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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 isolated anion compounds are the borate phosphates, which contain separate borate and phosphate groups. Some of the borophosphate structures resemble silicates.[1]

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

Formation

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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

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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

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name formula crystal system space group unit cell Å volume density comment refs
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)2B2P3O11(OH) monoclinic P21/c a=15.774 b=7.5213 c=8.9661 β=106.93° Z=4 1020.0 2.238 [5]
(NH4)3H2[BOB(PO4)3] infinite chains [6]
(NH4)4[H2B2P4O16] tetragonal P41212 [2]
(NH4)2BP2O7(OH) tetragonal P41212 a=7.2162 c=14.8258 Z=4 772.03 2.046 [5]
Na2[BP2O7(OH)] orthorhombic Pna21 a=6.8236, b=20.7911, c=13.1446, Z=12 layers [7]
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]
Na5[BOB(PO4)3)] infinite chains [6]
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 (monohydrogen­monophosphate­dihydrogenmonoborate­monophosphate) 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 [8]
(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 [9]
Na2[MgB3P2O11(OH)]·⁠2/3⁠H2O hexagonal P63 a=11.771, c=12.100, Z=6 2.537 colourless [10]
Na3[Al2B6P4O22(OH)3](H2O)6 orthorhombic Cmca a=6.9493 b=14.5529 c=24.027 [11]
Na3[Al2BP2O11](H2O)0.5 cubic I23 a=19.7822 [11]
K2B2P2O9 orthorhombic P212121 a=7.8227 b=8.1393 c=12.925 Z=4 822.9 2.468 [5]
K2BP2O7(OH) orthorhombic P212121 a=7.068 b=7.2396 c=14.116 Z=4 722.3 2.574 [5]
K3B4PO10 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 [12]
K7B2P5O19 [2]
K3[B5PO10(OH)3] loop branch [1]
LiK2BP2O8 P21/n [2]
Li3K2BP4O14 Cmca [2]
KBeBP2O8·⁠1/3⁠H2O cubic P213 a=12.427, Z=12 1,919 zeolite-ANA structure [4]
K2Na3B2P3O13 orthorhombic Cmc21 a = 13.924 b = 6.7673 c = 12.130 Z = 4 B2P3O13 chain [13]
KMg(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.463, c=15.815 loop branched chain [9]
Ca[BPO5] loop branch B2PO3 rings [1]
Sc(H2O)2[BP2O8]·H2O hexagonal P6522 a=9.5752, c=15.8145, Z=6 1,255.7 2.378 [14]
Sc(H2O)2[BP2O8] hexagonal P6522 a=9.535, c=15.768, Z=6 [14]
NaSc[BP2O6(OH)3]·HPO4 P21/c [2]
Ti[BP2O7(OH)3] I41/amd [2]
V2[B(PO4)3] [15]
(VO)2BP2O10 [16]
Li3V2[BP3O12(OH)][HPO4] P21/c [2]
Na2[VB3P2O12(OH)]·2.92H2O I-43m [15]
NH4VIII[BP2O8(OH)] monoclinic P21/c a=9.425, b=8.269, c=9.697, β=102.26°, Z=4 738.5 [17]
[ImH2]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 [18]
[enH2]2[Na(VO)10B(O)2(OPO3H)2}5]·22.5H2O [19]
[trienH4]4H[NH4(VO)12{B(O)2(OPO3)2}6]·14H2O orthorhombic Pbca a=21.45, b=16.315, c=29.65, Z=4 10378 1.920 [20]
[trienH4]4H[K(VO)12{O3POB(O)2OPO3}6]·16H2O orthorhombic Pbca a=21.537, b=16.267, c=29.717, Z=4 10411 1.996 [20]
KV[BP2O8(OH)] triclinic P1 [2]
Cr2[B(PO4)3] P63/m [15]
Na{Cr[BP2O7(OH)3]} monoclinic C2/c a=10.4220, b=8.2468, c=9.2053, β=116.568°, Z=4 707.63 [21]
Na8[Cr4B12P8O44(OH)4][P2O7]·nH2O I23 [2]
Na11K5[NaCr8B4P12O60H8]·H2O Pmnn [2]
H2Mn5(H2O)6[BP2O8]4•4H2O hexagonal P6122 a=9.655, c=15.791, Z=1.5 pale pink [22]
Mn[BPO4(OH)2] P3221 a=7.5750, c=12.927, Z=6 642.37 3.020 [23]
LiMn(H2O)2[BP2O8(OH)]·H2O P6522 [2]
(NH4)Mn(H2O)2(BP2O8)·H2O P6522 a = 9.6559, c = 15.7939 1275.3 [24]
