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 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]
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 [8]
K9[B4O5(OH)4]3(CO3)OH⋅7 H2O 1128.82 P62c a=11.207 c=17.193 Z=2 1870.2 2.005 [9]
K9[B4O5(OH)4]3(CO3)Cl·7H2O 1147.29 hexagonal P62c a=11.219 c=17.079 Z=2 1861.8 2.047 [10]
K9[B4O5(OH)4]3(CO3)Br·7H2O 1191.75 hexagonal P62c a=11.243 c=17.132 Z=2 1875.4 2.110 [10]
K9[B4O5(OH)4]3(CO3)I⋅7 H2O 1238.74 P62c a=11.234 c=17.158 Z=2 1875.2 2.194 [9]
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 [11]
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 [12]
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

 [13]
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][14]
Sakhaite Ca3Mg(BO3)2(CO3)2.(H2O)0.36 isometric Fd3m a = 14.685 Z=4 3166.8 [1][15]
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 [16]
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

 [17]
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][18]
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

 [19]
Rb9[B4O5(OH)4]3(CO3)Cl⋅7 H2O 1564.59 P62c a=11.325 c=17.181 Z=2 1908.3 2.502 [9]
Rb9[B4O5(OH)4]3(CO3)Br⋅7 H2O 1609.08 P62c a=11.482 c=17.463 Z=2 1993.9 2.680 [9]
Rb9[B4O5(OH)4]3(CO3)I⋅7 H2O 1656.07 P62c a=11.451 c=17.476 Z=2 1984.5 2.771 [9]
NaRb3B6O9(OH)3(HCO3) monoclinic P21 a = 8.988 Å, b = 8.889 Å, c = 10.068 Å, and β = 114.6° [20]
Sr2CuO2(CO3)0.85(BO3)0.15 I4 [1]
Moydite-(Y) Y[B(OH)4](CO3) orthorhombic [21]
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 [22]
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 [22]
Li9BaB15O27(CO3) P31c a=8.860, c=15.148 [1][23]
Ba3(BO3)(CO3)F 549.84 trigonal R3 a=10.1799 c=18.530 Z=9 1663.0 4.941 [24]
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 [25]
Mereheadite Pb47O24(OH)13Cl25(BO3)2(CO3) monoclinic Cm a = 17.372, b = 27.942, c = 10.6661, β = 93.152o 5169.6 [26]
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

 [27]
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

 [28]

References

  1. 1 2 3 4 5 6 7 8 9 10 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". Science China Materials. 62 (7): 1023–1032. doi:10.1007/s40843-018-9390-2. ISSN 2199-4501. S2CID 139665355.
  2. ↑ Moureau, Magdeleine; Brace, Gerald. Dictionnaire des Science... (in French). Editions OPHRYS. p. 774. ISBN 978-2-7108-1109-1.
  3. ↑ Ferraris, G.; Franchini-Angela, M. (1 February 1978). "Canavesite, a new carboborate mineral from Brosso, Italy". The Canadian Mineralogist. 16 (1): 69–73.
  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". www.mindat.org. Retrieved 2020-12-14.
  7. ↑ "Canavesite". www.mindat.org. Retrieved 2020-12-14.
  8. ↑ 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". New Journal of Chemistry. 44 (11): 4253–4256. doi:10.1039/D0NJ00249F. ISSN 1144-0546. S2CID 212875666.
  9. 1 2 3 4 5 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". Chemistry – A European Journal. 23 (43): 10451–10459. doi:10.1002/chem.201701926. ISSN 0947-6539. PMID 28575533.
  10. 1 2 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". Inorganic Chemistry. 58 (10): 6974–6982. doi:10.1021/acs.inorgchem.9b00593. ISSN 0020-1669. PMID 31042371. S2CID 143422681.
  11. ↑ 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". Crystallography Reports. 47 (4): 566–573. Bibcode:2002CryRp..47..566Y. doi:10.1134/1.1496054. ISSN 1562-689X. S2CID 54984045.
  12. ↑ "Chiyokoite". www.mindat.org. Retrieved 2020-12-15.
  13. ↑ "Carboborite". www.mindat.org. Retrieved 2020-12-14.
  14. ↑ "Borcarite". www.mindat.org. Retrieved 2020-12-14.
  15. ↑ "Sakhaite". www.mindat.org. Retrieved 2020-12-14.
  16. ↑ "Harkerite". www.mindat.org. Retrieved 2020-12-14.
  17. ↑ "Imayoshiite". www.mindat.org. Retrieved 2020-12-15.
  18. ↑ "Gaudefroyite". www.mindat.org. Retrieved 2020-12-14.
  19. ↑ "Numanoite". www.mindat.org. Retrieved 2020-12-14.
  20. ↑ Ding, Fenghua; Zhang, Weilong; Nisbet, Matthew L.; Zhang, Weiguo; Halasyamani, P. Shiv; Yang, Zhihua; Pan, Shilie; Poeppelmeier, Kenneth R. (17 December 2019). "NaRb3B6O9(OH)3(HCO3): A Borate-Bicarbonate Nonlinear Optical Material". Inorganic Chemistry. 59 (1): 759–766. doi:10.1021/acs.inorgchem.9b03026. PMID 31846311. S2CID 209408459.
  21. ↑ "Moydite-(Y)". www.mindat.org. Retrieved 2020-12-14.
  22. 1 2 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". Inorganic Chemistry. 57 (18): 11492–11497. doi:10.1021/acs.inorgchem.8b01362. ISSN 0020-1669. PMID 30148619. S2CID 52094773.
  23. ↑ 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". Journal of Solid State Chemistry. 203: 166–173. Bibcode:2013JSSCh.203..166H. doi:10.1016/j.jssc.2013.04.022.
  24. ↑ 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". Chemistry – A European Journal. 26 (70): 16628–16632. doi:10.1002/chem.202003606. ISSN 0947-6539. PMID 32910472. S2CID 221620474.
  25. ↑ 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". Inorganic Chemistry. 54 (8): 4138–4142. doi:10.1021/acs.inorgchem.5b00401. ISSN 0020-1669. PMID 25825990.
  26. ↑ Krivovichev, S. V.; Turner, R.; RumseY, M.; Siidra, O. I.; Kirk, C. A. (February 2009). "The crystal structure and chemistry of mereheadite". Mineralogical Magazine. 73 (1): 103–117. Bibcode:2009MinM...73..103K. doi:10.1180/minmag.2009.073.1.103. ISSN 0026-461X. S2CID 96947337.
  27. ↑ "Britvinite". www.mindat.org. Retrieved 2020-12-15.
  28. ↑ "Roymillerite". www.mindat.org. Retrieved 2020-12-15.
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