Chemistry:Sulfatomolybdate

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A sulfatomolybdate or molybdosulfate is a chemical compound containing sulfate groups links to molybdate groups via common oxygen atoms.

Sulfatomolybdates can contain molybdenum in four-, five- or six-fold coordination (MoO4, MoO5 or MoO6). The sulfato component is always tetrahedral (SO4). These substances increase the diversity of material structures, and so are under investigation for interesting material properties. These include laser, luminescence, phosphors and scintillators.[1] They are in the category of heteropolymolybdates.

The most similar compounds are the sulfatotungstates. Compounds with selenium instead of sulfur exists.[2] Other high-charge transition metals can form sulfatoniobates, sulfateovanadates and sulfatotantalates.[1]

Formation

Sulfatomolybdates have been made by dissolving molybdenum trioxide in molten potassium pyrosulfate, and other alkali pyrosulfates can be used to make other compounds.[1]

List

formula crystal system space group unit cell volume density comment ref
S2Mo18O624− 18-Molybdodisulfate(VI)(4−); yellow [3]
(SMo12O40)2- Keggin anion [4]
[C5N2H14]2[(S2Mo18O62)-O-VI]•8H2O orthorhombic a=17.993 b=13.580 c=1.4193 Z=2 3468.0 [5]
[C5N2H14]8(H3O)2[(S2Mo2Mo16O62)-Mo-V-O-VI]3 • (C5H5N)2 monoclinic a=22.665 b =13.74 9 c=32.912 β=104.31° Z=4 9.938 [5]
[C5H14N2][(MoO3)3(SO4)]·H2O orthorhombic P212121 a=8.5388 b=10.7467 c=18.113 1662.1 2.525 colourless [6]
[N(CH3)4]3[H(SO4)2-(MoO2(O2))3]· 3H2O monoclinic P2/n a = 13.497 b = 15.231 c = 32.603 β = 103.113° 6577 [7]
(Me4N)2SO4(MoO3)9 yellow [8]
(Et4N)2SO4(MoO3)9 yellow [8]
(Bu4N)2SO4(MoO3)9 yellow [8]
Na2[MoO2(SO4)2] orthorhombic Pbcn a=12.6264 b=7.8092 c =16.715 Z=8 1648.1 2.950 light green [9]
Na4[MoO2(SO4)3] orthorhombic P212121 Z=4 yellow; stable to 436°C [10]
Na[(CH3)4N]3S2Mo5O23·3H2O monoclinic P2/c a= 29.25 b= 12.85 c= 18.24 β= 123.89° Z= 6 colourless [11]
K2[Мо2(SO4)4] [12]
K4[MoO2(SO4)3] orthorhombic Pnma a=7.5931 b=17.128 c=10.5132 Z=4 1367.3 [10][9]
K2[MoO2(SO4)2] monoclinic P21/c a=9.5122 b=11.8520 c=8.2378 β=99.470 Z=4 916.06 2.863 light blue; melt 405-411°C [10][13][14]
K2[MoO2(SO4)2] monoclinic Cc Z=4 2.917 blue; SHG 2×KHP [10]
K2(Mo2O5)(SO4)2·3H2O triclinic P1_ 5.48124 b=9.5360 c=14.1235 α=97.401° β=99.906° γ=90.080° Z=2 720.94 Liangjunite [15]
K8[(MoO2)2(SO4)6 monoclinic P21/n a=9.4260 b=4.0022 c=10.3259 β=90.652° Z=2 1362.77 2.794 [1]
KNa(MoO2)(SO4)2 monoclinic P21/c a =9.6225 b = 11.4049 c = 8.1421 β = 99.179° Z= 4 882.10 hasanovite; insoluble in water [16][17]
KAl[(SO4)1.5·(MoO4)0.5] [18]
Cu3O(MoO4)(SO4) orthorhombic Pnma a = 7.420 b = 6.741 c = 13.548 Z=4 677.6 vergasovaite; olive-green [19][20]
Cu6O2(MoO4)3(SO4) monoclinic P21/m a = 7.5208 b = 6.8602 c = 14.0019 β = 93.471()° 721.09 4.560 [19]
Rb2[MoO2(SO4)2] [10]
Rb2SMo3013 P21/n a=9.221 b = 13.378 c = 10.815 β = 112.65° [21]
Rb2SMo3013•0.72H2O [21]
RbAl[(SO4)1.5·(MoO4)0.5] [18]
KGa[(SO4)1.5·(MoO4)0.5] [18]
RbGa[(SO4)1.5·(MoO4)0.5] [18]
KIn[(SO4)1.5·(MoO4)0.5] [18]
RbIn[(SO4)1.5·(MoO4)0.5] [18]
CsAl[(SO4)1.5·(MoO4)0.5] [18]
CsGa[(SO4)1.5·(MoO4)0.5] [18]
CsIn[(SO4)1.5·(MoO4)0.5] [18]
Tb18(MoO4)3(SO4)24•24H2O cubic a=6.652 [22]
Dy18(MoO4)3(SO4)24•24H2O a=6.638 [22]
Ho18(MoO4)3(SO4)24•24H2O cubic a=6.615 [22]
K2Na8(UO2)8Mo4O24 (S,Mo)O4 monoclinic C2/c a = 24.282 b = 12.117 c = 13.617 β = 106.33º Z= 4 3845.0 orange [23]

