Crystal Growth and Characterization of the Mixed-Cation Rb+/[XeF5]+ and Cs+/[XeF5]+ Salts

Article abstract of DOI:10.1002/ejic.201700097

Reactions between ASbF₆ (A = Rb, Cs) and [XeF₅][SbF₆] in anhydrous HF in 1:1 molar ratios yielded isotypic A[XeF₅][SbF₆]₂ compounds upon crystallization. The A[XeF₅][SbF₆]₂ (A = Rb, Cs) salts crystallize in two crystal modifications at low (α phase, 150 K) and ambient (β phase, 296 K) temperatures. Similar reactions between CsBiF₆ and [XeF₅][SbF₆] (1:1) yielded mixed-cation/mixed-anion compounds Cs[XeF₅][Bi_xSb_1–xF₆]₂ (x = 0.37–0.39). One of the two crystallographic positions of the pnictogen atoms is randomly occupied with both Bi (ca. 40 %) and Sb (ca. 60 %) atoms. The simultaneous presence of both [SbF₆]^– and [BiF₆]^– has been confirmed by Raman spectroscopy. The low- and high-temperature phases of Bi/Sb mixed-anion compounds are isotypic with the corresponding A[XeF₅][SbF₆]₂ (A = Rb, Cs) phases. No reactions were observed in the AAsF₆ (A = Rb, Cs)/[XeF₅][AsF₆], ASbF₆ (A = K, [H₃O]⁺)/[XeF₅][SbF₆], and KBF₄/[XeF₅][SbF₆] systems. In the CsBF₄/[XeF₅][SbF₆] system, a metathetical reaction occurred, leading to [XeF₅][BF₄] (orthorhombic at 150 K, Pbca space group) and CsSbF₆. The latter reacted further with [XeF₅][SbF₆], yielding Cs[XeF₅][SbF₆]₂. A double-displacement reaction also proceeded between Cs₂MnF₆ and [XeF₅][SbF₆] to give [XeF₅]₂[MnF₆] and CsSbF₆. The reaction between CsPF₆ and [XeF₅][SbF₆] proceeded with the displacement of the weaker Lewis acid, PF₅, with the stronger one, SbF₅, resulting in [Xe₂F₁₁][SbF₆] and CsSbF₆, which reacted with [XeF₅][SbF₆] to yield Cs[XeF₅][SbF₆]₂.

Full text of DOI:10.1002/ejic.201700097

A Journal of
Accepted Article
Title: Crystal growth and characterization of the mixed-cation Rb+/
[XeF5]+ and Cs+/[XeF5]+ salts
Authors: Zoran Mazej and Evheny Goreshnik
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10.1002/ejic.201700097
European Journal of Inorganic Chemistry
Crystal growth and characterization of the mixed-cation Rb+/[XeF5]+ and
Cs+/[XeF5]+ salts
Zoran Mazej,* Evgeny Goreshnik
Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova cesta 39,
SI–1000 Ljubljana, Slovenia
E-mail: zoran.mazej@ijs.si
http://k1.ijs.si/en/
https://www.ijs.si/ijsw/V001/JSI
Keywords: Alkali metals / Fluorides / Xenon hexafluoride / Structure elucidation
ABSTRACT: Reactions between ASbF6 (A = Rb, Cs) and [XeF5][SbF6] in anhydrous HF
(aHF) in 1:1 molar ratios yielded isotypic A[XeF5][SbF6]2 compounds upon crystallization.
The A[XeF5][SbF6]2 (A = Rb, Cs) salts crystallize in two crystal modifications at low (α-
phase, 150 K) and ambient (β-phase, 296 K) temperatures. Similar reaction between CsBiF6
and [XeF5][SbF6] (1:1) yielded mixed-cation/mixed-anion Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-
0.39). One of the two crystallographic positions of pnictide atoms is randomly occupied with
both Bi (~40 %) and Sb (~60 %) atoms. The simultanious presence of both [SbF6]- and [BiF6]-
has been confirmed by Raman spectroscopy. The low- and high-temperature phases of Bi/Sb
mixed-anion compounds are isotypic with the corresponding A[XeF5][SbF6]2 (A = Rb, Cs)
phases. No reactions were observed in AAsF6 (A = Rb, Cs) / [XeF5][AsF6], ASbF6 (A = K,
[H3O]+) / [XeF5][SbF6] and KBF4 / [XeF5][SbF6] systems. In CsBF4 / [XeF5][SbF6] system
methatetical reaction occured leading to [XeF5][BF4] (orthorhombic at 150 K, Pbca space
group) and CsSbF6. The latter reacted further with [XeF5][SbF6] yielding Cs[XeF5][SbF6]2.
Double displacement reaction proceeded also between Cs2MnF6 and [XeF5][SbF6] to give
[XeF5]2[MnF6] and CsSbF6. Reaction between CsPF6 and [XeF5][SbF6] proceeded with
displacement of weaker Lewis acid PF5 with stronger one SbF5 resulting in [Xe2F11][SbF6]
and CsSbF6 which reacted with [XeF5][SbF6] to yield Cs[XeF5][SbF6]2.
