Carbonate chloride explained
The carbonate chlorides are double salts containing both carbonate and chloride anions. Quite a few minerals are known. Several artificial compounds have been made. Some complexes have both carbonate and chloride ligands. They are part of the family of . In turn these are a part of mixed anion materials.
The carbonate chlorides do not have a bond from chlorine to carbon, however "chlorocarbonate" has also been used to refer to the chloroformates which contain the group ClC(O)O-.
Formation
Natural
Scapolite is produced in nature by metasomatism, where hot high pressure water solutions of carbon dioxide and sodium chloride modify plagioclase.[1]
Chloroartinite is found in Sorel cements exposed to air.[2]
Minerals
In 2016 27 chloride containing carbonate minerals were known.
| name | formula | crystal system | space group | unit cell | density | Optics refractive index | Raman spectrum | comments | reference |
|---|
| Alexkhomyakovite | K6(Ca2Na)(CO3)5Cl∙6H2O | hexagonal | P63/mcm | a=9.2691, c=15.8419, V=1178.72 Z = 2 | 2.25 | uniaxial (–), ω=1.543, ε=1.476 | | | [3] |
| Ashburtonite | HPb4Cu4(Si4O12)(HCO3)4(OH)4Cl | | | | | | | | [4] |
| Balliranoite | (Na,K)6Ca2(Si6Al6O24)Cl2(CO3) | hexagonal | P63 | a=12.695 c=5.325 V=743.2 Z=1 | 2.48 | uniaxial (+), ω=1.523, ε=1.525 | | | [5] |
| Barstowite | Pb4(CO3)Cl6.H2O | | | | | | | | |
| Mg2(CO3)Cl(OH).3H2O | | | | | | | | |
| Chlormagaluminite | (Mg,Fe2+)4Al2(OH)12(Cl, 0.5 CO3)2·2H2O | | 6/mmm | | 1.98-2.09 | ε=1.560 ω=1.540 | | | [6] |
| Davyne | | | | | | | | can substitute CO3 for SO4 | [7] |
| Decrespignyite-(Y) | Y4Cu(CO3)4Cl(OH)5·2H2O | | | | | | V4 bending 694, 718 and 746; V2 bending 791, 815, 837 and 849;v3 antisymmetric stretching 1391, 1414, 1489, 1547; also OH stretching[8] | light blue | [9] |
| Ca3CO3(OH,Cl)4.H2O | | | | | | | | |
| Hanksite | Na22K(SO4)9(CO3)2Cl | hexagonal | P63/m | a = 10.46 Å c = 21.19 Å; Z = 2 | | | | | |
| iowaite | Mg6Fe2(Cl,(CO3)0.5)(OH)16·4H2O | | | | | | | | [10] |
| Kampfite | Ba12(Si11Al5)O31(CO3)8Cl5 | monoclinic | Cc | a = 31.2329, b=5.2398, c=9.0966β = 106.933° | | uniaxial (–), nω = 1.642 nε = 1.594 | | | [11] |
| Marialite | Na4(AlSi3O8)3(Cl2,CO3,SO4) | | | | | | | | |
| Mineevite-(Y) | Na25BaY2(CO3)11(HCO3)4(SO4)2F2Cl | | | | | | | | [12] |
| Northupite | Na3Mg(CO3)2Cl | octahedral | Fd3 | Z=16 | | 1.514 | v4 bending 714; v3 antisymmetric stretching 1554 | | [13] |
| Phosgenite | Pb2CO3Cl2 | tetragonal | | a=8.15 c=8.87 | | | | | [14] |
| Reederite-(Y) | Na15Y2(CO3)9(SO3F)Cl | | | | | | | | |
| Sakhaite (with Harkerite) | Ca48Mg16Al(SiO3OH)4(CO3)16(BO3)28·(H2O)3(HCl)3or Ca12Mg4(BO3)7(CO3)4Cl(OH)2·H2O | | | | | | | | |
| Scapolite | Ca3Na5[Al<sub>8</sub>Si<sub>16</sub>O<sub>48</sub>]Cl(CO3) | | P42/n | a=12.07899 c=7.583467 V=1106.443 | | | | | [15] |
| Tatarskite | Ca6Mg2(SO4)2(CO3)2(OH)4Cl4•7H2O | orthorhombic | | | | Biaxial (-) nα = 1.567 nβ = 1.654 nγ = 1.722 | | | [16] |
| Tunisite | NaCa2Al4(CO3)4Cl(OH)8 | tetragonal | P4/nmm | a=11.198 c=6.5637 Z=2 | | | | | |
| Vasilyevite | (Hg2)10O6I3Br2Cl(CO3) | | P1 overbar | a 9.344, b 10.653, c 18.265, α=93.262 β=90.548 γ=115.422° V=1638.3 Z=2 | 9.57 | | | | | |
Artificial
| name | formula | | crystal system | space group | unit cell in Å | density | comment | reference |
