Nitronickelate

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The nitronickelates are a class of chemical compounds containing a

nitro groups
, -NO2. Nickel can be in a +2 or +3 oxidation state. There can be five (pentanitronickelates), or six, (hexanitronickelates) nitro groups per nickel atom. They can be considered the double nitrites of
nickel nitrite
.

formula name structure Remarks references
Rb3[Ni(NO2)5] trirubidium pentanitronickelate(II) [1]
Cs3[Ni(NO2)5] tricesium pentanitronickelate(II) dark red, formed from cesium nitrite and nickel nitrite in water [2]
K3[Ni(NO2)5]·KNO2 potassium pentanitronickelate potassium nitrite monoclinic, a = 7.240 Å, b = 10.946 Å, c = 7.120 Å, β = 98.086º; Z = 2; 4 nitro groups bonded to Ni by N, 1 by O (–ONO) formed by heating monohydrate at 100 °C dark purple;
hygroscopic
 [2][3][4]
K4[Ni(NO2)6]·H2O 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 KNO2 and NiCl2 mix in water; orange brown; stable in vacuum [2][3][4]
K2Ca[Ni(NO2)6] potassium calcium hexanitronickelate cubic, a = 10.31 Å, Z = 4 buff [5]
K2Sr[Ni(NO2)6] potassium strontium hexanitronickelate cubic, a = 10.5063 Å, Z = 4, density = 2.867 g/cm3 brown yellow [6]
K2Ba[Ni(NO2)6] potassium barium hexanitronickelate cubic Fm3 (and m3m), a = 10.7800 Å, Z = 4, density = 2.918 g/cm3 brown yellow [7]
K2Pb[Ni(NO2)6] potassium lead hexanitronickelate cubic Fm3, a = 10.577 Å, Z = 4, density = 3.480 g/cm3: No NO2 group disorder buff colour [8]
N(CH3)4[Ni(NO2)3] tetramethylammonium nickel nitrite TMNIN hexagonal perovskite P3m1, a = 9.103 Å, c = 7.082 Å, V = 508.2 Å3, Z = 2, density = 1.770 g/cm3; all nitros are bidentate, nickel either links to N or O of the NO2, 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(CH3)4 [2][9][10]

References

  1. doi:10.1039/J19660001485
    .
  2. ^
    doi:10.1021/ic50050a034
    .
  3. ^
    doi:10.1071/CH9731663
    .
  4. ^
    ISSN 1364-5447
    .
  5. doi:10.1039/J19680000085
    .
  6. doi:10.1107/S0567740876008121
    .
  7. doi:10.1107/S0567740875006590
    .
  8. doi:10.1107/S0567740875006589
    .
  9. doi:10.1021/cm00047a026
    .
  10. doi:10.1016/j.cclet.2014.05.028
    .
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