1
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10.1002/ejic.201700097
European Journal of Inorganic Chemistry
Introduction
Reactions between [XeF5][SbF6] and M(SbF6)2 (M =Ni, Mg, Cu, Zn, Co, Mn, Pd) in a
1:1 molar ratio yielded new type of [XeF5]+/M2+ mixed-cation [XeF5]M[SbF6]3 compounds.1,2
Similar attempts to prepare [XeF5]+/M2+ salts with M2+ = Ca, Sr, Ba, Cr, Fe, Ag, Cd, Hg were
only successful for Hg, where [XeF5]3[Hg(HF)]2[SbF6]7 was obtained.2 The crystal structures
of [XeF5]M[SbF6]3 (Ni, Mg, Cu, Zn, Co and low-temperature α-phase of Mn) are isotypic,
meanwhile the main features of the crystal structure of high-temperature β-[XeF5]Mn[SbF6]3
and low-temperature α- and high-temperature β-[XeF5]Pd[SbF6]3 are similar to the other
[XeF5]M[SbF6]3 compounds, i.e., there is a tri-dimensional framework made of rings of MF6
octahedra that share the apexes with SbF6 octahedra, forming cavities within which the
[XeF5]+ cations are located.1,2 Reaction between [XeF5][SbF6] and [NO2][SbF6] also gave a
new type of [XeF5]+ salts, i.e., NO2[XeF5][SbF6]2.1 The NO2[XeF5][SbF6]2, [XeF5]M[SbF6]3
(M = Ni, Mg, Cu, Zn, Co, Mn, Pd) and [XeF5]3[Hg(HF)]2[SbF6]7 have been the first
examples of [XeF5]+/metal and [XeF5]+/non-metal mixed-cation compounds.
In the course of further study, crystallizations of APnF6 (A = [H3O]+, K, Rb, Cs; Pn =
P, As, Sb, Bi), ABF4 (A = K, Cs) and Cs2MnF6 with [XeF5][PnF6] (Pn = As, Sb) were carried
out in anhydrous hydrogen fluoride (aHF) in an attempt to prepare new mixed-cation [XeF5]+/
metal salts with [PnF6]- (Pn = P, As, Sb, Bi) anions and with [BF4]- / [SbF6]- and [MnF6]2- /
[SbF6]- mixed-anions; as for example unknown A[XeF5][PnF6]2 (A = K, Rb, Cs; Pn = P, As,
Sb, Bi), A[XeF5][BF4][PnF6] and A2[XeF5][MnF6][PnF6] compounds. A new type of
A[XeF5](SbF6)2 mixed-cation salt was obtained for A = Rb and Cs and a new mixed-anion
Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39) compound was prepared. Corresponding crystals were
grown and the crystal structures were determined. The results are described in the present
paper.
Results and discussion
Reactions of APnF6 (A = [H3O]+, K, Rb, Cs; Pn = P, As, Sb, Bi), ABF4 (A = K, Cs) and
Cs2MnF6 with [XeF5][PnF6] (Pn = As, Sb).
List of starting mixtures between various alkali metal and [XeF5]+ salts together with
the list of phases observed in crystallization products is given in Table 1.
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10.1002/ejic.201700097
European Journal of Inorganic Chemistry
Table 1. Observed products in reactions of APnF6 (A = [H3O]+, K, Rb, Cs; Pn = P, As, Sb,
Bi), ABF4 (A = K, Cs) and Cs2MnF6 with [XeF5][PnF6] (Pn = As, Sb).
Reactant 1 Reactant 2
Observed crystalline phasesa Phases detected by Raman
spectroscopya
H3OSbF6 [XeF5][SbF6]
[XeF5][SbF6]b
H3OSbF6, [XeF5][SbF6]
[XeF5][SbF6]
KSbF6
RbSbF6
[XeF5][SbF6]
[XeF5][SbF6]
KSbF6, [XeF5][SbF6]
Rb[XeF5][SbF6]2, RbSbF6,
[XeF5][SbF6]
Rb[XeF5][SbF6]2,[XeF5][SbF6]
CsPF6
[XeF5][SbF6]
[XeF5][SbF6]
CsPF6, [Xe2F11][SbF6],
Cs[XeF5][SbF6]2
Cs[XeF5][SbF6]2,
[XeF5][SbF6]
Cs[XeF5][BixSb1-xF6]2
[XeF5][AsF6]
[XeF5][AsF6]
KBF4, [XeF5][SbF6]
[XeF5][BF4],
CsPF6, CsSbF6,
Cs[XeF5][SbF6]2
Cs[XeF5][SbF6]2, CsSbF6,
[XeF5][SbF6]
Cs[XeF5][BixSb1-xF6]2
RbAsF6, [XeF5][AsF6]
CsAsF6, [XeF5][AsF6]
/
/
CsSbF6
c
c
CsBiF6
RbAsF6
CsAsF6
KBF4
[XeF5][SbF6]
[XeF5][AsF6]
[XeF5][AsF6]
[XeF5][SbF6]
[XeF5][SbF6]
CsBF4
Cs[XeF5][SbF6]2
Cs2MnF6
[XeF5][SbF6]
CsSbF6, [XeF5]2[MnF6]b
/
aUnit cells of grown crystals were checked on a diffractometer. There is always a possibility that
crystalline phases present in minor amounts were overlooked. bPowdered material was also present.
cx = ~0.37-0.39.
Reactions between ASbF6 (A = Rb, Cs) and [XeF5][SbF6]3,4 in anhydrous HF (aHF) in
1:1 molar ratios yielded isotypic A[XeF5][SbF6]2 (A = Rb, Cs) upon crystallization (Eq. 1).
Traces of starting materials were also observed.
aHF, 298 K
ASbF6 (A = Rb, Cs) + [XeF5][SbF6] ⎯⎯⎯⎯→ A[XeF5][SbF6]2
(1)
When similar reactions were attempted between [XeF5][SbF6] and ASbF6 containing
smaller cations as A = K+, [H3O]+ only starting materials were recovered. The attempts to
prepare A[XeF5][AsF6]2 compounds by reactions between AAsF6 (A = Rb, Cs) and
[XeF5][AsF6]5 also failled. However, the reaction between CsBiF6 and [XeF5][SbF6] (1:1)
resulted in the growth of single crystals of mixed-cation / mixed-anion compound with
formula close to Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39).
