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[manuscript_SI_MDR.pdf](https://mdr.nims.go.jp/filesets/d35e6a8d-993a-4b9a-bd66-d1f6a94d18d9/download)
## Creator
[Norio Saito](https://orcid.org/0000-0002-6030-8475), Stéphane Cordier, [Takeo Ohsawa](https://orcid.org/0000-0001-7528-8940), [Noriko Saito](https://orcid.org/0000-0002-8104-0172), Takahiro Takei, Fabien Grasset, Jeffrey Scott Cross, [Naoki Ohashi](https://orcid.org/0000-0002-4011-0031)
## Rights
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © 2025 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.4c04648.[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)
## Other metadata
[Unraveling the Origin of Unusual Cs Atom Disorder in Cesium Octahedral Molybdenum Halide Cluster Compounds, Cs2[{Mo6Xi8}Xa6] (X = Cl and Br)](https://mdr.nims.go.jp/datasets/449f2c86-1b32-4031-8578-9be982304472)
## Fulltext
Template for Electronic Submission to ACS JournalsS1 Supporting Information Unraveling the origin of unusual Cs atom disorder in cesium octahedral molybdenum halide cluster compounds, Cs2[{Mo6Xi8}Xa6] (X = Cl and Br) Norio Saito,a,b Stéphane Cordier,c Takeo Ohsawa,a,d Noriko Saito,a,d Takahiro Takei,b Fabien Grasset,a,e Jeffrey Scott Cross,f Naoki Ohashia,d,e,g,* a NIMS-CNRS-Saint-Gobain International Collaboration Center, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan b Center for Crystal Science and Technology, University of Yamanashi, 7–32 Miyamae, Kofu, Yamanashi 400-8511, Japan c Univ Rennes, CNRS, ISCR, Institut des Sciences Chimiques de Rennes–UMR6226, F-35000 Rennes, France d Research Center for Electronic and Optical Materials, NIMS, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan e CNRS-Saint-Gobain-NIMS, IRL3629, Laboratory for Innovative Key Materials and Structures (LINK), NIMS, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan S2 f School of Materials and Chemical Technology, Department of Materials Science and Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro, Tokyo 152-8551, Japan g Materials DX Research Center for Element Strategy, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan S3 Figure S1. Unit cells of trigonal (a) CMCC and (b) CMBB, representing a A-B-A-B close-packed hexagonal stacking. Each unit cell contains two MC units (Z = 2). S4 Figure S2. Superlattice models of Cs2[{Mo6Xi8}Xa6] used in DFT-D calculations. Each superlattice contains 1−5 water molecules in the unit cell, with varying positions and orientations. The blue, red, green, yellow, and purple arrows indicate the individual water molecules incorporated into the superlattice and directions of their O−H bonds. The water molecules were arranged in an interstitial space