Thiogermanate
Class of chemical compounds
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 GeS4 4− , 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 Ge4 S6 Br4 ,[ 2] or Ge4 S6 I4 .[ 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
H4 Ge4 S10
thiogermanic acid
triclinic
P 1
a = 8.621, b = 9.899, c = 10.009, α = 85.963°, β = 64.714°, γ = 89.501°, Z = 2
[ 4] [ 5]
H2 Ge4 S9
thiogermanic acid
[ 4]
Li2 GeS3
hexagonal
P 61
a = 6.79364 c = 17.9072
[ 6]
[CH3 NH3 ]4 Ge2 S6
tetrakis(methylammonium) bis(μ-sulfido)-tetrakis(sulfido)-di-germanium
triclinic
P 1
a 7.3336 b 7.3760 c 10.0007, α 108.598° β 111.332° γ 90.297°
[ 7]
[CH3 CH2 NH3 ]4 Ge2 S6 •CH3 CH2 NH2
tetrakis(ethylammonium) bis(μ-sulfido)-tetrakis(sulfido)-di-germanium ethylamine
orthorhombic
Pnma
a 7.8501 b 18.3444 c 17.4386
[ 7]
[CH3 CH2 NH3 ]3 [CH3 NH3 ]Ge4 S10
tris(diethylammonium) methylammonium hexakis(μ-sulfido)-tris(sulfido)-tetra-germanium
Pa 3
a 17.9402 c 17.9402
[ 7]
(NH4 )2 [NH2 (CH3 )2 ]2 Ge2 S6
monoclinic
P 21 /c
a = 6.965, b = 15.7195, c = 7.2045, β = 92.765°
band gap 3.50 eV
[ 8]
(NH3 NH2 )2 [(RN Ge)2 (μ-S)2 S2 ]
[ 9]
[(R1 Ge)4 (μ-S)6 ]
R1 = CMe2 CH2 COMe
[ 9] [ 10]
(trenH2 )2 [Ge2 S6 ]
tren = tris(2-aminoethyl)amine
monoclinic
C 2/c
a=25.264 b=7.313 c=16.584 β=122.616 Z=4
2581
1.632
colourless
[ 11]
(enH)4 Ge2 S6
en = ethylenediamine
triclinic
P 1
a 7.859 b 9.514 c 9.727, α 64.21° β 66.80° γ 84.92°
[ 12]
Na4 Ge2 S6 · 14H2 O
triclinic
P 1
a = 9.978, b = 7.202, c = 9.601, α = 108.41 β = 92.39, γ = 91.69° Z = 1
[ 13]
Na6 Ge2 S7
[ 14]
Li4 MgGe2 S7
monoclinic
Cc
a=16.872 b=6.771 c=10.156 β=95.169°
SHG 0.7 ×AGS
[ 15]
Na(AlS2 )(GeS2 )4
monoclinic
P 21 /n
a = 6.803, b = 38.207, c = 6.947, β = 119.17°
[ 16]
Li10 GeP2 S12
tetragonal
lithium ion conductor
[ 17]
K6 Ge2 S7
[ 14]
[VO(dien)]2 GeS4
orthorhombic
Pna 21
a =19.831, b = 8.0814, c = 12.0889, Z = 4
1937.4
[ 18]
{[V(en)2 ]2 O}Ge2 S6
en = ethylenediamine
monoclinic
P 21 /n
a=8.352 b=12.682 c=11.339 β=94.75 Z=2
1196.9
1.931
black
[ 19]
[VO(dap)2 ]2 Ge2 S6 ·dap
dap = 1,2-diaminopropane
hexagonal
R 2 c ?
