Chemistry:Hydridonitride

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In chemistry, a hydridonitride (nitridohydride, nitride hydride, or hydride nitride) is a chemical compound that contains both hydride (H−
) and nitride (N3−) ions. These inorganic compounds are distinct from inorganic amides and imides as the hydrogen does not share a bond with nitrogen, and usually contain a larger proportion of metals.[citation needed]

Structure

The hydride ion H−
 is stabilised by being surrounded by electropositive elements such as alkalis or alkaline earths.[1] Quaternary compounds exist where nitrogen forms a complex with bonds to a transition or main group element. The hydride requires the presence of another alkaline earth element.[1]

Production

Hydridonitrides may be produced by a process called self-propagating high-temperature synthesis (SHS) where a metal nitride is ignited in a hydrogen atmosphere.[2]

A metal (Ti, Zr, Hf, Y) can also be ignited in an atmosphere mixing hydrogen and nitrogen, and a hydridonitride is formed exothermically.[3]

The molten metal flux technique involves dissolving metal nitrides and hydrides in an excess of molten alkaline earth metal, by heating till everything is molten, and then cooling until crystals form, but the metal is still liquid. Draining the liquid metal (and centrifuging) leaves the crystals of hydridonitride behind. A eutectic molten metal allows it to be cooled more.[1]

If liquid alkali metal is used as a flux to grow a hydridonitride crystal, excess metal can be removed using liquid ammonia.[4]

Properties

Some hydridonitrides are sensitive to water vapour in air.[5] For non-stoichimetric compounds, as the proportion of hydrogen increases, the unit cell dimensions also increase, so hydrogen is not merely filling holes.[6] When heated to a sufficiently high temperature, hydridonitrides lose hydrogen first to form a metallic nitride or alloy.[7]

Room temperature superconductor

One lutetium hydride doped with nitrogen is claimed to be a room-temperature superconductor at up to 21°C at a pressure of 1 GPa, which is considerably lower than for other polyhydrides.[8] This has been called "red matter"[9] as it is red under high pressure, but blue at ambient conditions.[10][11] The claim has been met with some skepticism as it was made by the same team that made similar claims retracted by Nature in 2022,[12][13][14][15][16] claimed observation of solid metallic hydrogen in 2016 as well as other allegations.[17] First attempts to replicate the results have failed.[18][19] Ashcroft suggested metallic hydrogen could superconduct in 1968[20] at great pressures and in 2004 similarly that dense group IVa hydrides (as the new material) could also be superconductors at more accessible pressures.[21]

List

name formula system space group unit cell

(lengths in Å, volume in Å3)

