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

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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

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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

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1. ^ a b c Haussermann, U.; Kranak, V. F.; Puhakainen, K. (2011). "Hydrogenous Zintl Phases: Interstitial Versus Polyanionic Hydrides". In Fassler, T. F. (ed.). Zintl Phases: Principles and Recent Developments. pp. 139–161.
2. ^ a b 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. ^ a b 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". Physical Review B. 74 (22): 224101. doi:10.1103/PhysRevB.74.224101. ISSN 1098-0121.
4. ^ a b c d e f g h Häussermann, Ulrich (October 2008). "Coexistence of hydrogen and polyanions in multinary main group element hydrides". Zeitschrift für Kristallographie. 223 (10): 628–635\. doi:10.1524/zkri.2008.1016. ISSN 0044-2968. S2CID 96199481.
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". Chemical Physics Letters. 460 (4–6): 432–437\. doi:10.1016/j.cplett.2008.06.018.4–6&rft.pages=432-437&rft.date=2008-07&rft_id=info:doi/10.1016/j.cplett.2008.06.018&rft.aulast=Wu&rft.aufirst=Hui&rft.au=Zhou,+Wei&rft.au=Udovic,+Terrence+J.&rft.au=Rush,+John+J.&rft.au=Yildirim,+Taner&rft_id=https://linkinghub.elsevier.com/retrieve/pii/S0009261408008300&rfr_id=info:sid/en.wikipedia.org:Silicide+hydride" class="Z3988">
6. ^ a b c Armbruster, Markus; Wörle, Michael; Krumeich, Frank; Nesper, Reinhard (October 2009). "Structure and Properties of Hydrogenated Ca, Sr, Ba, and Eu Silicides". Zeitschrift für anorganische und allgemeine Chemie. 635 (12): 1758–1766\. doi:10.1002/zaac.200900220.
7. ^ a b c 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)". Journal of the American Chemical Society. 130 (36): 12139–12147\. doi:10.1021/ja803664y. ISSN 0002-7863. PMID 18698774.
8. ^ a b 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)". Journal of Alloys and Compounds. 623: 164–177\. doi:10.1016/j.jallcom.2014.09.228.
9. ^ Bernardini, F.; Garbarino, G.; Sulpice, A.; Núñez-Regueiro, M.; Gaudin, E.; Chevalier, B.; Méasson, M.-A.; Cano, A.; Tencé, S. (2018-03-12). "Iron-based superconductivity extended to the novel silicide LaFeSiH". Physical Review B. 97 (10): 100504. arXiv:1701.05010. doi:10.1103/PhysRevB.97.100504. hdl:11584/247860. ISSN 2469-9950. S2CID 119004395.
10. ^ Bernardini, F.; Garbarino, G.; Sulpice, A.; Núñez-Regueiro, M.; Gaudin, E.; Chevalier, B.; Méasson, M.-A.; Cano, A.; Tencé, S. (2018-03-12). "Iron-based superconductivity extended to the novel silicide LaFeSiH". Physical Review B. 97 (10): 100504. arXiv:1701.05010. doi:10.1103/PhysRevB.97.100504. hdl:11584/247860. ISSN 2469-9950. S2CID 119004395.
11. ^ a b c Tencé, Sophie; Mahon, Tadhg; Gaudin, Etienne; Chevalier, Bernard; Bobet, Jean-Louis; Flacau, Roxana; Heying, Birgit; Rodewald, Ute Ch.; Pöttgen, Rainer (October 2016). "Hydrogenation studies on NdScSi and NdScGe". Journal of Solid State Chemistry. 242: 168–174\. doi:10.1016/j.jssc.2016.02.017.
12. ^ Werwein, Anton; Kohlmann, Holger (2020-07-31). "Synthesis and Crystal Structure of BaLaSi 2 H 0.80". Zeitschrift für anorganische und allgemeine Chemie. 646 (14): 1227–1230\. doi:10.1002/zaac.202000152. ISSN 0044-2313. S2CID 219060294.
13. ^ Tencé, Sophie; Mahon, Tadhg; Gaudin, Etienne; Chevalier, Bernard; Bobet, Jean-Louis; Flacau, Roxana; Heying, Birgit; Rodewald, Ute Ch.; Pöttgen, Rainer (October 2016). "Hydrogenation studies on NdScSi and NdScGe". Journal of Solid State Chemistry. 242: 168–174\. doi:10.1016/j.jssc.2016.02.017.
14. ^ a b c 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)". Journal of Applied Physics. 128 (14): 143903. doi:10.1063/5.0020513. ISSN 0021-8979. S2CID 225150947.

