Crystal structures of phases observed in [H3O]+/M2+/[SbF6]?system (M?=?Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Cd)

Article abstract of DOI:10.1016/j.jfluchem.2016.11.021

The reactions between the MO (M?=?Be, Mg, Ca, Sr, Ti, V, Nb, Mn, Ni, Cu, Pd, Zn, Hg, Sn, Pb) and SbF₅in liquid aHF were investigated. Reactions with the MO (M?=?Mg, Ni, Cu and Zn) yielded H₃OM(SbF₆)₃compounds. Both BeO and PdO didn't show any sign of reactivity meanwhile MO (M?=?V, Nb, Ti) gave products with M in oxidation state higher than two. The rest of the MO (M?=?Ca, Sr, Mn, Hg, Sn, Pb) formed mixtures of M(SbF₆)₂, H₃OSbF₆and/or H₃OSb₂F₁₁. Reactions between H₃OSbF₆and M(SbF₆)₂(M?=?Fe, Co, Ni) also gave H₃OM(SbF₆)₃compounds, meanwhile similar attempts with H₃OSbF₆and M(SbF₆)₂(M?=?Ca, Mn, Pd, Ag, Cd, Sn) to prepare [H₃O]⁺/M²⁺/[SbF₆]^?salts failled. However, slow crystallizations of H₃OSbF₆and M(SbF₆)₂(M?=?Mn, Pd, Cd) mixtures resulted in the single crystal growth of new (H₃O)₃M(SbF₆)₅phases which crystal structures are not isotypic. Similar procedure with H₃OSbF₆/Cr(SbF₆)₂mixture resulted in few light orange crystals of (H₃O)₃[Cr^IV(SbF₆)₆](Sb₂F₁₁)·HF. Its crystal structure determination showed the presence of discrete [Cr^IV(SbF₆)₆]^2?units where each of Cr atoms is found in a homoleptic coordination of six SbF₆groups.

Full text of DOI:10.1016/j.jfluchem.2016.11.021

Accepted Manuscript
Title: Crystal structures of phases observed in
+ 2+
H O] /M /[SbF ] system (M = Mg, Cr, Mn, Fe, Co, Ni,
3
−
[
6
Cu, Zn, Pd, Cd)
Author: Zoran Mazej Evgeny Goreshnik
PII:
S0022-1139(16)30415-8
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.jfluchem.2016.11.021
FLUOR 8908
To appear in:
FLUOR
Received date:
Revised date:
Accepted date:
26-10-2016
24-11-2016
28-11-2016
Please cite this article as: Zoran Mazej, Evgeny Goreshnik, Crystal structures of phases
observed in [H3O]+/M2+/[SbF6]− system (M=Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd,
Cd), Journal of Fluorine Chemistry http://dx.doi.org/10.1016/j.jfluchem.2016.11.021
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O] / M / [SbF
]- system (M = Mg, Cr, Mn,
+
2+
Crystal structures of phases observed in [H
Fe, Co, Ni, Cu, Zn, Pd, Cd)
3
6
,
Zoran Mazej*, Evgeny Goreshnik
Jožef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia, zoran.mazej@ijs.si
Phone: (+386) 1 477 3301
1

Graphical abstract
Highlights
-
-
H
3
OM(SbF
6
)
3
(M = Mg, Co, Ni Fe, Cu and Zn) compounds crystallize isotypically.
OSbF / M(SbF (M = Mn, Pd, Cd) mixtures result in a new
O) M(SbF
Crystal structure of each (H O) M(SbF
Slow crystallizations of H
3
6
6 2
)
type of compounds, i.e. (H
3
3
6
)
5
.
-
-
3
3
6
)
5
(M = Mn, Pd, Cd) represents a unique case.
IV
]2- units are present in (H
IV
Discrete [Cr (SbF
6
)
6
3
O)
3
[Cr (SbF
6
)
6
](Sb F11)·HF.
2
Abstract
The reactions between the MO (M = Be, Mg, Ca, Sr, Ti, V, Nb, Mn, Ni, Cu, Pd, Zn,
Hg, Sn, Pb) and SbF in liquid aHF were investigated. Reactions with the MO (M = Mg, Ni,
Cu and Zn) yielded H OM(SbF compounds. Both BeO and PdO didn't show any sign of
reactivity meanwhile MO (M = V, Nb, Ti) gave products with M in oxidation state higher
than two. The rest of the MO (M = Ca, Sr, Mn, Hg, Sn, Pb) formed mixtures of M(SbF
OSbF and/or H OSb 11. Reactions between H OSbF and M(SbF (M = Fe, Co, Ni)
also gave H OM(SbF compounds, meanwhile similar attempts with H OSbF and
M(SbF (M = Ca, Mn, Pd, Ag, Cd, Sn) to prepare [H
]- salts failled. However,
slow crystallizations of H OSbF and M(SbF (M = Mn, Pd, Cd) mixtures resulted in the
single crystal growth of new (H phases which crystal structures are not isotypic.
mixture resulted in few light orange crystals of
5
3
)
6 3
6
2
) ,
H
3
6
3
2
F
3
6
)
6 2
3
6
)
3
3
6
+
2+
6
)
2
3
O] /M /[SbF
6
3
6
)
6 2
3
O)
3
M(SbF
6
)
5
Similar procedure with H
3
OSbF
6
/ Cr(SbF
6
)
2
IV
(
H
3
O)
3
[Cr (SbF
6
)
6
](Sb
2
F11)·HF. Its crystal structure determination showed the presence of
IV
]2- units where each of Cr atoms is found in a homoleptic coordination of
discrete [Cr (SbF
6 6
)
six SbF groups.
6
Keywords: Oxonium salt; Hexafluoridoantimonate; Superacid; Crystal structure, Oxide.
2

