Two isopolyoxomolybdate {Mo36} cluster compounds are presented, where one incorporates two sodium ions into the {Mo36} cluster cavity and the other does not, showing different “sensitive coordination sites” to organic cation ligands TEAH+ (protonated triethanolamine) as identified by X-ray crystallography, and rationalized by DFT calculations. The compound (TEAH)6{Na2 [Mo36O112(H2O)14]}· 28H2O (1) crystallizes in the trinclinic space group P−1, a=15.8931(2) Å, b=17.3089(2) Å, c=18.1880(3) Å, \(\alpha=101.210(1)\), \(\beta= 95.481(1)\), \(\gamma=116.585(1)^{\circ}\), V=4292.95(10) Å3, D c=2.688 g cm−3. 16838 unique reflections and 1213 refined parameters were used in structure refinement. R1=0.032, R2=0.071. When sodium is eliminated from the reaction system, the new compound (TEAH)8[Mo36O112 (H2O)14]· 10 H2O (2) was also isolated and crystallographically characterized. Compound 2 crystallizes in the monoclinic space group P−1, a=16.3351(3) Å, b=16.5709(4) Å, c=18.5803(5) Å, \(\alpha=83.330(1)\), \(\beta=65.010(2)\), \(\gamma=85.107(2)^{\circ}\), V=4524.08(18) Å3, D c=2.525 g cm−3. 17591 unique reflections and 1016 refined parameters were used in structure refinement. R1=0.044, R2=0.128.
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This work was supported by the Leverhulme Trust (London), The Royal Society, The University of Glasgow and the EPSRC. The EPSRC provided funds for the X-ray diffractometer.
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Long, DL., Streb, C., Kögerler, P. et al. Observation and Theoretical Analysis of the “Sensitive Coordination Sites” in the Isopolyoxomolybdate Cluster \([\hbox{Mo}_{36}\hbox{O}_{112}(\hbox{H}_{2}\hbox{O})_{14}]^{8-}\) . J Clust Sci 17, 257–266 (2006). https://doi.org/10.1007/s10876-006-0058-9
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DOI: https://doi.org/10.1007/s10876-006-0058-9