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]

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]