Nickel compounds

Compounds of nickel are chemical compounds containing the element nickel which is a member of the group 10 of the periodic table. Most compounds in the group have an oxidation state of +2. Nickel is classified as a transition metal with nickel(II) having much chemical behaviour in common with iron(II) and cobalt(II). Many salts of nickel(II) are isomorphous with salts of magnesium due to the ionic radii of the cations being almost the same. Nickel forms many coordination complexes. Nickel tetracarbonyl was the first pure metal carbonyl produced, and is unusual in its volatility. Metalloproteins containing nickel are found in biological systems.

Nickel forms simple binary compounds with non metals including halogens, chalcogenides, and pnictides. Nickel ions can act as a cation in salts with many acids, including common oxoacids Salts of the hexaaqua ion (Ni•6H2O2+) are especially well known. Many double salts containing nickel with another cation are known. There are organic acid salts. Nickel can be part of a negatively charged ion (anion) making what is called a nickellate. Numerous quaternary compounds (with four elements) of nickel have been studied for super conductivity properties, as nickel is adjacent to copper and iron in the periodic table can can form compounds with the same structure as the high-temperature superconductors that are known.

Colour

Most of the common salts of nickel are green due to the presence of hexaaquanickel(II) ion, Ni(H2O)62+.

Geometry

Nickel atoms can connect to surrounding atoms or ligands in a variety of ways. Six coordinated nickel is the most common and is octahedral, but this can be distorted if ligands are not equivalent. For four coordinate nickel arrangements can be square planar, or tetrahedral. Five coordinated nickel is rarer.

Magnetism

Some nickel compounds are ferromagnetic at sufficiently low temperatures. In order to show magnetic properties the nickel atoms have to be close enough together in the solid structure.

Binary compounds

A binary compound of nickel contains one other element. Substances that contain only nickel atoms are not actually compounds.

In a noble gas matrix, nickel can form dimers, a molecule with two nickel atoms: Ni2.[1] Ni2 has a bonding energy of 2.07±0.01 eV. For Ni2+ the bond energy is around 3.3 eV. Nickel dimers and other clusters can also be formed in a gas and plasma phase by shooting a powerful laser at a nickel rod in cold helium gas.[2]

Oxides

Nickel oxides include Nickel(II) oxide and Nickel(III) oxide.

Hydroxides

Nickel hydroxides are used in nickel–cadmium and Nickel–metal hydride batteries. Nickel(II) hydroxide Ni(OH)2, the main hydroxide of nickel is coloured apple green. It is known as the mineral theophrastite. β-NiO(OH) is a black powder with nickel in the +3 oxidation state. It can be made by oxidising nickel nitrate in a cold alkaline solution with bromine. A mixed oxidation state hydroxide Ni3O2(OH)4 is made if oxidation happens in a hot alkaline solution. A Ni4+ hydroxide: nickel peroxide hydrate NiO2•H2O, can be made by oxidising with alkaline peroxide. It is black, and unstable and oxidises water.

Halides

nickel chloride hexahydrate

Nickel(II) fluoride NiF2 is yellow, crystallising in the rutile structure and can form a trihydrate, NiF2·3H2O.[3] A tetrahydrate also exists.[4]

Nickel chloride NiCl2 is yellow, crystallising in the cadmium chloride structure. It can form a hexahydrate, NiCl2·6H2O, a tetrahydrate NiCl2·4H2O over 29 °C and a dihydrate, NiCl2·2H2O over 64 °C.[3]

nickel bromide NiBr2 is yellow, also crystallising in the cadmium chloride structure. It can form a hexahydrate, NiBr2·6H2O.[3] Crystallisation above 29° forms a trihydrate NiBr2·3H2O, and a dihydrate NiBr2·2H2O.[5] Enneahydrate, NiBr2·9H2O can crstallise from water below 2 °C.[3] Nickelous hexammine bromide Ni(NH3)6Br2is violet or blue. It is soluble in boiling aqueous ammonia, but is insoluble in cold.[3] Diammine, monoammine, and dihydrazine nickel bromides also exist.[3]

With four bromide atoms nickel(II) forms a series of salts called tetrabromonickelates.

Nickel iodide NiI2 is black, also crystallising in the cadmium chloride structure. It can form a green hexahydrate, NiI2·6H2O.[3] Nickel iodide has a brown diammine NiI2•2NH3 and a bluish-violet hexammine NiI2•6NH3.[3]

Nickel(III) fluoride NiF3

Nickel(IV) fluoride NiF4

Chalcogenides

needles of Halls Gap Millerite

By reacting nickel with chalcogens, nickel sulfide, nickel selenide, and nickel telluride are formed. There are numerous sulfides: Ni1.5S, Ni17S18, Ni3S2 (heazlewoodite), Ni3S4 (polydymite), Ni9S8 (godlevskite), NiS (millerite) and two other NiS forms, NiS2 (vaesite) in pyrite structure. Black nickel tetrasulfide NiS4 is formed from ammonium polysulfide and nickel in water solution. Mixed and double sulfides of nickel also exist. Nickel with selenium forms several compounds Ni1−xSe 0≤x≤0.15, Ni2Se3, NiSe2 also known as a mineral penroseite.

Nickel forms two different polonides by heating nickel and polonium together: NiPo and NiPo2.[6]

Pnictides

The nickel arsenide nickeline

Non-stoichiometric compounds of nickel with phosphorus, arsenic and antimony exist, and some are found in nature. One interstitial nitride has formula Ni3N (hexagonal P6322, Z = 2, a = 4.6224 Å and c = 4.3059 Å).[7] In a solid nitrogen matrix, nickel atoms combine with nitrogen molecules to yield Ni(N2)4.[1]

Nickel phosphide Ni2P has density 7.33 and melts at 1100 °C.[4]

The mineral Nickelskutterudite has formula NiAs2-3, nickeline has formula NiAs and breithauptite has formula NiSb. NiAs melts at 967° and has density 7.77. NiSb melts at 1174°. It has the highest density of a nickel compound at 8.74 g/cm3.[4]

NiAsS gersdorffite, and NiSbS ullmannite, NiAsSe Jolliffeite are pnictide/chalcogenide compounds that occur as minerals.

Other

Nickel also forms carbides and borides. Nickel boride can take the forms Ni2B (a green/black solid), NiB, Ni3B, o-Ni4B3 and m-Ni4B3.[8] Nickel hydride NiH is only stable under high pressures of hydrogen.

Diatomic molecules

Hot nickel vapour reacting with other atoms in the gas phase can produce molecules consisting of two atoms. Nickel monofluoride can be observed by its emission spectrum in the gas phase.[9]

Nickel subchloride NiCl is formed in gaseous form when nickel chloride is vapourised, and is the most common in the gas phase above 1450 K. It is formed when nickel is exposed to hot, low pressure chlorine.[10]

Nickel monobromide, NiBr can exist in the gas phase when an electric discharge goes through NiBr2 gas.[9][11][12]

Nickelmonoiodide can exist in the gas phase.[9]

Formula wt distance energy refs
pm kcal/mol
NiH
NiF
NiCl
NiBr
NiI
Ni2 46 [2]
NiAu 58 [13]

Alloys

Compounds of nickel with other metals can be called alloys. The substances with fixed composition include nickel aluminide (NiAl) melting at 1638° with hexagonal structure.[4] NiY, NiY3, Ni3Y, Ni4Y, NiGd3,[14]

BaNi2Ge2 changes structure from orthorhombic to tetragonal around 480 °C.[15] THis is a ternary intermetallic compound. Others include BaNiSn3 and the superconductors SrNi2Ge2, SrNi2P2, SrNi2As2, BaNi2P2, BaNi2As2.[15]

Simple salts

Oxo acid salts

bright green crystals in two clusters on a white and grey rock
Mint green Annabergite, a nickel arsenite

Nickel(II) sulfate can crystallise with six water molecules yielding Retgersite or with seven making Morenosite which is isomorphic to Epsom salts. These contain the hexaquanickel(II) ion.[16] There is also an anhydrous form, a dihydrate and a tetrahydrate, the last two crystallised from sulfuric acid. The hexahydrate has two forms, a blue tetragonal form, and a green monoclinic form, with a transition temperature around 53 °C.[17] The heptahydrate crystallises from water below 31.5 above this blue hexhydrate forms, and above 53.3 the green form.[18] Heating nickel sulfate dehydrates it, and then 700° it loses sulfur trioxide, sulfur dioxide and oxygen.

