Hydridonitride

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

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 exothermicly.[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 hydridonitride 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 1GPa, 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		 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 CrN36−, CrN35−, 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 CrN35–, octahedral HBa611+ 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 < 1GPa blue [31][8]
Lutetium hydride nitride LuH3-xNy Immm super conductor at 1GPa 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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