Oxalate sulfates are mixed anion compounds containing oxalate and sulfate. They are mostly transparent, and any colour comes from the cations.

Related compounds include the sulfite oxalates[1] and oxalate selenates.[2]

Production

Oxalate sulfates may be deposited from a solution in water of the metal anions and sulfate with oxalic acid when evaporated. Crystals formed this way may be hydrates.[3]

Properties

Many crystal forms are non-centrosymmetric and have non-linear optical properties.[3]

When heated, oxalate sulfates will first dehydrate, and then give off carbon dioxide.[3]

List

name formula system space group unit cell Å volume density comment ref
lithium sulfate monohydrate oxalate ? triclinic P1 a = 3.4014 b = 5.0397 c = 6.120 α = 78.62° β= 84.95°

γ = 81.14°

101.45 band gap 4.57 eV

dielectric constant 29.7 stable below 83°C piezoelectric coefficient 6pC/N

 [3]
homopiperazinium dimagnesium dioxalate sulfate dihydrate C5H14N2•Mg2•[C2O4]2•SO4•2H2O monoclinic Ia a=11.5673 b=27.3352 c=16.6097 β=95.255° Z=12 5229.8 1.749 colourless [4]
piperazinium magnesium oxalate sulfate hydrate C4H12N2•Mg•[C2O4]•SO4•H2O monoclinic P21/c a=12.7330 b=8.9240 c=11.8172 β=115.502° Z=4 1211.95 1.724 colourless [4]
potassium sulphato oxalate ? triclinic a = 6.37 b = 7.03 c = 10.61 α = 93.96 ̊ β = 101.37 ̊ γ = 100.1 ̊ colourless > 300nm; SHG 1.6×KDP [5]
bapp = 1,4-bis(3-aminopropyl)piperazine (H4bapp)0.5·VO(SO4)(C2O4) triclinic P1 a=6.2031 b=8.6599 c=12.1853 α=77.130° β=76.207° γ=82.987° [6]
bipy=4,4′-bipyridine; (μ2-Oxalato-O,O',O'',O''')-tetrakis(2,2'-bipyridine)-di-chromium(iii) disulfate 2,2'-bipyridine solvate monohydrate [Cr2(bipy)4(C2O4)](SO4)·(bipy)0.5·H2O triclinic P1 a=11.610 b=12.668 c=17.155 α=77.297° β=83.957° γ=85.458° [7]
depa = 3-(diethylamino)propylamine H2depa⋅Mn2(SO4)(C2O4)2(H2O)⋅H2O orthorhombic Pbca a=14.6293 b=15.6671 c=17.3579 [6]
hpip = homopiperazine H2hpip·Mn2(SO4)(C2O4)2(H2O) orthorhombic P212121 a=9.9066 b=12.4496 c=13.6640 [8]
pip = piperazine; piperazinediium (μ-oxalato)-bis(μ-sulfato)-diaqua-di-manganese(ii) dihydrate H2pip·Mn2(SO4)2(C2O4)(H2O)4 triclinic P1 a 6.6501(4)Å b 7.7034(4)Å c 9.6810(5)Å, α 69.850(4)° β 70.553(5)° γ 83.921(4)° [9]
ipa = 3,3′-iminobis(N,N-dimethylpropylamine) bis(3-dimethylammoniopropyl)ammonium pentakis(μ-oxalato)-bis(μ-sulfato)-tetra-manganese(ii) dihydrate H3ipa⋅Mn2(SO4)(C2O4)2.5·H2O triclinic P1 a 9.9379(6)Å b 11.2423(6)Å c 11.6390(7)Å, α 86.793(5)° β 81.644(5)° γ 74.481(5)° [9]
dpta = dipropylenetriamine; bis(3-ammoniopropyl)ammonium tris(μ-oxalato)-bis(μ-sulfato)-bis(sulfato)-hexa-aqua-tetra-manganese(ii) H3dpta⋅Mn2(SO4)2(C2O4)1.5(H2O)3 triclinic P1 a 8.6819(3)Å b 10.1689(3)Å c 13.7456(5)Å, α 70.197(3)° β 73.406(3)° γ 87.636(3)° [9]
dmen = N,N-dimethylethylenediamine H2dmen·Mn(SO4)(C2O4) monoclinic P21/n a=9.8603 b=12.6525 c=10.0837 β=113.002° [10]
