+/Metal and [XeF5]+/Non-Metal Mixed-Cation Salts of Hexafluoridoantimonate(V)

Article abstract of DOI:10.1002/ejic.201500028

New types of [XeF₅]⁺ salts, i.e., NO₂XeF₅(SbF₆)₂ and XeF₅[Cu(SbF₆)₃], are derived from reactions between XeF₅SbF₆ and NO₂Sb

Full text of DOI:10.1002/ejic.201500028

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DOI:10.1002/ejic.201500028
[XeF5]+/Metal and [XeF5]+/Non-Metal Mixed-Cation Salts
of Hexafluoridoantimonate(V)
Zoran Mazej*[a] and Evgeny Goreshnik[a]
Keywords: Xenon / Fluorine / Antimony / Copper / Cations / Raman spectroscopy / Structure elucidation
New types of [XeF5]+ salts, i.e., NO2XeF5(SbF6)2 and XeF5-
[Cu(SbF6)3], are derived from reactions between XeF5SbF6
and NO2SbF6 or Cu(SbF6)2, respectively. The crystal struc-
ture of the former consists of [NO2]+ and [XeF5]+ cations and
[SbF6]– anions. The main feature of the crystal structure of
XeF5[Cu(SbF6)3] are rings of CuF6 octahedra that share ap-
exes with SbF6 octahedra connected into an infinite tridi-
mensional framework. This arrangement leads to the forma-
tion of cavities within which [XeF5]+ cations are located. Ra-
man spectra of both [NO2]+/[XeF5]+ and [XeF5]+/Cu2+ mixed-
cation hexafluorido-antimonates(V) are reported herein.
examples where in addition to [XeF5]+ other cations are
present. The compounds are well soluble in aHF allowing
growth of colorless single crystals of very good quality.
Introduction
The synthesis of XeF6 was reported for the first time in
1962,[1] followed by three later reports in 1963.[2–4] It was
observed fairly quickly that XeF6 is a very good fluoride
ion donor forming [XeF5]+ or [Xe2F11]+ salts. None of the
compounds reported so far contain any additional cations
and studies on crystal structure that we are aware of have
stated that they are simple [Xe2F11]+ or [XeF5]+ salts of
various fluorido anions, with square planar [MF4]– (M =
Ag, Au),[5,6] octahedral [MF6]– (M = As, V, Nb, Ru, Au,
Pt),[5,6] polymeric [MF5]– (M = Cr, Ge),[5,6] octahedral
[MF6]2– (M = Ni, Pd),[5,6] or oligomeric [Ti4F19]3– geome-
Scheme 1. Syntheses of NO2XeF5(SbF6)2 and XeF5[Cu(SbF6)3].
tries.[7] Exceptions are XeF2·n(XeF5AsF6) (n = 2, 1, 0.5),[8]
[10]
XeF2·(XeF5RuF6),[9] and (XeF5CrF5)·XeF4
where ad-
Crystal Structure and Raman Spectra of NO2XeF5(SbF6)2
and XeF5[Cu(SbF6)3]
ditional ligands (XeF2, XeF4) are present and the recently
reported [XeF5]+ and [Xe2F11]+ salts with [OsO3F3] and
[μ-F(OsO3F2)2] anions.[11]
The crystal structure of NO2XeF5(SbF6)2 consists of
[NO2]+ and [XeF5]+ cations and [SbF6]– anions.[12] The Xe1
and F4 atoms of the [XeF5]+ cations are situated at the 2c
crystallographic site (a special position) on a fourfold axis;
the F3 atom is located in a general position, resulting in
three additional symmetry-generated F3Ј atoms. All three
atoms of the [NO2]+ cations are located on a twofold axis.