structure comment optical reference
Lithium nitride hydride
Lithium hydridonitride 		Li
4NH 		tetragonal I41/a a = 4.9865, c = 9.877, V = 234.9, Z = 4 yellow [4]
calcium hydridonitride Ca
2NH 		cubic Fd3m a = 10.13, Z = 16 brown-black [5]
tricalcium silicon trinitride hydride Ca
3SiN
3H 		monoclinic C2/c a = 5.236, b = 10.461, c = 16.389, β = 91.182°, Z = 8 SiN
4 tetrahedra in chains, Ca
6H octahedra 		[1][22]
Titanium hydridonitride TiN
0.3H
1.1 		[6]
Ti
0.7V
0.3N
0.23H
0.8 		[6]
Ca
3CrN
3H 		hexagonal P63/m a= 7.22772 c=5.06172 Z=2 V=228.998 [23]
hexacalcium dichromium hexanitride hydride Ca
6Cr
2N
6H 		R3 a = 9.0042, c = 9.1898, Z = 3 planar CrN6−
3, CrN5−
3, octahedral Ca
6H11+ 		[1][24]
strontium hydridonitride Sr
2NH 		R3m a = 3.870, c = 18.958 orange-yellow or black [25]
Lithium distrontium dihydride nitride LiSr
2H
2N 		orthorhombic Pnma a = 7.4714, b = 3.7028, c = 13.2986, Z = 4 [SrH
5N
2]9−, [SrH
4N
3]11−, [LiH
3N]5− 		[26]
Ti
0.6Nb
0.4N
0.4H
1.1 		[6]
zirconium hydridonitride ZrN
0.17H
1.65 		[2]
Ti
0.88Zr
0.12N
0.28H
1.39 		[6]
Zr
0.7Nb
0.3N
0.33H
1.15 		[6]
ZrCr2N0.4H1.4 hexagonal P63/mmc a = 5.2263, c = 8.5777, catalytic ammonia synthesis [27]
barium hydridonitride Ba
2NH 		hexagonal R3m a = 4.0262, c = 20.469 pure H−
 conductor 		[28]
Tribarium chromium trinitride hydride Ba
3CrN
3H 		hexagonal P63/m a = 8.0270, c = 5.6240, Z = 2 V=313.83 planar CrN5−
3, octahedral HBa11+
6 		nonmagnetic insulator green [1]
Lithium dieuropium nitride trihydride LiEu
2NH
3 		orthorhombic Pnma a = 7.4213, b = 3.6726, c = 13.1281, Z = 4 [Eu3+H
7N
2]10− and [Eu2+H
6N
3]13− 		ruby red [29]
Lutetium hydride nitride LuH
3-xN
y 		Fm3m < 1 GPa blue [30][8]
Lutetium hydride nitride LuH
3-xN
y 		Immm super conductor at 1 GPa and 21 °C pink [8]
Hafnium hydridonitride HfNH
0.6 		hcp a = 3.241, c = 5.198 [7]
Hafnium hydridonitride HfNH hcp a = 3.216, c = 5.259 [7]
Thorium nitride hydride ThNH
2 		fcc a = 5.596 [31]
Lanthanum nitride hydride La2H3–xN trigonal P−3m1 a = 3.86615, c = 6.17859, V = 79.9792 layered anion ordering hydride-concentration driven metal–semiconductor transition [32]
Neodymium nitride hydride Nd2H3–xN trigonal P−3m1 a = 3.73439, c = 5.97775, V = 72.1950 layered anion ordering [32]
Gadolinium nitride hydride Gd2H3–xN trigonal P−3m1 a = 3.62778, c = 5.82556, V = 66.3972 layered anion ordering [32]

