1 (3)
Li7—Li2—Li4^xv	126.210 (14)	Si2—Li6B—Li3	53.69 (8)
Si2^xiii—Li2—Li4	58.378 (16)	Li4—Li6B—Li3	55.26 (9)
Si2^iv—Li2—Li4	121.622 (16)	Li4^v—Li6B—Li3	129.3 (3)
Li1^xiii—Li2—Li4	124.24 (2)	Si1—Li6B—Li3	114.84 (14)
Li1^iv—Li2—Li4	55.76 (2)	Li7—Li6B—Li3	77.97 (19)
Li7^viii—Li2—Li4	53.791 (14)	Li7ⁱⁱ—Li6B—Li3	103.89 (14)
Li7^xiv—Li2—Li4	126.210 (14)	Li5—Li6B—Li3^v	65.94 (17)
Li7^xv—Li2—Li4	126.210 (14)	Si2^v—Li6B—Li3^v	53.69 (8)
Li7—Li2—Li4	53.790 (15)	Si2—Li6B—Li3^v	129.1 (3)
Li4^xv—Li2—Li4	180.0	Li4—Li6B—Li3^v	129.3 (3)
Si2^xiii—Li2—Li5ⁱⁱⁱ	124.896 (15)	Li4^v—Li6B—Li3^v	55.26 (9)
Si2^iv—Li2—Li5ⁱⁱⁱ	55.104 (15)	Si1—Li6B—Li3^v	114.84 (14)
Li1^xiii—Li2—Li5ⁱⁱⁱ	130.096 (14)	Li7—Li6B—Li3^v	77.97 (19)
Li1^iv—Li2—Li5ⁱⁱⁱ	49.904 (14)	Li7ⁱⁱ—Li6B—Li3^v	103.89 (14)
Li7^viii—Li2—Li5ⁱⁱⁱ	129.00 (2)	Li3—Li6B—Li3^v	94.6 (3)
Li7^xiv—Li2—Li5ⁱⁱⁱ	51.00 (2)	Li5—Li6B—Li3^vi	114.65 (17)
Li7^xv—Li2—Li5ⁱⁱⁱ	116.42 (2)	Si2^v—Li6B—Li3^vi	52.18 (10)
Li7—Li2—Li5ⁱⁱⁱ	63.58 (2)	Si2—Li6B—Li3^vi	124.0 (3)
Li4^xv—Li2—Li5ⁱⁱⁱ	94.745 (17)	Li4—Li6B—Li3^vi	123.4 (3)
Li4—Li2—Li5ⁱⁱⁱ	85.255 (17)	Li4^v—Li6B—Li3^vi	52.90 (9)
Si2^xiii—Li2—Li5^iv	124.896 (15)	Si1—Li6B—Li3^vi	64.52 (16)
Si2^iv—Li2—Li5^iv	55.104 (15)	Li7—Li6B—Li3^vi	103.25 (14)
Li1^xiii—Li2—Li5^iv	130.096 (14)	Li7ⁱⁱ—Li6B—Li3^vi	74.81 (18)
Li1^iv—Li2—Li5^iv	49.904 (14)	Li3—Li6B—Li3^vi	177.4 (3)
Li7^viii—Li2—Li5^iv	63.58 (2)	Li3^v—Li6B—Li3^vi	87.879 (16)
Li7^xiv—Li2—Li5^iv	116.42 (2)	Li5—Li6B—Li3ⁱⁱ	114.65 (17)
Li7^xv—Li2—Li5^iv	51.00 (2)	Si2^v—Li6B—Li3ⁱⁱ	124.0 (3)
Li7—Li2—Li5^iv	129.00 (2)	Si2—Li6B—Li3ⁱⁱ	52.18 (10)
Li4^xv—Li2—Li5^iv	94.745 (17)	Li4—Li6B—Li3ⁱⁱ	52.90 (9)
Li4—Li2—Li5^iv	85.255 (17)	Li4^v—Li6B—Li3ⁱⁱ	123.4 (3)
Li5ⁱⁱⁱ—Li2—Li5^iv	86.65 (2)	Si1—Li6B—Li3ⁱⁱ	64.52 (16)
Li1—Li3—Si2	68.32 (3)	Li7—Li6B—Li3ⁱⁱ	103.25 (14)
Li1—Li3—Si2^xiii	156.96 (5)	Li7ⁱⁱ—Li6B—Li3ⁱⁱ	74.81 (18)
Si2—Li3—Si2^xiii	134.72 (4)	Li3—Li6B—Li3ⁱⁱ	87.879 (16)
Li1—Li3—Li4^xiii	86.20 (4)	Li3^v—Li6B—Li3ⁱⁱ	177.4 (3)
Si2—Li3—Li4^xiii	154.51 (5)	Li3^vi—Li6B—Li3ⁱⁱ	89.6 (3)
Si2^xiii—Li3—Li4^xiii	70.77 (3)	Li5^xiii—Li7—Li6A^xiii	62.25 (5)
Li1—Li3—Li4	138.67 (5)	Li5^xiii—Li7—Si1	163.20 (4)
Si2—Li3—Li4	70.35 (3)	Li6A^xiii—Li7—Si1	134.55 (6)
Si2^xiii—Li3—Li4	64.37 (3)	Li5^xiii—Li7—Li4^v	122.31 (2)
Li4^xiii—Li3—Li4	135.14 (4)	Li6A^xiii—Li7—Li4^v	93.38 (4)
Li1—Li3—Li6A^xii	111.01 (3)	Si1—Li7—Li4^v	63.27 (2)
Si2—Li3—Li6A^xii	124.37 (4)	Li5^xiii—Li7—Li4	122.31 (2)
