Nitride iodide explained

An iodide nitride is a mixed anion compound containing both iodide (I−) and nitride ions (N3−). Another name is metalloiodonitrides. They are a subclass of halide nitrides or pnictide halides.[1] Some different kinds include ionic alkali or alkaline earth salts, small clusters where metal atoms surround a nitrogen atom, layered group 4 element 2-dimensional structures (which could be exfoliated to a monolayer), and transition metal nitrido complexes counter-balanced with iodide ions. There is also a family with rare earth elements and nitrogen and sulfur in a cluster.

Related mixed-anion compounds include halogen variations: nitride fluoride, nitride chloride, and nitride bromide, and pnictogen variations phosphide iodide, arsenide iodide and antimonide iodides.

Production

Nitride iodides may be produced by heating metal nitrides with metal iodides. The ammonolysis process heats a metal iodide with ammonia.[2] A related method heats a metal or metal hydride with ammonium iodide. The nitrogen source could also be an azide or an amide.

List

nameformulaformula
weight		crystal
system		space
group		unit cell Åvolumedensitycommentsref
Li4NClhexagonalR3a=366.225 c=1977.18 Z=3[3]
calcium nitride iodideCa2NIP63/mmca = 3.8095, c = 14.530, Z = 2[4]
α-TiNIorthorhombicPmmna=3.941 b=3.51.5 c=8.955 Z=2black[5]
NCr(I)(NiPr2)2[6]
Cr(I)(N)(N(C(CD3)2CH3)(C6H3FMe))2 [7]
Zn2NIorthorhombicPnmaa=6.3590 b=6.2529 c=7.9549<6 GPa[8]
strontium nitride iodideSr2NI316.15trigonalRma = 4.0049 c = 23.055 Z=3320.244.918orange[9]
α-ZrNIorthorhombicPmmna=4.114 b=3.724 c=9.431 Z=2orange[10]
β-ZrNItrigonalRma=3.718 c=31.381 Z=6brown
[(pcp)Mo<sup>(IV)</sup>(N)(I)][Na(15-crown-5)] pcp=C6H3(OPiPr2)2[11]
Ba2NI
LiLa4N2I7orthorhombicPnmaa = 13.7417, b = 12.1345, c = 10.7991 Z=4@100K[12]
NaLa4N2I7orthorhombicPna21a=14.0018 b=10.9315 c=12.1021 Z=45.361colourless air sensitive[13]
Ce15N7I244245.6orthorhombicPnmaa=12.060 b=32.216 c=16.360 Z=45.48red; air sensitive[14]
NaCe4N2I7orthorhombicPna21a=13.9703 b=10.8932 c=12.0194 Z=45.446red air sensitive
NaPr4N2I7orthorhombicPna21a=13.9412 b=10.8578 c=11.9389 Z=45.524yellowish green air sensitive
NaNd4N2I7orthorhombicPna21a=13.9135 b=10.86 c=11.86 Z=45.638pinkish blue air sensitive
(NdI2)3N[15]
(NdI2)3N(DME)4[16]
NdI(S2N2)(THF)[17]
Nd3I5(S2N2)(S2)(THF)102088.72monoclinicP21a=12.393 b=43.389 c=12.684 β=90.013 Z=468202.034yellow
Ln3I5(S2)(S2N2)(THF)4(Phen)3[18]
Ln3I5(S2)(S2N2)(THF)3(Py)7
(SmI)3N2(THF)
ErI(S2N2)(THF)
Nd2ErClI4-(S2)(S2N2)(THF)7
Nd2ErCl2I3(S2)(S2N2)(THF)7
(DyI2)3N[19]
Dy3I5(S2)(S2N2)(THF)10
Nd2DyI5(S2)(S2N2)(THF)7
Nd2DyI5(S3)(S2N2)(THF)92034.88monoclinicP21/ca=23.1102 b=12.6551 c=23.8268 β =111.201 Z=46496.82.080[20]
Nd2TbI5(S2)(S2N2)(THF)9monoclinicP21/ca =23.1704 b =12.6340 c =23.8340, β =111.274° Z=4[21]
Nd2TmI5(S2)(S2N2)(THF)9monoclinicP21/ca =23.075 b =12.6540 c =23.809, β =111.460° Z=4
Nd2YbI5(S3)(S2N2)(THF)9monoclinicP21/ca=23.0959 b=12.6632 c=23.8387 β =111.363 Z=46493.02.092
α-HfNIorthorhombicPmmna=4.10.67 b=3.6944 c=9.382 Z=2
β-HfNItrigonalRma=3.689 c=31.329 Z=6brown
ThNItetragonalP4/nmma=4.107 c=9.242orange to golden grey[22]
UNItetragonalP4/nmma=3.99 c=9.20 Z=2[23]