1
. Introduction
Metal oxides MO (M = Mn, Zn, Cu) react with AsF
fluoride (aHF) yielding oxonium salts H OM(AsF (Mn, Zn) or H
respectively.[1] Few single crystalls of (H O) Hg F(AsF were grown from solution of HgO
in aHF acidified with large excess of AsF .[1] The compounds, H OM(AsF , can be also
prepared by a reaction between H OAsF and M(AsF (M = Mn, Co, Ni, Fe, Zn), meanwhile
similar reaction between H OAsF and CrF in aHF acidified with AsF gives only a mixture
of H OAsF and CrFAsF .[1,2,3] In the CdO/SbF /aHF system, the crystal structures of
OCd(SbF , (H O) Cd(SbF (Sb
O)[Cd(HF)] were determined.[4] Attempts to prepare [H
5
in anhydrous hydrogen
OMF(AsF (M = Cu),
3
6
)
3
3
)
6 2
3
2
2
6 5
)
5
3
)
6 3
3
6
6 2
)
3
6
2
5
3
6
6
5
H
3
6
)(Sb
2
F
11
)
2
3
2
6
)
3
2
F
11), (H
3
O)
2
Cd
2
F(SbF
6
)
5
and
+
2+
]-
(
H
3
4
(SbF
6
)
9
3
O] /M /[AsF
6
compounds, using TiO, VO, NbO, PdO, CdO, HgO, SnO and PbO, were unsuccessful.[1]
Since [SbF
]- anion is only slightly larger than [AsF ]- anion, is therefore not
surprising that crystal structures of many corresponding [AsF
]- and [SbF ]- salts are isotypic.
In the present study the reactions between MO (M = Be, Mg, Ca, Sr, Ti, V, Nb, Mn, Ni, Cu,
6
6
6
6
Pd, Zn, Hg, Sn, Pb) and SbF
5
3
in liquid aHF were conducted to find out whether the same type
O] /M /[AsF
]- system would be obtained, or whether the
+
2+
of compounds as in in the [H
6
larger size of [SbF
reactions between H
aHF were investigated.
6
]- would lead to the formation of new products. Additionally, some
3
OSbF and M(SbF (M = Ca, Cr, Mn, Fe, Co, Ni, Pd, Ag, Cd, Sn) in
6
)
6 2
2
. Results and Discussion
2
.1. Syntheses
There were no reactions between MO (M = Be, Pd) and SbF
Reactions between MO (M = V, Ti, Nb) and SbF in aHF resulted in products with M in
oxidation state higher than two. These findings are in agreement with the results of reactions
between the MO (M = V, Ti, Nb) and AsF in aHF.[1] The MO (M = V, Ti, Nb) don't react
with pure liquid aHF. The [SbF /aHF solutions - as
]–, the dominant species in diluted SbF
. Therefore, the higher
5
in aHF (Table 2).
5
5
6
5
used in this work, is a much weaker oxidant than molecular SbF
5
n+
oxidation state M (n = 3, 4 and/or 5) in isolated products are a consequence of
2
+
2+
disproportionation of low-oxidation-state M cations.[5] For example, the [Ti(HF)
stable only in a narrow "window" of acidity, i.e., only in aHF solutions containing SbF
concentrations between 2 and 3 M.[5] During reactions between MO and SbF in liquid aHF
6
] is
5
at
5
3

