Nickel double salts

Nickel can form various double salts.

Tutton's 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.

Mineral forms As a mineral the ammonium nickel salt, (NH4)2Ni(SO4)2, can be called nickelboussingaultite. With sodium, the double sulfate is nickelblödite Na2Ni(SO4)2 from the blödite family. Nickel can be substituted by other divalent metals of similar sized to make mixtures that crystallise in the same form.

Langbeinites

Anhydrous salts of the formula M2Ni2(SO4)3, which can be termed metal nickel trisulfates, 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.

Double halides

Fluorides Double fluorides include the fluoroanion salts, and those fluoronickelates such as NiF4 and NiF6:Mellor 405-406 KNiF3·H2O and NaNiF3·H2O – apple green coloured 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 hexahydrate (NiWO2F4·6H2O) and decahydrate (NiWO2F4·10H2O) manganic nickel pentafluoride (MnNiF4·7H2O) nickelous ferric fluoride (FeNiF5·7H2O)

Chlorides

Trichlorides 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.

Other double trichlorides include: potassium nickel trichloride (KNiCl3·5H2O)Mellor p419 yellow cesium nickel trichloride (CsNiCl3) lithium nickel trichloride (LiNiCl3·3H2O) nickel ammonium chloride hexahydrate (NH4NiCl3·6H2O)

Tetrachlorides

The tetrachloronickelates contain a tetrahedral NiCl42− and are dark blue. Some salts of organic bases are ionic liquids at standard conditions. Tetramethylammonium nickel trichloride is pink and very insoluble.

Other tetrachlorides include: hyrdrazinium nickel tetrachloride lithium nickel tetrachloride (Li2NiCl4·4H2O) – stable from 23 to 60°Mellor p420 rubidium nickel tetrachloride stannous nickel tetrachloride (SnCl2·NiCl2·6H2O)

Hexachlorides Double hexachlorides include: cadmium dinickel hexachloride (CdCl2•2NiCl2•12H2O) – crystallises in hexagonal system dicadmium dinickel hexachloride (2CdCl2•NiCl2•12H2O) – rhombic crystals, pleochroic varying from light to dark green. lithium nickel hexachloride Li4NiCl6·10H2O – stable from 0 to 23° stannic nickel hexachloride (SnCl4·NiCl2·6H2O) – tetragonal

Octochlorides Thallic nickel octochloride 2TlCl3·NiCl2·8H2O is bright green.

Oxychlorides Copper nickel dioxychloride 2CuO·NiCl2·6H2O and copper nickel trioxychloride 3CuO·NiCl2·4H2O exist.

Bromides

Double bromides include the tetrabromonickelates. Other salts include:Mellor 457 caesium nickel tribromide (CsNiBr3) copper nickel trioxybromide (3CuO·NiBr2·4H2O) didymium nickel bromide (2(Pr,Nd)Br3·3NiBr2·18H2O) – reddish brown, mixture of praseodymium and neodymium lanthanum nickel bromide (2LaBr3·3NiBr2·18H2O) mercuric nickel bromides (Hg2NiBr6) and (HgNiBr4) mercuric nickel oxybromide (6NiO·NiBr2•HgBr2•20H2O) – prepared by reacting nickel bromide with mercuric oxide nickel stannic bromide or nickel bromostannate (NiSnBr6·8H2O) – apple green

Iodides

The tetraiodonickelates are blood-red coloured salts of the NiI4 ion with large cations. The diperiodatonickelates of nickel(IV) are strong oxidisers, and akali monoperiodatonickelates also are known.

Double iodides include: mercuric nickel hexaiodide (2HgI2·NiI2) mercuric nickel tetraiodide (HgI2·NiI2) lead nickel hexaiodide (I2·2NiI2) Double nitrates

Lanthanides Nickel forms double nitrates with the lighter rare-earth elements. The solid crystals have the formula Ni3Me2(NO3)12•24H2O. 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, and 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. Ni3La2(NO3)12•24H2O becomes ferromagnetic below 0.393 K. These double nickel nitrates have been used to separate the rare earth elements by fractional crystallization.

