Phosphate phosphite

Short description: Class of chemical compounds

A phosphate phosphite is a chemical compound or salt that contains both phosphate and phosphite anions (PO3−
4 and PO3−
3). These are mixed anion compounds or mixed valence compounds. Some have third anions.

Phosphate phosphites frequently occur as metal organic framework (MOF) compounds which are of research interest for gas storage, detection or catalysis. In these phosphate and phosphite form bridging ligands to hard metal ions. Protonated amines are templates.[1]

## Contents

* 1 Naming
* 2 Production
* 3 Properties
* 4 Related
* 5 List
* 6 References

## Naming

A phosphate phosphite compound may also be called a phosphite phosphate.

## Production

Phosphate phosphite compounds are frequently produced by hydrothermal synthesis, in which a water solution of ingredients is enclosed in a sealed container and heated. Phosphate may be reduced to phosphite or phosphite oxidised to phosphate in this process.

## Properties

On heating,

## Related

Related to these are the nitrite nitrates and arsenate arsenites.

## List

name  | formula  | ratio PO4:PO3 | mw | system  | space group | unit cell (Å)  | volume  | density  | properties  | references

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1,4-Diammoniumbutane  | [(H3N(CH2)4NH3)2][Sc5F4(HPO3)6(H2PO3)2(PO4)]  | 1:8  | 1300.8  | monoclinic  | C2/m | a = 12.888,
b = 14.835,
c = 10.531,
β = 103.093°,
Z = 2 (at 93 K)  | 1961.2  |  |  | [2]
Imidazole  | [C3N2H5]2[VIII4(H2O)3(HPO3)4(HPO4)3]  | 3:4  | 1003.766  | trigonal  | P3c1  | a = 13.499,
c = 18.120,
Z = 12  | 2280.35  | 2.143  | green  | [3]
| (C3H10NO)6[V8(H2O)6(PO4)2(HPO3)12]  | 2:12  |  |  | P3c1  | a = 13.5393,
c = 18.2283  | 2893.8  |  | green  | [4]
| (C4H8N2)3[V8(H2O)6(PO4)2(HPO3)12]  | 2:12  |  |  | P3c1  | a = 13.4922,
c = 18.3589  | 2894.3  |  | green  | [4]
| Mn5(μ-OH2)2(PO4)2(HPO3)2·2H2O  | 2:2  |  |  |  |  |  |  |  | [5]
Iron(III) 2,2′-bipyridine phosphite−phposphate  | [FeIII(2,2′-bipyridine)(HPO3)(H2PO4)]  | 1:1  |  | monoclinic  |  | a = 10.5407,
b = 6.4298,
c = 10.6172,
β = 113.890°,
Z = 2  |  | 1.878  | colourless  | [6]
| FeIII(1,10-phenanthroline)(HPO3)(H2PO3)  | 1:1  |  | monoclinic  | P21/m | a = 10.180,
b = 6.424,
c = 11.6668,
β = 115.59°,
Z = 4  | 668.2  | 1.880  | yellow  | [7]
| {[C3H4N2]2[C5NH5]14[H15(Mo2O4)8Co16(PO4)14(HPO3)10(OH)3]}·5H2O  | 14:10  | 6685.09  | monoclinic  | C2/m | a = 29.724,
b = 24.623,
c = 20.687,
β = 126.760°,
Z = 2  | 12130  | 1.830  | red  | [8]
Tris(4-pyridyl)triazine zinc phosphate–phosphite  | C54H60N18O42P10Zn9 | ?  | 2531.23  | hexagonal  | P63 | a = 15.6464,
c = 19.788,
Z = 2  | 4195.2  |  | yellow  | [9]
1-(2-Aminoethyl)piperazine tetrazinc diphosphate diphosphite  | (C6H17N3)[Zn4(PO4)2(HPO3)2]  | 2:2  |  | monoclinic  | Cc | a = 5.327,
b = 17.146,
c = 22.071,
β = 94.58°,
Z = 4  | 2009.5  |  |  | [10]
Zinc phosphate-phosphite  | trans-(C6H15N2)2Zn4(PO4)2(HPO3)2 | 2:2  | 841.78  | monoclinic  | P21/n | a = 9.706,
b = 9.993,
c = 27.557,
β = 96.795°,
Z = 4  | 2654.0  | 2.107  |  | [11]
1,3-Cyclohexanebis(methylamine)  | [H2CHBMA][Zn1.5Mn(HPO3)2.5(PO4)]·5H2O  | 1:5  |  | monoclinic  | C2/c | a = 33.929,
b = 13.045,
c = 8.971,
β = 104.37°,
Z = 2  | 3846.5  |  |  | [12]
2-Hydroxypropylammonium dizinc hydrogenphosphite phosphate  | [C3H6(OH)NH3][Zn2(HPO3)(PO4)]  | 1:1  |  | triclinic  | P1 | a = 5.302,
b = 8.934,
c = 12.686,
α = 74.35°,
β = 88.54°,
γ = 73.94°  |  |  |  | [13]

