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Sulfidogermanates or thiogermanates are chemical compounds containing anions with sulfur atoms bound to germanium. They are in the class of chalcogenidotetrelates. Related compounds include thiosilicates, thiostannates, selenidogermanates, telluridogermanates and selenidostannates.

Coordination of sulfur around germanium is tetrahedral meaning there are four sulfur atoms symmetrically arranged. This basic structure can form ortho salts with GeS44−, oligomers, or polymeric structures.[1] Similar structures are also formed with heavy group 13 and group 14 elements due to their relatively stronger bonds with sulfur. Light elements from these groups have lower affinity for sulfur, so there are fewer compounds like this for boron, aluminium, carbon, and silicon.[1] Other heavy group 12 and 15 elements also form chalcogenidometallates which may have other kinds of coordination. Selenium forms similar compounds to sulfur in this family.[1]

Where sulfur is deficient, an anion is not formed, and instead cation-like covalent compounds can exist with halogens, such as Ge4S6Br4,[2] or Ge4S6I4.[3]

Production

The solvochemical method of production involves dissolving germanium oxide, sulfur and other salts in a heated solvent under pressure. The solvents can include simple alcohols, amines or N,N-dimethyl formamide. The containers can be glass tubes, quartz tubes, or teflon lined stainless steel.[1]