Reaction between CsPF6 and [XeF5][SbF6] proceeded with displacement of weaker
Lewis acid PF5 with stronger one SbF5 resulting in [Xe2F11][SbF6] and CsSbF6 (Eq. 2) which
further reacts with starting [XeF5][SbF6] to give Cs[XeF5][SbF6]2 (Eq. 3):
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10.1002/ejic.201700097
European Journal of Inorganic Chemistry
aHF, 298 K
CsPF6 + [XeF5][SbF6] ⎯⎯⎯⎯→ [Xe2F11][SbF6] + CsSbF6 + PF5↑
(2)
(3)
aHF, 298 K
CsSbF6 + [XeF5][SbF6] ⎯⎯⎯⎯→ Cs[XeF5][SbF6]2
6
It is possible that some 2XeF6·PF5 or so far unknown XeF6·PF5 were formed as an
intermediates. The former decomposes to XeF6 and PF5 at ambient temperature where XeF6
can react with [XeF5][SbF6] yielding [Xe2F11][SbF6] and the PF5 is removed as a gas. Traces
of starting CsPF6 were also detected.
The attempts were made to prepare [BF4]- / [SbF6]- mixed-anion compounds
containing both A+ (A = K, Cs) and [XeF5]+ cations. Only starting KBF4 and [XeF5][SbF6]
were recovered after crystalization in aHF solution. During the reaction between CsBF4 and
[XeF5][SbF6] methathetical reaction occured leading to [XeF5][BF4]7 and CsSbF6 (Eq. 4). The
latter reacts further with starting [XeF5][SbF6] yielding Cs[XeF5][SbF6]2 (Eq.3).
aHF, 298 K
CsBF4 + [XeF5][SbF6] ⎯⎯⎯⎯→ [XeF5][BF4] + CsSbF6
(4)
Double displacement reaction proceeded also between Cs2MnF6 and [XeF5][SbF6]
yielding [XeF5]2[MnF6]8,9 and CsSbF6 instead of desired Cs2[XeF5][MnF6][SbF6] compound.
Crystal structures of α- and β-Rb[XeF5][SbF6]2 (α = low temperature and β = high
temperature phase), α- and β-Cs[XeF5][SbF6]2, α- and β-Cs[XeF5][BixSb1-xF6]2 (x =
~0.37-0.39), [Xe2F11][SbF6] and [XeF5][BF4]
The corresponding crystal data and refinement results are summarized in Table 2.
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10.1002/ejic.201700097
European Journal of Inorganic Chemistry
Table 2. Crystal data and refinement results for α- and β-Rb[XeF5][SbF6]2, α- and β-
Cs[XeF5][SbF6]2, α- and β-Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39), [Xe2F11][SbF6] and
[XeF5][BF4].
Chem. formula
Fw (g/mol)
Crystal System
Space group
a (Å)
α-Rb[XeF5][SbF6]2 β-Rb[XeF5][SbF6]2 α-Cs[XeF5][SbF6]2 β-Cs[XeF5][SbF6]2
783.27
Tetragonal
P4/ncc
10.4699(4)
10.4699(4)
11.7801(7)
90
783.27
Tetragonal
P4/nmm
10.6487(8)
10.6487(8)
5.8860(7)
90
830.72
Tetragonal
P4/ncc
10.5321(3)
10.5321(3)
12.1395(5)
90
830.72
Tetragonal
P4/nmm
10.7376(6)
10.7376(6)
6.0075(5)
90
b (Å)
c (Å)
α (°)
β (°)
90
90
90
90
γ (°)
90
90
90
90
V (Å3)
1291.31(12)
4
667.44(12)
2
3.898
296
0.0174
0.0395
1346.57(8)
4
692.64(10)
2
Z
Dcalc (g/cm3)
T (K)
4.029
150
0.0250
0.0724
4.0971
150
0.0195
0.0421
3.983
296
0.0355
0.0782
a
R1
b
wR2
Chemical
formula
Fw (g/mol)
Crystal System
Space group
a (Å)
[Xe2F11][SbF6]
[XeF5][BF4]
α-Cs[XeF5]
β-Cs[XeF5]
[BixSb1-xF6]2
895.79
Tetragonal
P4/nmm
10.7535(7)
10.7535(7)
6.0508(5)
90
a
a
[BixSb1-yF6]2
897.53
Tetragonal
P4/ncc
10.5766(2)
10.5766(2)
12.1834(3)
90
707.34
Monoclinic
P21/n
8.5814(2)
9.0505(3)
15.5374(5)
90
313.11
Orthorhombic
Pbca
8.2576(8)
8.4377(6)
17.2236(17)
90
b (Å)
c (Å)
α (°)
β (°)
90
90
90
90
95.524(3)
90
1201.12(6)
4
90
90
γ (°)
V (Å3)
1362.89(7)
4
699.70(11)
2
1200.06(19)
8
Z
D
calc (g/cm3)
4.374
4.252
3.912
3.466
T (K)
150
0.0210
0.0465
296
0.0249
0.0635
150
0.0303
0.0789
150
0.0286
0.0707
b
R1
wR2
c
ax = ~0.37-0.39. Data of α- and β-phases were collected on different crystalls.bR1 is defined
as Σ║Fo│–│Fc║/Σ│Fo│for I > 2σ(I). cwR2 is defined as [Σ[w(Fo –Fc2)2]/Σw(Fo ) ] .