(Bis(Cyclohexane-1,3-bis(methylammonium)) bis(μ4-phosphato)-tetrakis(μ3-hydrogen phosphito)-manganese-tetra-zinc dihydrate)

| [H2CHBMA][Zn2Mn0.5(PO4)(HPO3)2]·H2O  | 1:2  |  | monoclinic  | C2/c | a = 33.929,
b = 13.045,
c = 8.971,
β = 104.37°,
Z = 4  | 3846  |  |  | [14]
Triethylenetetramine  | [C6N4H22]0.5[Zn3(PO4)2(HPO3)]  | 2:1  |  |  |  |  |  |  |  | [15]
Zinc potassium phosphite phosphate  |  |  |  |  |  |  |  |  |  | [16]
N,N,N′,N′-tetramethylenediamine (TMEDA)  | (C6N2H18)2(C6N2H17)Ga15(OH)8(PO4)2(HPO4)12(HPO3)6·2H2O  | 14:6  |  |  | P3 | a = 19.046,
c = 8.331,
Z = 1  | 2617.1  |  |  | [17]
Zirconium phosphate phosphite  | γ-ZrPO4·HPO2(OH)·2H2O  | 1:1  |  |  |  |  |  |  | layered  | [18]
Cadmium 1,10-phenanthroline phosphate phosphite oxalate  | Cd2(phen)2(H2PO4)(H2PO3)(C2O4)  | 1:1  |  |  |  |  |  |  | chains  | [19]
catena-(Tris(hexane-1,6-diaminium) octakis(μ3-phosphonato)-hexakis(μ3-phosphato)-tris(μ2-hydrogen phosphato)hexaaqua-nonaindium  | [In9(H2O)6(HPO3)13(H2PO3)2(PO4)(HPO4)][(C6N2H18)3]  | 2:15  |  | hexagonal  | P63/m | a = 13.7676,
c = 28.062  |  |  |  | [20]
4-Bipyridine  | (C10H10N2)1.5(H3O)3[In18(H2O)12(HPO4)12(HPO3)16(H2PO3)6]  | 12:16  |  | hexagonal  | P63/m | a = 13.784,
c = 28.058  | 4617  |  |  | [21]
catena-(Bis(propane-1,3-diammonium)-octakis(μ3-phosphito)-pentakis(μ2-hydrogen phosphito)-(μ2-dihydrogenphosphato)-hexaindium)  | [In6(HPO3)8(H2PO3)5(H2PO4)]·(C3N2H12)2 | 1:11  |  | orthorhombic  | Pna21 | a = 26.7974,
b = 9.8459,
c = 18.5441,
Z = 4  | 4892.8  |  |  | [22]
| Pb2Al(HPO3)3(H2PO4)  | 1:3  |  | orthorhombic  | Cmcm |  |  |  |  | [23]
| Pb2Ga(HPO3)3(H2PO4)  | 1:3  |  | orthorhombic  | Cmcm |  |  |  |  |
| Pb2Al(HPO3)2(HPO4)(H2PO4)  | 2:2  |  | orthorhombic  | Cmcm |  |  |  |  |
Rubidium uranium(VI,IV) phosphate-phosphite  | Rb2[(UO2)2(UIV)(PO4)2(HPO3)2(H2O)]  | 2:2  | 1316.94  | monoclinic  | C2/c | a = 16.2421,
b = 10.5049,
c = 11.0936,
β = 98.745°  | 1870.8  | 4.702  | orange-yellow  | [24]
Caesium uranium(IV) phosphate-phosphite  | Cs2[UIV3(PO4)2(HPO3)4]  | 2:4  | 1489.76  | monoclinic  | C2/m | a = 25.7396
b = 5.5906,
c = 7.6334,
β = 98.964°,
Z = 2  | 1085.03  | 4.560  | blue-green  | [24]
Caesium uranium(VI,IV) phosphate-phosphite  | Cs2[(UO2)(UIV)(HPO4)2(HPO3)2]  | 2:2  | 1123.78  | triclinic  | P1 | a = 6.8571,
b = 11.1190,
c = 12.0391,
α = 63.861°,
β = 77.481°,
γ = 79.331°,
Z = 2  | 800.22  | 4.664  | yellow-orange  | [24]
| Cs4[(UO2)8(HPO4)5(HPO3)5]·4H2O  | 5:5  |  | monoclinic  | C2/c | a = 18.5005,
b = 10.971,
c = 14.4752,
β = 104.513°  |  |  | yellow  | [25]
| Cs4[UIV6(PO4)8(HPO4)(HPO3)]  | 9:1  |  | orthorhombic  | Pmmn | a = 6.9321,
b = 26.935,
c = 10.9137  |  |  | pale green  | [25]
| Cs10[UIV10(PO4)4(HPO4)14(HPO3)5]·H2O  | 15:5  |  | monoclinic  | C2/m | a = 19.2966,
b = 20.2914,
c = 13.9293,
β = 126.839°  |  |  | green  | [25]
| Tl3[(UO2)2(H1.5PO4)(H0.5PO4)(H1.5PO3)2]  | 2:2  | 1503.07  | tetragonal  | P42/mbc | a = 13.5382,
c = 19.4008,
Z = 8  | 3555.8  | 5.615  | yellow-green  | [26]
| Tl2[(UO2)2(UIV)(H2O)(PO4)2(HPO3)2]  | 2:2  | 1550.71  | monoclinic  | C2/c | a = 16.2360,
b = 10.4995,
c = 11.0003,
β = 99.027°,
Z = 4  | 1851.99  | 5.562  | light green  | [26]

