Chemistry:Borate carbonate

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Short description: Mixed anion compound containing both borate and carbonate ions

The borate carbonates are mixed anion compounds containing both borate and carbonate ions. Compared to mixed anion compounds containing halides, these are quite rare. They are hard to make, requiring higher temperatures, which are likely to decompose carbonate to carbon dioxide. The reason for the difficulty of formation is that when entering a crystal lattice, the anions have to be correctly located, and correctly oriented.[1] They are also known as carbonatoborates or borocarbonates.[2] Although these compounds have been termed carboborate, that word also refers to the C=B=C5− anion, or CB11H12− anion.[3] This last anion should be called 1-carba-closo-dodecaborate[4] or monocarba-closo-dodecaborate.[5]

Some borate carbonates have additional different anions and can be borate carbonate halides or borate carbonate nitrites.

List

chem mw crystal system space group unit cell volume density comment references
Qilianshanite NaHCO3 · H3BO3 · 2H2O monoclinic a = 16.11 Å, b = 6.92 Å, c = 6.73 Å

β = 100.46°

1.635 Biaxial (-) nα = 1.351 nβ = 1.459 nγ = 1.486

2V: 50°

Max birefringence δ = 0.135

[6]
Canavesite Mg2(HBO3)(CO3) · 5H2O monoclinic a = 23.49(2) Å, b = 6.16(6) Å, c = 21.91(2) Å

β = 114.91(9)° Z=12?

1.790 Biaxial (+) nα = 1.485 nβ = 1.494 nγ = 1.505

2V: 86°

Max birefringence: δ = 0.020

[7]
Potassium bis(carbonato)borate hydrate K[B(CO2-μ-O-CO2)2]·2H2O orthorhombic Aba2 a=11.058 b=11.169 c=9.0504 Z=4 1117.8 spiro at boron [8]
NaK15[B4O5(OH)4]6(NO2)2(CO3)·7H2O 2035.26 hexagonal P62c a=11.1399 c=30.495 Z=2 3277.3 2.062 [9]
K9[B4O5(OH)4]3(CO3)OH⋅7 H2O 1128.82 P62c a=11.207 c=17.193 Z=2 1870.2 2.005 [10]
K9[B4O5(OH)4]3(CO3)Cl·7H2O 1147.29 hexagonal P62c a=11.219 c=17.079 Z=2 1861.8 2.047 [11]
K9[B4O5(OH)4]3(CO3)Br·7H2O 1191.75 hexagonal P62c a=11.243 c=17.132 Z=2 1875.4 2.110 [11]
K9[B4O5(OH)4]3(CO3)I⋅7 H2O 1238.74 P62c a=11.234 c=17.158 Z=2 1875.2 2.194 [10]
Ca4(Ca0.7Na0.3)3(Na0.7□ 0.3)Li5[B t12BΔ10O36(O,OH)6](CO3)(OH) · (OH,H2O) R3 a=8.99 c=35.91 Z=3 2513 2.62 [12]
Chiyokoite Ca3Si(CO3){[B(OH)4]0.5(AsO3)0.5}(OH)6 · 12H2O hexagonal P63 a = 11.0119, c = 10.5252 1,105.31 [13]
Carboborite Ca2Mg[B(OH)4]2(CO3)2 · 4H2O monoclinic a = 18.59 Å, b = 6.68 Å, c = 11.32 Å

β = 91.68°

Biaxial (-) nα = 1.507 nβ = 1.546 nγ = 1.569

Max Birefringence: δ = 0.062

[14]
Borcarite Ca4MgB4O5(OH)6(CO3)2 monoclinic C2/m a=17.840 b=8.380 c=4.445 β =102.04 649.906 2.790 Biaxial (-) nα = 1.590 nβ = 1.651 nγ = 1.657

