Crystal Chemistry of High-Temperature Borates
Abstract
:1. Introduction
2. Hierarchy of Basic Structural Clusters
2.1. Fundamental Structural Units
2.2. Combined Structural Units
2.3. Complete Radicals of Polyanions
3. Polymerization of Boron-Oxygen Radicals
4. Polymorphism of BnOm Polyanions
5. Isostructural Series
6. Structural Formulas of Polyborates
7. Classification
- (1)
- In crystal structures each boron atom is bonded with three or with four oxygen atoms in BO3–triangles and BO4–tetrahedra;
- (2)
- In one structure not only triangular or only tetrahedral coordination is possible, but both of them jointly as well;
- (3)
- Isolated BO3–triangles and BO4–tetrahedra are not found jointly, insular polyanions;
- (4)
- A decrease in the N = NM/NB ratio (N-factor), as well as an increase in cation size (although to a smaller extent), leads to an increase in the degree of polymerization of the anion and raises the n = n∆/nt number (at N ≤ 1), whereas an increase in cation charge causes the inverse tendency;
- (5)
- Polymerization, or the formation of chains, layers and frameworks, is actualizing by the sharing corners of triangles and tetrahedra (the sharing edges has up to now not been proved conclusively);
- (6)
- In 3D and 2D polyanions (less frequently in chainlike and insular ones), BO3–triangles and BO4–tetrahedra tend to combine into comparatively compact CSU, i.e., diborate (2∆ + 2t), triborate (2∆ + 1t), pentaborate (4∆ + 1t), boroxol (3∆), ditriborate (1∆ + 2t), dipentaborate (3∆ + 2t) and other single and double ringed boron-oxygen negative charged polymerized radicals;
- (7)
- Complex polyanions of anhydrous borates of uni- and divalent metals tend to twinning;
- (8)
- In most of complex polyanions, each oxygen atom is bonded with two boron atoms, for such compounds as MxO⋅mB2O3 with m > 1, there is n = m − 1 relationship (where n = n∆/nt);
- (9)
- As an exclusion for 2D and 3D highly condensed polyanions, the coordination numbers of oxygen atoms (relative to boron) can be equal to one or three (in cubic boracite even to four).
- (a)
- Borates proper (also, there is a sense to divide this very numerous group, having diverse cations, into two subgroups: aI—monocationic or “simple” borates and all-binary and more complex compounds);
- (b)
- Borosilicates;
- (c)
- Boroaluminates;
- (d)
- Boroberyllates;
- (e)
- Borocarbonates;
- (f)
- Boromolybdates and borotungstates.
8. Structural Aspects of Acid-Base Properties
9. Summary
Author Contributions
Funding
Conflicts of Interest
References
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Type of Metaborate Anion | Composition of [BO2]n Polyanion | Compound |
---|---|---|