List

formula name system space group cell Å volume density comments ref
H4Ge4S10 thiogermanic acid triclinic P1 a = 8.621, b = 9.899, c = 10.009, α = 85.963°, β = 64.714°, γ = 89.501°, Z = 2 [4][5]
H2Ge4S9 thiogermanic acid [4]
Li2GeS3 hexagonal P61 a = 6.79364 c = 17.9072 [6]
[CH3NH3]4Ge2S6 tetrakis(methylammonium) bis(μ-sulfido)-tetrakis(sulfido)-di-germanium triclinic P1 a 7.3336 b 7.3760 c 10.0007, α 108.598° β 111.332° γ 90.297° [7]
[CH3CH2NH3]4Ge2S6•CH3CH2NH2 tetrakis(ethylammonium) bis(μ-sulfido)-tetrakis(sulfido)-di-germanium ethylamine orthorhombic Pnma a 7.8501 b 18.3444 c 17.4386 [7]
[CH3CH2NH3]3[CH3NH3]Ge4S10 tris(diethylammonium) methylammonium hexakis(μ-sulfido)-tris(sulfido)-tetra-germanium Pa3 a 17.9402 c 17.9402 [7]
(NH4)2[NH2(CH3)2]2Ge2S6 monoclinic P21/c a = 6.965, b = 15.7195, c = 7.2045, β = 92.765° band gap 3.50 eV [8]
(NH3NH2)2[(RNGe)2(μ-S)2S2] [9]
[(R1Ge)4(μ-S)6] R1 = CMe2CH2COMe [9][10]
(trenH2)2[Ge2S6] tren = tris(2-aminoethyl)amine monoclinic C2/c a=25.264 b=7.313 c=16.584 β=122.616 Z=4 2581 1.632 colourless [11]
(enH)4Ge2S6 en = ethylenediamine triclinic P1 a 7.859 b 9.514 c 9.727, α 64.21° β 66.80° γ 84.92° [12]
Na4Ge2S6 · 14H2O triclinic P1 a = 9.978, b = 7.202, c = 9.601, α = 108.41 β = 92.39, γ = 91.69° Z = 1 [13]
Na6Ge2S7 [14]
Li4MgGe2S7 monoclinic Cc a=16.872 b=6.771 c=10.156 β=95.169° SHG 0.7 ×AGS [15]
Na(AlS2)(GeS2)4 monoclinic P21/n a = 6.803, b = 38.207, c = 6.947, β = 119.17° [16]
Li10GeP2S12 tetragonal lithium ion conductor [17]
K6Ge2S7 [14]
[VO(dien)]2GeS4 orthorhombic Pna21 a =19.831, b = 8.0814, c = 12.0889, Z = 4 1937.4 [18]
{[V(en)2]2O}Ge2S6 en = ethylenediamine monoclinic P21/n a=8.352 b=12.682 c=11.339  β=94.75 Z=2 1196.9 1.931 black [19]
[VO(dap)2]2Ge2S6·dap dap = 1,2-diaminopropane hexagonal R2c ? a=38.284 c=11.170 Z=18 14178 1.619 purple; hexagonal nanotubes [19]
Li4MnGe2S7 monoclinic Cc a=16.833 b=6.709 c=10.121 β=94.76° Z=4 1139.1 2.637 light pink [15][20]
{[Mn(2,2′-bipy)2(H2O)]2Ge4S10}·3H2O bipy = bipyridine triclinic P1 a=10.6511 b=13.0443 c=22.995, α=79.539 β=77.653° γ=79.737° Z=2 3036.6 1.570 [21]
{Mn(tepa)}2(μ-Ge2Se6) tetragonal I41/a [22]
Mn2(en)4Ge2S6 en=ethylenediamine [23]
[Mn(en)3]2Ge2S6 monoclinic C2/c a 15.115 b 10.530 c 22.897, 118.777° [12]
Mn2(dap)4Ge2S6 dap = 1,2-diaminopropane [23]
H2dienMnGeS4 dien = diethylenetriamine [23]
[(dien)2Mn]Ge2S4 dien=diethylenetriamine orthorhombic P212121 a=9.113, b=12.475, c=17.077, Z=4 1941 1D [Ge2S4]2− chains [24]
Mn3Ge2S7(NH3)4 orthorhombic Pbcn a=9.107 b=13.923 c=12.750 Z=4 1616.6 2.476 green [25]
[MnII(tren)]2(μ2-Ge2S6) tren = N,N,N-tris(2-aminoethyl)amine triclinic P1 a 7.631 b 8.039 c 11.957, α 98.952° β 101.263° γ 109.696° [26]
[MnII(tepa)]2(μ2-Ge2S6) tepa= tetraethylenepentaamine orthorhombic I 41/a a =25.770 b =25.770 c =9.812 [26]
[Fe(2,2′-bipy)3]2[Ge4S10]·10H2O monoclinic P21/c a=23.8411 b=13.6462 c=22.9029 β=93.400° Z=4 7438.1 1.643 [21]
{Fe(tepa)}2(μ-Ge2Se6) tetragonal I41/a [22]
K2FeGe3S8 triclinic P1 a = 7.016, b= 7.770, c = 14.342, α = 93.80°, β = 92.65°, γ = 114.04° [27]
