Nickel organic acid salts explained

The nickel organic acid salts are organic acid salts of nickel. In many of these the ionised organic acid acts as a ligand.

Nickel acetate has the formula (CH₃COO)₂Ni·4H₂O. It has monodentate acetate and hydrogen bonding. A dihydrate also exists. Nickel acetate is used to seal anodised aluminium.^[1]

Nickel formate decomposes when heated to yield carbon dioxide, carbon monoxide, hydrogen, water and finely divided porous nickel.^[2] All the nickel atoms are six coordinated, but half have four water molecules and two formate oxygens close to the atom, and the other half are coordinated by six oxygens of formate groups.^[3]

Aspergillus niger is able to dispose of otherwise toxic levels of nickel in its environment by forming nickel oxalate dihydrate crystals.^[4] nickel oxalate can also be formed in to various nanorods and nanofibres by use of surfacants.^[5] When heated nickel oxalate dihydrate dehydrates at 258° and decomposes to Ni metal^[6] over 316 °C.^[7] Double oxalate salts where oxalate is a ligand on the nickel atom may be called oxalatonickelates.

Other organic acid salts of nickel include nickel oleate, nickel propionate, nickel butyrate, nickel caprylate, nickel lactate, nickel benzoate, nickel bis(acetyl acetonate), nickel salicylate, nickel alkyl phenyl salicylate. Nickel stearate forms a green solution, however when precipitated with alcohol a gel is produced, that also contains a mixture of basic salts, and free stearic acid.^[8]

Nickel malonate, and nickel hydrogen malonate both crystallise with two molecules of water. They decomposes when heated to yield gaseous water, carbon dioxide, carbon monoxide, ethanol, acetic acid, methyl formate and ethyl formate. Nickel acetate exists as an intermediate and the final result is that solid nickel, nickel oxide, Ni₃C and carbon remain.^[9] With malonate nickel can form a bis-malonato-nickelate anion, which can form double salts.^[10] Nickel maleate can be made from maleic acid and nickel carbonate in boiling water. A dihydrate crystallises from the water solution.^[11] Nickel fumarate prepared from fumaric acid and nickel carbonate is pale green as a tetrahydrate, and mustard coloured as an anhydride. It decomposes when heated to 300° to 340° in vacuum. Decomposition mostly produces nickel carbide, carbon dioxide, carbon monoxide and methane. But also produced were butanes, benzene, toluene, and organic acid.^[12]

Nickel succinate can form metal organic framework compounds.^[13]

Nickel citrate complexes are found in leaves of some nickel accumulating plant species in New Caledonia such as Pycnandra acuminata.^[14] Citrate complexes include NiHcit, NiHcit₂³⁻, Nicit⁻, Nicit₂⁴⁻, and Ni₂H₂cit₂⁴⁻. (ordered from low to high pH). Also there is Ni₄H₄cit₃⁵⁻. Nickel citrate is important in nickel plating.^[15] When precipitation of nickel citrate is attempted a gel forms. This apparently consists of tangled fibres of [(C₆H₆O₇)Ni]_n, which can be reduced to nickel metal fibres less than a micron thick, and meters long.^[16] Double nickel citrates exist, including tetraanion citrate when pH is over 9.5.^[17] An amorphous nickel iron citrate Ni₃Fe₆O₄(C₆H₆O₇)₈·6H₂O produces carbon monoxide, carbon dioxide and acetone when heated over 200 °C leaving Trevorite, NiFe₂O₄ a nickel ferrite.^[18] A green crystalline nickel citrate with formula Ni₃(C₆H₅O₇)₂·10H₂O melts at 529K and decomposition starts at 333K.^[19]

Nickel glutarate in the form called Mil-77, [Ni₂₀{(C₅H₆O₄)₂₀(H₂O)₈}]⋅40H₂O is pale green. It crystallises in a porous structure containing twenty member rings. The 40 water molecules "occluded" in the porous channels come out when it is heated to 150 °C retaining the crystal framework. At 240 °C the crystal form changes and over 255° the remaining water is lost. Between 330° and 360° the organic components burn and it is destroyed.^[20]

Cyclopropane carboxylic acid forms two basic salts with nickel, a hydrate with density 1.554 Mg/m³ and an anhydrous form Ni₅(OH)₂(C₄H₅O₂)₈ with density 2.172 mg/m³.^[21]

Nickel trifluoroacetate tetrahydrate exists, as well as two emerald green acid trifluoroacetates, a bridged trinuclear form [Ni₃(CF₃COO)₆(CF₃COOH)₆](CF₃COOH) and a hydrated acid form [Ni₃(CF₃COO)₆(CF₃COOH)₂(H₂O)₄](CF₃COOH)₂ both with triclinic crystal form. The first has density 2.205 and the second 2.124. They are made by dissolving the nickel trifluoroacetate tetrahydrate in trifluoroacetic acid either anhydrous or 1% hydrated.^[22]

Nickel naphthenate is used as a fuel additive to suppress smoke,^[23] as a rubber catalyst and as an oil additive.