+
oxygen atoms are protonated yielding [H
3
O] cations meanwhile initial formation of solvated
2
+
low-oxidation-state [M(HF)
n
] cations is followed by disproportionation to metallic form and
higher fluorides. The finely divided metals would redissolve to give Mn+.
Reactions between the MO (M = Ca, Sr, Mn, Hg, Sn, Pb) and SbF
5
in aHF yielded
mixtures of H
observed in the AsF
Reactions between metal oxides MO (M = Mg, Ni, Cu, Zn) and SbF
oxonium salts H OM(SbF . Same type of products was obtained by reacting of H
with M(SbF (M = Fe, Co, Ni) in aHF.
After attempted reactions between between H
only starting materials were recovered (Table 3). Slow crystallizations from H
M(SbF (M = Mn, Pd, Cd) mixtures resulted in a new type of compounds, i.e.
O) M(SbF . Single crystal structure determinations revealed that all three compounds are
not isotypic with each other. In the case of Mn the isolated [H
corresponds to H OMn(AsF [3] meanwhile no such product was observed for larger
SbF
]– anion. The prolonged crystal growth from H
mixture gave few light orange single crystals of (H
3
OSbF
6
/H
3
OSb
2
F
11 and M(SbF
6
)
2
. With exception of Mn, the same trend was
5
system. [1]
5
in aHF yielded
OSbF
3
6
)
3
3
6
)
6 2
3
OSbF
6
and M(SbF
6
)
2
(M = Ca, Mn, Sn)
OSbF and
3
6
)
6 2
(
H
3
3
)
6 5
O] /M /[AsF
]– salt
+
2+
3
6
3
)
6 3
[
6
3
OSbF
6
and Cr(SbF
6
)
2
crystallization
IV
3
O)
3
[Cr (SbF
SbF
aHF.[6] There the presence of Cr(IV) could be explained by oxidation of Cr(II) with [XeF
6
)
6
](Sb
2
F
11)·HF. The same
type of crystals was obtained after crystallization from XeF
5
6
and Cr(SbF
6
2
) mixture in
+
5
] .
2
+
In the H
3
OSbF
6
/Cr(SbF
6
) /aHF system the low oxidation state Cr cations could reduce
2
+
protons from [H
3
O] , releasing water which is a strong base in aHF and it is again protonated
2
+
3+
by the solvent, i.e. superacid HF.[7] This would only explain the oxidation of Cr to Cr .
During long-lasting crystallizations there is a possibility of diffusion of water vapor through
the walls of the reaction vessel, made of fluorocarbon polymers.[8] Superacids are good
media to stabilize low oxidation state cations, but lowered acidities can lead to
+
disproportionation.[5] It might be possible that the presence of [H
3
O] itself could be
sufficient to initiate disproportionation of Cr(II) yielding Cr(IV) compound.
2
.2. Crystal structures of H
3
OM(SbF
6
)
3
(A = Mg, Fe, Co, Ni, Cu, Zn) and (H
3
O)
3
M(SbF
6
5
) (M
=
Mn, Pd, Cd)
Compounds of the type of H
known H OM(AsF (Fe, Co, Ni, Zn, Mn) compounds.[1,2,3,9] The sizes of M crystal radii
are very similar (the M sizes for the coordination number six increase in the order Ni < Mg
3
OM(SbF
6
)
3
(M = Mg, Fe, Co, Ni, Cu, Zn) are isotypic with the
2
+
3
)
6 3
2
+
4

<
Cu < Zn < Co < Fe < Mn [10]). Since there haven't been any indications about existence of
2
+
]– ions is on the
OM(XF (M =
]– framework
H
3
OMn(SbF
6
)
3
, it seems that the combination of larger Mn and [SbF
6
border of stability of the main feature of the crystal structures of isotypic H
3
)
6 3
divalent metal, X = As, Sb) compounds, i.e. three-dimensional [M(XF
)
6 3
2
+
composed of M cations interconnected by XF
6
octahedra, forming cavities within which
+
2+
[
H
3
O] cations are located (Fig. 1). Therefore, Mn prefers to form (H
3
O)
3
Mn(SbF
M(SbF
M = Ni, Mg, Cu, Zn, Co, Mn, Pd) compounds. Their crystal structures consist of similar
three-dimensional [M(XF OM(XF ) (M = divalent metal, X = As, Sb)
]– framework as in H
compounds (Fig. 1), although slightly modified for larger Mn and Pd.[6] Since the sizes of the
6
)
5
instead
2
+
of H
3
OMn(SbF
6
)
3. The influence of larger Mn is also evident in the case of XeF
5
)
6 3
(
6
)
3
3
6
2
+
2+
2+
Pd (1.00 Å for C.N. = 6) and Cd (0.95 Å for C.N. = 6) [10] are close to that of Mn (0.97
Å) [10] is not unexpected that they also form different types of compounds, i.e.
2
+
(
H
3
O)
3
M(SbF
6
) (M = Cd, Pd), as smaller M cations (M = Mg, Fe, Co, Ni, Cu, Zn).
5
Summary of the refinement results and other crystallographic information for
IV
H
3
OMg(AsF
6
)
3
, (H
3
O)
3
M(SbF
6
)
5
(M = Mn, Pd) and (H
3
O)
3
[Cr (SbF
6
)
6
](Sb F11)·HF are
2
provided in Table 1.
5
-
The crystal structure of (H
3
O)
3
Mn(SbF
6
)
5
consists of infinite zig-zag ([Mn
2
(SbF
]– (Fig. 2),
]- (Sb6) anions, and [H O]+
cations (which provide additional positive charge) are located between the columns.
6
)
9
] )
n
2
1
2
1
columns, i.e. –(trans-η -SbF
6
)–[Mn(η -SbF
6
)
3
]–(cis-η -SbF
6
)
2
–[Mn(η -SbF
6 3
)
oriented parallel to each other along b-axis (Fig. S1). Free [SbF
6
3
5
-
Within each ([Mn
units with the bridging F atoms in cis-position. Each of Mn is additionally linked to one
neighbouring Mn atom by one SbF (Sb1) unit with the bridging F atoms in trans position.
The coordination around each Mn is completed with three terminal SbF (Sb3, Sb4, Sb5)
2
(SbF
6
)
9
] )
n
column two adjacent Mn atoms are bridged by two SbF (Sb2)
6
6
6
groups. On such a way, manganese is octahedrally coordinated with six F atoms with Mn–F
distances (2.087(3) - 2.146(3) Å) that correlate well with the values of Mn–F bond lengths
(
2.118(4) - 2.133(4) Å) determined in Mn(SbF
fluorine atom; 1.907(3) - 1.925(3) Å) are elongated relative to the Sb–F
fluorine atom; 1.835(3) - 1.881(3) Å). The corresponding Sb–F and Sb–F
Mn(SbF are in the range 1.918(4) - 1.941(4) Ǻ and 1.832(4) - 1.856(4) Ǻ, respectively.[11]
6
)
2
.[11] The Sb–F
b
bonds (F
bonds (F
bonds in
b
= bridging
t
t
= terminal
b
t
)
6 2
5