located at the hexagonal channel between Cs2 sites (i.e. Cs3 site), and in some models (SL-C, SL-M, and SL-N), between the stacking of the MC unit and Cs1 site. The initial orientations of the water molecules were set so that their O−H bonds point toward Xas of the MC unit. S5 Figure S3. Crystal structure models of Cs2[{Mo6Xi8}Xa6] adopted in SR-XRD structure refinements: (a) Model I: Trigonal phase without any disorder, (b) Model II: Trigonal phase with Cs2 splitting, (c) Model III: Trigonal phase with an O atom (water molecule) in Cs3 site, (d) Model IV: Trigonal phase with Cs2 splitting and an O atom in Cs3 site. S6 Figure S4. SR-XRD Rietveld refinements of hydrated CMCC, purified CMCC, and purified CMBB. Red circles and black line show the observed and simulated profiles, respectively. Green line indicates the difference between the observed and simulated profiles. Blue marks show the diffraction positions in the simulated profile. S7 Table S1. Summary of the SR-XRD Rietveld refinements of the MC-based compounds. Hydrated CMCC Purified CMCC Purified CMBB Radiation source Synchrotron X-ray Wavelength / Å 0.653 Chemical formula CsMo3Cl7O0.45 CsMo3Cl7O0.17 CsMo3Br7O0.41 Formula weight 676.1 671.6 986.61 Temperature / K 300 Crystal system Trigonal Space group 31P c (no. 163) Lattice parameters / Å a = 9.830(8) c = 14.176(8) V = 1186.2(15) a = 9.790(4) c = 14.221(5) V = 1180.4(9) a = 10.175(33) c = 15.045(36) V = 1349.0(70) Z 2 Goodness of fit (S) 13.34 5.22 4.66 Rp / % 4.00 2.09 1.18 Rwp / % 5.88 3.04 1.59 S8 Table S2. Refined structure factors of the MC-based compounds assuming the model IV illustrated in Fig. S3d: (a) Hydrated CMCC (Space group: 31P c , Rwp = 5.88%, Rp = 4.00%, and S = 13.34) Atom Site Occup. x y z Uiso / Å2 Mo 12i 1.0 0.6554(1) 0.1794(1) 0.1752(1) 0.0144(2) Cl1 4f 1.0 2/3 1/3 0.0401(3) 0.0352(13) Cl2 12i 1.0 0.9553(2) 0.3292(2) 0.1779(2) 0.0315(7) Cl3 12i 1.0 0.6542(2) −0.0370(2) 0.0871(2) 0.0307(7) Cs1 2c 1.0 2/3 1/3 3/4 0.0534(6) Cs2 4e 0.50 0 0 0.0268(1) 0.0209(7) O1 2a 0.89 0 0 1/4 0.0331(52) S9 (b) Purified CMCC (Space group: 31P c , Rwp = 3.04%, Rp = 2.09%, and S = 5.22) Atom Site Occup. x y z Uiso / Å2 Mo 12i 1.0 0.6658(1) 0.1793(1) 0.1756(1) 0.0156(2) Cl1 4f 1.0 2/3 1/3 0.0394(2) 0.0235(8) Cl2 12i 1.0 0.9563(2) 0.3291(2) 0.1777(1) 0.0236(5) Cl3 12i 1.0 0.6534(2) −0.0375(2) 0.0856(1) 0.0311(5) Cs1 2c 1.0 2/3 1/3 3/4 0.0501(5) Cs2 4e 0.50 0 0 0.0160(2) 0.0248(5) O1 2a 0.34 0 0 1/4 1.020(97) (c) Purified CMBB (Space group: 31P c , Rwp = 1.59%, Rp = 1.18%, and S = 4.66) Atom Site Occup. x y z Uiso / Å2 Mo 12i 1.0 0.6685(3) 0.1861(2) 0.1799(1) 0.0124(5) Br1 4f 1.0 2/3 1/3 0.0415(2) 0.0136(6) Br2 12i 1.0 0.9573(2) 0.3279(2) 0.1773(1) a) Br3 