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Nitronickelate

The nitronickelates are a class of chemical compounds containing a nickel atom complexed by nitro groups, -NO. Nickel can be in a +2 or +3 oxidation state. There can be five (pentanitronickelates), or six, (hexanitronickelates) nitro groups per nickel atom. The can be considered the double nitrites of nickel nitrite.

formula

name

structure

Remarks

references

Rb[Ni(NO)]

trirubidium pentanitronickelate(II)

Cs[Ni(NO)]

tricesium pentanitronickelate(II)

dark red, formed from cesium nitrite and nickel nitrite in water

K[Ni(NO)]

potassium hexanitronickelate

4 nitro groups bonded to Ni by N, 2 by O (-ONO)

formed by heating monohydrate at 100 °C dark purple; hygroscopic

K[Ni(NO)]•HO

potassium hexanitronickelate monohydrate

hexagonal a=7.634 Å c=22.45 Å Z=3; nitro groups bonded to Ni via N; water not coordinated

formed from KNO and NiCl mix in water; orange brown; stable in vacuum

KCa[Ni(NO)]

potassium calcium hexanitronickelate

cubic a=10.31 Z=4

buff

KSr[Ni(NO)]

potassium strontium hexanitronickelate

cubic a=10.5063 Z=4 density=2.867

brown yellow

KBa[Ni(NO)]

potassium barium hexanitronickelate

cubic Fm3 (and m3m) a=10.7800 Z=4 density=2.918

brown yellow

KPb[Ni(NO)]

potassium lead hexanitronickelate

cubic Fm3 a=10.577 Z=4 density=3.480: No NO group disorder

buff colour;

N(CH)[Ni(NO)]

tetramethylammonium nickel nitrite TMNIN

Hexagonal Perovskite Pm1 a=9.103 Å c=7.082 Å V=508.2 Å Z=2 density=1.770 all nitros are bidentate, nickel either links to N or O of the NO, forming a chain of nickel alternating with ONO

yellow brown; one-dimensional Heisenberg antiferromagnet; Haldane material; phase transitions at 409.1 and 428.4 K due to rotation of N(CH)