Although Pd compound has similar formula, i.e. (H
with Mn compound. It crystallizes in two crystal modifications at low (α-phase, 200 K) and
ambient (β-phase, 293 K) temperatures. -(H O) Pd(SbF crystallizes in monoclinic space
3
O)
3
Pd(SbF
6
)
5
, it is not isotypic
3
3
)
6 5
group, meanwhile -phase is triclinic (Table 1). Beside more dense packing in the α-phase,
with a packing index of 75.6% whereas respective value for the β-phase is 73.5%, there are no
significant differences between both phases. Therefore, only description of crystal structure of
the high-temperature phase is given.
1
]–(cis-η2-
(Sb2) units
(Sb1, Sb3, Sb4,
O] cations are located between the anionic moieties (Fig. S2). The Pd–
The mean structural feature of (H
3
O)
3
Pd(SbF
6
)
5
represents [Pd(η -SbF
6 4
)
1
SbF
6
)
2
–[Pd(η -SbF
6
)
4
] moiety consisted of two Pd atoms bridged by two SbF
6
(
Fig. 3). The coordination of each Pd is completed by four terminal SbF
6
+
Sb5) groups. The [H
3
F bonds range from 2.163(2) Ǻ to 2.203(2) Å (β-phase) and from 2.150(5) to 2.209(5) Å (-
phase). The Pd–F bond lengths in Pd(AsF are equal to 2.183(5) - 2.190(5) Å.[12] The Sb–
F bonds are of similar length as in (H O) Mn(SbF (α-phase: Sb–F = 1.913(5) - 1.941(5) Å,
= 1.832(6) - 1.878(5) Å; -phase: Sb–F = 1.908(2) - 1.926(2) Å, Sb–F = 1.820(3) -
)
6 2
3
3
6
)
5
b
Sb–F
t
b
t
1
.877(3) Å).
The numerous repeated attempts to obtain the good-quality X-ray diffraction data of
Cd(SbF were unsuccessful. The structure refinement did not lead to the satisfactory
(
H
3
O)
3
)
6 5
results. Therefore, the given structure is to be understood as merely modelling connectivity
where is clearly visible that it represents the third structure type of (H O) M(SbF (M = Mn,
3
3
)
6 5
Pd, Cd) compounds. In contrast to (H
3
O)
3
M(SbF
6
)
5
(M = Mn, Pd) where crystal structure of
5
-
]– anions and [H
+
the former consists of ([Mn
and crystal structure of the latter of [Pd(SbF
cations, the crystal structure of (H O) Cd(SbF
groups forming cavities within which "free" [SbF
2
(SbF
6
)
9
] )
n
columns, "free" [SbF
]–(SbF –[Pd(SbF
is a three-dimensional framework formed of
]– anions and
6
3
O] cations,
6
)
4
6
)
2
6
)
4
] moieties and [H
O]+
3
3
3
6 5
)
Cd atoms linked through SbF
6
6
+
[
H
3
O] cations are located (Fig. S3).
It’s well known that oxygen and fluorine atoms are sometimes technically difficult to
distinguish by X-ray diffraction. In the crystal structure of yellow-orange
IV
(
H
3
O)
3
[Cr (SbF
6
)
6
](Sb F11)·HF the positions of hydrogen atoms could not be unambiguously
2
determined. Therefore, grown crystals could hypothetically also correspond to the
V
+
(
H
3
O)
2
[Cr (SbF
6
)
6
](Sb
2
F
11)·2HF if we assume that one of the [H O] cations is in reality HF.
3
III
III
Option with Cr , i.e. (H
3
O)
4
[Cr (SbF
6
)
6
](Sb F11), has been excluded on the basis that Cr(III)
2
6

