Structure–property relationships in lithium superionic conductors having a Li₁₀GeP₂S₁₂-type structure

The crystal structures of the superionic conductors Li_9.81Sn_0.81P_2.19S₁₂ and Li_10.35Si_1.35P_1.65S₁₂, both having a Li₁₀GeP₂S₁₂ (LGPS)-type structure, were determined by neutron diffraction analysis over the temperature range 12–800 K. The maximum entropy method was also employed to clarify the lithium distribution in these materials. The Sn system showed one-dimensional diffusion in the c direction over a wide temperature range, even though the Ge-based system typically exhibits three-dimensional conduction at higher temperatures. The ionic conduction mechanisms of analogous Si, Ge and Sn phases with LGPS-type structures are discussed on the basis of the observed structural parameter changes.

Computing details

For all structures, program(s) used to refine structure: Z-Rietveld; software used to prepare material for publication: Oishi, R. et al., (2009). Nuc. Instrum. Methods Phys. Res. 600, 94-96.

(Li10.35Si1.35P1.65S12_at_17K)

Crystal data

Li10.35P1.65S12Si1.35	Z = 2
Mr = 545.64	Dx = 1.939 Mg m^−3
Tetragonal, P4_2/nmc:1	Neutron radiation, λ = 0.36< lambda < 10.18 Ang Å
a = 8.64390 (3) Å	Cell parameters from 730 reflections
c = 12.50773 (8) Å	T = 17 K
V = 934.54 (1) Å^3	Block, pink

Data collection

IMateria at J-Parc diffractometer	k = →
Radiation source: time-of-flight, J-Parc	l = →
h = →

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Biso*/Beq	Occ. (<1)
Li1	0.2574 (3)	0.2666 (3)	0.1929 (2)	5.14639	0.437 (4)
Li2	0	0.5	0.9456 (2)	2.300442 (18)	0.931 (4)
Li3	0.24753 (17)	0.24753 (17)	0	13.41118	0.845 (8)
Li4	0	0	0.2510 (3)	7.77867	0.808 (4)
Si1	0	0.5	0.68952 (8)	1.624267	0.675
P1	0	0.5	0.68952 (8)	1.624267	0.325
P2	0	0	0.5	2.070252
S1	0	0.18931 (11)	0.40750 (8)	1.565613
S2	0	0.29798 (11)	0.09791 (8)	1.746229
S3	0	0.69485 (13)	0.78945 (8)	1.471874

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Li1	0.078175	0.031813	0.085558	0.004867	−0.009445	−0.029992
Li2	0.047295	0.036966	0.003146	0	0	0
Li3	0.071518	0.071518	0.366528	−0.052218	0.088371	−0.088371
Li4	0.071759	0.168304	0.055492	0	0	0
Si1	0.040112	0.016603	0.005000	0	0	0
P1	0.040112	0.016603	0.005000	0	0	0
P2	0.028211	0.028211	0.022239	0	0	0
S1	0.043187	0.006029	0.010271	0	0	0.000327
S2	0.035254	0.012782	0.018313	0	0	−0.010520
S3	0.031918	0.012240	0.011766	0	0	0.001494

Geometric parameters (Å, º)