2
2 2 ½
Crystal structures of high-temperature forms (β) of Rb[XeF5][SbF6]2, Cs[XeF5][SbF6]2
and Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39)
High temperature modification β-Rb[XeF5][SbF6]2
β-Rb[XeF5][SbF6]2 crystallizes in the tetragonal P4/ncc space group (No. 129). Its
crystal structure consists of Rb+ and [XeF5]+ cations and [SbF6]- anions that show an eclipsed
stacks when the crystal structure is viewing along c-axis (Figure 1).
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10.1002/ejic.201700097
European Journal of Inorganic Chemistry
Figure 1. Packing of Rb+ and [XeF5]+ cations and [SbF6]- anions in the crystal structure of β-
Rb[XeF5][SbF6]2.
Figure 2. Part of the crystal structure of β-Rb[XeF5][SbF6]2 (thermal ellipsoids are drawn at
the 50% probability level).
The Xe1 and F1 atoms are located at the intersection of 4-fold axis and four mirror
planes (Figure 2). Other four crystallographically equivalent F2 atoms of [XeF5]+ cation
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10.1002/ejic.201700097
European Journal of Inorganic Chemistry
occupy 8i positions, resulting in four identical Xe–Feq bonds. The XeF5 units have so well
known slightly distorted pseudo-octahedral symmetry,7 where the axial Xe−Fax distance
(Xe1−F1: 1.790(5) Å) is slightly shorter than the equatorial (4 × Xe1−F2eq: 1.823(2) Å). Each
of the [XeF5]+ cations makes further secondary bonds (Figure 2) with four fluorine atoms (F4)
of four different [SbF6]- anions (4 × Xe1···F4 = 2.752(3) Å). The sum of the Xe···F van der
Waals radii is 3.63 Å.10 The [SbF6]- fluorine atoms involved in these contacts are arranged
symmetrically around the pseudo four-fold axis of the XeF5 unit (i.e., around the sterically
active nonbonding valence-electron pair of Xe). Each of F2eq atoms of XeF5 group is involved
in weak interaction (3.543(3) Å) with different Rb+ cation (Figure 2).
Each Rb+ cation is bonded to eight, by symmetry related, fluorine atoms of eight
different [SbF6]- anions and to four crystallographically equivalent fluorine atoms of four
[XeF5]+ cations. Since Rb1 is located at 4m2 intersection (2a special Wyckoff position), the
twelve Rb···F contacts of each Rb1 can be divided in two groups, where eight Rb···F(−SbF5)
contacts of the first group are relatively short (8 × 2.970(2) Å) and four Rb····F(−XeF4)
contacts of the second group are long (4 × 3.543(3) Å).
The Sb1 atom, located at the intersection of 2-fold axis and a mirror plane, is
coordinated by a pair of symmetry related F4 atoms and four F3 atoms (Figure 2). The F4
atoms are involved in further bonding with xenon atoms of [XeF5]+ cations and F3 atoms in
further bonding with Rb+ cations. The two Sb–F4(···XeF5) bond lengths, that are in trans
position, are slightly elongated (1.880(2) Å) in comparison to the rest of four Sb–F3(···Cs)
bonds (1.852(2) Å).
High temperature modification β-Cs[XeF5][SbF6]2
The crystal structure of β-Cs[XeF5][SbF6]2 (Table 2) is structurally related to β-
Rb[XeF5][SbF6]2. The main difference is that SbF6 groups in the former exhibit a 2-fold
rotational disorder of the F3 fluorine positions around the F4−Sb1−F4 axis containing non-
disordered F4 fluorine atoms (Figure 3).
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10.1002/ejic.201700097
European Journal of Inorganic Chemistry
Figure 3. Asymmetric unit cell of β-Cs[XeF5][SbF6]2 (296 K) that shows two-fold disorder
of the [SbF6]- anion and Cs+ and [XeF5]+ cations. Thermal ellipsoids are drawn at the 50%
probability level.
The geometry of XeF5 units is β-Cs[XeF5][SbF6]2 the same as in Rb compound
(Xe1−F1ax: 1.794(13) Å), Xe1−F2eq: 1.830(5) Å). Each of the XeF5 units makes secondary
bonds with the four fluorine atoms (F4) of four [SbF6]- anions (4 × Xe···F = 2.772(6) Å) and
each Cs+ is bonded to eight fluorine atoms of eight [SbF6]- anions (8 × 3.07(3)-3.08(3) Å) and
to four fluorine atoms of four [XeF5]+ cations (4 × 3.583(5) Å). Four fluorine atoms (F3;
disordered on two positions) of [SbF6]- anions are involved in further bonding with Cs+
cations, and two non-disordered fluorine atoms (F4) with Xe atoms of [XeF5]+ cations.
High temperature modification β-Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39)
High-temperature phase β-Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39) is isotypic with the
β-Cs[XeF5][SbF6]2 (Table 2). The Bi and Sb atoms are randomly distributed on the same 4e
Wyckoff position on the intersection of 2-fold axis and mirror plane of the P4/nmm cell with
the Bi:Sb molar ratio close to 1:1.5. As in β-Cs[XeF5][SbF6]2, the BiF6/SbF6 groups show a 2-
fold rotational disorder of four fluorine atoms. The main structural features are: Xe1−F1ax:
1.807(9) Å), 4 × Xe1−F2eq: 1.826(4) Å); four secondary Xe···F interactions with four
[(Bi/Sb)F6]- anions (4 × Xe1···F4 = 2.761(5) Å); each Cs+ is coordinated to eight fluorine
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10.1002/ejic.201700097
European Journal of Inorganic Chemistry
atoms of eight [(Bi/Sb)F6]- anions (8 × 2.99(2)/3.13(2) Å) and to four fluorine atoms of four
[XeF5]+ cations (4 × 3.594(4) Å). Four fluorine atoms (disordered on two positions) of
[(Bi/Sb)F6]- anions are involved in further bonding with Cs+ cations, and two non-disordered
fluorine atoms with xenon atoms of [XeF5]+ cations.