Notes and References

  1. Headspith. David A.. Francesconi. M. Grazia. October 2009. Transition Metal Pnictide-Halides: A Class of Under-Explored Compounds. Topics in Catalysis. en. 52. 11. 1611–1627. 10.1007/s11244-009-9282-5. 93522549. 1022-5528.
  2. Schurz. Christian M.. Shlyk. Larysa. Schleid. Thomas. Niewa. Rainer. January 2011. Superconducting nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I). Zeitschrift für Kristallographie. 226. 4. 395. 10.1524/zkri.2011.1350. 2011ZK....226..395S. 93973409. 0044-2968. free.
  3. Marx. Rupert. February 1997. Preparation and Crystal Structure of Lithium Nitride Chloride Li4NCl. Journal of Solid State Chemistry. en. 128. 2. 241–246. 10.1006/jssc.1996.7196. 1997JSSCh.128..241M.
  4. Hadenfeldt . C. . Herdejürgen . H. . February 1987 . Darstellung und Kristallstruktur der Calciumnitridhalogenide Ca2NCl und Ca2NBr . Zeitschrift für anorganische und allgemeine Chemie . de . 545 . 2 . 177–183 . 10.1002/zaac.19875450220 . 0044-2313.
  5. Schurz . Christian M. . Shlyk . Larysa . Schleid . Thomas . Niewa . Rainer . January 2011 . Superconducting nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I) . Zeitschrift für Kristallographie . 226 . 4 . 395 . 10.1524/zkri.2011.1350 . 2011ZK....226..395S . 93973409 . 0044-2968. free .
  6. Odom . Aaron L. . Cummins . Christopher C. . 1996-02-06 . A Chromium(VI) Nitrido−Silylmethyl Complex and a Chromium(V) μ-Nitrido Dimer: Synthetic and Structural Details . Organometallics . en . 15 . 3 . 898–900 . 10.1021/om950842k . 0276-7333.
  7. Deprotonated 2,3:5,6-Dibenzo-7- aza bicyclo[2.2.1]hepta-2,5-diene as a Nitrido Nitrogen Source by Anthracene Elimination: Synthesis of an Iodide(nitride)chromium(VI) Complex. Angewandte Chemie International Edition. 1998. 10.1002/(SICI)1521-3773(19980420)37:7<945::AID-ANIE945>3.0.CO;2-X. Mindiola. Daniel J.. Cummins. Christopher C.. 37. 7. 945–947. 29711483.
  8. Li . Xiaofeng . Xue . Lin . Tang . Lijuan . Hu . Ziyu . 2015 . Pressure modulates the phase stability and physical properties of zinc nitride iodine . RSC Advances . en . 5 . 96 . 78754–78759 . 10.1039/C5RA14426D . 2015RSCAd...578754L . 2046-2069.
  9. Bailey . Andrew S. . Gregory . Duncan H. . Hubberstey . Peter . Wilson . Claire . 2007-09-15 . Crystal growth and redetermination of strontium nitride iodide, Sr 2 NI . Acta Crystallographica Section E . 63 . 9 . i177 . 10.1107/S1600536807039797 . 1600-5368.
  10. Yamanaka . Shoji . Itoh . Kojiro . Fukuoka . Hiroshi . Yasukawa . Masahiro . 2000-02-01 . High-Pressure Synthesis of the Polymorph of Layer Structured Compounds MNX (M = Zr, Hf; X = Cl, Br, I) . Inorganic Chemistry . en . 39 . 4 . 806–809 . 10.1021/ic991058l . 11272580 . 0020-1669.
  11. Song . Jinyi . Liao . Qian . Hong . Xin . Jin . Li . Mézailles . Nicolas . 2021-05-25 . Conversion of Dinitrogen into Nitrile: Cross‐Metathesis of N 2 ‐Derived Molybdenum Nitride with Alkynes . Angewandte Chemie International Edition . en . 60 . 22 . 12242–12247 . 10.1002/anie.202015183 . 33608987 . 231969654 . 1433-7851.
  12. Schurz . Christian M. . Niewa . Rainer . Schleid . Thomas . January 2020 . LiLa4N2I7 as the first lithium-containing nitride halide of the lanthanides: Synthesis, crystal structure and spectroscopic characterization . Solid State Sciences . en . 99 . 106047 . 10.1016/j.solidstatesciences.2019.106047. 2020SSSci..9906047S . 209706784 .