K2CoGe3S8 monoclinic P21 a = 7.1089, b = 11.8823, c = 16.759, β = 96.604° [27]
[{Co(tepa)}2(μ-Ge2S6)] tepa= tetraethylenepentaamine tetragonal I41/a [22]
[dienH2][Co(dien)2][Ge2S6] dien = diethylenetriamine triclinic P1 a 11.3224 b 14.6492 c 18.3710, α 71.000° β 78.352° γ 73.441° Z=4 2741.5 1.715 yellow [28]
[dienH2][Co(dien)2][Ge2S6] triclinic P1 a 11.3224 b 14.6492 c 18.3710, α 71.000° β 78.352° γ 73.441° Z=1 679.62 1.730 yellow [28]
[dienH2][Co(dien)2][Ge2S6] orthorhombic Pbca a=15.2110 b=16.7025 c=21.8821 Z=8 5559.4 1.692 yellow [28]
[dienH2][Co(dien)2][Ge2S6] orthorhombic Pca21 a=a=14.7043 b=9.0099 c=21.4540 Z=4 2842.3 1.655 yellow [28]
[Ni(cyclam)]3[Ni(cyclam)(H2O)2][Ge4S10]2·21H2O cyclam = 1,4,8,11-tetraazacyclotetradecane monoclinic Cc a=35.915 b=10.047 c=30.607 β =115.32 Z=4 9983 1.778 [21]
[Ni(en)3]2Ge2S6 en=ethylenediamine orthorhombic Pbca a 15.56 b 11.226 c 18.07 [12]
[Ni(dien)2]3[Ge3Sb8S21]·0.5H2O dien = diethylenetriamine [29]
[Ni(trien)2]2Ge4S10 bis(bis(triethylenetetramine)-nickel) hexakis(μ2-sulfido)-tetrasulfido-tetra-germanium monoclinic C2/c a =21.618 b =10.957 c =22.719, β=111.224° [30]
[{Ni(tepa)}2(μ-Ge2S6)] tetrakis(μ2-sulfido)-disulfido-bis(tetraethylenepentamine)-di-germanium-di-nickel orthorhombic Pbca a =15.151 b =13.083 c =15.255 [30]
[NiII(dien)2]2(Ge2S6) dien = diethylenetriamine monoclinic P 21/n a 10.093 b 14.219 c 11.703, β 91.631° [26]
[NiII(dien)2](H2pipe)(Ge2S6) pipe = piperazine triclinic P1 a 6.980 b 8.530 c 11.527, α 93.03° β 106.29° γ 101.95° [26]
[NiII(tepa)]2(μ2-Ge2S6) tepa = tetraethylenepentamine orthorhombic Pbca a =15.147 b =13.0552 c =15.238 [26]
[(CH3CH2)4N]3CuGe4S10 catena-[hexakis(tetraethylammonium) hexadecakis(μ-sulfido)-tetrakis(sulfido)-octa-germanium-di-copper] monoclinic P 21/n a 15.0956 b 14.2127 c =19.5889, β 91.131° [7]
[H4teta]5[Cu40Ge15S60]·2.5(teta) [31]
Cu(AlS2)(GeS2)4 monoclinic P21/n a 6.796 b 37.628 c 6.8797, β 119.52° [16]
Cu4MnGe2S7 monoclinic Cc a=16.7443 b=6.47893 c=9.8060 β=93.188° [15]
Cu4FeGe2S7 monoclinic C2 a=11.7405 b=5.3589 c=8.3420 β=98.661° [15]
Cu4CoGe2S7 monoclinic C2 a=11.7280 b=5.3399 c=8.3313 β=98.668° [15]
Cu4NiGe2S7 monoclinic C2 a=11.703 b=5.333 c=8.311 β=98.37° [15]
Sr2CoGe2OS6 tetrahedral P421m a=9.4056 c=6.1741 Z=2 546.19 3.574 dark green; oxysulfide [32]
Y3LiGeS7 [33]
[Y2(tepa)2(μ-OH)2(μ-Ge2S6)](tepa)0.5·H2O monoclinic C2/c a=19.638 b=14.415 c=16.910 β=122.47 Z=4 4038.6 1.863 colourless [11]
KYGeS4 [34]
[{RNGe(μ-S)3}4Pd6]·MeOH RN = CMe2CH2CMeNNH2 [9]
Ag10Ge3S11 monoclinic Cc a = 2.6244 b = 0.65020 c = 2.5083 β = 109.910° [35]
[(CH3CH2)4N]3AgGe4S10 catena-[hexakis(tetraethylammonium) hexadecakis(μ-sulfido)-tetrakis(sulfido)-di-silver-octa-germanium] monoclinic P 21/n a 15.1898 b 14.3043 c 19.5059, β 91.056° [7]
Ag(AlS2)(GeS2)4 monoclinic P21/n a 6.799 b 38.4169 c 6.813 β 119.65° [16]
Li4CdGe2S7 monoclinic Cc a=17.4432 b=6.9353 c=10.3271 β=93.9042° [15]
Na4CdGe2S7 monoclinic P21/c a=7.0813 b=11.9007 c=15.5759 β=90.791° [15]
Y3Cd0.5GeS7 [33]
