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Nickel double salts

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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.[1]

Mineral forms

As a mineral the ammonium nickel salt, (NH4)2Ni(SO4)2 · 6 H2O, can be called nickelboussingaultite.[2] 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.[3]

Langbeinites

See also: 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.[citation needed]

Double halides

Fluorides

Double fluorides include the fluoroanion salts, and those fluoronickelates such as NiF4 and NiF6:[4]

  • 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.[5]

Other double trichlorides include:

  • potassium nickel trichloride (KNiCl3·5H2O)[6]
  • yellow cesium nickel trichloride (CsNiCl3)[6]
  • lithium nickel trichloride (LiNiCl3·3H2O)[6]
  • nickel ammonium chloride hexahydrate (NH4NiCl3·6H2O)[7]

Tetrachlorides

See also: Tetrachloronickelate

The tetrachloronickelates contain a tetrahedral NiCl42− and are dark blue. Some salts of organic bases are ionic liquids at standard conditions.[8] Tetramethylammonium nickel trichloride is pink and very insoluble.[9]

Other tetrachlorides include:

  • hyrdrazinium nickel tetrachloride[6]
  • lithium nickel tetrachloride (Li2NiCl4·4H2O) – stable from 23 to 60°[10]
  • rubidium nickel tetrachloride[10]
  • stannous nickel tetrachloride (SnCl2·NiCl2·6H2O)[10]

Hexachlorides

Double hexachlorides include:

Octochlorides

Thallic nickel octochloride 2TlCl3·NiCl2·8H2O is bright green.[10]

Oxychlorides

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

Bromides

See also: Tetrabromonickelate

Double bromides include the tetrabromonickelates. Other salts include:[11][12]

  • 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

See also: Tetraiodonickelate

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.[citation needed]

Double iodides include:[13]

  • mercuric nickel hexaiodide (2HgI2·NiI2 · 6 H2O)
  • mercuric nickel tetraiodide (HgI2·NiI2 · 6 H2O)
  • lead nickel hexaiodide (I2·2NiI2 · 3 H2O)

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.[14] Ni3La2(NO3)12•24H2O becomes ferromagnetic below 0.393 K.[15] These double nickel nitrates have been used to separate the rare earth elements by fractional crystallization.[16]

Actinides

Nickel thorium nitrate has formula NiTh(NO3)6 · 8 H2O. 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°.[17] The hexahydrate has Pa3 cubic structure.[17]

Double nitrites

This paragraph is an excerpt from Nitronickelate.[edit]

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.

Double amides

Various double amides containing nickel clusters have been made using liquid ammonia as a solvent. These are called amidonickel compounds.[18]

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[18]
  • Li4Ni4(NH2)12·NH3, Na2Ni(NH2)4[19]
  • Na2Ni(NH2)4•NH3[18]
  • Na2Ni(NH2)4•2NH3[20] – orange red
  • K2Ni(NH2)4•0.23KNH2[18]
  • Rb2Ni(NH2)4•0.23RbNH2[18]
  • 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)[18]

Double hydrides

Double hydrides of nickel exist, such as Mg2NiH4.[21]

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.[22]

Double tetrafluoroberyllates

See also: Tetrafluoroberyllate

Nickel forms double salts with Tutton's salt structure with tetrafluoroberyllate and a range of cations including ammonia,[23] potassium, rubidium, cesium,[24] and thallium.[25]

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.[26]