Crystal structures of low-temperature forms (α) of Rb[XeF5][SbF6]2, Cs[XeF5][SbF6]2
and Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39)
At 150 K all three low-temperature modifications, i.e., α-forms of Rb[XeF5][SbF6]2,
Cs[XeF5][SbF6]2 and Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39), crystallize isotipically in the
tetragonal P4/nсс space group (No. 130). In contrary to β-Cs[XeF5][SbF6]2 and β-
Cs[XeF5][BixSb1-xF6]2, all fluorine atoms of SbF6(BiF6) groups in corresponding α-phases are
ordered.
Figure 4. Arrangement of heavy atoms (Cs/Rb = red, Xe = violet, Sb/Bi = yellow) in the
crystal structures of α- (left) and β- (right) forms of Rb[XeF5][SbF6]2, Cs[XeF5][SbF6]2 and
Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39). View along c- (above) and b-axes (below).
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10.1002/ejic.201700097
European Journal of Inorganic Chemistry
Figure 5. Arrangement of fluorine atoms (Rb = red, Xe = violet, Sb = yellow, F = green) in
the crystal structures of α- (above) and β- (below) forms of Rb[XeF5][SbF6]2. View along b-
axis. Thermal ellipsoids are drawn at the 50% probability level.
Comparison of α- and β-forms shows that heavy atoms form a similar arrangement
(Figure 4) meanwhile fluorine atoms are located on different positions (Figure 5). As a
consequence, the unit cell of α-form is doubled (Table 2) and F atoms of SbF6 and XeF5
groups are not anymore stacked in an eclipsed positions as in β-forms but staggered when
viewing along c-axis (Figure 6).
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European Journal of Inorganic Chemistry
Figure 6. Packing of Rb+ and [XeF5]+ cations and [SbF6]- anions in the crystal structure of α-
Rb[XeF5][SbF6]2.
It seems that at low temperature the tilting of SbF6 and XeF5 groups is due to the
packing requirements. The low-temperature structures demonstrate higher packing index,
82.9% for α-Rb[XeF5][SbF6]2, 82.3% for α-Cs[XeF5][SbF6]2, in comparison with value 79.8
% for β-form of Rb[XeF5][SbF6]2 (because of partial disordering of F atoms it is not possible
to calculate packing index of β-Cs[XeF5][SbF6]2).
The main structural features of α-Rb[XeF5][SbF6]2 are (Figure 7): Xe1−F1ax: 1.792(6)
Å), 4 × Xe1−F2eq: 1.835(2) Å); four secondary Xe···F interactions with four [SbF6]- anions (4
× Xe1···F5 = 2.738(2) Å); each Rb+ is coordinated to eight fluorine atoms of eight [SbF6]-
anions (4 × Rb···F4 = 2.865(2) Å, 4 × Rb···F3 = 3.069 (2) Å) and to four fluorine atoms (F2)
of four [XeF5]+ cations (4 × 3.484(2) Å). Four fluorine atoms (2 × F3, 2 × F4) of [SbF6]-
anions are involved in further bonding with Rb+ cations, and two fluorine atoms (F5) with
xenon atoms of [XeF5]+ cations. Similarly as in β-forms the two Sb–F5(···XeF5) bond lengths
are slightly elongated (1.887(2) Å) in comparison to the rest of four Sb–F3/F4(···Rb) bonds (4
× 1.868(2) Å).
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Figure 7. Part of the crystal structure of α-Rb[XeF5][SbF6]2 (thermal ellipsoids are drawn at
the 50% probability level).
The corresponding bond lengths in isotypic α-Cs[XeF5][SbF6]2 compound are:
Xe1−F1ax: 1.800(4) Å), 4 × Xe1−F2eq: 1.840(2) Å; four secondary Xe···F(–SbF5) interactions
(4 × Xe1···F5 = 2.761(2) Å); each Cs+ is coordinated to eight fluorine atoms of eight [SbF6]-
anions (4 × Cs···F4 = 3.205(2) Å, 4 × Cs···F3 = 2.968(2) Å) and to four fluorine atoms (F2) of
four [XeF5]+ cations (4 × 3.513(2) Å)). Two Sb–F5(···XeF5) bond lengths, that are in trans
position, are slightly elongated (1.892(2) Å) in comparison to other four Sb–F3/F4(···Cs)
bonds (2 × 1.858(2) Å, 2 × 1.863(2) Å).
Similar situation is in α-Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39): Xe1−F1ax: 1.805(5)
Å), 4 × Xe1−F2eq: 1.838(2) Å; four secondary Xe···F(−SbF5) interactions (4 × Xe1···F =
2.748(2) Å); each Cs+ is coordinated to eight fluorine atoms of eight [(Bi/Sb)F6]- anions (4 ×
Cs···F4 = 3.209(3) Å, 4 × Cs···F3 = 2.948 (3) Å) and to four fluorine atoms (F2) of four
[XeF5]+ cations (4 × 3.544(2) Å).
