Crystal structure reinvestigation of silver(I) fluoride, AgF

Lozinšek, M.; Belak Vivod, M.; Dragomir, M.

doi:10.1107/S2414314623000184

inorganic compounds

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Volume 8| Part 1| January 2023| x230018

https://doi.org/10.1107/S2414314623000184

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Crystal structure reinvestigation of silver(I) fluoride, AgF

Matic Lozinšek,^a,^b ^* Matic Belak Vivod ^a,^b and Mirela Dragomir ^a,^b

^aJožef Stefan Institute, Jamova cesta 39, 1000 Ljubljana, Slovenia, and ^bJožef Stefan International Postgraduate School, Jamova cesta 39, 1000, Ljubljana, Slovenia
^*Correspondence e-mail: matic.lozinsek@ijs.si

Edited by M. Weil, Vienna University of Technology, Austria (Received 13 December 2022; accepted 7 January 2023; online 24 January 2023)

A crystal structure reinvestigation of AgF based on a low-temperature high-resolution single-crystal X-ray diffraction data is reported. Silver(I) fluoride crystallizes in the rock salt structure type (Fm $[\overline{3}]$ m) with a unit-cell parameter of 4.92171 (14) Å at 100 K, resulting in an Ag—F bond length of 2.46085 (7) Å.

Keywords: silver(I) fluoride; silver fluorides; crystal structure; single-crystal X-ray diffraction.

CCDC reference: 2235315

Structure description

Crystal structure data of the following binary silver fluorides can be retrieved from the Inorganic Crystal Structure Database (ICSD; Bergerhoff et al., 1983 ; Zagorac et al., 2019 ): Ag₂F, AgF, AgF₂, AgF₃, Ag₂F₅, and Ag₃F₈ (Table 1).

Table 1
Crystal structure data of binary silver fluorides reported in the ICSD database (only one entry for each crystalline phase is given)

PND = powder neutron diffraction; PXRD = powder X-ray diffraction; SCXRD = single-crystal X-ray diffraction.

Compound	Space group	Unit-cell parameters	Method, conditions	Reference
Ag₂F	P $[\overline{3}]$ m1	a = 2.99877 (5) Å, c = 5.6950 (2) Å	PND, 300 K	Williams (1989)
AgF	Fm $[\overline{3}]$ m	a = 4.92 Å	PXRD	Ott (1926)
AgF₂	P2₁/n	a = 3.34 Å, b = 4.57 Å, c = 4.65 Å, β = 84.5°	PXRD, 123 K / 195 K	Baturina et al. (1967)
AgF₂	Pbca	a = 5.568 (1) Å, b = 5.831 (1) Å, c = 5.101 (1) Å	SCXRD	Jesih et al. (1990)
AgF₂	Pbcn	a = 5.476 (10) Å, b = 8.331 (15) Å, c = 5.787 (7) Å	Synchrotron PXRD, 14.8 GPa	Grzelak et al. (2017b)
AgF₂	Pca2₁	a = 5.475 (7) Å, b = 4.704 (6) Å, c = 5.564 (6) Å	Synchrotron PXRD, 10 GPa	Grzelak et al. (2017a)
AgF₃	P6₁22	a = 5.0782 (2) Å, c = 15.4523 (8) Å	PND	Žemva et al. (1991)
Ag₂F₅	P $[\overline{1}]$	a = 4.999 (2) Å, b = 11.087 (5) Å, c = 7.357 (3) Å, α = 90.05 (3)°, β = 106.54 (4)°, γ = 90.18 (4)°	SCXRD	Fischer & Müller (2002)
Ag₃F₈	P2₁/n	a = 5.04664 (8) Å, b = 11.0542 (2) Å, c = 5.44914 (9) Å, β = 97.170 (2)°	Synchrotron PXRD, 299 K	Graudejus et al. (2000)