Isolated rings | [B3∆O6] = [B3O6] | α-Na2O·B2O3 K2O·B2O3 Rb2O·B2O3 Cs2O·B2O3 β-BaO·B2O3 |
Chain (one-dimensional, 1D) | [B2∆O4]1D = [B2O4]1D | α-Li2O·B2O3 CaO·B2O3 (I) SrO·B2O3 (I) |
[(B∆O2)2B2tO4]1D = [B4O8]1D | Calciborite CaO·B2O3 (II) | |
[(B∆O2)4BtO2]1D = [B6O12]1D | Ln2O3·3B2O3 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb) | |
[(B∆O2)2Al2tO4](1D) = [B2Al2O8]1D | 2CaO·Al2O3 B2O3 | |
[(BO2)2Al2tO4]1D = [B2Al2O8]1D | 2SrO·B2O3·Al2O3 | |
[B3tO6](1D) = [B3O6]1D (exc. Si) | Stillwellite Ce2O3·B2O3·2SiO2 | |
[B2∆O4](D) = [B2O4]1D (exc. Mo, W) | La2O3·B2O3·2MoO3 La2O3·B2O3·2WO3 | |
Ribbon (one-dimensional, 1D) | [(B∆O2)4(AltO2)2]1D = [B4Al2O12]1D [(B∆O2)4(GatO2)2]1D = [B4Ga2O12]1D | 3Li2O·Al2O3·2B2O3 3Li2O·Ga2O3·2B2O3 |
Layer (two-dimensional, 2D) | [(B∆O2)4B6tO12]2D = [B10O20]2D | Ln2O3·2CoO·5B2O3 (Ln = La-Nd, Sm-Ho) |
Framework (three-dimensional, 3D) | [BtO2]3D = [BO2]3D | γ-Li2O·B2O3 |
[B3tO6]3D = [B3O6]3D | CaO·B2O3 (II) SrO·B2O3 (II) | |
[B3tO6]3D = [B3O6]3D | CuO·B2O3 | |
[B6tO12]3D = [B6O12]3D | 4ZnO·3B2O3 | |
[(B6∆O2.5)(B∆O1.5)B4O8]3D = [B6O12]3D | CaO·B2O3 (III) SrO·B2O3 (III) | |
[(B2tO4)(Si2O4)](3D) = [Si2B2O8]3D | Danburite—CaO·B2O3·2SiO2 |
Type of polyanion | Composition of B4O7 Based Polyanion | Compound |
---|---|---|
Layers (two-dimensional, 2D) | [(B2∆BtO5.5)(B3∆B2tO8.5)]2D = [B8O14]2D | α-Na2O·2B2O3 |
Frameworks (three- dimensional, 3D) | [B2∆B2tO7]3D = [B4O7]3D | LiO·2B2O3 |
[B2∆B2tO7]2(3D) = [B4O7]2(3D) | MgO·2B2O3, MnO·2B2O3, ZnO·2B2O3, CdO·2B2O3 | |
[(B2∆B2tO7)(B∆B2tO5.5)(B∆O1.5)]3D = [B8O14]3D | K2O·2B2O3 | |
[(B2∆B2tO7)(B2∆BtO5)(BtO2)]3D = [B8O14]3D | CaO·2B2O3 | |
[B4tO7]3D = [B4O7]3D | SrO·2B2O3, PbO·2B2O3 | |
[(B3∆B2tO8.5)(B∆B2tO5.5)]3D = [B8O14]3D | BaO·2B2O3 |
Radical | Type of Polyanion | Composition B3O5 and B8O13 Based Polyanions | Compound |
---|---|---|---|
B3O5 | Layers (two-dimensional, 2D) | [(B4∆BtO8)(B2∆BtO5)(BtO2)]2(2D) = [B9O15]2(2D) | β-Na2O·3B2O3 |
Frameworks (three-dimensional,3D) | [(B4∆BtO8)(B2∆B2tO7)]2(3D) = [B9O15]2(3D) | α-Na2O·3B2O3 | |
[B2∆BtO5]3D = [B3O5]3D | Cs2O·3B2O3 | ||
B8O13 | Frameworks (three-dimensional, 3D) | [(B4∆BtO8)(B2∆BtO5)]2(3D) = [B8O13]2(3D) | α-Na2O·4B2O3 |
[(B4∆BtO8)(B2∆BtO5)]2(3D) = [B8O13]2(3D) | 0.6Ag2O·0.4Na2O·4B2O3; BaO·4B2O3 |
Formula in Oxides (Bulk Composition) | Structural Formula | ||
---|---|---|---|
Complete | Abbreviated | ||
α-Li2O·B2O3 | α-Li2[B∆2O4]1D | α-Li2[B△2O4]1D | α-Li2[B2O4] |
γ-Li2O·B2O3 | γ-Li[BtO2]3D | γ-Li[BtO2]3D | γ-Li[BO2] |
γ-3Li2O·7B2O3·2LiCl | γ-Li4Cl[(B∆3Bt3O10.5)(B∆O1.5)]3D | γ-Li4Cl[B△4Bt3O12]3D | γ-Li4Cl[B7O12] |
Li2O·2B2O3 | Li2[(B∆2Bt2O7)]3D | Li2[B△2Bt2O7]3D | Li2[B4O7] |
MI2O·B2O3 (MI = Na-Cs) | MI3[(B∆3O6)] | MI3[B△3O6] | MI3[B3O6] |
α-Na2O·2B2O3 | α-Na4[(B∆2BtO5.5)(B∆3Bt2O8.5)]2D | α-Na4[B△5Bt3O14]2D | α-Na4[B8O14] |