Results and Discussion
Synthesis of NO2XeF5(SbF6)2 and XeF5[Cu(SbF6)3]
The reaction between XeF5SbF6 and NO2SbF6 at ambi- Additionally, the nitrogen atom is placed at the intersection
ent temperature in anhydrous hydrogen fluoride (aHF) as a of three twofold axes (special position 2a) resulting in equal
solvent yields the first mixed-cation [NO2]+/[XeF5]+ com- N–O distances. The Sb atoms occupy the 4f special position
pound NO2XeF5(SbF6)2. In a similar way, but using on a twofold axis resulting in three pairs of equivalent
Cu(SbF6)2 instead of NO2SbF6, XeF5[Cu(SbF6)3] has been Sb–F bonds of the [SbF6]– anion. In the latter, the F4 and
synthesized (Scheme 1). Both compounds represent the first F5 atoms are disordered between two positions around the
F3–Sb1–F3Ј axis, with almost a 3:2 occupancy ratio be-
[a] Department of Inorganic Chemistry and Technology,
tween F4a and F5a atoms on the one side and F4b and
F5b on the other.
Jozef Stefan Institute,
Jamova 39, 1000 Ljubljana, Slovenia
E-mail: zoran.mazej@ijs.si
http://k1.ijs.si/en/
http://www.ijs.si/ijsw/JSI
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201500028.
The [XeF5]+ cation is based on pseudo-octahedral AX5E
VSEPR arrangements of bond pairs (X) and lone pairs (E),
which give rise to a square-pyramidal geometry. The
Xe–Fax bond [1.811(2) Å] is shorter than the remaining four
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Xe–Feeq distances [1.832(1) Å]. Each [XeF5]+ forms four
secondary contacts (2.786 Å) with F3 atoms coordinated to
four different SbF6 groups. The Sb–F3 distances involved
in secondary bonding with [XeF5]+ cations are 1.894(1) Å.
In the linear [NO2]+ cations the N–O bond lengths are
equal to 1.101(2) Å (Figure 1).
Figure 3. Part of the crystal structure of XeF5[Cu(SbF6)3] showing
the [XeF5]+ cation located in the cavity (bright octahedra: SbF6
units, dark octahedra CuF6 units). The secondary contacts between
the [XeF5]+ cation and four [SbF6]– anions are also shown; thermal
ellipsoids are drawn at the 50% probability level.
Figure 1. Packing of [NO2]+ and [XeF5]+ cations, and [SbF6]–
anions in the crystal structure of NO2XeF5(SbF6)2. Thermal ellip-
soids are drawn at the 50% probability level. Only one of the two
orientations of the disordered [SbF6]– anions is depicted.
A similar motif has been observed in AM(AsF6)3 (A =
[H3O]+, [NH4]+, O2+, NO+, K+, M = Mn; Fe, Co, Ni, Zn)
compounds where single charged cations (A) are also found
in a tridimensional framework consisting of MF6 and AsF6
octahedra (Figures S1 and S2).[14–16] There are two crystal-
lographically independent Cu atoms. The CuF6 octahedra
are distorted and their coordination can be described as
4+2 elongated octahedra [2ϫ1.918(2)/2ϫ1.968(2) Å and
2ϫ2.128(2) Å] for Cu1 and as 2+4 compressed octahedra
[2ϫ1.926(2) Å and 2ϫ2.038(2)/2ϫ2.073(2) Å] in the case
of Cu2.
The main feature of the XeF5[Cu(SbF6)3] structure are
rings of CuF6 octahedra sharing apexes with SbF6 octahe-
dra connected into an infinite tridimensional framework
(Figure 2).[13] In this arrangement cavities are formed where
[XeF5]+ cations are located (Figure 3). Because of the sec-
ondary Xe···F contacts they are slightly shifted from the
center of the cavities.
Such unusual compressed coordination has been ob-
served before in CuFAsF6, H3OCuF(AsF6)2, KCuAlF6, and
CsCuAlF6.[17,18] The shape of [XeF5]+ is similar to that in
NO2XeF5(SbF6)2 with an Xe–Fax bond length [1.798(2) Å]
shorter than in the case of Xe–Feq [1.827(2)–1.835(2) Å].