Li1—S1^i	2.474 (3)	Li4—S3^vii	2.6858 (12)
Li1—S2	2.537 (3)	P1—S2^viii	2.0886 (12)
Li1—S3^ii	2.412 (3)	P1—S3	2.0973 (12)
Li1—S3^iii	2.352 (3)	Si1—S2^viii	2.0886 (12)
Li2—S1^iv	2.7275 (11)	Si1—S3	2.0973 (12)
Li2—S2^v	2.584 (2)	P2—S1	2.0040 (9)
Li2—S3	2.579 (2)	Li1—Li1^ix	1.462 (6)
Li3—S1^vi	2.5297 (17)	Li1—Li3	2.420 (3)
Li3—S2	2.5035 (11)	Li1—Li4	3.284 (2)
Li4—S1	2.551 (3)	Li1—Li4^x	2.993 (3)
Li4—S2	3.210 (3)	Li2—Li3^v	3.1310 (6)
S1^viii—Li2—S1^iv	159.87 (12)	S2—Li4—S2^xiii	106.74 (12)
S1^viii—Li2—S2^xi	97.40 (4)	S2—Li4—S3^vii	83.54 (13)
S1^viii—Li2—S3^xii	82.39 (10)	S3^vii—Li4—S3^iii	158.28 (16)
S2^v—Li2—S2^xi	85.03 (9)	S2^iv—Si1—S2^viii	113.46 (12)
S2^v—Li2—S3^xii	96.72 (7)	S3—Si1—S2^iv	109.08 (9)
S2^v—Li2—S3	178.26 (14)	S3—Si1—S3^xii	106.84 (11)
S3^xii—Li2—S3	81.54 (9)	S2^iv—P1—S2^viii	113.46 (12)
S1—Li4—S1^xiii	79.79 (12)	S3—P1—S2^iv	109.08 (9)
S1—Li4—S2	86.73 (8)	S3—P1—S3^xii	106.84 (11)
S1—Li4—S2^xiii	166.52 (18)	S1—P2—S1^xiv	109.47 (6)
S1—Li4—S3^vii	98.31 (6)	S1—P2—S1^xiii	109.48 (7)

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

(Li10.35Si1.35P1.65S12_at_300K)

Crystal data

Li10.35P1.65S12Si1.35	Z = 2
Mr = 545.64	Dx = 1.914 Mg m^−3
Tetragonal, P4_2/nmc:1	Neutron radiation, λ = 0.36< lambda < 10.18 Ang Å
a = 8.68385 (5) Å	Cell parameters from 785 reflections
c = 12.55589 (10) Å	T = 300 K
V = 946.83 (1) Å^3	Block, pink

Data collection

IMateria at J-Parc diffractometer	k = →
Radiation source: time-of-flight, J-Parc	l = →
h = →

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Biso*/Beq	Occ. (<1)
Li1	0.2550 (4)	0.2692 (4)	0.1944 (3)	9.05156	0.458 (4)
Li2	0	0.5	0.9463 (3)	3.73737	0.916 (4)
Li3	0.2440 (2)	0.2440 (2)	0	14.68352	0.800 (8)
Li4	0	0	0.2476 (3)	8.67697	0.829 (5)
Si1	0	0.5	0.69004 (9)	2.06803	0.675
P1	0	0.5	0.69004 (9)	2.06806	0.325
P2	0	0	0.5	2.96973
S1	0	0.18822 (13)	0.40740 (9)	2.80081
S2	0	0.29734 (13)	0.10026 (10)	2.68149
S3	0	0.69407 (13)	0.78954 (9)	1.72865

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Li1	0.075459	0.032454	0.236004	−0.000746	0.009891	−0.059798
Li2	0.072026	0.053349	0.016627	0	0	0
Li3	0.094023	0.094023	0.369853	−0.076527	0.093789	−0.093789
Li4	0.062485	0.184723	0.082473	0	0	0
Si1	0.031924	0.036249	0.010402	0	0	0
P1	0.031925	0.036249	0.010402	0	0	0
P2	0.032611	0.032611	0.047613	0	0	0
S1	0.070822	0.018858	0.016737	0	0	0.005882
S2	0.045910	0.021227	0.034746	0	0	−0.016313
S3	0.030940	0.006539	0.028201	0	0	0.000353

Geometric parameters (Å, º)

