Carbonate chloride

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 halocarbonates. In turn these halocarbonates are a part of mixed anion materials.

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.[3]

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 [4]
Ashburtonite HPb4Cu4(Si4O12)(HCO3)4(OH)4Cl [3]
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
Chlorartinite 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]
Defernite 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=9.0966

β = 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[8] [13][14]
Phosgenite Pb2CO3Cl2 tetragonal a=8.15 c=8.87 [13]
Reederite-(Y) Na15Y2(CO3)9(SO3F)Cl [12]
Sakhaite (with Harkerite) Ca48Mg16Al(SiO3OH)4(CO3)16(BO3)28·(H2O)3(HCl)3or Ca12Mg4(BO3)7(CO3)4Cl(OH)2·H2O [3]
Scapolite Ca3Na5[Al8Si16O48]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 Im3 a=12.4754 V=1941.6 Z=8 4.687 colourless [20]
Er3(OH)6(CO3)Cl cubic Im3m a=12.4127 V=1912.5 Z=8 4.857 pink [20]
K{Mg(H2O)6}2[Ru2(CO3)4Cl2]·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(H2O)4}2Ru2(CO3)4(H2O)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 [21]
trisodium cobalt dicarbonate chloride Na3Co(CO3)2Cl cubic Fd3 a=13.9959 Z=16 2.75 spin-frustrated antiferromagnetic [3][22]
trisodium manganese dicarbonate chloride Na3Mn(CO3)2Cl cubic a=14.163 brown [23]
di-magnesium hexahydrate trihydrogencarbonate chloride Mg2(H2O)6(HCO3)3Cl R3c a=8.22215 c=39.5044 V=2312.85 Z=6 1.61 decompose 125 °C [2]
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[Si10O25]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 [La13(ccnm)6(CO3)14(H2O)6(phen)18] 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[Dy76O10(OH)138(OAc)20(L)44(H2O)34]•2CO3•4 Cl2•L•2OAc (nicknamed Dy76) and (H3O)6[Dy48O6(OH)84(OAc)4(L)15(hmp)18(H2O)20]•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(CO3)]2.2H2O gluH=glutamic acid, and Na[Pt(gln)Cl2(CO3)].H2O gln=glutamine.[30] Rhodium complexes include Rh2(bipy)2(CO3)2Cl (bipy=bipyridine)[31]

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References
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