Each XeF5 group forms four secondary bond contacts
(2.739, 2.872, 2.88, and 3.068 Å) with F atoms belonging to
four [SbF6]– anions. The Sb–F distances of three crystallo-
graphically unique SbF6 groups can be divided into three
groups. The shortest are in the range 1.835(2)–1.847(2) Å
for terminal F atoms (Ft). The Sb–Ft bond lengths where
Ft are involved in secondary contacts with Xe atoms are
slightly longer [1.870(2)–1.877(2) Å] but shorter than Sb–Fb
bonds where fluorine atoms (Fb) bridge Sb and Cu atoms
[1.894(2)–1.952(2) Å].
Raman Spectra of NO2XeF5(SbF6)2 and XeF5[Cu(SbF6)3]
Raman spectra of NO2XeF5(SbF6)2 (1) and XeF5[Cu-
(SbF6)3] (2) are shown in Figure 4 and given in Table 1.
The Raman spectra recorded for the powdered samples
obtained by synthesis and the Raman spectra recorded for
the single crystals of (1) and (2) were essentially identical.
The strong Raman band at 654 cm–1 in the Raman spec-
trum of (1) could be assigned to a symmetric stretching (ν1)
mode and the weak ones at 547/552 cm–1 and 288 cm–1 to
Figure 2. The crystal structure of XeF5[Cu(SbF6)3] showing rings
of CuF6 units sharing apexes with SbF6 units, connected into an
infinite tridimensional framework. The [XeF5]+ cations are located
in the cavities (dark spheres: Sb; bright spheres: Cu; XeF5 units
have thicker Xe–F bonds).
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and v5(SbF6) were observed at 596 and 271/290 cm–1,
respectively (Figure S2). For this reason, the strongest band
in the Raman spectrum of (2) (Figure 4) at 675 cm–1 was
assigned to v1(SbF6) and the weak band at 283 cm–1 to
v5(SbF6). The bands between 705–723 cm–1, which are
otherwise Raman inactive in Oh symmetry, are assigned to
v3(SbF6) because of the lowering of the symmetry in the
solid state. The remainder of the vibrational bands are as-
signed to [XeF5]+ cations where (Xe–F)ax stretching vi-
brations (v1), the in-phase (Xe–F)eq stretching vibrations in
the XeF4 moiety (v2), and the out-of-plane in-phase bend-
ing vibration of XeF4 (v3) are found in the ranges 650–680,
580–630, and 330–360 cm–1, respectively.[20]
The weak bands at 620–660 belong to the doubly degen-
erate asymmetric stretching vibration of the XeF4 moiety
(v7), medium weak bands at 410/420 cm–1 to the Fax–Xe–
Figure 4. Raman spectra of NO2XeF5(SbF6)2 (1) and XeF5[Cu-
(SbF6)3] (2).
F
eq bending vibration (v8), very weak bands at 260/270 cm–1
to the out-of-plane bending (out of phase) vibration of
XeF4 (v5), and the medium weak bands at 570/580 cm–1 to
the out-of-phase stretching vibration of XeF4 (v4). Since the
ranges of different vibration modes observed in various
[XeF5]+ salts overlap[20] the given assignment of vibration
modes of the [XeF5]+ cation is only tentative. The possibil-
ity that some of the cation vibrational bands overlap with
the anionic ones could also not be completely excluded.
Table 1. Experimental Raman frequencies and intensities for
NO2XeF5(SbF6)2 (1) and XeF5[Cu(SbF6)3] (2).
1
2
Assignments
[XeF5]+
[SbF6]– [NO2]+
ν1(Σ+)
1405(50)
723(5)
715(5)
705(10)
ν3(F1u
ν3(F1u
ν3(F1u
)
)
)
687(5)
678(90)
654(100)
681(sh)
675(100)
654(10)
635(sh)
631(95)
610(20)
ν1(A1)
ν7(E)
Conclusions
ν1(A1g)
NO2XeF5(SbF6)2 and XeF5[Cu(SbF6)3] are the first ex-
amples of [XeF5]+/metal and [XeF5]+/non-metal mixed-cat-
ion compounds. Their syntheses shows that the preparation
of various new [XeF5]+ salts should be explored, which may
lead to many new mixed-cation [XeF5]+ phases in the fu-
ture.
