Borate carbonate explained

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. They are also known as carbonatoborates or borocarbonates.^[1] Although these compounds have been termed carboborate, that word also refers to the C=B=C⁵⁻ anion, or CB₁₁H₁₂⁻ anion.^[2] This last anion should be called 1-carba-closo-dodecaborate^[3] or monocarba-closo-dodecaborate.^[4]

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 Åβ = 100.46°		1.635	Biaxial (-) nα = 1.351 nβ = 1.459 nγ = 1.4862V: 50° Max birefringence δ = 0.135	^[5]
Canavesite	Mg2(HBO3)(CO3) · 5H2O		monoclinic		a = 23.49(2) Å, b = 6.16(6) Å, c = 21.91(2) Åβ = 114.91(9)° Z=12?		1.790	Biaxial (+) nα = 1.485 nβ = 1.494 nγ = 1.5052V: 86° Max birefringence: δ = 0.020	^[6]
Potassium bis(carbonato)borate hydrate	K[B(CO<sub>2</sub>-μ-O-CO<sub>2</sub>)<sub>2</sub>]·2H2O		orthorhombic	Aba2	a=11.058 b=11.169 c=9.0504 Z=4	1117.8		spiro at boron	^[7]
	NaK15[B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub>]6(NO2)2(CO3)·7H2O	2035.26	hexagonal	P2c	a=11.1399 c=30.495 Z=2	3277.3	2.062		^[8]
	K9[B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub>]3(CO3)OH⋅7 H2O	1128.82		P2c	a=11.207 c=17.193 Z=2	1870.2	2.005		^[9]
	K9[B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub>]3(CO3)Cl·7H2O	1147.29	hexagonal	P2c	a=11.219 c=17.079 Z=2	1861.8	2.047		^[10]
	K9[B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub>]3(CO3)Br·7H2O	1191.75	hexagonal	P2c	a=11.243 c=17.132 Z=2	1875.4	2.110
	K9[B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub>]3(CO3)I⋅7 H2O	1238.74		P2c	a=11.234 c=17.158 Z=2	1875.2	2.194
	Ca4(Ca0.7Na0.3)3(Na0.7□ 0.3)Li5[B <sup>t</sup><sub>12</sub>B<sup>Δ</sup><sub>10</sub>O<sub>36</sub>(O,OH)<sub>6</sub>](CO3)(OH) · (OH,H2O)			R3	a=8.99 c=35.91 Z=3	2513	2.62		^[11]
Chiyokoite	Ca3Si(CO3)(OH)6 · 12H2O		hexagonal	P63	a = 11.0119, c = 10.5252	1,105.31			^[12]
Carboborite	Ca2Mg[B(OH)<sub>4</sub>]2(CO3)2 · 4H2O		monoclinic		a = 18.59 Å, b = 6.68 Å, c = 11.32 Åβ = 91.68°			Biaxial (-) nα = 1.507 nβ = 1.546 nγ = 1.569Max 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	^[14]
Sakhaite	Ca3Mg(BO3)2(CO3)2.(H2O)0.36		isometric	Fdm	a = 14.685 Z=4	3166.8			^[15]
	Ca12Mg4(BO3)7(CO3)4(OH)Cl.H2O			Fd
Harkerite	Ca12Mg4Al(BO3)3(SiO4)4(CO3)5 · H2O		trigonal	Rm	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)<sub>4</sub>](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	^[18]
Numanoite	Ca4Cu(B4O6(OH)6)(CO3)2		monoclinic	C2/m	a = 17.794 Å, b = 8.381 Å, c = 4.4494 Åβ = 102.42° Z=2			bluish greenBiaxial (-) nα=1.618 nβ=1.658 nγ=1.672 2V: 60° Max birefringence: δ = 0.054	^[19]
	Rb9[B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub>]3(CO3)Cl⋅7 H2O	1564.59		P2c	a=11.325 c=17.181 Z=2	1908.3	2.502
	Rb9[B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub>]3(CO3)Br⋅7 H2O	1609.08		P2c	a=11.482 c=17.463 Z=2	1993.9	2.680
	Rb9[B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub>]3(CO3)I⋅7 H2O	1656.07		P2c	a=11.451 c=17.476 Z=2	1984.5	2.771
	NaRb3B6O9(OH)3(HCO3)		monoclinic	P21	a = 8.988 Å, b = 8.889 Å, c = 10.068 Å, and β = 114.6°				^[20]
	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			I
	Sr(Na0.4Sr0.1)Na2[B<sub>5</sub>O<sub>8</sub>(OH)<sub>2</sub>] · (CO3)1 − x			B2/b					^[22]
Moydite-(Y)	Y[B(OH)<sub>4</sub>](CO3)		orthorhombic						^[23]
	K6[Cd<sub>2</sub>(CO<sub>3</sub>)<sub>2</sub>(B<sub>12</sub>O<sub>18</sub>)(OH)<sub>6</sub>]	1099.19	orthorhombic	Pnnm	a=13.0603 b=9.1059 c=12.3860 Z=2	1473.0	2.478	colorless	^[24]
	Rb6[Cd<sub>2</sub>(CO<sub>3</sub>)<sub>2</sub>(B<sub>12</sub>O<sub>18</sub>)(OH)<sub>6</sub>]	1377.41	orthorhombic	Pnnm	a=13.3484 b=9.2665 c=12.4946 Z=2	1545.5	2.960	colorless
	Ba2(BO3)1-x(CO3)xClx x=0.1			Pm1
	Ba3[B<sub>6</sub>O<sub>10</sub>(OH)<sub>2</sub>](CO3)	730.905	monoclinic		a=6.5351, b=8.3455, c =11.3489, and β = 98.9568° Z=2	611.4	3.970		^[25]
	Ba5(CO3)2(BO3)2	924.34	orthorhombic	Pnma	a=7.923 b=17.508 c=9.114 Z=4	1268.4	4.84		^[26]
	Ba4Sr(CO3)2(BO3)2	874.63	orthorhombic	Pnma	a=7.731 b=17.349 c=9.048 Z=4	1213.6	7.787
	Ba6[B<sub>12</sub>O<sub>21</sub>(OH)<sub>2</sub>](CO3)2	1443.80	monoclinic		a =6.5485, b = 19.361, c = 18.120, and β = 90.893° Z=4	2297.0	4.175
	Li9BaB15O27(CO3)			P1c	a=8.860, c=15.148				^[27]
	Ba3(BO3)(CO3)F	549.84	trigonal	R	a=10.1799 c=18.530 Z=9	1663.0	4.941		^[28]
	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	^[29]
Mereheadite	Pb47O24(OH)13Cl25(BO3)2(CO3)		monoclinic	Cm	a = 17.372, b = 27.942, c = 10.6661, β = 93.152^o	5169.6			^[30]
Britvinite	[Pb<sub>7</sub>(OH)<sub>3</sub>F(BO<sub>3</sub>)<sub>2</sub>(CO<sub>3</sub>)][Mg<sub>4.5</sub>(OH)<sub>3</sub>(Si<sub>5</sub>O<sub>14</sub>)]		triclinic	P1	a = 9.3409, b = 9.3579, c = 18.833α = 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	^[31]
Roymillerite	Pb24Mg9(Si10O28)(CO3)10(BO3)(SiO4)(OH)13O5		triclinic	P	a = 9.316, b = 9.316, c = 26.463α = 83.295°, β = 83.308°, γ = 60.023° Z=1	1971.2	5.973	Biaxial (-) nα = 1.860 nβ = 1.940 nγ = 1.9402V 5° Max birefringence δ = 0.080	^[32]