Crystal structure of [Xe2F11][SbF6]
In 1964, Gard and Cady reported that varying the proportions of the reactants SbF5
and XeF6, it is possible to prepare each of the crystalline solids: 2XeF6·SbF5, XeF6·SbF5, and
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XeF6·2SbF5.4 The crystal structures of the latter two have been recently determined and they
are both [XeF5]+ salts, i.e., [XeF5][SbF6] and [XeF5][Sb2F11].3 No structural data have been
reported so far for the 2XeF6·SbF5 compound. The [Xe2F11][SbF6] crystallizes in a monoclinic
P21/n space group (Table 2). Its crystal structure consists of [Xe2F11]+ cations and [SbF6]-
anions (Figure 8) in agreement with Barttlet's prediction11 that 2XeF6·SbF5 is also probably
[Xe2F11]+ salt. It is isotypic with [Xe2F11][VF6] (monoclinic, P21/n, Z = 4, a = 8.551(1) Å, b =
o
8.896(1) Å, c = 15.703(1) Å and β = 93.31(2) at ambient temperature).12 Another known
example, i.e., the crystal structure of [Xe2F11][AuF6] has similar unit cell parameters (Z = 4, a
= 9.115(6) Å, b = 8.542(25) Å, c = 15.726(20) Å at ambient temperature) but it has been
reported to crystallize in orthorhombic Pnma space group.11 Major difference in
crystallographic sense arise because of mirror plane perpendicular to b axis that is not present
in monoclinic [Xe2F11][VF6]12 and [Xe2F11][SbF6]. The [Xe2F11]+ cation is composed of two
XeF5 groups bridged by additional common fluoride ion. The geometries of [Xe2F11]+ cations
in [Xe2F11][XF6] (X = V, Sb, Au) are practically identical. In all three compounds the Xe–F–
o
Xe angles are close to 170 o (V: 166.5(4) o 12, Sb = 166.2(2) , Au =169(2) o 11) and Xe–Fb(–
Xe) bond lengths are found to be in the same range (V: 2.262(8)/2.227(8) Å12, Sb: 2.240(4)
/2.268(4) Å, Au: 2.21(1)/2.26(1) Å11)
Figure 8. Part of the crystal structure of [Xe2F11][SbF6] (thermal ellipsoids are drawn at the
50% probability level).
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Crystal structure of [XeF5][BF4]
In 1978, Adams and Bartlett reported about the growth of single crystals of XeF6·BF3
by vacuum sublimation.7 The [XeF5][BF4] has been reported to crystallize in orthorhombic
crystal system with lattice parameters a = 8.41(2) Å , b = 8.60(2) Å, c = 17.47(4) Å and Z =
8).7 Their crystal data were obtained from precession photographs where during the
measurement single crystal of XeF6·BF3 decomposed in the beam. The space group could not
be unambiguously determined.
Our results confirmed that [XeF5][BF4] is orthorhombic and that the correct space
group is Pbca. Each [XeF5]+ cation forms three Xe···F secondary contacts between Xe atoms
and F atoms belonging to BF4 groups (2.578(3)/2.604(2)/2.733(2) Å). Three B–F bonds of
BF4, involved in those secondary contacts (Figure 9), are slightly elongated (1.398(5)/
1.404(5)/ 1.409(5) Å) in comparison to remaining B1–F6 bond (1.353(5)Å).
Figure 9. Part of the crystal structure of [XeF5][BF4] (thermal ellipsoids are drawn at the 50%
probability level).
Raman spectra of Rb[XeF5][SbF6]2, Cs[XeF5][SbF6]2 and Cs[XeF5][BixSb1-xF6]2 (x =
~0.37-0.39)
The Raman spectra of the Rb[XeF5][SbF6]2, Cs[XeF5][SbF6]2 and Cs[XeF5][BixSb1-
xF6]2 (x = ~0.37-0.39) were acquired on the randomly orientated single crystals (Table 3,
Figure 10). All crystals were first checked on a diffractometer. Since they were recorded on a
single crystals some of the intensities could vary. In some cases, the additional spectra were
measured on the powdered crystals.
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Table 3. Raman frequencies and intensities for the Rb[XeF5][SbF6]2 (1), Cs[XeF5][SbF6]2 (2),
Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39) (3)
1a
2a
3a
Assignt.
[XeF5]+ b [SbF6]- [BiF6]-
696(3)
683(70)
669(5)
679(40)
674(30)
ν1(A1)
ν7(E)
658(100) 659(100) 655(50)
ν1(A1g)
ν2(A1)
ν4(B1)
ν1(A1g)
633(50)
621(20)
632(50)
621(45)
626(40)
617(40)
589(100)
594(2)
580(10)
562(5)
548(2)
585(5)
575(20)
557(5)
545(7)
569(10)
ν2(Eg)
541(2)
504(5)
418(2)
311(2)
ν2(Eg)
421(5)
310(2)
294(10)
290(10)
282(5)
419(5)
312(5)
300(2)
292(5)
283(5)
266(2)
ν8(E)
ν3(A1)
ν6(B2)
ν5(F2g)
ν5(F2g)
ν5(B1)
ν5(F2g)
ν5(F2g)
282(2)
266(1)
237(2)
230(2)
aSpectra were recorded on the randomly oriented single crystals sealed in a quartz glass
capillaries at 23 °C using 632.8 nm excitation. Values in parentheses denote relative Raman
b
intensities (cm-1). Vibrational bands of [XeF5]+ cations: (Xe−F)ax stretching vibrations (v1),
the in-phase (Xe-F)eq stretching vibrations in the XeF4 moiety (v2), out-of-plane bending in-
phase bending vibration of XeF4 (v3), out-of-phase stretching vibration of XeF4 (v4), out-of-
plane bending (out of phase) vibration of XeF4 (v5), in plane symmetric bending of XeF4 (v6),
doubly degenerate asymmetric stretching vibration of the XeF4 moiety (v7), and Fax−Xe−Feq
bending vibration (v8).