When Nickel benzoate is heated in a vacuum, carbon dioxide, carbon monoxide, benzene, benzoic acid, phenol, biphenyl, nickel, nickel oxide, and nickel carbide are formed.^[24] It can crystallise as anhydrous, a trihydrate or a tetrahydrate.

Nickel terephthalate can be made by a double decomposition of sodium terephthalate and nickel nitrate. Nickel terephthalate precipitates. Its solubility is 0.38 g/100g water at 25 °C. In ammonium hydroxide a violet solution forms. Boiling acetic acid converts the nickel to nickel acetate. The terephthalate converts to a basic salt when boiled in water. Understating this compound is important when reducing coloured contaminants in polymers made from terephthalate.^[25]

Listing

formula	name	mol	struct	cell Å			°	V	Z	density	colour	refs
		wt		a	b	c	β	Å^3		g/cm^3
	Nickel formate hydrate		monoclinic	8.60	7.06	9.21	96°50′	4
[Ni<sub>20</sub>{(C<sub>5</sub>H<sub>6</sub>O<sub>4</sub>)<sub>20</sub>(H<sub>2</sub>O)<sub>8</sub>}]	Nickel glutarate		cubic	16.581				4559			pale green
	nickel cyclopropane carboxylate hydrate		orthorhombic	14.810	24.246	24.607		8836	4	1.554	bright green
Ni5(OH)2(C4H5O2)8	nickel cyclopropane carboxylate		orthorhombic	19.406	18.466	21.579	90	7733	8	2.172	pale green
[Ni<sub>3</sub>(CF<sub>3</sub>COO)<sub>6</sub>(CF<sub>3</sub>COOH)<sub>6</sub>](CF3COOH)	Nickel acid trifluoroacetate		trigonal	13.307		53.13		8148	6	2.205	emerald green
[Ni<sub>3</sub>(CF<sub>3</sub>COO)<sub>6</sub>(CF<sub>3</sub>COOH)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>](CF3COOH)2	Nickel acid trifluoroacetate hydrate		triclinic	9.12	10.379	12.109	α=84.59° β=72.20° γ=82.80°	1080.9	1	2.124	emerald green
K2[Ni(C<sub>6</sub>H<sub>5</sub>O<sub>7</sub>)(H<sub>2</sub>O)<sub>2</sub>]2·4H2O	potassium nickel citrate		triclinic	6.729	9.100	10.594	α=94.86 β=100.76 γ=103.70	613.5	1	1.942	green	^[26]
K2[Ni<sub>2</sub>(C<sub>6</sub>H<sub>5</sub>O<sub>7</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]·4H2O	Dipotassium tetraaquabis(μ-citrato-k^4O:O,O'',O''')nickelate(II) tetrahydrate|717.94|monoclinic|10.616|13.006|9.0513|93.09|1247.8|2|1.911|green|^[27] |-|N(CH3)4[Ni<sub>4</sub>(C<sub>6</sub>H<sub>4</sub>O<sub>7</sub>)<sub>3</sub>(OH)(H<sub>2</sub>O)]·18H2O|tetramethyl ammonium nickel basic citrate||triclinic|11.84|14.29|20.93|96.16 β=106.36 γ=94.89|3352|1||bright green extremely weak|^[28] |-|Na2[Ni(C<sub>6</sub>H<sub>4</sub>O<sub>7</sub>)]|disodium nickel citrate||||||||||green dec 371||-|(NH4)2[Ni(HCit){{hydrate|2}}]2|Dimeric ammonium diaquocitratonickelate (II) dihydrate|639.79|triclinic|6.407|9.471|9.6904|α=105.064 β=91.99 γ=89.33|567.5|1|1.872|green|^[29] |-|(NH4)4[Ni(HCit)<sub>2</sub>]|tetrammonium dicitratonickelate (11) dihydrate|545.10|monoclinic|9.361|13.496|9.424|115.476|1074.9|2|1.684|||-|Na2[Ni(HCit){{hydrate|2}}]2|Dimeric sodium diaquocitratonickelate (II) dihydrate||||||||||||-|K2[Ni(HCit){{hydrate|2}}]2|Dimeric potassium diaquocitratonickelate (II) dihydrate||||||||||||-|(NH4)2[Ni(H<sub>2</sub>O)<sub>6</sub>][Ti(H<sub>2</sub>cit)<sub>3</sub>]2·6H2O||1547.43|hexagonal|15.562||7.690||1605.5|1|1.600|light green|^[30] |-|[Ni(C<sub>5</sub>H<sub>7</sub>O<sub>2</sub>)<sub>2</sub>]3|Nickel(II) acetylacetonate|256.91|orthorhombic|23.23|9.64|15.65||3505|4|1.46|dark green|^[31] |-|Ni[C<sub>4</sub>O<sub>4</sub>]|nickel squarate||?cubic|8.068|8.068|8.068|90°|525||1.93|green|^[32] |-|Ni[C<sub>4</sub>O<sub>4</sub>]|nickel squarate octahydrate|428.93|monoclinic|10.288|6.372|12.852|106.98|805.8|2|1.768|green|^[33] |-|Ni[C<sub>5</sub>O<sub>5</sub>]|Nickel croconate trihydrate||orthorhombic||||||||green|^[34] |-|K2[Ni(C<sub>5</sub>O<sub>5</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]|Polydi-μ2-aqua-di-μ5-croconato(2-)-nickel(II)dipotassium(I) tetrahydrate]|525.11|monoclinic|8.015|6.660|16.489|90.20|880.1|2|1.982|green|^[35] |-|Ni(C5H5COO)2|nickel dibenzoate tetrahydrate|354.98|monoclinic|6.1341|34.180|6.9793|95.331|1457.0|4|1.618|light green|^[36] |-|Ni(C5H5COOCOOH)2|nickel dihydrogen diphthalate hexahydrate||monoclinic|16.024|5.574|12.500|113.42||2|1.611||^[37] |-|Ni[C<sub>6</sub>H<sub>4</sub>(COO)<sub>2</sub>]|Nickel terephthalate||||||||||green||-|Ni(OH)[C<sub>6</sub>H<sub>4</sub>(COO)(COOH)]|basic nickel terephthalate||||||||||green||} References

