Sulfatomolybdate

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. They are in the category of heteropolymolybdates.

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

Formation

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

List

formula crystal system space group unit cell volume density comment ref
S2Mo18O624− 18-Molybdodisulfate(VI)(4−); yellow
(SMo12O40)2- Keggin anion
[C5N2H14]2[(S2Mo18O62)-O-VI]•8H2O orthorhombic a=17.993 b=13.580 c=1.4193 Z=2 3468.0
[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
[C5H14N2][(MoO3)3(SO4)]·H2O orthorhombic P212121 a=8.5388 b=10.7467 c=18.113 1662.1 2.525 colourless
[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
(Me4N)2SO4(MoO3)9 yellow
(Et4N)2SO4(MoO3)9 yellow
(Bu4N)2SO4(MoO3)9 yellow
Na2[MoO2(SO4)2] orthorhombic Pbcn a=12.6264 b=7.8092 c =16.715 Z=8 1648.1 2.950 light green
Na4[MoO2(SO4)3] orthorhombic P212121 Z=4 yellow; stable to 436°C
Na[(CH3)4N]3S2Mo5O23·3H2O monoclinic P2/c a= 29.25 b= 12.85 c= 18.24 β= 123.89° Z= 6 colourless
K2[Мо2(SO4)4]
K4[MoO2(SO4)3] orthorhombic Pnma a=7.5931 b=17.128 c=10.5132 Z=4 1367.3
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
K2[MoO2(SO4)2] monoclinic Cc Z=4 2.917 blue; SHG 2×KHP
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
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
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
KAl[(SO4)1.5·(MoO4)0.5]
Cu3O(MoO4)(SO4) orthorhombic Pnma a = 7.420 b = 6.741 c = 13.548 Z=4 677.6 vergasovaite; olive-green
Cu6O2(MoO4)3(SO4) monoclinic P21/m a = 7.5208 b = 6.8602 c = 14.0019 β = 93.471()° 721.09 4.560
Rb2[MoO2(SO4)2]
Rb2SMo3013 P21/n a=9.221 b = 13.378 c = 10.815 β = 112.65°
Rb2SMo3013•0.72H2O
RbAl[(SO4)1.5·(MoO4)0.5]
KGa[(SO4)1.5·(MoO4)0.5]
RbGa[(SO4)1.5·(MoO4)0.5]
KIn[(SO4)1.5·(MoO4)0.5]
RbIn[(SO4)1.5·(MoO4)0.5]
CsAl[(SO4)1.5·(MoO4)0.5]
CsGa[(SO4)1.5·(MoO4)0.5]
CsIn[(SO4)1.5·(MoO4)0.5]
Tb18(MoO4)3(SO4)24•24H2O cubic a=6.652
Dy18(MoO4)3(SO4)24•24H2O a=6.638
Ho18(MoO4)3(SO4)24•24H2O cubic a=6.615
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

References

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  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−". Bulletin of the Chemical Society of Japan. 62 (7): 2184–2188. doi:10.1246/bcsj.62.2184. ISSN 0009-2673.
  4. ↑ "The Electronic Structures of Dawson-type Heteropoly Anion Molybdodisulfate". Chinese Journal of Chemical Physics. 13 (1): 36–42. 2000.
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  6. ↑ Gutnick, Jesse R.; Muller, Eric A.; Narducci Sarjeant, Amy; Norquist, Alexander J. (2004-10-01). "[C5H14N2][(MoO3)3(SO4)]·H2O: Sulfated α-Molybdena Chains". Inorganic Chemistry. 43 (21): 6528–6530. Bibcode:2004InCh...43.6528G. doi:10.1021/ic049192f. ISSN 0020-1669. PMID 15476344.
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  10. 1 2 3 4 5 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) e202500275. 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)4N]3S2Mo5O23·3H2O". Chemistry Letters. 17 (2): 343–346. doi:10.1246/cl.1988.343. ISSN 0366-7022.
  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". Russian Journal of General Chemistry. 86 (1): 5–8. doi:10.1134/S1070363216010023. ISSN 1070-3632.
  13. ↑ Wessels, Vivien; Baldauf, Jasper Arne; Pöttgen, Rainer; Höppe, Henning A. (2026). "Stratified sulfatometallates: unlocking a new dimension in sulfatomolybdates". Dalton Transactions. 55 (9): 3723–3732. doi:10.1039/D5DT03061G. ISSN 1477-9226. PMID 41685958.
  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". Mineralogical Magazine: 1–23. doi:10.1180/mgm.2025.10162. ISSN 0026-461X.
  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.
  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. Bibcode:2025CryRp..70..215Z. doi:10.1134/S1063774524602934.
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  19. 1 2 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". Journal of Structural Chemistry. 65 (12): 2371–2383. doi:10.1134/S0022476624120023. ISSN 0022-4766.
  20. ↑ Berlepsch, Peter; Armbruster, Thomas; Brugger, Joel; Bykova, Elena Y.; Kartashov, Pavel M. (1999-02-11). "The crystal structure of vergasovaite Cu3O[(Mo,S)O4SO4]9 and its relation to synthetic Cu3O[MoO4]2". European Journal of Mineralogy. 11 (1): 101–110. Bibcode:1999EJMin..11..101B. doi:10.1127/ejm/11/1/0101. ISSN 0935-1221.
  21. 1 2 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". Zeitschrift für Naturforschung B. 34 (12): 1683–1685. doi:10.1515/znb-1979-1212. ISSN 1865-7117.
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  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". Journal of Geosciences: 115–121. doi:10.3190/jgeosci.166.