Silicide hydride

A silicide hydride is a mixed anion compound that contains silicide (Si4− or clusters) and hydride (H−) anions. The hydrogen is not bound to silicon in these compounds. These can be classed as interstitial hydrides, Hydrogenated zintl phases, or Zintl phase hydrides.[1] In the related silanides, SiH3− anions or groups occur. Where hydrogen is bonded to the silicon, this is a case of anionic hydride, and where it is bonded to a more complex anion, it would be termed polyanionic hydride.[1]

Silicide hydrides may be prepared by heating a Zintl phase or metal silicide under hydrogen pressure, of perhaps 20 atmospheres.[2]

## Properties

In CaSiD1+x the deuterium atom (D) fits in a tetrahedral hole between three calcium and one silicon atoms. The Si-D distance is 1.82 Å, quite a bit further than then a Si-H covalent bond.[3]

## List

formula  | system  | space group  | unit cell Å  | volume  | density  | comment  | reference

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Li4Si2H  | orthorhombic  | Cmmm |  |  |  | zigzag Si chains Si-Si 2.39  | [4]
CaSiH  |  |  |  |  |  |  | [3]
CaSiH1+x x<1.2  | orthorhombic  | Pnma | a = 14.4884, b = 3.8247, c = 11.2509, Z = 3  |  |  | zigzag Si chains Si-Si 2.47  | [4]
CaAlSiH  | trigonal  |  | Z=1  |  |  | Al-H bond semimetal  | [4]
Ca2SiH2.41 | amorphous  |  | a=5.969 b=3.6146 c=6.815  |  |  | reversible hydrogen storage  | [4]
Ca5Si3H0.53 | tetrahedral  | I4/mcm | a=7.6394 c=14.7935 Z=4  | 863.33  |  |  | [1][5]
SrSiH1.6 | orthorhombic  | Pnma |  |  |  |  | [6]
SrAlSiH  |  | P3m1  |  |  |  | Al-H bond semimetal  | [4]
SrGaSiH  | trigonal  | P3m1  | Z=1  |  |  | grey; Ga-H 1.71 semimetal  | [4][7]
Sr21Si2O5H21+x | cubic  | Fd3m | a = 19.1190  |  |  |  | [8]
BaSiH3.4 | orthorhombic  | Pnma |  |  |  |  | [6]
Ba3Si4Hx (x = 1–2)  | tetrahedral  | I4/mcm | a ≈ 8.44, c ≈ 11.95, Z = 8  |  |  | Si46– in a butterfly-shape  | [2]
Ba21Si2O5H21+x | cubic  | Fd3m | a = 20.336  |  |  |  | [8]
BaAlSiH  |  |  |  |  |  | Al-H bond semimetal  | [4]
BaGaSiH  | trigonal  | P3m1  | a=4.2934 c=5.186 Z=1  | 82.79  |  | grey; air stable; Ga-H 1.71 semimetal  | [4][7]
BaGaSiD  | trigonal  | P3m1  | a=4.2776 c=5.1948 Z=1  | 82.32  |  | grey  | [7]
LaFeSiH  | tetragonal  | P4/nmm | a=4.0270 c=8.0374  |  |  |  | [9]
LaFeSiH  | orthorhombic  | Cmme | a=5.6831 b=5.7037 c=7.9728  |  |  | at 15K; superconductor Tc=9.7K  | [10]
La3Pd5SiD~1.6 | orthorhombic  | Imma | a=13.193 b=7.638 c=7.916  | 801.8  |  | <9.5 bar  | [11]
La3Pd5SiD~2.71 | orthorhombic  | Imma | a=13.102 b=7.673 c=8.168  | 821.3  |  |  | [11]
La3Pd5SiD~5 | orthorhombic  | Pmnb | a=13.16 b=7.91 c=8.20  | 854  |  | >75 bar  | [11]
BaLaSi2D0.80 | orthorhombic  | Cmcm | a = 4.6443, b = 15.267, c = 6.7630  |  |  |  | [12]
NdScSiH1.5 | tetrahedral  | I4/mmm | a=4.221 c=16.928 Z=4  |  |  |  | [13]
EuSiH1.8 | orthorhombic  | Pnma |  |  |  |  | [6]
GdMnSiH  | tetragonal  | P4/nmm |  |  |  |  | [14]
GdFeSiH  | tetragonal  | P4/nmm | a=3.901 c=7.503  | 114.2  |  |  | [14]
GdCoSiH  | tetragonal  | P4/nmm | a=3.879 c=7.439  | 111.9  |  |  | [14]

