Supplementary Material for:
Synthesis, Structure, Physicochemical Characterization and Electronic
Structure of Thio-Lithium Super Ionic Conductors, Li4GeS4 and Li4SnS4
Joseph H. MacNeil,1 Danielle M. Massi,2 Jian-Han Zhang2, Kimberly A. Rosmus,2 Carl D.
Brunetta,2 Taylor A. Gentile,2 and Jennifer A. Aitken*2
1
2
Department of Chemistry, Chatham University, 1 Woodland Road, Pittsburgh, PA 15232, USA
Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave., Pittsburgh,
PA 15282, USA
*author to whom correspondence should be addressed.
Email: aitkenj@duq.edu
Phone:(412) 396-1670
Fax: (412) 396-5683
1
Table of Contents
Source and purity of reagent chemicals
3
Selected interatomic distances (Å) and angles (°) for Li4GeS4.
4
Selected interatomic distances (Å) and angles (°) for Li4SnS4.
5
Symmetry equivalent positions for room temperature and 100K
structures of Li4SnS4.
6-8
Comparison of fractional atomic coordinates for structure reports
of Li4GeS4.
9-10
X-Ray Powder Diffractogram for Li4GeS4.
11
X-Ray Powder Diffractogram for Li4SnS4.
12
2
Source and Purity of Reagent Chemicals
The chemicals in this work were used as obtained except for the germanium metal, which
was first pulverized using an impact mortar and pestle and then ground in a ceramic mortar and
pestle before use.
Li2S powder
98% (99.9%-Li)
Strem Chemicals Inc., Newburyport, MA
Zn power
99.999%
Strem Chemicals Inc., Newburyport, MA
Sn powder
99.999%
Strem Chemicals Inc., Newburyport, MA
Fe powder
99.99%
Strem Chemicals Inc., Newburyport, MA
Ge metal pieces
99.999%
Strem Chemicals Inc., Newburyport, MA
sublimed S powder
99.5%
Fisher Scientific Pittsburgh, PA
methanol
ACS grade
BDH, Bridgeport, NJ
ethanol
200 proof, ACS grade
PHARMCO-APPER, Brookfield, CN
heptane
99%
Acros Organics, Morris Plains, NJ
3
Selected interatomic distances (Å) and angles (°) for Li4GeS4.
Li(1)-S(3)
2.5570(5) × 2
S(3)-Li(1)-S(2)
87.27(2) × 2
Li(1)-S(2)
2.5893(6) × 2
S(3)-Li(1)-S(2)
92.73(2) × 2
Li(1)-S(1)
2.9092(6) × 2
S(1)-Li(1)-S(2)
86.91(2) × 2
Li(1)-Li(3)
2.756(2) × 2
S(1)-Li(1)-S(3)
88.70(2) × 2
Li(1)-Ge(1)
3.1718(6) × 2
S(1)-Li(1)-S(3)
91.30(2) × 2
Li(1)-Li(2)
3.251(2) × 2
S(1)-Li(1)-S(2)
93.09(2) × 2
S(1)-Li(1)-S(1)
180.0
S(2)-Li(1)-S(2)
180.00(1)
S(3)-Li(1)-S(3)
180.0
Li(2)-S(2)
2.450(2) × 2
S(1)-Li(2)-S(3)
92.61(8)
Li(2)-S(1)
2.493(3)
S(1)-Li(2)-S(2)
107.93(7) × 2
Li(2)-S(3)
2.498(3)
S(2)-Li(2)-S(2)
114.2(1)
Li(2)-Ge(1)
3.022(3)
S(2)-Li(2)-S(3)
115.65(7) × 2
Li(3)-S(2)
2.384(2)
S(2)-Li(3)-S(3)
93.19(7)
Li(3)-S(1)
2.405(2)
S(1)-Li(3)-S(2)
98.97(8)
Li(3)-S(3)
2.550(2)
S(1)-Li(3)-S(3)
104.39(8)
Li(3)-S(2)
2.576(3)
S(2)-Li(3)-S(2)
109.75(9)
S(1)-Li(3)-S(2)
119.98(9)
S(2)-Li(3)-S(3)
124.42(9)
Ge(1)-S(2)
2.2087(5) × 2
S(2)-Ge(1)-S(3)
106.36(1) × 2
Ge(1)-S(1)
2.2174(8)
S(1)-Ge(1)-S(3)
108.57(1)
Ge(1)-S(3)
2.2279(7)
S(2)-Ge(1)-S(2)
111.47(2)
S(2)-Ge(1)-S(1)
111.87(1) × 2
4
Selected interatomic distances (Å) and angles (°) for Li4SnS4.
