1. Hisanori Yamane, Shinsaku Amano
Supplementary information
Synthesis of suboxides, Ti8(SnxBi1−x)O7 and Ti11.17(Sn0.85Bi0.15)3O10 , using a Bi flux and their crystal structures
Hisanori Yamane, Shinsaku Amano
contents
Fig. S1 Twin structure of Ti8(Sn0.72Bi0.28)O7.
Table S1
Anisotropic displacement parameters (Uij/Å2) of Ti8(SnxBi1−x)O7 and Ti11.17(Sn0.85Bi0.15)3O10.
Fig. S2　 Atomic arrangements around Ti3 and Ti4 sites, Ti4-centered Sn/Bi octahedra, and O–Ti megatetrahedron of Ti11.17(Sn0.85Bi0.15)3O10.
Fig. S3 Observed (blue line), calculated (red line) and difference (gray line) powder XRD patterns of sample B3. The tick marks below the pattern represent the diffraction angles of all possible Bragg reflections.
Table S2
Atomic coordinates and equivalent isotropic displacement parameters (Ueq/Å2) for Ti8(Sn0.77Bi0.23)O7 by the Rietveld analysis for the powder XRD pattern (Fig. S3).
Fig. S4 Powder XRD pattern of sample B4.
Fig. S5 Electrical resistivity of a Ti8(Sn0.77Bi0.23)O7 sintered polycrystalline bulk.

2. a a’ c b’ b 46º twin plane O Ti Bi/Sn (1 5 0)
Fig. S1 Twin structure of Ti8(Sn0.72Bi0.28)O7.

3. Table S1
Anisotropic displacement parameters (Uij/Å2) of Ti8(SnxBi1−x)O7 and Ti11.17(Sn0.85Bi0.15)3O10.
formula
Atom
U11
U22
U33
U23
U13
−U12
Ti8(Sn0.41Bi0.59)O7
Ti1
0.0038(2)
0.0060(2)
(19)
− (13)
Ti2
0.0077(3)
0.0039(3)
0.0090(3)
Ti3
0.0035(3)
0.0038(3)
0.0041(2)
Sn/Bi
(11)
(11)
(11) O1
0.0059(8)
0.0049(7)
0.0039(7)
−0.0005(5) O2
0.0045(10)
0.0057(9)
0.0034(9) O3
0.0066(15)
0.0070(14)
0.0031(13)
Ti8(Sn0.65Bi0.35)O7
(19)
(19)
(18)
− (12)
0.0069(3)
0.0026(2)
0.0037(2)
0.0028(2)
0.0039(2)
(12)
(12)
(12)
0.0054(7)
0.0033(6)
0.0043(7)
−0.0001(5)
0.0044(9)
0.0047(9)
0.0026(9)
0.0059(13)
0.0057(13)
0.0028(13)
Ti8(Sn0.72Bi0.28)O7
(19)
(18)
− (13)
0.0030(2)
0.0075(3)
0.0042(2)
0.0033(2)
(13)
(13)
(13)
0.0055(7)
0.0040(7)
−0.0003(5)
0.0043(9)
0.0051(9)
0.0038(9)
0.0050(13)
0.0065(13)
0.0039(13)
Ti8(Sn0.935Bi0.065)O7
(17)
(17)
(16)
− (11)
0.0056(2)
0.0065(2)
0.0034(2)
0.0043(2)
(13)
(13)
(13)
0.0044(6)
0.0042(6)
0.0046(6)
0.0035(8)
0.0043(8)
0.0052(8)
0.0039(12)
0.0058(12)
0.0042(12)
Ti11.17(Sn0.85Bi0.15)3O10
0.0041(5)
0.0049(10)
−0.0013(9)
0.0177(4)
0.0079(4)
0.0147(15)
Ti4
0.006(3)
Ti5
0.0068(7)
0.0184(3)
0.0127(2)
0.0031(16)
0.0062(10)
−0.0010(13)
0.0065(9)
0.0008(9)

4. O1 O2 Ti1 Ti5 Ti1 Ti2 O1 O1 O1 O1 Ti3 Sn/Bi Sn/Bi Sn/Bi Ti4 Sn/Bia c b
Sn/Bi
Ti1
Ti4
Ti2
Sn/Bi
Sn/Bi
Sn/Bi
Sn/Bi
Sn/Bi
O–Ti megatetrahedron
Ti4-centered Sn/Bi octahedron
Fig. S2　 Atomic arrangements around Ti3 and Ti4 sites, Ti4-centered Sn/Bi octahedra, and O–Ti megatetrahedron of Ti11.17(Sn0.85Bi0.15)3O10.

5. Diffraction angle, 2θ / º (CuKα)90 80 70 60 50 40 30 20 10
Counts
40,000
35,000
30,000
25,000
20,000
15,000
10,000
5,000
Fig. S3 Observed (blue line), calculated (red line) and difference (gray line) powder XRD patterns of sample B3. The tick marks below the pattern represent the diffraction angles of all possible Bragg reflections.
Table S2
Atomic coordinates and equivalent isotropic displacement parameters (Ueq/Å2) for Ti8(Sn0.77Bi0.23)O7 by the Rietveld analysis for the powder XRD pattern (Fig. S2).
formula
Atom
Site
Occ. x y z
Beq
Ti8(Sn0.77Bi0.23)O7
Ti1 8q 1
0.3171(4)
(18)
1/2
0.8
Ti2 4g
0.1797(5)
Ti3 4i
0.2037(3)
Sn/Bi 2c
0.773(8)/0.228(8) O1 8p
0.1720(12)
0.1189(5) O2
0.3213(9) O3 2d
Space group Cmmm
a = (2) Å, b = (5) Å, c = (8) Å
R-Bragg = %, Rwp = %, Rp = 8.79 %, GOF = 5.56

6. 10 20 30 40 50 60 70
Diffraction angle, 2 θ/ deg. (CuKα)
Intensity, I (a. u.)
(Ti2O)
(TiO1.51)
(TiO)
Fig. S4 Powder XRD pattern of sample B4.

7. 0.8
0.6
0.4
0.2
0.0
Resistivity, ρ/Ωm 10−5
300
250
200
150
100 50
Temperature, T/K
Fig. S5 Electrical resistivity of a Ti8(Sn0.77Bi0.23)O7 sintered polycrystalline bulk.