2V: 30°

Max birefringence: δ = 0.067

[1][15]
Sakhaite Ca3Mg(BO3)2(CO3)2.(H2O)0.36 isometric Fd3m a = 14.685 Z=4 3166.8 [1][16]
Ca12Mg4(BO3)7(CO3)4(OH)Cl.H2O Fd3 [1]
Harkerite Ca12Mg4Al(BO3)3(SiO4)4(CO3)5 · H2O trigonal R3m a = 18.131 Å α = 33.46° 1614 Uniaxial nα = 1.649 - 1.653 nβ = 1.649 - 1.653 [17]
Imayoshiite Ca3Al(CO3)[B(OH)4](OH)6 · 12H2O hexagonal P63 a = 11.026, c = 10.605 1,117 1.79 Uniaxial (-) nω = 1.497(2) nε = 1.470(2)

Max birefringence δ = 0.027

[18]
Gaudefroyite Ca4Mn3O3(BO3)3CO3 hexagonal P63/m a = 10.6 Å, c = 5.9 Å 574 3.529 black

Uniaxial (+) nω = 1.805 - 1.810 nε = 2.015 - 2.020

Max Birefringence:δ = 0.210

[1][19]
Numanoite Ca4Cu(B4O6(OH)6)(CO3)2 monoclinic C2/m a = 17.794 Å, b = 8.381 Å, c = 4.4494 Å

β = 102.42° Z=2

bluish green

Biaxial (-) nα=1.618 nβ=1.658 nγ=1.672

2V: 60°

Max birefringence: δ = 0.054

[20]
Rb9[B4O5(OH)4]3(CO3)Cl⋅7 H2O 1564.59 P62c a=11.325 c=17.181 Z=2 1908.3 2.502 [10]
Rb9[B4O5(OH)4]3(CO3)Br⋅7 H2O 1609.08 P62c a=11.482 c=17.463 Z=2 1993.9 2.680 [10]
Rb9[B4O5(OH)4]3(CO3)I⋅7 H2O 1656.07 P62c a=11.451 c=17.476 Z=2 1984.5 2.771 [10]
NaRb3B6O9(OH)3(HCO3) monoclinic P21 a = 8.988 Å, b = 8.889 Å, c = 10.068 Å, and β = 114.6°
Sr5(CO3)2(BO3)2 orthorhombic Pnma a = 7.387 b = 16.556 c = 8.971 Z = 4 UV cut off 190 nm [21]
Sr2CuO2(CO3)0.85(BO3)0.15 I4 [1]
Sr(Na0.4Sr0.1)Na2[B5O8(OH)2] · (CO3)1 − x B2/b [22]
Moydite-(Y) Y[B(OH)4](CO3) orthorhombic [23]
Ba2(BO3)1-x(CO3)xClx x=0.1 P3m1 [1]
Ba3[B6O10(OH)2](CO3) 730.905 monoclinic a=6.5351, b=8.3455, c =11.3489, and β = 98.9568° Z=2 611.4 3.970 [24]
Ba5(CO3)2(BO3)2 924.34 orthorhombic Pnma a=7.923 b=17.508 c=9.114 Z=4 1268.4 4.84 [1]
Ba4Sr(CO3)2(BO3)2 874.63 orthorhombic Pnma a=7.731 b=17.349 c=9.048 Z=4 1213.6 7.787 [1]
Ba6[B12O21(OH)2](CO3)2 1443.80 monoclinic a =6.5485, b = 19.361, c = 18.120, and β = 90.893° Z=4 2297.0 4.175 [24]
Li9BaB15O27(CO3) P31c a=8.860, c=15.148 [1][25]
Ba3(BO3)(CO3)F 549.84 trigonal R3 a=10.1799 c=18.530 Z=9 1663.0 4.941 [26]
Pb7O(OH)3(CO3)3(BO3) 1756.19 hexagonal P63/mc a=10.519 c=8.90 Z=2 853 6.839 SHG 4.5×KDP [27]
Mereheadite Pb47O24(OH)13Cl25(BO3)2(CO3) monoclinic Cm a = 17.372, b = 27.942, c = 10.6661, β = 93.152o 5169.6 [28]
Britvinite [Pb7(OH)3F(BO3)2(CO3)][Mg4.5(OH)3(Si5O14)] triclinic P1 a = 9.3409, b = 9.3579, c = 18.833