Si2^xiii—Li3—Li6A^xii	59.21 (3)	Li6A^xiii—Li7—Li4	93.38 (4)
Li4^xiii—Li3—Li6A^xii	63.89 (4)	Si1—Li7—Li4	63.27 (2)
Li4—Li3—Li6A^xii	92.17 (4)	Li4^v—Li7—Li4	109.66 (4)
Li1—Li3—Li6A^xiii	111.01 (3)	Li5^xiii—Li7—Si2^xiii	60.933 (17)
Si2—Li3—Li6A^xiii	124.37 (4)	Li6A^xiii—Li7—Si2^xiii	58.58 (2)
Si2^xiii—Li3—Li6A^xiii	59.21 (3)	Si1—Li7—Si2^xiii	124.156 (15)
Li4^xiii—Li3—Li6A^xiii	63.89 (4)	Li4^v—Li7—Si2^xiii	148.06 (4)
Li4—Li3—Li6A^xiii	92.17 (4)	Li4—Li7—Si2^xiii	61.815 (18)
Li6A^xii—Li3—Li6A^xiii	108.10 (8)	Li5^xiii—Li7—Si2^xvi	60.933 (17)
Li1—Li3—Li5	54.48 (2)	Li6A^xiii—Li7—Si2^xvi	58.58 (2)
Si2—Li3—Li5	57.97 (2)	Si1—Li7—Si2^xvi	124.156 (15)
Si2^xiii—Li3—Li5	131.88 (2)	Li4^v—Li7—Si2^xvi	61.815 (18)
Li4^xiii—Li3—Li5	107.49 (3)	Li4—Li7—Si2^xvi	148.06 (4)
Li4—Li3—Li5	102.23 (3)	Si2^xiii—Li7—Si2^xvi	107.79 (3)
Li6A^xii—Li3—Li5	164.79 (5)	Li5^xiii—Li7—Li2^v	72.37 (2)
Li6A^xiii—Li3—Li5	76.55 (4)	Li6A^xiii—Li7—Li2^v	109.87 (3)
Li1—Li3—Li5^viii	54.48 (2)	Si1—Li7—Li2^v	97.64 (2)
Si2—Li3—Li5^viii	57.97 (2)	Li4^v—Li7—Li2^v	68.809 (17)
Si2^xiii—Li3—Li5^viii	131.88 (2)	Li4—Li7—Li2^v	156.71 (4)
Li4^xiii—Li3—Li5^viii	107.48 (3)	Si2^xiii—Li7—Li2^v	131.80 (3)
Li4—Li3—Li5^viii	102.23 (3)	Si2^xvi—Li7—Li2^v	53.233 (8)
Li6A^xii—Li3—Li5^viii	76.55 (4)	Li5^xiii—Li7—Li2	72.37 (2)
Li6A^xiii—Li3—Li5^viii	164.79 (5)	Li6A^xiii—Li7—Li2	109.87 (3)
Li5—Li3—Li5^viii	95.40 (4)	Si1—Li7—Li2	97.64 (2)
Li1—Li3—Li6B	98.86 (11)	Li4^v—Li7—Li2	156.71 (4)
Si2—Li3—Li6B	56.17 (14)	Li4—Li7—Li2	68.810 (17)
Si2^xiii—Li3—Li6B	96.70 (11)	Si2^xiii—Li7—Li2	53.233 (8)
Li4^xiii—Li3—Li6B	132.00 (14)	Si2^xvi—Li7—Li2	131.80 (3)
Li4—Li3—Li6B	56.51 (11)	Li2^v—Li7—Li2	103.06 (3)
Li6A^xii—Li3—Li6B	147.86 (12)	Li5^xiii—Li7—Li6B	135.66 (19)
Li6A^xiii—Li3—Li6B	69.93 (11)	Li6A^xiii—Li7—Li6B	73.41 (15)
Li5—Li3—Li6B	47.28 (10)	Si1—Li7—Li6B	61.14 (18)
Li5^viii—Li3—Li6B	114.13 (14)	Li4^v—Li7—Li6B	57.84 (5)
Li1—Li3—Li6B^viii	98.86 (11)	Li4—Li7—Li6B	57.84 (5)
Si2—Li3—Li6B^viii	56.17 (14)	Si2^xiii—Li7—Li6B	96.57 (11)
Si2^xiii—Li3—Li6B^viii	96.70 (11)	Si2^xvi—Li7—Li6B	96.57 (11)
Li4^xiii—Li3—Li6B^viii	132.00 (14)	Li2^v—Li7—Li6B	126.62 (4)
Li4—Li3—Li6B^viii	56.51 (11)	Li2—Li7—Li6B	126.62 (4)
Li6A^xii—Li3—Li6B^viii	69.93 (11)	Li5^xiii—Li7—Li6B^xiii	50.66 (18)
Li6A^xiii—Li3—Li6B^viii	147.86 (12)	Li6A^xiii—Li7—Li6B^xiii	11.59 (14)
Li5—Li3—Li6B^viii	114.13 (14)	Si1—Li7—Li6B^xiii	146.14 (18)
