Chemistry:Nitronickelate
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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
- ↑ 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.
- ↑ 2.0 2.1 2.2 2.3 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.
- ↑ 3.0 3.1 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.
- ↑ 4.0 4.1 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)]"] (in en). Journal of the Chemical Society, Dalton Transactions (4): 595–601. doi:10.1039/DT9940000595. ISSN 1364-5447. https://pubs.rsc.org/en/content/articlelanding/1994/dt/dt9940000595.
- ↑ 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.
- ↑ 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. Bibcode: 1976AcCrB..32.2524T.
- ↑ 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. Bibcode: 1975AcCrB..31.1970T.
- ↑ 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. Bibcode: 1975AcCrB..31.1968T.
- ↑ 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.
- ↑ 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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