α-Na2O·3B2O3 | α-Na6[(B2Bt2O7)(B∆4BtO8)]2(3D) | α-Na6[B△6Bt3O15]2(3D) | α-Na6[B9O15]2 |
β-Na2O·3B2O3 | β-Na6[(B∆2BtO5)(B∆4BtO8)(BtO2)]2(2D) | β-Na6[B△6Bt3O15]2(2D) | β-Na6[B9O15]2 |
α-Na2O·4B2O3 | α-Na4[(B∆2BtO5)(B∆4BtO8)]2(3D) | α-Na4[B△6Bt2O13]2(3D) | α-Na4[B8O13]2 |
K2O·2B2O3 | K4[(B∆Bt2O5.5)(B∆2Bt2O7)(B∆O1.5)]3D | K4[B△4Bt4O14]3D | K4[B8O14] |
5K2O·19B2O3 | K2.5[(B∆2BtO5)(B∆4BtO8)(B∆O1.5)(Bt0.5O)]3D | K5[B△14Bt5O31]3D | K5[B19O31] |
α-K2O·5B2O3 | α-K2[(B∆4BtO8)]2(3D) | α-K2[B△4BtO8]2(3D) | α-K2[B5O8]2 |
β-MI2O·5B2O3 (MI = K, Rb) | β-MI2[(B∆4BtO8)]2(3D) | β-MI2[B△4BtO8]2(3D) | β-MI2[B5O8]2 |
Cs2O·3B2O3 | Cs[(B∆2BtO5)]3D | Cs[B△2BtO5]3D | Cs[B3O5] |
Cs2O·9B2O3 | Cs2[(B∆3O4.5)2(B∆2BtO5)]2(3D) | Cs2[B△8BtO14]2(3D) | Cs2[B9O14]2 |
0.6Ag2O·0.4Na2O·4B2O3 | Ag2.4Na1.6[(B∆2BtO5)(B∆4BtO8)]2(3D) | Ag2.4Na1.6[B△6Bt2O13]2(3D) | Ag2.4Na1.6[B8O13]2 |
5MIIO·7B2O3·MIIAI2—rhomb. and trig. Boracites (MII = Mg, Mn, Zn, Cd, Co, Ni, Cu; AI = Cl, NO3)—rhomb. (MII = Mg, Mn, Zn, Fe, Co, Ni, Cu; AI = F, Cl)—trig. | M3IIAI[(B∆O1.5)2(Bt6O11.5)]3D | M3IIAI[B△Bt6O13]3D | M3IIAI[B7O13] |
5MIIO·7B2O3·MIIAI2—cub. Boracites (MII = Mg, Mn, Fe, Ni, Co, Cu; AI = Cl, Br, NO3) | M3IIAI[(Bt7O13)]3D | M3IIAI[Bt7O13]3D | M3IIAI[B7O13] |
MIIO·2B2O3 (MII = Mg, Mn, Zn, Cd) | M2II[(B∆2Bt2O7)]2(3D) | M2II[B∆2Bt2O7)]2(3D) | M2II[B4O7)]2 |
MIIO·B2O3-I (MII = Ca, Sr) | MII[(B∆2O4)]1D | MII[B∆2O4]1D | MII[B2O4] |
CaO·B2O3-II (calciborate) | Ca2[(B∆O2)2Bt2O4)]1D | Ca2[B∆2Bt2O4]1D | Ca2[B4O8] |
MIIO·B2O3-III (MII = Ca, Sr) | M3II[(B∆O1.5)(B∆O2)(BtO2)(Bt3O6)]3D | M3II[B∆2Bt4O12]3D | M3II[(B6O12)] |
MIIO·B2O3-IV (MII = Ca, Sr) | M3II[(Bt3O6)2]3D | M3II[(Bt3O6)2]3D | M3II[(Bt3O6)2] |
2CaO·3B2O3 | Ca2[(B∆2Bt3O9)2(BtO2)]3D | Ca2[B∆2Bt4O11]3D | Ca2[B6O11] |
CaO·2B2O3-II | Ca2[(B∆2BtO5)(B∆2Bt2O7)(BtO2)]3D | Ca2[B∆4Bt4O14]3D | Ca2[B8O14] |
MIIO·2B2O3 (MII = Sr, Po) | MII[(Bt4O7)]3D | MII[Bt4O7]3D | MII[B4O7] |
β-BaO·B2O3 | Ba3[(B∆3O6)2] | Ba3[(B∆3O6)2] | Ba3[(B3O6)2] |
BaO·2B2O3 | Ba2[(B∆Bt2O5.5)(B∆3Bt2O8.5)]3D | Ba2[B∆4Bt4O14]3D | Ba2[B8O14] |
BaO·4B2O3 | Ba2[(B∆2BtO5)(B∆4BtO8)]2(3D) | Ba2[B∆6Bt2O13]2(3D) | Ba2[B8O13]2 |
4ZnO·3B2O3 | Zn4O[(Bt6O12)]3D | Zn4O[Bt6O12]3D | Zn4O[B6O12] |
CuO·B2O3 | Cu3[(Bt3O6)2]3D | Cu3[(Bt3O6)2]3D | Cu3[(B3O6)2] |
5Al2O3·B2O3 | Al2[(Alt3O6)(B∆O3)]3D | Al2[Alt3B∆O9]3D | Al2[Al3BO9] |
R2O3·3B2O3 (R = La-Tb) | R2[(B∆2Bt2O8)(B∆O2)2]1D | R2[B∆4Bt2O12]1D | R2[B6O12] |
By the Composition of Anion Formers | By Cation Valency | By Cation Type (and Size) | By the Value of N Factor (N = NM/NB) | ||||||
---|---|---|---|---|---|---|---|---|---|
N > 1 | N = 1 | n = n∆/nt = m − 1, where m—coeff. from MxO·mB2O3 * | |||||||
1 < N ≤ 1/2 | 1/2 < N ≤1/3 | N < 1/3 | |||||||