fluoride compounds are green. The possibility that instead of some of HF molecules or H O
3
–
groups we have only free fluoride anions (F ) is also unlikely. Therefore only two possibilities
IV
were taken into account, i.e., (H
3
O)
3
[Cr (SbF
6
)
6
](Sb F11)·HF and
2
V
(
H
3
O)
3
[Cr (SbF
6
)
6
](Sb F11)·2HF. Chromium compounds with a Cr(V) in a fluoride
2
environment are red to deep red, meanwhile chromium compounds, with Cr(IV) coordinated
to fluoride ligands, are yellow, orange or brick red. On the basis of that we assume that the
IV
formulation (H
3
O)
3
[Cr (SbF
6
)
6
](Sb
2
F11)·HF is correct. Additionally, average Cr–Fav bond
IV
IV
distance (1.888 Ǻ) in (H
CrF (1.836 Ǻ),[13] RbCrF
14] than to Cr –Fav bond lengths determined in Cr(V) fluorides (NaCrF
3
O)
3
[Cr (SbF
6
)
6
](Sb F11)·HF is closer to Cr –Fav bond lengths in
2
4
5
(1.824 Ǻ),[14] CsCrF
5
(1.810 Ǻ),[14] K
2
CrF
6
·2HF (1.820 Ǻ)
V
[
6
(1.740 Ǻ) [14],
KCrF
6
: 1.750 Ǻ [14]; RbCrF
5
: 1.7582 Ǻ [14]).
IV
)
]2–
The crystal structure of (H
groups, [Sb
crystallographically independent Sb
ordered F ligands, meanwhile part of the second Sb
3
O)
3
[Cr (SbF
6
)
6
](Sb
2
F
11)·HF consists of [Cr(SbF
6
6
+
2
F
11]– anions, non-coordinated HF molecules and [H
11 units. First Sb
11 group (Sb9/Sb10) is disordered. The
3
O] cations. There are two
2
F
2
F11 unit (Sb7/Sb8) has completely
2
F
Sb10 atom was split over two position, i.e., Sb10 and Sb11. Despite the rather large thermal
ellipsoids of some fluorine atoms connected to the Sb(10/11), all attempts to split their
positions (with exception of F94) to obtain a reasonable model of the disordering were
unsuccessful.
IV
The most interesting feature in the crystal structure of (H
3
O)
3
[Cr (SbF
6
)
6
](Sb F11)·HF
2
2
–
is the presence of discrete [Cr(SbF
6
) ] groups where each is Cr(IV) is found in a homoleptic
6
coordination of six SbF groups (Fig. 4). Such moieties haven't been observed before.
6
2
.3. Raman spectra of H
3
OM(SbF
6
)
3
(A = Mg, Fe, Co, Ni, Cu, Zn) compounds
(A = Mg, Fe, Co, Ni, Cu, Zn) are shown in Fig. 5 and
Raman spectra of H
3
OM(SbF
)
6 3
Fig. S4 (Supplementary Material). Since they all show similar features only Raman spectrum
of Mg compound is discussed.
-1
The bands at 671, 596, and 305/292/275 cm are assigned to the v (A1g symmetry)
1
and v
2
(E
g
symmetry) Sb–F stretching normal modes and the v
5
(T2g symmetry) bending
–
-1
normal modes, respectively, of [SbF
6
] anion. Bands in the region 500560 cm are typical
for species where one fluorine bridges two different atoms, and can be readily assigned to
-1
MFSb stretching modes. The rest of the bands (213 and 119 cm ) belongs to lattice
7

vibrations. The similarity of Raman spectra (Fig. 5 and Fig. S4) agrees with X-ray single
crystal (Mg) and X-ray powder diffraction results (Table S1) which show that all
H
3
OM(SbF
6
3
) (A = Mg, Fe, Co, Ni, Cu, Zn) compounds are isotypic.
3
. Conclusions
The H OM(SbF
corresponding oxides (MO; M = Mg, Ni, Cu, Zn) and/or by reactions between H
M(SbF (M = Fe, Co). They crystallize isotypically with H OM(AsF (M = Mn, Co, Ni,
3
6
)
3
(Mg, Fe, Co, Ni, Cu Zn) compounds can be prepared from the
OSbF and
3
6
6
)
2
3
6 3
)
Fe, Zn) compounds.[1,2,3]
Reactions between H
3
OSbF
6
and M(SbF
OSbF and M(SbF
resulted in a new type of compounds, i.e., (H O) M(SbF
represents a unique case. It seems that (H O) M(SbF
product, while H OSbF and M(SbF are favoured kinetically.
The use of H mixture led to the growth of few light yellow-orange
11)·HF which were found on the surface of green
6
)
2
(M = Mn, Pd) were unsuccessful
meanwhile slow crystallizations of H
3
6
6
)
2
(M = Mn, Pd, Cd) mixtures
, where each crystal structure
3
3
)
6 5
3
3
6
5
) is the thermodynamically more stable
3
6
)
6 2
3
OSbF
6
/ Cr(SbF
6 2
)
IV
crystals of (H
3
O)
3
[Cr (SbF
6
)
6
](Sb
2
F
undissolved material. The crystal structure determination has shown the presence of discrete
IV
]2- units where each Cr atom is found in a homoleptic coordination of six SbF
[
Cr (SbF
6
)
6
6
units.
+
2+
-
2+
The attempts to synthesize [H
3
O] /M /[SbF ] salts with M = Be, Ca, Sr, Ti, V, Nb,
6
Ag, Hg, Sn, Pb) failled.
4
. Experimental
4
.1. Apparatus and Reagents
All the manipulations were carried out under anhydrous conditions. The volatile
compounds, such as aHF, SbF and F , were handled on a vacuum line constructed from
nickel-Teflon and the non-volatile materials were handled in a dry box (M. Braun) in an argon
atmosphere (<0.5 ppm H O). Reactions were carried out in FEP (tetrafluoroethylene-
5
2
2
hexafluoropropylene; Polytetra GmbH, Germany) reaction vessels (height 250300 mm with
inner diameter 15.5 mm and outer diameter 18.75 mm) equipped with PTFE valves [15] and
PTFE coated stirring bars. Before use all reaction vessels were passivated with elemental
fluorine (Solvay Fluor and Derivate GmbH, Germany). BeO (Schuchardt Munchen), MgO
(
Merck, >97 %), TiO (Alfa Aesar, 99.5%), VO (Alfa Aesar, 99.5 %), MnO (Alfa Aesar, 99.99
), NiO (Ventron, 99%), CuO (Alfa Aesar, 99.9 %), PdO (Alfa Products, 99.9 %), ZnO
%
8