Ag4SnGe2S7 monoclinic Cc a=11.3398 b=6.9706 c=15.4885 β=91.213° yellow; ∞[SnGe2S8]6– chains [15]
Na9Sb(Ge2S6)2 monoclinic C2/m a=7.5857 b=11.574 c=6.817 β=106.587 Z=1 573.7 2.905 yellow [36]
[Ge(en)3][GeSb2S6] orthorhombic Pbca [1]
[(Me)2NH2]6[Ge2Sb2S7][Ge4S10] triclinic P1 microporous, can exchange dimethyl ammonium for alkalis [28][37]
[dabcoH]2[Ge2Sb3S10] dabco = 1,4-diazabicyclo[2.2.2]octane [28]
DMAH[dabcoH]2[Ge2Sb3S10] dabco = 1,4-diazabicyclo[2.2.2]octane monoclinic C2 [1]
[DMAH]2GeSb3S6 P41212 [1]
[AEPH2][GeSb2S6]·CH3OH AEP = N-(2-aminoethyl)piperazine orthorhombic Pbca a=6.7183 b=18.3065 c=31.5007 Z=8 3874.2 2.303 yellow [28][38]
[CH3NH3]20Ge10Sb28S72·7H2O monoclinic C2/c a =29.2964 b=29.3261 c=41.601 β=100.084° [39]
[(CH3CH2CH2)2NH2]3Ge3Sb5S15·0.5(C2H5OH) triclinic P1 a=9.7628 b=15.7590 c=17.0313, α=79.868° β=75.010° γ=81.094° [39]
[Mn(en)3][GeSb2S6] dien = diethylenetriamine orthorhombic Pbca a=13.374 b=17.607 c=18.562 Z=8 4370.8 2.26 yellow [28][40]
[Co(en)3][GeSb2S6] orthorhombic Pbca
[Co(dien)2]2[GeSb4S10] dien = diethylenetriamine orthorhombic Pbca a=14.684 b=17.133 c=33.478 Z=8 8422 2.205 yellow [28][40]
[Ni(en)3][GeSb2S6] orthorhombic Pbca
[Ni(dien)2]3[Ge3Sb8S21]·0.5H2O monoclinic C2/m a =17.604 b =30.660 c =15.348 β =114.69° [28]
La(dien)2(μ–η1,η2-GeS3(SH)) monoclinic C2/c a=27.837 b=16.993 c=8.318 β =103.96 Z=8 3818.7 1.903 red [41]
KLaGeS4 monoclinic P21 a=6.6645 b=6.7079 c=8.7248 β=107.519° Z=2 371.95 SHG 1.2×AgGaS2; band gap 3.34 eV; birefringence 0.098 @ 1064 nm [34]
Nd(dien)2(μ–η1,η2-GeS3(SH)) monoclinic C2/c a=27.694 b=16.845 c=8.287 β =103.791 Z=8 3754.4 1.955 red [41]
[Pr(dien)3]2[Ge2S6]Cl2 dien = diethylenetriamine monoclinic P21/n a=11.637 b=14.143 c=15.120 β=98.149° Z=4 2463 1.765 green [42]
[Sm(dien)3]2[Ge2S6]Cl2 dien = diethylenetriamine monoclinic P21/n 11.532 b=14.423 c=14.573 β=97.105° Z=4 2405 1.834 light yellow [42]
Sm3Zn0.5GeS7 [33]
Eu3Ge3S9 a=8.468 b=11.76 c=8.389 α=90.49° β=104.56° γ=69.53° Z=2 4.22 meas [43]
[Eu(dien)3]2[Ge2S6]Cl2 dien = diethylenetriamine monoclinic P21/n a=11.567 b=14.633 c=14.465 β=96.434 Z=4 2432.9 1.818 yellow [11]
Gd3Cd0.5GeS7 [33]
[Gd(dien)3]2[Ge2S6]Cl2 dien = diethylenetriamine monoclinic P21/n 11.548 b=14.677 c=14.427 β=96.332° Z=4 2430.4 1.834 colourless [42]
[Dy(dien)3]2[Ge2S6]Cl2 dien = diethylenetriamine monoclinic P21/n a=11.503 b=14.645 c=14.340 β=96.178° Z=4 2401.8 1.870 light yellow [42]
[Ho(trien)(en)GeS3(SH)] trien = triethylenetetramine [42]
Er2(tepa)2(μ-OH)2(μ-Ge2S6)]n·nH2O tepa = tetraethylenepentamine [44]
[Er2(dien)4(μ-OH)2][Ge2S6] dien = diethylenetriamine monoclinic P21/n 11.710 b=11.318 c=13.548 β=97.635° Z=4 1779.6 2.088 red [42]
Tm2(tepa)2(μ-OH)2(μ-Ge2S6)]n·nH2O tepa = tetraethylenepentamine [44]
Li4HgGe2S7 monoclinic Cc a=16.876 b=6.7764 c=10.161 β=93.360° [15]
Ag4HgGe2S7 monoclinic Cc a=17.4546 b=6.8093 c=10.5342 β=93.3980° [15]
[(Me)2NH2][BiGeS4] monoclinic P21 a=6.7290 b c=10.6748 β=105.789 Z=2 479.72 3.156 red [45]

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