Nitro­sonium tetra­fluorido­borate, NOBF4

Lozinšek, M.

doi:10.1107/S2414314621012153

inorganic compounds

IUCrDATA

ISSN: 2414-3146

Volume 6| Part 11| November 2021| x211215

https://doi.org/10.1107/S2414314621012153

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Nitrosonium tetrafluoridoborate, NOBF₄

Matic Lozinšek ^a ^*

^aDepartment of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova cesta 39, 1000 Ljubljana, Slovenia
^*Correspondence e-mail: matic.lozinsek@ijs.si

Edited by M. Weil, Vienna University of Technology, Austria (Received 9 November 2021; accepted 16 November 2021; online 18 November 2021)

The crystal structure of oxidonitrogen(1+) tetrafluoridoborate (nitrosonium tetrafluoridoborate), NO⁺BF₄⁻, was refined on the basis of single-crystal X-ray diffraction data at 150 K. The compound crystallizes in the baryte structure type with orthorhombic Pnma symmetry. The crystal structure exhibits cationic disorder with equal occupation of N and O atoms at the same site.

Keywords: crystal structure; tetrafluoridoborate; nitrosonium; redetermination.

CCDC reference: 2122392

Structure description

Numerous nitrosonium fluorido salts are known (e.g., Sunder et al., 1979 ; Mazej et al., 2009 ) and several of them have been structurally characterized (e.g., Adam et al., 1996 ). Nonetheless, for nitrosonium tetrafluoridoborate (NOBF₄), which is an efficient one-electron oxidant, nitrosating and diazotizing agent (Olah et al., 2004 ), only the unit-cell parameters derived from X-ray powder diffraction data have been reported previously (a = 6.983 Å, b = 8.911 Å, c = 5.675 Å, space group Pbnm; Evans et al., 1964 ). Nitrosonium tetrafluoridoborate crystallizes in the baryte (BaSO₄) structure type and is isotypic with ammonium, alkali metal (K, Rb, Cs) (Clark & Lynton, 1969 ) and dioxygen(1+) tetrafluoridoborates (Wilson et al., 1971 ). The current unit cell (Table 1) refined from single-crystal X-ray data at 150 K is in good agreement with the aforementioned previously published values.

Table 1
Experimental details

Crystal data
Chemical formula	NO⁺BF₄⁻
M_r	116.82
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	150
a, b, c (Å)	8.8588 (3), 5.6268 (2), 6.8460 (2)
V (Å³)	341.25 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.31
Crystal size (mm)	0.24 × 0.19 × 0.12

Data collection
Diffractometer	New Gemini, Dual, Cu at home/near, Atlas
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Rigaku Corporation, The Woodlands, TX, USA.]$ )
T_min, T_max	0.948, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	16165, 976, 824
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.864

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.081, 1.10
No. of reflections	976
No. of parameters	37
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.28
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Rigaku Corporation, The Woodlands, TX, USA.]$ ), SUPERFLIP (Palatinus & Chapuis, 2007 ; Palatinus & van der Lee, 2008 ; Palatinus et al., 2012 ), SHELXL (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ), DIAMOND (Brandenburg, 2005 ) and publCIF (Westrip, 2010 ).

The asymmetric unit of the NOBF₄ crystal structure is composed of atoms B1, F1, and F2, which coincide with the crystallographic mirror plane (Wyckoff position 4c; site symmetry .m.), whereas atoms F3 and disordered N1/O1, are located on general positions (Wyckoff position 8d) (Fig. 1). The BF₄⁻ anion has a slightly distorted tetrahedral shape, with F—B—F bond angles ranging from 108.42 (6) to 111.11 (7)° and B—F bond lengths of 1.3863 (10), 1.3872 (10) and 1.4042 (6) Å involving atoms F1, F2, and F3, respectively. Similar values were observed in NO₂BF₄ (Krossing et al., 2007 ) and other BF₄⁻ salts (Radan et al., 2011 ; Lozinšek et al., 2009 ) or complexes (Tavčar & Žemva, 2005 ). The NO⁺ cation is disordered across a crystallographic mirror plane, with atoms N1 and O1 sharing the same site. It is noteworthy that the orientational cationic disorder in the salt NOBF₄ was studied previously by heat capacity measurements from 10 to 304 K (Callanan et al., 1981 ). The N—O bond length of 1.0216 (10) Å in NOBF₄ is similar to the values reported for other nitrosonium fluoride salts, for instance: 1.052 (6) Å in NOUF₆ at 100 K (Scheibe et al., 2016 ) and 1.012 (6) Å in NOSbF₆ at 150 K (Mazej & Goreshnik, 2021 ), with both salts also exhibiting disordered NO⁺ groups. Each anion is surrounded by seven cations and vice versa, with fourteen (N/O)⋯F contacts shorter than 3.0 Å; the shortest contacts [2.6211 (6), 2.6222 (6), and 2.6560 (6) Å] involve atom F3. In the crystal structure, the NO⁺ cations are oriented parallel to the b axis (Fig. 2).

