Chemistry:Nitridogermanate

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The nitridogermanates are chemical compounds containing germanium atoms bound to nitrogen. The simplest anion is GeN48−, but these are often condensed, with the elimination of nitrogen. Nitridogermanates can form quite a few structures. Germanium can be in three different oxidation states. In the +2 oxidation state there is [GeIIN2]4− which has a boomerang shape. The most common is the +4 state with [GeIVN3]5− is a planar three pointed star, and [GeIVN4]8− as tetrahedra. Condensation of the tetrahedra yields [Ge2 IVN6]10−. The +3 state is rare, and represented by [GeIII 2N6]12− with a covalent bond between the two germanium atoms.[1] A few compounds also contain germanium in negative oxidation states −2 and −4 and so can be considered germanides as well.

Synthesis

Reduced compounds may be produced by using a flux of molten sodium. Nitrogen may be introduced by using sodium azide. Alkaline earth elements increase the solubility of nitrogen in molten sodium. Containers can be made from sealed tubes of niobium or tantalum. The sodium can be evaporated by heating to over 300°C in a vacuum.[2]

Properties

Nitridogermanates tend to be unstable in air, as they react with water vapour to form ammonia.

Related

Nitridogermanates are in the category of nitridotetralates, or more generally nitridometallates, tetrel pnictides or pnictidometallates. Related compounds include the nitridosilicates, and rare nitridostannates. By varying the pnictogen, there are also the phosphidogermanates. Other similar compounds are the nitridogallates and nitridomanganates.

Subtypes may be termed nitridoalumogermanates or nitridomagnesogermanates, if they contain aluminium or magnesium.

