Borophosphate

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The borophosphates are mixed anion compounds containing borate and phosphate anions, which may be joined together by a common oxygen atom. Compounds that contain water or hydroxy groups can also be included in the class of compounds.[1]

Borophosphates can be classified by whether or not they are hydrated, and the anion structure, which can be single, double, triple, isolated ring, isolated branched ring, simple chain, branched chain, loop chain, layers, or three-dimensional network.[1] The single anion compounds are the borate phosphates, which contain separate borate and phosphate groups. Some of the borophosphate structures resemble silicates.[1]

Related compounds include , which have aluminium instead of boron, gallophosphates,[2] with gallium in place of boron, and by substituting the phosphate: , , .

Formation[]

Borophosphates can be formed by heating compounds together at up to 900 °C. The products are dense, anhydrous, and do not contain organic substances.[2]

Solvothermal synthesis uses a non water solvent such as ethylene glycol to dissolve the product.[2]

The flux method crystallises from a molten flux of boric acid and sodium dihydrogen phosphate at around 171.[3]

The hydrothermal method heats the ingredients with water under pressure up to 200 °C. The ingredients are boric acid, phosphoric acid, metal salts, or organic bases. Products often contain hydrogen.[2]

The ionothermal synthesis method uses an ionic liquid such as 1-alkyl-3-methylimidazolium bromide as a solvent. This can be done at atmospheric pressure and temperatures under 100 °C.[2]

Characteristics[]

Borophosphate compounds have been investigated for magnetic, electrical, optical and catalytic properties. Some borophosphates are porous and so have surface for interaction on their interiors, not just their surface. They can reversibly absorb water, or have channels that can allow ions to conduct. The reflection of a labelled tetrahedron cannot be superimposed (even with rotation or movements), so the compounds containing phosphate and borate tetrahedrons can be non-centrosymmetric, or chiral.[2]

List[]

