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Tetrafluoroberyllate
Anion

Tetrafluoroberyllate or orthofluoroberyllate is an anion with the chemical formula [BeF4]2−. It contains beryllium and fluorine. This fluoroanion has a tetrahedral shape, with the four fluorine atoms surrounding a central beryllium atom. It has the same size, charge, and outer electron structure as sulfate SO2−4. Therefore, many compounds that contain sulfate have equivalents with tetrafluoroberyllate. Examples of these are the langbeinites, and Tutton's salts.

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Properties

The Be–F bond length is between 145 and 153 pm. The beryllium is sp3 hybridized, leading to a longer bond than in BeF2, where beryllium is sp hybridized.1 In trifluoroberyllates, there are actually BeF4 tetrahedra arranged in a triangle, so that three fluorine atoms are shared on two tetrahedra each, resulting in a formula of Be3F9.2

In the tetrafluoroberyllates, the tetrahedra can rotate to various degrees. At room temperature, they are hindered from moving. But as temperature increases, they can rotate around the threefold axis, (i.e. a line through one fluorine atom and the beryllium atom) with a potential barrier of 12.5 kcal/mol (52 kJ/mol). At higher temperatures, the movement can become isotropic (not limited to rotation on one axis) with a potential barrier of 14.5 kcal/mol (61 kJ/mol).3

Similar compounds have magnesium or zinc in a similar position as beryllium, e.g. K2[MgF4] (potassium tetrafluoromagnesate) or [NH4]2[ZnF4] (ammonium tetrafluorozincate) but these are not as stable.4

Tetrafluoroberyllate has a biological effect by inhibiting F-ATPase adenosine triphosphate producing enzymes in mitochondria and bacteria. It does this by attempting to react with adenosine diphosphate because it resembles phosphate. However once it does this it remains stuck in the F1 part of the enzyme and inhibits it from further function.5

Simple salts

NameChemical formulaMolar mass (g/mol)CAS numberCrystal systemDensity (g/cm3)Melting point (°C)Solubility in water(g/(100 ml))
lithium tetrafluoroberyllateLi2[BeF4]98.892.1676472 °C7slight (1.25 at 20 °C, 5.78 at 40 °C)8
sodium tetrafluoroberyllateNa2BeF4130.98533313871-27-7Orthorhombic92.47575 °Cslight (1.33 at 0 °C, 1.44 at 20 °C, 2.73 at 90 °C)10
potassium tetrafluoroberyllateK2BeF4163.207787-50-0orthorhombic a = 5.691 Å, b = 7.278 Å, c = 9.896 Å11 as for strontium orthosilicate122.6413
potassium tetrafluoroberyllate dihydrateK2BeF4·2H2O199.233
ammonium tetrafluoroberyllate(NH4)2BeF4121.082714874-86-3orthorhombic a = 5.91 Å, b = 7.64 Å, c = 10.43 Å1.71decomposes 280 °C1432.3 at 25 °C15
rubidium tetrafluoroberyllateRb2BeF4255.941orthorhombic a = 5.87 Å, b = 7.649 Å, c = 10.184 Å163.7217
caesium tetrafluoroberyllateCs2BeF4350.8167orthorhomic a = 8.03 Å, b = 10.81 Å, c = 0.622 Å4.32
thallium tetrafluoroberyllateTl2BeF4493.7724orthorhombic a = 7.7238 Å, b = 5.9022 Å, c = 10.4499 Å186.88419
silver tetrafluoroberyllateAg2BeF4300.7422
magnesium tetrafluoroberyllateMgBeF4109.3108
calcium tetrafluoroberyllateCaBeF4125.082.95920
strontium tetrafluoroberyllateSrBeF4172.6orthorhombic a = 5.291 Å, b = 6.787 Å, c = 8.307 Å3.84insoluble
barium tetrafluoroberyllateBaBeF4222.3334.1721insoluble
radium tetrafluoroberyllateRaBeF422311.005795insoluble
hexaqua ferrous tetrafluoroberyllateFeBeF4·6H2O23
heptaqua ferrous tetrafluoroberyllateFeBeF4·7H2O241.894
heptaqua nickel tetrafluoroberyllateNiBeF4·7H2O25
hexaqua nickel tetrafluoroberyllateNiBeF4·6H2O26
heptaqua cobalt tetrafluoroberyllateCoBeF4·7H2O271.867
hexaqua cobalt tetrafluoroberyllateCoBeF4·6H2O281.891
pentaqua copper tetrafluoroberyllateCuBeF4·5H2O29
heptaqua zinc tetrafluoroberyllateZnBeFe4·7H2O30
lead tetrafluoroberyllatePbBeF4292.26.13531
hydrazinium tetrafluoroberyllateN2H6BeF4119.0668a = 5.58 Å, b = 7.337 Å, c = 9.928 Å, α = 90°, β = 98.22°, γ = 90°32
triglycine tetrafluoroberyllate(NH2CH2COOH)3·H2BeF4312.2212396-72-7monoclinic3334
ethylene diamine fluoroberyllate(NH2CH2CH2NH2)·H2BeF435decomposes 330 °C
propylenediamine tetrafluoroberyllate(NH2CH2CH2CH2NH2)·H2BeF436
propylene-1,2-diamine tetrafluoroberyllate(NH2CH(CH3)CH2NH2)·H2BeF437monoclinic a = 5.535 Å, b = 13.560 Å, c = 9.6048 Å, β = 106.73 Å, V = 690.4 Å3, Z = 4381.55
benzidine fluoroberyllate(NH2C6H4C6H4NH2)·H2BeF439ins
tetramethyl ammonium tetrafluoroberyllate[N(CH3)4]2BeF440
tetramine silver tetrafluoroberyllate[Ag(NH3)2]2BeF441
[Cu(NH3)2]2BeF442
[Cu(NH3)4]2BeF4·H2O43
[Zn(NH3)4]2BeF444
[Cd(NH3)4]2BeF445
[Ni(NH3)6]2BeF446
[Ni(NH3)4]2BeF4·2H2O47
[Ni(NH3)2]2BeF448
[Co(NH3)6]2BeF4·3H2O49