(
Sigma Aldrich, 99.99 %), NbO (Alfa Aesar), CdO (Sigma Aldrich, 99.5 %), HgO (Alfa
Aesar, 99 %), SnO (Alfa Aesar, 99.9 %), PbO (Johnson Matthey GmbH, 99.99%), CaF
Merck), CrF (ABCR, 99 %), MnF (Alfa Aesar, 99 %), CoF (Johnson Matthey GmbH, 99
(Aldrich, 99 %) were used as supplied. CaO (Kemika
2
(
2
2
2
%
), NiF
2
(Alfa Products, 99.9%), SnF
2
o
Zagreb) was treated for 5 h at 1100 C in air atmosphere, SrO was prepared from SrCO
3
o
(
Riedel de Haen, pure) at 1000 C in air atmosphere, CdF
2
was prepared by pressure
fluorination of CdCl
2
·H
2
O with elemental fluorine in liquid aHF in FEP reaction vessel, FeF
2
o
was prepared by treating of powdered Fe metal with HF at 180 C for two weeks, AgF
2
was
obtained by fluorination of AgNO
3
in liquid aHF. M(SbF
6
2
) (M = Ca, Mn, Fe, Ni, Cr, Ag, Cd,
Sn) [16,17] and H
3
OSbF
6
[18] were prepared as described previously. SbF was prepared by
5
o
fluorination of SbF
3
in a nickel autoclave at 200 C for 24 h and distillated twice before use.
Anhydrous HF (Fluka, Purum) was treated with K
2
NiF (Ozark Mahoning) for several hours
6
prior to use.
4
.2. Raman Spectroscopy
Raman spectra were recorded (10–20 scans) on a Renishaw Raman Imaging
Microscope System 1000, with the 632.8 nm exciting line of a He-Ne laser (50 mW) with a
-1
resolution of 2 cm and on Horiba Jobin-YvonLabRAM HR spectrometer using the 632.81
nm excitation line of He-Ne laser (17 mW). Some of the Raman spectra are given in
Supplementary Material (Figs. S4 and S5).
4
.3. Powder X–ray Diffraction Photographs
X-ray powder diffraction photographs (Table S1) were obtained using the Debye-
Scherrer technique with Ni-filtered CuK
α
radiation. Samples were loaded into quartz
capillaries (0.3 mm) in a dry-box. Intensities were estimated visually.
4
.4. Reactions between MO (M = Be, Mg, Ca, Sr, Ti, V, Nb, Mn, Ni, Cu, Zn, Pd, Hg, Sn, Pb)
and SbF in aHF
MO was loaded in a reaction vessel in a glove-box (Table 2). aHF and SbF
5
5
were
condensed onto the reaction mixture and the reaction vessel was brought to room temperature.
The reaction mixtures were left stirring at room temperature (Table 2). Volatiles were slowly
pumped off at room temperature for few hours, leaving colourless (Be, Mg, Ca, Sr, Mn, Cu,
Zn, Hg, Sn, Pb), yellow (Ni), black (Pd), greenish-yellow (V), greyish (Ti, Nb) solids (Table
2
).
9

In the case of Pd additional experiment was done. Fluorine was added onto
PdO/SbF /aHF reaction mixture resulting in a green solution from which green material was
recovered (Table 1).
5
4
.5. Attempted Reactions between MO (M = Ti, V, Nb) and liquid aHF
Around 100 mg of MO (M = Ti, V, Nb) was loaded in a reaction vessel in a glove-
box. After 5-6 ml of aHF was condensed onto them, the reaction vessels were brought to
room temperature. After one week of intesive stirring there was no visible change. Volatiles
were pumped away and only starting MO were recovered.
4
.6. Reactions between H
3
OSbF
6
and M(SbF
6
)
2
(M = Ca, Mn,Fe, Co Ni, Sn) and SbF in
5
aHF
Appropriate mixtures of H
3
OSbF
6
and M(SbF
6
)
2
(M = Ca, Mn, Fe, Co, Ni, Sn) were
were condensed onto the reaction
loaded in a reaction vessel in a glove-box and aHF and SbF
5
mixture and the reaction vessel was brought to room temperature (Table 3). Colourless (Ca,
Mn, Fe, Sn), pink (Co), yellow (Ni), solutions were obtained. Volatiles were slowly pumped
off at room temperature, leaving behind colourless (Ca, Mn, Fe, Sn), pink (Co) and yellow
(
Ni) solids (Table 3).
4
.7. Crystal Growth
Crystal growth of the products obtained by reactions between MO (M = Mg, Ca, Ni,
Cu, Zn, Sn) and SbF in aHF (Table 2), crystal growth of the products obtained by reactions
between H OSbF and M(SbF (M= Ca, Mn, Fe, Co, Ni, Pd, Sn) in aHF (Tables 2 and 3)
and direct crystal growth of H OSbF / M(SbF (M = Cr, Ag, Cd) mixtures (Table 3) were
5
3
6
6 2
)
3
6
)
6 2
carried out in a double Tshaped apparatus consisting of two FEP tubes (19 mm. o.d., and 6
mm. o.d.). Starting materials were loaded into the wider arm of the crystallization vessel in a
dry-box. aHF (~4–8 ml) was then condensed onto the starting material at 77 K. The
crystallization mixtures were brought up to ambient temperature and the clear solutions were
decanted into the narrower arm. The evaporation of the solvent from these solutions was
carried out by maintaining a temperature gradient corresponding to about 10 K between both
tubes. The effect of this treatment was to enable aHF to be slowly evaporated from narrower
into wider tube leaving the crystals. When the HF level in the narrower arm of crystallization
vessel ceased to further decrease, it was necessary to increase the temperature gradient. This
1
0