[NH4]4[Mn9B2(OH)2(HPO4)4(PO4)6] monoclinic C2/c a=32.603, b=10.617, c=10.718, β=108.26°, Z=4 3523 2.971 light pink [25]
(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 [9]
Na5(H3O){Mn3[B3O3(OH)]3(PO4)6}·2H2O hexagonal P63/m a=11.9683, c=12.1303, Z=2 [26]
Na5(NH4)Mn3[B9P2O33(OH)3]·⁠3/2⁠H2O P63 [2]
Na2[MnB3P2O11(OH)]·⁠2/3⁠H2O hexagonal P63 a=11.940, c=12.098, Z=6 2.670 colourless [10]
KMnBP2O7(OH)2 monoclinic P21/c a=6.659, b=12.049, c=9.790, β=109.12°, Z=4 742.2 orange-red luminescence [27]
KMn(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.639, c=15.931 loop branched chain [9]
K5Mn2B2P5O19(OH)2 P21/n [2]
FeIII2[B(PO4)3] P63/m [15]
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 hexagonal a=9.4583, c=15.707, Z=6 1216.9 2.543 [28]
Fe[BPO4(OH)2] P3221 a=7.4844, c=12.844, Z=6 623.06 3.129 [23]
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, Z=48 [29]
NH4FeIII[BP2O8(OH)] monoclinic P21/c a=9.393, b=8.285, c=9.689, β=102.07°, Z=4 737.4 [17]
(NH4)0.75Fe(H2O)2[BP2O8]·⁠1/4⁠H2O P6522 [2]
(C3H12N2)[FeB2P3O12(OH)] Ima2 [2]
(C4H12N2)[FeB2P3O12(OH)] Ima2 [2]
(dienH3)(dienH2)0.5[FeII*III2B4P7O26(OH)4] P1 [2]
NaFe[BP2O7(OH)3] triple
sodium diaquoiron(II) catena-[monoboro-diphosphate] monohydrate NaFe(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.499, c=15.931 loop branched chain [9]
Na2[FeB3P2O11(OH)]·⁠2/3⁠H2O hexagonal P63 a=11.812, c=12.067, Z=6 2.742 light yellow [10]
potassium diaquoiron(II) catena-[monoboro-diphosphate] hemihydrate KFe(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.510, c=15.952 loop branched chain [9]
K2Fe2[B2P4O16(OH)2] monoclinic P21/c a=9.372, b=8.146, c=9.587, β=101.18°, Z=2 718.0 B2P2O4 ring with phosphate sides [30]
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 [31]
Co[BPO4(OH)2] P3121 a=7.4554, c=12.7397, Z=6 613.24 3.229 [23]
(NH4)7Co4(H2O)[B2P4O15(OH)2]2[H2PO4][HPO4] Pnma [2]
(NH4)8[Co2B4P8O30(OH)4] P1 [2]
(NH4)Co(H2O)2(BP2O8)·H2O P6122 a = 9.501 c = 15.582 1218.2 [24]
CoII(H2O)2[B2P2O8(OH)2]·H2O P21/c [2]
[Co(en)3][B2P3O11(OH)2] [32]
CoB2P3O12(OH)·H2en [33]
Co(C4H12N2)[B2P3O12(OH)] orthorhombic Ima2 a=12.4635, b=9.4021, c=11.4513, Z=4 1341.90 [34]
H2Co5(H2O)6[BP2O8]4•4H2O 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 [9]
NaCoH2BP2O9 monoclinic P21/c a=6.547, b=11.404, c=9.650, β=107.37 687.6 2.905 pink; discovered in Tunisia [35]
Na2[CoB3P2O11(OH)]·⁠2/3⁠H2O hexagonal P63 a=11.759, c=12.099, Z=6 2.781 purple [10]
Na5(H3O){Co3[B3O3(OH)]3(PO4)6}·2H2O hexagonal P63/m a=11.7691, c=12.112, Z=2 [26]
Na6Co3B2P5O21Cl·H2O Pnma
KCo(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.483, c=15.827 loop branched chain [9]
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)·en orthorhombic Pbca a=9.3501, b=12.2426, c=20.880 2,390.1 2.471 purple; layered [36][37]
(NH4)7Co4(H2O)[B2P4O15(OH)2]2[H2PO4][HPO4] Orthorhombic Pnma a=16.9206, b=10.5592, c=22.000, Z=4 3,930.6 2.386 pink [38]
(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 [9]
Na2[NiB3P2O11(OH)]·⁠2/3⁠H2O hexagonal P63 a=11.728, c=12.074, Z=6 2.799 yellow [10]
Na5(H3O){Ni3[B3O3(OH)]3(PO4)6}·2H2O hexagonal P63/m a=11.7171, c=12.0759, Z=2 [26]
KNi(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.392, c=15.842 loop branched chain [9]
Cu3[B2P3O12(OH)3] monoclinic Cc a=6.1895, b=13.6209, c=11.9373, β=97.62°, Z=4 997.5 [39]
Cu(H2O)2[B2P2O8(OH)2] [40]
Cu2(H2O)[BP2O8(OH)] Pbca [2]