Nickel sulfite can be formed by bubbling sulfur dioxide through nickel carbonate suspended in water. A solution is formed that slowly loses sulfur dioxide, and which crystallises nickel sulfite hexahydrate. Crystals are frequently in the shape of stars, caused by the two opposite triangular enantiomorphs growing base to base. nickel sulfite hexahydrate is highly piezoelectric. Optically it is uniaxial negative with refractive indexes ω=1.552 ε=1.509.[19] When heated it dehydrates and then ends up making nickel oxide and nickel sulfate.[20]

Nickel thiosulfate NiS2O3 has the same structure as the magnesium salt. It has alternating layers of octahedral shaped nickel2+ hexahydrate, and tetrahedral shaped S2O32− perpendicular to the β direction.[21] When heated to 90 °C it decomposes to form NiS. NiS2O3 can be made from BaS2O3 and NiSO4.[22] Nickel sulfamate can be used for nickel or mixed nickel-tungsten plating.[23] It can be formed by the action of sulfamic acid on nickel carbonate.[24]

Nickel selenite NiSeO3 has many different hydrates, anhydrous NiSeO3•​1⁄3H2O, NiSeO3•H2O, NiSeO3•2H2O (which is also a mineral called ahlfeldite), and NiSeO3•4H2O.[25]

Nickel nitrate commonly crystallises with six water molecules,[16] but can also be anhydrous, or with two, four or nine waters.[26] triphenylphosphine oxide nickel nitrate [(C6H6)3PO]2Ni(NO3)2 is non ionic, with nitrato as a ligand. It can be made from nickel perchlorate. It is yellow and melts at 266 °C.[27]

Nickel carbonate NiCO3•6H2O, hellyerite,[28] crystallising with six water molecules, precipitates when an alkali bicarbonate is added to a Ni aqueous solution.[16] Basic nickel carbonate, zaratite, with the formula Ni4CO3(OH)6(H2O)4, is produced when alkali carbonates are added to a nickel solution. Nickel phosphate, Ni3(PO4)2•7H2O is also insoluble.[16] A number of other phosphates have been made, including nanoporous substances resembling zeolites named with "Versailles Santa Barbara" or VSB. The nanoporous nickel phosphates can accommodate sufficiently small molecules and selectively catalyse reactions on them.[29] A nickel arsenate, Ni3(AsO4)2·8H2O occurs as the mineral annabergite.[30]

Nickel perchlorate, Ni(ClO4)2•6H2O,[16] nickel chlorate, Ni(ClO3)2•6H2O[31]nickel chromate (NiCrO4), nickel chromite (NiCr2O4), nickel(II) titanate, nickel bromate Ni(BrO3)2•6H2O,[32] nickel iodate (Ni(IO3)2•4H2O), nickel stannate (NiSnO3•2H2O)[4] are some other oxy-salts.

The uranates include NiU2O6,[33] NiUO4 α and β forms (orthorhombic a=6.415 Å; b=6.435 Å; c=6.835 Å),[34] and NiU3O10.[34]

