Hydridonitride

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

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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

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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

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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

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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

[edit]
name formula system space group unit cell

(lengths in Å, volume in Å3)

structure comment optical reference
Lithium nitride hydride
Lithium hydridonitride 		Li4NH tetragonal I41/a a = 4.9865, c = 9.877, V = 234.9, Z = 4 yellow [4]
calcium hydridonitride Ca2NH cubic Fd3m a = 10.13, Z = 16 brown-black [5]
tricalcium silicon trinitride hydride Ca3SiN3H monoclinic C2/c a = 5.236, b = 10.461, c = 16.389, β = 91.182°, Z = 8 SiN4 tetrahedra in chains, Ca6H octahedra [1][22]
Titanium hydridonitride TiN0.3H1.1 [6]
Ti0.7V0.3N0.23H0.8 [6]
Ca3CrN3H hexagonal P63/m a= 7.22772 c=5.06172 Z=2 V=228.998 [23]
hexacalcium dichromium hexanitride hydride Ca6Cr2N6H R3 a = 9.0042, c = 9.1898, Z = 3 planar CrN6−3, CrN5−3, octahedral Ca6H11+ [1][24]
strontium hydridonitride Sr2NH R3m a = 3.870, c = 18.958 orange-yellow or black [25]
Lithium distrontium dihydride nitride LiSr2H2N orthorhombic Pnma a = 7.4714, b = 3.7028, c = 13.2986, Z = 4 [SrH5N2]9−, [SrH4N3]11−, [LiH3N]5− [26]
Ti0.6Nb0.4N0.4H1.1 [6]
zirconium hydridonitride ZrN0.17H1.65 [2]
Ti0.88Zr0.12N0.28H1.39 [6]
Zr0.7Nb0.3N0.33H1.15 [6]
barium hydridonitride Ba2NH hexagonal R3m a = 4.0262, c = 20.469 pure H− conductor [27]
Tribarium chromium trinitride hydride Ba3CrN3H hexagonal P63/m a = 8.0270, c = 5.6240, Z = 2 V=313.83 planar CrN5−3, octahedral HBa11+6 nonmagnetic insulator green [28][29][1]
Lithium dieuropium nitride trihydride LiEu2NH3 orthorhombic Pnma a = 7.4213, b = 3.6726, c = 13.1281, Z = 4 [Eu3+H7N2]10− and [Eu2+H6N3]13− ruby red [30]
Lutetium hydride nitride LuH3−xNy Fm3m < 1 GPa blue [31][8]
Lutetium hydride nitride LuH3−xNy Immm super conductor at 1 GPa and 21 °C pink [8]
Hafnium hydridonitride HfNH0.6 hcp a = 3.241, c = 5.198 [7]
Hafnium hydridonitride HfNH hcp a = 3.216, c = 5.259 [7]
Thorium nitride hydride ThNH2 fcc a = 5.596 [32]

References

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  19. ^ Ming, Xue; Zhang, Ying-Jie; Zhu, Xiyu; Li, Qing; He, Chengping; Liu, Yuecong; Huang, Tianheng; Liu, Gan; Zheng, Bo; Yang, Huan; Sun, Jian; Xi, Xiaoxiang; Wen, Hai-Hu (2023-05-11). "Absence of near-ambient superconductivity in LuH2±xNy". Nature. 620 (7972): 72–77. doi:10.1038/s41586-023-06162-w. ISSN 1476-4687. PMC 10396964. PMID 37168015. S2CID 258638296.
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  21. ^ Ashcroft, N. W. (2004-05-06). "Hydrogen Dominant Metallic Alloys: High Temperature Superconductors?". Physical Review Letters. 92 (18): 187002. Bibcode:2004PhRvL..92r7002A. doi:10.1103/PhysRevLett.92.187002. PMID 15169525.
  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; Kobayashi, Shintaro; Kawaguchi, Shogo; Abou-Hamad, Edy; Kuroki, Kazuhiko; Tassel, Cédric; Abakumov, Artem M.; Kobayashi, Yoji (2022-09-26). "Topochemical Synthesis of Ca 3 CrN 3 H Involving a Rotational Structural Transformation for Catalytic Ammonia Synthesis". Angewandte Chemie International Edition. 61 (39): e202209187. doi:10.1002/anie.202209187. ISSN 1433-7851. PMID 35929578. S2CID 251349324.
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  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. ^ 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.
  28. ^ Falb, Nathaniel W.; Neu, Jennifer N.; Besara, Tiglet; Whalen, Jeffrey B.; Singh, David J.; Siegrist, Theo (2019-03-04). "Ba 3 CrN 3 H: A New Nitride-Hydride with Trigonal Planar Cr 4+". Inorganic Chemistry. 58 (5): 3302–3307. doi:10.1021/acs.inorgchem.8b03367. ISSN 0020-1669. PMID 30762348. S2CID 73438467.
  29. ^ Siegrist, Theo; Singh, David J.; Whalen, Jeffrey B.; Besara, Tiglet; Neu, Jennifer N.; Falb, Nathaniel W. (2019). "Ba3CrN3H: A New Nitride-Hydride with Trigonal Planar Cr4+". Inorganic Chemistry. 58 (5): 3302–3307. doi:10.26434/chemrxiv.7418429. PMID 30762348. S2CID 239569566.
  30. ^ Blaschkowski, Björn; Schleid, Thomas (August 2012). "Mixed-Valent Europium in the Nitride Hydride LiEu2NH3". Zeitschrift für anorganische und allgemeine Chemie. 638 (10): 1592. doi:10.1002/zaac.201204051.
  31. ^ Jin, ChangQing; Ceperly, David (8 March 2023). "Hopes raised for room-temperature superconductivity, but doubts remain". Nature. 615 (7951): 221–222. Bibcode:2023Natur.615..221J. doi:10.1038/d41586-023-00599-9. PMID 36890377. S2CID 257407330.
  32. ^ 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.
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