List

name formula formula

weight

crystal

system

space

group

unit cell Å volume density comments ref
α-Ge3N4
phenacite phase of germanium nitride β-Ge3N4
spinel germanium nitride γ-Ge3N4 Fd3m a 8.2125Å b 8.2125Å c 8.2125 [3]
Ca2GeN2 tetragonal P42/mbc a = 11.2004, c = 5.0482, Z = 8 black [2][4]
Ca4GeN4 monoclinic P21/c a = 9.2823, b = 6.0429, c = 11.1612, β = 116.498°, Z = 4 orange [2]
pentacalcium nitridodigermanate Ca5[Ge2N6] C2/c a 9.836 b 6.0519 c 12.757 β 100.2° colourless [5][6]
Ca6[Ge2N6] trigonal R3 a=9.2078 c=9.2679 680.5 3.439 grey; band gap 1.1 eV [1]
Ca7[GeN6] orthorhombic Pbcn a = 10.826, b = 6.194, c = 13.121 Z=4 879.8 3.301 yellow with N3− [7]
Ca0.8Li0.2Al0.8Ge1.2N3 a = 9.9822, b = 5.7763, c = 5.1484, Z = 4 [8]
Li4Ca13Ge6N18 monoclinic C2/c a = 12.328 b = 12.662 c = 14.711 β = 108.688° 2175.2 3.776 clear [9]
Mg5Ca2GeN6 P63/mmc a = 3.453, c = 17.51 180.8 [2][10]
Mg5Ca4Ge3N10 monoclinic C2/m a = 11.269, b = 3.327, c = 8.008, β = 109.80° Z=4 282.4 colourless; layered [2][11]
ZnGeN2
strontium gallium germanium subnitirde Sr2GeGaN monoclinic P21/c a=6.885 b=4.0432 c=8.680 β =108.454 Z=2 229.21 4.804 black glossy [12]
Li3Ca4(Ga3Ge)N8 [13]
α-Sr2[GeN2] 275.85 tetragonal P42/mbc a=11.773 c=5.409 Z=8 749.7 black [1][14]
β-Sr2[GeN2] 275.85 orthorhombic Cmac a=5.441 b=11.377 c=12.229 Z=8 756.9 4.841 black with blue sheen [14][15]
Sr3Ge2N2 436.1 monoclinic P21/m a = 9.032, b = 3.883, c = 9.648, β = 112.42°, Z=2 312.9 4.630 dark blue-grey [16]
Sr4[GeN4] monoclinic P21/c a = 9.7923, b = 6.3990, c = 11.6924 β = 115.966° dark red [17]
Sr5[Ge2N6] 667.36 monoclinic C2/c a = 10.408, b = 6.521, c = 13.565, β = 100.29° Z = 4 905.8 4.893 yellow/ orange [1][5]
Sr7[GeN6] orthorhombic Pbcn a = 11.526, b = 6.587, c = 13.836 Z=4 1050.5 4.869 red with N3−; Sr in 4-fold coordination [1][7]
Sr6[Ge2N6] trigonal R3 a=9.6655 c=9.6655 790.91 4.755 black; band gap 0.2 eV [1]
Sr8Ge2[GeN4] monoclinic Cc a = 10.1117, b = 17.1073, c = 10.0473, β = 115.966° black [17]
pentastrontium nitridodigermanate Sr6Ge5N2 916.69 orthorhombic Pmmn a = 4.0007, b = 17.954, c = 9.089 Z=2 652.8 4.663 black; unstable in air [18]
Strontium Germanium Nitride Sr11Ge4N6 1338.24 tetragonal P4nbm a=7.278 c=18.681 Z=2 989.5 4.491 black; contains Ge4− [19]
Sr17Ge6N14 triclinic P1 a = 7.5392, b = 9.7502, c = 11.6761, α = 103.308°, β = 94.651°, γ = 110.248° black; contains Ge4− [17]
Li4Sr3Ge2N6 monoclinic C2/m a=6.1398, b=10.021, c=6.3130, β=91.279°, Z=2 [20]
Mg3SrGeN4 tetragonal I4/m a = 8.316, c = 3.398, Z = 2 [2][21]
MgSr3GeN4 orthorhombic Pnna a=5.939, b=10.320, c=9.618, Z=6 yellow [2][22][15]
Ba3Ge2N2 monoclinic P21/m a = 9.61196, b = 4.0466, c = 10.1337 β = 113.55° Z=2 361.61 5.375 metallic; contains Ge2− [23]
Ba6Ge5N2 1215.01 orthorhombic Pmmn a = 4.1620, b = 18.841, c = 9.6116 Z=2 753.7 5.354 black; unstable in air [18]
Ba9Ge3N10 rhombohedral R3c a=7.9399 c=17.282 Z=2 943.53 5.610 black [24]
MgBa3GeN4 orthorhombic Pnma a=6.159 b=10.558 c=10.048 Z=4 653.4 5.743 yellow [2][25]
Mg3BaGeN4 tetragonal I4/m a = 8.392, c = 3.4813, Z = 2 [26]
barium gallium germanium subnitirde Ba2GeGaN monoclinic P21/c a 7.249 b 4.21 c 9.314 β 108.87° black glossy [27]