formula name mol struct cell Å ° V Z density colour refs
wt a b c β Å3 g/cm3
NiSO3•6H2O nickel sulfite hexahydrate hexagonal 8.794 9.002 603 2.04 emerald green [19][35]
NiSO3•3H2O nickel sulfite trihydrate light green [36]
NiSO3•3N2H4•H2O nickel sulfite trihydrazine hydrate rose [20]
NiSO3•2N2H4•H2O nickel sulfite dihydrazine hydrate blue [20]
Nickel thiosulfate hexahydrate 463.03 orthorhombic 9.282 14.44 6.803 912.1 4 2.03 green [21]
diaqua (4,4´-dimethylbipyridine- N,N´)(methanol) thiosulfato(S) nickel(II) triclinic 8.157 9.685 11.714 α=76.73 β=73.56 γ=78.23 854.2 2 [37]
aqua terpyridine(N,N´,N´´) thiosulfato(S,O) nickel(II) hemihydrate monoclinic,C2/c 27.866 9.274 14.216 114.24˚ 3350. 8 [37]
bis(dipyridylamine) thiosulfato(S,O) nickel(II) hemihydrate orthorhombic, Iba2 12.986 16.821 19.479 4254.9 8 [37]
NiS2O3(2,9-dimethyl-1,10-phenanthroline)(H2O)·H2O·CH3OH monoclinic, C2/c 26.269 7.641 18.381 97.00 3662 8 [38]
NiS2O3(2,9-dimethyl-1,10-phenanthroline) monoclinic, P21/n 11.108 10.955 11.666 103.32˚ 1381.4 4 [38]
Ni(NH2SO3)2•4H2O Nickel sulfamate tetrahydrate 322.95 triclinic P1 6.33 6.73 6.78 α= 88.9 β=67.87 γ=67.76 245.27 1 2.19 green [24]
Ni(SO3F)2 nickel fluorosulfate yellow [39]
NiSeO3 anhydrous nickel selenite 742.68 C2/c 15.4915 9.9355 14.8416 111.173 2130.15 32 4.630 yellow brown [25]
NiSeO3 anhydrous nickel selenite 742.68 Orthorhombic 5.8803 7.5235 4.9394 218.52 yellow green high pressure [40]
NiSeO3•1/3H2O alpha nickel selenite one third hydrate triclinic P1 8.1383 8.4034 8.5724 α=123.713 β=90.174 γ=111.823 435.83 2 1.429 citron yellow [25]
NiSeO3•1/3H2O beta nickel selenite one third hydrate triclinic P1 8.0222 8.2133 8.4364 α=68.654 β=61.782 γ=66.363 438.11 2 1.422 citron yellow [25]
NiSeO3•2H2O nickel selenite dihydrate monoclinic 6.3782 8.7734 7.5467 81.451 417.61 4 3.524 yellow brown [25]
NiSeO3•4H2O nickel selenite tetrahydrate light green [25]
NiSe2O5 anhydrous nickel pyroselenite Pnab Orthorhombic 60754 10.3662 6.7913 427.71 4 4.605 light yellow [25]
Ni12F2(SeO3)8(OH)6 nickel hydroxo fluoro selenite Dumortierite structure hexagonal P63mc 12.702 4.922 1 [41]
Ni12(SeO3)8(OH)8 nickel hydroxy selenite Dumortierite structure hexagonal P63mc 12.7004 4.9201 687.28 1 pale green [41]
NiTeO3 anhydrous nickel tellurite Orthorhombic 5.9564 7.4986 5.2128 232.83 yellow green high pressure [40]
Ni3TeO6 trinickel tellurate Hexagonal 5.103 5.103 13.781 4.272 [42]
NiTe2O5 nickel pyrotellurite Orthorhombic 8.869 8.441 12.126 5.042 [42]
Ni2Te3O8 Monoclinic 12.392 5.207 11.496 98.6 5.702 [42]
Ni6(TeO3)4(OH)4 nickel hydroxy tellurite hexagonal 12.993 4.958 2 light green [43]
Ni5Te4O12Cl2 nickel tellurium oxychloride 1066.585 Monoclinic 19.5674 5.2457 16.3084 125.289 1366.38 4 5.186 orange [44]
Ni5Te4O12Br2 nickel tellurium oxybromide 1155.77 Monoclinic 20.255 5.2498 16.3005 124.937 1421.0 4 5.403 orange [44]
Ni5Te4O12I2 nickel tellurium oxyiodide Monoclinic 20.766 5.230 16.464 125.79 1451.1 4 brown [44]
Ni11(HPO3)8(OH)6 nickel hydroxyphosphite hexagonal 12.6329 4.9040 677.77 1 light green [45]
(hydrate) nickel molybdate monoclinic 11.923 8.220 14.007 113.01 1264 [46]
Ni(NO3)2•2H2O nickel nitrate dihydrate triclinic 5.09465 7.10410 8.42881 γ=78.698 β=102.7640 α=83.1985 287.5 [46]
Ni(NO3)2•4H2O nickel nitrate tetrahydrate triclinic 7.5710 6.623 16.26 γ=97.26 β= 90.015 α=82.57 802.3 [46]
NiN2O2 nickel hyponitrite light green [47]
NiP2O6•12H2O nickel hypodiphosphate orthorhombic Pnmm 11.2418 18.5245 7.3188 1523.1 4 2.142 [48]
Ni3(PO4)2 nickel phosphate monoclinic 10.1059 4.6964 5.8273 91.138 276.52 2 4.396 greenish yellow [49]
α-Ni2P2O7 nickel pyrophosphate monoclinic 6.9177 8.275 8.974 113.879 469.7 4 4.12 ∃ α',β and δ forms [50]
NiHPO4 nickel hydrogen orthophosphate beige yellow [51]
(hydrate) nickel trimetaphosphate [51]
(hydrate) nickel tetrametaphosphate [51]
Ni2P4O12 nickel cyclotetraphosphate monoclinic C12/c1 11.611 8.218 9.826 118.41 824.7 4 green [52]
Ni12H6(PO4)8(OH)6 nickel hydroxy phosphate hexagonal 12.4697 4.9531 1 light green [43]
Nanoporous nickel phosphate VSB-1 hexagonal 19.834 5.0379 1710 [29]
Ni20[(OH)12(H2O)6][(HPO4)8(PO4)4]•12H2O Nanoporous nickel phosphate VSB-5 hexagonal 18.153 6.387 1827 [29]
Ni3P6O18•17H2O nickel hexametaphosphate triclinic 9.109 9.267 10.75113 α=84.885 β=102.44 γ=101.64 867.4 pale green [53]
Ni3(AsO4)2·8H2O annabergite Monoclinic 10.179 13.309 4.725 105 2 light green [54]
Ni12H6(AsO4)8(OH)6 nickel hydroxy arsenate hexagonal 12.678 5.0259 1 light green [43]
NiAs2O4 Nickel arsenite [55]
Ni3(AsO4)3 o-nickel orthoarsenate 454.01 orthorhombic 5.943 11.263 8.164 546.5 4 5.517 [56]
Ni3(AsO4)3 m-nickel orthoarsenate xanthiosite 453.91 monoclinic 5.764 9.559 10.194 92.95 560.9 4 5.394 golden yellow [56]
Ni8.5As3O16 Aerugite 979.8 trigonal 5.9511 27.567 281.9 1 5.772 dark green [57]
NiSb2O4 Nickel antimonite tetragonal 8.6388 5.9052 413.58 (at 240K) [58]
NiSb2O6 Nickel metaantimonate
nickel antimony oxide		 P42/mnm 4.62957 9.1981 2 [59]
Ni(H2O)6[Sb(OH)6]2 bottinoite Nickel hydroxy antimonate P3 16.060 9.792 2187.2 6 pale blue [60]
NiTa2O6 Nickel metatantalate P42/mnm 4.71581 9.1163 2 [59]
NiSn(SO3F)6 nickel tin fluorosulfate light yellow [39]
Ni(SO3CF3)2 nickel trifluoromethanesulfonate [61]
NiSn(SO3CF3)6 nickel tin triflate light yellow [39]
(Ni,Mg)10Ge3O16 871.7 trigonal R3 5.8850 28.6135 286.1 1 5.060 [62]
NiCO3 anhydrous nickel carbonate 118.72 rhombohedral 4.6117 14.735 271.39 6 4.358 [63]
Ni2SiO4 nickel orthosilicate
liebenbergite
nickel silicate olvine		 orthorhombic Pbnm 4.727 10.120 5.911 285.0 4 [64]
Ni2GeO4 nickel orthogermanate cubic Fd3m 8.221 8 [65]
Ni(CN)2 anhydrous nickel cyanide tetragonal quad layer 4.8570 12.801 4 [66]
NiB4O7 γ-nickelborate P6522 4.256 34.905 547.5 6 [67]

Fluoro acid salts

Nickel tetrafluoroborate, Ni(BF4)2•6H2O is very soluble in water, alcohol and acetonitrile. It is prepared by dissolving nickel carbonate in tetrafluoroboric acid.[68][69] Nickel tetrafluoroberyllate NiBeF4•xH2O, can be hydrated with six or seven water molecules.[70] Both nickel hexafluorostannate and nickel fluorosilicate crystallise in the trigonal system.[71] Nickel hexafluorogermanate NiGeF6 has a rosy-tan colour and a hexagonal crystal with a = 5.241 Å unit cell volume is 92.9 Å3. It is formed in the reaction with GeF4 and K2NiF6.[72] Nickel fuorotitanate crystallises in hexagonal green crystals. It can be made by dissolving nickel carbonate, and titanium dioxide in hydrofluoric acid. The crystal dimensions are a = 9.54, c = 9.91 density = 2.09 (measure 2.03).[73]

Ni(AsF6)2, Ni(SbF6)2, Ni(BiF6)2 are made by reacting the hexafluoro acid with NiF2 in hydrofluoric acid.[72] They all have hexagonal crystal structure, resembling the similar salts of the other first row transition metals.[72] For Ni(AsF6)2 a = 4.98, c = 26.59, and V = 571, formula weight Z=3.[72] Ni(SbF6)2 is yellow with a = 5.16Å, c = 27.90Å Z = 3. The structure resembles LiSbF6, but with every second metal along the c axis missing.[74]

Others include the green fluorohafnate NiHfF6•6H2O, and Ni2HfF8•12H2O,[75] NiZrF6•6H2O[76]

Chloroacid salts

Nickel tetrachloroiodate Ni(ICl4)2 can be made by reacting iodine with nickel chloride. It consists of green needles.[77]

Nitrogen anion salts

Nickel cyanide tetrahydrate Ni(CN)2•4H2O is insoluble in water, but dissolves in aqueous ammonia.[4] It forms double salts with interesting structures.[66]

Nickel azide Ni(N3)2 is a sensitive explosive. It can be made by treating nickel carbonate with hydrazoic acid. Acetone causes the precipitation of the hydrous solid salt, which is green. At 490K it slowly decomposes to nitrogen and nickel metal powder, losing a half of the nitrogen in four hours.[78] Nickel azide is complexed by one azo group when dissolved in water, but in other solvents, the nickel atom can have up to four azo groups attached.[79] Nickel azide forms a dihydrate: Ni(N3)2•2H2O and a basic salt called nickel hydroxy azide Ni(OH)N3.[80]

Nickel amide, Ni(NH2)2 is a deep red compound that contains Ni6 clusters surrounded by 12 NH2 groups.[81] Nickel amide also forms a series of double salts. Other homoleptic nickel amides derived by substituting the hydrogen atoms are Ni[N(C6H5)2]2 (diphenyl) and boryl amides Ni[NBMes2Mes]2 and Ni[NBMes2C6H5]2.[82]

Organic acid salts

Nickel acetate has the formula (CH3COO)2Ni·4H2O. It has monodentate acetate and hydrogen bonding. A dihdrate also exists. Nickel acetate is used to seal anodised aluminium.[83]

Nickel formate decomposes when heated to yield carbon dioxide, carbon monoxide, hydrogen, water and finely divided porous nickel.[84] 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.[85]

