Nitride fluoride

Nitride fluorides containing nitride and fluoride ions with the formula NF4-. They can be electronically equivalent to a pair of oxide ions O24-. Nitride fluorides were discovered in 1996 by Lavalle et al. They heated diammonium technetium hexafluoride to 300 °C to yield TcNF.[1] Another preparation is to heat a fluoride compound with a nitride compound in a solid state reaction.[2] The fluorimido ion is F-N2- and is found in a rhenium compound.[3]

name formula ratio

N:F

 system space group unit cell Å volume density properties references
dimagnesium fluoride nitride Mg2NF 1:1 tetragonal I41/amd a = 4.186 c = 10.042 [1]
H-Mg2NF 1:1 [1]
Mg3NF3 1:3 cubic Pm-3m a = 4.216 light green [1]
dicalcium fluoride nitride Ca2NF 1:1 cubic Fd3_m a=10.0215 Z=16 1006.46 2.987 light yellow [1]
dichromium fluoride nitride Cr2NF3 1:1 dark green [4]
dicobalt fluoride nitride Co2NF 1:1 [1]
dicopper fluoride nitride Cu2NF 1:1 [1]
CaMgNF 1:1 [1]
Fe4N3F3 1:1 [5]
α-Zn2NF 1:1 orthorhombic P212121 a = 5.850 b = 5.892 c = 6.536 band gap 2.7 [1]
β-Zn2NF 1:1 tetragonal P41212 a = 5.873 c = 6.532 band gap 2.8 [1]
α-Zn9N4F6 4:6 [1]
β-Zn9N4F6 4:6 [1]
Zn7N4F 4:1 [1]
distrontium fluoride nitride Sr2NF 1:1 Fd3_m a=10.692 Z=16 yellowish brown [1][6]
distrontium fluoride nitride Sr2NF 1:1 Fd3m a=10.765 Z=16 dark red [6]
SrCaNF 1:1 cubic Fd3_m a=10.340 Z=16 1105.6 3.862 yellow [7]
YNF3 1:3 hexagonal a = 5.93 c = 4.79 [8]
Zr4ON3F5 3:5 monoclinic P1121/b a = 5.1217 b = 2 1.513 c = 5.3669 γ = 90,128°, Z = 4
ZrNF 1:1 monoclinic P21/c a = 5.227 b = 5.026 c = 5.191, β = 98.98° [1]
Na0.3ZrNF1.3 1:1.3 P63/mmc a = 3.654 c = 18.266 [9]
TcNF 1:1 hexagonal a = 5.98 c = 4.79 [1]
dibarium fluoride nitride Ba2NF 1:1 Fm-3 m a=5.5.679, Z=2 dark violet [10]
LaNxF3-3x cubic a = 5.847-5.871 [1]
Ce3NF6 1:6 a = 5.8027 F− conductor [11][2]
Pr3NF6 1:6 a = 5.7723 [11]
Gd3NF6 1:6 cubic a = 5.617 [1]
Ce2MnN3F2−δ tetragonal P4/nmm a = 3.8554 c = 13.088 Nitridomanganate [12]
LiSr2[TaN3]F 3:1 orthorhombic Pbca a = 10.768 b = 5.591 c = 15.891 Z = 8 956.7 Nitridotantalate red, air sensitive [13]
ReNF 1:1 tetragonal a = 5.88 c = 13.00 [1]
Bi3NF6 1:6 orthorhombic Pbcm a = 5.8174 b = 5.7018 c = 18.5113 Z = 4 614.01 8.165 grey, moisture sensitive [14]
ThNF 1:1 rhombohedral a = 7.13 [1]
ThNxF4-3x tetragonal a = 4.06 – 4.148 c = 5.845 – 5.839 [1]
UNxFy (UNF) 1:1 orthorhombic a = 5.632-5.643, b = 5.602-5.610, c = 5.712-5.707 [1]
Complexes
(AsPh4+)2[Tc2O2N2F4]2- 1:2 yellow O bridged [15]
Rb4[F4TcNOTcNF4] orange yellow [15]
Cs4[F4TcNOTcNF4] orange yellow [15]
H[TcNF4] 1:4 [15]
(NEt4)3(NH4)[Tc4N4O4F8] yellow green [15]
molecules
phosphonitrile fluoride trimer (NPF2)3 1:2 rhombohedral triple point 27.8 °C; nα=1.388 nβ=1.419 nγ=1.443 [16][17]
phosphonitrile fluoride tetramer (NPF2)4 1:2 monoclinic triple point 30.5 °C [16]
phosphonitrile fluoride polymer (NPF2)n 1:2 [16]
ReNF3 1:3 brown [18]
rhenium tetrafluoride nitride ReNF4 1:4 orthorhombic a=5.64 b=14.76 c=4.26 354.6 yellow molecular mp 85 °C [18]
fluoroimidorhenium pentafluoride ReNF6 1:6 monoclinic a=5.298 b=9.286 c=9.979 β =109.4 Z=4 463.2 4.507 orange molecular N-F bond mp 80 °C [18]