The vibrational bands which can be unambiguously assigned to the [XeF5]+
cations7,13,14 are (Xe−F)ax stretching vibrations (v1) found at ~680 cm-1, the in-phase (Xe−F)eq
stretching vibrations in the XeF4 moiety (v2) at ~630 cm-1, and out-of-plane bending in-phase
bending vibration of XeF4 (v3) at ~310 cm-1. The weak band at 669 cm-1 observed in the
Raman spectrum of Rb(XeF5)(SbF6)2 can be tentatively assigned to the doubly degenerate
asymmetric stretching vibration of the XeF4 moiety (v7), medium weak bands at ~420 cm-1 to
the Fax−Xe−Feq bending vibration (v8), the medium weak bands at ~620 cm-1 to the out-of-
phase stretching vibration of XeF4 (v4). The very weak bands at ~266 cm-1 and stronger ones
at ~300 cm-1 could be only partly assigned to out-of-plane bending (out of phase) vibration of
the XeF4 (v5) and to in plane symmetric bending of the XeF4 (v6).
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European Journal of Inorganic Chemistry
Cs[XeF5][SbF6]2
Cs[XeF5][Bi0.4Sb0.6F6]2
Rb[XeF5][SbF6]2
100
300
500
700
900
cm-1
Figure 10. Raman spectra of the Rb[XeF5][SbF6]2, Cs[XeF5][SbF6]2 and Cs[XeF5][BixSb1-
xF6]2 (x = ~0.37-0.39) recorded at room temperature on a randomly orientated single-crystals
sealed in the quartz capillaries using the 632.8 nm excitation.
The bands in 655-659, 569-580 and 282-292 cm-1 region are assigned to the v1 (A1g
symmetry) and v2 (Eg symmetry) Sb–F stretching normal modes and the v5 (T2g symmetry)
bending normal modes, respectively, of [SbF6]- anion. Corresponding SbF6 bands in CsSbF6
are 650 cm-1 (v1), 570 cm-1 (v2) and 283/276 cm-1 (v5), respectively.15 Additional vibrational
bands at 589 cm-1, 504 cm-1 and 237/230 cm-1 observed in the Raman spectrum of
Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39) are assigned to v1, v2 and v5 vibrational modes of the
[BiF6]- anion. In CsBiF6, corresponding vibrational bands of found at 579 cm-1 (v1) 526 cm-1
(v2) and 241/231 cm-1 (v5).16
Conclusions
Reactions of APnF6 (A = [H3O]+, K, Rb, Cs; Pn = P, As, Sb, Bi), ABF4 (A = K, Cs),
and Cs2MnF6 with [XeF5][PnF6] (Pn = As, Sb) may end in one of three possibilities: 1) no
reaction, 2) double displacement reaction or 3) formation of new coordination compound
containing both reactants, i.e., a new type of mixed-cation [XeF5]+/Cs+ and [XeF5]+/Rb+ salts
of [SbF6]- and [BiF6]-/[SbF6]- as Rb[XeF5][SbF6]2, Cs[XeF5][SbF6]2 and Cs[XeF5][BixSb1-
xF6]2 (x = ~0.37-0.39). Their crystal structure determination showed that all three new
compounds crystallize in two crystal modifications at low (α-phase, 150 K) and at high (β-
phase, 296 K) temperatures.
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The non-existence of K[XeF5][SbF6]2 probably reflects a size mismatch between the
small K+ cations, large [XeF5]+ cations and the [SbF6]- anions. The attempts to prepare
A[XeF5][PnF6]2 (A = K, Rb, Cs; Pn = P, As), A[XeF5][BF4][PnF6] and
A2[XeF5][MnF6][PnF6] compounds also failed.
Since Rb[XeF5][SbF6]2, Cs[XeF5][SbF6]2 and Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39)
may be obtained from APnF6 (A = Cs, Rb; Pn = Bi, Sb) + [XeF5][SbF6] starting materials, it
seems that the enthalpy factor is slightly in favor of the formation reaction (Eq. 1). The
volume of Rb[XeF5][SbF6]2 per formula unit (for β-phase ׽333.72 Å3) is almost the same
than that of the reactant mixture (׽328.61 Å3). Difference is only 1.5 % but here it should be
17
taken into account that crystal data of RbSbF6 and Rb[XeF5][SbF6]2, from which formula
unit volumes have been calculated, were collected both at ambient temperature, meanwhile
crystal structure of [XeF5][SbF6]3 has been determined at 200 K. The situation is the same for
Cs[XeF5][SbF6]2 (volume per formula unit is 346.32 Å3 and the sum of volumes per formula
15
unit for CsSbF6 and [XeF5][SbF6]3 is 344.09 Å3). That results indicate that the entropy
contribution doesn't play a significant role.
Experimental
CAUTION: Anhydrous HF and some fluorides are highly toxic and must be handled in a well-
ventilated hood and protective clothing must be worn at all times! XeF6 and all of its products
are susceptible to moisture and react with water forming XeO3, a shock-sensitive compound
that detonates easily.
Materials and methods
Reagents. Anhydrous HF (Linde AG, Pullach, Germany, 99.995%) was treated with K2NiF6
(Advance Research Chemicals, Inc.) for several hours prior to use. The KF (Ventron, 99.9%),
RbF (Aldrich, 99%), CsF (Aldrich, 99.9%) and BF3 (Union Carbide Austria, 99.5%) were
19
used as supplied. The H3OSbF6,18 [XeF5][AsF6],5 [XeF5][SbF6],3 and Cs2MnF6
were
21
synthesized as previously described. The PF5,20 AsF5,21 SbF5,22 BiF5
were prepared by
high-pressure fluorination of P2O5, As2O3, SbF3 or BiF3, respectively, by elemental fluorine at
elevated temperature. The KSbF6, RbSbF6, RbAsF6, CsPF6, CsAsF6, CsSbF6, CsBiF6, KBF4
and CsBF4 were prepared by the reactions between corresponding alkali metal fluorides and
Lewis acids (BF3, PnF5, Pn = P, As, Sb and Bi) in aHF as a solvent at ambient temperature.