name formula mw crystal system space group unit cell Å volume density comment references
Li[B3PO6(OH)3] looped chain B3O3 rings OH on B and P [1]
Li2B3PO8 P1 [2]
Li3BP2O8 P1 [2]
NH4BeBP2O8·1/3H2O cubic P213 zeolite-ANA structure [4]
(NH4)2[B3PO7(OH)2] looped chain B3O3 rings OH on B [1]
(NH4)4[H2B2P4O16] P41212 [2]
Na2[BP2O7(OH)] orthorhombic Pna21 a=6.8236, b=20.7911, c = 13.1446 Z = 12 layers [5]
Na3B6PO13 orthorhombic Pnma a=9.3727 b=16.2307 c=6.7232 Z=4 8 member rings [3]
Na3BP2O8 monoclinic C2/c a=12.567 b=10.290 c=10.210 β=92.492 Z=2 infinite chains [3]
NaBeBP2O8·1/3H2O cubic P213 zeolite-ANA structure [4]
Na13(H2O)2[B6P11O42(OH)2]Cl2·H2O F23 [2]
MgBPO4(OH)2 P3121 [2]
dimagnesium (monohydrogenmonophosphatedihydrogenmonoborate-monophosphate Mg2[BP2O7(OH)3] triclinic P1 a=6.452 b=6.455 c=8.360 α=82.50 β=82.56 γ=80.98 Z=1 338.8 triple [6]
(H3O)Mg(H2O)2[BP2O8]·H2O P6122 [2]
Mg3(H2O)6(B(OH)3PO4)2 double [1]
LiMg(H2O)2[BP2O8]·H2O P6522 [2]
NaMg(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.428 c=15.820 loop branched chain [7]
Na2[MgB3P2O11(OH)]·0.67H2O hexagonal P63 a=11.771 c=12.100 Z=6 2.537 colourless [8]
K3B4PO10 351.51 triclinic P1 a=6.546 b=6.567 c=12.930 α=86.04 β=81.40 γ=60.42 Z=2 477.9 2.443 colourless 2D sheet [9]
K7B2P5O19 [2]
K3[B5PO10(OH)3] loop branch [1]
LiK2BP2O8 P21/n [2]
Li3K2BP4O14 Cmca [2]
KBeBP2O8·1/3H2O 254.19 cubic P213 a=12.427 Z=12 1,919 zeolite-ANA structure [4]
KMg(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.463 c=15.815 loop branched chain [7]
Ca[BPO5] loop branch B2PO3 rings [1]
Sc(H2O)2[BP2O8]·H2O 299.76 hexagonal P6522 a=9.5752 c=15.8145 Z=6 1,255.7 2.378 [10]
Sc(H2O)2[BP2O8] hexagonal P6522 a=9.535 c=15.768 Z=6 [10]
NaSc[BP2O6(OH)3]·HPO4 P21/c [2]
Ti[BP2O7(OH)3] I41/amd [2]
V2[B(PO4)3] [11]
(VO)2BP2O10 [12]
Li3V2[BP3O12(OH)][HPO4] P21/c [2]
Na2[VB3P2O12(OH)]·2.92H2O I-43m [11]
NH4VIII[BP2O8(OH)] monoclinic P21/c a=9.425, b=8.269, c=9.697, β=102.26° Z=4 738.5 [13]
(imidazolium)3.8(H3O)1.2[(VIVO)4(BO)2(PO4)5]·0.3H2O monoclinic C2/c a = 9.4737, b = 22.144, c = 17.219, β = 105.936°, Z = 4 layered [14]
(H3NCH2CH2NH3)2[Na(VO)10{HO3POB(O)2OPO3H}5]·22.5H2O [15]
[H3NC2H4NH2C2H4NH2C2H4NH3]4H[NH4(VO)12{O3POB(O)2OPO3}6]·14H2O 3000.09 orthorhombic Pbca a = 21.45, b = 16.315, c = 29.65 Z=4 10378 1.920 [16]
[H3NC2H4NH2C2H4NH2C2H4NH3]4H[K(VO)12{O3POB(O)2OPO3}6]·16H2O 3129.25 orthorhombic Pbca a = 21.537, b = 16.267, c = 29.717, Z = 4 10411 1.996 [16]
KV[BP2O8(OH)] triclinic P1 [2]
Cr2[B(PO4)3] P63/m [11]
H2Mn5(H2O)6[BP2O8]4•4H2O hexagonal P6122 a=9.655 c=15.791 (Z=1.5) pale pink [17]
Na8[Cr4B12P8O44(OH)4][P2O7]·nH2O I23 [2]
Na11K5[NaCr8B4P12O60H8]·H2O Pmnn [2]
