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.

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.[3]

nameformulacrystal systemspace groupunit celldensityOptics refractive indexRaman spectrumcommentsreference
AlexkhomyakoviteK6(Ca2Na)(CO3)5Cl∙6H2OhexagonalP63/mcma=9.2691, c=15.8419, V=1178.72 Z = 22.25uniaxial (–), ω=1.543, ε=1.476[4]
AshburtoniteHPb4Cu4(Si4O12)(HCO3)4(OH)4Cl[3]
Balliranoite(Na,K)6Ca2(Si6Al6O24)Cl2(CO3)hexagonalP63a=12.695 c=5.325 V=743.2 Z=12.48uniaxial (+), ω=1.523, ε=1.525[5]
BarstowitePb4(CO3)Cl6.H2O
ChlorartiniteMg2(CO3)Cl(OH).3H2O
Chlormagaluminite(Mg,Fe2+)4Al2(OH)12(Cl, 0.5 CO3)2·2H2O6/mmm1.98-2.09ε=1.560 ω=1.540[6]
Davynecan substitute CO3 for SO4[7]
Decrespignyite-(Y)Y4Cu(CO3)4Cl(OH)5·2H2OV4 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]
DeferniteCa3CO3(OH,Cl)4.H2O
HanksiteNa22K(SO4)9(CO3)2ClhexagonalP63/ma = 10.46 Å

c = 21.19 Å; Z = 2

iowaiteMg6Fe2(Cl,(CO3)0.5)(OH)16·4H2O[10]
KampfiteBa12(Si11Al5)O31(CO3)8Cl5monoclinicCca = 31.2329, b=5.2398, c=9.0966

β = 106.933°

uniaxial (–), nω = 1.642 nε = 1.594[11]
MarialiteNa4(AlSi3O8)3(Cl2,CO3,SO4)
Mineevite-(Y)Na25BaY2(CO3)11(HCO3)4(SO4)2F2Cl[12]
NorthupiteNa3Mg(CO3)2CloctahedralFd3Z=161.514v4 bending 714; v3 antisymmetric stretching 1554[8][13][14]
PhosgenitePb2CO3Cl2tetragonala=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]
ScapoliteCa3Na5[Al8Si16O48]Cl(CO3)P42/na=12.07899 c=7.583467 V=1106.443[15]
TatarskiteCa6Mg2(SO4)2(CO3)2(OH)4Cl4•7H2OorthorhombicBiaxial (-) nα = 1.567 nβ = 1.654 nγ = 1.722[16]
TunisiteNaCa2Al4(CO3)4Cl(OH)8tetragonalP4/nmma=11.198 c=6.5637 Z=2
Vasilyevite(Hg2)10O6I3Br2Cl(CO3)P1 overbara 9.344, b 10.653, c 18.265, α=93.262 β=90.548 γ=115.422° V=1638.3 Z=29.57

Artificial

nameformulacrystal systemspace groupunit cell in Ådensitycommentreference
K5Na2Cu24(CO3)16Cl3(OH)20•12H2OcubicF23a=15.463 V=3697.5 Z=23.044dark blue[17]
Y8O(OH)15(CO3)3Cl1197.88hexagonalP63a=9.5089 c=14.6730 Z=2 V=1148.973.462[18]
Lu8O(OH)15(CO3)3Cl1886.32hexagonalP63a=9.354 c=14.415 V=1092.3 Z=25.689colourless[19]
Y3(OH)6(CO3)ClcubicIm3ma=12.66 V=2032 Z=83.035colourless[20]
Dy3(OH)6(CO3)ClcubicIm3a=12.4754 V=1941.6 Z=84.687colourless[20]
Er3(OH)6(CO3)ClcubicIm3ma=12.4127 V=1912.5 Z=84.857pink[20]
K{Mg(H2O)6}2[Ru2(CO3)4Cl2]·4H2O889.06monoclinicP21/ca=11.6399 b=11.7048 c=11.8493 β=119.060 V=1411.6 Z=22.092red-brown[21]
K2[{Mg(H2O)4}2Ru2(CO3)4(H2O)Cl]Cl2·2H2O880.58orthorhombicFmm2a=14.392 b=15.699 c=10.741 V=2426.8 Z=42.391dark brown[21]
trisodium cobalt dicarbonate chlorideNa3Co(CO3)2ClcubicFd3a=13.9959 Z=162.75spin-frustrated antiferromagnetic[3][22]
trisodium manganese dicarbonate chlorideNa3Mn(CO3)2Clcubica=14.163brown[23]
di-magnesium hexahydrate trihydrogencarbonate chlorideMg2(H2O)6(HCO3)3ClR3ca=8.22215 c=39.5044 V=2312.85 Z=61.61decompose 125 °C[2]
tripotassium tricalcium selenite tricarbonate chlorideK3Ca3(SeO3)(CO3)3Cl579.97hexagonalP63a=10.543 c=7.060 V=706.0 Z=22.991[24]
LiBa9[Si10O25]Cl7(CO3)Z=23.85layer silicate[25][26]
Ba3Cl4CO3orthorhombicPnmaa=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•4Cl2•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]

References