Li1—S1^i	2.509 (4)	Li4—S3^vii	2.6973 (12)
Li1—S2	2.522 (4)	P1—S2^viii	2.0900 (14)
Li1—S3^ii	2.393 (3)	P1—S3	2.0978 (13)
Li1—S3^iii	2.387 (3)	Si1—S2^viii	2.0900 (14)
Li2—S1^iv	2.7512 (13)	Si1—S3	2.0978 (13)
Li2—S2^v	2.614 (3)	P2—S1	2.0052 (10)
Li2—S3	2.591 (3)	Li1—Li1^ix	1.439 (9)
Li3—S1^vi	2.577 (3)	Li1—Li3	2.452 (4)
Li3—S2	2.508 (13)	Li1—Li4	3.288 (4)
Li4—S1	2.588 (4)	Li1—Li4^x	3.012 (4)
Li4—S2	3.176 (3)	Li2—Li3^v	3.1441 (7)
S1^viii—Li2—S1^iv	159.53 (14)	S2—Li4—S2^xiii	108.75 (14)
S1^viii—Li2—S2^xi	97.55 (5)	S2—Li4—S3^vii	84.21 (16)
S1^viii—Li2—S3^xii	82.24 (13)	S3^vii—Li4—S3^iii	160.08 (18)
S2^v—Li2—S2^xi	84.64 (11)	S2^iv—Si1—S2^viii	114.72 (12)
S2^v—Li2—S3^xii	97.11 (9)	S3—Si1—S2^iv	108.74 (9)
S2^v—Li2—S3	178.25 (17)	S3—Si1—S3^xii	106.90 (11)
S3^xii—Li2—S3	81.13 (10)	S2^iv—P1—S2^viii	114.72 (12)
S1—Li4—S1^xiii	78.34 (13)	S3—P1—S2^iv	108.74 (9)
S1—Li4—S2	86.45 (8)	S3—P1—S3^xii	106.90 (11)
S1—Li4—S2^xiii	164.8 (2)	S1—P2—S1^xiv	109.63 (7)
S1—Li4—S3^vii	97.71 (6)	S1—P2—S1^xiii	109.15 (8)

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

(Li10.35Si1.35P1.65S12_at_800K)

Crystal data

Li10.35P1.65S12Si1.35	Z = 2
Mr = 545.64	Dx = 1.863 Mg m^−3
Tetragonal, P4_2/nmc:1	Neutron radiation, λ = 0.36< lambda < 10.18 Ang Å
a = 8.76517 (5) Å	Cell parameters from 714 reflections
c = 12.67003 (12) Å	T = 800 K
V = 973.42 (1) Å^3	Block, pink

Data collection

IMateria at J-Parc diffractometer	k = →
Radiation source: time-of-flight, J-Parc	l = →
h = →

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Biso*/Beq	Occ. (<1)
Li1	0.2505 (8)	0.2752 (7)	0.1938 (6)	12.05178	0.434 (6)
Li2	0	0.5	0.9499 (4)	4.11743	0.883 (8)
Li3	0.2408 (3)	0.2408 (3)	0	20.2803	0.904 (13)
Li4	0	0	0.2408 (6)	9.94020	0.747 (8)
Si1	0	0.5	0.69087 (15)	2.175236	0.675
P1	0	0.5	0.69087 (15)	2.175236	0.325
P2	0	0	0.5	3.50034
S1	0	0.1873 (2)	0.41033 (16)	3.98171
S2	0	0.29969 (18)	0.10290 (15)	2.62142
S3	0	0.6901 (2)	0.78983 (14)	2.37275

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Li1	0.076038	0.065359	0.316516	0.008146	−0.004752	−0.122378
Li2	0.096951	0.054313	0.005183	0	0	0
Li3	0.151853	0.151853	0.466863	−0.114763	0.084863	−0.084863
Li4	0.097897	0.192836	0.086957	0	0	0
Si1	0.038714	0.023358	0.020580	0	0	0
P1	0.038714	0.023358	0.020580	0	0	0
P2	0.038216	0.038216	0.056568	0	0	0
S1	0.084201	0.031275	0.035813	0	0	0.001597
S2	0.047956	0.017220	0.034429	0	0	−0.017118
S3	0.039089	0.007505	0.043562	0	0	−0.003196

Geometric parameters (Å, º)