Mn[BPO4(OH)2] 194.74 P3221 a=7.5750 c=12.927 Z=6 642.37 3.020 [18]
LiMn(H2O)2[BP2O8(OH)]·H2O P6522 [2]
[NH4]4[Mn9B2(OH)2(HPO4)4(PO4)6] monoclinic C2/c a = 32.603, b = 10.617, c = 10.718, and β = 108.26° Z=4 3523 2.971 light pink [19]
(NH4)6[Mn3B6P9O36(OH)3]·4H2O C2 [2]
(NH4)7Mn4(H2O)[B2P4O15(OH)2]2[H2PO4][HPO4] Pnma [2]
(C3H12N2)[MnB2P3O12(OH)] [2]
(C4H12N2)[MnB2P3O12(OH)] Ima2 [2]
NaMn(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.589 c=15.939 loop branched chain [7]
Na5(H3O){Mn3[B3O3(OH)]3(PO4)6}·2H2O hexagonal P63/m a = 11.9683 Å, c = 12.1303 Å, and Z = 2 [20]
Na5(NH4)Mn3[B9P2O33(OH)3]·1.5H2O P63 [2]
Na2[MnB3P2O11(OH)]·0.67H2O hexagonal P63 a=11.940 c=12.098 Z=6 2.670 colourless [8]
KMnBP2O7(OH)2 monoclinic P21/c a = 6.659, b = 12.049, c = 9.790 Å, β = 109.12° Z=4 742.2 orange‐red luminescence [21]
KMn(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.639 c=15.931 loop branched chain [7]
K5Mn2B2P5O19(OH)2 P21/n [2]
FeIII2[B(PO4)3] P63/m [11]
Fe[B2P2O7(OH)5] monoclinic C2/c a=17.745 b=6.720 c=7.059 β =109.01 Z=4 796 2.808 unbranched chain [1]
Fe(H2O)2BP2O8·H2O 310.65 hexagonal a=9.4583 c=15.707 Z=6 1216.9 2.543 [22]
Fe[BPO4(OH)2] 196.65 P3221 a=7.4844 c=12.844 Z=6 623.06 3.129 [18]
FeII(H2O)2[B2P2O8(OH)2]·H2O P21/c [2]
Fe1.834IIFe0.166IIIB0.5[PO3(OH)]0.8(HPO3)2.033 cubic I43d a = 21.261 Å, Z = 48 [23]
NH4FeIII[BP2O8(OH)] monoclinic P21/c a=9.393, b=8.285, c=9.689, β=102.07° Z=4 737.4 [13]
(NH4)0.75Fe(H2O)2[BP2O8]·0.25H2O P6522 [2]
(C3H12N2)[FeB2P3O12(OH)] Ima2 [2]
(C4H12N2)[FeB2P3O12(OH)] Ima2 [2]
(C4N3H16)(C4N3H15)0.5[FeII*III2B4P7O26(OH)4] P1 [2]
NaFe[BP2O7(OH)3] triple
sodium iron(II) diaqua catena-[monoboro-diphosphate] monohydrate NaFe(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.499 c=15.931 loop branched chain [7]
Na2[FeB3P2O11(OH)]·0.67H2O hexagonal P63 a=11.812 c=12.067 Z=6 2.742 light yellow [8]
potassium iron(II) diaqua catena-[monoboro-diphosphate] hemihydrate KFe(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.510 c=15.952 loop branched chain [7]
K2Fe2[B2P4O16(OH)2] monoclinic P21/c a = 9.372 , b = 8.146 , c = 9.587, β = 101.18° and Z = 2 718.0 B2P2O4 ring with phosphate sides [24]
KFeBP2O8(OH) P21/c [2]
CaFe[BP2O7(OH)3] C2/c [2]
Ca0.5Fe(H2O)2[BP2O8]·H2O P6522 [2]
Co5[BP3O14] double + phosphate [1]
Co3[BPO7] monoclinic Cm a=9.774, b=12.688, c=4.9057, β=119.749° Z=4 528.2 [25]
Co[BPO4(OH)2] 198.73 P3121 a=7.4554 c=12.7397 Z=6 613.24 3.229 [18]
(NH4)7Co4(H2O)[B2P4O15(OH)2]2[H2PO4][HPO4] Pnma [2]
(NH4)8[Co2B4P8O30(OH)4] P1 [2]
CoII(H2O)2[B2P2O8(OH)2]·H2O P21/c [2]
[Co(en)3][B2P3O11(OH)2] [26]
CoB2P3O12(OH)·C2H10N2 [27]