632(50)
626(40)
581(10)
571(15)
552(10)
547(10)
ν2(A1)
ν2(A1)
ν4(B1)
ν4(B1)
574(5)
ν2(Eg)
ν2(Eg)
494(1)
406(15)
418(10)
362(1)
312(3)
ν8(E)
Experimental Section
ν3(A1)
ν3(A1)
ν3(A1)
308(sh)
297(5)
290(sh)
283(4)
General: Volatile materials (anhydrous HF, F2, and SbF5) were han-
dled in a nickel vacuum line and an all-PTFE vacuum system
equipped with PTFE valves as described previously.[21] The nonvol-
atile materials were manipulated in a dry box (M. Braun, Ger-
many). The residual water in the atmosphere within the dry box
never exceeded 2 ppm. The reactions were carried out in FEP
(tetrafluoroethylene-hexafluoropropylene; Polytetra GmbH, Ger-
many) reaction vessels (height 250–300 mm with inner diameter
15.5 mm and outer diameter 18.75 mm) equipped with PTFE
valves and PTFE-coated stirring bars. Prior to their use all reaction
vessels were passivated with elemental fluorine (Solvay Fluor and
Derivate GmbH, Germany).
288(10)
281(sh)
274(sh)
263(1)
ν5(F1g)
272(2)
ν5(B1)
ν5(B1)
v2(SbF6) and to bending (ν5) modes, respectively. The corre-
sponding bands of the [SbF6]– anion in the Raman spec-
trum of NO2SbF6 are at 661(vs), 576(w)/568(ms) and
283(m)/294(w) cm–1.[19] The Raman band at 1405 cm–1 is
assigned to the [NO2]+ cation.[19] As already mentioned, the
crystal structure of (2) resembles the structure type of AM-
(AsF6)3 compounds[14–16] where strong interactions between
M2+ cations and [AsF6]– anions are observed via shared
bridging fluorine atoms resulting in a similar tridimensional
framework (Figure S1) as shown in Figure 2. Further in-
vestigations show that (H3O)Cu(SbF6)3 appears to be iso-
structural and its Raman spectra show that the ν1 mode of
CoF3,[22] XeF2,[23] and Cu(SbF6)2
were prepared as described
[24]
previously. NO2F was prepared by a modified method[25] by reac-
tion between NO2 and CoF3 in a nickel autoclave at 270 °C.
NO2SbF6 and XeFSbF6 were prepared by reaction between NO2F
or XeF2 and SbF5 in anhydrous HF. XeF5SbF6 was synthesized by
reaction between XeFSbF6 and elemental F2 in aHF as solvent in
the presence of a UV light source [400 W medium pressure mercury
lamp (Baird and Tatlock, London, Type 400 LQ)].
Raman spectra with a resolution 0.5 cm–1 were recorded at room
the SbF6 group is shifted to 672 cm–1, meanwhile v2(SbF6) temperature with a HORIBA JOBIN YVON LabRam-HR spec-
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[3] E. E. Weaver, B. Weinstock, C. P. Knop, J. Am. Chem. Soc.
trometer equipped with an Olympus BXFM-ILHS microscope.
Samples were excited by the 632.8 nm emission line of a He–Ne
laser with regulated power in the range 20–0.0020 mW, which
equals a power of 17–0.0017 mW focused to a 1 μm spot on the
top surface of the sample using a 50x microscope objective. The
Raman spectra of both the bulk material and the single crystal
were essentially identical. X-ray powder diffraction patterns were
obtained using the Debye–Scherrer technique with Ni-filtered Cu-
Kα radiation. Samples were loaded into quartz capillaries (0.3 mm)
in a dry box. Intensities were estimated visually.