o
o
was accomplished by slowly cooling the larger arm in a cryostat from +12 C to –30 C and
o
down to –55 C to induce crystallization.
Single crystals of colourless H
Mn, Cd), pink H OCo(SbF and green (H
corresponding starting compounds. All other attempts to prepare single crystals of
3
OM(SbF
6
)
3
(M = Mg, Zn) and (H
3
O)
3
M(SbF
6
) (M =
5
3
6
)
3
3
O) Pd(SbF
3
6 5
)
were grown from solutions of
+
2+
]– compounds failed (Tables 2 and 3).
OSbF /Cr(SbF proceeded in a similar way as reported for
OSbF /Cr(SbF mixture, green
[
H
3
O] /M /[SbF
Crystallization of H
SbF /Cr(SbF mixture. After addition of aHF onto H
6
3
6
)
6 2
XeF
5
6
6
)
2
3
6
)
6 2
precipitate formed immediately with a colorless clear liquid phase present above. The liquid
phase with some undissolved green material was poured into the narrower arm of
crystallization vessel. After 40 days a few yellow-orange crystals of
IV
(
H
3
O)
3
[Cr (SbF
6
)
6
](Sb F11)·HF were grown on the surface of the green insoluble material.
2
Everything was covered with a sticky, very dense liquid phase, most likely a mixture of HF
and SbF
5
.
Crystallization products were immersed in perfluorinated oil (ABCR, FO5960,
melting point 263 K) in a dry-box. Single crystals were then selected from the crystallization
products under the microscope (at temperatures between 265 to 273 K) outside the dry-box
and then transferred into the cold nitrogen stream of the diffractometer.
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 (Fig. S5).
4
.8. X-ray Structure Determinations
Single-crystal data of (H O)M(SbF
diffractometer equipped with a Mercury CCD area detector, using graphite monochromatized
MoK radiation. Because of poor quality of H OM[SbF (M = Zn, Co) crystals only lattice
3
6
) (M = Co, Zn) were collected on a Rigaku AFC7
3
α
3
6 3
]
parameters were determined.
Single-crystal data for (H
3
O)Mg(SbF
6
)
3
, (H
3
O)
3
M(SbF
6
5
) (M = Mn, Pd, Cd) and
IV
(
H
3
O)
3
[Cr (SbF
6
)
6
](Sb F11)·HF were collected on a Gemini A diffractometer equipped with
2
an Atlas CCD detector, using graphite monochromated Mo–Kα radiation. The data were
treated using the CrysAlisPro software suite program package.[19] Analytical absorption
corrections were applied to all the data sets. The structures were solved with the charge-
flipping method using the Superflip program[20] (Olex crystallographic software[21]). The
electron density map, obtained with Superflip software, was analyzed using the EDMA
program[22], which gave initial models of the structures. Some structures were solved using
1
1

the SHELXS program.[23] Structure refinement was performed with the SHELXL-2014[24]
software, implemented in the program package WinGX.[25] The structure drawings were
generated by DIAMOND 4.2.2 software.[26]
IV
During the refinement of (H
3
O)
3
[Cr (SbF
6
)
6
](Sb F11)·HF, the twinning law -1 0 0 0 -
2
1
0 0 0 1 was derived using TwinRotMat procedure implemented in the Platon software [27].
Its use resulted in a nearly 1:1 ratio of two different domains. Because of too large thermal
parameters of Sb10 atom and because of the presence of noticeable peak of residual electron
density near this atom, the Sb10 atom was split over two position, i.e. Sb10 and Sb11. The
occupancy of ½ was set for both of them. Because of strongly elongated thermal ellipsoid for
F94 atom, the position of the latter was also split, and the ratio between occupancies of F94a
and F94b centres were refined giving at the final stage ratio 0.58:0.42.
Peaks of electron density found outside the coordination sphere of Sb or Cr atoms,
were identified as O (H O) or F (HF) moieties. Because of rather poor quality of collected
3
diffraction data the positions of hydrogen atoms weren't localized. Proposed distinction
+
between O and F atoms (i.e. [H
3
O] cations and neutral HF molecules) was done on the basis
of: a) occupancy refinement, b) analysis of the number and geometry of the closest
X···FSbF (X = O or F) contacts, c) assumption that the chromium oxidation state is +4 (see
5
paragraph 2.1.) and d) charge balance requirements.
All hydrogen atoms in the crystal structure of (H
3
O)Mg(SbF
and LT-(H O) Pd(SbF
localized from the difference Fourier maps. Positions of the rest of hydrogen atoms in the
latter two compounds, and all hydrogen atoms in structures of HT-(H O) Pd(SbF were
6
)
3
and some hydrogen
atoms in the crystal structures of (H
3
O)
3
Mn(SbF
6
)
5
3
3
)
6 5
compounds were
3
3
)
6 5
placed on reported positions on the basis of geometrical reasons, i.e. taking into account the
+
geometry of [H
3
O] cation and the orientation of closest O···F contacts. Before the final
refinement isotropic thermal parameters of hydrogen atoms were set as 1.2 equivalent thermal
parameter of respective oxygen atom and geometrical restrictions (DFIX) have been used.
The CIF's files 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432046 ((H
3
O)
), CSD432049 ((H
](Sb
3
Mn(SbF
6
)
5
), CSD432047 (LT-(H
3
O)
3
Pd(SbF
6
)
5
), CSD 432048 (HT-
(
(
H
3
O)
3
Pd(SbF
6
)
5
3
O)Mg(SbF ) and CSD432050
6 3
)
IV
(H O)
3
3
[Cr (SbF
6
)
6
2
F11)·HF).
1
2