Co(C4H12N2)[B2P3O12(OH)] orthorhombic Ima2 a = 12.4635, b = 9.4021, c = 11.4513 Z=4 1341.90 [28]
H2Co5(H2O)6[BP2O8]4•4H2O 1919.74 hexagonal P6122 a=9.639 c=15.931 (Z=1.5) purple
LiCo(H2O)2[BP2O8]·H2O P6522
NaCo(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.455 c=15.847 loop branched chain [7]
NaCoH2BP2O9 300.69 monoclinic P21/c a=6.547 b=11.404 c=9.650 β=107.37 687.6 2.905 pink; discovered in Tunisia [29]
Na2[CoB3P2O11(OH)]·0.67H2O hexagonal P63 a=11.759 c=12.099 Z=6 2.781 purple [8]
Na5(H3O){Co3[B3O3(OH)]3(PO4)6}·2H2O hexagonal P63/m a = 11.7691, c = 12.112 Å, and Z = 2 [20]
Na6Co3B2P5O21Cl·H2O Pnma
KCo(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.483 c=15.827 loop branched chain [7]
CaCo(H2O)[BP2O8(OH)]·H2O P1 [2]
(K0.17Ca0.42)Co(H2O)2[BP2O8]·H2O P6522 [2]
(Co0.6Mn0.4)2(H2O)[BP3O9(OH)4] P212121 [2]
cobalt borophosphate ethylenediamine CoB2P3O12(OH) · C2H10N2 889.18 orthorhombic Pbca a=9.3501 b=12.2426 c=20.880 2,390.1 2.471 purple; layered [30][31]
(NH4)7Co4(H2O)[B2P4O15(OH)2]2[H2PO4][HPO4] 1412.03 Orthorhombic Pnma a=16.9206 b=10.5592 c=22.000 Z=4 3,930.6 2.386 pink [32]
(NH4)2(C4H12N2)[Co2B4P6O24(OH)2]·H2O I41/a [2]
NiBPO4(OH)2 P3121 [2]
Ni(H2O)2[B2P2O8(OH)2]·H2O P21/c [2]
LiNi(H2O)2[BP2O8]·H2O P6522 [2]
NaNi(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.371 c=15.831 loop branched chain [7]
Na2[NiB3P2O11(OH)]·0.67H2O hexagonal P63 a=11.728 c=12.074 Z=6 2.799 yellow [8]
Na5(H3O){Ni3[B3O3(OH)]3(PO4)6}·2H2O hexagonal P63/m a = 11.7171, c = 12.0759, and Z = 2 [20]
KNi(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.392 c=15.842 loop branched chain [7]
Cu3[B2P3O12(OH)3] monoclinic Cc a=6.1895, b=13.6209, c=11.9373, β=97.62°, Z=4 997.5 [33]
Cu(H2O)2[B2P2O8(OH)2] [34]
Cu2(H2O)[BP2O8(OH)] Pbca [2]
LiCu2[BP2O8(OH)2] C2/c [2]
LiCu2[BP2O8(OH)2] P212121 [2]
Na2[CuB3P2O11(OH)]·0.67H2O hexagonal P63 a=11.554 c=12.314 Z=6 2.862 sky-blue [8]
Na4Cu3[B2P4O15(OH)2]•2HPO4 ring with side phosphate and extra phosphate
Na5KCu3[B9P6O33(OH)3]·H2O P63/m [2]
Zn(C4H12N2)[B2P3O12(OH)] orthorhombic Ima2 a = 12.4110, b = 9.4550, c = 11.4592 Z=4 1344.69 [28]
lithium zinc diaqua catena-[monoboro-diphosphate]- monohydrate LiZn(H2O)2[BP2O8] · H2O hexagonal P61 a=9.469 c=15.667 Z=6 1216.6 spiral ribbons [35]
Na[ZnBP2O8]⋅H2O hexagonal P6122 a=9.5404, c=14.7780 Z=6 1164.88 [36]
NaZn(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.456 c=15.828 loop branched chain [7]
Na2[ZnB3P2O11(OH)]·0.67H2O hexagonal P63 a=11.963 c=12.363 Z=6 2.683 colourless [8]
NH4[ZnBP2O8] triclinic P1 a=7.437 b=7.612 c=7.850 α=119.05 β=101.59 γ=103.43 Z=2 351.18 2.687 [37]
Na[ZnBP2O8] triclinic P1 [2]