References

  1. ↑ 1.0 1.1 1.2 1.3 1.4 1.5 Falb, Nathaniel W.; Neu, Jennifer N.; Besara, Tiglet; Whalen, Jeffrey B.; Singh, David J.; Siegrist, Theo (14 February 2019). "Ba3CrN3H: A New Nitride-Hydride with Trigonal Planar Cr". Inorganic Chemistry 58 (5): 3302–3307. doi:10.1021/acs.inorgchem.8b03367. PMID 30762348. https://figshare.com/articles/Ba3CrN3H_A_New_Nitride-Hydride_with_Trigonal_Planar_Cr4_/7418429.  ChemRxiv
  2. ↑ 2.0 2.1 Aleksanyan, A.G; Aghajanyan, N.N; Dolukhanyan, S.K; Mnatsakanyan, N.L; Harutyunyan, Kh.S; Hayrapetyan, V.S (January 2002). "Thermal-radiation synthesis of zirconium hydridonitrides and carbohydrides". Journal of Alloys and Compounds 330-332: 559–563. doi:10.1016/S0925-8388(01)01519-5. http://fire-ball-2007.narod.ru/32245614.pdf. 
  3. ↑ Dolukhanyan, S. K.; Aleksanyan, A. G.; Shekhtman, V. Sh.; Hakobyan, H. G.; Mayilyan, D. G.; Aghadjanyan, N. N.; Abrahamyan, K. A.; Mnatsakanyan, N. L. et al. (2 July 2010). "Synthesis of transition metal hydrides and a new process for production of refractory metal alloys: An autoreview". International Journal of Self-Propagating High-Temperature Synthesis 19 (2): 85–93. doi:10.3103/S1061386210020020. 
  4. ↑ 4.0 4.1 Niewa, R.; Zherebtsov, D. A. (January 2002). "Redetermination of the crystal structure of tetralithium mononitride monohydride, Li4NH". Zeitschrift für Kristallographie - New Crystal Structures 217 (JG): 317–318. doi:10.1524/ncrs.2002.217.jg.317. ISSN 2197-4578. 
  5. ↑ 5.0 5.1 Brice, Jean-Francois; Motte, Jean-Pierre; Courtois, Alain; Protas, Jean; Aubry, Jacques (February 1976). "Etude structurale de Ca2NH par diffraction des rayons X, diffraction des neutrons et résonance magnétique nucléaire du proton dans le solide". Journal of Solid State Chemistry 17 (1–2): 135–142. doi:10.1016/0022-4596(76)90213-9. Bibcode: 1976JSSCh..17..135B. 
  6. ↑ 6.0 6.1 6.2 6.3 6.4 6.5 Hampton, Michael D.; Schur, Dmitry V.; Zaginaichenko, Svetlana Yu; Trefilov, V. I. (2012-12-06). "Structural Peculiarities of Multicomponent Hydridonitrides on the Basis of Metals of IV–V Groups Produced by SHS Method" (in en). Hydrogen Materials Science and Chemistry of Metal Hydrides. Springer Science & Business Media. p. 361. doi:10.1007/978-94-010-0558-6_35. ISBN 978-94-010-0558-6. https://books.google.com/books?id=4otqCQAAQBAJ&pg=PA360. 
  7. ↑ 7.0 7.1 7.2 Dolukhanyan, S (May 1995). "Interaction of hafnium with hydrogen and nitrogen in the combustion regime" (in en). International Journal of Hydrogen Energy 20 (5): 391–395. doi:10.1016/0360-3199(94)00059-9. Bibcode: 1995IJHE...20..391D. 
  8. ↑ 8.0 8.1 8.2 Dasenbrock-Gammon, Nathan; Snider, Elliot; McBride, Raymond; Pasan, Hiranya; Durkee, Dylan; Khalvashi-Sutter, Nugzari; Munasinghe, Sasanka; Dissanayake, Sachith E. et al. (2023-03-09). "Evidence of near-ambient superconductivity in a N-doped lutetium hydride" (in en). Nature 615 (7951): 244–250. doi:10.1038/s41586-023-05742-0. ISSN 0028-0836. PMID 36890373. Bibcode: 2023Natur.615..244D. https://www.nature.com/articles/s41586-023-05742-0.  (Retracted, see doi:10.1038/s41586-023-06774-2, PMID 37935926)
  9. ↑ Crane, Leah (8 March 2023). "'Red matter' superconductor could transform electronics – if it works". New Scientist 257 (3430): 9. doi:10.1016/S0262-4079(23)00455-4. https://www.newscientist.com/article/2363376-red-matter-superconductor-could-transform-electronics-if-it-works/. 