References

  1. ↑ 1.0 1.1 1.2 1.3 Wessels, Vivien; Hämmer, Matthias; Simrit Kaur, Narayan; Bayarjargal, Lkhamsuren; Höppe, Henning A. (2026-01-04). "On New Alkaline Sulfatometallates: Cs6[(WO2)2O(SO4)4, K8[(MoO2)2(SO4)6], K7.9Sr0.1[(WO2)2(SO4)6] and Na4[MoO2(SO4)3]"] (in en). Zeitschrift für anorganische und allgemeine Chemie. doi:10.1002/zaac.202500168. ISSN 0044-2313. https://onlinelibrary.wiley.com/doi/10.1002/zaac.202500168. 
  2. ↑ Nagazi, Ichraf; Haddad, Amor (February 2012). "Synthesis, characterization and crystal structure of a novel Strandberg-type polyoxoselenomolybdate Rb4[Se2Mo5O21]·2H2O". Materials Research Bulletin 47 (2): 356–361. doi:10.1016/j.materresbull.2011.11.014. 
  3. ↑ Himeno, Sadayuki; Hori, Toshitaka; Saito, Atsuyoshi (1989-07-01). "Spectroscopic and Electrochemical Characterization of 18-Molybdodisulfate(VI)(4−), S2Mo18O624−" (in en). Bulletin of the Chemical Society of Japan 62 (7): 2184–2188. doi:10.1246/bcsj.62.2184. ISSN 0009-2673. https://academic.oup.com/bcsj/article/62/7/2184/7345549. 
  4. ↑ "The Electronic Structures of Dawson-type Heteropoly Anion Molybdodisulfate". Chinese Journal of Chemical Physics 13 (1): 36–42. 2000. 
  5. ↑ 5.0 5.1 Sun, Yue-Xia; Zhang, Zhi-Bin; Sun, Qi; Xu, Yan (2011). "Syntheses, Characterization and Catalytic Properties of Two New Wells-Dawson Molybdosulfates". Chinese Journal of Inorganic Chemistry 27 (3): 556–560. 
  6. ↑ Gutnick, Jesse R.; Muller, Eric A.; Narducci Sarjeant, Amy; Norquist, Alexander J. (2004-10-01). "[C 5 H 14 N 2 [(MoO 3 ) 3 (SO 4 )]·H 2 O: Sulfated α-Molybdena Chains"] (in en). Inorganic Chemistry 43 (21): 6528–6530. doi:10.1021/ic049192f. ISSN 0020-1669. PMID 15476344. https://pubs.acs.org/doi/10.1021/ic049192f. 
  7. ↑ Hashimoto, Masato; Ichida, Hikaru; Sasaki, Yukiyoshi (1996-02-01). "PREPARATION AND STRUCTURE OF TETRAMETHYLAMMONIUM HYDROGEN TRIPEROXOTRIMOLYBDODISULFATE TRIHYDRATE, [N(CH 3 ) 4 3 [H(SO 4 ) 2 -(MoO 2 (O 2 )) 3 ]· 3H 2 O"] (in en). Journal of Coordination Chemistry 37 (1–4): 349–359. doi:10.1080/00958979608023565. ISSN 0095-8972. https://www.tandfonline.com/doi/full/10.1080/00958979608023565. 
  8. ↑ 8.0 8.1 8.2 Hori, Toshitaka; Himeno, Sadayuki (1987-01-05). "Preparation of a Yellow Heteropoly Molybdosulfate" (in en). Chemistry Letters 16 (1): 53–56. doi:10.1246/cl.1987.53. ISSN 0366-7022. https://academic.oup.com/chemlett/article/16/1/53/7395391. 
  9. ↑ 9.0 9.1 Schäffer, Susan J. Cline; Berg, Rolf W. (2008-03-15). "Tetrapotassium cis -dioxido- trans -bis(sulfato-κ O )sulfato(κ 2 O , O ′)molybdate(VI)". Acta Crystallographica Section E 64 (3): i20. doi:10.1107/S1600536808003851. ISSN 1600-5368. PMID 21201837. PMC 2960843. https://journals.iucr.org/paper?S1600536808003851. 