References

  1. ↑ 1.0 1.1 1.2 1.3 1.4 1.5 Link, Lukas; Pathak, Manisha; Jach, Franziska; Koželj, Primoz; Ormeci, Alim; Höhn, Peter; Niewa, Rainer (29 March 2021). "The Reduced Nitridogermanates(III) Ca 6 [Ge 2 N 6 and Sr 6 [Ge 2 N 6 ] with Ge−Ge Bonds"]. Angewandte Chemie International Edition 60 (14): 7691–7696. doi:10.1002/anie.202017270. ISSN 1433-7851. PMID 33524200. 
  2. ↑ 2.0 2.1 2.2 2.3 2.4 2.5 2.6 2.7 Yamane, Hisanori; DiSalvo, Francis J. (September 2018). "Sodium flux synthesis of nitrides" (in en). Progress in Solid State Chemistry 51: 27–40. doi:10.1016/j.progsolidstchem.2017.08.002. https://linkinghub.elsevier.com/retrieve/pii/S0079678617300146. 
  3. ↑ Leinenweber, K.; O'Keeffe, M.; Somayazulu, M.; Hubert, H.; McMillan, P. F.; Wolf, G. H. (1999). "Synthesis and Structure Refinement of the Spinel, γ-Ge3N4" (in en). Chemistry – A European Journal 5 (10): 3076–3078. doi:10.1002/(SICI)1521-3765(19991001)5:10<3076::AID-CHEM3076>3.0.CO;2-D. ISSN 1521-3765. https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/%28SICI%291521-3765%2819991001%295%3A10%3C3076%3A%3AAID-CHEM3076%3E3.0.CO%3B2-D. 
  4. ↑ Clarke, S. J.; DiSalvo, F. J. (2000-06-01). "New Calcium Germanium Nitrides: Ca 2 GeN 2 , Ca 4 GeN 4 , and Ca 5 Ge 2 N 6" (in en). Inorganic Chemistry 39 (12): 2631–2634. doi:10.1021/ic991427d. ISSN 0020-1669. PMID 11197019. https://pubs.acs.org/doi/10.1021/ic991427d. 
  5. ↑ 5.0 5.1 Junggeburth, Sebastian C.; Oeckler, Oliver; Schnick, Wolfgang (July 2008). "Sr5Ge2N6 – A Nitridogermanate with Edge-sharing Double Tetrahedra" (in de). Zeitschrift für anorganische und allgemeine Chemie 634 (8): 1309–1311. doi:10.1002/zaac.200800049. https://onlinelibrary.wiley.com/doi/10.1002/zaac.200800049. 
  6. ↑ Ottinger, Frank; Nesper, Reinhard (July 2005). "Synthesis and Crystal Structure of the Nitridosilicates Ca5[Si2N6 and Ca7[NbSi2N9]"] (in de). Zeitschrift für anorganische und allgemeine Chemie 631 (9): 1597–1602. doi:10.1002/zaac.200500094. ISSN 0044-2313. https://onlinelibrary.wiley.com/doi/10.1002/zaac.200500094. 
  7. ↑ 7.0 7.1 Junggeburth, Sebastian C.; Oeckler, Oliver; Johrendt, Dirk; Schnick, Wolfgang (2008-12-15). "Nitridogermanate Nitrides Sr 7 [GeN 4 N 2 and Ca 7 [GeN 4 ]N 2 : Synthesis Employing Sodium Melts, Crystal Structure, and Density-Functional Theory Calculations"] (in en). Inorganic Chemistry 47 (24): 12018–12023. doi:10.1021/ic801562c. ISSN 0020-1669. PMID 19006293. https://epub.ub.uni-muenchen.de/14461/1/ic801562c.pdf. 
  8. ↑ Häusler, Jonas; Eisenburger, Lucien; Oeckler, Oliver; Schnick, Wolfgang (2018-02-14). "Ammonothermal Synthesis and Crystal Structure of the Nitridoalumogermanate Ca 1- x Li x Al 1- x Ge 1+ x N 3 ( x ≈ 0.2): Ammonothermal Synthesis and Crystal Structure of the Nitridoalumogermanate Ca 1- x Li x Al 1- x Ge 1+ x N 3 ( x ≈ 0.2)" (in en). European Journal of Inorganic Chemistry 2018 (6): 759–764. doi:10.1002/ejic.201701314. https://onlinelibrary.wiley.com/doi/10.1002/ejic.201701314. 
  9. ↑ Park, Dong-Gon (2012-05-20). "Synthesis and Crystal Structure of a New Quaternary Nitride, Li4Ca13Ge6N18". Bulletin of the Korean Chemical Society 33 (5): 1759–1761. doi:10.5012/BKCS.2012.33.5.1759. 