12i 1.0 0.6551(2) −0.0357(2) 0.0867(1) 0.0250(7) Cs1 2c 1.0 2/3 1/3 3/4 0.0558(15) Cs2 4e 0.50 0 0 0.0228(4) 0.0182(20) O1 2a 0.81 0 0 1/4 0.412(44) a) Uiso is constrained to be the same as that of Br1. S10 Table S3. Summary of the lattice parameters (Å) of the (a) CMBB and (b) CMCC superlattices optimized by DFT-D calculations. The #H2O column shows the number (n) of the water molecules incorporated in the superlattice, and the Sym. column indicates assumable space group of the fully relaxed superlattice. ΔV (%) indicates a difference between the lattice volumes of the water-incorporated superlattice and the original one (no water molecule). ΔH/n (eV) normalizes the enthalpy difference in both superlattices (ΔH) by n of the water-incorporated superlattice. ΔH/nV (eV/Å3) shows ΔH/n normalized by the lattice volume (V) of the water-incorporated superlattice. Atomic arrangement of each superlattice is shown in Fig. S2. (a) CMBB: Model #H2O Sym. Lattice parameters Enthalpy a b c α β γ V ΔV ΔH/n ΔH/nV SL-A 1 P1 19.851 17.119 14.793 90.09 90.27 90.15 5027.0 +0.04 467.77 0.093 SL-B 1 P1 19.801 17.128 14.807 89.73 90.04 89.70 5021.9 −0.06 468.00 0.093 SL-C 1 P1 19.802 17.123 14.934 90.14 90.11 90.07 5063.8 +0.77 467.51 0.092 SL-D 2 P1 19.871 17.113 14.753 89.70 90.21 89.65 5016.6 −0.17 468.07 0.093 SL-E 2 P1 19.791 17.175 14.760 89.74 89.90 89.60 5016.8 −0.16 468.07 0.093 SL-F 3 P1 19.745 17.232 14.738 89.60 89.62 89.50 5014.2 −0.22 468.06 0.093 SL-G 4 P1 19.757 17.255 14.642 89.19 89.58 89.07 4990.2 −0.69 468.10 0.094 SL-H 4 P1 19.764 17.237 14.595 88.83 89.59 88.75 4969.9 −1.10 468.13 0.094 SL-I 4 P1 19.677 17.309 14.719 89.32 89.18 89.23 5011.7 −0.27 468.05 0.093 SL-J 4 P1 19.644 17.306 14.748 89.07 89.07 89.14 5011.9 −0.26 468.03 0.093 SL-M 4 P1 19.684 17.279 14.871 89.59 89.31 89.53 5057.1 +0.64 467.92 0.093 SL-N 5 P1 19.656 17.326 14.845 89.23 89.12 89.23 5053.9 +0.58 467.95 0.093 SL-O 0 31P c 19.780 17.133 14.828 90.00 90.01 90.00 5025.1 − − − S11 (b) CMCC: Model #H2O Sym. Lattice parameters Enthalpy a b c α β γ V ΔV ΔH/n ΔH/nV SL-A 1 P1 19.119 16.563 13.362 89.68 89.93 89.67 4316.6 −0.01 468.09 0.108 SL-B 1 P1 19.095 16.571 13.833 89.67 90.05 89.76 4376.8 1.38 467.30 0.107 SL-D 2 P1 19.088 16.610 13.617 89.90 89.74 89.87 4317.2 0 468.08 0.108 SL-G 4 P1 19.052 16.669 13.584 89.36 89.41 89.33 4313.4 −0.09 468.09 0.109 SL-H 4 P1 19.046 16.673 13.580 89.43 89.31 89.39 4311.5 −0.13 468.09 0.109 SL-I 4 P1 19.055 16.706 13.564 89.18 89.27 89.16 4316.6 −0.01 468.08 0.108 SL-J 4 P1 19.081 16.718 13.535 89.67 89.40 89.69 4317.3 0.01 468.06 0.108 SL-K 4 P1 19.092 16.618 13.576 89.38 89.76 89.52 4306.9 −0.24 468.11 0.109 SL-L 4 P1 19.051 16.654 13.580 89.01 