  10. ↑ 10.0 10.1 10.2 10.3 10.4 Wessels, Vivien; Kraus, Fabian; Bayarjargal, Lkhamsuren; Krug von Nidda, Hans-Albrecht; Eickerling, Georg; Höppe, Henning A. (11 November 2025). "On The Existence of Highly Condensed Sulfatotungstates and Sulfatomolybdates". ChemistryEurope 3 (6). doi:10.1002/ceur.202500275. 
  11. ↑ Himeno, Sadayuki; Hori, Toshitaka; Tanaka, Hiroshi; Saito, Atsuyoshi (1988-02-05). "Synthesis of Sodium Tetramethylammonium Pentamolybdodisulfate(VI)(4-) Trihydrate, Na[(CH3)4N3S2Mo5O23·3H2O"] (in en). Chemistry Letters 17 (2): 343–346. doi:10.1246/cl.1988.343. ISSN 0366-7022. https://academic.oup.com/chemlett/article/17/2/343/7396265. 
  12. ↑ Khripun, V. D.; Krapivin, M. A.; Tsyleva, K. S.; Sukhodolov, N. G.; Kondrat’ev, Yu. V. (January 2016). "State of molybdenum clusters in solutions: III. Formation enthalpies of intermediate products of stepwise K2[Мо2(SO4)4 oxidation in 1 M H2SO4 solution"] (in en). Russian Journal of General Chemistry 86 (1): 5–8. doi:10.1134/S1070363216010023. ISSN 1070-3632. http://link.springer.com/10.1134/S1070363216010023. 
  13. ↑ Wessels, Vivien; Baldauf, Jasper Arne; Pöttgen, Rainer; Höppe, Henning A. (2026). "Stratified sulfatometallates: unlocking a new dimension in sulfatomolybdates" (in en). Dalton Transactions. doi:10.1039/D5DT03061G. ISSN 1477-9226. PMID 41685958. https://xlink.rsc.org/?DOI=D5DT03061G. 
  14. ↑ Noerbygaard, T. (January 1998). "The Reaction Between MoO3 and Molten K2S2O7 Forming K2MoO2(SO4)2, Studied by Raman and IR Spectroscopy and X-Ray Crystal Structure Determination". ECS Proceedings Volumes 1998-11 (1): 553–573. doi:10.1149/199811.0553PV. 
  15. ↑ Gu, Xiangping; Yang, Hexiong; Liu, Guanghua (2025-10-01). "Liangjunite, K 2 (Mo 2 O 5 )(SO 4 ) 2 ·3H 2 O, a new mineral from the Freedom #2 mine, the Marysvale volcanic field, Utah, USA" (in en). Mineralogical Magazine: 1–23. doi:10.1180/mgm.2025.10162. ISSN 0026-461X. https://www.cambridge.org/core/product/identifier/S0026461X2510162X/type/journal_article. 
  16. ↑ Mirakov, м. а.; Pautov, L. а.; Siidra, о. I.; Makhmadsharif, S.; Karpenko, V. Yu.; Plechov, P. Yu. (2023-01-01). "Hasanovite KNa(MoO2)(SO4)2, a New Mineral from Natural Underground Coal Fires at the Fan-Yagnob Coal Deposit, Tajikistan". Zapiski RMO (Proceedings of the Russian Mineralogical Society) CLII (1): 18–36. doi:10.31857/S0869605523010082. ISSN 2658-4352. https://journals.rcsi.science/0869-6055/article/view/136724. 