The crystal structure of silver subfluoride, Ag₂F, was elucidated from powder and single-crystal X-ray diffraction data (Ott & Seyfarth, 1928 ; Terrey & Diamond, 1928 ; Argay & Náray-Szabó, 1966 ) as well as studied by powder neutron diffraction measurements from room temperature to 20 K (Williams, 1989 ). Silver(I) fluoride, AgF, has been investigated at ambient conditions only by powder X-ray diffraction (Ott, 1926 ; Bottger, & Geddes, 1972 ). The high-pressure structural behavior of AgF was thoroughly studied by powder X-ray diffraction (Halleck et al., 1972 ; Jamieson et al., 1975 ), powder neutron diffraction experiments to 6.5 GPa (Hull & Berastegui, 1998 ), and by synchrotron powder X-ray diffraction measurements up to 39 GPa (Grzelak et al., 2017a ). Silver(II) fluoride, AgF₂, was studied by powder X-ray diffraction (Ruff & Giese, 1934 ; Charpin et al., 1966 ; Baturina et al., 1967 ; Kiselev et al., 1988 ) and its crystal structure determined from single-crystal X-ray diffraction data (Jesih et al., 1990 ), as well as by powder neutron diffraction (Charpin et al., 1970 ; Fischer et al., 1971 ). Moreover, the high-pressure structural behavior of AgF₂ was explored employing synchrotron X-ray diffraction (Grzelak et al., 2017a,b ). The crystal structure of silver(III) fluoride, AgF₃, was refined from powder neutron diffraction data and synchrotron powder X-ray diffraction data was also measured (Žemva et al., 1991 ). A mixed-valence silver(II,III) fluoride Ag₂F₅, or Ag^IIF[Ag^IIIF₄], was structurally characterized by single-crystal X-ray diffraction (Fischer & Müller, 2002 ), whereas the crystal structure of Ag₃F₈, or Ag^II[Ag^IIIF₄]₂, was determined by synchrotron powder X-ray diffraction (Graudejus et al., 2000 ). Two recent reports explored the pressure–composition phase diagram of binary silver fluorides by theoretical methods (Kurzydłowski et al., 2021 ; Rybin et al., 2022 ).

Herein, a low-temperature high-resolution (0.54 Å) single-crystal X-ray diffraction measurement of AgF (rock salt structure type, Fm $[\overline{3}]$ m) is reported (Fig. 1). The unit-cell parameter (Table 2) is in good agreement with the previously reported room-temperature value of 4.936 (1) Å (Bottger & Geddes, 1972). The Ag—F bond length determined from the current low-temperature data is 2.46085 (7) Å.

Table 2
Experimental details

Crystal data
Chemical formula	AgF
M_r	126.87
Crystal system, space group	Cubic, Fm $[\overline{3}]$ m
Temperature (K)	100
a (Å)	4.92171 (14)
V (Å³)	119.22 (1)
Z	4
Radiation type	Ag Kα, λ = 0.56087 Å
μ (mm⁻¹)	8.51
Crystal size (mm)	0.06 × 0.05 × 0.05

Data collection
Diffractometer	XtaLAB Synergy-S, Dualflex, Eiger2 R CdTe 1M
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 )
T_min, T_max	0.724, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	730, 37, 37
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.926

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.011, 0.020, 1.28
No. of reflections	37
No. of parameters	3
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.55
Computer programs: CrysAlis PRO (Rigaku OD, 2022), OLEX2.solve and OLEX2 (Dolomanov et al., 2009 ), SHELXL (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2005 ) and publCIF (Westrip, 2010 ).

Figure 1
The rock salt-type structure of AgF. Displacement ellipsoids are drawn at the 50% probability level.

Synthesis and crystallization

Agglomerated single-crystals with typical dimensions of ∼50 µm were recovered from a solid-state reaction (T = 310 °C) where AgF (Thermo Scientific, 99+%) was used as a starting material. A small amount of sample was placed onto a watch glass and covered with a protective layer of perfluorodecalin (Fluorochem, 96.0%, cis and trans) inside a nitrogen-filled glovebox (Vigor, H₂O < 0.1 ppm). The sample was examined under a polarizing microscope outside the glovebox, and selected crystals were mounted on a MiTeGen Dual Thickness MicroLoops with the aid of Baysilone-Paste (Bayer-Silicone, mittelviskos).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Structural data

