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]
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]
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] | |
[{RNGe(μ-S)3}4Pd6]·MeOH | RN = CMe2CH2CMeNNH2 | [9] | ||||||
Ag10Ge3S11 | monoclinic | Cc | a = 2.6244 b = 0.65020 c = 2.5083 β = 109.910° | [34] | ||||
[(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 | [35] | |
[Ge(en)3][GeSb2S6] | orthorhombic | Pbca | [1] | |||||
[(Me)2NH2]6[Ge2Sb2S7][Ge4S10] | triclinic | P1 | microporous, can exchange dimethyl ammonium for alkalis | [28] [36] | ||||
[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] [37] |
[CH3NH3]20Ge10Sb28S72·7H2O | monoclinic | C2/c | a =29.2964 b=29.3261 c=41.601 β=100.084° | [38] | ||||
[(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° | [38] | ||||
[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] [39] |
[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] [39] |
[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 | [40] | |
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 | [40] | |
[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 | [41] |
[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 | [41] |
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 | [42] | |||||
[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 | [41] |
[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 | [41] |
[Ho(trien)(en)GeS3(SH)] | trien = triethylenetetramine | [41] | ||||||
Er2(tepa)2(μ-OH)2(μ-Ge2S6)]n·nH2O | tepa = tetraethylenepentamine | [43] | ||||||
[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 | [41] |
Tm2(tepa)2(μ-OH)2(μ-Ge2S6)]n·nH2O | tepa = tetraethylenepentamine | [43] | ||||||
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 | [44] |
The borate fluorides or fluoroborates are compounds containing borate or complex borate ions along with fluoride ions that form salts with cations such as metals. They are in the broader category of mixed anion compounds. They are not to be confused with tetrafluoroborates (BF4) or the fluorooxoborates which have fluorine bonded to boron.
The borate carbonates are mixed anion compounds containing both borate and carbonate ions. Compared to mixed anion compounds containing halides, these are quite rare. They are hard to make, requiring higher temperatures, which are likely to decompose carbonate to carbon dioxide. The reason for the difficulty of formation is that when entering a crystal lattice, the anions have to be correctly located, and correctly oriented. They are also known as borocarbonates. Although these compounds have been termed carboborate, that word also refers to the C=B=C5− anion, or CB11H12− anion. This last anion should be called 1-carba-closo-dodecaborate or monocarba-closo-dodecaborate.
The selenide iodides are chemical compounds that contain both selenide ions (Se2−) and iodide ions (I−) and one or metal atoms. They are in the class of mixed anion compounds or chalcogenide halides.
The iodate fluorides are chemical compounds which contain both iodate and fluoride anions (IO3− and F−). In these compounds fluorine is not bound to iodine as it is in fluoroiodates.
The sulfate fluorides are double salts that contain both sulfate and fluoride anions. They are in the class of mixed anion compounds. Some of these minerals are deposited in fumaroles.
The borosulfates are heteropoly anion compounds which have sulfate groups attached to boron atoms. Other possible terms are sulfatoborates or boron-sulfur oxides. The ratio of sulfate to borate reflects the degree of condensation. With [B(SO4)4]5- there is no condensation, each ion stands alone. In [B(SO4)3]3- the anions are linked into a chain, a chain of loops, or as [B2(SO4)6]6− in a cycle. Finally in [B(SO4)2]− the sulfate and borate tetrahedra are all linked into a two or three-dimensional network. These arrangements of oxygen around boron and sulfur can have forms resembling silicates. The first borosulfate to be discovered was K5[B(SO4)4] in 2012. Over 75 unique compounds are known.
The borophosphates are mixed anion compounds containing borate and phosphate anions, which may be joined together by a common oxygen atom. Compounds that contain water or hydroxy groups can also be included in the class of compounds.
The boroselenites are heteropoly anion chemical compounds containing selenite and borate groups linked by common oxygen atoms. They are not to be confused with the boroselenates with have a higher oxidation state for selenium, and extra oxygen. If selenium is replaced by sulfur, it would be a borosulfite. Boroselenites are distinct from selenoborates in which selenium replaces oxygen in borate, or perselenoborates which contain Se-Se bonds as well as Se-B bonds. The metal boroselenites were only discovered in 2012.
Borate sulfides are chemical mixed anion compounds that contain any kind of borate and sulfide ions. They are distinct from thioborates in which sulfur atoms replace oxygen in borates. There are also analogous borate selenides, with selenium ions instead of sulfur.
The borate bromides are mixed anion compounds that contain borate and bromide anions. They are in the borate halide family of compounds which also includes borate fluorides, borate chlorides, and borate iodides.
The borate iodides are mixed anion compounds that contain both borate and iodide anions. They are in the borate halide family of compounds which also includes borate fluorides, borate chlorides, and borate bromides.
Fluoride nitrates are mixed anion compounds that contain both fluoride ions and nitrate ions. Compounds are known for some amino acids and for some heavy elements. Some transition metal fluorido complexes that are nitrates are also known. There are also fluorido nitrato complex ions known in solution.
Selenide borates, officially known as borate selenides, are chemical mixed anion compounds that contain any kind of borate and selenide ions. They are distinct from selenoborates in which selenium atoms replace oxygen in borates. There are also analogous borate sulfides, with sulfur ions instead of selenium.
Selenogallates are chemical compounds which contain anionic units of selenium connected to gallium. They can be considered as gallates where selenium substitutes for oxygen. Similar compounds include the thiogallates and selenostannates. They are in the category of chalcogenotrielates or more broadly chalcogenometallates.
Sulfidostannates, or thiostannates are chemical compounds containing anions composed of tin linked with sulfur. They can be considered as stannates with sulfur substituting for oxygen. Related compounds include the thiosilicates, and thiogermanates, and by varying the chalcogen: selenostannates, and tellurostannates. Oxothiostannates have oxygen in addition to sulfur. Thiostannates can be classed as chalcogenidometalates, thiometallates, chalcogenidotetrelates, thiotetrelates, and chalcogenidostannates. Tin is almost always in the +4 oxidation state in thiostannates, although a couple of mixed sulfides in the +2 state are known,
Arsenidosilicates are chemical compounds that contain anions with arsenic bonded to silicon. They are in the category of tetrelarsenides, pnictidosilicates, or tetrelpnictides. They can be classed as Zintl phases or intermetallics. They are analogous to the nitridosilicates, phosphidosilicates, arsenidogermanates, and arsenidostannates. They are distinct from arsenate silicates which have oxygen connected with arsenic and silicon, or arsenatosilicates with arsenate groups sharing oxygen with silicate.
Selenidogermanates are compounds with anions with selenium bound to germanium. They are analogous with germanates, thiogermanates, and telluridogermanates.
Iodate nitrates are mixed anion compounds that contain both iodate and nitrate anions.
Oxalate sulfates are mixed anion compounds containing oxalate and sulfate. They are mostly transparent, and any colour comes from the cations.
Tellurogermanates or telluridogermanates are compounds with anions with tellurium bound to germanium. They are analogous with germanates, thiogermanates and selenidogermanates.