Li1—S1^i	2.576 (7)	Li4—S3^vii	2.744 (2)
Li1—S2	2.489 (8)	P1—S2^viii	2.080 (2)
Li1—S3^ii	2.375 (6)	P1—S3	2.085 (2)
Li1—S3^iii	2.477 (7)	Si1—S2^viii	2.080 (2)
Li2—S1^iv	2.786 (2)	Si1—S3	2.085 (2)
Li2—S2^v	2.616 (4)	P2—S1	1.9965 (17)
Li2—S3	2.624 (5)	Li1—Li1^ix	1.490 (17)
Li3—S1^vi	2.617 (4)	Li1—Li3	2.476 (8)
Li3—S2	2.534 (2)	Li1—Li4	3.315 (7)
Li4—S1	2.704 (7)	Li1—Li4^x	3.058 (7)
Li4—S2	3.155 (5)	Li2—Li3^v	3.1654 (11)
S1^viii—Li2—S1^iv	159.3 (2)	S2—Li4—S2^xiii	112.8 (3)
S1^viii—Li2—S2^xi	97.66 (8)	S2—Li4—S3^vii	85.5 (3)
S1^viii—Li2—S3^xii	82.0 (2)	S3^vii—Li4—S3^iii	163.8 (3)
S2^v—Li2—S2^xi	84.32 (17)	S2^iv—Si1—S2^viii	115.18 (15)
S2^v—Li2—S3^xii	98.43 (14)	S3—Si1—S2^iv	108.80 (12)
S2^v—Li2—S3	177.2 (3)	S3—Si1—S3^xii	106.08 (14)
S3^xii—Li2—S3	78.81 (16)	S2^iv—P1—S2^viii	115.18 (15)
S1—Li4—S1^xiii	74.77 (2)	S3—P1—S2^iv	108.80 (12)
S1—Li4—S2	86.23 (14)	S3—P1—S3^xii	106.08 (14)
S1—Li4—S2^xiii	161.0 (4)	S1—P2—S1^xiv	108.89 (9)
S1—Li4—S3^vii	96.44 (10)	S1—P2—S1^xiii	110.63 (9)

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

(Li9.81Sn0.81P2.19S12_at_12K)

Crystal data

Li9.81P2.19S12Sn0.81	Z = 2
Mr = 616.86	Dx = 2.133 Mg m^−3
Tetragonal, P4_2/nmc:1	Neutron radiation, λ = 0.36< lambda < 10.18 Ang Å
a = 8.70054 (3) Å	Cell parameters from 762 reflections
c = 12.68610 (8) Å	T = 12 K
V = 960.33 (1) Å^3	Block, grey

Data collection

IMateria at J-Parc diffractometer	k = →
Radiation source: time-of-flight, J-Parc	l = →
h = →

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Biso*/Beq	Occ. (<1)
Li1	0.2551 (5)	0.2718 (4)	0.1817 (4)	6.5 (3)	0.486 (6)
Li2	0	0.5	−0.0607 (6)	8.3 (3)	0.781 (8)
Li3	0.2408 (4)	0.2408 (4)	0	14.2 (5)	0.717 (13)
Li4	0	0	0.2458 (4)	4.1 (2)	0.744 (9)
Sn1	0	0.5	0.68727 (10)	1.92 (3)	0.405
P1	0	0.5	0.68727 (10)	1.92 (3)	0.595
P2	0	0	0.5	1.91 (4)
S1	0	0.18890 (18)	0.40917 (16)	2.09 (5)
S2	0	0.29195 (19)	0.1023 (2)	3.45 (5)
S3	0	0.7005 (2)	0.78737 (16)	2.35 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Li1	0.102 (8)	0.035 (5)	0.111 (5)	0.012 (3)	−0.007 (4)	−0.051 (4)
Li2	0.071 (6)	0.039 (5)	0.204 (8)	0	0	0
Li3	0.074 (5)	0.074 (5)	0.394 (13)	−0.034 (4)	0.115 (4)	−0.115 (4)
Li4	0.034 (6)	0.080 (6)	0.043 (5)	0	0	0
Sn1	0.0271 (11)	0.0268 (10)	0.0191 (10)	0	0	0
P1	0.0271 (11)	0.0268 (10)	0.0191 (10)	0	0	0
P2	0.0212 (8)	0.0212 (8)	0.0300 (16)	0	0	0
S1	0.0486 (14)	0.0186 (15)	0.0121 (13)	0	0	0.0030 (15)
S2	0.0531 (16)	0.0332 (14)	0.0448 (15)	0	0	−0.0083 (13)
S3	0.0339 (16)	0.0290 (13)	0.0265 (15)	0	0	0.0033 (14)