Borates | Monocationic (simple) | Monovalent | a | Li ↓ Cs | Orthoborates with isolated BO3 triangles | Metaborates, insular and chainlike ** | Polyborates, 3D and seldom - layered | Polyborates, 3D and seldom - layered | Polyborates, 3D |
b | Ag Tl | Same | 0 | 0 | 0 | Same | |||
Divalent | a | Be ↓ Ba | Same | Pyroborates | Metaborates, insular and chainlike** | Polyborates, 3D | Same | ||
b | Zn, Cd, Mn, Fe, Co, Ni, Cu, Pb | Same | Same | Metaborates, 3D | Same | Same | |||
Trivalent | a | Al | Orthoborates with BO4 tetrahedra | Orthoborates with BO3 triangles | - | - | - | ||
b | Sc, Ti, V, Cr, Ga, In | - | Same | - | - | - | |||
c | Fe | Orthoborates with BO4 tetrahedra | Same | - | - | - | |||
d | Y, La-Nd, Sm-Yb | 0 | Same | - | Metaborates, chainlike | - | |||
e | Bi | Orthoborates with BO3 triangles | - | - | 0 | 0 | |||
Tetravalent | Th | - | - | 0 | - | - | |||
Pentavalent | P, As, Ta, Nb | - | Orthoborates with BO3 triangles | - | - | - | |||
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | ||
Borates | Binary and more complex | M+M2+ | Orthoborates with BO3 triangles | - | - | - | - | ||
M+M3+ | Same | 0 | 0 | - | - | ||||
M+M5+ | Same | Pyroborates | - | - | - | ||||
M2+M2+ | - | Same | - | - | - | ||||
M2+M3+ | Orthoborates with BO3 triangles and BO4 tetrahedra | - | Metaborates, layered (t) | Metaborates, layered (∆ + t) | - | ||||
M2+M4+ | - | Orthoborates with BO3 triangles | - | - | - | ||||
M3+M3+ | - | Orthoborates with BO3 triangles | Metaborates with B tetrahedrons | - | - | ||||
Boron silicates | M2+M3+, M3+, M2+ | Orthocompounds | Metacompounds, chainlike | - | - | Polycompounds, 3D | |||
Boron aluminates | M2+, M3+ | - | Same | Polycompounds, layered and 3D | - | - | |||
Boron beryllates | M+ | - | - | Polycompounds, layered | Polycompounds, layered and 3D | - | |||
Boron carbonates | M2+M3+ | Orthocompounds | - | - | - | - | |||
Boron molybdates and boron tungstanates | M M3+ | - | - | Metacompounds, chainlike | - | - |
I. Borates of Monovalent Elements | |||||||||
---|---|---|---|---|---|---|---|---|---|
N | Cations | ||||||||
Li | Na (Ag) | K | Rb | Cs | Tl | ||||
Orthoborates (with isolated B triangles) | 5 | - | 0 | - | - | - | - | ||
3 | α-Li3[BO3] β from – 0 | 0 | - | - | - | Tl3[BO3] | |||
5/2 | - | 0 | - | - | - | - | |||
2 | - | 0 | - | - | - | - | |||
3/2 | 0 | 0 | - | - | - | - | |||
Fluoroborates (with isol. BF4 tetr.) | 1 | - | Na[BF4] | K[BF4] | Rb[BF4] | Cs[BF4] | Tl[BF4] | ||
Metaborates (ins. with boroxol gr.) * | 1 | α-Li2[B2O4]1D γ-Li[BO2]3D | α-Na3[B3O6] β phase – 0 | K3[B3O6] | α from - 0 | Cs3[B3O6] | 0 | ||