## References

1. ↑ 1.0 1.1 1.2 Haussermann, U.; Kranak, V. F.; Puhakainen, K. (2011). "Hydrogenous Zintl Phases: Interstitial Versus Polyanionic Hydrides". in Fassler, T. F.. Zintl Phases: Principles and Recent Developments. pp. 139–161.
2. ↑ 2.0 2.1 Kranak, Verina F.; Benson, Daryn E.; Wollmann, Lukas; Mesgar, Milad; Shafeie, Samrand; Grins, Jekabs; Häussermann, Ulrich (2 February 2015). "Hydrogenous Zintl Phase Ba 3 Si 4 H x ( x = 1–2): Transforming Si 4 "Butterfly" Anions into Tetrahedral Moieties". Inorganic Chemistry 54 (3): 756–764. doi:10.1021/ic501421u. PMID 25247666.
3. ↑ 3.0 3.1 Wu, H.; Zhou, W.; Udovic, T. J.; Rush, J. J.; Yildirim, T. (2006-12-07). "Structure and hydrogen bonding in CaSiD 1 + x: Issues about covalent bonding" (in en). Physical Review B 74 (22). doi:10.1103/PhysRevB.74.224101. ISSN 1098-0121. https://link.aps.org/doi/10.1103/PhysRevB.74.224101.
4. ↑ 4.0 4.1 4.2 4.3 4.4 4.5 4.6 4.7 Häussermann, Ulrich (October 2008). "Coexistence of hydrogen and polyanions in multinary main group element hydrides" (in en). Zeitschrift für Kristallographie 223 (10): 628–635. doi:10.1524/zkri.2008.1016. ISSN 0044-2968. https://www.degruyter.com/document/doi/10.1524/zkri.2008.1016/html.
5. ↑ Wu, Hui; Zhou, Wei; Udovic, Terrence J.; Rush, John J.; Yildirim, Taner (July 2008). "Structural variations and hydrogen storage properties of Ca5Si3 with Cr5B3-type structure" (in en). Chemical Physics Letters 460 (4–6): 432–437. doi:10.1016/j.cplett.2008.06.018. https://linkinghub.elsevier.com/retrieve/pii/S0009261408008300.
6. ↑ 6.0 6.1 6.2 Armbruster, Markus; Wörle, Michael; Krumeich, Frank; Nesper, Reinhard (October 2009). "Structure and Properties of Hydrogenated Ca, Sr, Ba, and Eu Silicides" (in en). Zeitschrift für anorganische und allgemeine Chemie 635 (12): 1758–1766. doi:10.1002/zaac.200900220. https://onlinelibrary.wiley.com/doi/10.1002/zaac.200900220.
7. ↑ 7.0 7.1 7.2 Evans, Michael J.; Holland, Gregory P.; Garcia-Garcia, Francisco J.; Häussermann, Ulrich (2008-09-10). "Polyanionic Gallium Hydrides from AlB 2 -Type Precursors AeGaE (Ae = Ca, Sr, Ba; E = Si, Ge, Sn)" (in en). Journal of the American Chemical Society 130 (36): 12139–12147. doi:10.1021/ja803664y. ISSN 0002-7863. PMID 18698774. https://pubs.acs.org/doi/10.1021/ja803664y.
8. ↑ 8.0 8.1 Jehle, Michael; Hoffmann, Anke; Kohlmann, Holger; Scherer, Harald; Röhr, Caroline (February 2015). "The 'sub' metallide oxide hydrides Sr 21 Si 2 O 5 H 12 + x and Ba 21 M 2 O 5 H 12 + x ( M = Zn, Cd, Hg, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi)" (in en). Journal of Alloys and Compounds 623: 164–177. doi:10.1016/j.jallcom.2014.09.228. https://linkinghub.elsevier.com/retrieve/pii/S092583881402430X.
9. ↑ Bernardini, F.; Garbarino, G.; Sulpice, A.; Núñez-Regueiro, M.; Gaudin, E.; Chevalier, B.; Méasson, M.-A.; Cano, A. et al. (2018-03-12). "Iron-based superconductivity extended to the novel silicide LaFeSiH" (in en). Physical Review B 97 (10). doi:10.1103/PhysRevB.97.100504. ISSN 2469-9950. https://link.aps.org/doi/10.1103/PhysRevB.97.100504.
10. ↑ Bernardini, F.; Garbarino, G.; Sulpice, A.; Núñez-Regueiro, M.; Gaudin, E.; Chevalier, B.; Méasson, M.-A.; Cano, A. et al. (2018-03-12). "Iron-based superconductivity extended to the novel silicide LaFeSiH" (in en). Physical Review B 97 (10). doi:10.1103/PhysRevB.97.100504. ISSN 2469-9950. https://link.aps.org/doi/10.1103/PhysRevB.97.100504.
11. ↑ 11.0 11.1 11.2 Tencé, Sophie; Mahon, Tadhg; Gaudin, Etienne; Chevalier, Bernard; Bobet, Jean-Louis; Flacau, Roxana; Heying, Birgit; Rodewald, Ute Ch. et al. (October 2016). "Hydrogenation studies on NdScSi and NdScGe" (in en). Journal of Solid State Chemistry 242: 168–174. doi:10.1016/j.jssc.2016.02.017. https://linkinghub.elsevier.com/retrieve/pii/S0022459616300433.
12. ↑ Werwein, Anton; Kohlmann, Holger (2020-07-31). "Synthesis and Crystal Structure of BaLaSi 2 H 0.80" (in en). Zeitschrift für anorganische und allgemeine Chemie 646 (14): 1227–1230. doi:10.1002/zaac.202000152. ISSN 0044-2313.
13. ↑ Tencé, Sophie; Mahon, Tadhg; Gaudin, Etienne; Chevalier, Bernard; Bobet, Jean-Louis; Flacau, Roxana; Heying, Birgit; Rodewald, Ute Ch. et al. (October 2016). "Hydrogenation studies on NdScSi and NdScGe" (in en). Journal of Solid State Chemistry 242: 168–174. doi:10.1016/j.jssc.2016.02.017. https://linkinghub.elsevier.com/retrieve/pii/S0022459616300433.
14. ↑ 14.0 14.1 14.2 Ovchenkova, I. A.; Nikitin, S. A.; Tereshina, I. S.; Karpenkov, A. Yu.; Ovchenkov, Y. A.; Ćwik, J.; Koshkid'ko, Yu. S.; Drulis, H. (2020-10-14). "Hydrogen-induced extremely large change in Curie temperatures in layered GdTSiH (T = Mn, Fe, Co)" (in en). Journal of Applied Physics 128 (14): 143903. doi:10.1063/5.0020513. ISSN 0021-8979. http://aip.scitation.org/doi/10.1063/5.0020513.

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