Citation: Tong-Qing SUN, Qian-Qian WANG, Yong-Fa KONG, Jing-Jun XU. Synthesis, Structure and Characterization of a New Silicophosphate, K₂SiP₄O₁₃, with a Six-fold Coordinated Si[J]. Chinese Journal of Structural Chemistry, ;2021, 40(2): 256-263. doi: 10.14102/j.cnki.0254-5861.2011-2851 shu

Synthesis, Structure and Characterization of a New Silicophosphate, K₂SiP₄O₁₃, with a Six-fold Coordinated Si

School of Physics and the MOE Key Laboratory of Weak-light Nonlinear Photonics, Nankai University, Tianjin 300071, China

Corresponding author: Tong-Qing SUN, suntq@nankai.edu.cn
Received Date: 16 April 2020
Accepted Date: 10 June 2020

Fund Project: the Natural Science Foundation of Tianjin City 17JCYBJC17800the National Natural Science Foundation of China 21271109the National Natural Science Foundation of China 11674179

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A potassium silicophosphate, K₂SiP₄O₁₃, has been synthesized in molten polyphosphoric acid. It crystalizes in the triclinic space group P\begin{document}$ \overline 1 $\end{document} (No. 2) with a = 4.8327(10), b = 7.7403(15), c = 14.485(3) Å, α = 82.29(3)°, β = 83.31(3)°, γ = 81.95°, V = 529.02(19) Å³, Z = 2. The crystallographic structure features 2D layers of [SiP₄O₁₃]_∞ in the ab plane with counter cations K⁺ residing among the layers, and the anionic framework of [SiP₄O₁₃]_∞ is composed of six-fold coordinated Si atoms and tetraphosphate anions by sharing vertex O atoms. The title compound was characterized by powder X-ray diffraction, IR and Raman spectroscopies, UV-vis diffuse reflectance spectroscopy, thermogravimetry and differential scanning calorimetry.
- synthesis,
- silicophosphate,
- SiO₆ octahedral coordination,
- crystal structure
1. [1]
  Styskalik, A.; Babiak, M.; Machac, P.; Relichova, B.; Pinkas, J. New adamantane-like silicophosphate cage and its reactivity toward tris(pentafluorophenyl)borane. Inorg. Chem. 2017, 56, 10699‒10705. doi: 10.1021/acs.inorgchem.7b01572
2. [2]
  Zeng, H. D.; Jiang, Q.; Liu, Z.; Li, X.; Ren, J.; Chen, G. R.; Liu, F. D.; Peng, S. Unique sodium phosphosilicate glasses designed through extended topological constraint theory. J. Phys. Chem. B 2014, 118, 5177‒5193. doi: 10.1021/jp5018357
3. [3]
  Sawangboon, N.; Nizamutdinova, A.; Uesbeck, T.; Limbach, R.; Meechoowas, E.; Tapasa, K.; Möncke, D.; Wondraczek, L.; Kamitsos, E. I.; Wüllen, L. V.; Brauer, D. S. Modification of silicophosphate glass composition, structure, and properties via crucible material and melting conditions. Int. J. Appl. Glass Sci. 2020, 11, 46‒57. doi: 10.1111/ijag.13958
4. [4]
  Abdelghany, A. M.; Zeyada, H. M.; ElBatal, H. A.; Fetouh, R. Synthesis and spectral properties of Nd₂O₃-doped sodium silicophosphate glass. Silicon 2016, 8, 325‒330. doi: 10.1007/s12633-015-9308-5
5. [5]
  Unithrattil, S.; Arunkumar, P.; Kim, Y. H.; Kim, H. J.; Vu, N. H.; Heo, J.; Chung, W. J.; Im, W. B. A phosphosilicate compound, NaCa₃PSiO₈ structure solution and luminescence properties. Inorg. Chem. 2017, 56, 15130‒15137. doi: 10.1021/acs.inorgchem.7b02456
6. [6]