bis(N,N-dimethylpropane-1,3-diaminium) bis(μ-oxalato)-bis(μ-sulfato)-di-manganese triclinic P1 a=8.5307 b=9.0432 c=9.6913 α=69.632° β=64.639° γ=88.148° [11]
butane-1,4-diaminium bis(μ-oxalato)-(μ-sulfato)-aqua-di-manganese triclinic P1 a=8.5468 b=10.0050 c=10.6532 α=75.445° β=79.787° γ=71.848° [11]
Na2Fe(C2O4)SO4⋅H2O orange; most air sensitive [12]
(μ-oxalato)-(μ-sulfato)-iron-di-potassium K2[Fe(C2O4)(SO4)] monoclinic P21/c a=5.8735 b=10.2169 c=13.1491 β=91.226° [13]
tris(μ-oxalato)-bis(μ-sulfato)-tri-iron-tetra-potassium K4[Fe3(C2O4)3(SO4)2] monoclinic P21/c a 13.739 b 5.496 c 12.774 β 97.677° [13]
acid oxalo-bisulfate of roseocobalt ?? Co2(HN3)10(C2O4)(SO4)2 ·H2O·H2C2O4 speculative [14]
[Co(NH3)4(C2O4)]2SO4·2H2O [15]
[Co(NH3)4(C2O4)]2S2O6 [15]
tris(μ-aqua)-tris(μ-oxalato)-tris(μ-sulfato)-tri-cobalt-hexa-sodium Na2[Co(C2O4)(SO4)]·H2O hexagonal P62m a=10.2322 c=6.4774 [13]
tris(μ-oxalato)-bis(μ-sulfato)-bis(2-((2-aminoethyl)amino)ethanaminium)-tetraaqua-tetra-cobalt triclinic P1 a=8.6065 b=9.5595 c=9.5987 α=77.884° β=82.744° γ=87.356° [16]
bis(μ-oxalato)-bis(μ-sulfato)-bis(4-(2-aminoethyl)piperazin-1-ium)-tri-cobalt triclinic P1 a=8.4331 b=9.4691 c=9.5144 α=71.522° β=64.356° γ=89.622° [16]
1,4-dimethylpiperazinedi-ium bis(μ-oxalato)-hepta-aqua-tri-cobalt bis(sulfate) (H2dmp)(SO4)3Co3(C2O4)2(H2O)7 orthorhombic Pnma a=11.1050 b=16.4221 c=13.9815 violet [17]
Bis[tris(oxamide dioxime-2N,N')cobalt(III)] oxalate bis(sulfate) dodecahydrate [Co(C2H6N4O2)3]2(C2O4)(SO4)212H2O triclinic P1 a = 9.430 b = 11.782 c = 12.812 α = 65.494° β = 83.088° γ = 86.735° Z=1 1285.7 1.698 at 193K; red [18]
homopiperazinium dizinc dioxalate sulfate hydrate C5H14N2•Zn2•[C2O4]2•SO4•H2O monoclinic P21 a=15.8356 b=13.5022 c=15.9578 β=109.075° Z=8 3224.7 2.154 colourless [4]
homopiperazinium dizinc dioxalate sulfate dihydrate C5H14N2•Zn2•[C2O4]2•SO4•2H2O monoclinic Ia a=11.5681 b=27.1755 c=16.5979 β=94.946° Z=12 5198.4 2.074 colourless [4]
bis(4-(2-aminoethyl)piperazin-1-ium)-bis(μ-oxalato)-bis(μ-sulfato)-tri-zinc triclinic P1 a=8.407 b=9.523 c=9.543 α=108.39° β=115.52° γ=90.17° [11]
1,4-dimethylpiperazinedi-ium bis(sulfate) bis(μ-oxalato)-hepta-aqua-tri-zinc (H2dmp)(SO4)3Zn3(C2O4)2(H2O)7 orthorhombic Pnma a 11.1058 b 16.3449 c 14.0064 colourless [17]
(Hgly)2·Zn(SO4)(C2O4) monoclinic C2 a 19.1509 b 5.4000 c 12.8206 β 102.878° [19]
RbFe(SO4)(C2O4)0.5·H2O monoclinic P21/c a = 7.9193, b = 9.4907, c = 8.8090, β = 95.180°, Z = 4 [20]
bis(μ3-sulfato)-bis(μ2-oxalato)-diaqua-di-yttrium diammonium [NH4][Y(H2O)(SO4)(C2O4)] monoclinic P21/n a=6.534 b=8.527 c=13.745 β=92.87° [21]
bis(μ3-Sulfato-O,O,O',O'',O''')-(μ2-oxalato-O,O',O'',O''')-(μ2-piperazine-diium-1,4-diacetato-O,O')-diaqua-di-yttrium(iii) Y2(H2pda)(C2O4)(SO4)2(H2O)2] monoclinic C2/c a 19.392 b 6.2757 c 16.999 β 108.279° [22]
levinsonite-(Y) (Y,Nd,Ce)Al(SO4)2(C2O4) · 12H2O monoclinic P2/n a = 10.289 Å, b = 9.234, c = 11.015

