Nitride fluoride explained

Nitride fluorides containing nitride and fluoride ions with the formula NF^4-. They can be electronically equivalent to a pair of oxide ions O₂^4-. 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-N^2- 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	^[4]
	H-Mg2NF	1:1						H for 1250-1350 °C and 20 kbar
	Mg3NF3	1:3	cubic	Pmm	a = 4.216			light green
dicalcium fluoride nitride	Ca2NF	1:1	cubic	Fdm	a = 10.0215, Z = 16	1006.46	2.987	light yellow
dichromium fluoride nitride	Cr2NF3	1:3						dark green	^[5]
dicobalt fluoride nitride	Co2NF	1:1
dicopper fluoride nitride	Cu2NF	1:1
	CaMgNF	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
β			Zn2NF	1:1-->	tetragonal	P41212	a = 5.873, c = 6.532				band gap 2.8 eV
	Zn9N4F6	2:3						2 allotropes
	Zn7N4F	4:1
distrontium fluoride nitride	Sr2NF	1:1		Fdm	a = 10.692, Z = 16			yellowish brown	^[7]
				Sr2NF	1:1	-->	Fd3m	a = 10.765, Z = 16			dark red
	SrCaNF	1:1	cubic	Fdm	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°
	NaZr3N3F4	3:4		P63/mmc	a = 3.654, c = 18.266				^[10]
	TcNF	1:1	hexagonal		a = 5.98, c = 4.79
dibarium fluoride nitride	Ba2NF	1:1		Fmm	a = 5.679, Z = 2			dark violet	^[11]
	LaNF3(1-x

||x:3(1-x}||cubic|| ||a = 5.847 - 5.871|| || || |||-| ||Ce₃NF₆||1:6|| || ||a = 5.8027|| || ||F⁻ conductor||^[12] |-| ||Pr₃NF₆||1:6|| || ||a = 5.7723|| || || |||-| ||Gd₃NF₆||1:6||cubic|| ||a = 5.617|| || || |||-| ||Ce₂MnN₃F_2−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|| || || |||-| ||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|| || || |||-| ||ThNF_4-3x|| ||tetragonal || ||a = 4.06  - 4.148, c = 5.845  - 5.839| || || |||-| ||UNF (UNF)||1:1||orthorhombic|| ||a = 5.632 - 5.643, b = 5.602 - 5.610, c = 5.712 - 5.707|| || || |||-!colspan=10|Complexes|-| ||(AsPh)₂[O₂(TcNF₂)₂]^2-||1:2|| || || || || ||yellow, O-bridged||^[16] |-| ||Rb₄[O(TcNF₄)₂]||1:4|| || || || || ||orange yellow|||-| ||Cs₄[O(TcNF₄)₂]||1:4|| || || || || ||orange yellow|||-| ||H[TcNF₄]||1:4|| || || || || || |||-| ||(NEt₄)₃(NH₄)[Tc₄N₄O₄F₈]|| || || || || || ||yellow green|||-!colspan=10|molecules|-|phosphonitrile fluoride (trimer)||(NPF₂)₃||1:2||rhombohedral|| || || || ||triple point 27.8 °C; refractive index n_α = 1.388, n_β = 1.419, n_γ = 1.443||^{[17] [18]} |-|phosphonitrile fluoride (tetramer)||(NPF₂)₄||1:2||monoclinic|| || || || ||triple point 30.5 °C|||-|poly-phosphonitrile fluoride||(NPF₂)||1:2|| || || || || || |||-| ||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|||-|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|||-|}

Notes and References

1. Synthesis and Characterization of Single Crystalline Metal Nitride Fluorides. Youngstown State University. 2016. en. Mohanad A.. Al-Azzawi.
2. Noetzel . Gerd . Schweda . Eberhard . Wiemhöfer . Hans-Dieter . Ionic Conductivity of Ce3NF6 . Zeitschrift für anorganische und allgemeine Chemie . February 2010 . 636 . 2 . 389–394 . 10.1002/zaac.200900472.
3. Dehnicke. Kurt.. Straehle. Joachim.. May 1993. N-Halogenoimido complexes of transition metals. Chemical Reviews. en. 93. 3. 981–994. 10.1021/cr00019a007. 0009-2665.
4. Andersson . Sten . Magnesium nitride fluorides . Journal of Solid State Chemistry . April 1970 . 1 . 3-4 . 306–309 . 10.1016/0022-4596(70)90109-X.
5. Westland. Alan D.. February 1973. The reaction of chromium(II) fluoride with nitrogen. Journal of Inorganic and Nuclear Chemistry. en. 35. 2. 451–456. 10.1016/0022-1902(73)80556-1.
6. Book: Day, P.. [{{GBUrl|2oGP3_eJ7SgC|p=127}} Electronic Structure and Magnetism of Inorganic Compounds]. 1977. Royal Society of Chemistry. 978-0-85186-291-0. 127. en.
7. Wagner. T.R.. November 2002. Preparation and single-crystal structure analysis of Sr2NF. Journal of Solid State Chemistry. en. 169. 1. 13–18. 10.1016/S0022-4596(02)00002-6. 2002JSSCh.169...13W.
8. Web site: Keino. Oscar Kipruto. December 2017. Investigations of Mixed-Anion Analogs of Manganite Perovskites and Bimetallic Group II Nitride Fluorides.
9. PREPARATION OF NEW METAL NITRIDE-FLUORIDES AND OTHER HIGH-TEMPERATURE STUDIES. 1982. Thesis. Richard Henry. Ashcraft. 1911/15665.
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. en. 17. 21. 5291–5296. 10.1021/cm051018h. 0897-4756.
11. Seibel. H. Wagner. T.R. August 2004. Preparation and crystal structure of Ba2NF. Journal of Solid State Chemistry. en. 177. 8. 2772–2776. 10.1016/j.jssc.2004.04.026. 2004JSSCh.177.2772S.
12. 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. en. 83. 2. 324–331. 10.1016/0022-4596(89)90182-5. 1989JSSCh..83..324V.
13. Headspith. David A.. Sullivan. Eirin. Greaves. Colin. Francesconi. M. Grazia. 2009. Synthesis and characterisation of the quaternary nitride-fluoride Ce2MnN3F2−δ. Dalton Transactions. en. 42. 9273–9. 10.1039/b908591b. 20449206. 1477-9226.
14. Pust. Philipp. Schnick. Wolfgang. September 2011. LiSr2[TaN3]F – a Single Chain Nitridotantalate. Zeitschrift für anorganische und allgemeine Chemie. en. 637. 11. 1486–1489. 10.1002/zaac.201100207.
15. 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. en. 114. 1. 73–78. 10.1006/jssc.1995.1011. 1995JSSCh.114...73H.
16. Web site: Balasekaran. Samundeeswari Mariappan. July 2013. Fluorido complexes of Technetium. Freie Universität Berlin.
17. Seel. F.. Langer. J.. July 1958. Über Phosphornitrilfluoride. I. Zeitschrift für anorganische und allgemeine Chemie. de. 295. 5–6. 316–326. 10.1002/zaac.19582950506. 0044-2313.
18. 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. de. 302. 1–2. 81–87. 10.1002/zaac.19593020108. 0044-2313.
19. 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. en. 3. 567–571. 10.1039/dt9870000567. 0300-9246.