Oxalatonickelate

The oxalatonickelates are a class of compounds that contain nickel complexed by oxalate groups. They form a series of double salts, and include clusters with multiple nickel atoms. Since oxalate functions as a bidentate ligand it can satisfy two coordinate positions around the nickel atom, or it can bridge two nickel atoms together.

The shape around the nickel atom is octahedral for diaquabis(oxalato)nickelate. The colour of this is green due to the Ni(–O–)6 chromophore. The absorption in infrared is at 8,300 9,060 13,400, 15,260, and 26,160 cm−1.[1] The ligand field parameters are 10 Dq=8800 cm−1 and B=1000 cm−1.[1]

formula name other names structure colour or decomposition CAS Number references
[(C2O4)2Ni]2− bis(oxalato)nickelate (2−) [2]
Li2[(C2O4)2Ni]•6H2O dilithium bis(oxalato)nickelate (2−) dehydrate 80° decompose 345° 112678-94-1 [3]
Na2[(C2O4)2Ni]•3H2O disodium bis(oxalato)nickelate (2−) dehydrates at 85°, decompose over 320° 107996-66-5 [4][5]
[NH4]2[(C2O4)2Ni]•3H2O diammonium bis(oxalato)nickelate (2−) dehydrate 180-262° deaminate 262-338 °C 108559-31-5 [4][6]
K2[(C2O4)2Ni•2H2O]•4H2O dipotassium trans-diaquabis(oxalato-O,O')nickelate(II)-water (1/4) potassium bis oxalate nickel(II) tetrahydrate monoclinic a=8.647 b=6.627 c=12.118 β=101.58° V=680.3 Z=2 density=2.05 / 2.04 green 14244-63-4 [7][8][9][10]
Co[(C2O4)2Ni]•5H2O cobalt(II)bis(oxalato)nickelate(II)pentahydrate light pink [11]
Mn[(C2O4)2Ni]•4H2O manganese(II)bis(oxalato)nickelate(II)tetrahydrate light blue [12]
Cd[(C2O4)2Ni]•4H2O cadmium(II)bis(oxalato)nickelate(II)tetrahydrate blue [11]

Because the Ni2+ ion resembles many other divalent metal ions, it can be substituted by them, or substitute for them in other oxalate compounds to form mixed oxalates where the proportions can vary continuously. For example, magnesium nickel oxalate dihydrate.[13]

References
  1. Morrison, J.T.; Baker, W.A. (January 1969). "Nickel(II) complexes with oxygen and sulfur donors". Inorganica Chimica Acta. 3: 463–467. doi:10.1016/S0020-1693(00)92534-9.
  2. Macintyre, Jane E. (1997). Dictionary of Inorganic Compounds, Supplement 4. CRC Press. p. 453. ISBN 9780412750205. Retrieved 21 April 2016.
  3. Saha, H.L.; Mitra, S. (June 1987). "Thermal decomposition reactions of metal carboxylato complexes in the solid state. III. Thermographic and differential thermal studies of metal oxalato, malonato and succinato complexes". Thermochimica Acta. 116: 53–64. doi:10.1016/0040-6031(87)88164-9.
  4. Macintyre, Jane E. (1997). Dictionary of Inorganic Compounds, Supplement 4. CRC Press. p. 251. ISBN 9780412750205. Retrieved 21 April 2016.
  5. Saha, H.L.; Mitra, S. (January 1987). "Thermal decomposition reactions of metal carboxylato complexes in the solid state. I. Thermographic and differential thermal studies of metal oxalato, malonato and succinato complexes". Thermochimica Acta. 109 (2): 331–342. doi:10.1016/0040-6031(87)80029-1.
  6. Saha, H.L.; Mitra, S. (March 1987). "Thermal decomposition reactions of metal carboxylato complexes in the solid state. II. Thermographic and differential thermal studies of metal oxalato, malonato and succinato complexes". Thermochimica Acta. 112 (2): 275–287. doi:10.1016/0040-6031(87)88284-9.
  7. Román, P.; Guzmán-Miralles, C.; Luque, A. (15 July 1993). "Structure of dipotassium trans-diaquabis(oxalato-O,O')nickelate(II)–water (1/4)" (PDF). Acta Crystallographica Section C. 49 (7): 1336–1339. doi:10.1107/S0108270193000940.
  8. Narsimhulu, M.; Raju, B.; Saritha, A.; Narayana Rao, D.; Hussain, K.A. (September 2015). "A new room-temperature ultraviolet emission material: ". Physica B: Condensed Matter. 472: 45–48. Bibcode:2015PhyB..472...45N. doi:10.1016/j.physb.2015.05.019.
  9. Macintyre, Jane E. (1993-07-15). Dictionary of Inorganic Compounds, Supplement 1. CRC Press. p. 45. ISBN 9780412490903. Retrieved 25 April 2016.
  10. Macintyre, Jane E. (1997). Dictionary of Inorganic Compounds, Supplement 4. CRC Press. p. 222. ISBN 9780412750205. Retrieved 21 April 2016.
  11. Deb, Nidhuban; Baruah, S. D.; Dass, N. N. (2000). "Synthesis, Characterization and Thermal Decomposition of ( and )". Journal of Thermal Analysis and Calorimetry. 59 (3): 791–797. doi:10.1023/A:1010153720786. S2CID 94453246.
  12. Deb, Nidhuban (July 2005). "Thermal decomposition of manganese(II)bis(oxalato)nickelate(II)tetrahydrate". Journal of Thermal Analysis and Calorimetry. 81 (1): 61–65. doi:10.1007/s10973-005-0746-y. S2CID 94799986.
  13. Packter, A.; Omomo, A. (1984). "The coprecipitation of Magnesium Nickel Oxalate Dihydrate Powders (solid solutions) from aqueous solution: Precipitate compositions and Coprecipitate Mechanisms". Crystal Research and Technology. 19 (4): 467–476. doi:10.1002/crat.2170190406.
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