α = 80.365°, β = 75.816°, γ = 59.870° Z=2

1378.7 5.51 Biaxial (-) nα = 1.896 nβ = 1.903 nγ = 1.903

2V 20°

Max birefringence δ = 0.007

[29]
Roymillerite Pb24Mg9(Si10O28)(CO3)10(BO3)(SiO4)(OH)13O5 triclinic P1 a = 9.316, b = 9.316, c = 26.463

α = 83.295°, β = 83.308°, γ = 60.023° Z=1

1971.2 5.973 Biaxial (-) nα = 1.860 nβ = 1.940 nγ = 1.940

2V 5°

Max birefringence δ = 0.080

[30]

References

  1. ↑ 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 Zhang, Xueyan; Wu, Hongping; Yu, Hongwei; Yang, Zhihua; Pan, Shilie (2019-07-01). "Ba4M(CO3)2(BO3)2 (M=Ba, Sr): two borate-carbonates synthesized by open high temperature solution method" (in en). Science China Materials 62 (7): 1023–1032. doi:10.1007/s40843-018-9390-2. ISSN 2199-4501. 
  2. ↑ Moureau, Magdeleine; Brace, Gerald (in fr). Dictionnaire des Science.... Editions OPHRYS. p. 774. ISBN 978-2-7108-1109-1. https://books.google.com/books?id=bgFAR2Qp51sC&pg=PA774. 
  3. ↑ Ferraris, G.; Franchini-Angela, M. (1 February 1978). "Canavesite, a new carboborate mineral from Brosso, Italy" (in en). The Canadian Mineralogist 16 (1): 69–73. https://pubs.geoscienceworld.org/canmin/article-abstract/16/1/69/11256/Canavesite-a-new-carboborate-mineral-from-Brosso?redirectedFrom=fulltext. 
  4. ↑ Douvris, Christos; Michl, Josef (9 October 2013). "Update 1 of: Chemistry of the Carba- closo -dodecaborate(−) Anion, CB11H12–". Chemical Reviews 113 (10): PR179–PR233. doi:10.1021/cr400059k. PMID 23944158. 
  5. ↑ Tanaka, Naoki; Shoji, Yoshiaki; Fukushima, Takanori (13 June 2016). "Convenient Route to Monocarba- closo -dodecaborate Anions". Organometallics 35 (11): 2022–2025. doi:10.1021/acs.organomet.6b00309. 
  6. ↑ "Qilianshanite". https://www.mindat.org/min-3332.html. 
  7. ↑ "Canavesite". https://www.mindat.org/min-879.html. 
  8. ↑ Tombul, Mustafa; TüRkmenoglu, Elmas; Sahin, Onur (2021-08-10). "Unprecedented Formation of Potassium Borate Based Carbonate from Chloral Hydrate, Potassium Carbonate and Boric Acid" (in en). X-ray Structure Analysis Online 37: 45–47. doi:10.2116/xraystruct.37.45. ISSN 1883-3578. https://www.jstage.jst.go.jp/article/xraystruct/37/0/37_45/_article. 
  9. ↑ Cao, Yuchen; Zhang, Bingbing; Liu, Hongkun; Li, Danni; Wang, Ying (2020). "NaK 15 [B 4 O 5 (OH) 4 6 (NO 2 ) 2 (CO 3 )·7H 2 O: assembly of an unprecedented mixed anion inorganic compound via a facile hydrothermal route"] (in en). New Journal of Chemistry 44 (11): 4253–4256. doi:10.1039/D0NJ00249F. ISSN 1144-0546. http://xlink.rsc.org/?DOI=D0NJ00249F. 
