Thiogermanate

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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.

Contents

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

formulanamesystemspace groupcell Åvolumedensitycommentsref
H4Ge4S10thiogermanic acidtriclinicP1a = 8.621, b = 9.899, c = 10.009, α = 85.963°, β = 64.714°, γ = 89.501°, Z = 2 [4] [5]
H2Ge4S9thiogermanic acid [4]
Li2GeS3hexagonalP61a = 6.79364 c = 17.9072 [6]
[CH3NH3]4Ge2S6tetrakis(methylammonium) bis(μ-sulfido)-tetrakis(sulfido)-di-germaniumtriclinicP1a 7.3336 b 7.3760 c 10.0007, α 108.598° β 111.332° γ 90.297° [7]
[CH3CH2NH3]4Ge2S6•CH3CH2NH2tetrakis(ethylammonium) bis(μ-sulfido)-tetrakis(sulfido)-di-germanium ethylamineorthorhombicPnmaa 7.8501 b 18.3444 c 17.4386 [7]
[CH3CH2NH3]3[CH3NH3]Ge4S10tris(diethylammonium) methylammonium hexakis(μ-sulfido)-tris(sulfido)-tetra-germaniumPa3a 17.9402 c 17.9402 [7]
(NH4)2[NH2(CH3)2]2Ge2S6monoclinicP21/ca = 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)aminemonoclinicC2/ca=25.264 b=7.313 c=16.584 β=122.616 Z=425811.632colourless [11]
(enH)4Ge2S6en = ethylenediaminetriclinicP1a 7.859 b 9.514 c 9.727, α 64.21° β 66.80° γ 84.92° [12]
Na4Ge2S6 · 14H2OtriclinicP1a = 9.978, b = 7.202, c = 9.601, α = 108.41 β = 92.39, γ = 91.69° Z = 1 [13]
Na6Ge2S7 [14]
Li4MgGe2S7monoclinicCca=16.872 b=6.771 c=10.156 β=95.169°SHG 0.7 ×AGS [15]
Na(AlS2)(GeS2)4monoclinicP21/na = 6.803, b = 38.207, c = 6.947, β = 119.17° [16]
Li10GeP2S12tetragonallithium ion conductor [17]
K6Ge2S7 [14]
[VO(dien)]2GeS4orthorhombicPna21a =19.831, b = 8.0814, c = 12.0889, Z = 41937.4 [18]
{[V(en)2]2O}Ge2S6en = ethylenediaminemonoclinicP21/na=8.352 b=12.682 c=11.339  β=94.75 Z=21196.91.931black [19]
[VO(dap)2]2Ge2S6·dapdap = 1,2-diaminopropanehexagonalR2c ?a=38.284 c=11.170 Z=18141781.619purple; hexagonal nanotubes [19]
Li4MnGe2S7monoclinicCca=16.833 b=6.709 c=10.121 β=94.76° Z=41139.12.637light pink [15] [20]
{[Mn(2,2′-bipy)2(H2O)]2Ge4S10}·3H2Obipy = bipyridinetriclinicP1a=10.6511 b=13.0443 c=22.995, α=79.539 β=77.653° γ=79.737° Z=23036.61.570 [21]
{Mn(tepa)}2(μ-Ge2Se6)tetragonalI41/a [22]
Mn2(en)4Ge2S6en=ethylenediamine [23]
[Mn(en)3]2Ge2S6monoclinicC2/ca 15.115 b 10.530 c 22.897, 118.777° [12]
Mn2(dap)4Ge2S6dap = 1,2-diaminopropane [23]
H2dienMnGeS4dien = diethylenetriamine [23]
[(dien)2Mn]Ge2S4dien=diethylenetriamineorthorhombicP212121a=9.113, b=12.475, c=17.077, Z=419411D [Ge2S4]2− chains [24]
Mn3Ge2S7(NH3)4orthorhombicPbcna=9.107 b=13.923 c=12.750 Z=41616.62.476green [25]