Aspergillus niger is able to dispose of otherwise toxic levels of nickel in its environment by forming nickel oxalate dihydrate crystals.[86] nickel oxalate can also be formed in to various namorods and nanofibres by use of surfacants.[87] When heated nickel oxalate dihydrate dehydrates at 258° and decomposes to NiO over 316 °C.[88] 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.[89]

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.[90] With malonate nickel can form a bis-malonato-nickelate anion, which can form double salts.[91] Nickel maleate can be made from maleic acid and nickel carbonate in boiling water. A dihydrate crystallises from the water solution.[92] 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.[93]

Nickel succinate can form metal organic framework compounds.[94]

Nickel citrate complexes are found in leaves of some nickel accumulating plant species in New Caledonia such as Pycnandra acuminata.[95] 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.[96] 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.[97] Double nickel citrates exist, including tetraanion citrate when pH is over 9.5.[98] 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.[99] A green crystalline nickel citrate with formula Ni3(C6H5O7)2·10H2O melts at 529K and decomposition starts at 333K.[100]

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.[101]

Cyclopropane carboxylic acid forms two basic salts with nickel, a hydrate Ni9(OH)2(H2O)6(C4H5O2)8·2H2O with density 1.554 Mg/m3 and an anhydrous form Ni5(OH)2(C4H5O2)8 with density 2.172 mg/m3.[102]

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.[103]

Nickel naphthenate is used as a fuel additive to suppress smoke,[104] 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.[105] It can crystallise as anhydrous, a trihydrate or a tetrahydrate.[106]

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.[107]

formula name mol struct cell Å ° V Z density colour refs
wt a b c β Å3 g/cm3
Ni(HCOO)2.2H2O Nickel formate hydrate monoclinic 8.60 7.06 9.21 96°50′ 4 [85]
[Ni20{(C5H6O4)20(H2O)8}]⋅40 H2O Nickel glutarate cubic 16.581 4559 pale green [101]
Ni9(OH)2(H2O)6(C4H5O2)8·2H2O nickel cyclopropane carboxylate hydrate orthorhombic 14.810 24.246 24.607 8836 4 1.554 bright green [102]
Ni5(OH)2(C4H5O2)8 nickel cyclopropane carboxylate orthorhombic 19.406 18.466 21.579 90 7733 8 2.172 pale green [102]
[Ni3(CF3COO)6(CF3COOH)6](CF3COOH) Nickel acid trifluoroacetate trigonal 13.307 53.13 8148 6 2.205 emerald green [103]
[Ni3(CF3COO)6(CF3COOH)2(H2O)4](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 [103]
K2[Ni(C6H5O7)(H2O)2]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 [108]
K2[Ni2(C6H5O7)2(H2O)4]·4H2O Dipotassium tetraaquabis(μ-citrato-k4O:O',O'',O''')nickelate(II) tetrahydrate 717.94 monoclinic 10.616 13.006 9.0513 93.09 1247.8 2 1.911 green [109]
N(CH3)4[Ni4(C6H4O7)3(OH)(H2O)]·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 [108][110]
Na2[Ni(C6H4O7)]•2H2O disodium nickel citrate green dec 371 [98]
(NH4)2[Ni(HCit)•2H2O]2•2H2O 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 [111]
(NH4)4[Ni(HCit)2]•2H2O tetrammonium dicitratonickelate (11) dihydrate 545.10 monoclinic 9.361 13.496 9.424 115.476 1074.9 2 1.684 [111]
Na2[Ni(HCit)•2H2O]2•2H2O Dimeric sodium diaquocitratonickelate (II) dihydrate [111]
K2[Ni(HCit)•2H2O]2•2H2O Dimeric potassium diaquocitratonickelate (II) dihydrate [111]
(NH4)2[Ni(H2O)6][Ti(H2cit)3]2·6H2O 1547.43 hexagonal 15.562 7.690 1605.5 1 1.600 light green [112]
[Ni(C5H7O2)2]3 Nickel(II) acetylacetonate 256.91 orthorhombic 23.23 9.64 15.65 3505 4 1.46 dark green [113]
Ni[C4O4]•2H2O nickel squarate ?cubic 8.068 8.068 8.068 90° 525 1.93 green [114]
Ni[C4O4]•8H2O nickel squarate octahydrate 428.93 monoclinic 10.288 6.372 12.852 106.98 805.8 2 1.768 green [115]
Ni[C5O5]•3H2O Nickel croconate trihydrate orthorhombic green [116]
K2[Ni(C5O5)2(H2O)2]•4H2O Poly[[di-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 [117]
Ni(C5H5COO)2•2H2O nickel dibenzoate tetrahydrate 354.98 monoclinic 6.1341 34.180 6.9793 95.331 1457.0 4 1.618 light green [106]
Ni(C5H5COOCOOH)2•6H2O nickel dihydrogen diphthalate hexahydrate monoclinic 16.024 5.574 12.500 113.42 2 1.611 [118]
Ni[C6H4(COO)2]•4H2O Nickel terephthalate green [107]
Ni(OH)[C6H4(COO)(COOH)]•H2O basic nickel terephthalate green [107]

Double salts

Nickel is one of the metals that can form Tutton's salts. The singly charged ion can be any of the full range of potassium, rubidium, cesium, ammonium (NH4), or thallium.[119] As a mineral the ammonium nickel salt, (NH4)2Ni(SO4)2·6 H2O, can be called nickelboussingaultite.[120] With sodium, the double sulfate is nickelblödite Na2Ni(SO4)2·4 H2O from the blödite family. Nickel can be substituted by other divalent metals of similar sized to make mixtures that crystallise in the same form.[121]

Nickel forms double salts with Tutton's salt structure with tetrafluoroberyllate with the range of cations of ammonia,[122] potassium, rubidium, cesium,[123] and thallium.[124]

Anhydrous salts of the formula M2Ni2(SO4)3, which can be termed metal nickel triusulfates, belong to the family of langbeinites. The known salts include (NH4)2Ni2(SO4)3, K2Ni2(SO4)3 and Rb2Ni2(SO4)3, and those of Tl and Cs are predicted to exist.

Some minerals are double salts, for example Nickelzippeite Ni2(UO2)6(SO4)3(OH)10 · 16H2O which is isomorphic to cobaltzippeite, magnesiozippeite and zinczippeite, part of the zippeite group.[125]

Double hydrides of nickel exist, such as Mg2NiH4.[126]

