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 N:F ratio system space group unit cell (Å) volume density properties references
dimagnesium fluoride nitride L-Mg2NF 1:1 tetragonal I41/amd a = 4.186, c = 10.042 decompose over 1000 °C to MgF2, Mg gas and N2 [1][4]
H-Mg2NF 1:1 H for 1250-1350 °C and 20 kbar [1][4]
Mg3NF3 1:3 cubic Pm3m a = 4.216 light green [1][4]
dicalcium fluoride nitride Ca2NF 1:1 cubic Fd3m a = 10.0215, Z = 16 1006.46 2.987 light yellow [1]
dichromium fluoride nitride Cr2NF3 1:3 dark green [5]
dicobalt fluoride nitride Co2NF 1:1 [1]
dicopper fluoride nitride Cu2NF 1:1 [1]
CaMgNF 1:1 [1]
Fe4N3F3 1:1 [6]
α Zn2NF 1:1 orthorhombic P212121 a = 5.850, b = 5.892, c = 6.536 band gap 2.7 eV [1]
β tetragonal P41212 a = 5.873, c = 6.532 band gap 2.8 eV
Zn9N4F6 2:3 2 allotropes [1]
Zn7N4F 4:1 [1]
distrontium fluoride nitride Sr2NF 1:1 Fd3m a = 10.692, Z = 16 yellowish brown [1][7]
Fd3m a = 10.765, Z = 16 dark red [7]
SrCaNF 1:1 cubic Fd3m a = 10.340, Z = 16 1105.6 3.862 yellow [8]
YNF3 1:3 hexagonal a = 5.93, c = 4.79 [9]
Zr4ON3F5 3:5 monoclinic P1121/b a = 5.1217, b = 21.513, 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]
NaZr3N3F4 3:4 P63/mmc a = 3.654, c = 18.266 [10]
TcNF 1:1 hexagonal a = 5.98, c = 4.79 [1]
dibarium fluoride nitride Ba2NF 1:1 Fm3m a = 5.679, Z = 2 dark violet [11]
LaNxF3(1-x} x:3(1-x} cubic a = 5.847–5.871 [1]
Ce3NF6 1:6 a = 5.8027 F− conductor [12][2]
Pr3NF6 1:6 a = 5.7723 [12]
Gd3NF6 1:6 cubic a = 5.617 [1]
Ce2MnN3F2−δ tetragonal P4/nmm a = 3.8554, c = 13.088 Nitridomanganate [13]
LiSr2[TaN3]F 3:1 orthorhombic Pbca a = 10.768, b = 5.591, c = 15.891, Z 8 956.7 Nitridotantalate, red, air sensitive [14]
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 [15]
ThNF 1:1 rhombohedral a = 7.13 [1]
ThNxF4-3x tetragonal [1]
UNxFy (UNF) 1:1 orthorhombic a = 5.632–5.643, b = 5.602–5.610, c = 5.712–5.707 [1]
Complexes
(AsPh+
4)2[O2(TcNF2)2]2-		 1:2 yellow, O-bridged [16]
Rb4[O(TcNF4)2] 1:4 orange yellow [16]
Cs4[O(TcNF4)2] 1:4 orange yellow [16]
H[TcNF4] 1:4 [16]
(NEt4)3(NH4)[Tc4N4O4F8] yellow green [16]
molecules
phosphonitrile fluoride (trimer) (NPF2)3 1:2 rhombohedral triple point 27.8 °C; refractive index nα = 1.388, nβ = 1.419, nγ = 1.443 [17][18]
phosphonitrile fluoride (tetramer) (NPF2)4 1:2 monoclinic triple point 30.5 °C [17]
poly-phosphonitrile fluoride (NPF2)n 1:2 [17]
ReNF3 1:3 brown [19]
rhenium tetrafluoride nitride ReNF4 1:4 orthorhombic a = 5.64, b = 14.76, c = 4.26 354.6 yellow, molecular, mp 85 °C [19]
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 bonded, mp 80 °C [19]
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  8. ^ Keino, Oscar Kipruto (December 2017). "Investigations of Mixed-Anion Analogs of Manganite Perovskites and Bimetallic Group II Nitride Fluorides".
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  10. ^ 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.
  11. ^ 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.
  12. ^ a b 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.
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  19. ^ a b c 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): 567–571. doi:10.1039/dt9870000567. ISSN 0300-9246.