Figure 1
Expanded asymmetric unit of NOBF₄ with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) x, −y + $[{1\over 2}]$ , z.]

Figure 2
View of the packing in the unit cell of the NOBF₄ crystal structure.

Synthesis and crystallization

A sample of NOBF₄ suitable for single-crystal X-ray diffraction was obtained from a commercial source (Alfa Aesar, 98%). Crystals were placed onto a watch glass and covered with a protective layer of perfluorodecalin (ABCR, AB102850, 98%, cis and trans) inside an argon-filled glovebox (MBraun, H₂O < 0.5 ppm). A suitable colorless crystal was selected under a polarizing microscope outside the glovebox, mounted on a MiTeGen Dual Thickness MicroLoop with the aid of Baysilone-Paste, and quickly transferred into a cold nitrogen stream of the X-ray diffractometer.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The coordinates and anisotropic displacement parameters of the disordered atoms O1 and N1 sharing the same site were constrained to be equal (EXYZ, EADP) and their site occupancy factor set to 0.5.

Structural data

CCDC reference: 2122392

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314621012153/wm4156sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621012153/wm4156Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2021); cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: Superflip (Palatinus & Chapuis, 2007; Palatinus & van der Lee, 2008; Palatinus et al., 2012); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009), DIAMOND (Brandenburg, 2005); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Oxidonitrogen(1+) tetrafluoridoborate top

Crystal data top

NO⁺·BF₄⁻	D_x = 2.274 Mg m⁻³
M_r = 116.82	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 8015 reflections
a = 8.8588 (3) Å	θ = 3.8–37.6°
b = 5.6268 (2) Å	µ = 0.31 mm⁻¹
c = 6.8460 (2) Å	T = 150 K
V = 341.25 (2) Å³	Irregular, clear colourless
Z = 4	0.24 × 0.19 × 0.12 mm
F(000) = 224

Data collection top

New Gemini, Dual, Cu at home/near, Atlas diffractometer	976 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	824 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Detector resolution: 10.6426 pixels mm^-1	θ_max = 37.9°, θ_min = 3.8°
ω scans	h = −15→15
Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2021)	k = −9→9
T_min = 0.948, T_max = 0.975	l = −11→11
16165 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Primary atom site location: iterative
R[F² > 2σ(F²)] = 0.025	w = 1/[σ²(F_o²) + (0.045P)² + 0.0254P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.081	(Δ/σ)_max < 0.001
S = 1.10	Δρ_max = 0.22 e Å⁻³
976 reflections	Δρ_min = −0.28 e Å⁻³
37 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	Occ. (<1)
F1	0.34796 (7)	0.250000	0.97160 (7)	0.02402 (13)
F2	0.59689 (6)	0.250000	0.88293 (9)	0.02508 (13)
F3	0.42423 (4)	0.45243 (7)	0.70118 (6)	0.02149 (11)
B1	0.44886 (9)	0.250000	0.81682 (11)	0.01500 (14)
O1	0.31375 (5)	0.34078 (9)	0.35238 (7)	0.02274 (12)	0.5
N1	0.31375 (5)	0.34078 (9)	0.35238 (7)	0.02274 (12)	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0301 (3)	0.0280 (3)	0.0140 (2)	0.000	0.00714 (18)	0.000
F2	0.0191 (2)	0.0290 (3)	0.0272 (3)	0.000	−0.01088 (19)	0.000
F3	0.02134 (18)	0.02461 (19)	0.01852 (18)	0.00146 (13)	−0.00060 (11)	0.00719 (12)
B1	0.0152 (3)	0.0187 (3)	0.0111 (3)	0.000	−0.0013 (2)	0.000
O1	0.0181 (2)	0.0266 (2)	0.0235 (2)	0.00024 (16)	−0.00237 (14)	0.00430 (17)
N1	0.0181 (2)	0.0266 (2)	0.0235 (2)	0.00024 (16)	−0.00237 (14)	0.00430 (17)

Geometric parameters (Å, º) top

F1—B1	1.3863 (10)	F3—B1	1.4042 (6)
F2—B1	1.3872 (10)	O1—N1ⁱ	1.0216 (10)

F1—B1—F2	111.11 (7)	F2—B1—F3ⁱ	109.32 (4)
F1—B1—F3ⁱ	109.32 (4)	F2—B1—F3	109.32 (4)
F1—B1—F3	109.31 (4)	F3ⁱ—B1—F3	108.42 (6)

Symmetry code: (i) x, −y+1/2, z.

Funding information

The author is grateful for research funding from the Jožef Stefan Institute Director's Fund, the Slovenian Research Agency (N1-0189, P1-0045), and the European Research Council (950625).

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