Thiogermanate

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]