a=38.284 c=11.170 Z=18
14178
1.619
purple; hexagonal nanotubes
[ 19]
Li4 MnGe2 S7
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 (H2 O)]2 Ge4 S10 }· 3H2 O
bipy = bipyridine
triclinic
P 1
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-Ge2 Se6 )
tetragonal
I 41 /a
[ 22]
Mn2 (en)4 Ge2 S6
en=ethylenediamine
[ 23]
[Mn(en)3 ]2 Ge2 S6
monoclinic
C 2/c
a 15.115 b 10.530 c 22.897, 118.777°
[ 12]
Mn2 (dap)4 Ge2 S6
dap = 1,2-diaminopropane
[ 23]
H2 dienMnGeS4
dien = diethylenetriamine
[ 23]
[(dien)2 Mn]Ge2 S4
dien=diethylenetriamine
orthorhombic
P 21 21 21
a =9.113, b =12.475, c =17.077, Z =4
1941
1D [Ge2 S4 ]2− chains
[ 24]
Mn3 Ge2 S7 (NH3 )4
orthorhombic
Pbcn
a=9.107 b=13.923 c=12.750 Z=4
1616.6
2.476
green
[ 25]
[MnII (tren)]2 (μ 2 -Ge2 S6 )
tren = N,N,N-tris(2-aminoethyl)amine
triclinic
P 1
a 7.631 b 8.039 c 11.957, α 98.952° β 101.263° γ 109.696°
[ 26]
[MnII (tepa)]2 (μ 2 -Ge2 S6 )
tepa= tetraethylenepentaamine
orthorhombic
I 41 /a
a =25.770 b =25.770 c =9.812
[ 26]
[Fe(2,2′-bipy)3 ]2 [Ge4 S10 ]· 10H2 O
monoclinic
P 21 /c
a=23.8411 b=13.6462 c=22.9029 β =93.400° Z=4
7438.1
1.643
[ 21]
{Fe(tepa)}2 (μ-Ge2 Se6 )
tetragonal
I 41 /a
[ 22]
K2 FeGe3 S8
triclinic
P 1
a = 7.016, b= 7.770, c = 14.342, α = 93.80°, β = 92.65°, γ = 114.04°
[ 27]
K2 CoGe3 S8
monoclinic
P 21
a = 7.1089, b = 11.8823, c = 16.759, β = 96.604°
[ 27]
[{Co(tepa)}2 (μ-Ge2 S6 )]
tepa= tetraethylenepentaamine
tetragonal
I 41 /a
[ 22]
[dienH2 ][Co(dien)2 ][Ge2 S6 ]
dien = diethylenetriamine
triclinic
P 1
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 ][Ge2 S6 ]
triclinic
P 1
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 ][Ge2 S6 ]
orthorhombic
Pbca
a=15.2110 b=16.7025 c=21.8821 Z=8
5559.4
1.692
yellow
[ 28]
[dienH2 ][Co(dien)2 ][Ge2 S6 ]
orthorhombic
Pca 21
a=a=14.7043 b=9.0099 c=21.4540 Z=4
2842.3
1.655
yellow
[ 28]
[Ni(cyclam)]3 [Ni(cyclam)(H2 O)2 ][Ge4 S10 ]2 · 21H2 O
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 ]2 Ge2 S6
en=ethylenediamine
orthorhombic
Pbca
a 15.56 b 11.226 c 18.07
[ 12]
[Ni(dien)2 ]3 [Ge3 Sb8 S21 ]·0.5H2 O
dien = diethylenetriamine
[ 29]
[Ni(trien)2 ]2 Ge4 S10
bis(bis(triethylenetetramine)-nickel) hexakis(μ2 -sulfido)-tetrasulfido-tetra-germanium
monoclinic
C 2/c
a =21.618 b =10.957 c =22.719, β= 111.224°
[ 30]
[{Ni(tepa)}2 (μ -Ge2 S6 )]
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 (Ge2 S6 )
dien = diethylenetriamine
monoclinic
P 21 /n
a 10.093 b 14.219 c 11.703, β 91.631°
[ 26]
[NiII (dien)2 ](H2 pipe)(Ge2 S6 )
pipe = piperazine
triclinic
P 1
a 6.980 b 8.530 c 11.527, α 93.03° β 106.29° γ 101.95°
[ 26]
[NiII (tepa)]2 (μ 2 -Ge2 S6 )
tepa = tetraethylenepentamine
orthorhombic
Pbca
a =15.147 b =13.0552 c =15.238
[ 26]
[(CH3 CH2 )4 N]3 CuGe4 S10
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]
[H4 teta]5 [Cu40 Ge15 S60 ]·2.5(teta)
[ 31]
Cu(AlS2 )(GeS2 )4
monoclinic
P 21 /n
a 6.796 b 37.628 c 6.8797, β 119.52°
[ 16]
Cu4 MnGe2 S7
monoclinic
Cc
a=16.7443 b=6.47893 c=9.8060 β=93.188°
[ 15]
Cu4 FeGe2 S7
monoclinic
C 2
a=11.7405 b=5.3589 c=8.3420 β=98.661°
[ 15]
Cu4 CoGe2 S7
monoclinic
C 2
a=11.7280 b=5.3399 c=8.3313 β=98.668°
[ 15]
Cu4 NiGe2 S7
monoclinic
C 2
a=11.703 b=5.333 c=8.311 β=98.37°
[ 15]
Sr2 CoGe2 OS6
tetrahedral
P 4 21 m
a =9.4056 c =6.1741 Z=2
546.19
3.574
dark green; oxysulfide
[ 32]
Y3 LiGeS7
[ 33]
[Y2 (tepa)2 (μ-OH)2 (μ-Ge2 S6 )](tepa)0.5 ·H2 O