  17. ↑ Zubkova, N. V.; Pekov, I. V.; Potekhina, N. V.; Pushcharovsky, D. Yu. (April 2025). "Natural Anhydrous Sulfates with Alkali Cations: Structural Features, Comparative Crystal Chemistry, and Genetic Mineralogy". Crystallography Reports 70 (2): 215–234. doi:10.1134/S1063774524602934. 
  18. ↑ 18.0 18.1 18.2 18.3 18.4 18.5 18.6 18.7 18.8 Alekseev, F. P.; Kozhevnikova, N. M.; Mokhosoev, M. V. (May 1979). "Chemistry and sequence of conversions during reaction of potassium, rubidium, and cesium molybdates with aluminum, gallium, and indium sulfates" (in en). Bulletin of the Academy of Sciences of the USSR Division of Chemical Science 28 (5): 875–878. doi:10.1007/BF00963287. ISSN 0568-5230. http://link.springer.com/10.1007/BF00963287. 
  19. ↑ 19.0 19.1 Borisov, A. S.; Siidra, O. I.; Charkin, D. O.; Nikolaevich, G. V.; Baikina, A. S.; Nazarchuk, E. V.; Holzheid, A. (December 2024). "Synthesis and Crystal Structure of Cu6O2(MoO4)3(SO4), New Copper Molybdate Oxosulfate, Structurally Related to Vergasovaite and Glikinite" (in en). Journal of Structural Chemistry 65 (12): 2371–2383. doi:10.1134/S0022476624120023. ISSN 0022-4766. https://link.springer.com/10.1134/S0022476624120023. 
  20. ↑ Berlepsch, Peter; Armbruster, Thomas; Brugger, Joel; Bykova, Elena Y.; Kartashov, Pavel M. (1999-02-11). "The crystal structure of vergasovaite Cu3O[(Mo,S)O4SO49 and its relation to synthetic Cu3O[MoO4]2"] (in en). European Journal of Mineralogy 11 (1): 101–110. doi:10.1127/ejm/11/1/0101. ISSN 0935-1221. http://www.schweizerbart.de/papers/ejm/detail/11/83125/The_crystal_structure_of_vergasovaite_Cu3O_Mo_S_O?af=crossref. 
  21. ↑ 21.0 21.1 Fuchs, Joachim; Kreusler, Hans-Ulrich; Förster, Achim (1979-12-01). "Die Kristallstruktur des Rubidiumtrimolybdatosulfats Rb 2 SMo 3 O 13 / The Structure of the Rubidiumtrimolybdatosulfate Rb 2 SMo 3 O 13" (in en). Zeitschrift für Naturforschung B 34 (12): 1683–1685. doi:10.1515/znb-1979-1212. ISSN 1865-7117. https://www.degruyter.com/document/doi/10.1515/znb-1979-1212/html. 
  22. ↑ 22.0 22.1 22.2 Zvoleiko, P T; Get'man, E I; Mokhosoev, M V (Dec 1, 1978). "Sulfato-molybdates in the systems of Ln2(MoO4)3-Ln2(SO4)3, where Ln -Tb, Dy, Ho and Er". Zh. Neorg. Khim 23 (12): 3198–3201. https://www.osti.gov/etdeweb/biblio/6051084. 
  23. ↑ Krivovichev, S.V. (2014-04-12). "K2Na8(UO2)8Mo4O24[(S,Mo)O4, the first uranium molybdosulfate: synthesis, crystal structure, and comparison to related compounds"] (in en). Journal of GEOsciences: 115–121. doi:10.3190/jgeosci.166. http://www.jgeosci.org/detail/jgeosci.166. 



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