β = 108.50°

 992.4 2.181 Biaxial (+) Refractive index:

nα = 1.480 nβ = 1.490 nγ = 1.550

 [23][24]
thfa = tetrahydrofurfurylamine; bis(tetrahydrofurfurylammonium) tris(μ-oxalato)-(μ-sulfato)-di-indium(iii) dihydrate (Hthfa)2·In2(SO4)(C2O4)3·2H2O monoclinic P21/c a=10.7581 b=12.9985 c=19.9093 β=92.876° [8]
bapp = N,N′-bis(3-aminopropyl)piperazine H4bapp·[In2(SO4)3(C2O4)2(H2O)2]·H2O monoclinic I2/a a=13.8931 b=14.6792 c=15.2418 β=111.153° [10]
bis(1-ethylpiperazinedi-ium) tris(μ-oxalato)-bis(sulfato)-di-indium H2epip·[In2(SO4)2(C2O4)3] tetragonal I41/a a=26.0767 c=8.9467 colourless [17]
Piperazinediium bis(μ2-oxalato-O,O',O'',O''')-bis(μ2-sulfato-O,O')-diaqua-di-indium dihydrate [C4N2H12]0.5InSO4C2O4·2H2O monoclinic P21/c a=6.478 b=11.067 c=14.317 β=100.302° [25]
Hgly·In(SO4)(C2O4)(gly) monoclinic P21 a 6.5179(2)Å b 10.9928(3)Å c 18.0301(6)Å, α 90° β 93.9700(10)° [19]
CsMn(SO4)(C2O4)0.5·H2O monoclinic P21/c a = 8.065, b = 9.610, c = 9.219, β = 94.564°, Z = 4 [20]
CsFe(SO4)(C2O4)0.5·H2O monoclinic P21/c a = 7.9377, b = 9.5757, c = 9.1474, β = 96.104°, Z = 4 [20]
La2(C2O4)(SO4)2(H2O)3 monoclinic P21/n a=9.838 b=9.817 c=13.111 β=104.258° [26]
bis(μ3-sulfato)-bis(μ2-oxalato)-diaqua-di-lanthanum diammonium [NH4][La(H2O)(SO4)(C2O4)] monoclinic P21/n a=6.629 b=8.673 c=13.867 β=93.35° [21]
(μ4-Piperazine-diium-1,4-diacetato-O,O',O'',O''')-bis(μ3-sulfato-O,O',O'')-(μ2-oxalato-O,O',O'',O''')-diaqua-di-cerium(iii) dihydrate Ce2(H2pda)(C2O4)(SO4)2(H2O)2 · 2H2O monoclinic C2/c a 19.353 b 6.836 c 16.400 β 94.312° [22]
coskrenite-(Ce) (Ce,Nd,La)2(C2O4)(SO4)2 · 12H2O triclinic a = 6.007(1) Å, b = 8.368(2) Å, c = 9.189(2) Å

