Borate carbonate

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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

chemmwcrystal systemspace groupunit cellvolumedensitycommentreferences
Qilianshanite NaHCO3 · H3BO3 · 2H2Omonoclinica = 16.11 Å, b = 6.92 Å, c = 6.73 Å

β = 100.46°

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

2V: 50°

Max birefringence δ = 0.135

 [6]
Canavesite Mg2(HBO3)(CO3) · 5H2Omonoclinica = 23.49(2) Å, b = 6.16(6) Å, c = 21.91(2) Å

β = 114.91(9)° Z=12?

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

2V: 86°

Max birefringence: δ = 0.020

 [7]
Potassium bis(carbonato)borate hydrateK[B(CO2-μ-O-CO2)2]·2H2OorthorhombicAba2a=11.058 b=11.169 c=9.0504 Z=41117.8spiro at boron [8]
NaK15[B4O5(OH)4]6(NO2)2(CO3)·7H2O2035.26hexagonalP62ca=11.1399 c=30.495 Z=23277.32.062 [9]
K9[B4O5(OH)4]3(CO3)OH⋅7 H2O1128.82P62ca=11.207 c=17.193 Z=21870.22.005 [10]
K9[B4O5(OH)4]3(CO3)Cl·7H2O1147.29hexagonalP62ca=11.219 c=17.079 Z=21861.82.047 [11]
K9[B4O5(OH)4]3(CO3)Br·7H2O1191.75hexagonalP62ca=11.243 c=17.132 Z=21875.42.110 [11]
K9[B4O5(OH)4]3(CO3)I⋅7 H2O1238.74P62ca=11.234 c=17.158 Z=21875.22.194 [10]
Ca4(Ca0.7Na0.3)3(Na0.7□ 0.3)Li5[B t12BΔ10O36(O,OH)6](CO3)(OH) · (OH,H2O)R3a=8.99 c=35.91 Z=325132.62 [12]
Chiyokoite Ca3Si(CO3){[B(OH)4]0.5(AsO3)0.5}(OH)6 · 12H2OhexagonalP63a = 11.0119, c = 10.52521,105.31 [13]
Carboborite Ca2Mg[B(OH)4]2(CO3)2 · 4H2Omonoclinica = 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)2monoclinicC2/ma=17.840 b=8.380 c=4.445 β =102.04649.9062.790Biaxial (-) 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)0.36isometricFd3ma = 14.685 Z=43166.8 [1] [16]
Ca12Mg4(BO3)7(CO3)4(OH)Cl.H2OFd3 [1]
Harkerite Ca12Mg4Al(BO3)3(SiO4)4(CO3)5 · H2OtrigonalR3ma = 18.131 Å α = 33.46°1614Uniaxial nα = 1.649 - 1.653 nβ = 1.649 - 1.653 [17]
Imayoshiite Ca3Al(CO3)[B(OH)4](OH)6 · 12H2OhexagonalP63a = 11.026, c = 10.6051,1171.79Uniaxial (-) nω = 1.497(2) nε = 1.470(2)

Max birefringence δ = 0.027

 [18]
Gaudefroyite Ca4Mn3O3(BO3)3CO3hexagonalP63/ma = 10.6 Å, c = 5.9 Å5743.529black

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

Max Birefringence:δ = 0.210

 [1] [19]
Numanoite Ca4Cu(B4O6(OH)6)(CO3)2monoclinicC2/ma = 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 H2O1564.59P62ca=11.325 c=17.181 Z=21908.32.502 [10]
Rb9[B4O5(OH)4]3(CO3)Br⋅7 H2O1609.08P62ca=11.482 c=17.463 Z=21993.92.680 [10]
Rb9[B4O5(OH)4]3(CO3)I⋅7 H2O1656.07P62ca=11.451 c=17.476 Z=21984.52.771 [10]
NaRb3B6O9(OH)3(HCO3)monoclinicP21a = 8.988 Å, b = 8.889 Å, c = 10.068 Å, and β = 114.6° [21]
Sr5(CO3)2(BO3)2orthorhombicPnmaa = 7.387 b = 16.556 c = 8.971 Z = 4UV cut off 190 nm [22]
Sr2CuO2(CO3)0.85(BO3)0.15I4 [1]
Sr(Na0.4Sr0.1)Na2[B5O8(OH)2] · (CO3)1 − xB2/b [23]
Moydite-(Y)Y[B(OH)4](CO3)orthorhombic [24]
K6[Cd2(CO3)2(B12O18)(OH)6]1099.19orthorhombicPnnma=13.0603 b=9.1059 c=12.3860 Z=21473.02.478colorless [25]
Rb6[Cd2(CO3)2(B12O18)(OH)6]1377.41orthorhombicPnnma=13.3484 b=9.2665 c=12.4946 Z=21545.52.960colorless [25]
Ba2(BO3)1-x(CO3)xClx x=0.1P3m1 [1]
Ba3[B6O10(OH)2](CO3)730.905monoclinica=6.5351, b=8.3455, c =11.3489, and β = 98.9568° Z=2611.43.970 [26]
Ba5(CO3)2(BO3)2924.34orthorhombicPnmaa=7.923 b=17.508 c=9.114 Z=41268.44.84 [1]
Ba4Sr(CO3)2(BO3)2874.63orthorhombicPnmaa=7.731 b=17.349 c=9.048 Z=41213.67.787 [1]
Ba6[B12O21(OH)2](CO3)21443.80monoclinica =6.5485, b = 19.361, c = 18.120, and β = 90.893° Z=42297.04.175 [26]
Li9BaB15O27(CO3)P31ca=8.860, c=15.148 [1] [27]
Ba3(BO3)(CO3)F549.84trigonalR3a=10.1799 c=18.530 Z=91663.04.941 [28]
Pb7O(OH)3(CO3)3(BO3)1756.19hexagonalP63/mca=10.519 c=8.90 Z=28536.839SHG 4.5×KDP [29]
Mereheadite Pb47O24(OH)13Cl25(BO3)2(CO3)monoclinicCma = 17.372, b = 27.942, c = 10.6661, β = 93.152o5169.6 [30]
Britvinite [Pb7(OH)3F(BO3)2(CO3)][Mg4.5(OH)3(Si5O14)]triclinicP1a = 9.3409, b = 9.3579, c = 18.833