Sodium tetrafluoroberyllate has several crystalline forms. Below 220 °C it takes the same form as orthorhombic olivine, and this is called γ phase. Between 220 °C and 320 °C it is in the α′ form. When temperature is raised above 320 °C it changes to the hexagonal α form. When cooled the α′ form changes to β form at 110 °C and this can be cooled to 70 °C before changing back to the γ form.50 It can be formed by melting sodium fluoride and beryllium fluoride.51 The gas above molten sodium tetrafluoroberyllate contains BeF2 and NaF gas.52

Lithium tetrafluoroberyllate takes on the same crystal form as the mineral phenacite. As a liquid it is proposed for the molten salt reactor, in which it is called FLiBe. The liquid salt has a high specific heat, similar to that of water. The molten salt has a very similar density to the solid. The solid has continuous void channels through it, which reduces its density.53 Li2BeF4 can be crystallised from aqueous solution using (NH4)2BeF4 and LiCl.54

Potassium tetrafluoroberyllate has the same structure as anhydrous potassium sulfate, as does rubidium and caesium tetrafluoroberyllate. Potassium tetrafluoroberyllate can make solid solutions with potassium sulfate.55 It can be used as a starting point to make the non-linear optic crystal KBe2BO3F2 which has the highest power handling capacity and shortest UV performance of any borate.56 It is quite soluble in water, so beryllium can be extracted from soil in this form.57

Ammonium tetrafluoroberyllate decomposes on heating by losing NH4F vapour, progressively forming NH4BeF3, then NH4Be2F5 and finally BeF2.58

Thallium tetrafluoroberyllate can be made by dissolving beryllium fluoride and thallium carbonate together in hydrofluoric acid and then evaporating the solution.59

Radium tetrafluoroberyllate is used as a standard neutron source. The alpha particles from the radium cause neutrons to be emitted from the beryllium. It is precipitated from a radium chloride solution mixed with potassium tetrafluoroberyllate.60

Magnesium tetrafluoroberyllate can be precipitated from a hot saturated solution of ammonium tetrafluoroberyllate and a magnesium salt.61 However, if the temperature reaches boiling point MgF2 is precipitated instead.62

Calcium tetrafluoroberyllate resembles zircon in the way it melts and crystallises.63

Strontium tetrafluoroberyllate can be made in several forms. The γ form is produced by cooling a melt of SrF2 and Be2 and the β form is made by precipitating from a water solution. When melted and heated to 850–1145 °C, Be2 gas evaporates leaving behind molten SrF2.64

The barium tetrafluoroberyllate is very insoluble and can be used for gravimetric analysis of beryllium.65

H2BeF4 is an acid that can be produced from Ag2BeF4 and HCl. It only exists in aqueous solution.66

Triglycine tetrafluoroberyllate (TGFB) is ferroelectric with a transition point of 70 °C.67 The crystals can be formed by dissolving BeF2 in water, adding HF and then glycine. When the solution is cooled triglycine tetrafluoroberyllate forms. Cs2BeF4 and Tl2BeF4 in the solution reduce growth on the 001 direction so that tabular shaped crystals of TGFB form. The thallium compound can cut growth on the 001 axis by 99%.68

Double salts

Tuttons salts

The Tuttons salt (NH4)2Mn(BeF4)2·6(H2O) is made from a solution of NH4BeF3 mixed with NH4MnF3.69 The equivalent of alums are hard to make because the trivalent ion will often form a complex with fluoride in preference to the beryllium fluoride. However the violet coloured acid and rubidium chrome alum exist at chilly temperatures for a few hours.70