α = 99.90(2)°, β = 105.55(2)°, γ = 107.71(2)°

 2.881 Biaxial (-) refractive indices: nα = 1.544 nβ = 1.578 nγ = 1.602; Birefringence: δ = 0.058 [27][28]
zugshunstite-(Ce) (Ce,Nd,La)Al(SO4)2(C2O4) · 12H2O Monoclinic C2/c a = 8.718 b = 18.313 c = 13.128

β = 93.90°

 2091 2.121 Large REE; pink in incandescent light; blue in fluorescent light; Biaxial (+) refractive index: nα = 1.455 nβ = 1.485 nγ = 1.528; [29][24]
(μ4-Piperazine-diium-1,4-diacetato-O,O',O'',O''')-bis(μ3-sulfato-O,O',O'')-(μ2-oxalato-O,O',O'',O''')-diaqua-di-praseodymium(iii) dihydrate Pr2(H2pda)(C2O4)(SO4)2(H2O)2 · 2H2O monoclinic C2/c a 19.295 b 6.8100 c 16.377 β 94.369° [22]
heptakis(μ-oxalato)-bis(μ-sulfato)-tetradecaaqua-hexa-neodymium dihydrate Nd6(SO4)2(C2O4)7(H2O)14·H2O triclinic P1 a=6.0817 b=11.8807 c=16.0749 α=73.230° β=80.873° γ=88.976° [30]
N,N'-dimethylethane-1,2-diaminium tetrakis(μ-sulfato)-tris(μ-oxalato)-octaaqua-tetra-neodymium [C4H14N2]·Nd4(SO4)4(C2O4)3(H2O)8 triclinic P1 a=7.0649 b=11.2771 c=11.8318 α=67.370° β=80.035° γ=82.821° [30]
bis(μ3-Sulfato-O,O,O',O'',O''')-(μ2-oxalato-O,O',O'',O''')-(μ2-piperazine-diium-1,4-diacetato-O,O')-diaqua-di-neodymium(iii) Nd2(H2pda)(C2O4)(SO4)2(H2O)2] monoclinic C2/c a=19.702 b=6.348 c=17.352 β=109.973° [22]
bis(1,4-Diazoniabicyclo[2.2.2]octane) tetrakis(μ2-oxalato-O,O',O'',O''')-tetrakis(μ2-sulfato-O,O',O'')-octa-aqua-tetra-neodymium(iii) dihydrate [C6N2H14][Nd2(C2O4)2(SO4)2(H2O)4]·H2O monoclinic P21/c a=8.523 b=28.628 c=9.306 β=96.497° [31]
(μ4-Piperazine-diium-1,4-diacetato-O,O',O'',O''')-bis(μ3-sulfato-O,O',O'')-(μ2-oxalato-O,O',O'',O''')-diaqua-di-europium(iii) dihydrate Eu2(H2pda)(C2O4)(SO4)2(H2O)2 · 2H2O monoclinic C2/c a=19.143 b=6.722 c=16.323 β=94.58° [22]
(μ5-Oxalato)-(μ3-sulfato)-(μ2-aqua)-aqua-europium-silver AgEu(μ5-C2O4)(SO4)(H2O)2 monoclinic P21/c a=6.627 b=13.848 c=8.983 β=96.985° [32]
tetrakis(μ2-oxalato)-bis(μ2-sulfato)-dodeca-aqua-tetra-erbium monohydrate Er4(SO4)2(C2O4)4(H2O)12·H2O monoclinic P21/c a=10.5598 b=12.8404 c=12.0835 β=93.327° [30]
bis(μ3-sulfato)-bis(μ2-oxalato)-diaqua-di-samarium diammonium [NH4][Sm(H2O)(SO4)(C2O4)] monoclinic P21/n a=6.619 b=8.660 c=13.853 β=93.30° [21]
(μ5-Oxalato)-(μ3-sulfato)-(μ2-aqua)-aqua-samarium-silver AgSm(μ5-C2O4)(SO4)(H2O)2 monoclinic P21/c a=6.630 b=13.829 c=9.001 β=97.128° [32]
(NH4)[Gd(C2O4)(SO4)(H2O)] large magnetocaloric effect [33]