Li(1)-S(3)
2.6518(6) × 2
S(3)-Li(1)-S(2)
88.59(2) × 2
Li(1)-S(2)
2.6771(7) × 2
S(3)-Li(1)-S(2)
91.41(2) × 2
Li(1)-S(1)
2.8573(6) × 2
S(1)-Li(1)-S(2)
86.74(2) × 2
Li(1)-Li(3)
2.782(3) × 2
S(1)-Li(1)-S(3)
88.13(2) × 2
Li(1)-Sn(1)
3.2777(6) × 2
S(1)-Li(1)-S(3)
91.87(2) × 2
Li(1)-Li(2)
3.350(3) × 2
S(1)-Li(1)-S(2)
93.26(2) × 2
S(1)-Li(1)-S(1)
180.0
S(2)-Li(1)-S(2)
180.0
S(3)-Li(1)-S(3)
180.0
Li(2)-S(2)
2.433(2) × 2
S(1)-Li(2)-S(3)
97.4(1)
Li(2)-S(1)
2.587(4)
S(1)-Li(2)-S(2)
106.6(1) × 2
Li(2)-S(3)
2.501(4)
S(2)-Li(2)-S(2)
109.4(1)
Li(2)-Sn(1)
3.118(4)
S(2)-Li(2)-S(3)
117.5(1) × 2
Li(3)-S(2)
2.405(3)
S(2)-Li(3)-S(3)
94.1(1)
Li(3)-S(1)
2.438(3)
S(1)-Li(3)-S(2)
100.4(1)
Li(3)-S(3)
2.571(3)
S(1)-Li(3)-S(3)
104.5(1)
Li(3)-S(2)
2.511(3)
S(2)-Li(3)-S(2)
111.6(1)
S(1)-Li(3)-S(2)
118.9(1)
S(2)-Li(3)-S(3)
122.6(1)
Sn(1)-S(2)
2.3755(6) × 2
S(2)-Sn(1)-S(3)
105.78(2) × 2
Sn(1)-S(1)
2.3757(9)
S(1)-Sn(1)-S(3)
106.07(2)
Sn(1)-S(3)
2.4072(8)
S(2)-Sn(1)-S(2)
111.57(2)
S(2)-Sn(1)-S(1)
113.43(1) x 2
5
Symmetry equivalent positions for
room temperature and 100K structures of Li4SnS4
Original Coordinates
Data for the 296 K structure are reported using the conventions of the International Tables for
Crystallography (Volume A) for expressing the asymmetric unit in space group 62, i.e.
(0 ≤ x ≤ ½ ); (0 ≤ y ≤ ¼); (0 ≤ z ≤ 1). Initial data for the 100 K structure were taken from the file
cm_3011315_si_002.cif, supplied as supporting material for Chem. Mater., 13 (2012) 47144721. by Kaib et al.
296 K
x
y
z
100 K
x
y
z
Sn
0.0915
0.25
0.642
Sn
0.41339
0.25
0.63477
S1
0.083
0.25
0.2671
S1
0.4086
0.25
0.2626
S2
0.1608
0.0013
0.7835
S3
0.33254
0.49341
0.76654
S3
0.4323
0.25
0.7659
S2
0.57562
0.25
0.7641
Li1
0
0
0
Li4
0.465
0.517
-0.009
Li3
0.287
0.706
0.499
Li2
0.4085
0.25
0.1257
Li2
0.5696
0.25
0.162
Li3
0.1777
0.0035
0.1785
Li1
0.3396
0.4955
0.154
Common Origin Transformation
To convert the two unit cells to a common origin, the following transformation was applied to
the 100K data:
x’ = (-x) + 0.5
6
296 K
x
y
z
100 K
x
y
z
Sn
0.0915
0.25
0.642
Sn
0.08661
0.25
0.63477
S1
0.083
0.25
0.2671
S1
0.0914
0.25
0.2626
S2
0.1608
0.0013
0.7835
S3
0.16746
0.49341
0.76654
S3
0.4323
0.25
0.7659
S2
-0.07562
0.25
0.7641
Li1
0
0
0
Li4
0.035
0.517
-0.009
Li3
0.213
0.706
0.499
Li2
0.4085
0.25
0.1257
Li2
-0.0696
0.25
0.162
Li3
0.1777
0.0035
0.1785
Li1
0.1604
0.4955
0.154
Equivalent Positions
To make comparison of the fractional coordinates easier, the atom positions in the 100 K
solution that were not directly comparable were converted using the symmetry equivalent
positions for space group 62. The specific transformations were as follows:
Atom
Site
Symmetry Equivalent Position Applied
Sn
4c
(x,y,z)
S1
4c
(x,y,z)
S3
8d
(x, -y+ ½ , z)
S2
4c
(x + ½ , y, -z + ½ )
Li4
8d
(-x + ½ , y + ½ , z + ½ )
Li3
8d
(-x + ½ , y + ½ , z + ½ )
Li2
4c
(x + ½ , y, -z + ½ )
Li1
8d
(x, -y+ ½ , z)
7
Final Results
296K
x
y
z
100K
x
y
z
Sn
0.0915
0.25
0.642
Sn
0.08661
0.25
0.63477
S1
0.083
0.25
0.2671
S1
0.0914
0.25
0.2626
S2
0.1608
0.0013
0.7835
S3
0.16746
0.00659
0.76654
S3
0.4323
0.25
0.7659
S2
0.42438
0.25
0.7359
Li1
0
0
0
Li4
0.465
0.017
0.491
Li3
0.287
0.206
0.999
Li2
0.4085
0.25
0.1257
Li2
0.4304
0.25
0.338
Li3
0.1777
0.0035
0.1785
Li1
0.1604
0.0045
0.154
In the 100K solution the Li3 and Li4 atoms each have 50% occupancy. The x and z fractional
coordinates of Li(2) and Li(3) are highlighted in the table above, as these are the positions that
show the greatest variation between structural solutions.
8
Comparison of fractional atomic coordinates a for structure reports of Li4GeS4.
Matusushita & Kanatzidis 1
This work
Atom
siteb
x
y
z
atom
siteb
x
y
z
Li(1)
4a
0.0000
0.0000
0.0000
Li(1)c
8d
0.0022
0.0143
0.0262
Li(2)
4c
0.4117
0.2500
0.1294
Li(2)
4c
0.4117
0.2500
0.1294d
Li(3)
8d
0.1777
0.0000
0.1915
Li(3)
8d
0.1777
0.0000
0.1925
Ge(1)
4c
0.0890
0.2500
0.6485
Ge(1)
4c
0.0890
0.2500
0.6486
S(1)
4c
0.0862
0.2500
0.2906
S(1)
4c
0.0862
0.2500
0.2904
S(2)
8d
0.1567
0.0149
0.7787
S(2)
8d
0.1567
0.0149
0.7787d
S(3)
4c
0.4391
0.2500
0.7308
S(3)
4c
0.4391
0.2500
0.7308
Kanno et al. 2
Murayama et al. 3
Li(3)c
8d
0.3050
0.2030
0.9820
Li(3)
4a
0.0000
0.0000
0.0000
Li(2)
4c
0.4240
0.2500
0.3290
Li(1)
4c
0.4127
0.2500
0.1315
Li(1)
8d
0.1650
0.0040
0.1750
Li(2)
8d
0.1768
0.0027
0.1997
Ge(1)
4c
0.0897
0.2500
0.6495
Ge(1)
4c
0.0892
0.2500
0.6494
S(2)
4c
0.0857
0.2500
0.2933
S(2)
4c
0.0871
0.2500
0.2966
S(1)
8d
0.1557
0.0135
0.7764
S(1)
8d
0.1572
0.0149
0.7758
S(3)
4c
0.4387
0.2500
0.7292
S(3)
4c
0.4390
0.2500
0.7315
a
The coordinates reported in the previously published works have been transformed into equivalent
positions, in order to compare directly to those obtained in this work.
b
The site is defined as the Wyckoff letter and multiplicity.
c
This lithium site is 50% occupied.
Two typographical errors (wrong signs) were found in Kanatzidis’ publication and corrected here.
d
9
[1]
Y. Matusushita, M. G. Kanatzidis, Z. Naturforsch 53b (1998) 23-30.
[2]
R. Kanno, T. Hata, Y. Kawamoto, M. Irie, Solid State Ionics 130 (2000) 97 –104.
[3]
M. Murayama, R. Kanno, Y. Kawamoto, T. Kamiyama, Solid State Ionics 154-155 (2002)
789-794.
10
X-Ray Powder Diffraction Data for Li4GeS4
11
X-Ray Powder Diffraction Data for Li4SnS4
12