References
  1. Al-Azzawi, Mohanad A. (2016). Synthesis and Characterization of Single Crystalline Metal Nitride Fluorides (Thesis). Youngstown State University.
  2. Noetzel, Gerd; Schweda, Eberhard; Wiemhöfer, Hans-Dieter (February 2010). "Ionic Conductivity of Ce3NF6". Zeitschrift für anorganische und allgemeine Chemie. 636 (2): 389–394. doi:10.1002/zaac.200900472.
  3. Dehnicke, Kurt.; Straehle, Joachim. (May 1993). "N-Halogenoimido complexes of transition metals". Chemical Reviews. 93 (3): 981–994. doi:10.1021/cr00019a007. ISSN 0009-2665.
  4. Westland, Alan D. (February 1973). "The reaction of chromium(II) fluoride with nitrogen". Journal of Inorganic and Nuclear Chemistry. 35 (2): 451–456. doi:10.1016/0022-1902(73)80556-1.
  5. Day, P. (1977). Electronic Structure and Magnetism of Inorganic Compounds. Royal Society of Chemistry. p. 127. ISBN 978-0-85186-291-0.
  6. Wagner, T.R. (November 2002). "Preparation and single-crystal structure analysis of Sr2NF". Journal of Solid State Chemistry. 169 (1): 13–18. Bibcode:2002JSSCh.169...13W. doi:10.1016/S0022-4596(02)00002-6.
  7. Keino, Oscar Kipruto (December 2017). "Investigations of Mixed-Anion Analogs of Manganite Perovskites and Bimetallic Group II Nitride Fluorides".
  8. Ashcraft, Richard Henry (1982). PREPARATION OF NEW METAL NITRIDE-FLUORIDES AND OTHER HIGH-TEMPERATURE STUDIES (Thesis thesis). hdl:1911/15665.
  9. Stoltz, C.; Ramesha, K.; Piccoli, P.; Toby, B. H.; Eichhorn, B. W. (October 2005). "A 0.3 ZrNF 1.3 Phases (A = Na, K) with Layered ZrNCl-Type Structures Prepared by Anion Metathesis". Chemistry of Materials. 17 (21): 5291–5296. doi:10.1021/cm051018h. ISSN 0897-4756.
  10. Seibel, H; Wagner, T.R (August 2004). "Preparation and crystal structure of Ba2NF". Journal of Solid State Chemistry. 177 (8): 2772–2776. Bibcode:2004JSSCh.177.2772S. doi:10.1016/j.jssc.2004.04.026.
  11. Vogt, T.; Schweda, E.; Laval, J.P.; Frit, B. (December 1989). "Neutron powder investigation of praseodymium and cerium nitride fluoride solid solutions". Journal of Solid State Chemistry. 83 (2): 324–331. Bibcode:1989JSSCh..83..324V. doi:10.1016/0022-4596(89)90182-5.
  12. Headspith, David A.; Sullivan, Eirin; Greaves, Colin; Francesconi, M. Grazia (2009). "Synthesis and characterisation of the quaternary nitride-fluoride Ce2MnN3F2−δ". Dalton Transactions (42): 9273–9. doi:10.1039/b908591b. ISSN 1477-9226. PMID 20449206.
  13. Pust, Philipp; Schnick, Wolfgang (September 2011). "LiSr2[TaN3]F - a Single Chain Nitridotantalate". Zeitschrift für anorganische und allgemeine Chemie. 637 (11): 1486–1489. doi:10.1002/zaac.201100207.
  14. Hofmann, M.; Schweda, E.; Strähle, J.; Laval, J.P.; Frit, B.; Estermann, M.A. (January 1995). "Synthesis and Structure of Bi3NF6: A Member with n = 3 of the Vernier Phases MnX2n+1". Journal of Solid State Chemistry. 114 (1): 73–78. Bibcode:1995JSSCh.114...73H. doi:10.1006/jssc.1995.1011.
  15. Balasekaran, Samundeeswari Mariappan (July 2013). "Fluorido complexes of Technetium". Freie Universität Berlin.
  16. Seel, F.; Langer, J. (July 1958). "Über Phosphornitrilfluoride. I". Zeitschrift für anorganische und allgemeine Chemie (in German). 295 (5–6): 316–326. doi:10.1002/zaac.19582950506. ISSN 0044-2313.
  17. Jagodzinski, H.; Langer, J.; Oppermann, I.; Seel, F. (November 1959). "Über Phosphornitrilfluoride. II. Zur Struktur und Kristallographie der Phosphornitrilfluoride". Zeitschrift für anorganische und allgemeine Chemie (in German). 302 (1–2): 81–87. doi:10.1002/zaac.19593020108. ISSN 0044-2313.
  18. Fawcett, John; Peacock, Raymond D.; Russell, David R. (1987). "Preparation of the nitrenes ReF5(NF), ReF5(NCl), and ReF5(NBr). X-Ray crystal structures of ReF5(NF) and ReF5(NCl)". Journal of the Chemical Society, Dalton Transactions (3): 567. doi:10.1039/dt9870000567. ISSN 0300-9246.
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