monoclinic
C 2/c
a=19.638 b=14.415 c=16.910 β =122.47 Z=4
4038.6
1.863
colourless
[ 11]
KYGeS4
[ 34]
[{RN Ge(μ-S)3 }4 Pd6 ]·MeOH
RN = CMe2 CH2 CMeNNH2
[ 9]
Ag10 Ge3 S11
monoclinic
Cc
a = 2.6244 b = 0.65020 c = 2.5083 β = 109.910°
[ 35]
[(CH3 CH2 )4 N]3 AgGe4 S10
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
P 21 /n
a 6.799 b 38.4169 c 6.813 β 119.65°
[ 16]
Li4 CdGe2 S7
monoclinic
Cc
a=17.4432 b=6.9353 c=10.3271 β=93.9042°
[ 15]
Na4 CdGe2 S7
monoclinic
P 21 /c
a=7.0813 b=11.9007 c=15.5759 β=90.791°
[ 15]
Y3 Cd0.5 GeS7
[ 33]
Ag4 SnGe2 S7
monoclinic
Cc
a =11.3398 b =6.9706 c =15.4885 β =91.213°
yellow; ∞ [SnGe2 S8 ]6– chains
[ 15]
Na9 Sb(Ge2 S6 )2
monoclinic
C 2/m
a=7.5857 b=11.574 c=6.817 β= 106.587 Z=1
573.7
2.905
yellow
[ 36]
[Ge(en)3 ][GeSb2 S6 ]
orthorhombic
Pbca
[ 1]
[(Me)2 NH2 ]6 [Ge2 Sb2 S7 ][Ge4 S10 ]
triclinic
P 1
microporous, can exchange dimethyl ammonium for alkalis
[ 28] [ 37]
[dabcoH]2 [Ge2 Sb3 S10 ]
dabco = 1,4-diazabicyclo[2.2.2]octane
[ 28]
DMAH[dabcoH]2 [Ge2 Sb3 S10 ]
dabco = 1,4-diazabicyclo[2.2.2]octane
monoclinic
C 2
[ 1]
[DMAH]2 GeSb3 S6
P 41 21 2
[ 1]
[AEPH2 ][GeSb2 S6 ]·CH3 OH
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]
[CH3 NH3 ]20 Ge10 Sb28 S72 ·7H2 O
monoclinic
C 2/c
a =29.2964 b =29.3261 c =41.601 β =100.084°
[ 39]
[(CH3 CH2 CH2 )2 NH2 ]3 Ge3 Sb5 S15 ·0.5(C2 H5 OH)
triclinic
P 1
a =9.7628 b =15.7590 c =17.0313, α =79.868° β =75.010° γ =81.094°
[ 39]
[Mn(en)3 ][GeSb2 S6 ]
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 ][GeSb2 S6 ]
orthorhombic
Pbca
[Co(dien)2 ]2 [GeSb4 S10 ]
dien = diethylenetriamine
orthorhombic
Pbca
a=14.684 b=17.133 c=33.478 Z=8
8422
2.205
yellow
[ 28] [ 40]
[Ni(en)3 ][GeSb2 S6 ]
orthorhombic
Pbca
[Ni(dien)2 ]3 [Ge3 Sb8 S21 ]·0.5H2 O
monoclinic
C 2/m
a =17.604 b =30.660 c =15.348 β =114.69°
[ 28]
La(dien)2 (μ–η1 ,η2 -GeS3 (SH))
monoclinic
C 2/c
a=27.837 b=16.993 c=8.318 β =103.96 Z=8
3818.7
1.903
red
[ 41]
KLaGeS4
monoclinic
P 21
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
C 2/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 [Ge2 S6 ]Cl2
dien = diethylenetriamine
monoclinic
P 21 /n
a=11.637 b=14.143 c=15.120 β =98.149° Z=4
2463
1.765
green
[ 42]
[Sm(dien)3 ]2 [Ge2 S6 ]Cl2
dien = diethylenetriamine
monoclinic
P 21 /n
11.532 b=14.423 c=14.573 β =97.105° Z=4
2405
1.834
light yellow
[ 42]
Sm3 Zn0.5 GeS7
[ 33]
Eu3 Ge3 S9
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 [Ge2 S6 ]Cl2
dien = diethylenetriamine
monoclinic
P 21 /n
a=11.567 b=14.633 c=14.465 β =96.434 Z=4
2432.9
1.818
yellow
[ 11]
Gd3 Cd0.5 GeS7
[ 33]
[Gd(dien)3 ]2 [Ge2 S6 ]Cl2
dien = diethylenetriamine
monoclinic
P 21 /n
11.548 b=14.677 c=14.427 β =96.332° Z=4
2430.4
1.834
colourless
[ 42]
[Dy(dien)3 ]2 [Ge2 S6 ]Cl2
dien = diethylenetriamine
monoclinic
P 21 /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 -Ge2 S6 )]n ·nH2 O
tepa = tetraethylenepentamine
[ 44]
[Er2 (dien)4 (μ-OH)2 ][Ge2 S6 ]
dien = diethylenetriamine
monoclinic
P 21 /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 -Ge2 S6 )]n ·nH2 O
tepa = tetraethylenepentamine
[ 44]
Li4 HgGe2 S7
monoclinic
Cc
a=16.876 b=6.7764 c=10.161 β=93.360°
[ 15]
Ag4 HgGe2 S7
monoclinic
Cc
a=17.4546 b=6.8093 c=10.5342 β=93.3980°
[ 15]
[(Me)2 NH2 ][BiGeS4 ]
monoclinic
P 21
a=6.7290 b c=10.6748 β =105.789 Z=2
479.72
3.156
red
[ 45]
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