  10. ↑ Chang, Kenneth (8 March 2023). "New Room-Temperature Superconductor Offers Tantalizing Possibilities". The New York Times. https://www.nytimes.com/2023/03/08/science/room-temperature-superconductor-ranga-dias.html. 
  11. ↑ Service, Robert F. (8 March 2023). "'Revolutionary' blue crystal resurrects hope of room temperature superconductivity". Science 379 (6636). doi:10.1126/science.adh4968. 
  12. ↑ Dasenbrock-Gammon, Nathan; Snider, Elliot; McBride, Raymond; Pasan, Hiranya; Durkee, Dylan; Khalvashi-Sutter, Nugzari; Munasinghe, Sasanka; Dissanayake, Sachith E. et al. (9 March 2023). "Evidence of near-ambient superconductivity in a N-doped lutetium hydride". Nature 615 (7951): 244–250. doi:10.1038/s41586-023-05742-0. PMID 36890373. Bibcode: 2023Natur.615..244D. https://www.nature.com/articles/s41586-023-05742-0.  (Retracted, see doi:10.1038/s41586-023-06774-2, PMID 37935926)
  13. ↑ Woodward, Aylin (8 March 2023). "The Scientific Breakthrough That Could Make Batteries Last Longer". Wall Street Journal. https://www.wsj.com/articles/superconductor-breakthrough-energy-reddmatter-90dfa165. 
  14. ↑ "'Revolutionary' blue crystal resurrects hope of room temperature superconductivity". https://www.science.org/content/article/revolutionary-blue-crystal-resurrects-hope-room-temperature-superconductivity. 
  15. ↑ Margo Anderson (March 8, 2023). "Room-Temperature Superconductivity Claimed". Institute of Electrical and Electronics Engineers. https://spectrum.ieee.org/room-temperature-superconductor. 
  16. ↑ Wood, Charlie; Savitsky, Zack (8 March 2023). "Room-Temperature Superconductor Discovery Meets With Resistance". Simons Foundation. https://www.quantamagazine.org/room-temperature-superconductor-discovery-meets-with-resistance-20230308/. 
  17. ↑ Garisto, Dan (2023-03-09). "Allegations of Scientific Misconduct Mount as Physicist Makes His Biggest Claim Yet" (in en). Physics 16. doi:10.1103/Physics.16.40. Bibcode: 2023PhyOJ..16...40G. https://physics.aps.org/articles/v16/40. 
  18. ↑ Wilkins, Alex (17 March 2023). "'Red matter' superconductor may not be a wonder material after all" (in en-US). https://www.newscientist.com/article/2364955-red-matter-superconductor-may-not-be-a-wonder-material-after-all/. 
  19. ↑ Ming, Xue; Zhang, Ying-Jie; Zhu, Xiyu; Li, Qing; He, Chengping; Liu, Yuecong; Huang, Tianheng; Liu, Gan et al. (2023-05-11). "Absence of near-ambient superconductivity in LuH2±xNy" (in en). Nature 620 (7972): 72–77. doi:10.1038/s41586-023-06162-w. ISSN 1476-4687. PMID 37168015. 
  20. ↑ Ashcroft, N. W. (1968-12-23). "Metallic Hydrogen: A High-Temperature Superconductor?". Physical Review Letters 21 (26): 1748–1749. doi:10.1103/PhysRevLett.21.1748. Bibcode: 1968PhRvL..21.1748A. https://link.aps.org/doi/10.1103/PhysRevLett.21.1748. 
  21. ↑ Ashcroft, N. W. (2004-05-06). "Hydrogen Dominant Metallic Alloys: High Temperature Superconductors?". Physical Review Letters 92 (18). doi:10.1103/PhysRevLett.92.187002. PMID 15169525. Bibcode: 2004PhRvL..92r7002A. https://link.aps.org/doi/10.1103/PhysRevLett.92.187002. 
  22. ↑ Dickman, Matthew J.; Schwartz, Benjamin V. G.; Latturner, Susan E. (27 July 2017). "Low-Dimensional Nitridosilicates Grown from Ca/Li Flux: Void Metal Ca8In2SiN4 and Semiconductor Ca3SiN3H". Inorganic Chemistry 56 (15): 9361–9368. doi:10.1021/acs.inorgchem.7b01532. PMID 28749660. 