[MnII(tren)]2(μ2-Ge2S6)tren = N,N,N-tris(2-aminoethyl)aminetriclinicP1a 7.631 b 8.039 c 11.957, α 98.952° β 101.263° γ 109.696° [26]
[MnII(tepa)]2(μ2-Ge2S6)tepa= tetraethylenepentaamineorthorhombicI 41/aa =25.770 b =25.770 c =9.812 [26]
[Fe(2,2′-bipy)3]2[Ge4S10]·10H2OmonoclinicP21/ca=23.8411 b=13.6462 c=22.9029 β=93.400° Z=47438.11.643 [21]
{Fe(tepa)}2(μ-Ge2Se6)tetragonalI41/a [22]
K2FeGe3S8triclinicP1a = 7.016, b= 7.770, c = 14.342, α = 93.80°, β = 92.65°, γ = 114.04° [27]
K2CoGe3S8monoclinicP21a = 7.1089, b = 11.8823, c = 16.759, β = 96.604° [27]
[{Co(tepa)}2(μ-Ge2S6)]tepa= tetraethylenepentaaminetetragonalI41/a [22]
[dienH2][Co(dien)2][Ge2S6]dien = diethylenetriaminetriclinicP1a 11.3224 b 14.6492 c 18.3710, α 71.000° β 78.352° γ 73.441° Z=42741.51.715yellow [28]
[dienH2][Co(dien)2][Ge2S6]triclinicP1a 11.3224 b 14.6492 c 18.3710, α 71.000° β 78.352° γ 73.441° Z=1679.621.730yellow [28]
[dienH2][Co(dien)2][Ge2S6]orthorhombicPbcaa=15.2110 b=16.7025 c=21.8821 Z=85559.41.692yellow [28]
[dienH2][Co(dien)2][Ge2S6]orthorhombicPca21a=a=14.7043 b=9.0099 c=21.4540 Z=42842.31.655yellow [28]
[Ni(cyclam)]3[Ni(cyclam)(H2O)2][Ge4S10]2·21H2Ocyclam = 1,4,8,11-tetraazacyclotetradecanemonoclinicCca=35.915 b=10.047 c=30.607 β =115.32 Z=499831.778 [21]
[Ni(en)3]2Ge2S6en=ethylenediamineorthorhombicPbcaa 15.56 b 11.226 c 18.07 [12]
[Ni(dien)2]3[Ge3Sb8S21]·0.5H2Odien = diethylenetriamine [29]
[Ni(trien)2]2Ge4S10bis(bis(triethylenetetramine)-nickel) hexakis(μ2-sulfido)-tetrasulfido-tetra-germaniummonoclinicC2/ca =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-nickelorthorhombicPbcaa =15.151 b =13.083 c =15.255 [30]
[NiII(dien)2]2(Ge2S6)dien = diethylenetriaminemonoclinicP 21/na 10.093 b 14.219 c 11.703, β 91.631° [26]
[NiII(dien)2](H2pipe)(Ge2S6)pipe = piperazinetriclinicP1a 6.980 b 8.530 c 11.527, α 93.03° β 106.29° γ 101.95° [26]
[NiII(tepa)]2(μ2-Ge2S6)tepa = tetraethylenepentamineorthorhombicPbcaa =15.147 b =13.0552 c =15.238 [26]
[(CH3CH2)4N]3CuGe4S10catena-[hexakis(tetraethylammonium) hexadecakis(μ-sulfido)-tetrakis(sulfido)-octa-germanium-di-copper]monoclinicP 21/na 15.0956 b 14.2127 c =19.5889, β 91.131° [7]
[H4teta]5[Cu40Ge15S60]·2.5(teta) [31]
Cu(AlS2)(GeS2)4monoclinicP21/na 6.796 b 37.628 c 6.8797, β 119.52° [16]
Cu4MnGe2S7monoclinicCca=16.7443 b=6.47893 c=9.8060 β=93.188° [15]
Cu4FeGe2S7monoclinicC2a=11.7405 b=5.3589 c=8.3420 β=98.661° [15]
Cu4CoGe2S7monoclinicC2a=11.7280 b=5.3399 c=8.3313 β=98.668° [15]
Cu4NiGe2S7monoclinicC2a=11.703 b=5.333 c=8.311 β=98.37° [15]