formula name mol struct cell Å ° V Z density colour refs
wt a b c β Å3 g/cm3
Li2[NiF(PO4)] Lithium nickel fluorophosphate 186.56 orthorhombic 10.473 6.289 10.846 714.3 8 3.469 [127]
Na2[NiF(PO4)] sodium nickel fluorophosphate 218.645 Pbcn 90 823.4 [128]
Na2Ni(SO4)2•4H2O nickelblödite 368.867 monoclinic 11.045 8.193 5.535 100.50 2.487 green [129]
K2Ni2(SO4)3 potassium nickel trisulfate 483.77 orthorhombic 9.8436 9.8436 9.8436 90 3.369 [130]
Rb2Ni2(SO4)3 rubidium nickel trisulfate 576.51 9.9217 9.9217 9.9217 90 3.921 [131]
(NH4)2Ni2(SO4)3 ammonium nickel trisulfate 441.65 orthorhombic 9.904 9.904 9.904 90 3.02 [132]
(NH4)4Ni3(SO4)5 ammonium nickel pentasulfate 728.56 yellow [133]
NiLa(SeO3)2Cl nickel lanthanum diselenite chloride 486.977 hexagonal 8.666 18.662 1194.2 6 (153K) [134]
NiNd10(SeO3)12Cl8 nickel Neodymium diselenite chloride monoclinic 15.8175 1578,68 19.276 114.202 7407 4 (153K) [135]
Ni6Fe3+2(SO4)(OH)16•4(H2O) honessite 904.08 trigonal 3.083 26.71 219.86 0.25 1.71 green [136]
NiTi(SO4)3 nickel titanium sulfate monoclinic 8.254 8.54 14.1444 124.967 817 4 3.21 [137]
Na2Ni(SeO4)2•2H2O sodium nickel selenate dihydrate triclinic 5.507 5.905 7.172 α = 108.56 °, β = 99.07 °, γ = 106.35 ° 204.2 1 [138]
K2Ni(SeO4)2•2H2O potassium nickel selenate dihydrate [139]
K2Ni(SeO4)2•6H2O potassium nickel selenate Tuttons salt 527.52 monoclinic a b c 104.45 4 2.559 bright green [140]
Rb2Ni(SeO4)2•6H2O rubidium nickel selenate Tuttons salt 619.62 monoclinic a b c 105.20 4 2.856 bright green [140]
Cs2Ni(SeO4)2•6H2O caesium nickel selenate Tuttons salt 713.62 monoclinic 9.426 12.961 6.473 106.17 759.5 2 3.114 bright emerald green [140][141]
(NH4)2Ni(SeO4)2•6H2O ammonium nickel selenate Tuttons salt 485.68 monoclinic a b c 106.29 4 2.243 bright green [140]
Tl2Ni(SeO4)2•6H2O thallium nickel selenate Tuttons salt monoclinic a b c 105.60 4 3.993 bright green [142]
K2NiP2O7 310.85 monoclinic P21 9.230 17.540 8.32 91.44 1346.3 8 3.067 [143]
K6Sr2Ni5(P2O7)5 786.55 monoclinic P21/c 11.038 9.53 7.438 100.13 1578 2 3.309 yellow [143]
NaNi2(SO4)2[(H2O)(OH)] monoclinic C2/m Natrochalcite-type 8.605 6.185 7.336 114.78 354.5 2 [144]
BaNi2(PO4)2 barium nickel phosphate Trigonal R-3 4.8112 4.8112 23.302 467.1 3 green [145]
BaNi2(AsO4)2 barium nickel arsenate Trigonal R-3 4.945 4.945 23.61 532.59 3 5.31 [145]
BaNi2(VO4)2 barium nickel vanadate Trigonal R-3 5.0375 5.0375 22.33 3 [146]
Na4Ni7(AsO4)6 tetrasodium heptanickel hexaarsenate 1336.3 monoclinic C2/m 14.538 14.505 10.6120 118.299 1970.3 4 brown [147]
K2Ni(CO3)2•H2O potassium nickel carbonate
Potassium tetraaquadicarbonatonickelate		 monoclinic Baylissite-type 6.755 6.156 12.2406 113.265 467.6 2 2.34 [148]
Rb2Ni(CO3)2•H2O Rubidium nickel carbonate monoclinic Baylissite-type 6.971 6.348 12.2807 114.289 495.34 2 2.83 [149]
NiTh(NO3)6•8H2O nickel thorium nitrate Monoclinic P21/c 9.089 8.728 13.565 96.65 1068.8(2) [150]
K[NiGa2(PO4)3(H2O)2] Potassium nickel(II) gallium phosphate hydrate 558.17 Monoclinic C2/c 13.209 10.173 8.813 107.68 1128.4 Z = 4 [151]
KNi3(PO4)P2O7 Potassium trinickel(II) orthophosphate diphosphate 484.14 Monoclinic 9.8591 9.3953 9.9778 118.965 808.63 4 [152]
KNiPO4 potassium nickel phosphate [153]
KNiPO4•6H2O potassium nickel phosphate hexahydrate monoclinic P21 6.8309 11.0610 6.1165 91.045 462.07 2 [154]
NiK4(P3O9)2•7H2O nickel potassium tricyclophosphate hydrate orthorhombic Fm2m 23.03 11.882 8.732 4 blue [155]
NiK4(P3O9)2 nickel potassium tricyclophosphate triclinic P-1 6.143 6.80 12.80 α=102.8 β=89.7 γ=66.03 473.56 1 [155]
NaK5Ni5(P2O7)4 Sodium pentapotassium pentanickel tetra(diphosphate) 1207.80 triclinic 7.188 9.282 10.026(5) α=109.31 β=90.02 γ=104.07 610.0 1 [156]
NH4NiPO4.H2O ammonium nickel phosphate hydrate orthorhombic 5.566 8.760 4.742 231.2 [157]
NH4NiPO4.6H2O ammonium nickel phosphate hydrate
Ni-struvite		 Orthorhombic Pmn21 6.924 6.104 11.166 471.5 2 [158][159][160]
LiNiPO4 lithium nickel phosphate orthorhombic 10.032 5.855 4.681 274.9 4 brown [161]
NaNiPO4 sodium nickel phosphate Pnma maricite structure 8.7839 6.7426 5.0368 298.31 4 yellow [162]
NaNiPO4 sodium nickel phosphate Pnma triphylite form 4.98 6.13 9.98 304.23 [163]
Na4Ni7(PO4)6 Cm 10.550 13.985 6.398 104.87 912.4 2 3.906 [162][164]
NaNiPO4•7H2O sodium nickel phosphate heptahydrate tetrahedral P42/mmc 6.7390 10.9690 498.15 2 [154]
Na3NiP3O10•12H20 trisodium nickel triphosphate dodecahydrate monoclinic (pseudoorthorhombic) 15.0236 9.1972 14.6654. 90.0492 2014.46 1.967 light green [165]
Na2Ni3(OH)2(PO4)2 sodium nickel hydroxide phosphate monoclinic 14.259 5.695 4.933 104.28 2 3.816 [166]
NiNa4(P3O9)2•6H2O nickel tetrasodium cyclotriphosphate hexahydrate triclinic 6.157 6.820 10.918 α=80.21 β=97.8 γ=119.5 409.8 1 [167]
NiRb4(P3O9)2 nickel tetrarubidium cyclotriphosphate P-31c 7.288 7.288 20.343 2 [168]
NiCs4(P3O9)2•6H2O nickel tetracaesium cyclotriphosphate hydrate orthorhombic 19.992 6.500 18.445 4 [155]
NiCs4(PO3)6 nickel tetracaesium cyclotriphosphate rhombohedral P-31c 11.602 11.602 9.078 1058.24 2 [155]
NiAg4(P3O9)2•6H2O nickel tetrasilver cyclotriphosphate hexahydrate triclinic 9.209 8.053 6.841 α=89.15 β=102.94 γ=97.24 1 [169]
NiAg4(P3O9)2 nickel tetrasilver cyclotriphosphate triclinic 6.100 6.783 10.764 α = 78.66 β=96.85 γ=113.36 401 1 [169]
Ni(NH4)4(P3O9)2•4H2O nickel tetraammonium cyclotriphosphate tetrahydrate monoclinic 2 [170]
TlNi4(PO4)3 Thallium nickel triphosphate orthorhombic Cmc21 4 pale yellow [171]
Tl4Ni6(PO4)6 Thallium nickel hexaphosphate monoclinic Cm 4 yellow brown [171]
Tl2Ni4P2O7(PO4)2 monoclinic C2/c 8 brown [171]
NiMnSb Nickel manganese antimonide cubic 5.945 210.1 4 7.57 [172]
NiMnSi Nickel manganese silicide Orthorhombic 5.8967 3.6124 6.9162 147.32 4 [173][174]
NiMnGe orthorhombic Pnma 6.053 3.769 7.090 161.75 2 [175]
NiFeGe hexagonal [175]
TiNiSi orthorhombic [175]
NaNiIO6 sodium nickel periodate orthorhombic 8.599 2.492 10.281 220.3 [176]
KNiIO6 potassium nickel periodate orthorhombic 12.09 3.683 6.062 269.9 [176]
KNiIO6 potassium nickel periodate triclinic 6.4203 5.075 4.223 α= 65.07 β= 92.717 γ=109.95 116.51 [176]