CCDC reference: 2235315

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314623000184/wm4179sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623000184/wm4179Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2022); cell refinement: CrysAlis PRO (Rigaku OD, 2022); data reduction: CrysAlis PRO (Rigaku OD, 2022); program(s) used to solve structure: olex2.solve 1.5 (Dolomanov et al., 2009); program(s) used to refine structure: SHELXL 2019/2 (Sheldrick, 2015); molecular graphics: OLEX2 1.5 (Dolomanov et al., 2009), DIAMOND (Brandenburg, 2005); software used to prepare material for publication: OLEX2 1.5 (Dolomanov et al., 2009), publCIF (Westrip, 2010).

Silver(I) fluoride top

Crystal data top

AgF	Ag Kα radiation, λ = 0.56087 Å
M_r = 126.87	Cell parameters from 689 reflections
Cubic, Fm3m	θ = 5.7–31.2°
a = 4.92171 (14) Å	µ = 8.51 mm⁻¹
V = 119.22 (1) Å³	T = 100 K
Z = 4	Irregular, colourless
F(000) = 224	0.06 × 0.05 × 0.05 mm
D_x = 7.068 Mg m⁻³

Data collection top

XtaLAB Synergy-S, Dualflex, Eiger2 R CdTe 1M diffractometer	37 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Ag) X-ray Source	37 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.050
Detector resolution: 13.3333 pixels mm^-1	θ_max = 31.3°, θ_min = 5.7°
ω scans	h = −9→8
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	k = −9→8
T_min = 0.724, T_max = 1.000	l = −8→8
730 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Primary atom site location: iterative
R[F² > 2σ(F²)] = 0.011	w = 1/[σ²(F_o²) + 0.2914P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.020	(Δ/σ)_max < 0.001
S = 1.28	Δρ_max = 0.59 e Å⁻³
37 reflections	Δρ_min = −0.55 e Å⁻³
3 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ag1	0.000000	0.000000	0.000000	0.01650 (12)
F1	0.500000	0.000000	0.000000	0.0199 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.01650 (12)	0.01650 (12)	0.01650 (12)	0.000	0.000	0.000
F1	0.0199 (8)	0.0199 (8)	0.0199 (8)	0.000	0.000	0.000

Geometric parameters (Å, º) top

Ag1—F1ⁱ	2.4609 (1)	Ag1—F1ⁱⁱⁱ	2.4609 (1)
Ag1—F1ⁱⁱ	2.4609 (1)	Ag1—F1^iv	2.4609 (1)
Ag1—F1	2.4609 (1)	Ag1—F1^v	2.4609 (1)

F1ⁱ—Ag1—F1	90.0	Ag1^vi—F1—Ag1	90.0
F1^v—Ag1—F1ⁱⁱⁱ	180.0	Ag1^vii—F1—Ag1^viii	180.0
F1^v—Ag1—F1ⁱⁱ	90.0	Ag1^vii—F1—Ag1^ix	90.0
F1^iv—Ag1—F1ⁱⁱⁱ	90.0	Ag1^x—F1—Ag1^viii	90.0
F1—Ag1—F1ⁱⁱ	90.0	Ag1—F1—Ag1^ix	90.0
F1^iv—Ag1—F1ⁱⁱ	90.0	Ag1^x—F1—Ag1^ix	90.0
F1ⁱ—Ag1—F1^v	90.0	Ag1—F1—Ag1^viii	90.0
F1ⁱ—Ag1—F1^iv	90.0	Ag1^vi—F1—Ag1^x	90.0
F1—Ag1—F1^v	90.0	Ag1—F1—Ag1^vii	90.0
F1ⁱ—Ag1—F1ⁱⁱ	180.0	Ag1^vi—F1—Ag1^ix	180.0
F1^iv—Ag1—F1^v	90.0	Ag1^x—F1—Ag1^vii	90.0
F1—Ag1—F1^iv	180.0	Ag1—F1—Ag1^x	180.0
F1ⁱ—Ag1—F1ⁱⁱⁱ	90.0	Ag1^vi—F1—Ag1^viii	90.0
F1—Ag1—F1ⁱⁱⁱ	90.0	Ag1^viii—F1—Ag1^ix	90.0
F1ⁱⁱⁱ—Ag1—F1ⁱⁱ	90.0	Ag1^vi—F1—Ag1^vii	90.0