## References

1. ↑ Petrosyants, S. P. (December 2013). "Coordination polymers of indium, scandium, and yttrium" (in en). Russian Journal of Inorganic Chemistry 58 (13): 1605–1624. doi:10.1134/S0036023613130032. ISSN 0036-0236. http://link.springer.com/10.1134/S0036023613130032.
2. ↑ Miller, Stuart R. (2007-12-17). Scandium bearing open framework materials (Thesis thesis). University of St Andrews. hdl:10023/570.
3. ↑ Ramaswamy, Padmini; Mandal, Sukhendu; Hegde, Nayana N; Prabhu, Ramanath; Banerjee, Debmalya; Bhat, S. V.; Natarajan, Srinivasan (April 2010). "Synthesis, Structure, and Magnetic Properties of Amine-Templated Transition-Metal Phosphites" (in en). European Journal of Inorganic Chemistry 2010 (12): 1829–1838. doi:10.1002/ejic.200901206. https://onlinelibrary.wiley.com/doi/10.1002/ejic.200901206.
4. ↑ 4.0 4.1 曉文, 鄭 (18 July 1991). "亞磷酸釩及磷酸鉬的合成,結構鑑定及性質研究". p. 28. http://ir.lib.ncu.edu.tw:88/thesis/pdf/2002/GC89223009.pdf.
5. ↑ "Mn（II）取代磷酸铝和磷酸锰微孔化合物的水热合成与表征--《吉林大学》2005年博士论文". https://cdmd.cnki.com.cn/Article/CDMD-10183-2005107315.htm.
6. ↑ Mandal, Sukhendu; Pati, Swapan K.; Green, Mark A.; Natarajan, Srinivasan (February 2005). "The First One-Dimensional Iron Phosphite−Phosphate, [FeIII(2,2′-bipyridine)(HPO3)(H2PO4): Synthesis, Structure, and Magnetic Properties"] (in en). Chemistry of Materials 17 (3): 638–643. doi:10.1021/cm049064p. ISSN 0897-4756. https://pubs.acs.org/doi/10.1021/cm049064p.
7. ↑ Mandal, Sukhendu; Green, Mark A.; Natarajan, Srinivasan (2005-12-10). "Synthesis, structure and magnetic properties of a new one-dimensional iron phosphite, [FeIII(1,10-phenanthroline)(HPO3)(H2PO3)"] (in en). Current Science 89 (11): 1899–1903. ISSN 0011-3891. http://www.ias.ac.in/currsci/dec102005/1899.pdf.
8. ↑ Miao, Hao; Wan, Hong-Xiang; Liu, Ming; Zhang, Yu; Xu, Xiao; Ju, Wei-Wei; Zhu, Dun-ru; Xu, Yan (2014). "Two novel organic–inorganic hybrid molybdenum(V) cobalt/nickel phosphate compounds based on isolated nanosized Mo/Co(Ni)/P cluster wheels" (in en). J. Mater. Chem. C 2 (32): 6554–6560. doi:10.1039/C4TC00944D. ISSN 2050-7526. http://xlink.rsc.org/?DOI=C4TC00944D.
9. ↑ Zhang, Jie; Yao, Zhenguo; Liao, Shijun; Dai, Jingcao; Fu, Zhiyong (2013). "A hybrid metal phosphate–phosphite material grafted with electron deficient organic components showing interesting fluorescent and photosensitive properties" (in en). Journal of Materials Chemistry A 1 (16): 4945. doi:10.1039/c3ta10478h. ISSN 2050-7488. http://xlink.rsc.org/?DOI=c3ta10478h.
10. ↑ Chen, Xiaoxin; Wang, Yu; Yu, Jihong; Zou, Yongchun; Xu, Ruren (July 2004). "(C6H17N3)[Zn4(PO4)2(HPO3)2: a new layered zinc phosphate–phosphite templated by 1-(2-Aminoethyl) piperazine"] (in en). Journal of Solid State Chemistry 177 (7): 2518–2522. doi:10.1016/j.jssc.2004.03.039. Bibcode: 2004JSSCh.177.2518C. https://linkinghub.elsevier.com/retrieve/pii/S0022459604001458.