|---|
| K5Na2Cu24(CO3)16Cl3(OH)20•12H2O | | cubic | F23 | a=15.463 V=3697.5 Z=2 | 3.044 | dark blue | [17] |
| Y8O(OH)15(CO3)3Cl | 1197.88 | hexagonal | P63 | a=9.5089 c=14.6730 Z=2 V=1148.97 | 3.462 | | [18] |
| Lu8O(OH)15(CO3)3Cl | 1886.32 | hexagonal | P63 | a=9.354 c=14.415 V=1092.3 Z=2 | 5.689 | colourless | [19] |
| Y3(OH)6(CO3)Cl | | cubic | Im3m | a=12.66 V=2032 Z=8 | 3.035 | colourless | [20] |
| Dy3(OH)6(CO3)Cl | | cubic | Im | a=12.4754 V=1941.6 Z=8 | 4.687 | colourless | |
| Er3(OH)6(CO3)Cl | | cubic | Imm | a=12.4127 V=1912.5 Z=8 | 4.857 | pink | |
| K2[Ru<sub>2</sub>(CO<sub>3</sub>)<sub>4</sub>Cl<sub>2</sub>]·4H2O | 889.06 | monoclinic | P21/c | a=11.6399 b=11.7048 c=11.8493 β=119.060 V=1411.6 Z=2 | 2.092 | red-brown | [21] |
| K2[{Mg(H<sub>2</sub>O)<sub>4</sub>}2Ru<sub>2</sub>(CO<sub>3</sub>)<sub>4</sub>(H<sub>2</sub>O)Cl]Cl2·2H2O | 880.58 | orthorhombic | Fmm2 | a=14.392 b=15.699 c=10.741 V=2426.8 Z=4 | 2.391 | dark brown | |
| trisodium cobalt dicarbonate chloride | Na3Co(CO3)2Cl | | cubic | Fd | a=13.9959 Z=16 | 2.75 | spin-frustrated antiferromagnetic | [22] |
| trisodium manganese dicarbonate chloride | Na3Mn(CO3)2Cl | | cubic | | a=14.163 | | brown | [23] |
| di-magnesium hexahydrate trihydrogencarbonate chloride | Mg2(H2O)6(HCO3)3Cl | | | Rc | a=8.22215 c=39.5044 V=2312.85 Z=6 | 1.61 | decompose 125 °C | |
| tripotassium tricalcium selenite tricarbonate chloride | K3Ca3(SeO3)(CO3)3Cl | 579.97 | hexagonal | P63 | a=10.543 c=7.060 V=706.0 Z=2 | 2.991 | | [24] |
| LiBa9[Si<sub>10</sub>O<sub>25</sub>]Cl7(CO3) | | | | Z=2 | 3.85 | layer silicate | [25] [26] |
| Ba3Cl4CO3 | | orthorhombic | Pnma | a=8.407, b=9.589, c=12.483 Z=4 | | | [27] |
|
Complexes
The "lanthaballs" are lanthanoid atom clusters held together by carbonate and other ligands. They can form chlorides. Examples are [La<sub>13</sub>(ccnm)<sub>6</sub>(CO<sub>3</sub>)<sub>14</sub>(H<sub>2</sub>O)<sub>6</sub>(phen)<sub>18</sub>] Cl3(CO3)·25H2O where ccnm is carbamoylcyanonitrosomethanide and phen is 1,10-phenanthroline. Praseodymium (Pr) or cerium (Ce) can substitute for lanthanum (La).[28] Other lanthanide cluster compounds include :(H3O)6[Dy<sub>76</sub>O<sub>10</sub>(OH)<sub>138</sub>(OAc)<sub>20</sub>(L)<sub>44</sub>(H<sub>2</sub>O)<sub>34</sub>]•2CO3•4Cl2•L•2OAc (nicknamed Dy76) and (H3O)6[Dy<sub>48</sub>O<sub>6</sub>(OH)<sub>84</sub>(OAc)<sub>4</sub>(L)<sub>15</sub>(hmp)<sub>18</sub>(H<sub>2</sub>O)<sub>20</sub>]•CO3•14Cl•2H2O (termed Dy48-T) with OAc=acetate, and L=3-furancarboxylate and Hhmp=2,2-bis(hydroxymethyl)propionic acid.[29]
Platinum can form complexes with carbonate and chloride ligands, in addition to an amino acid. Examples include the platinum compound [Pt(gluH)Cl(CO<sub>3</sub>)]2.2H2O gluH=glutamic acid, and Na[Pt(gln)Cl<sub>2</sub>(CO<sub>3</sub>)].H2O gln=glutamine.[30] Rhodium complexes include Rh2(bipy)2(CO3)2Cl (bipy=bipyridine)[31]
Notes and References
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- Dinnebier. Robert E.. Jansen. Martin. 2008-12-01. The Crystal Structure of [Mg2(H2O)6(HCO3)3]+Cl–, Containing a Magnesium-based Hetero-polycation. Zeitschrift für Naturforschung B. 63. 12. 1347–1351. 10.1515/znb-2008-1201. 196866126. 1865-7117. free.
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