Double fluorides include the above-mentioned fluoroanion salts, and those fluoronickelates such as NiF4 and NiF6. Other odd ones include an apple green coloured KNiF3·H2O and NaNiF3·H2O, aluminium nickel pentafluoride AlNiF5·7H2O, ceric nickelous decafluoride Ce2NiF10·7H2O, niobium nickel fluoride Ni3H4Nb2F20·19H2O, vanadium nickel pentafluoride VNiF5·7H2O, vanadyl nickel tetrafluoride VONiF4·7H2O, chromic nickelous pentafluoride CrNiF5·7H2O, molybdenum nickel dioxytetrafluoride NiMoO2F4·6H2O, tungsten nickel dioxytetrafluoride NiWO2F4·6H2O and NiWO2F4·10H2O, manganic nickel pentafluoride MnNiF4·7H2O, nickelous ferric fluoride FeNiF5·7H2O.[177]

Nickel trichloride double salts exist which are polymers. Nickel is in octahedral coordination, with double halogen bridges. Examples of this include RbNiCl3, pinkish tan coloured H2NN(CH3)3NiCl3.[178] Other double trichlorides include potassium nickel trichloride KNiCl3·5H2O,[179] yellow cesium nickel trichloride CsNiCl3,[179] lithium nickel trichloride LiNiCl3·3H2O,[179] hyrdrazinium nickel tetrachloride,[179] and nickel ammonium chloride hexahydrate NH4NiCl3·6H2O.[4]

The tetrachloronickelates contain a tetrahedral NiCl42− and are dark blue. Some salts of organic bases are ionic liquids at standard conditions.[180] tetramethylammonium nickel trichloride is pink and very insoluble.[181] Other tetrachlorides include rubidium nickel tetrachloride, lithium nickel tetrachloride Li2NiCl4·4H2O stable from 23 to 60°, stannous nickel tetrachloride , stannic nickel hexachloride is tetragonal.[182]

Lithium nickel hexachloride Li4NiCl6·10H2O is stable from 0 to 23°.

Copper nickel dioxychloride 2CuO·NiCl2·6H2O, and copper nickel trioxychloride 3CuO·NiCl2·4H2O.[179]

Cadmium dinickel hexachloride, crystallises in hexagonal system, dicadmium dinickel hexachloride, has rhombic crystals, and is pleochroic varying from light to dark green.[182]

Thallic nickel octochloride is bright green.[182]

Double bromides include the tetrabromonickelates, and also caesium nickel tribromide, CsNiBr3 copper nickel trioxybromide, 3Cu0·NiBr2·4H2O mercuric nickel bromide, Hg2NiBr6, HgNiBr4. Aqueous nickel bromide reacting with mercuric oxide yields mercuric nickel oxybromide, didymium nickel bromide, is reddish brown (mixture of praseodymium and neodymium) Lanthanum nickel bromide, nickel stannic bromide (or nickel bromostannate) NiSnBr6·8H2O is apple green.[183][184]

The tetraiodonickelates are blood red coloured salts of the NiI4 ion with large cations. Double iodides known include mercuric nickel hexaiodide 2HgI2•NiI2•6H2O, mercuric nickel tetraiodide HgI2•NiI2•6H2O, and lead nickel hexaiodide I2•2NiI2•3H2O.[3]

The diperiodatonickelates of nickel IV are strong oxidisers, and akali monoperiodatonickelates also are known.

Nickel forms double nitrates with the lighter rare earth elements. The solid crystals have the formula . The metals include La Ce Pr Nd Sm Gd and the non rare earth Bi. Nickel can also be replaced by similar divalent ions, Mg, Mn Co Zn. For the nickel salts melting temperatures range from 110.5° for La, 108.5° for Ce, 108° for Pr, 105.6° for Nd, 92.2° for Sm and down to 72.5° for Gd The Bi salt melting at 69°. Crystal structure is hexagonal with Z=3.[185] becomes ferromagnetic below 0.393 K.[186] These double nickel nitrates have been used to separate the rare earth elements by fractional crystallization.[187]

Nickel thorium nitrate has formula NiTh(NO3)6•8H2O. Nickel atoms can be substituted by other ions with radius 0.69 to 0.83 Å. The nitrates are coordinated on the thorium atom and the water to the nickel. Enthalp of solution of the octahydrate is 7 kJ/mol. Enthalpy of formation is -4360 kJ/mol. At 109° the octahydrate becomes , and at 190° and anhydrous at 215°.[150] The hexahydrate has Pa3 cubic structure.[150]

Various double amides containing nickel clusters have been made using liquid ammonia as a solvent. Substances made include red Li3Ni4(NH2)11·NH3 (Pna21; Z = 4; a = 16.344(3) Å; b = 12.310(2) Å; c = 8.113(2) Å v=1631 D=1.942), and Cs2Ni(NH2)4•NH3 (P21/c; Z = 4; a =9.553(3) Å; b = 8.734(3) Å; c = 14.243(3) Å; β = 129.96(3)° V=910 D=2.960). These are called amidonickel compounds.[188] Yet others include Li4Ni4(NH2)12·NH3, Na2Ni(NH2)4,[189] orange red Na2Ni(NH2)4•2NH3,[190] Na2Ni(NH2)4•NH3, K2Ni(NH2)4•0.23KNH2, and Rb2Ni(NH2)4•0.23RbNH2.[188]

Nickel dihydrogen phosphide (Ni(PH2)2) can form orange, green or black double salts KNi(PH2)3) that crystallise from liquid ammonia. They are unstable above -78 °C, giving off ammonia, phosphine and hydrogen.[191]

Ternary chalcogenides

Nickel forms a series of double nickel oxides with other elements, which may be termed "nickelates". These double nickel oxides are not listed on this page. There are also many well defined double compounds with sulfur, selenium and tellurium.

formula name colour structure production references
NH4NiS5 ammonium nickel sulphide black NH4 polysulfide+NiSO4 [192][193]
K2Ni3S4 potassium nickel tetrasulfide bronze yellow Fddd a=10.023 b=26.074 c=5.704 NiSO4 K2CO3 S [192][194][195]
K2Ni11S10 potassium nickel decasulfide dark metallic green NiO+KCNS [192] J. Milbauer
Na2Ni3S4 sodium nickel tetrasulfide dark yellow NiSO4 Na2CO3 S [192] R. Schneider
KNi2S2 potassium dinickel disulfide orange yellow Ni foil, S, K at 723K [15][196]
K2Ni3Se4 potassium nickel tetraselenide gold Fddd a=10.468 b=26.496 c=5.995 [197][198]
KNi2Se2 potassium dinickel diselenide purple-red I4/mmmtetragonal a=3.909, c=13.4142 Ni foil, Se shot, K at 723K [15][199]
CsNi2Se2 caesium dinickel diselenide tetragonal a=3.988, c=14.419 heat elements [200]
TlNi2Se2 Thallium dinickel diselenide gold metallic tetragonal heat elements together in closed quartz tube [201]
Rb2Ni3S4 rubidium nickel tetrasulphide metallic greenish gold Fmmm orthorhombic a=9.901 Å, b=13.606 Å and c=5.861 Z=4 layered; ferromagnetic only after water immersion [197][202]
Rb2Ni3Se4 rubidium nickel tetraselenide golden metallic Fddd orthorhombic a = 10.555 Å, b = 27.588 Å, c = 6.031 Å, Z = 8 layered; ferromagnetic only after water immersion Rb2CO3 S Ni [203]
Cs2Ni3S4 cesium nickel tetrasulphide greenish gold Fmmm a=10.038 b=14.552 c=5.934 [198][203]
Cs2Ni3S4 cesium nickel tetrasulphide gold Fmmm a=10.540 b=14.624 c=6.194 [198]
Cs0.9Ni3.1Se3 Hexagonal P63/m a = 9.26301(4) Å and c = 4.34272(2) Å quasi-one-dimensional electric conductor [204]
BaNi4S5 Barium nickel pentasulfide bronze yellow NiSO4 K2CO3 S [192] R. Schneider; I. and L. Bellucci
Pb2Ni3S2 lead nickel disulfide melt 790° PbS Ni [205] W Guertler; W Guertler H Schack
(Ni,Fe)9S8 Pentlandite bronze yellow melt 870 [205] T. Scheerer
Fe2Ni2S4 ferrous nickel tetrasulfide melt 840 [206] K Bornemann
Fe2Ni2S3 ferrous nickel trisulfide stable over 575°, melt 886, [207] K Bornemann
Fe3Ni4S5 ferrous nickel pentasulfide below 575 [207] K Bornemann
Fe4Ni2S5 [207] K Bornemann
Fe2Ni3S4 [207] K Bornemann
Fe3Ni4S5 [207] K Bornemann
Fe2Ni2S3 [207] K Bornemann
FeNi2S4 Violarite dark violet grey mineral oxidate
Ni3Sn2S2 [208]
Ni3Bi2S2 superconducting [208]
Ni3Bi2Se2 superconducting [208]
NiSnS3 nickel thiostannate greenish black orthorhombic a=6.88 b=7.89 c=11.95 Z=8 V=644 NiCl2 + SnS2 [209]
NiGeS33 nickelselenogermanate [210]
Ta2NiS5 Orthorhombic [211]
Ta2NiSe5 monoclinic β=90.53 [211]
Ta2Ni2Te4 [212]
Ta2Ni3Te5 [212]