1963, 85, 111–112.
[4] F. B. Dudley, G. Gard, G. H. Cady, Inorg. Chem. 1963, 2, 228–
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ˇ
[5] B. Zemva, Croat. Chem. Acta 1988, 61, 163–187.
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[7] Z. Mazej, E. Goreshnik, Eur. J. Inorg. Chem. 2009, 4503–4506.
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[8] B. Zemva, L. Golicˇ, J. Slivnik, Vestn. Slov. Kem. Drus. 1983,
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In a dry box corresponding amounts of XeF5SbF6 and NO2SbF6
[or Cu(SbF6)2] were loaded into a FEP reaction vessel. aHF (3 mL)
was condensed onto the solid at 77 K and the reaction mixture was
brought to ambient temperature. The reaction mixtures were stirred
for 1 d at ambient temperature resulting in clear colorless solutions.
Volatiles were slowly pumped off at ambient temperature for 2 h
leaving behind a colorless solid. The final masses of the isolated
solids were 151 mg (calcd. for NO2XeF5[SbF6]2: 158 mg) and
190 mg (calcd. for [XeF5]Cu[SbF6]3: 187 mg). The Raman spectra
were recorded, and the X-ray powder diffraction diagrams were
obtained.
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[10] K. Lutar, I. Leban, T. Ogrin, B. Zemva, Eur. J. Solid State
Inorg. Chem. 1992, 29, 713–727.
[11] M. J. Hughes, H. P. A. Mercier, G. J. Schrobilgen, Inorg. Chem.
2010, 49, 3501–3515.
[12] Crystal data for NO2XeF5[SbF6]2: colorless block, Mr
=
743.82, tetragonal space group P4212, a = 10.6274(2), c =
5.9731(1) Å, V = 674.61(2) Å3, Z = 2, ρcalcd. = 3.662 gcm–3,
F(000) = 664, T = 150 K; 11576 reflections up to θ = 30.0°
collected, thereof 927 with I Ͼ 2σ(I), 941 independent reflec-
tions, 64 parameters. Final R indices: R1 = 0.012 (all), wR2 =
0.026 (all). The final difference Fourier synthesis gave a min./
max. residual electron density of 0.59/–0.40 eÅ–3.
[13] Crystal data for XeF5[Cu(SbF6)3]: colorless block, Mr
=
For both NO2XeF5[SbF6]2 and XeF5[Cu(SbF6)3] a T-shaped appa-
ratus consisting of two FEP tubes (19 and 6 mm outer diameter)
was used for single crystal growth. NO2XeF5[SbF6]2 and XeF5-
[Cu(SbF6)3] (approximately 90 mg) were loaded into the wider arm
of the crystallization vessel in the dry box. aHF (≈ 3 mL) was then
condensed onto the starting material at 77 K. The crystallization
mixture was brought up to ambient temperature and the clear col-
orless solution was decanted into the narrower arm. The evapora-
tion of the solvent from this solution was carried out by main-
taining a temperature gradient corresponding to about 10 K be-
tween both tubes for 5 wk. The result of this treatment was to
slowly condense the aHF from the narrower into the wider tube,
leaving behind the crystals.[26] Selected single crystals were then
placed inside 0.5 mm quartz capillaries in a dry box and their Ra-
man spectra recorded.
997.12, monoclinic space group P21/n, a = 10.8166(4), b =
10.2511(4),
c
=
15.4289(4) Å,
β
=
90.073(3)°,
V
=
1710.79(10) Å–3, Z = 4, ρcalcd. = 3.871 gcm–3, F(000) = 1772,
T = 150 K; 29493 reflections up to θ = 29.9° collected, thereof
4293 with I Ͼ 2σ(I), 4457 independent reflections, 257 param-
eters. Final R indices: R1 = 0.019 (all), wR2 = 0.038 (all). The
final difference Fourier synthesis gave a min./max. residual
electron density of 0.82/–2.31 eÅ–3.