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

1378.75.51Biaxial (-) nα = 1.896 nβ = 1.903 nγ = 1.903

2V 20°

Max birefringence δ = 0.007

 [31]
RoymilleritePb24Mg9(Si10O28)(CO3)10(BO3)(SiO4)(OH)13O5triclinicP1a = 9.316, b = 9.316, c = 26.463

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

1971.25.973Biaxial (-) nα = 1.860 nβ = 1.940 nγ = 1.940

2V 5°

Max birefringence δ = 0.080

 [32]

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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.
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  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.
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  7. ↑ "Canavesite". www.mindat.org. Retrieved 2020-12-14.
  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". X-ray Structure Analysis Online. 37: 45–47. doi: 10.2116/xraystruct.37.45 . ISSN   1883-3578.
  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". New Journal of Chemistry. 44 (11): 4253–4256. doi:10.1039/D0NJ00249F. ISSN   1144-0546. S2CID   212875666.
  10. 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.
  11. 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.
  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". Crystallography Reports. 47 (4): 566–573. Bibcode:2002CryRp..47..566Y. doi:10.1134/1.1496054. ISSN   1562-689X. S2CID   54984045.
  13. ↑ "Chiyokoite". www.mindat.org. Retrieved 2020-12-15.
  14. ↑ "Carboborite". www.mindat.org. Retrieved 2020-12-14.
  15. ↑ "Borcarite". www.mindat.org. Retrieved 2020-12-14.
  16. ↑ "Sakhaite". www.mindat.org. Retrieved 2020-12-14.
  17. ↑ "Harkerite". www.mindat.org. Retrieved 2020-12-14.
  18. ↑ "Imayoshiite". www.mindat.org. Retrieved 2020-12-15.
  19. ↑ "Gaudefroyite". www.mindat.org. Retrieved 2020-12-14.
  20. ↑ "Numanoite". www.mindat.org. Retrieved 2020-12-14.
  21. ↑ 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.
  22. ↑ 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". Journal of Molecular Structure. 1247: 131382. doi:10.1016/j.molstruc.2021.131382. S2CID   239659311.
  23. ↑ 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". Crystallography Reports. 54 (1): 6–12. Bibcode:2009CryRp..54....6B. doi:10.1134/S1063774509010027. ISSN   1063-7745. S2CID   97956754.
  24. ↑ "Moydite-(Y)". www.mindat.org. Retrieved 2020-12-14.
  25. 1 2 Chen, Wei-Feng; Zou, Mei-Jun; Li, Jing-Jing; Zhang, Yi-Nan; Lan, You-Zhao; Cheng, Jian-Wen; Yang, Guo-Yu (2024-05-09). "M 6 [Cd 2 (CO 3 ) 2 (B 12 O 18 )(OH) 6 ] (M = K, Rb): Borate–Carbonates with Two CdCO 3 Embedded in a Cyclic Oxoboron Anion". Inorganic Chemistry. doi:10.1021/acs.inorgchem.4c01367. ISSN   0020-1669. PMID   38723292.
  26. 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.
  27. ↑ 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.
  28. ↑ 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.
  29. ↑ 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.
  30. ↑ 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.
  31. ↑ "Britvinite". www.mindat.org. Retrieved 2020-12-15.
  32. ↑ "Roymillerite". www.mindat.org. Retrieved 2020-12-15.
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