  10. ↑ Poesl, Christine; Schnick, Wolfgang (August 2016). "Ca 2 Mg 5 GeN 6 - A Layered Nitridomagnesogermanate: Ca 2 Mg 5 GeN 6 - A Layered Nitridomagnesogermanate" (in en). Zeitschrift für anorganische und allgemeine Chemie 642 (16): 882–886. doi:10.1002/zaac.201600200. https://onlinelibrary.wiley.com/doi/10.1002/zaac.201600200. 
  11. ↑ Poesl, Christine; Schnick, Wolfgang (2017-03-17). "Ca 4 Mg 5 Ge 3 N 10 and Sr 2 Mg 3 GaN 4.33 : Two Mg-Containing Nitrides and Their Structural Relation to (Sr,Ba) 2 Si 5 N 8: Ca 4 Mg 5 Ge 3 N 10 and Sr 2 Mg 3 GaN 4.33 : Two Mg-Containing Nitrides and Their Structural Relation to (Sr,Ba) 2 Si 5 N 8" (in en). European Journal of Inorganic Chemistry 2017 (11): 1498–1503. doi:10.1002/ejic.201601532. https://onlinelibrary.wiley.com/doi/10.1002/ejic.201601532. 
  12. ↑ Park, Dong-Gon (2009-06-20). "Synthesis and Crystal Structure of the New Quaternary Subnitride, Sr2GeGaN". Bulletin of the Korean Chemical Society 30 (6): 1379–1382. doi:10.5012/BKCS.2009.30.6.1379. 
  13. ↑ Park, Dong Gon; DiSalvo, Francis J. (September 2015). "Synthesis and Crystal Structure of a New Quinary Nitride: Li 3 Ca 4 (Ga 3 Ge)N 8" (in en). Bulletin of the Korean Chemical Society 36 (9): 2359–2362. doi:10.1002/bkcs.10431. https://onlinelibrary.wiley.com/doi/10.1002/bkcs.10431. 
  14. ↑ 14.0 14.1 Bedjaoui, A.; Bouhemadou, A.; Bin-Omran, S. (2016-04-02). "Structural, elastic and thermodynamic properties of tetragonal and orthorhombic polymorphs of Sr 2 GeN 2 : an ab initio investigation" (in en). High Pressure Research 36 (2): 198–219. doi:10.1080/08957959.2016.1167202. ISSN 0895-7959. Bibcode: 2016HPR....36..198B. https://www.tandfonline.com/doi/full/10.1080/08957959.2016.1167202. 
  15. ↑ 15.0 15.1 Park, Dong-Gon (2005-05-20). "Synthesis and Structure of a Second Polymorph of Strontium Germanium Nitride: β-Sr2GeN2". Bulletin of the Korean Chemical Society 26 (5): 786–790. doi:10.5012/BKCS.2005.26.5.786. 
  16. ↑ Clarke, S. J.; Kowach, G. R.; DiSalvo, F. J. (January 1996). "Synthesis and Structure of Two New Strontium Germanium Nitrides: Sr 3 Ge 2 N 2 and Sr 2 GeN 2" (in en). Inorganic Chemistry 35 (24): 7009–7012. doi:10.1021/ic960518x. ISSN 0020-1669. PMID 11666880. https://pubs.acs.org/doi/10.1021/ic960518x. 
  17. ↑ 17.0 17.1 17.2 Link, Lukas; Niewa, Rainer (2020-07-31). "Diversity of Strontium Nitridogermanates(IV): Novel Sr 4 [GeN 4 ], Sr 8 Ge 2 [GeN 4 ], and Sr 17 Ge 2 [GeN 3 ] 2 [GeN 4 ] 2" (in en). Zeitschrift für anorganische und allgemeine Chemie 646 (14): 1105–1109. doi:10.1002/zaac.202000008. ISSN 0044-2313. 
  18. ↑ 18.0 18.1 Park, Dong-Gon (2005-10-20). "Synthesis and Structure of Sr6Ge5N2 and Ba6Ge5N2". Bulletin of the Korean Chemical Society 26 (10): 1543–1548. doi:10.5012/BKCS.2005.26.10.1543. 
  19. ↑ Gál, Zoltán A.; Clarke, Simon J. (2005). "Sr 11 Ge 4 N 6 : a new nitride composed of [GeN 2 Sr 7 ] 4+ antiperovskite-type slabs and [Sr 4 Ge] 4+ layers, separated by sheets of bent [Ge II N 2 ] 4− ions". Chem. Commun. (6): 728–730. doi:10.1039/B413534B. PMID 15685318. 