Notes and References

1. Book: Moureau . Magdeleine . Brace . Gerald . Dictionnaire des Science... . Editions OPHRYS . 978-2-7108-1109-1 . 774 . fr.
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3. Douvris . Christos . Michl . Josef . Update 1 of: Chemistry of the Carba- closo -dodecaborate(−) Anion, CB₁₁H₁₂^– . Chemical Reviews . 9 October 2013 . 113 . 10 . PR179–PR233 . 10.1021/cr400059k. 23944158 .
4. Tanaka . Naoki . Shoji . Yoshiaki . Fukushima . Takanori . Convenient Route to Monocarba- closo -dodecaborate Anions . Organometallics . 13 June 2016 . 35 . 11 . 2022–2025 . 10.1021/acs.organomet.6b00309.
5. Web site: Qilianshanite. 2020-12-14. www.mindat.org.
6. Web site: Canavesite. 2020-12-14. www.mindat.org.
7. 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 . en . 37 . 45–47 . 10.2116/xraystruct.37.45 . 1883-3578. free .
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. en. 44. 11. 4253–4256. 10.1039/D0NJ00249F. 212875666. 1144-0546.
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10. 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. en. 58. 10. 6974–6982. 10.1021/acs.inorgchem.9b00593. 31042371. 143422681. 0020-1669.
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12. Web site: Chiyokoite. 2020-12-15. www.mindat.org.
13. Web site: Carboborite. 2020-12-14. www.mindat.org.
14. Web site: Borcarite. 2020-12-14. www.mindat.org.
15. Web site: Sakhaite. 2020-12-14. www.mindat.org.
16. Web site: Harkerite. 2020-12-14. www.mindat.org.
17. Web site: Imayoshiite. 2020-12-15. www.mindat.org.
18. Web site: Gaudefroyite. 2020-12-14. www.mindat.org.
19. Web site: Numanoite. 2020-12-14. www.mindat.org.
20. Ding . Fenghua . Zhang . Weilong . Nisbet . Matthew L. . Zhang . Weiguo . Halasyamani . P. Shiv . Yang . Zhihua . Pan . Shilie . Kenneth Poeppelmeier . Poeppelmeier . Kenneth R. . NaRb3B6O9(OH)3(HCO3): A Borate-Bicarbonate Nonlinear Optical Material . Inorganic Chemistry . 17 December 2019 . 59 . 1 . 759–766 . 10.1021/acs.inorgchem.9b03026. 31846311 . 209408459 .
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 . Journal of Molecular Structure . en . 1247 . 131382 . 10.1016/j.molstruc.2021.131382. 239659311 .
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 . Crystallography Reports . en . 54 . 1 . 6–12 . 10.1134/S1063774509010027 . 2009CryRp..54....6B . 97956754 . 1063-7745.
23. Web site: Moydite-(Y). 2020-12-14. www.mindat.org.
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25. 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. en. 57. 18. 11492–11497. 10.1021/acs.inorgchem.8b01362. 30148619. 52094773. 0020-1669.
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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. en. 203. 166–173. 10.1016/j.jssc.2013.04.022. 2013JSSCh.203..166H.
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31. Web site: Britvinite. 2020-12-15. www.mindat.org.
32. Web site: Roymillerite. 2020-12-15. www.mindat.org.