11. ↑ Wang, Yu; Yu, Jihong; Du, Yu; Shi, Zhan; Zou, Yongcun; Xu, Ruren (2002). "Hydrothermal synthesis and characterization of a new inorganic–organic hybrid layered zinc phosphate–phosphite (C6H15N2)2Zn4(PO4)2(HPO3)2" (in en). J. Chem. Soc., Dalton Trans. (21): 4060–4063. doi:10.1039/B204876K. ISSN 1472-7773. http://xlink.rsc.org/?DOI=B204876K.
12. ↑ "Synthesis and Structure of Manganese Zinc Phosphate-phosphite with Extra Large Twenty-membered Ring Channels–《Chemical Journal of Chinese Universities》2007年12期". https://en.cnki.com.cn/Article_en/CJFDTotal-GDXH200712007.htm.
13. ↑ Fu, Zhiyong; Zhang, Jie; Tan, Yi; Song, Desheng; Liu, Changchun; Wu, Jiaqi (2011-11-10). "Synthesis, structure, and base-catalytic performance of a laminar zinc phosphite-phosphate" (in en). Journal of Coordination Chemistry 64 (21): 3808–3816. doi:10.1080/00958972.2011.631533. ISSN 0095-8972. https://www.tandfonline.com/doi/full/10.1080/00958972.2011.631533.
14. ↑ Chen, Guangyan; Su, Hao; Yu, Jianguo; Yang, Yang; Zhao, Yongnan; Fu, Zhifeng (July 2009). "Separation of 1,3-Cyclohexanebis(methylamine) Isomers by Template Synthesis of Open-Framework Bimetallic Phosphites" (in en). Zeitschrift für anorganische und allgemeine Chemie 635 (9–10): 1463–1469. doi:10.1002/zaac.200801317.
15. ↑ Rao, C. N. R. (2003-09-12) (in en). Advances In Chemistry: A Selection Of C N R Rao's Publications (1994–2003). World Scientific. pp. 478. ISBN 978-981-4485-05-0. https://books.google.com/books?id=cRTJCgAAQBAJ&pg=PA478.
16. ↑ "Studies on polymerization of zinc potassium phosphite-phosphate the non-toxic anticorrosive pigment--《JOURNAL OF SHANTOU UNIVERSITY(NATURAL SCIENCE EDITION)》1995年01期". https://en.cnki.com.cn/Article_en/CJFDTotal-STDX501.008.htm.
17. ↑ Zhou, Guangpeng; Yang, Yulin; Fan, Ruiqing; Liu, Xinrong; Hong, Hengwu; Wang, Fuping (July 2010). "Hydrothermal synthesis and characterization of a new organically templated three-dimensional open-framework gallium phosphate–phosphite (C6N2H18)2(C6N2H17)Ga15(OH)8(PO4)2(HPO4)12(HPO3)6·2H2O" (in en). Solid State Sciences 12 (7): 1103–1106. doi:10.1016/j.solidstatesciences.2010.04.013. Bibcode: 2010SSSci..12.1103Z. https://linkinghub.elsevier.com/retrieve/pii/S1293255810001664.
18. ↑ Alberti, G.; Costantino, U.; Vivani, R.; Biswas, R.K. (June 1992). "Preparation and some preliminary investigations of ion exchange and intercalation properties of γ-zirconium phosphate phosphite" (in en). Reactive Polymers 17 (3): 245–253. doi:10.1016/0923-1137(92)90271-3. https://linkinghub.elsevier.com/retrieve/pii/0923113792902713.