Actinides Nickel thorium nitrate has formula NiTh(NO3)6. 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. Enthalpy of solution of the octahydrate is 7 kJ/mol. Enthalpy of formation is -4360 kJ/mol. At 109° the octahydrate becomes NiTh(NO3)6•6H2O, and at 190° NiTh(NO3)6•3H2O and anhydrous at 215°. The hexahydrate has Pa cubic structure.

Double nitrites

Double amides Various double amides containing nickel clusters have been made using liquid ammonia as a solvent. These are called amidonickel compounds.

These include:

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) – red Li4Ni4(NH2)12·NH3, Na2Ni(NH2)4 Na2Ni(NH2)4•NH3 Na2Ni(NH2)4•2NH3 – orange red K2Ni(NH2)4•0.23KNH2 Rb2Ni(NH2)4•0.23RbNH2 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)

Double hydrides Double hydrides of nickel exist, such as Mg2NiH4.

Double dihydrogen phosphides 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.

Double tetrafluoroberyllates

Nickel forms double salts with Tutton's salt structure with tetrafluoroberyllate and a range of cations including ammonia, potassium, rubidium, cesium, and thallium. Other minerals 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.

Table of nickel double salts

formulanamemolstructcell Å°VZdensitycolourrefswtabcβÅ3g/cm3Li2[NiF(PO4)]Lithium nickel fluorophosphate186.56orthorhombic10.4736.28910.846714.383.469Na2[NiF(PO4)]sodium nickel fluorophosphate218.645Pbcn90823.4Na2Ni(SO4)2nickelblödite368.867monoclinic11.0458.1935.535100.502.487greenK2Ni2(SO4)3potassium nickel trisulfate483.77orthorhombic9.84369.84369.8436903.369Rb2Ni2(SO4)3rubidium nickel trisulfate576.519.92179.92179.9217903.921(NH4)2Ni2(SO4)3ammonium nickel trisulfate441.65orthorhombic9.9049.9049.904903.02(NH4)4Ni3(SO4)5ammonium nickel pentasulfate728.56yellowNiLa(SeO3)2Clnickel lanthanum diselenite chloride486.977hexagonal8.66618.6621194.26(153K)NiNd10(SeO3)12Cl8nickel Neodymium diselenite chloridemonoclinic15.81751578,6819.276114.20274074(153K)Ni6Fe3+2(SO4)(OH)16honessite 904.08trigonal3.083 26.71219.860.251.71greenNiTi(SO4)3nickel titanium sulfatemonoclinic 8.254 8.5414.1444 124.96781743.21Na2Ni(SeO4)2sodium nickel selenate dihydratetriclinic5.5075.9057.172α = 108.56 °, β = 99.07 °, γ = 106.35 °204.21K2Ni(SeO4)2potassium nickel selenate dihydrateK2Ni(SeO4)2potassium nickel selenate Tuttons salt527.52monoclinicabc104.4542.559bright greenRb2Ni(SeO4)2rubidium nickel selenate Tuttons salt619.62monoclinicabc105.2042.856bright greenCs2Ni(SeO4)2caesium nickel selenate Tuttons salt713.62monoclinic9.42612.9616.473106.17759.523.114bright emerald green open access(NH4)2Ni(SeO4)2ammonium nickel selenate Tuttons salt485.68monoclinicabc106.2942.243bright greenTl2Ni(SeO4)2thallium nickel selenate Tuttons saltmonoclinicabc105.6043.993bright greenK2NiP2O7310.85monoclinic P219.23017.5408.3291.441346.383.067K6Sr2Ni5(P2O7)5786.55monoclinic P21/c11.0389.537.438100.13157823.309yellowNaNi2(SO4)2[(H2O)(OH)]monoclinic C2/m Natrochalcite-type8.6056.1857.336114.78354.52BaNi2(PO4)2barium nickel phosphateTrigonal R-34.81124.811223.302467.13greenBaNi2(AsO4)2barium nickel arsenateTrigonal R-34.9454.94523.61532.5935.31BaNi2(VO4)2barium nickel vanadateTrigonal R-35.03755.037522.333Na4Ni7(AsO4)6tetrasodium