Geometric parameters (Å, º)

Li1—S1^i	2.447 (5)	Li4—S3^vii	2.640 (2)
Li1—S2	2.443 (4)	P1—S2^viii	2.107 (2)
Li1—S3^ii	2.442 (4)	P1—S3	2.157 (2)
Li1—S3^iii	2.428 (4)	Sn1—S2^viii	2.107 (2)
Li2^iv—S1^v	2.734 (2)	Sn1—S3	2.157 (2)
Li2^iv—S2^iv	2.748 (7)	P2—S1	2.0073 (17)
Li2^iv—S3	2.600 (6)	Li1—Li1^ix	1.775 (12)
Li3—S1^vi	2.606 (4)	Li1—Li3	2.324 (6)
Li3—S2	2.504 (3)	Li1—Li4	3.343 (5)
Li4—S1	2.645 (5)	Li1—Li4^x	3.054 (5)
Li4—S2	3.125 (4)	Li2^iv—Li3^iv	3.173 (2)
S1^viii—Li2^iv—S1^v	163.9 (4)	S2—Li4—S2^xiii	108.74 (18)
S1^viii—Li2^iv—S2^xi	96.05 (8)	S2—Li4—S3^vii	84.67 (5)
S1^viii—Li2^iv—S3^xii	84.04 (18)	S3^vii—Li4—S3^iii	161.7 (2)
S2^iv—Li2^iv—S2^xi	82.4 (2)	S2^v—Sn1—S2^viii	118.46 (17)
S2^iv—Li2^iv—S3^xii	96.66 (19)	S3—Sn1—S2^v	107.52 (11)
S2^iv—Li2^iv—S3	179.0 (4)	S3—Sn1—S3^xii	107.89 (12)
S3^xii—Li2^iv—S3	84.3 (2)	S2^v—P1—S2^viii	118.5 (2)
S1—Li4—S1^xiii	76.84 (16)	S3—P1—S2^v	107.5 (6)
S1—Li4—S2	87.21 (11)	S3—P1—S3^xii	107.9 (12)
S1—Li4—S2^xiii	164.0 (3)	S1—P2—S1^xiv	109.24 (6)
S1—Li4—S3^vii	97.18 (7)	S1—P2—S1^xiii	109.93 (12)

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

(Li9.81Sn0.81P2.19S12_at_300K)

Crystal data

Li9.81P2.19S12Sn0.81	Z = 2
Mr = 616.86	Dx = 2.110 Mg m^−3
Tetragonal, P4_2/nmc:1	Neutron radiation, λ = 0.36< lambda < 10.18 Ang Å
a = 8.73764 (3) Å	Cell parameters from 481 reflections
c = 12.71660 (7) Å	T = 300 K
V = 970.87 (1) Å^3	Block, grey

Data collection

IMateria at J-Parc diffractometer	k = →
Radiation source: time-of-flight, J-Parc	l = →
h = →