  20. ↑ Park, Dong Gon; Gál, Zoltán A.; DiSalvo, Francis J. (April 2003). "Synthesis and structure of Li4Sr3Ge2N6: a new quaternary nitride containing Ge2N610− anions". Journal of Solid State Chemistry 172 (1): 166–170. doi:10.1016/S0022-4596(03)00009-4. Bibcode: 2003JSSCh.172..166P. 
  21. ↑ Park, Dong Gon; Dong, Yongkwan; DiSalvo, Francis J. (December 2008). "Sr(Mg3Ge)N4 and Sr(Mg2Ga2)N4: New isostructural Mg-containing quaternary nitrides with nitridometallate anions of and in a 3D-network structure" (in en). Solid State Sciences 10 (12): 1846–1852. doi:10.1016/j.solidstatesciences.2008.04.001. https://linkinghub.elsevier.com/retrieve/pii/S1293255808001398. 
  22. ↑ Park, Dong Gon; Gál, Zoltán A.; DiSalvo, Francis J. (October 2003). "Sr3GeMgN4: new quaternary nitride containing Mg" (in en). Journal of Alloys and Compounds 360 (1–2): 85–89. doi:10.1016/S0925-8388(03)00370-0. https://linkinghub.elsevier.com/retrieve/pii/S0925838803003700. 
  23. ↑ Yamane, Hisanori; DiSalvo, Francis J. (August 1996). "A barium germanium nitride, Ba3Ge2N2, containingx1|Ge2− and GeN24− anions". Journal of Alloys and Compounds 241 (1–2): 69–74. doi:10.1016/0925-8388(96)02326-2. 
  24. ↑ Park, Dong-Gon (2008-12-20). "Ba9Ge3N10 : A New Ternary Nitride Containing Isolated Planar Triangular Anions of [GeN3]5-". Bulletin of the Korean Chemical Society 29 (12): 2413–2418. doi:10.5012/BKCS.2008.29.12.2413. 
  25. ↑ Park, Dong-Gon (2011-01-20). "A Structural Comparison between a New Quaternary Nitride, Ba3GeMgN4, and Its Isostructural Sr analogue". Bulletin of the Korean Chemical Society 32 (1): 353–355. doi:10.5012/BKCS.2011.32.1.353. https://doi.org/10.5012/BKCS.2011.32.1.353. 
  26. ↑ Poesl, Christine; Niklaus, Robin; Schnick, Wolfgang (2017-05-10). "The Crystal Structure of Nitridomagnesogermanate Ba[Mg 3 GeN 4 :Eu 2+ and Theoretical Calculations of Its Electronic Properties: The Crystal Structure of Nitridomagnesogermanate Ba[Mg 3 GeN 4 ]:Eu 2+ and Theoretical Calculations of Its Electronic Properties"] (in en). European Journal of Inorganic Chemistry 2017 (18): 2422–2427. doi:10.1002/ejic.201700096. https://onlinelibrary.wiley.com/doi/10.1002/ejic.201700096. 
  27. ↑ Clarke, S.J.; DiSalvo, F.J. (August 1997). "Synthesis and structure of the subnitrides Ba2GeGaN and (BaxSr1−x)3Ge2N2; x≈0.7" (in en). Journal of Alloys and Compounds 259 (1–2): 158–162. doi:10.1016/S0925-8388(97)00095-9. 
Salts and covalent derivatives of the nitride ion
NH3 He(N2)11
Li3N Be3N2 BN β-C3N4
g-C3N4 		N2 NxOy NF3 Ne
Na3N Mg3N2 AlN Si3N4 PN
P3N5 		SxNy
SN
S4N4 		NCl3 Ar
K3N Ca3N2 ScN TiN VN CrN
Cr2N 		MnxNy FexNy CoN Ni3N CuN Zn3N2 GaN Ge3N4 As Se NBr3 Kr
Rb3N Sr3N2 YN ZrN NbN β-Mo2N Tc Ru Rh PdN Ag3N CdN InN Sn Sb Te NI3 Xe
Cs3N Ba3N2   Hf3N4 TaN WN Re Os Ir Pt Au Hg3N2 TlN Pb BiN Po At Rn
Fr3N Ra3N   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
La CeN Pr Nd Pm Sm Eu GdN Tb Dy Ho Er Tm Yb Lu
Ac Th Pa UN Np Pu Am Cm Bk Cf Es Fm Md No Lr



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