Nitronickelate

The nitronickelates are a class of chemical compounds containing a nickel atom complexed by 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. Hathaway, B. J.; Slade, R. C. (1966). "The properties of trirubidium pentanitronickelate(II)". Journal of the Chemical Society A: Inorganic, Physical, Theoretical: 1485. doi:10.1039/J19660001485.
  2. Goodgame, David M. L.; Hitchman, M. A. (April 1967). "Spectroscopic studies of some compounds with octahedral polynitrite anions". Inorganic Chemistry. 6 (4): 813–816. doi:10.1021/ic50050a034.
  3. Green, RW; Bell, B (1973). "Complex nickel nitrites. I. Complexes of N-substituted Propane-1,3-diamines". Australian Journal of Chemistry. 26 (8): 1663. doi:10.1071/CH9731663.
  4. Grey, Ian E.; Hitchman, Michael A.; Rowbottom, Graham L.; Scarlett, Nicola V. Y.; Wilson, Jenny (1994-01-01). "Crystal and molecular structure and spectra of K4[Ni(NO2)6]·H2O and K3[Ni(NO2)4(O2N)]". Journal of the Chemical Society, Dalton Transactions (4): 595–601. doi:10.1039/DT9940000595. ISSN 1364-5447.
  5. Hathaway, B. J.; Slade, R. C. (1968). "The influence of cations on the properties of the hexanitrometallate anions in the K2MIIMII(NO2)6 type of complex of the nickel(II) and copper(II) ions". Journal of the Chemical Society A: Inorganic, Physical, Theoretical: 85. doi:10.1039/J19680000085.
  6. Takagi, S.; Joesten, M. D.; Lenhert, P. G. (15 August 1976). "Potassium strontium hexanitrocuprate(II) and potassium strontium hexanitronickelate(II)". Acta Crystallographica Section B. 32 (8): 2524–2526. doi:10.1107/S0567740876008121.
  7. Takagi, S.; Joesten, M. D.; Lenhert, P. G. (15 July 1975). "Potassium barium hexanitronickelate(II)". Acta Crystallographica Section B. 31 (7): 1970–1972. doi:10.1107/S0567740875006590.
  8. Takagi, S.; Joesten, M. D.; Lenhert, P. G. (15 July 1975). "Potassium lead hexanitronickelate(II)". Acta Crystallographica Section B. 31 (7): 1968–1970. doi:10.1107/S0567740875006589.
  9. Chou, Liang-Kuei; Abboud, Khalil A.; Talham, Daniel R.; Kim, W. W.; Meisel, Mark W. (November 1994). "Structure- and Orientation-Dependent Magnetic Susceptibility of Tetramethylammonium Nickel Nitrite, (CH3)4N[Ni(NO2)3]: An S = 1 One-Dimensional Heisenberg Antiferromagnet". Chemistry of Materials. 6 (11): 2051–2055. doi:10.1021/cm00047a026.
  10. Kong, Li-Hui; Fu, Da-Wei; Ye, Qiong; Ye, Heng-Yun; Zhang, Yi; Xiong, Ren-Gen (June 2014). "Iso-structural phase transition in tetramethylammonium nickel(II) nitrite [(CH3)4N][Ni(NO2)3]". Chinese Chemical Letters. 25 (6): 844–848. doi:10.1016/j.cclet.2014.05.028.
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