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Salts and covalent derivatives of the silicide ion

| SiH4
+H |  |  |  | He

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LiSi | Be2Si | SiB3
SiB6
+B | SiC
+C | Si3N4

+N | SiO2 | SiF4 | Ne
NaSi | Mg2Si | Al  | Si4− | SiP, SiP2

+P | SiS2
-S | SiCl4 | Ar
KSi | CaSi
CaSi2 |  | ScSi Sc5Si3 Sc2Si3 Sc5Si4 | TiSi
TiSi2 | V3Si V5Si3, V6Si5, VSi2, V6Si5 | Cr3Si Cr5Si3, CrSi, CrSi2 | MnSi, MnSi2, Mn9Si2, Mn3Si, Mn5Si3, Mn11Si9 | FeSi2
FeSi
Fe5Si3
Fe2Si
Fe3Si | CoSi, CoSi2, Co2Si, Co3Si  | NiSi, more… | Cu17Si3, Cu56Si11, Cu5Si, Cu33Si7, Cu4Si, Cu19Si6, Cu3Si, Cu87Si13 | Zn  | Ga  | GeSi
+Ge | SiAs, SiAs2
-As
+As | SiSe2 SiSe  | SiBr4 | Kr
RbSi | SrSi2 |  | YSi Y5Si3, Y5Si4, Y3Si5, YSi1.4 | ZrSi Zr5Si3, Zr5Si4, ZrSi2, Zr3Si2, Zr2Si, Zr3Si  | Nb4Si Nb5Si3 | MoSi2
Mo3Si Mo5Si3 | Tc  | RuSi Ru2Si, Ru4Si3, Ru2Si3 | RhSi Rh2Si, Rh5Si3, Rh3Si2, Rh20Si13 | PdSi Pd5Si, Pd9Si2, Pd3Si, Pd2Si  | Ag  | Cd  | In  | Sn  | Sb  | TeSi2 Te2Si3 | SiI4 | Xe
CsSi | Ba2Si BaSi2, Ba5Si3 Ba3Si4 | *  | Lu5Si3 | HfSi Hf2Si, Hf3Si2, Hf5Si4, HfSi2 | Ta9Si2, Ta3Si, Ta5Si3 | WSi2 W5Si3 | ReSi Re2Si, ReSi1.8 Re5Si3 | OsSi | IrSi | PtSi | Au  | Hg  | Tl  | Pb  | Bi  | Po  | At  | Rn
Fr  | Ra  | **  | Lr  | Rf  | Db  | Sg  | Bh  | Hs  | Mt  | Ds  | Rg  | Cn  | Nh  | Fl  | Mc  | Lv  | Ts  | Og

*  | LaSi2 La5Si3, La3Si2, La5Si4, LaSi  | CeSi2 Ce5Si3, Ce3Si2, Ce5Si4, CeSi, Ce3Si5 | PrSi2 Pr5Si3, Pr3Si2, Pr5Si4, PrSi  | NdSi Nd5Si3, Nd5Si4, Nd5Si3, Nd3Si4, Nd2Si3, NdSix | Pm  | SmSi2 Sm5Si4, Sm5Si3, SmSi, Sm3Si5 | Eu?  | GdSi2 Gd5Si3, Gd5Si4, GdSi  | TbSi2 SiTb, Si4Tb5, Si3Tb5 | DySi2 DySi  | HoSi2 Ho5Si3, Ho5Si4, HoSi, Ho4Si5 | ErSi2 Er5Si3, Er5Si4, ErSi  | Tm?  | YbSi Si1.8Yb, Si5Yb3, Si4Yb3, Si4Yb5, Si3Yb5
**  | Ac  | ThSi | PaSi | USi2 | NpSi2 | PuSi | Am  | Cm  | Bk  | Cf  | Es  | Fm  | Md  | No
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