19. ↑ Li, Jing; Li, Ting; Zeng, Hongmei; Zou, Guohong; Lin, Zhien (September 2018). "Solvent-free synthesis of inorganic-organic hybrid solids with chainlike, layered, and open-framework structures" (in en). Inorganic Chemistry Communications 95: 8–11. doi:10.1016/j.inoche.2018.06.022. https://linkinghub.elsevier.com/retrieve/pii/S1387700318304623.
20. ↑ Dong, Zhaojun; Yan, Yan; Li, Yi; Li, Jiyang; Yu, Jihong; Xu, Ruren (May 2011). "A new open-framework indium phosphate–phosphite containing intersecting extra-large 16-ring channels" (in en). Inorganic Chemistry Communications 14 (5): 727–730. doi:10.1016/j.inoche.2011.02.019. https://linkinghub.elsevier.com/retrieve/pii/S1387700311000943.
21. ↑ Li, Hui Duan (June 2014). "Construction of a Novel 3D Indium Phosphate–Phosphite with Extra-Large 16-MRs Channels: Synthesis, Structure and Fluorescence Property". Advanced Materials Research 936: 901–904. doi:10.4028/www.scientific.net/AMR.936.901. ISSN 1662-8985. https://www.scientific.net/AMR.936.901.
22. ↑ Huang, Liangliang; Song, Tianyou; Fan, Yong; Yang, Lei; Wang, Liping; Zhang, Hua; Wang, Li; Xu, Jianing (August 2010). "Hydrothermal syntheses, characterizations of novel three-dimensional indium phosphite and indium phosphite–phosphate with intersecting 8-membered ring channels: [In3(H2PO3)3(HPO3)4·(trans-C6N2H16) and [In6(HPO3)8(H2PO3)5(H2PO4)]·(C3N2H12)2"] (in en). Microporous and Mesoporous Materials 132 (3): 409–413. doi:10.1016/j.micromeso.2010.03.020. https://linkinghub.elsevier.com/retrieve/pii/S1387181110000892.
23. ↑ 李, 天予 (2020-07-17). "含鉛離子和三價金屬陽離子之混亞磷酸 -磷酸鹽化合物合成及結構和性質探討". http://ir.lib.ncu.edu.tw:88/thesis/view_etd.asp?URN=107223037.
24. ↑ 24.0 24.1 24.2 Villa, Eric M.; Marr, Connor J.; Jouffret, Laurent J.; Alekseev, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E. (2012-06-18). "Systematic Evolution from Uranyl(VI) Phosphites to Uranium(IV) Phosphates" (in en). Inorganic Chemistry 51 (12): 6548–6558. doi:10.1021/ic3000735. ISSN 0020-1669. PMID 22646238. https://pubs.acs.org/doi/10.1021/ic3000735.
25. ↑ 25.0 25.1 25.2 Villa, Eric M.; Marr, Connor J.; Diwu, Juan; Alekseev, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E. (2013-01-18). "From Order to Disorder and Back Again: In Situ Hydrothermal Redox Reactions of Uranium Phosphites and Phosphates" (in en). Inorganic Chemistry 52 (2): 965–973. doi:10.1021/ic302198w. ISSN 0020-1669. PMID 23301654. https://pubs.acs.org/doi/10.1021/ic302198w.
26. ↑ 26.0 26.1 Villa, Eric M.; Alekseev, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E. (2013-04-03). "Syntheses, Structures, and Comparisons of Thallium Uranium Phosphites, Mixed Phosphate-Phosphites, and Phosphate" (in en). Crystal Growth & Design 13 (4): 1721–1729. doi:10.1021/cg400046a. ISSN 1528-7483. https://pubs.acs.org/doi/10.1021/cg400046a.