LiCu2[BP2O8(OH)2] C2/c [2]
LiCu2[BP2O8(OH)2] P212121 [2]
Na2[CuB3P2O11(OH)]·⁠2/3⁠H2O hexagonal P63 a=11.554, c=12.314, Z=6 2.862 sky-blue [10]
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 [34]
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 [41]
Na[ZnBP2O8]⋅H2O hexagonal P6122 a=9.5404, c=14.7780, Z=6 1164.88 [42]
NaZn(H2O)2[BP2O8]•H2O hexagonal P6122 a=9.456, c=15.828 loop branched chain [9]
Na2[ZnB3P2O11(OH)]·⁠2/3⁠H2O hexagonal P63 a=11.963, c=12.363, Z=6 2.683 colourless [10]
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 [43]
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 [43]
[trienH4]1.5[Zn6B6P12O48]·⁠3/2⁠H2O hexagonal P6522 a=9.6685, c=14.8879; Z=1 [44]
RBPO Rb3B11P2O23 Triclinic P1 a=7.785, b=7.839, c=7.963, α=89,774, β=89.129, γ=88.211, Z=2 485.6 2.753 transparent above 168 nm; SHG 2.5× KDP; birefringence =0.071@1064 nm [45]
Rb[P2B2O8(OH)] network [1]
Li3Rb2BP4O14 Cmca [2]
Rb3B11PO19F3 trigonal R3 a=11.3715 c=12.0240 Z=3 1346.53 2.839 colourless; decompose > 470 °C; SHG 1.3 × KDP [46]
K2RbB4PO10 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 [12]
K2RbB8PO16 birefringence 0.057@1064 nm [47]
K0.9Rb2.1B8PO16 monoclinic Cc a=11.3446 b=6.5485 c=19.354 β=101.315° 1409.9 2.761 birefringence 0.075@532 nm; band gap 6.16 eV;SHG 0.7 × KDP [48]
Rb2Co3(H2O)2[B4P6O24(OH)2] orthorhombic Pbca a = 9.501, b = 12.272, c = 20.074, Z = 4 [49]
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 [43]
Sr[BPO5] P3221 loop branch B2PO3 rings [1]
KSrBP2O8 I42d a=7.109, c=13.882 [50]
SrFe[BP2O8(OH)2] C2/c [2]
SrCo2BPO7 monoclinic P21/c a=6.485, b=9.270, c=10.066, β=111.14, Z=4 548.7 red [51]
AgMg(H2O)2[BP2O8]·H2O P6522 [2]
⁠2/3⁠H2O P6522 [2]
(Ag0.57Ni0.22)Ni(H2O)2[BP2O8]·⁠2/3⁠H2O P6522 [2]
Na3Cd3BP4O16 orthorhombic Pmc21 a=13.6854, b=5.335, c=18.2169, Z=4 SHG 1.1×KDP [2][52]
NH4Cd(H2O)2(BP2O8)·0.72H2O hexagonal P65 a=9.698, c=16.026, Z=6 1305.3 2.886 colourless [53]
In2[B(PO4)3] P63/m [15]
Cs[P2B2O8(OH)] 3D network [1]
Li2Cs2B2P4O15
K2CsB4PO10 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 [12]
Cs2Cr3(BP4O14)(P4O13) 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− [54]
CsFe(BP3O11) orthorhombic Pnma a=8.5375, b=12.7829, c=8.3346, Z=4 909.59 3.434 [N(PO4)(P2O7)]4- [54]
Cs2Co3(H2O)2[B4P6O24(OH)2] orthorhombic Pbca a=9.5526, b=12.3190, c=20.1123 2366.8 pink [2][55]
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 [43]
Ba[BPO5] P3221 [2]
Ba[BP3O12] orthorhombic Ibca a=7.066, b=14.268, c=22.159 2233.9 4.209 [1][56]
BaB2P2O8F2 monoclinic P21/n a=4.4719 b=20.499 c=7.8896 β=92.955° Z=4 722.3 3.558 birefringence 0.007 @ 532 nm
KBaBP2O8 I42d a=7.202, c=14.300 [50]
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 [56]
Na3PbII[B(O3POH)4] I41/a [2]
KPbBP2O8 I42d [2]
PbII4Cl{Co2[B(OH)2P2O8](PO4)2]} 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 [57]
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 [57]
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 P41212 a=12.2376, c=33.9468, Z=4 5083.8 yellow; microporous [58]

References

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  1. ^ a b c d e f g h i j k l m n o Kniep, Rüdiger; Engelhardt, Holger; Hauf, Cornelia (October 1998). "A First Approach to Borophosphate Structural Chemistry". Chemistry of Materials. 10 (10): 2930–2934. doi:10.1021/cm980263g. ISSN 0897-4756.
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