  Deng, Y.; Eames, C.; Chotard, J. N.; Lalère, F.; Seznec, V.; Emge, S.; Pecher, O.; Grey, C. P.; Masquelier, C.; Islam, M. S. Structural and mechanistic insights into fast lithium-ion conduction in Li₄SiO₄-Li₃PO₄ solid electrolytes. J. Am. Chem. Soc. 2015, 137, 9136‒9145. doi: 10.1021/jacs.5b04444
7. [7]
  Porkodi, P.; Yegnaraman, V.; Kamaraj, P.; Kalyanavalli, V.; Jeyakumar, D. Synthesis of NASICON — a molecular precursor-based approach. Chem. Mater. 2008, 20, 6410‒6419. doi: 10.1021/cm800208k
8. [8]
  Stearns, L. A.; Groy, T. L.; Leinenweber, K. High-pressure synthesis and crystal structure of silicon phosphate hydroxide, SiPO₄(OH). J. Solid State Chem. 2005, 178, 2594‒2061. doi: 10.1016/j.jssc.2005.05.030
9. [9]
  Kowalke, J.; Arnold, C.; Ponomarev, I.; Jäger, C.; Kroll, P.; Brendler, E.; Kroke, E. Structural insight into layered silicon hydrogen phosphates containing [SiO₆] octahedra prepared by different reaction routes. Eur. J. Inorg. Chem. 2019, 828‒836.
10. [10]
  Leinenweber, K.; Stearns, L. A.; Nite, J. M.; Németh, P.; Groy, T. L. Structure of a new form of silicon phosphate (SiP₂O₇) synthesized at high pressures and temperatures. J. Solid State Chem. 2012, 190, 221‒225. doi: 10.1016/j.jssc.2012.02.031
11. [11]
  Poojary, D. M.; Borade, R. B.; Clearfield, A. Structural characterization of silicon orthophosphate. Inorg. Chim. Acta 1993, 208, 23‒29. doi: 10.1016/S0020-1693(00)82879-0
12. [12]
  Islam, S. M.; Glaum, R.; Pelka, A.; Daniels, J.; Hoffbauer, W. The first phosphates of heptavalent rhenium. Z. Anorg. Allg. Chem. 2013, 639, 2463‒2472. doi: 10.1002/zaac.201300289
13. [13]
  Köenigstein, K.; Jansen, M. Ein einfacher weg zu silicium in oktaedrischer sauerstoffkoordination. Chem. Ber. 1994, 127, 1213‒1218. doi: 10.1002/cber.19941270706
14. [14]
  Khabbouchia, M.; Hosnia, K.; Meznia, M.; Srasraa, E. Simplified synthesis of silicophosphate materials using an activated metakaolin as a natural source of active silica. Appl. Clay Sci. 2018, 158, 169‒176. doi: 10.1016/j.clay.2018.03.027
15. [15]
  Ding, Q. R.; Zhao, S. E.; Xiao, H.; Li, Y. Q.; Liu, S.; Li, L. N.; Li, C. S.; Wang, Y. S.; Hong, M. C.; Luo, J. H. An uncommon hypervalent fluorooxosilicophosphate. Chem. Asian J. 2019, 14, 4174‒4178. doi: 10.1002/asia.201901410
16. [16]
  Han, G. P.; Lei, B. H.; Yang, Z. H.; Wang, Y.; Pan, S. L. A fluorooxosilicophosphate with an unprecedented SiO₂F₄ species. Angew. Chem. Int. Ed. 2018, 57, 9828‒9832. doi: 10.1002/anie.201805759
17. [17]
  Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. 2009, 42, 339‒341. doi: 10.1107/S0021889808042726
18. [18]
  Sheldrick, G. M. SHELXT – integrated space-group and crystal-structure determination. Acta Cryst. 2015, A71, 3‒8.
19. [19]
  Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Cryst. 2015, C71, 3‒8.
20. [20]
  Spek, A. L. Structure validation in chemical crystallography. Acta Cryst. 2009, D65, 148‒155.
21. [21]
  Zhao, S. E.; Gong, P. F.; Luo, S. Y.; Bai, L.; Lin, Z. S.; Ji, C. M.; Chen, T. L.; Hong, M. C.; Luo, J. H. Deep-ultraviolet transparent phosphates RbBa₂(PO₃)₅ and Rb₂Ba₃(P₂O₇)₂ show nonlinear optical activity from condensation of [PO₄]³⁻ units. J. Am. Chem. Soc. 2014, 136, 8560‒8563. doi: 10.1021/ja504319x
22. [22]