  10. ↑ 10.0 10.1 10.2 10.3 10.4 Liu, Lili; Yang, Yun; Huang, Junben; Dong, Xiaoyu; Yang, Zhihua; Pan, Shilie (August 2017). "Design and Synthesis of a Series of Novel Mixed Borate and Carbonate Halides" (in en). Chemistry – A European Journal 23 (43): 10451–10459. doi:10.1002/chem.201701926. ISSN 0947-6539. PMID 28575533. https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201701926. 
  11. ↑ 11.0 11.1 Zhang, Xueyan; Wu, Hongping; Cheng, Shichao; Han, Guopeng; Yang, Zhihua; Pan, Shilie (2019-05-20). "K 9 [B 4 O 5 (OH) 4 3 (CO 3 )X·7H 2 O (X = Cl, Br): Syntheses, Characterizations, and Theoretical Studies of Noncentrosymmetric Halogen Borate–Carbonates with Short UV Cutoff Edges"] (in en). Inorganic Chemistry 58 (10): 6974–6982. doi:10.1021/acs.inorgchem.9b00593. ISSN 0020-1669. PMID 31042371. https://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00593. 
  12. ↑ Yamnova, N. A.; Egorov-Tismenko, Yu. K.; Dimitrova, O. V.; Kantor, A. P. (2002-07-01). "Crystal structure of new synthetic Ca,Na,Li-carbonate-borate" (in en). Crystallography Reports 47 (4): 566–573. doi:10.1134/1.1496054. ISSN 1562-689X. Bibcode: 2002CryRp..47..566Y. https://doi.org/10.1134/1.1496054. 
  13. ↑ "Chiyokoite". https://www.mindat.org/min-54035.html. 
  14. ↑ "Carboborite". https://www.mindat.org/min-891.html. 
  15. ↑ "Borcarite". https://www.mindat.org/min-723.html. 
  16. ↑ "Sakhaite". https://www.mindat.org/min-3504.html. 
  17. ↑ "Harkerite". https://www.mindat.org/min-1819.html. 
  18. ↑ "Imayoshiite". https://www.mindat.org/min-44007.html. 
  19. ↑ "Gaudefroyite". https://www.mindat.org/min-1660.html. 
  20. ↑ "Numanoite". https://www.mindat.org/min-29100.html. 
  21. ↑ Chen, Jiongquan; Yang, Zhihua; Wu, Kui; Yang, Yun; Pan, Shilie (January 2022). "Sr5(CO3)2(BO3)2: A new family member of isostructural mixed borate and carbonate Ba4M(BO3)2(CO3)2 (M = Ba, Sr) with isolated BO3 and CO3 groups" (in en). Journal of Molecular Structure 1247: 131382. doi:10.1016/j.molstruc.2021.131382. https://linkinghub.elsevier.com/retrieve/pii/S0022286021015106. 
  22. ↑ Belokoneva, E. L.; Dimitrova, O. V.; Mochenova, N. N. (January 2009). "Synthetic Na,Sr-carbonatoborate with a new type of pentaborate layer: The OD nature of the structure and its correlation with volkovskite, veatchites, and hilgardites" (in en). Crystallography Reports 54 (1): 6–12. doi:10.1134/S1063774509010027. ISSN 1063-7745. Bibcode: 2009CryRp..54....6B. http://link.springer.com/10.1134/S1063774509010027. 
  23. ↑ "Moydite-(Y)". https://www.mindat.org/min-2798.html. 