  23. ↑ Cao, Yu; Kirsanova, Maria A.; Ochi, Masayuki; Al Maksoud, Walid; Zhu, Tong; Rai, Rohit; Gao, Shenghan; Tsumori, Tatsuya et al. (2022-09-26). "Topochemical Synthesis of Ca 3 CrN 3 H Involving a Rotational Structural Transformation for Catalytic Ammonia Synthesis" (in en). Angewandte Chemie International Edition 61 (39). doi:10.1002/anie.202209187. ISSN 1433-7851. PMID 35929578. Bibcode: 2022ACIE...61E9187C. 
  24. ↑ Bailey, Mark S.; Obrovac, Mark N.; Baillet, Emilie; Reynolds, Thomas K.; Zax, David B.; DiSalvo, Francis J. (September 2003). "Ca 6 [Cr 2 N 6 ]H, the First Quaternary Nitride−Hydride" (in en). Inorganic Chemistry 42 (18): 5572–5578. doi:10.1021/ic0343206. ISSN 0020-1669. PMID 12950205. 
  25. ↑ Sichla, Th.; Altorfer, F.; Hohlwein, D.; Reimann, K.; Steube, M.; Wrzesinski, J.; Jacobs, H. (1997). "Kristallstrukturbestimmung an einer Strontium-hydrid-imid-nitrid-Phase - Sr2(H)N/SrNH bzw. Sr2(D)N/SrND - mit Röntgen-, Neutronen- und Synchrotron-Strahlung" (in de). Zeitschrift für anorganische und allgemeine Chemie 623 (1–6): 414–422. doi:10.1002/zaac.19976230166. ISSN 0044-2313. 
  26. ↑ Blaschkowski, Björn; Schleid, Thomas (November 2007). "Darstellung und Kristallstruktur des Lithium-Strontium-Hydridnitrids LiSr2H2N". Zeitschrift für anorganische und allgemeine Chemie 633 (15): 2644–2648. doi:10.1002/zaac.200700315. 
  27. ↑ Cao, Yu; Wei, Zefeng; Al Maksoud, Walid; Rai, Rohit; Kobayashi, Yoji; Kageyama, Hiroshi (November 2023). "Zr-based Laves phases with nitride/hydride ions for ammonia synthesis" (in en). Solid State Sciences 145. doi:10.1016/j.solidstatesciences.2023.107331. Bibcode: 2023SSSci.14507331C. https://linkinghub.elsevier.com/retrieve/pii/S1293255823002236. 
  28. ↑ Altorfer, F; Buhrer, W; Winkler, B; Coddens, G; Essmann, R; Jacobs, H (May 1994). "H−-jump diffusion in barium-nitride-hydride Ba2NH". Solid State Ionics 70-71: 272–277. doi:10.1016/0167-2738(94)90322-0. 
  29. ↑ Blaschkowski, Björn; Schleid, Thomas (August 2012). "Mixed-Valent Europium in the Nitride Hydride LiEu2NH3" (in en). Zeitschrift für anorganische und allgemeine Chemie 638 (10): 1592. doi:10.1002/zaac.201204051. Bibcode: 2012ZAACh.638.1592B. 
  30. ↑ Jin, ChangQing; Ceperly, David (8 March 2023). "Hopes raised for room-temperature superconductivity, but doubts remain". Nature 615 (7951): 221–222. doi:10.1038/d41586-023-00599-9. PMID 36890377. Bibcode: 2023Natur.615..221J. 
  31. ↑ Peterson, D.T; Nelson, S.O (August 1981). "Equilibrium hydrogen pressures in the Th-N-H system". Journal of the Less Common Metals 80 (2): 221–226. doi:10.1016/0022-5088(81)90095-3. 
  32. ↑ 32.0 32.1 32.2 Wei, Zefeng; Takatsu, Hiroshi; Ubukata, Hiroki; Kato, Daichi; Cao, Yu; Murayama, Kantaro; Zhu, Tong; Tassel, Cédric et al. (2026-04-08). "Chemically Defined Ln 2 H 3– x N Nitride-Hydrides via High-Pressure Synthesis and Topochemical Hydrogen Intercalation" (in en). Journal of the American Chemical Society 148 (13): 14559–14567. doi:10.1021/jacs.6c02443. ISSN 0002-7863. PMID 41914633. https://pubs.acs.org/doi/10.1021/jacs.6c02443. 
Salts and covalent derivatives of the nitride ion
NH3 He(N2)11
Li3N Be3N2 BN β-C3N4
g-C3N4 		N2 NxOy NF3 Ne
Na3N Mg3N2 AlN Si3N4 PN
P3N5 		SxNy
SN
S4N4 		NCl3 Ar
K3N Ca3N2 ScN TiN VN CrN
Cr2N 		MnxNy FexNy CoN Ni3N CuN Zn3N2 GaN Ge3N4 As Se NBr3 Kr
Rb3N Sr3N2 YN ZrN NbN β-Mo2N Tc Ru Rh PdN Ag3N CdN InN Sn Sb Te NI3 Xe
Cs3N Ba3N2   Hf3N4 TaN WN Re Os Ir Pt Au Hg3N2 TlN Pb BiN Po At Rn
Fr3N Ra3N   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
La CeN Pr Nd Pm Sm Eu GdN Tb Dy Ho Er Tm Yb Lu
Ac Th Pa UN Np Pu Am Cm Bk Cf Es Fm Md No Lr



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