Symmetry codes: (i) x−1/2, y+1/2, z; (ii) x−1/2, y−1/2, z; (iii) x−1/2, y, z+1/2; (iv) x−1, y, z; (v) x−1/2, y, z−1/2; (vi) x+1/2, y+1/2, z; (vii) x+1/2, y, z−1/2; (viii) x+1/2, y, z+1/2; (ix) x+1/2, y−1/2, z; (x) x+1, y, z.

Crystal structure data of binary silver fluorides reported in the ICSD database (only one entry for each crystalline phase is given) top

PND = powder neutron diffraction; PXRD = powder X-ray diffraction; SCXRD = single-crystal X-ray diffraction.

Compound	Space group	Unit-cell parameters	Method, conditions	Reference
Ag₂F	P3m1	a = 2.99877 (5) Å, c = 5.6950 (2) Å	PND, 300 K	Williams (1989)
AgF	Fm3m	a = 4.92 Å	PXRD	Ott (1926)
AgF₂	P2₁/n	a = 3.34 Å, b = 4.57 Å, c = 4.65 Å, β = 84.5°	PXRD, 123 K / 195 K	Baturina et al. (1967)
AgF₂	Pbca	a = 5.568 (1) Å, b = 5.831 (1) Å, c = 5.101 (1) Å	SCXRD	Jesih et al. (1990)
AgF₂	Pbcn	a = 5.476 (10) Å, b = 8.331 (15) Å, c = 5.787 (7) Å	Synchrotron PXRD, 14.8 GPa	Grzelak et al. (2017b)
AgF₂	Pca2₁	a = 5.475 (7) Å, b = 4.704 (6) Å, c = 5.564 (6) Å	Synchrotron PXRD, 10 GPa	Grzelak et al. (2017a)
AgF₃	P6₁22	a = 5.0782 (2) Å, c = 15.4523 (8) Å	PND	Žemva et al. (1991)
Ag₂F₅	P1	a = 4.999 (2) Å, b = 11.087 (5) Å, c = 7.357 (3) Å, α = 90.05 (3)°, β = 106.54 (4)°, γ = 90.18 (4)°	SCXRD	Fischer & Müller (2002)
Ag₃F₈	P2₁/n	a = 5.04664 (8) Å, b = 11.0542 (2) Å, c = 5.44914 (9) Å, β = 97.170 (2)°	Synchrotron PXRD, 299 K	Graudejus et al. (2000)

Funding information

Funding for this research was provided by: Slovenian Research Agency (grant Nos. J2-2496 and P2-0105); European Research Council (ERC) and Marie Skłodowska-Curie Individual Fellowship (MSCA-IF) under the European Union's Horizon 2020 research and innovation programme (grant Nos. 950625 and 101031415); Jožef Stefan Institute Director's Fund.