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Phosphates

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Li3PO4 | Be |  |  |  |  |  |  |  |  |  |  | BPO4 | C | (NH4)3PO4 | O | F | Ne
Na3PO4 | Mg3(PO4)2 |  |  |  |  |  |  |  |  |  |  | AlPO4 | Si | P | S | Cl | Ar
K3PO4 | Ca3(PO4)2 | ScPO4 | Ti | V | Cr | Mn3(PO4)2 | Fe3(PO4)2
FePO4 | Co3(PO4)2 | Ni3(PO4)2 | Cu3(PO4)2 | Zn3(PO4)2 | GaPO4 | Ge | As | Se | Br | Kr
Rb3PO4 | Sr3(PO4)2 | YPO4 | Zr3(PO4)4 | Nb | Mo | Tc | Ru | Rh | Pd | Ag3PO4 | Cd3(PO4)2 | InPO4 | Sn | Sb | Te | I | Xe
Cs3PO4 | Ba3(PO4)2 | *  | Hf | Ta | W | Re | Os | Ir | Pt | Au | Hg | Tl3PO4 | Pb3(PO4)2 | BiPO4 | Po | At | Rn
Fr | Ra | **  | Rf | Db | Sg | Bh | Hs | Mt | Ds | Rg | Cn | Nh | Fl | Mc | Lv | Ts | Og |  |  |  |  |  |  |  |
|  | ↓ |  |  |  |  |  |  |  |  |  |  |  |  |  |  |
| * | LaPO4 | CePO4 | PrPO4 | NdPO4 | Pm | Sm | Eu | Gd | Tb | Dy | Ho | ErPO4 | TmPO4 | Yb | Lu |
| ** | Ac | Th3(PO4)4 | Pa | U(PO4)2 | Np | Pu | Am | Cm | Bk | Cf | Es | Fm | Md | No | Lr |

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