Sr2CoGe2OS6tetrahedralP421ma=9.4056 c=6.1741 Z=2546.193.574dark green; oxysulfide [32]
Y3LiGeS7 [33]
[Y2(tepa)2(μ-OH)2(μ-Ge2S6)](tepa)0.5·H2OmonoclinicC2/ca=19.638 b=14.415 c=16.910 β=122.47 Z=44038.61.863colourless [11]
KYGeS4 [34]
[{RNGe(μ-S)3}4Pd6]·MeOHRN = CMe2CH2CMeNNH2 [9]
Ag10Ge3S11monoclinicCca = 2.6244 b = 0.65020 c = 2.5083 β = 109.910° [35]
[(CH3CH2)4N]3AgGe4S10catena-[hexakis(tetraethylammonium) hexadecakis(μ-sulfido)-tetrakis(sulfido)-di-silver-octa-germanium]monoclinicP 21/na 15.1898 b 14.3043 c 19.5059, β 91.056° [7]
Ag(AlS2)(GeS2)4monoclinicP21/na 6.799 b 38.4169 c 6.813 β 119.65° [16]
Li4CdGe2S7monoclinicCca=17.4432 b=6.9353 c=10.3271 β=93.9042° [15]
Na4CdGe2S7monoclinicP21/ca=7.0813 b=11.9007 c=15.5759 β=90.791° [15]
Y3Cd0.5GeS7 [33]
Ag4SnGe2S7monoclinicCca=11.3398 b=6.9706 c=15.4885 β=91.213°yellow; ∞[SnGe2S8]6– chains [15]
Na9Sb(Ge2S6)2monoclinicC2/ma=7.5857 b=11.574 c=6.817 β=106.587 Z=1573.72.905yellow [36]
[Ge(en)3][GeSb2S6]orthorhombicPbca [1]
[(Me)2NH2]6[Ge2Sb2S7][Ge4S10]triclinicP1microporous, 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]octanemonoclinicC2 [1]
[DMAH]2GeSb3S6P41212 [1]
[AEPH2][GeSb2S6]·CH3OHAEP = N-(2-aminoethyl)piperazineorthorhombicPbcaa=6.7183 b=18.3065 c=31.5007 Z=83874.22.303yellow [28] [38]
[CH3NH3]20Ge10Sb28S72·7H2OmonoclinicC2/ca =29.2964 b=29.3261 c=41.601 β=100.084° [39]
[(CH3CH2CH2)2NH2]3Ge3Sb5S15·0.5(C2H5OH)triclinicP1a=9.7628 b=15.7590 c=17.0313, α=79.868° β=75.010° γ=81.094° [39]
[Mn(en)3][GeSb2S6]dien = diethylenetriamineorthorhombicPbcaa=13.374 b=17.607 c=18.562 Z=84370.82.26yellow [28] [40]
[Co(en)3][GeSb2S6]orthorhombicPbca
[Co(dien)2]2[GeSb4S10]dien = diethylenetriamineorthorhombicPbcaa=14.684 b=17.133 c=33.478 Z=884222.205yellow [28] [40]
[Ni(en)3][GeSb2S6]orthorhombicPbca
[Ni(dien)2]3[Ge3Sb8S21]·0.5H2OmonoclinicC2/ma =17.604 b =30.660 c =15.348 β =114.69° [28]
La(dien)2(μ–η1,η2-GeS3(SH))monoclinicC2/ca=27.837 b=16.993 c=8.318 β =103.96 Z=83818.71.903red [41]
KLaGeS4monoclinicP21a=6.6645 b=6.7079 c=8.7248 β=107.519° Z=2371.95SHG 1.2×AgGaS2; band gap 3.34 eV; birefringence 0.098 @ 1064 nm [34]
Nd(dien)2(μ–η1,η2-GeS3(SH))monoclinicC2/ca=27.694 b=16.845 c=8.287 β =103.791 Z=83754.41.955red [41]
[Pr(dien)3]2[Ge2S6]Cl2dien = diethylenetriaminemonoclinicP21/na=11.637 b=14.143 c=15.120 β=98.149° Z=424631.765green [42]
[Sm(dien)3]2[Ge2S6]Cl2dien = diethylenetriaminemonoclinicP21/n11.532 b=14.423 c=14.573 β=97.105° Z=424051.834light yellow [42]
Sm3Zn0.5GeS7 [33]
Eu3Ge3S9a=8.468 b=11.76 c=8.389 α=90.49° β=104.56° γ=69.53° Z=24.22 meas [43]