Table of nickel double salts

More information formula, name ...
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 [27]
Na2[NiF(PO4)] sodium nickel fluorophosphate 218.645 Pbcn 90 823.4 [28]
Na2Ni(SO4)2 · 4 H2O nickelblödite 368.867 monoclinic 11.045 8.193 5.535 100.50 2.487 green [29]
K2Ni2(SO4)3 potassium nickel trisulfate 483.77 orthorhombic 9.8436 9.8436 9.8436 90 3.369 [30]
Rb2Ni2(SO4)3 rubidium nickel trisulfate 576.51 9.9217 9.9217 9.9217 90 3.921 [31]
(NH4)2Ni2(SO4)3 ammonium nickel trisulfate 441.65 orthorhombic 9.904 9.904 9.904 90 3.02 [32]
(NH4)4Ni3(SO4)5 ammonium nickel pentasulfate 728.56 yellow [33]
NiLa(SeO3)2Cl nickel lanthanum diselenite chloride 486.977 hexagonal 8.666 18.662 1194.2 6 (153K) [34]
NiNd10(SeO3)12Cl8 nickel Neodymium diselenite chloride monoclinic 15.8175 1578,68 19.276 114.202 7407 4 (153K) [35]
Ni6Fe3+2(SO4)(OH)16 · 4 H2O honessite 904.08 trigonal 3.083 26.71 219.86 0.25 1.71 green [36]
NiTi(SO4)3 nickel titanium sulfate monoclinic 8.254 8.54 14.1444 124.967 817 4 3.21 [37]
Na2Ni(SeO4)2 · 2 H2O sodium nickel selenate dihydrate triclinic 5.507 5.905 7.172 α = 108.56 °, β = 99.07 °, γ = 106.35 ° 204.2 1 [38]
K2Ni(SeO4)2 · 2 H2O potassium nickel selenate dihydrate [39]
K2Ni(SeO4)2 · 6 H2O potassium nickel selenate Tuttons salt 527.52 monoclinic a b c 104.45 4 2.559 bright green [40]
Rb2Ni(SeO4)2 · 6 H2O rubidium nickel selenate Tuttons salt 619.62 monoclinic a b c 105.20 4 2.856 bright green [40]
Cs2Ni(SeO4)2 · 6 H2O caesium nickel selenate Tuttons salt 713.62 monoclinic 9.426 12.961 6.473 106.17 759.5 2 3.114 bright emerald green [40][41]
(NH4)2Ni(SeO4)2 · 6 H2O ammonium nickel selenate Tuttons salt 485.68 monoclinic a b c 106.29 4 2.243 bright green [40]
Tl2Ni(SeO4)2 · 6 H2O thallium nickel selenate Tuttons salt monoclinic a b c 105.60 4 3.993 bright green [42]
K2NiP2O7 310.85 monoclinic P21 9.230 17.540 8.32 91.44 1346.3 8 3.067 [43]
K6Sr2Ni5(P2O7)5 786.55 monoclinic P21/c 11.038 9.53 7.438 100.13 1578 2 3.309 yellow [43]
NaNi2(SO4)2[(H2O)(OH)] monoclinic C2/m Natrochalcite-type 8.605 6.185 7.336 114.78 354.5 2 [44]
BaNi2(PO4)2 barium nickel phosphate Trigonal R-3 4.8112 4.8112 23.302 467.1 3 green [45]
BaNi2(AsO4)2 barium nickel arsenate Trigonal R-3 4.945 4.945 23.61 532.59 3 5.31 [45]
BaNi2(VO4)2 barium nickel vanadate Trigonal R-3 5.0375 5.0375 22.33 3 [46]
Na4Ni7(AsO4)6 tetrasodium heptanickel hexaarsenate 1336.3 monoclinic C2/m 14.538 14.505 10.6120 118.299 1970.3 4 brown [47]
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 [48]
Rb2Ni(CO3)2 · H2O Rubidium nickel carbonate monoclinic Baylissite-type 6.971 6.348 12.2807 114.289 495.34 2 2.83 [49]
NiTh(NO3)6 · 8 H2O nickel thorium nitrate Monoclinic P21/c 9.089 8.728 13.565 96.65 1068.8(2) [17]
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 [50]
KNi3(PO4)P2O7 Potassium trinickel(II) orthophosphate diphosphate 484.14 Monoclinic 9.8591 9.3953 9.9778 118.965 808.63 4 [51]
KNiPO4 potassium nickel phosphate [52]