  Zhong, Y.; Shan, P.; Sun, T. Q.; Hu, Z. P.; Liu, H. D.; Liu, S. G.; Kong, Y. F.; Xu, J. J. Growth and theoretical study on the deep ultraviolet transparent β-CsBa₂(PO₃)₅ nonlinear optical crystal. CrystEngComm. 2019, 21, 4690‒4695. doi: 10.1039/C9CE00636B
23. [23]
  Halasyamani, P. S. Asymmetric cation coordination in oxide materials: influence of lone-pair cations on the intra-octahedral distortion in d⁰ transition metals. Chem. Mater. 2004, 16, 3586‒3592. doi: 10.1021/cm049297g
24. [24]
  Brown, I. D. Recent developments in the methods and applications of the bond valence model. Chem. Rev. 2009, 109, 6858‒6919. doi: 10.1021/cr900053k
25. [25]
  Zhao, D.; Xie, Z.; Hu, J. M.; Zhang, H.; Zhang, W. L.; Yang, S. L.; Cheng, W. D. Structure determination, electronic and optical properties of NaGe₂P₃O₁₂ and Cs₂GeP₄O₁₃. J. Mol. Struct. 2009, 922, 127‒134. doi: 10.1016/j.molstruc.2009.01.009
26. [26]
  Chudinova, N.; Murashova, E. Synthesis and structure of double phosphates of titanium and alkalimetals. Proc. Est. Acad. Sci. Chem. 2000, 49, 29‒35.
27. [27]
  Kraus, W.; Nolze, G. POWDER CELL — a program for the representation and manipulation of crystal structures and calculation of the resulting X-ray powder patterns. J. Appl. Cryst. 1996, 29, 301‒303. doi: 10.1107/S0021889895014920
28. [28]
  Schildhammer, D.; Fuhrmann, G.; Petschnig, L. L.; Wurst, K.; Vitzthum, D.; Seibald, M.; Schottenberger, H.; Huppertz, H. Structural redetermination and photoluminescence properties of the niobium oxyphosphate (NbO)₂P₄O₁₃. Inorg. Chem. 2017, 56, 2736‒2741. doi: 10.1021/acs.inorgchem.6b02891
29. [29]
  Rao, K. J.; Baskaran, N.; Ramakrishnan, P. A.; Ravi, B. G.; Karthikeyan, A. Structural and lithium ion transport studies in sol gel-prepared lithium silicophosphate glasses. Chem. Mater. 1998, 10, 3109‒3123. doi: 10.1021/cm980216o
30. [30]
  Calahoo, C.; Zwanziger, J. W.; Butler, I. S. Mechanical-structural investigation of ion-exchanged lithium silicate glass using micro-Raman spectroscopy. J. Phys. Chem. C 2016, 120, 7213‒7232.
31. [31]
  Arroyabe, E.; Kaindl, R.; Töobbens, D. M.; Kahlenberg, V. Synthesis, crystal structure, and vibrational spectroscopy of K₂Ca₄Si₈O₂₁ — an unusual single-layer silicate containing Q² and Q³ units. Inorg. Chem. 2009, 48, 11929‒11934. doi: 10.1021/ic901762u
32. [32]
  Zhu, Z. Y.; Gu, S. X.; Li, S. S.; Chen, C.; Xiao, S. Q.; Tao, H. Z. Effects of six-fold coordinated silicon on structure and properties of BaO-SiO₂-P₂O₅ glasses. J. Wuhan Univ. Technol.-Mat. Sci. Ed. 2019, 34, 1043‒1048.
33. [33]
  Bai, Z. Y.; Hu, C. L.; Liu, L. H.; Zhang, L. Z.; Huang, Y. S.; Yuan, F. F.; Lin, Z. B. KMg(H₂O)PO₄: a deep-ultraviolet transparent nonlinear optical material derived from KTiOPO₄. Chem. Mater. 2019, 31, 9540‒9545.
34. [34]
  Bai, Z. Y.; Liu, L. H.; Zhang, L. Z.; Huang, Y. S.; Yuan, F. F.; Lin, Z. B. K₂SrP₄O₁₂: a deep-UV transparent cyclophosphate as a nonlinear optical crystal. Chem. Commun. 2019, 55, 8454‒8457.
35. [35]
  Lee, M. H.; Yang, C. H.; Jan, J. H. Band-resolved analysis of nonlinear optical properties of crystalline and molecular materials. Phys. Rev. B 2004, 70, 235110.
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Synthesis, Structure and Characterization of a New Silicophosphate, K₂SiP₄O₁₃, with a Six-fold Coordinated Si