ˇ
[14] K. Lutar, B. Zemva, H. Borrmann, Eur. J. Solid State Inorg.
Chem. 1996, 33, 957–969.
[15] Z. Mazej, E. Goreshnik, J. Fluorine Chem. 2009, 130, 399–405.
[16] Z. Mazej, E. Goreshnik, Z. Jaglicˇic´, Eur. J. Inorg. Chem. 2012,
1734–1741.
[17] Z. Mazej, I. Arcˇon, P. Benkicˇ, A. Kodre, A. Tressaud, Chem.
Eur. J. 2004, 10, 5052–5058.
[18] M. A. Halcrow, Chem. Soc. Rev. 2013, 42, 1784–1795.
[19] A. M. Qureshi, F. Aubke, Can. J. Chem. 1970, 48, 3117–3123.
[20] Sh. Sh. Nabiev, Russ. J. Inorg. Chem. 1995, 40, 1936–1943.
Supporting Information (see footnote on the first page of this arti-
cle): Details of crystal structure determination, Figures S1 and S2
ˇ
[21] Z. Mazej, P. Benkicˇ, K. Lutar, B. Zemva, J. Fluorine Chem.
showing the crystal structures of AM(AsF6)3 (A = A+, M = M2+
)
2001, 112, 173–183.
ˇ
compounds and the Raman spectrum of H3OCu(SbF6)3 (Figure
S3).
[22] Z. Mazej, K. Lutar, B. Zemva, Acta Chim. Slov. 1999, 46, 229–
238.
ˇ
[23] A. Smalc, K. Lutar, in: Inorganic Syntheses (Ed.: R. N.
Grimes), Wiley, New York, 1992, vol. 29, p. 1.
[24] Z. Mazej, J. Fluorine Chem. 2004, 125, 1723–1733.
Acknowledgments
[25] R. A. Davis, D. A. Rausch, Inorg. Chem. 1963, 2, 1300–1301.
[26] Further details of the crystal structure determinations can be
found, in: the Supporting Information and the CIF files may
be obtained from Fachinformationszentrum Karlsruhe,
Germany, 76344 Eggenstein-Leopoldshafen, Germany (E-mail:
The authors gratefully acknowledge the Slovenian Research Ag-
ency (ARRS) for financial support of the present study within the
research program P1-0045 Inorganic Chemistry and Technology.
crysdata@fiz-karlsruhe.de;
http://www.fiz-karlsruhe.de/
request_for_deposited_data.html) by quoting the appropriate
CSD number: CSD-428808 {NO2XeF5(SbF6)2} and CSD-
428809 {XeF5[Cu(SbF6)3]}.
ˇ
[1] J. Slivnik, B. Brcˇic´, B. Volavsˇek, J. Marsel, V. Vrsˇcˇaj, A. Smalc,
B. Frlec, Z. Zemljicˇ, Croat. Chem. Acta 1962, 34, 253.
[2] J. G. Malm, I. Sheft, C. L. Chernick, J. Am. Chem. Soc. 1963,
85, 110–111.
Received: January 13, 2015
Published Online: ᭿
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Noble Gas Chemistry
Z. Mazej,* E. Goreshnik .................. 1–5
NO2XeF5(SbF6)2 and XeF5[Cu(SbF6)3] are
the first examples of [XeF5]+/metal and
[XeF5]+/non-metal mixed-cation com-
pounds. The crystal structure of NO2-
XeF5(SbF6)2 is composed of [NO2]+ and
[XeF5]+ cations and [SbF6]– anions. In the
crystal structure of XeF5[Cu(SbF6)3] the
[XeF5]+ cations are located in cavities pre-
sent in the tridimensional framework made
up of CuF6 and SbF6 octahedra sharing
joint apexes.
[XeF5]+/Metal and [XeF5]+/Non-Metal
Mixed-Cation Salts of Hexafluoridoanti-
monate(V)
Keywords: Xenon / Fluorine / Antimony /
Copper / Cations / Raman spectroscopy /
Structure elucidation
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