Polyoxometallates

Nickel can enter into metal oxygen clusters with other high oxidation state elements to form polyoxometalates. These may stabilise higher oxidation states of nickel, or show catalytic properties.

Nonamolybdonickelate(IV), [NiMo9O32]6− can oxidise aromatic hydrocarbons to alcohols.[213]

There is a dark brown heptamolybdonickelate(IV) potassium salt, K2H8NiMo7O28·6H2O.[214]

13-Vanadonickelate(IV) compounds exist such as K7NiV13O38•16H2O with black octahedral crystals. It can be made from isopolyvanadate, with nickel(II) oxidised by peroxydisulfate at a pH around 4.[215] Nickel(IV) heteropolyniobates also exists such as the dark maroon Na12NiNb12O38•21H2O.[216] An alternate orange red hydrate perhaps with 44 water molecules also exists. With nickel-II (tetramethylammonium)6[H3NiNb9O28•17H2O forms a green salt that is very soluble in water, but hardly soluble in ethanol.[217]

H43K14Na6Nb32 Ni10O183 is a nickel-cation-bridged polyoxoniobate which crystallises in the monoclinic system with cell dimensions a=15.140 b=24.824 c=25.190 Å and β=103.469 and two formulas per unit cell.[218]

Na8Li12[Ni2(P2W15O56)2]•74H2O forms a sandwich structure, and Na4Li5[Ni3(OH)3(H2O)3P2W16O59]•48H2O is a Wells-Dawson polyoxometalate.[219]

Acid salts

Nickel hydrofluoride, H5NiF7·6H2O is made by using excess hydrofluoric acid solution on nickel carbonate. It is deep green.[3]

Basic salts

Nickel oxyfluoride Ni4F4O(OH)2 is green.[3]

Nickelous enneaoxydiiodide 9NiO•Nil2•15H2O forms when solutions of nickel iodide are exposed to air and evaporated.[3]

Complexes

Sample of potassium tetracyanonickelate hydrate

Simple complexes of nickel include hexaquonickel(II), yellow tetracyanonickelate [Ni(CN)4]2−, red pentacyanonickelate [Ni(CN)5]3− only found in solution, [Ni(SCN)4]2− and [Ni(SCN)6]4−. Halo- complexes include [NiCl4]2−, [NiF4]2−, [NiF6]4−, [NiCl2(H2O)4] [Ni(NH3)4(H2O)2]2+, [Ni(NH3)6]2+, [Ni(en)3)]2+.[16] Some complexes have fivefold coordination. N[CH2CH2NMe2]3 (tris(N,N-dimethyl-2-aminoethyl)amine); P(o-C6H4SMe)3; P(CH2CH2CH2AsMe2)3.[16]

Other ligands for octahedral coordination include PPh3, PPh2Me and thiourea.[16]

Nickel tetrahedral complexes are often bright blue and 20 times or more intensely coloured than the octahedral complexes.[16] The ligands can include selections of neutral amines, arsines, arsine oxides, phosphines or phosphine oxides and halogens.[16]

Several nickel atoms can cluster together in a compound with other elements to produce nickel cluster complexes. One example where nickel atoms form a square pyramid is a nickel hydride cluster complexed by triphenyl phosphine ligands and bonding a hydrogen atom on each edge. Another example has a square planar Ni4H4 shape in its core.[220]

Nickel bis(dimethylglyoximate), an insoluble red solid is important for gravimetric analysis.

Bio molecules

Active site of Nickel superoxide dismutase

Cofactor F430 contains nickel in a tetrapyrrole derivative, and is used in the production of methane. Some hydrogenase enzymes contain a nickel-iron cluster as an active site in which the nickel atom is held in place by cysteine or selenocysteine.[221] Plant ureases contain a bis-μ-hydroxo dimeric nickel cluster.[222] CO-methylating acetyl-CoA synthase contains two active nickel atoms, one is held in a square planar coordination by two cysteine and two amide groups, and the other nickel is held by three sulfur atoms. It is used to catalyse the reduction of carbon monoxide to acetyl-CoA.[223]

Nickel superoxide dismutase (or Ni-SOD) from Streptomyces contains six nickel atoms. The nickel holding is done by a "nickel binding hook" which as the amino acid pattern H2N-His-Cys-X-X-Pro-Cys-Gly-X-Tyr-rest of protein, where the bold bits are ligands for the nickel atom.[224]

Nickel transporter proteins exist to move nickel atoms in the cell. in E. coli these are termed NikA, NikB, NikC, NikD, NikE. In order to come through a cell membrane a nickel permease protein is used. In Alcaligenes eutrophus the gene for this is hoxN.[225]

Organometallics

Well known nickel organometalic (or organonickel) compounds include Nickelocene, bis(cyclooctadiene)nickel(0) and nickel tetracarbonyl. Nickel[226][227]

Nickel tetracarbonyl was the first discovered organonickel compound. It was discovered that carbon monoxide corroded a nickel reaction chamber valve. And then that the gas coloured a bunsen burner flame green, and then that a nickel mirror condensed from heating the gas. The Mond process was thus inspired to purify nickel.[228] The Nickel tetracarbonyl molecule is tetrahedral, with a bond length for nickel to carbon of 1.82 Å.[228] Nickel tetracarbonyl easily starts breaking apart over 36° forming Ni(CO)3, Ni(CO)2, and Ni.[228] Ni(CO) and NiC appear in mass spectroscopy of nickel carbonyl.[228]

There are several nickel carbonyl cluster anions formed by reduction from nickel carbonyl. These are [Ni2(CO)5]2−, dark red [Ni3(CO)8]2−, [Ni4(CO)9]2−, [Ni5(CO)9]2−, [Ni6(CO)12]2−. Salts such as Cd[Ni4(CO)9] and Li2[Ni3(CO)8]•5acetone can be crystallised.[229]

Mixed cluster carbonyl anions like [Cr2Ni3(CO)16]2−, [Mo2Ni3(CO)16]2− and [W2Ni3(CO)16]2− [Mo<Ni4(CO)14]2− can form salts with bulky cations like tetraethylammonium. The brown [NiCo3(CO)11]− changes to red [Ni2Co4(CO)14]2−.[230]

With oxygen or air the explosive Ni(CO)3O2 can be formed from nickel carbonyl.[231]

Yet other ligands can substitute for carbon monoxide in nickel carbonyl. These lewis base ligands include triphenylphosphine, triphenoxyphosphine, trimethoxyphosphine, tributylphosphine, triethoxyphosphine, triethylisonitrolphosphine, triphenylarsine, and triphenylstibine.