  13. Schurz . Christian M. . Schleid . Thomas . October 2010 . The first quaternary lanthanide(III) nitride iodides: NaM4N2I7 (M=La–Nd) . Journal of Solid State Chemistry . en . 183 . 10 . 2253–2260 . 10.1016/j.jssc.2010.07.025. 2010JSSCh.183.2253S .
  14. Mattausch . Hansj Ürgen . Kremer . Reinhard K. . Simon . Arndt . April 1996 . Synthese, Kristallstruktur und magnetische Eigenschaften von Ce15N7I24 . Zeitschrift für anorganische und allgemeine Chemie . de . 622 . 4 . 649–654 . 10.1002/zaac.19966220413 . 0044-2313.
  15. Fagin . A. A. . Fukin . G. K. . Cherkasov . A. V. . Shestakov . A. F. . Pushkarev . A. P. . Balashova . T. V. . Maleev . A. A. . Bochkarev . M. N. . 2016 . Ln 3 I 5 (S 2 N 2)(S 2)(THF) 10 – a new type of molecular compounds . Dalton Transactions . en . 45 . 11 . 4558–4562 . 10.1039/C5DT04742K . 26842841 . 1477-9226.
  16. Kuzyaev . Dmitry M. . Maleev . Alexander A. . Kulikova . Tatyana I. . Vorozhtsov . Dmitry L. . Bochkarev . Mikhail N. . February 2017 . Reactivity of Neodymium and Samarium Nitrides . Journal of Chemical Research . en . 41 . 2 . 82–84 . 10.3184/174751917X14839766277332 . 99205962 . 1747-5198.
  17. Fagin . A. A. . Kuznetsova . O. V. . Rumyantsev . R. V. . Baranov . E. V. . Fukin . G. K. . Bochkarev . M. N. . March 2022 . Lanthanide Iodide Nitride Sulfide Clusters . Russian Journal of Coordination Chemistry . en . 48 . 3 . 146–152 . 10.1134/S1070328422020026 . 247387448 . 1070-3284.
  18. Fagin . A. A. . Kuzyaev . D. M. . Burin . M. A. . Kuznetsova . O. V. . Khamaletdinova . N. M. . Kulikova . T. I. . Shestakov . A. F. . Lopatina . T. I. . Vorozhtsov . D. L. . Bochkarev . M. N. . February 2018 . On the Reactivity and Stability of Iodide–Nitride–Sulfide Clusters of Neodymium and Dysprosium . Russian Journal of Coordination Chemistry . en . 44 . 2 . 127–131 . 10.1134/S1070328418020045 . 103790629 . 1070-3284.
  19. Fagin . A.A. . Kuznetsova . O.V. . Balashova . T.V. . Cherkasov . A.V. . Fukin . G.K. . Bochkarev . M.N. . January 2018 . Iodide-sulfides of dysprosium: Elucidation of the pathway to lanthanide iodide-sulfide-nitride clusters . Inorganica Chimica Acta . en . 469 . 227–230 . 10.1016/j.ica.2017.09.030.
  20. Fagin . A. A. . Kuznetsova . O. V. . Rumyantcev . R. V. . Fukin . G. K. . Marugin . A. V. . Bochkarev . M. N. . September 2019 . Neodymium–Dysprosium and Neodymium–Ytterbium Iodide–Sulfide–Nitride Clusters: Synthesis and Luminescence . Journal of Cluster Science . en . 30 . 5 . 1277–1281 . 10.1007/s10876-019-01552-5 . 146044754 . 1040-7278.
  21. Fagin . A.A. . Kuzyaev . D.M. . Maleev . A.A. . Baranov . E.V. . Rumyantcev . R.V. . Fukin . G.K. . Shestakov . A.F. . Suchkov . A.I. . Marugin . A.V. . Bochkarev . M.N. . May 2019 . Heterolanthanide three-nuclear iodide-sulfide-nitride clusters. Unusual synthesis way and structure . Inorganica Chimica Acta . en . 490 . 200–203 . 10.1016/j.ica.2019.03.021. 107891753 .
  22. Juza . Robert . Sievers . Rolf . December 1968 . Nitridhalogenide des Thoriums . Zeitschrift für anorganische und allgemeine Chemie . de . 363 . 5–6 . 258–272 . 10.1002/zaac.19683630505 . 0044-2313.
  23. Juza . R. . Meyer . W. . April 1969 . Über Uran-Nitrid-Chlorid, -Bromid und -Jodid . Zeitschrift für anorganische und allgemeine Chemie . de . 366 . 1–2 . 43–50 . 10.1002/zaac.19693660105 . 0044-2313.

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