Tutton's salts (also called schoenites) containing magnesium with fluoroberyllate are difficult to produce, as the solutions tend to precipitate insoluble MgF2.71

nameformulamolecular weightCAScrystal formdensitymelting pointsolubility g/100ml
potassium lithium tetrafluoroberyllateKLiBeF4131.05P63, a = 8.781 Å, b = 5.070 Å c = 8.566 Å72
rubidium lithium tetrafluoroberyllateRbLiBeF4177.41P6322, a = 8.980 Å, b = 5.185 Å c = 8.751 Å73
caesium lithium tetrafluoroberyllateCsLiBeF4224.852P21/n, a = 9.328 Å b = 5.356 Å, c = 8.736 Å, γ = 89.82°74
acid chromium fluoroberyllate tetracosihydrateH2Cr2(BeF4)4·24H2O75878.40
ammonium chromium fluoroberyllate tetracosihydrate(NH4)2Cr2(BeF4)4·24H2O76912.46
rubidium chromium fluoroberyllate tetracosihydrateRb2Cr2(BeF4)4·24H2O771047.32
manganese ammonium fluoroberyllate hydrate(NH4)2Mn(BeF4)2·6H2O78369.1181.75879
Rb2Fe(BeF4)2·6H2O80504.884
ferrous ammonium fluoroberyllate hydrate(NH4)2Fe(BeF4)2·6H2O81370.02582
nickel potassium fluoroberyllate hydrateK2Ni(BeF4)2·6H2O83414.91384
nickel rubidium fluoroberyllate hydrateRb2Ni(BeF4)2·6H2O85507.732
Cs2Ni(BeF4)2·6H2O86602.608
nickel ammonium fluoroberyllate hydrate(NH4)2Ni(BeF4)2·6H2O87372.874P21/a, a = 9.201 Å, b = 12.482 Å, c = 6.142 Å, β = 106.57 Å, V = 676.0 Å3 Z = 2881.84389
cobalt potassium fluoroberyllate hydrateK2Co(BeF4)2·6H2O90415.23391
cobalt rubidium fluoroberyllate hydrateRb2Co(BeF4)2·6H2O92507.972
cobalt ammonium fluoroberyllate hydrate(NH4)2Co(BeF4)2·6H2O93372.8741.82194
copper rubidium fluoroberyllate hydrateRb2Cu(BeF4)2·6H2O95512.585
copper ammonium fluoroberyllate hydrate(NH4)2Cu(BeF4)2·6H2O96377.7261.85897
zinc rubidium fluoroberyllate hydrateRb2Zn(BeF4)2·6H2O98514.42
zinc ammonium fluoroberyllate hydrate(NH4)2Zn(BeF4)2·6H2O99379.561.859100
cadmium rubidium fluoroberyllate hydrateRb2Cd(BeF4)2·6H2O101561.45
cadmium ammonium fluoroberyllate hydrate(NH4)2Cd(BeF4)2·6H2O102426.591

Alums

Tetrafluoroberyllate salts equivalent to alums also exist with formula MABF4·12H2O, where M is univalent, and A trivalent. These are not common as fluoride often form insoluble products with the trivalent ions. Methods to produce these include evaporating mixed fluoride solutions under reduced pressure at 0 °C, or dissolving beryllium and other metal hydroxides in hydrofluoric acid at room temperature, cooled, and them mixing with cold ethyl alcohol, causing cooling and crystallisation.103 The unit cell dimensions are slightly smaller (by 0.03–0.05 Å) than the corresponding sulfate alums.104

nameformulamolecular weightCAScrystal formdensitymelting pointsolubility g/100ml
ammonium aluminium tetrafluoroberyllate alumNH4AlBeF4·12H2O105
potassium aluminium tetrafluoroberyllate alumKAlBeF4·12H2O106
potassium chromium tetrafluoroberyllate alumKCrBeF4·12H2O107
ammonium chromium tetrafluoroberyllate alumNH4CrBeF4·12H2Ocubic a = 12.218 Å, Z = 4108
rubidium chromium tetrafluoroberyllate alumRbCrBeF4·12H2O12.214 Å109
caesium chromium tetrafluoroberyllate alumCsCrBeF4·12H2O12.323 Å110
thallium chromium tetrafluoroberyllate alumTlCrBeF4·12H2O12.195 Å111
rubidium iron tetrafluoroberyllate alumRbFeBeF4·12H2O112
caesium iron tetrafluoroberyllate alumCsFeBeF4·12H2O113
monomethyl chromium tetrafluoroberyllate alumCH3NH3CrBeF4·12H2O12.496 Å114
guanidium chromium tetrafluoroberyllate alumC(NH2)3CrBeF4·12H2O12.538 Å115on heating forms a rhombohedral hexahydrate stable from 30 °C to 90 °C

References

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