K[ZnBP2O8] monoclinic C2/c a=12.617, b=12.773, c=8.415, β=91.25° Z=8 1355.8 2.991 [37]
(H4triethylenetetramine)1.5[Zn6B6P12O48] · 1.5H2O hexagonal P6522 a = 9.6685, c = 14.8879; Z = 1 [38]
Rb[P2B2O8(OH)] network [1]
Li3Rb2BP4O14 Cmca [2]
K2RbB4PO10 397.88 triclinic P1 a=6.5577 b=6.5931 c=13.098 α=84.626 β=80.514 γ=60.457 Z=2 485.9 2.719 colourless [9]
Rb2Co3(H2O)2[B4P6O24(OH)2] orthorhombic Pbca a = 9.501, b = 12.272, c = 20.074, Z = 4 [39]
Rb[ZnBP2O8] triclinic P1 a=7.439 b=7.639 c=7.861 α=118.82 β=101.73 γ=103.51 Z=2 353.4 3.304 [37]
Sr[BPO5] P3221 loop branch B2PO3 rings [1]
KSrBP2O8 I42d a = 7.109, c = 13.882 [40]
SrFe[BP2O8(OH)2] C2/c [2]
SrCo2BPO7 359.26 monoclinic P21/c a=6.485 b=9.270 c=10.066 β=111.14 Z=4 548.7 red [41]
AgMg(H2O)2[BP2O8]·H2O P6522 [2]
(Ag0.79Co0.11)Co(H2O)2[BP2O8]·0.67H2O P6522 [2]
(Ag0.57Ni0.22)Ni(H2O)2[BP2O8]·0.67H2O P6522 [2]
Na3Cd3BP4O16 orthorhombic Pmc21 a = 13.6854, b = 5.335, c = 18.2169, and Z = 4 SHG 1.1×KDP [2][42]
NH4Cd(H2O)2(BP2O8)·0.72H2O 378.13 hexagonal P65 a=9.698, c=16.026, Z=6 1305.3 2.886 colourless [43]
In2[B(PO4)3] P63/m [11]
Cs[P2B2O8(OH)] 3D network [1]
Li2Cs2B2P4O15
K2CsB4PO10 351.51 triclinic P1 a=6.6235 b=6.6243 c=13.273 α=79.734 β=86.558 γ=60.095 Z=2 496.46 2.979 colourless [9]
Cs2Cr3(BP4O14)(P4O13) 1112.39 monoclinic P21/c a=14.7918 b=15.819 c=9.7037 β=92.450 Z=4 876.9 3.257 green; [B(P2O7)2]5− [44]
CsFe(BP3O11) 468.48 orthorhombic Pnma a=8.5375 b=12.7829 c=8.3346 Z=4 909.59 3.434 [N(PO4)(P2O7)]4- [44]
Cs2Co3(H2O)2[B4P6O24(OH)2] orthorhombic Pbca 9.5526, b = 12.3190, c = 20.1123 2366.8 pink [2][45]
Cs[ZnBP2O8] triclinic P1 a=7.506 b=7.914 c=8.038 α=1198.05 β=102.96 γ=104.50 Z=2 373.9 3.545 [37]
Ba[BPO5] P3221 [2]
Ba[BP3O12] orthorhombic Ibca a=7.066 b=14.268 c=22.159 2233.9 4.209 [1][46]
KBaBP2O8 I42d a = 7.202, c = 14.300 [40]
BaFe[BP2O8(OH)] P1 [2]
BaCo[BP2O8(OH)] P1 [2]
Pb[BPO5] loop branch B2PO3 rings [1]
Pb3[(PO4)2BPO4] orthorhombic Pbca a=6.946 b=14.199 c=21.116 Z=8 2082.5 5.851 open branch, 2 PO4 extra on each B [46]
Na3PbII[B(O3POH)4] I41/a [2]
KPbBP2O8 I42d [2]
PbII4{Co2[B(OH)2P2O8](PO4)2]}Cl R3c [2]
RbPbBP2O8 I42d [2]
BiCo2BP2O10 P21/m [2]
BiNi2BP2O10 P21/m [2]
K2(UO2)12[B(H2PO4)4](PO4)8(OH)(H2O)6 tetragonal I42m a = 21.8747, c = 7.0652 3380.7 [47]
K5(UO2)2[B2P3O12(OH)]2(OH)(H2O)2 monoclinic P21 a = 6.7623, b = 19.5584, c = 11.0110, β = 95.579° 1449.42 [47]
Ag2(NH4)3{(UO2)2[B3O(PO4)4(HPO4)2]}·H2O P1 [2]
Ag2−x(NH4)3{(UO2)2[B2P5−yAsyO20−x(OH)x]} Pcmn [2]
Cs3(UO2)3[B(PO4)4]∙(H2O)0.5 3215.02 P41212 a=12.2376 c=33.9468 Z=4 5083.8 yellow; microporous [48]

References[]

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