K[Gd(C2O4)(SO4)(H2O)] monoclinic P21/c a = 6.5849 b = 8.5660 c = 14.7660(2) Å, β = 112.470° Z=4 769.66 3.439 colourless [34]
potassium aquaterbium(III) oxalate sulfate KTb(C2O4)(SO4)(H2O) monoclinic a = 6.527 b = 8.507 c = 14.591 β = 112.65° Z=4 747.7 at 113K; colourless [35]
(μ6-Oxalato)-(μ4-oxalato)-bis(μ3-sulfato)-diaqua-di-silver-di-terbium AgTb(μ4-C2O4)0.5(μ6-C2O4)0.5(SO4)(H2O) monoclinic C2/m a=13.693 b=6.889 c=9.0885 β=116.73° [32]
(μ6-Oxalato)-(μ4-oxalato)-bis(μ3-sulfato)-diaqua-di-dysprosium-di-silver AgDy(μ4-C2O4)0.5(μ6-C2O4)0.5(SO4)(H2O) monoclinic C2/m a=13.683 b=6.881 c=9.080 β=116.731° [32]
bis(1-ethyl-3-methyl-1H-imidazol-3-ium) (μ-oxalato)-bis(μ-sulfato)-tetraoxo-di-uranium monohydrate monoclinic P21/c a=11.579 b=17.312 c=13.694 β=108.178° yellow [36]
(NH4)4[(UO2)2(C2O4)(SO4)2(NCS)2]⋅6H2O orthorhombic Pbam a = 12.0177 b = 18.6182 c = 6.757 Z=2 [37]
Tetrapotassium bis(μ2-oxalato)-tetraoxo-bis(sulfato)-di-uranium(vi) hexahydrate K2[UO2(C2O4)SO4] · 3H2O triclinic P1 a=5.743 b=9.544 c=11.845 α=89.49° β=84.95° γ=83.01° [38]
K4[(UO2)2C2O4(SO4)2(NCS)2] orthorhombic Pbam a = 11.5548 b = 7.0847 c = 13.5172 β = 93.130° Z=2 1104.90 [39]
Di-rubidium dioxo-(oxalato-O,O')-(μ3-sulfato)-uranium monohydrate Rb2[UO2SO4(C2O4)] · H2O orthorhombic Pna21 a=9.720 b=17.037 c=6.852 [38][40]
Rb4[(UO2)2C2O4(SO4)2(NCS)2] orthorhombic Pbam a = 11.5854 b = 7.3841 c = 13.9072 β = 95.754 V = Z=2 1183.7 [39]
Cs4[(UO2)2(C2O4)(SO4)2(NCS)2] · 4H2O orthorhombic Pbam a = 11.6539 b = 18.379 c = 6.7216 Z=2 [37]
Tetracesium dioxo-bis(oxalato-O,O')-(sulfato-O)-uranium(vi) hydrate Cs4[UO2(C2O4)2SO4] · 2.7H2O orthorhombic Pbca a=9.546 b=21.119 c=21.499 [38]

References

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  28. ↑ Alpers, Charles N.; Jambor, John L.; Nordstrom, D. (17 December 2018). Sulfate Minerals: Crystallography, Geochemistry, and Environmental Significance. Walter de Gruyter GmbH & Co KG. pp. 89–90. ISBN 978-1-5015-0866-0.
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  31. ↑ Xu, Ning; Xing, Yan; Liu, Xianchun; Song, Danhui; Ma, Ling; Sun, Xiujuan (March 2009). "Synthesis, Structure and Photoluminescent Properties of [C 6 N 2 H 14 ][Nd 2 (C 2 O 4 ) 2 (SO 4 ) 2 (H 2 O) 4 ]·H 2 O, a New Organically Templated Neodymium(III) Oxalate-sulfate". Zeitschrift für anorganische und allgemeine Chemie. 635 (3): 558–562. doi:10.1002/zaac.200801309.
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