Synthetic Apparatus. All the manipulations were carried out under anhydrous conditions.
The volatile compounds, such as aHF and F2, were handled on a vacuum line constructed
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10.1002/ejic.201700097
European Journal of Inorganic Chemistry
from nickel-Teflon and the non-volatile materials were handled in a dry box (M. Braun) in an
argon atmosphere (<0.5 ppm H2O). Single crystals were grown in T-shaped crystallization
vessels comprised of two FEP (tetrafluoroethylene-hexafluoropropylene block copolymer;
Polytetra GmbH, Germany) tubes (one 16 mm i.d. × 19 mm. o.d. and the other 4 mm i.d. × 6
mm. o.d.) equipped with PTFE valves. Before use, the above-mentioned crystallization
vessels were passivated with elemental fluorine (Solvay).
Reactions and crystal Growth in APnF6 (A = [H3O]+, K, Rb, Cs; Pn = P, As, Sb, Bi) /
[XeF5][PnF6] (Pn = As, Sb), ABF4 (A = K, Cs) / [XeF5][SbF6] and Cs2MnF6 /[XeF5][SbF6]
systems. The mixtures of APnF6 (A = [H3O]+, K, Rb, Cs; Pn = P, As, Sb, Bi) and
[XeF5][PnF6] (X = As, Sb) in 1:1 molar ratio, ABF4 (A = K, Cs) and [XeF5][SbF6] in 1:1
molar ration, Cs2MnF6 and [XeF5][SbF6] in 1:1 molar ratio were loaded into reaction vessel
inside a dry box. aHF (5-10 ml) was condensed onto the solid at 77 K and the reaction
mixture was brought to ambient temperature. The reaction mixture was left stirring for 1 days
at ambient temperature. The resulting clear solution was decanted into the 6-mm o.d. side
arm. Evaporation of the solvent from this solution was carried out by maintaining a
o
temperature gradient of ca. 10–20 C between both tubes for several weeks. Slow distillation
of aHF from the 6-mm o.d. tube into the 19-mm o.d. tube resulted in crystal growth inside the
6-mm o.d. tube.
Selected single crystals were transferred to 0.3 mm quartz capillaries inside the dry
box and their Raman spectra were recorded at several random positions. In some cases the
Raman spectra were also measured on powdered crystals.
X-ray Single Crystal Structure Determinations. Crystals were immersed in
perfluorodecalin (Fluorochem, Cat. Code: 003283, melting point 263 K) inside a dry box,
selected under a microscope, and mounted on the goniometer head of the diffractometer in a
cold nitrogen stream. Crystals sealed in quartz-glass capillaries were used for the structure
determination at room temperature.
Single-crystal data were collected on a Gemini A diffractometer equipped with an
Atlas CCD detector, using graphite monochromated Mo–Kα radiation. The data were treated
using the CrysAlisPro software suite program package.23 Analytical absorption corrections
were applied to all the data sets. The structures of β-Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39)
and β-Rb[XeF5][SbF6]2 were solved with the charge-flipping method using the Superflip
program24 (Olex crystallographic software25). The electron density map, obtained with
Superflip software, was analyzed using the EDMA program26, which gave initial models of
the structures. Structures of β-Cs[XeF5][SbF6]2, [Xe2F11][SbF6] and [XeF5][BF4] were solved
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10.1002/ejic.201700097
European Journal of Inorganic Chemistry
using the SHELXT program.27 Other structures were solved using the SHELXS program.28
Structure refinement was performed with the SHELXL-201429 software, implemented in the
program package WinGX.30 The figures were prepared using the DIAMOND 4.3 software.31
Further details of the crystal-structure determinations can be found in CIF's files that
can be obtained from Fachinformationszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen,
Germany
(e-mail:
crysdata@fiz-karlsruhe.de;
http://www.fiz-
karlsruhe.de/request_for_deposited_data.html) on quoting the appropriate CSD number:
CSD−432543 (α-Rb[XeF5][SbF6]2; 150 K), CSD−432544 (β-Rb[XeF5][SbF6]2, 296 K),
CSD−32539 (α-Cs[XeF5][SbF6]2, 150 K), CSD−432540 (β-Cs[XeF5][SbF6]2, 296 K),
CSD−432541 (α-Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39) 150 K), CSD−432542 (β-
Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39), 296 K), CSD−432545 ([Xe2F11][SbF6]) and
CSD−432546 ([XeF5][BF4]).
Raman Spectroscopy. Raman spectra with a resolution 0.5 cm-1 were recorded at room
temperature on a HORIBA JOBIN YVON LabRam-HR spectrometer equipped with the
Olympus BXFM-ILHS microscope. Samples were excited by the 632.8 nm emission line of a
He–Ne laser with the power 20 mW which equals to the power 17 mW focused to a 1 μm spot
through a 50x microscope objective on to the top surface of the sample.
Acknowledgements
Authors gratefully acknowledge the financial support from the Slovenian Research
Agency (research core funding No. P1-0045).
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Table of Contents
Reactions of APnF6 (A = [H3O]+, K, Rb, Cs; Pn = P, As, Sb, Bi), ABF4 (A = K, Cs), and
Cs2MnF6 with [XeF5][PnF6] (Pn = As, Sb) may end in one of three ways: a) no reaction, b)
double displacement reaction or c) formation of A[XeF5][SbF6]2 (A = Rb, Cs) and
Cs[XeF5][BixSb1-xF6]2 (x = ~0.37-0.39). All three compounds crystallize in two crystal
modifications at low (150 K) and at high (296 K) temperatures.
21
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