Li5^viii—Li3—Li6B^viii	47.28 (10)	Li4^v—Li7—Li6B^xiii	99.96 (10)
Li6B—Li3—Li6B^viii	94.6 (3)	Li4—Li7—Li6B^xiii	99.96 (10)
Li1—Li3—Li6B^xii	112.27 (10)	Si2^xiii—Li7—Li6B^xiii	55.54 (4)
Si2—Li3—Li6B^xii	134.21 (13)	Si2^xvi—Li7—Li6B^xiii	55.54 (4)
Si2^xiii—Li3—Li6B^xii	54.31 (10)	Li2^v—Li7—Li6B^xiii	103.19 (11)
Li4^xiii—Li3—Li6B^xii	55.03 (13)	Li2—Li7—Li6B^xiii	103.19 (11)
Li4—Li3—Li6B^xii	96.40 (11)	Li6B—Li7—Li6B^xiii	85.00 (3)
Li6A^xii—Li3—Li6B^xii	9.86 (10)	Li5^xiii—Li7—Li5ⁱⁱⁱ	106.63 (4)
Li6A^xiii—Li3—Li6B^xii	98.97 (16)	Li6A^xiii—Li7—Li5ⁱⁱⁱ	168.88 (6)
Li5—Li3—Li6B^xii	160.95 (12)	Si1—Li7—Li5ⁱⁱⁱ	56.57 (2)
Li5^viii—Li3—Li6B^xii	84.41 (12)	Li4^v—Li7—Li5ⁱⁱⁱ	93.01 (3)
Li6B—Li3—Li6B^xii	148.83 (4)	Li4—Li7—Li5ⁱⁱⁱ	93.02 (3)
Li6B^viii—Li3—Li6B^xii	79.609 (14)	Si2^xiii—Li7—Li5ⁱⁱⁱ	117.29 (2)
Li3ⁱⁱ—Li4—Li3	107.43 (3)	Si2^xvi—Li7—Li5ⁱⁱⁱ	117.29 (2)
Li3ⁱⁱ—Li4—Li6B	72.1 (2)	Li2^v—Li7—Li5ⁱⁱⁱ	64.282 (19)
Li3—Li4—Li6B	68.24 (17)	Li2—Li7—Li5ⁱⁱⁱ	64.281 (19)
Li3ⁱⁱ—Li4—Li6B^viii	72.1 (2)	Li6B—Li7—Li5ⁱⁱⁱ	117.71 (18)
Li3—Li4—Li6B^viii	68.24 (17)	Li6B^xiii—Li7—Li5ⁱⁱⁱ	157.29 (18)
Li6B—Li4—Li6B^viii	109.86 (19)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, −y+1/2, z; (iii) −x+1/2, y+1/2, −z+1; (iv) −x+1/2, y+1/2, −z; (v) x, y, z+1; (vi) x+1/2, −y+1/2, z+1; (vii) −x+1/2, y−1/2, −z; (viii) x, y, z−1; (ix) x+1/2, −y+1/2, z−1; (x) −x, −y, −z; (xi) −x+1/2, y−1/2, −z+1; (xii) x−1/2, −y+1/2, z−1; (xiii) x−1/2, −y+1/2, z; (xiv) −x, −y+1, −z+1; (xv) −x, −y+1, −z; (xvi) x−1/2, −y+1/2, z+1.

Experimental details

Crystal data
Chemical formula	Li₁₃Si₄
M_r	202.58
Crystal system, space group	Orthorhombic, Pbam
Temperature (K)	100
a, b, c (Å)	7.9488 (4), 15.1248 (8), 4.4661 (2)
V (Å³)	536.93 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.781, 0.818
No. of measured, independent and observed [I > 2σ(I)] reflections	25938, 2429, 2333
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	1.000

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.015, 0.044, 1.08
No. of reflections	2429
No. of parameters	60
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.40

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2012), publCIF (Westrip, 2010).

Acknowledgements

This work has been funded by the Fonds der Chemischen Industrie and the SolTech (Solar Technologies go Hybrid) program of the State of Bavaria.

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