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Biso*/Beq	Occ. (<1)
Li1	0.2562 (4)	0.2740 (4)	0.1866 (4)	7.4 (2)	0.473 (5)
Li2	0	0.5	−0.0511 (5)	7.9 (2)	0.803 (7)
Li3	0.2431 (3)	0.2431 (3)	0	17.6 (5)	0.750 (10)
Li4	0	0	0.2440 (4)	5.7 (2)	0.709 (7)
Sn1	0	0.5	0.68834 (8)	2.14 (2)	0.405
P1	0	0.5	0.68834 (8)	2.14 (2)	0.595
P2	0	0	0.5	2.33 (3)
S1	0	0.18790 (14)	0.40867 (11)	2.19 (4)
S2	0	0.29308 (17)	0.10320 (18)	3.83 (4)
S3	0	0.70019 (18)	0.78795 (12)	2.52 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Li1	0.093 (6)	0.081 (5)	0.105 (5)	0.005 (3)	0.004 (4)	−0.016 (4)
Li2	0.109 (6)	0.041 (4)	0.149 (6)	0	0	0
Li3	0.085 (4)	0.085 (4)	0.499 (15)	−0.055 (4)	0.121 (4)	−0.121 (4)
Li4	0.036 (6)	0.091 (6)	0.090 (5)	0	0	0
Sn1	0.0296 (9)	0.0326 (9)	0.0193 (7)	0	0	0
P1	0.0296 (9)	0.0326 (9)	0.0193 (7)	0	0	0
P2	0.0268 (7)	0.0268 (7)	0.0349 (14)	0	0	0
S1	0.0549 (12)	0.0131 (11)	0.0151 (10)	0	0	0.0020 (10)
S2	0.0545 (14)	0.0411 (11)	0.0500 (12)	0	0	−0.0054 (10)
S3	0.0389 (13)	0.0319 (10)	0.0251 (12)	0	0	0.0047 (11)

Geometric parameters (Å, º)

Li1—S1^i	2.474 (4)	Li4—S3^vii	2.6510 (17)
Li1—S2	2.482 (4)	P1—S2^viii	2.107 (18)
Li1—S3^ii	2.408 (4)	P1—S3	2.1597 (17)
Li1—S3^iii	2.446 (4)	Sn1—S2^viii	2.1074 (18)
Li2^iv—S1^v	2.7746 (17)	Sn1—S3	2.160 (17)
Li2^iv—S2^iv	2.668 (5)	P2—S1	2.0111 (12)
Li2^iv—S3	2.692 (5)	Li1—Li1^ix	1.669 (9)
Li3—S1^vi	2.599 (3)	Li1—Li3	2.391 (5)
Li3—S2	2.534 (2)	Li1—Li4	3.358 (4)
Li4—S1	2.661 (5)	Li1—Li4^x	3.036 (5)
Li4—S2	3.125 (4)	Li2^iv—Li3^iv	3.1580 (12)
S1^viii—Li2^iv—S1^v	158.8 (2)	S2—Li4—S2^xiii	110.06 (18)
S1^viii—Li2^iv—S2^xi	97.79 (9)	S2—Li4—S3^vii	84.95 (5)
S1^viii—Li2^iv—S3^xii	81.9 (2)	S3^vii—Li4—S3^iii	162.3 (2)
S2^iv—Li2^iv—S2^xi	85.31 (18)	S2^v—Sn1—S2^viii	118.17 (13)
S2^iv—Li2^iv—S3^xii	96.82 (14)	S3—Sn1—S2^v	107.54 (10)
S2^iv—Li2^iv—S3	177.9 (3)	S3—Sn1—S3^xii	108.18 (12)
S3^xii—Li2^iv—S3	81.04 (17)	S2^v—P1—S2^viii	118.2 (13)
S1—Li4—S1^xiii	76.21 (15)	S3—P1—S2^v	107.54 (10)
S1—Li4—S2	86.86 (10)	S3—P1—S3^xii	108.18 (12)
S1—Li4—S2^xiii	163.1 (3)	S1—P2—S1^xiv	109.48 (7)
S1—Li4—S3^vii	96.93 (7)	S1—P2—S1^xiii	109.45 (9)

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

(Li9.81Sn0.81P2.19S12_at_800K)

Crystal data

Li9.81P2.19S12Sn0.81	Z = 2
Mr = 616.86	Dx = 2.063 Mg m^−3
Tetragonal, P4_2/nmc:1	Neutron radiation, λ = 0.36< lambda < 10.18 Ang Å
a = 8.81049 (3) Å	Cell parameters from 338 reflections
c = 12.79398 (7) Å	T = 800 K
V = 993.13 (1) Å^3	Block, grey

Data collection

IMateria at J-Parc diffractometer	k = →
Radiation source: time-of-flight, J-Parc	l = →
h = →