89.41 89.06 4307.0 −0.24 468.11 0.109 SL-O 0 31P c 19.117 16.557 13.640 90.00 90.00 90.00 4317.2 − − − S12 Figure S5. Projection of the water-incorporated CMBB superlattice (Z = 8), optimized by DFT-D calculations, into trigonal unit cell with Z = 2. n/Z indicates the amount of water molecules (n) per the MC units in the original superlattice. During the lattice projection, duplicate atoms are regarded as the same position using a threshold distance of 0.15 Å to obtain simple structural representation. S13 Table S4. Refined structure factors of the MC-based compounds assuming the disorders of the Cs atoms illustrated in Fig. 6: (a) Hydrated CMCC (Space group: P31c, Rwp = 5.21%, Rp = 3.60%, and S = 11.82) Atom Site Occup. x y z Uiso / Å2 Mo1 6c 1.0 0.5124 0.1823 0.1792 0.0147 Mo2 6c 1.0 0.5154 0.3380 0.3286 a) Cl1 6c 1.0 0.0292 0.3268 0.0895 0.0262 Cl2 6c 1.0 0.3216 0.3631 0.4161 b) Cl3 6c 1.0 0.3736 0.0491 0.3315 0.0273 Cl4 6c 1.0 0.3764 0.3370 0.1861 c) Cl5 2b 1.0 1/3 2/3 −0.0327 c) Cl6 2b 1.0 1/3 2/3 0.5453 c) Cs1A 2b 0.62 1/3 2/3 0.2658 0.0313 Cs1B 2b 0.04 1/3 2/3 0.2458 d) Cs1C 2b 0.34 1/3 2/3 0.2287 d) Cs2A 2a 0.21 0 0 0.0250 0.0304 Cs2B 2a 0.58 0 0 −0.0225 e) Cs2C 2a 0.21 0 0 −0.0356 e) O1 2a 0.88 0 0 0.2360 0.0319 Uiso is constrained to be the same as that of Mo1 for a), Cl1 for b), Cl3 for c), Cs1A for d), and Cs2A for e). S14 (b) Purified CMCC (Space group: P31c, Rwp = 2.80%, Rp = 1.95%, and S = 4.83) Atom Site Occup. x y z Uiso / Å2 Mo1 6c 1.0 0.5130 0.1798 0.1691 0.0155 Mo2 6c 1.0 0.5138 0.3349 0.3180 a) Cl1 6c 1.0 0.0340 0.3317 0.0810 0.0259 Cl2 6c 1.0 0.3201 0.3604 0.4092 b) Cl3 6c 1.0 0.3742 0.0437 0.3231 0.0213 Cl4 6c 1.0 0.3705 0.3265 0.1779 c) Cl5 2b 1.0 1/3 2/3 −0.0483 c) Cl6 2b 1.0 1/3 2/3 0.5303 c) Cs1A 2b 0.33 1/3 2/3 0.2646 0.0324 Cs1B 2b 0.36 1/3 2/3 0.2413 d) Cs1C 2b 0.31 1/3 2/3 0.2223 d) Cs2A 2a 0.44 0 0 0.0131 0.0289 Cs2B 2a 0.56 0 0 −0.0164 e) O1 2a 0.20 0 0 0.3291 0.1780 Uiso is constrained to be the same as that of Mo1 for a), Cl1 for b), Cl3 for c), Cs1A for d), and Cs2A for e). S15 (c) Purified CMBB (Space group: P31c, Rwp = 1.56%, Rp = 1.15%, and S = 4.57) Atom Site Occup. x y z Uiso / Å2 Mo1 6c 1.0 0.5139 0.1814 0.1909 0.0107 Mo2 6c 1.0 0.5204 0.3287 0.3307 a) Br1 6c 1.0 0.0381 0.3431 0.1039 0.0269 Br2 6c 1.0 0.3124 0.3456 0.4306 b) Br3 6c 1.0 0.3617 0.0404 0.3397 0.0109 Br4 6c 1.0 0.3792 0.3347 0.1940 c) Br5 2b 1.0 1/3 2/3 −0.0353 c) Br6 2b 1.0 1/3 2/3 0.5465 c) Cs1A 2b 0.50 1/3 2/3 0.2791 0.0354 Cs1B 2b 0.50 1/3 2/3 0.2544 d) Cs2A 2a 0.13 0 0 0.0525 0.0271 Cs2B 2a 0.87 0 0 −0.0084 e) O1 2a 0.72 0 0 0.2832 0.1853 Uiso is constrained to be the same as that of Mo1 for a), Br1 for b), Br3 for c), Cs1A for d), and Cs2A for e).