KNiPO4 · 6 H2O potassium nickel phosphate hexahydrate monoclinic P21 6.8309 11.0610 6.1165 91.045 462.07 2 [53]
NiK4(P3O9)2 · 7 H2O nickel potassium tricyclophosphate hydrate orthorhombic Fm2m 23.03 11.882 8.732 4 blue [54]
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 [54]
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 [55]
NH4NiPO4·H2O ammonium nickel phosphate hydrate orthorhombic 5.566 8.760 4.742 231.2 [56]
NH4NiPO4·6H2O ammonium nickel phosphate hydrate
Ni-struvite		 Orthorhombic Pmn21 6.924 6.104 11.166 471.5 2 [57][58][59]
LiNiPO4 lithium nickel phosphate orthorhombic 10.032 5.855 4.681 274.9 4 brown [60]
NaNiPO4 sodium nickel phosphate Pnma maricite structure 8.7839 6.7426 5.0368 298.31 4 yellow [61]
NaNiPO4 sodium nickel phosphate Pnma triphylite form 4.98 6.13 9.98 304.23 [62]
Na4Ni7(PO4)6 Cm 10.550 13.985 6.398 104.87 912.4 2 3.906 [61][63]
NaNiPO4 · 7 H2O sodium nickel phosphate heptahydrate tetrahedral P42/mmc 6.7390 10.9690 498.15 2 [53]
Na3NiP3O10 · 12 H2O trisodium nickel triphosphate dodecahydrate monoclinic (pseudoorthorhombic) 15.0236 9.1972 14.6654. 90.0492 2014.46 1.967 light green [64]
Na5Ni2(PO4)3 · H2O Pentasodium dinickel triphosphate hydrate monoclinic space group P21/n 14.0395 5.185 16.4739 110.419 [65]
Na6Ni2(PO4)3OH orthorhombic Pcmb 7.501 21.4661 7.173 [65]
Na2Ni3(OH)2(PO4)2 sodium nickel hydroxide phosphate monoclinic 14.259 5.695 4.933 104.28 2 3.816 [66]
NiNa4(P3O9)2 · 6 H2O nickel tetrasodium cyclotriphosphate hexahydrate triclinic 6.157 6.820 10.918 α=80.21 β=97.8 γ=119.5 409.8 1 [67]
NiRb4(P3O9)2 nickel tetrarubidium cyclotriphosphate P-31c 7.288 7.288 20.343 2 [68]
NiCs4(P3O9)2 · 6 H2O nickel tetracaesium cyclotriphosphate hydrate orthorhombic 19.992 6.500 18.445 4 [54]
NiCs4(PO3)6 nickel tetracaesium cyclotriphosphate rhombohedral P-31c 11.602 11.602 9.078 1058.24 2 [54]
NiAg4(P3O9)2 · 6 H2O nickel tetrasilver cyclotriphosphate hexahydrate triclinic 9.209 8.053 6.841 α=89.15 β=102.94 γ=97.24 1 [69]
NiAg4(P3O9)2 nickel tetrasilver cyclotriphosphate triclinic 6.100 6.783 10.764 α = 78.66 β=96.85 γ=113.36 401 1 [69]
Ni(NH4)4(P3O9)2 · 4 H2O nickel tetraammonium cyclotriphosphate tetrahydrate monoclinic 2 [70]
TlNi4(PO4)3 Thallium nickel triphosphate orthorhombic Cmc21 4 pale yellow [71]
Tl4Ni6(PO4)6 Thallium nickel hexaphosphate monoclinic Cm 4 yellow brown [71]
Tl2Ni4P2O7(PO4)2 monoclinic C2/c 8 brown [71]
NiMnSb Nickel manganese antimonide cubic 5.945 210.1 4 7.57 [72]
NiMnSi Nickel manganese silicide Orthorhombic 5.8967 3.6124 6.9162 147.32 4 [73][74]
NiMnGe orthorhombic Pnma 6.053 3.769 7.090 161.75 2 [75]
NiFeGe hexagonal [75]
TiNiSi orthorhombic [75]
NaNiIO6 sodium nickel periodate orthorhombic 8.599 2.492 10.281 220.3 [76]
KNiIO6 potassium nickel periodate orthorhombic 12.09 3.683 6.062 269.9 [76]
KNiIO6 potassium nickel periodate triclinic 6.4203 5.075 4.223 α= 65.07 β= 92.717 γ=109.95 116.51 [76]
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