  24. ↑ 24.0 24.1 Liao, Chun-Jui; Wen, Yuh-Sheng; Lii, Kwang-Hwa (2018-09-17). "High-Temperature, High-Pressure Hydrothermal Synthesis of Ba 3 [B 6 O 10 (OH) 2 (CO 3 ) and Ba 6 [B 12 O 21 (OH) 2 ](CO 3 ) 2 , Two Barium Borate Carbonates with 2D Layer and 3D Framework Structures"] (in en). Inorganic Chemistry 57 (18): 11492–11497. doi:10.1021/acs.inorgchem.8b01362. ISSN 0020-1669. PMID 30148619. https://pubs.acs.org/doi/10.1021/acs.inorgchem.8b01362. 
  25. ↑ Heyward, Carla; McMillen, Colin D.; Kolis, Joseph (July 2013). "Hydrothermal synthesis and structural analysis of new mixed oxyanion borates: Ba11B26O44(PO4)2(OH)6, Li9BaB15O27(CO3) and Ba3Si2B6O16" (in en). Journal of Solid State Chemistry 203: 166–173. doi:10.1016/j.jssc.2013.04.022. Bibcode: 2013JSSCh.203..166H. https://linkinghub.elsevier.com/retrieve/pii/S0022459613002168. 
  26. ↑ Huang, Chunmei; Zhang, Fangfang; Cheng, Shichao; Yang, Zhihua; Li, Hao; Pan, Shilie (2020-11-16). "Ba 3 (BO 3 )(CO 3 )F: The First Borate Carbonate Fluoride Synthesized by the High-Temperature Solution Method" (in en). Chemistry – A European Journal 26 (70): 16628–16632. doi:10.1002/chem.202003606. ISSN 0947-6539. PMID 32910472. https://onlinelibrary.wiley.com/doi/10.1002/chem.202003606. 
  27. ↑ Abudoureheman, Maierhaba; Wang, Li; Zhang, Xianming; Yu, Hongwei; Yang, Zhihua; Lei, Chen; Han, Jian; Pan, Shilie (2015-04-20). "Pb 7 O(OH) 3 (CO 3 ) 3 (BO 3 ): First Mixed Borate and Carbonate Nonlinear Optical Material Exhibiting Large Second-Harmonic Generation Response" (in en). Inorganic Chemistry 54 (8): 4138–4142. doi:10.1021/acs.inorgchem.5b00401. ISSN 0020-1669. PMID 25825990. https://pubs.acs.org/doi/10.1021/acs.inorgchem.5b00401. 
  28. ↑ Krivovichev, S. V.; Turner, R.; RumseY, M.; Siidra, O. I.; Kirk, C. A. (February 2009). "The crystal structure and chemistry of mereheadite" (in en). Mineralogical Magazine 73 (1): 103–117. doi:10.1180/minmag.2009.073.1.103. ISSN 0026-461X. Bibcode: 2009MinM...73..103K. https://www.cambridge.org/core/product/identifier/S0026461X00005144/type/journal_article. 
  29. ↑ "Britvinite". https://www.mindat.org/min-30905.html. 
  30. ↑ "Roymillerite". https://www.mindat.org/min-50357.html. 


Carbonates
H2CO3 He
Li2CO3,
LiHCO3 		BeCO3 B C (NH4)2CO3,
NH4HCO3 		O F Ne
Na2CO3,
NaHCO3,
Na3H(CO3)2 		MgCO3,
Mg(HCO3)2 		Al2(CO3)3 Si P S Cl Ar
K2CO3,
KHCO3 		CaCO3,
Ca(HCO3)2 		Sc Ti V Cr MnCO3 FeCO3 CoCO3 NiCO3 CuCO3 ZnCO3 Ga Ge As Se Br Kr
Rb2CO3 SrCO3 Y Zr Nb Mo Tc Ru Rh Pd Ag2CO3 CdCO3 In Sn Sb Te I Xe
Cs2CO3,
CsHCO3 		BaCO3   Hf Ta W Re Os Ir Pt Au Hg Tl2CO3 PbCO3 (BiO)2CO3 Po At Rn
Fr Ra   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
La2(CO3)3 Ce2(CO3)3 Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Ac Th Pa UO2CO3 Np Pu Am Cm Bk Cf Es Fm Md No Lr



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