Nickel forms dark blue planar complexes with 1,2-Diimino-3,5-cyclohexadiene or bisacetylbisaniline [(C6H5N-C(CH3)=)2]2Ni. Another planar bis compound of nickel is formed with phenylazothioformamide C6H5N=NC(S)NR2, and dithizone C6H5N=NC(S)NHNHC6H5.[232] tetrasulfur tetranitride when reduced with nickel carbonyl makes Ni[N2S2H]2 also coloured dark violet.[232]

One nickellabenzene is known where nickel substitutes for carbon in benzene. At nickel the plane of the molecule is bent, however the connection to the ring has aromatic character.[233]

Alkoxy compounds

Nickel tert-butoxide Ni[OC(CH3)3]2 is coloured violet. It is formed in the reaction of di-tert-butylperoxide with nickel carbonyl.[228]

Nickel dimethoxide is coloured green.[234] There are also nickel chloride methoxides with formulae: NiClOMe, Ni3Cl2(OMe)4 and Ni3Cl(OMe)5 in which Nickel and oxygen appear to form a cubane-type cluster.[235]

Other alkoxy compounds known for nickel include nickel dipropoxide, nickel di-isopropoxide, nickel tert-amyloxide, and nickel di-tert-hexanoxide.[236] These can be formed by crystallising nickel chloride from the corresponding alcohol, which forms an adduct. This is then heated with a base.[237] Nickel(II) alkoxy compounds are polymeric and non-volatile.[238]

Ziegler catalysis uses nickel as a catalyst. In addition it uses diethylaluminum ethoxide, phenylacetylene and triethylaluminium It converts ethylene into 1-butene. It can dimerise propylene. The catalyst, when combined with optically active phosphines, can produce optically active dimers. An intermediate formed is tris(ethylene)nickel.(CH2=CH2)3Ni in which the ethylene molecules connect to the nickel atom side on.[239]

Homoletptic bimetallic alkoxides have two different metals, and the same alkoxy group. They include Ni[(μ-OMe)3AlOMe]2, Ni[Al(OBut)4]2 (nickel tetra-tert-butoxyaluminate) and Ni[Al(OPri)4]2. (nickel tetra-isopropoxyaluminate a pink liquid)[240] Potassium hexaisoproxynoibate and tantalate can react with nickel chloride to make Ni[Nb(OPri)6]2 and Ni[Ta(OPri)6]2. Ni[Zr2(OPri)9]2 The bimetallic alkoxides are volatile and can dissolve in organic solvents.[241] A trimetallic one exists [Zr2(OPri)9]Ni[Al(OPri)4].[242] NiGe(OBut)8], NiSn(OBut)8] and NiPb(OBut)8] are tricyclic. [Ni2μ3-OEt)2(μ-OEt)8Sb4(OEt)6]

Heteroleptic bitmetallic ethoxides have more than one variety of alkoxy group, e.g. Ni[(μ-OPri)(μ-OBut)Al(OBut)2]2 which is a purple solid.

Oxoalkoxides contain extra oxygen in addition to the alcohol. With only nickel, none are known, but with antimony an octanuclear molecule exists [Ni5Sb3(μ4-O)2(μ3-OEt)3(-OEt)9(OEt)3(EtOH)4].[243]

Aryloxy compounds

There are many nickel compounds with the formula template Ni(OAr)XL2 and Ni(OAr)2L2. L is a ligand with phosphorus or nitrogen atoms. OAr is a phenol group or O- attached to an aromatic ring. Often an extra molecule of the phenol is hydrogen bonded to the oxygen attached to nickel.[244]

μ-bonded molecules

Others include cyclododecatriene nickel.

Sulfur rings

Nickel bis-dithiobenzoate can form a violet coloured sodium salt.[228]

Two bisperfluoromethyl-l,2-dithietene molecules react with nickel carbonyl to make a double ring compound with nickel linked to four sulfur atoms. This contains four trifluoromethyl groups and is dark purple. Instead of this methyl or phenyl can substitute. These can be made by substituted acetylenes with sulfur on nickel carbonyl, or on nickel sulfide. Bis-diphenyldithiene nickel has a planar structure[245]

Nickel chalcogen cluster compound

A hexameric compound [Ni(SR)2]6 is produced in the reaction of nickel carbonyl with dialkyl sulfides (RSR).[245]

Nickel can be part of a cubane-type cluster with iron and chalcogens. The metal atoms are arranged in a tetrahedron shape, with the sulfur or selenium making up another tetrahedron that combines to make a cube. For example, the [NiFe3S4(PPh3)(SEt)3]2− is a dianion that has a tetraethyl ammonium salt. Similar ion clusters are [NiFe3Se4(PPh3)(SEt)3]2− and [NiFe3Se4(SEt)4]3−.[246] In the natural world cube shaped metal sulfur clusters can have sulfur atoms that are part of cysteine.

[Ni4Se23]4− has a cube with Ni(IV)4Se4 at its core, and then the nickel atoms are bridge across the cube faces by five Se3 chains and one Se4 chain. It is formed as a tetraethylammonium salt, from Li2Se, Se, NEt4Cl and nickel dixanthate in dimethylformamide as a solvent. This reaction also produces (NEt4)2Ni(Se4)2.[247]

Nitrosyl compounds

When liquid nickel carbonyl is dissolved in liquid hydrogen chloride, it can react with nitrosyl chloride to form a dimer Ni(NOCl)2. This then decomposes to Ni(NO)Cl2, which is polymeric.[228]

Nickel carbonyl reacting with nitric oxide yields blue coloured mononitrosyl nickel NiNO. With cyclohexane as well, pale blue Ni(NO2)NO is produced with nitrous oxide as a side product. With cyclopentadiene as well, π-C5H5NiNO is produced.[228]

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  228. 1 2 3 4 5 6 7 8 Jolly, P. W.; Wilke, G. (1974). The organic chemistry of nickel. 1. New York: Academic Press. pp. 1–9. ISBN 0-12-388401-2.
  229. ↑ Jolly, P. W.; Wilke, G. (1974). The organic chemistry of nickel. 1. New York: Academic Press. pp. 20–22. ISBN 0-12-388401-2.
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  232. 1 2 Jolly, P. W.; Wilke, G. (1974). The organic chemistry of nickel. 1. New York: Academic Press. p. 19. ISBN 0-12-388401-2.
  233. ↑ Wright, L. James (2017). Metallabenzenes: An Expert View. John Wiley & Sons. p. 97. ISBN 9781119068099.
  234. ↑ Bradley], D.C. (2001). Alkoxo and aryloxo derivatives of metals. San Diego: Academic Press. p. 97. ISBN 0-12-124140-8.
  235. ↑ Bradley, Don C.; Mehrotra, R. C.; Rothwell, Ian; Sin, A. (2001). Alkoxo and aryloxo derivatives of metals. San Diego: Academic Press. p. 100. ISBN 978-0-12-124140-7.
  236. ↑ Bradley, Don C.; Mehrotra, R. C.; Rothwell, Ian; Sin, A. (2001). Alkoxo and aryloxo derivatives of metals. San Diego: Academic Press. p. 11. ISBN 978-0-12-124140-7.
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  239. ↑ Jolly, P. W.; Wilke, G. (1975). The organic chemistry of nickel. 2. New York: Academic Press. p. 3. ISBN 0-12-388402-0.
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  245. 1 2 Jolly, P. W.; Wilke, G. (1974). The organic chemistry of nickel. 1. New York: Academic Press. pp. 18–19. ISBN 0-12-388401-2.
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