References

Argay, G. & Náray-Szabó, I. (1966). Acta Chim. Acad. Sci. Hung. 49, 329–337. CAS Google Scholar
Baturina, É. A., Luk'yanychev, Y. A. & Rastorguev, L. N. (1967). J. Struct. Chem. 7, 591–592. CrossRef Google Scholar
Bergerhoff, G., Hundt, R., Sievers, R. & Brown, I. D. (1983). J. Chem. Inf. Comput. Sci. 23, 66–69. CrossRef CAS Web of Science Google Scholar
Bottger, G. L. & Geddes, A. L. (1972). J. Chem. Phys. 56, 3735–3739. CrossRef CAS Google Scholar
Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Charpin, P., Dianoux, A.-J., Marquet-Ellis, H. & Nguyen-Nghi (1966). C. R. Seances Acad. Sci., Ser. C, 263, 1359–1361. Google Scholar
Charpin, P., Plurien, P. & Mériel, P. (1970). Bull. Soc. Fr. Mineral. Cristallogr. 93, 7–13. CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fischer, P., Schwarzenbach, D. & Rietveld, H. M. (1971). J. Phys. Chem. Solids, 32, 543–550. CrossRef ICSD CAS Web of Science Google Scholar
Fischer, R. & Müller, B. G. (2002). Z. Anorg. Allg. Chem. 628, 2592–2596. CrossRef CAS Google Scholar
Graudejus, O., Wilkinson, A. P. & Bartlett, N. (2000). Inorg. Chem. 39, 1545–1548. CrossRef ICSD PubMed CAS Google Scholar
Grzelak, A., Gawraczyński, J., Jaroń, T., Kurzydłowski, D., Budzianowski, A., Mazej, Z., Leszczyński, P. J., Prakapenka, V. B., Derzsi, M., Struzhkin, V. V. & Grochala, W. (2017a). Inorg. Chem. 56, 14651–14661. CrossRef ICSD CAS PubMed Google Scholar
Grzelak, A., Gawraczyński, J., Jaroń, T., Kurzydłowski, D., Mazej, Z., Leszczyński, P. J., Prakapenka, V. B., Derzsi, M., Struzhkin, V. V. & Grochala, W. (2017b). Dalton Trans. 46, 14742–14745. CrossRef CAS PubMed Google Scholar
Halleck, P. M., Jamieson, J. C. & Pistorius, C. W. F. T. (1972). J. Phys. Chem. Solids, 33, 769–773. CrossRef CAS Google Scholar
Hull, S. & Berastegui, P. (1998). J. Phys.: Condens. Matter, 10, 7945–7955. CrossRef CAS Google Scholar
Jamieson, J. C., Halleck, P. M., Roof, R. B. & Pistorius, C. W. F. T. (1975). J. Phys. Chem. Solids, 36, 939–944. CrossRef CAS Google Scholar
Jesih, A., Lutar, K., Žemva, B., Bachmann, B., Becker, S., Müller, B. G. & Hoppe, R. (1990). Z. Anorg. Allg. Chem. 588, 77–83. CrossRef ICSD CAS Google Scholar
Kiselev, Yu. M., Popov, A. I., Timakov, A. A., Bukharin, K. V. & Sukhoverkhov, V. F. (1988). Russ. J. Inorg. Chem 33, 708–710. Google Scholar
Kurzydłowski, D., Derzsi, M., Zurek, E. & Grochala, W. (2021). Chem. Eur. J. 27, 5536–5545. PubMed Google Scholar
Ott, H. (1926). Z. Kristallogr. 63, 222–230. CrossRef CAS Google Scholar
Ott, H. & Seyfarth, H. (1928). Z. Kristallogr. 67, 430–433. CrossRef CAS Google Scholar
Rigaku OD (2022). CrysAlis PRO. Rigaku Corporation, Wrocław, Poland. Google Scholar
Ruff, O. & Giese, M. (1934). Z. Anorg. Allg. Chem. 219, 143–148. CrossRef CAS Google Scholar
Rybin, N., Chepkasov, I., Novoselov, D. Y., Anisimov, V. I. & Oganov, A. R. (2022). J. Phys. Chem. C, 126, 15057–15063. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Terrey, H. & Diamond, H. (1928). J. Chem. Soc. pp. 2820–2824. CrossRef Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Williams, A. (1989). J. Phys. Condens. Matter, 1, 2569–2574. CrossRef ICSD CAS Google Scholar
Zagorac, D., Müller, H., Ruehl, S., Zagorac, J. & Rehme, S. (2019). J. Appl. Cryst. 52, 918–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Žemva, B., Lutar, K., Jesih, A., Casteel, W. J. Jr, Wilkinson, A. P., Cox, D. E., Von Dreele, R. B., Borrmann, H. & Bartlett, N. (1991). J. Am. Chem. Soc. 113, 4192–4198. Google Scholar

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inorganic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure reinvestigation of silver(I) fluoride, AgF

Structure description

Synthesis and crystallization

Refinement

Structural data

Funding information

References

inorganic compounds