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Thiogermanate

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(Перенаправлено из тиогерманитов )

Сульфидогерманиты или тиогерманаты - это химические соединения, содержащие анионы с атомами серы, связанными с германия . Они находятся в классе халкогенидотетрататов . Связанные соединения включают тиозиликаты , тиостаннаты , Selenidogermanates , Telluridogermanates и Selenidostannates .

Координация серы вокруг германия является тетраэдрическим значением. Существует четыре атома серы, симметрично расположенные. Эта основная структура может образовывать орто -соли с GES 4 4− , олигомеры или полимерные структуры. [ 1 ] Подобные структуры также образуются с помощью тяжелых элементов группы 13 и группы 14 из -за их относительно более сильных связей с серной. Световые элементы из этих групп имеют более низкую аффинность к серу, поэтому существует меньше таких соединений для бора, алюминия, углерода и кремния. [ 1 ] Другие элементы тяжелой группы 12 и 15 также образуют халкогенометаллические, которые могут иметь другие виды координации. Селен образует сходные соединения с серой в этом семействе. [ 1 ]

Если сера недостаточна, анион не образуется, и вместо этого могут существовать катионные ковалентные соединения с галогенами, такими как GE 4 S 6 Br 4 , [ 2 ] или GE 4 S 6 I 4 . [ 3 ]

Производство

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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

[edit]
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]