Notes and References

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3. Krogmann. Klaus. Mattes. Rainer . Die Kristallstruktur von Nickelformiat, $\backslash ce$. Zeitschrift für Kristallographie - Crystalline Materials . January 1963. 118. 1–6. 10.1524/zkri.1963.118.16.291 . 96378396. de.
4. Magyarosy . A. . Laidlaw. R.. Kilaas . R. . Echer . C. . Clark . D. . Keasling. J. . Nickel accumulation and nickel oxalate precipitation by Aspergillus niger . Applied Microbiology and Biotechnology . 1 July 2002. 59. 2–3 . 382–388 . 10.1007/s00253-002-1020-x. 12111174 . 2352955 .
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6. Web site: Pyrophoric Nickel Hydrogenation Catalyst / Nickel Oxalate Preparation . .
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30. Deng . Yuan-Fu . Zhang . Hua-Lin . Hong . Qi-Ming . Weng . Wei-Zheng . Wan . Hui-Lin . Zhou . Zhao-Hui . Titanium-based mixed oxides from a series of titanium(IV) citrate complexes . Journal of Solid State Chemistry . November 2007 . 180 . 11 . 3152–3159 . 10.1016/j.jssc.2007.08.033. 2007JSSCh.180.3152D .
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35. Chen . Hong-Yu . Fang . Qi . Xue . Gang . Yu . Wen-Tao . Polydi-μ2-aqua-di-μ5-croconato(2–)-nickel(II)dipotassium(I) tetrahydrate . Acta Crystallographica Section C . 19 November 2005 . 61 . 12 . m535–m537 . 10.1107/S0108270105036322. 16330841 .
36. Vráblová . Anna . Falvello . Larry R. . Campo . Javier . Miklovič . Jozef . Boča . Roman . Černák . Juraj . Tomás . Milagros . Preparation, First Structure Analysis, and Magnetism of the Long-Known Nickel Benzoate Trihydrate - A Linear Ni···Ni···Ni Polymer and Its Parallels with the Active Site of Urease . European Journal of Inorganic Chemistry . February 2016 . 2016 . 6 . 928–934 . 10.1002/ejic.201501255. 10261/148104 . free .
37. Adiwidjaja . G. . Küppers . H. . Nickel dihydrogen diphthalate hexahydrate . Acta Crystallographica Section B . 15 May 1976 . 32 . 5 . 1571–1574 . 10.1107/S0567740876005840. free .