Polyborates (skeletal, sometimes compounds, layered with diborate – D, triborate – T, pentaborate – P, boroxol – B, ditriborate – DT, dipentaborate – DP rings and additional B triangles and tetrahedrons; n = n∆/nt = m − 1) | 2/3 | - | 0 | - | - | - | - | ||
4/7 | α and β Cl, Br and I “boracites” – 0 γ-Li4Cl[B7O12]3D | - | - | - | - | - | |||
1/2 | Li4[B4O7]2(3D)2(D) | (α)-Na4[B8O14]2D ** (T+DP) β and γ phase - 0 | K4[B8O14]3D | 0 | 0 | 0 | |||
2/5 | 0 | 0 | - | - | - | - | |||
1/3 | 0 | α-Na6[B9O15]2(3D) 2(D + P) β-Na6[B9O15]2(2D) 2(P + T + t) γ-form – 0 | 0 | 0 | Cs[B3O5](3D) (T) | 0 | |||
5/19 | - | - | K5[B19O31]3D | - | - | - | |||
1/4 | 0 | α-(Na,Ag)4[B8O13]2(3D) 2(T + P) β modification – 0 | 0 | 0 | 0 | 0 | |||
1/5 | α, β and γ phases – 0 | α-K2[B5O8]2(3D) 2(P) β-K2[B5O8]2(3D) 2(P), γ phase - 0 | α phase – 0 β-Rb2[B5O8]2(3D) 2(P) | α, β, γ phases - 0 | 0 | ||||
1/9 | 0 | α, β, and γ phases – 0 | 0 | 0 | Cs2[B9O14]2(3D) 2(B + T) β phase | - | |||
II. Borates with Cations of Transition Metals | |||||||||
N | Cations | ||||||||
Zn | Cd | Mn | Fe | Co | Ni | Cu | Pb | ||
Orthoborates (with isolated BO3 triangles) | 3 | - | - | Wiserite Mn3[BO3]F3 | - | - | - | - | - |
2 | - | - | Mn2[BO3]F | - | - | - | - | 0 (α and β forms) | |
3/2 | α-Zn3[BO3]2 | 0 (α and β forms) | Jimboite Mn3[BO3]2 | - | 0 | Ni3[BO3]2 | 0 | - | |
5/4 | 0 (α and β forms) | - | - | - | - | - | - | - | |
Pyroborates (with isol.2) | 1 | - | Cd2[B2O5] | Mn2[B2O5] | Fe2[B2O5] | Co2[B2O5] | 0 | - | 0 (α and β forms) |
Metaborates (skeletal) | 1/2 | 0 (α and β forms) Zn4O[B6O12] * (t) | - | 0 | 0 | 0 | 0 | Cu3[(B3O6)2] (t) | 0 |
Polyborates (skeletal) | 3/7 | cub., rhomb. and trig. F, Cl, Br, I and NO3 “boracites” | Cl, Br, I and NO3 “boracites” | cub., rhomb. and trig. F, Cl, Br, I and NO3 “boracites” | cub. and trig. F, Cl, Br, I and NO3 “boracites” | cub., rhomb. and trig. F, Cl, Br, I and NO3 “boracites” | cub. and rhomb. Cl, Br, I and NO3 “boracites” | cub. and rhomb. Cl, Br, I and NO3 “boracites” | - |
1/3 | - | 0 | - | - | - | - | - | - | |
1/4 | Zn2[B4O7]2 2D | Cd2[B4O7]2 2D | Mn2[B4O7]2 2D | - | - | - | - | Pb[B4O7] (t) | |
1/6 | 0 | - | 0 | - | - | - | - | - |
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Leonyuk, N.I.; Maltsev, V.V.; Volkova, E.A. Crystal Chemistry of High-Temperature Borates. Molecules 2020, 25, 2450. https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25102450
Leonyuk NI, Maltsev VV, Volkova EA. Crystal Chemistry of High-Temperature Borates. Molecules. 2020; 25(10):2450. https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25102450
Chicago/Turabian StyleLeonyuk, Nikolay I., Victor V. Maltsev, and Elena A. Volkova. 2020. "Crystal Chemistry of High-Temperature Borates" Molecules 25, no. 10: 2450. https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25102450