Carbonate chloride

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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.

Contents

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
Alexkhomyakovite K6(Ca2Na)(CO3)5Cl∙6H2OhexagonalP63/mcma=9.2691, c=15.8419, V=1178.72 Z = 22.25uniaxial (–), ω=1.543, ε=1.476 [4]
Ashburtonite HPb4Cu4(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]
Barstowite Pb4(CO3)Cl6.H2O
Chlorartinite Mg2(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]
Davyne can 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]
Defernite Ca3CO3(OH,Cl)4.H2O
Hanksite Na22K(SO4)9(CO3)2ClhexagonalP63/ma = 10.46 Å

c = 21.19 Å; Z = 2

iowaite Mg6Fe2(Cl,(CO3)0.5)(OH)16·4H2O [10]
Kampfite Ba12(Si11Al5)O31(CO3)8Cl5monoclinicCca = 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)2CloctahedralFd3Z=161.514v4 bending 714; v3 antisymmetric stretching 1554 [8] [13] [14]
Phosgenite Pb2CO3Cl2tetragonala=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/na=12.07899 c=7.583467 V=1106.443 [15]
Tatarskite Ca6Mg2(SO4)2(CO3)2(OH)4Cl4•7H2OorthorhombicBiaxial (-) nα = 1.567 nβ = 1.654 nγ = 1.722 [16]
Tunisite NaCa2Al4(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 system space group unit 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=162.75 spin-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•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]

References

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