heptanickel hexaarsenate1336.3monoclinic C2/m14.53814.50510.6120118.2991970.34brownK2Ni(CO3)2potassium nickel carbonatePotassium tetraaquadicarbonatonickelatemonoclinic Baylissite-type6.7556.15612.2406113.265467.622.34 Rb2Ni(CO3)2Rubidium nickel carbonatemonoclinic Baylissite-type6.9716.34812.2807114.289495.3422.83NiTh(NO3)6nickel thorium nitrateMonoclinic P21/c9.0898.72813.56596.651068.8(2)K[NiGa2(PO4)3(H2O)2]Potassium nickel(II) gallium phosphate hydrate558.17Monoclinic C2/c13.20910.1738.813107.681128.4Z = 4KNi3(PO4)P2O7Potassium trinickel(II) orthophosphate diphosphate484.14Monoclinic9.85919.39539.9778118.965808.634KNiPO4potassium nickel phosphateKNiPO4potassium nickel phosphate hexahydratemonoclinic P216.830911.06106.116591.045462.072NiK4(P3O9)2nickel potassium tricyclophosphate hydrateorthorhombic Fm2m23.0311.8828.7324blueNiK4(P3O9)2nickel potassium tricyclophosphatetriclinic P-16.1436.8012.80α=102.8 β=89.7 γ=66.03473.561NaK5Ni5(P2O7)4Sodium pentapotassium pentanickel tetra(diphosphate)1207.80triclinic7.1889.28210.026(5)α=109.31 β=90.02 γ=104.07610.01ammonium nickel phosphate hydrateorthorhombic5.5668.7604.742231.2ammonium nickel phosphate hydrateNi-struviteOrthorhombic Pmn216.9246.10411.166471.52LiNiPO4lithium nickel phosphateorthorhombic10.0325.8554.681274.94brownNaNiPO4sodium nickel phosphatePnma maricite structure8.78396.74265.0368298.314yellowNaNiPO4sodium nickel phosphatePnma triphylite form4.986.139.98304.23Na4Ni7(PO4)6Cm10.55013.9856.398104.87912.423.906NaNiPO4sodium nickel phosphate heptahydratetetrahedral P42/mmc6.739010.9690498.152Na3NiP3O10trisodium nickel triphosphate dodecahydratemonoclinic (pseudoorthorhombic)15.02369.197214.6654.90.04922014.461.967light greenNa5Ni2(PO4)3Pentasodium dinickel triphosphate hydratemonoclinic space group P21/n14.03955.18516.4739110.419Na6Ni2(PO4)3OHorthorhombic Pcmb7.50121.46617.173Na2Ni3(OH)2(PO4)2sodium nickel hydroxide phosphatemonoclinic14.2595.6954.933104.2823.816NiNa4(P3O9)2nickel tetrasodium cyclotriphosphate hexahydratetriclinic6.1576.82010.918α=80.21 β=97.8 γ=119.5409.81NiRb4(P3O9)2nickel tetrarubidium cyclotriphosphateP-31c7.2887.28820.3432NiCs4(P3O9)2nickel tetracaesium cyclotriphosphate hydrateorthorhombic 19.9926.50018.4454NiCs4(PO3)6nickel tetracaesium cyclotriphosphaterhombohedral P-31c11.60211.6029.0781058.242NiAg4(P3O9)2nickel tetrasilver cyclotriphosphate hexahydratetriclinic9.2098.0536.841α=89.15 β=102.94 γ=97.241NiAg4(P3O9)2nickel tetrasilver cyclotriphosphatetriclinic6.1006.78310.764α = 78.66 β=96.85 γ=113.364011Ni(NH4)4(P3O9)2nickel tetraammonium cyclotriphosphate tetrahydratemonoclinic2TlNi4(PO4)3Thallium nickel triphosphateorthorhombic Cmc214pale yellowTl4Ni6(PO4)6Thallium nickel hexaphosphatemonoclinic Cm4yellow brownTl2Ni4P2O7(PO4)2monoclinic C2/c8brownNiMnSbNickel manganese antimonidecubic5.945210.147.57NiMnSiNickel manganese silicideOrthorhombic5.89673.61246.9162147.324NiMnGeorthorhombic Pnma6.0533.7697.090161.752NiFeGehexagonalTiNiSiorthorhombicNaNiIO6sodium nickel periodateorthorhombic8.5992.49210.281220.3KNiIO6potassium nickel periodateorthorhombic12.093.6836.062269.9KNiIO6potassium nickel periodatetriclinic6.42035.0754.223α= 65.07 β= 92.717 γ=109.95116.51

References