References

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  23. ^ Jump up to: a b c Luo, Hai-Ying; Zhou, Jian; Cao, Shumei (2019). "A series of new hybrid chalcogenogermanates: the rare examples of chalcogenogermanates combined with trivalent vanadium complexes". Dalton Transactions. 48 (29): 10907–10914. doi:10.1039/C9DT02077B. ISSN 1477-9226. PMID 31282904. S2CID 195828996.
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  29. ^ Zhou, Jian; Liu, Xing; Liang, Guoming; Liang, Weijiang; Hu, Feilong; Zhu, Ligang (January 2013). "[Ni(dien)2]3[Ge3Sb8S21]·0.5H2O: A new 2-D layered thiogermanate–thioantimonate with metal complexes as template ions". Inorganic Chemistry Communications. 27: 92–96. doi:10.1016/j.inoche.2012.10.015.
  30. ^ Jump up to: a b Liang, Jing-Jing; Zhao, Jing; Tang, Wei-Wei; Zhang, Yong; Jia, Ding-Xian (June 2011). "Ethylene polyamine influence on the transition metal thiogermanates: Solvothermal syntheses and characterizations of [Ni(trien)2]2Ge4S10 and [{Ni(tepa)}2(μ-Ge2S6)]". Inorganic Chemistry Communications. 14 (6): 1023–1026. doi:10.1016/j.inoche.2011.03.062.
  31. ^ Tang, Shimei; Zhou, Jian; Liu, Xing; Xiao, Hong-Ping (June 2018). "A new 3-D cuprous thiogermanate with rare 3-D [Cu-S-Cu]n network". Materials Today Communications. 15: 88–93. doi:10.1016/j.mtcomm.2018.02.035. S2CID 103265774.
  32. ^ Zhang, Nan; Xu, Qian-Ting; Shi, Zhi-Hui; Yang, Mei; Guo, Sheng-Ping (2022-10-31). "Characterizations and Nonlinear-Optical Properties of Pentanary Transition-Metal Oxysulfide Sr 2 CoGe 2 OS 6". Inorganic Chemistry. 61 (43): 17002–17006. doi:10.1021/acs.inorgchem.2c03283. ISSN 0020-1669. PMID 36265201. S2CID 253044751.
  33. ^ Jump up to: a b c d Gao, Lihua; Wu, Xiaowen; Xu, Jingjing; Tian, Xinyu; Zhang, Bingbing; Wu, Kui (December 2021). "Rational combination of multiple structural groups on regulating nonlinear optical property in hexagonal Ln3MGeS7 polar crystals". Journal of Alloys and Compounds. 900: 163535. doi:10.1016/j.jallcom.2021.163535. S2CID 245626019.
  34. ^ Jump up to: a b Liu, Yang; Li, Xiangming; Wu, Shuchang; Ma, Mengjie; Jiang, Xiaoming; Wu, Yuandong; Mei, Dajiang (2024-06-03). "A Rare Earth Chalcogenide Nonlinear Optical Crystal KLaGeS 4 : Achieving Good Balance among Band Gap, Second Harmonic Generation Effect, and Birefringence". Inorganic Chemistry. doi:10.1021/acs.inorgchem.4c00842. ISSN 0020-1669.
  35. ^ Fedorchuk, A.O.; Lakshminarayana, G.; Tokaychuk, Y.O.; Parasyuk, O.V. (November 2013). "The crystal structure of novel silver sulphogermanate Ag10Ge3S11". Journal of Alloys and Compounds. 576: 134–139. doi:10.1016/j.jallcom.2013.04.110.
  36. ^ Wu, Xiaowen; Hu, Yi; Pan, Hui; Su, Zhi (2016). "Na 9 Sb(Ge 2 Q 6 ) 2 (Q = S, Se): two new antimony( iii ) quaternary chalcogenides with ethane-like [Ge 2 Q 6 ] 6− ligands". RSC Advances. 6 (101): 99475–99481. doi:10.1039/C6RA22000B. ISSN 2046-2069.
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  38. ^ Feng, Mei-Ling; Hu, Chun-Li; Wang, Kai-Yao; Du, Cheng-Feng; Huang, Xiao-Ying (2013). "[AEPH2][GeSb2S6]·CH3OH: a thiogermanate–thioantimonate featuring an infinite ribbon-like structure with an unusual {GeSb3S11} unit and exhibiting the ability of photocatalytic degradation of organic dye". CrystEngComm. 15 (25): 5007. doi:10.1039/c3ce40143j. ISSN 1466-8033.
  39. ^ Jump up to: a b Zhang, Bo; Feng, Mei-Ling; Cui, Hong-Hua; Du, Cheng-Feng; Qi, Xing-Hui; Shen, Nan-Nan; Huang, Xiao-Ying (2015-09-08). "Syntheses, Crystal Structures, Ion-Exchange, and Photocatalytic Properties of Two Amine-Directed Ge–Sb–S Compounds". Inorganic Chemistry. 54 (17): 8474–8481. doi:10.1021/acs.inorgchem.5b01181. ISSN 0020-1669. PMID 26291119.
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  41. ^ Jump up to: a b Zhou, Jian; Li, Rong; Ling, Xing; Chen, Rong; Hu, Feilong; Zeng, Yanfang (2013). "The first examples of thiogermanate anion [GeS 3 (SH)] 3− as a bridging ligand to a lanthanide complex". Dalton Trans. 42 (6): 1961–1964. doi:10.1039/C2DT32389C. ISSN 1477-9226. PMID 23165504.
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  43. ^ Bugli, G.; Carré, D.; Barnier, S. (1978-11-01). "Structure cristalline du thiogermanate d'europium Eu 3 Ge 3 S 9". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 34 (11): 3186–3189. doi:10.1107/S0567740878010456. ISSN 0567-7408.
  44. ^ Jump up to: a b Tang, Shimei; Cao, Shumei; Zhou, Jian (July 2018). "A Series of Lanthanide Chalcogenidogermanates Displaying Two Types of 1-D Polymeric Chains". Journal of Cluster Science. 29 (4): 777–783. doi:10.1007/s10876-018-1402-6. ISSN 1040-7278. S2CID 103263516.
  45. ^ Feng, Mei-Ling; Qi, Xing-Hui; Zhang, Bo; Huang, Xiao-Ying (2014). "[(Me)2NH2][BiGeS4]: the first organically directed bismuth thiogermanate with Rb+ ion exchange property". Dalton Transactions. 43 (22): 8184–8187. doi:10.1039/c4dt00173g. ISSN 1477-9226. PMID 24781350.
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