[Eu(dien)3]2[Ge2S6]Cl2dien = diethylenetriaminemonoclinicP21/na=11.567 b=14.633 c=14.465 β=96.434 Z=42432.91.818yellow [11]
Gd3Cd0.5GeS7 [33]
[Gd(dien)3]2[Ge2S6]Cl2dien = diethylenetriaminemonoclinicP21/n11.548 b=14.677 c=14.427 β=96.332° Z=42430.41.834colourless [42]
[Dy(dien)3]2[Ge2S6]Cl2dien = diethylenetriaminemonoclinicP21/na=11.503 b=14.645 c=14.340 β=96.178° Z=42401.81.870light yellow [42]
[Ho(trien)(en)GeS3(SH)]trien = triethylenetetramine [42]
Er2(tepa)2(μ-OH)2(μ-Ge2S6)]n·nH2Otepa = tetraethylenepentamine [44]
[Er2(dien)4(μ-OH)2][Ge2S6]dien = diethylenetriaminemonoclinicP21/n11.710 b=11.318 c=13.548 β=97.635° Z=41779.62.088red [42]
Tm2(tepa)2(μ-OH)2(μ-Ge2S6)]n·nH2Otepa = tetraethylenepentamine [44]
Li4HgGe2S7monoclinicCca=16.876 b=6.7764 c=10.161 β=93.360° [15]
Ag4HgGe2S7monoclinicCca=17.4546 b=6.8093 c=10.5342 β=93.3980° [15]
[(Me)2NH2][BiGeS4]monoclinicP21a=6.7290 b c=10.6748 β=105.789 Z=2479.723.156red [45]

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References

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  2. ↑ Pohl, Siegfried (March 1976). "Ge4S6Br4—The First Sulfide Halide of Germanium". Angewandte Chemie International Edition in English. 15 (3): 162. doi:10.1002/anie.197601621.
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  5. ↑ Poling, Steven A.; Nelson, Carly R.; Sutherland, Jacob T.; Martin, Steve W. (2003-11-01). "Crystal Structure of Thiogermanic Acid H 4 Ge 4 S 10". Inorganic Chemistry. 42 (23): 7372–7374. doi:10.1021/ic034659s. ISSN   0020-1669. PMID   14606829.
  6. ↑ Roh, Jihun; Do, Namgyu; Manjón-Sanz, Alicia; Hong, Seung-Tae (2023-10-02). "Li 2 GeS 3 : Lithium Ionic Conductor with an Unprecedented Structural Type". Inorganic Chemistry. 62 (39): 15856–15863. doi:10.1021/acs.inorgchem.3c01431. ISSN   0020-1669.
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  8. ↑ Zhang, Jian-Han; Su, Zhi-Zhong; Luo, Ju-Xiang; Zhao, Yi; Wang, Hong-Gang; Ying, Shao-Ming (May 2020). "Synthesis, structure, and characterization of a mixed amines thiogermanate [NH4]2[NH2(CH3)2]2Ge2S6". Polyhedron. 182: 114486. doi:10.1016/j.poly.2020.114486. S2CID   216378118.
  9. 1 2 3 Halvagar, Mohammad Reza; Hassanzadeh Fard, Zohreh; Xiong, Lin; Dehnen, Stefanie (2009-08-03). "Facile Access to the Hydrazone Functionalized PdGeS Cluster [{R N Ge(μ-S) 3 } 4 Pd 6 ] from the Thiogermanate Anion [{R N Ge} 2 (μ-S) 2 S 2 ] 2−". Inorganic Chemistry. 48 (15): 7373–7377. doi:10.1021/ic900853e. ISSN   0020-1669. PMID   19586024.
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