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Biso*/Beq	Occ. (<1)
Li1	0.2815 (10)	0.2780 (7)	0.1970 (8)	14.4 (6)	0.451 (7)
Li2	0	0.5	−0.0509 (5)	9.5 (3)	0.798 (7)
Li3	0.2452 (4)	0.2452 (4)	0	21.8 (8)	0.795 (14)
Li4	0	0	0.2406 (4)	9.4 (4)	0.710 (9)
Sn1	0	0.5	0.69148 (10)	3.31 (3)	0.405
P1	0	0.5	0.69148 (10)	3.31 (3)	0.595
P2	0	0	0.5	3.35 (4)
S1	0	0.18796 (16)	0.40966 (15)	3.77 (5)
S2	0	0.2925 (2)	0.1040 (2)	5.98 (6)
S3	0	0.6970 (2)	0.79120 (15)	4.02 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Li1	0.181 (11)	0.050 (6)	0.32 (2)	0.017 (6)	0.124 (8)	−0.027 (7)
Li2	0.192 (10)	0.072 (5)	0.097 (6)	0	0	0
Li3	0.079 (4)	0.079 (4)	0.67 (3)	−0.000457 (46442095)	0.106 (4)	−0.106 (4)
Li4	0.082 (9)	0.230 (13)	0.044 (6)	0	0	0
Sn1	0.0549 (13)	0.0367 (12)	0.0343 (11)	0	0	0
P1	0.0549 (13)	0.0367 (12)	0.0343 (11)	0	0	0
P2	0.0398 (9)	0.0398 (9)	0.0476 (19)	0	0	0
S1	0.0912 (19)	0.0231 (15)	0.0291 (15)	0	0	0.0219 (14)
S2	0.0781 (19)	0.0530 (14)	0.0961 (17)	0	0	−0.0015 (15)
S3	0.0529 (18)	0.0531 (15)	0.0468 (16)	0	0	0.0325 (16)

Geometric parameters (Å, º)

Li1—S1^i	2.379 (6)	Li4—S3^vii	2.7002 (18)
Li1—S2	2.754 (11)	P1—S2^viii	2.143 (2)
Li1—S3^ii	2.415 (7)	P1—S3	2.154 (2)
Li1—S3^iii	2.461 (6)	Sn1—S2^viii	2.143 (2)
Li2^iv—S1^v	2.795 (18)	Sn1—S3	2.1541 (19)
Li2^iv—S2^iv	2.697 (5)	P2—S1	2.0195 (15)
Li2^iv—S3	2.663 (5)	Li1—Li1^ix	1.545 (15)
Li3—S1^vi	2.593 (4)	Li1—Li3	2.557 (10)
Li3—S2	2.571 (3)	Li1—Li4	3.530 (8)
Li4—S1	2.724 (5)	Li1—Li4^x	2.858 (10)
Li4—S2	3.113 (4)	Li2^iv—Li3^iv	3.1829 (12)
S1^viii—Li2^iv—S1^v	159.2 (2)	S2—Li4—S2^xiii	111.74 (19)
S1^viii—Li2^iv—S2^xi	97.62 (9)	S2—Li4—S3^vii	85.16 (6)
S1^viii—Li2^iv—S3^xii	82.1 (2)	S3^vii—Li4—S3^iii	162.7 (2)
S2^iv—Li2^iv—S2^xi	85.37 (19)	S2^v—Sn1—S2^viii	117.07 (17)
S2^iv—Li2^iv—S3^xii	96.65 (15)	S3—Sn1—S2^v	108.01 (5)
S2^iv—Li2^iv—S3	178.0 (3)	S3—Sn1—S3^xii	107.36 (11)
S3^xii—Li2^iv—S3	81.34 (18)	S2^v—P1—S2^viii	117.07 (17)
S1—Li4—S1^xiii	74.86 (17)	S3—P1—S2^v	108.01 (5)
S1—Li4—S2	86.70 (12)	S3—P1—S3^xii	107.36 (11)
S1—Li4—S2^xiii	161.6 (3)	S1—P2—S1^xiv	109.12 (5)
S1—Li4—S3^vii	96.86 (7)	S1—P2—S1^xiii	110.17 (11)

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