Acknowledgements
The authors (Z.M., E. G.) gratefully acknowledge the Slovenian Research Agency (ARRS)
for the financial support of the present study within the research program: P1–0045 Inorganic
Chemistry and Technology. They are also very grateful to Prof. Florian Kraus for measuring
some X-ray powder diffraction patterns.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the online version, at...
1
3

References
[
[
[
[
[
1] Z. Mazej, E. Goreshnik, Z. Jagličić, Eur. J. Inorg. Chem. (2012) 17341741.
2] Z. Mazej, E. Goreshnik, J. Fluorine Chem.130 (2009) 399–405.
3] K. Lutar, B. Žemva, H. Borrmann, Eur. J. Solid State Inorg.Chem. 33 (1996) 957–969.
4] Z. Mazej, G. Tavčar, Inorg. Chim. Acta 377 (2011) 69–76.
5] T. A. O’Donnell, Superacids and Acidic Melts as Inorganic Chemical Reaction Media,
VCH Publishers, New York, 1993.
[
[
(
[
6] Z. Mazej, E. Goreshnik, Eur. J. Inorg. Chem. (2016) 3356–3364.
7] C.G. Barraclough, R.W. Cockman, T.A. O'Donnell, W.S.J. Schofield, Inorg. Chem. 21
1982) 2519–2521.
8] Z. Mazej, E. Goreshnik, J. Fluorine. Chem. (2016), in press, DOI:
1
0.1016/j.jfluchem.2016.05.014.
[
[
[
[
[
[
[
9] Z. Mazej, E. Goreshnik, Z. Kristallogr. 230 (2015) 123–130.
10] R. D. Shannon, Acta Crystallogr A 32 (1976) 751–767.
11] P. Benkič, Z. Mazej, Z. anorg. allg. Chem. 627 (2001) 1952–1957.
12] Z. Mazej, P. Benkič, A. Tressaud, B. Žemva, Eur. J. Inorg. Chem. (2004) 1827–1834.
13] P. Benkič, Z. Mazej, B. Žemva, Angew. Chem. Int. Ed. 41 (2002) 1398–1399.
14] Z. Mazej, E. Goreshnik, Eur. J. Inorg. Chem. 2008 (2008) 1795–1812.
15] PTFE valves were constructed and made at Jožef Stefan Institute in a similar way as
shown in: O'Donnelll, The Chemistry of Fluorine; in Comprehensive Inorganic Chemistry,
Pergamon Press, Oxford, 1973, p. 1918.
[
16] D. Gantar, I. Leban, B. Frlec, J.H. Holloway, J. Chem. Soc., Dalton Trans (1987) 2379–
383.
2
[
[
[
17] Z. Mazej, J. Fluorine Chem. 125 (2004) 1723–1733.
18] K.O. Christe, C.J. Schack, R.D. Wilson, Inorg. Chem. 14 (1975) 2224–2230.
19] CrysAlisPro, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014
CrysAlis171 .NET).
[
[
20] L. Palatinus, G. Chapuis, J. Appl. Cryst. 40 (2007) 786–790.
21] O.V. Dolomanov, L.J. Bourhis, R.J. Gildea, J.A.K. Howard, H. Puschmann, J. Appl.
Cryst. 42 (2009) 339–341.
[
[
22] L. Palatinus, S. Jagannatha Prathapa, S. van Smaalen J. Appl. Cryst. 45 (2012) 575
23] G. M. Sheldrick, Acta Cryst. A64 (2008) 112–122.
1
4

[
[
[
24] G.M. Sheldrick, Acta Cryst. C71 (2015) 3−8.
25] L.J. Farrugia., J. App. Cryst. 45 (2012) 849–854.
26] Diamond - Crystal and Molecular Structure Visualization Crystal Impact - Dr. H. Putz &
Dr. K. Brandenburg GbR, Kreuzherrenstr. 102, 53227 Bonn, Germany
http://www.crystalimpact.com/diamond
[
27] A.L. Spek, Acta Cryst. D65 (2009) 148–155.
1
5

2
+
Fig. 1. Three-dimensional framework composed of M cations interconnected by XF
6
+
+
+
+
+
+
octahedra in the crystal structures of AM(XF
6
)
3
(A = [O
2
] , [NO] , [NH ] , K , Rb , Cs ,
4
[
XeF
5
]+; M = divalent metal; X = As, Sb). Single charged cations are omitted for clarity.
5
-
Fig. 2. Part of the ([Mn
2
(SbF
6
)
9
] )
n
column in the crystal structure of (H
3
O)
3
6 5
Mn(SbF )
(
thermal ellipsoids are drawn at the 50% probability level).
1
6

1
2
1
Fig. 3. The [Pd(η -SbF
6
)
4
]–(cis-η -SbF
6
)
2
–[Pd(η -SbF
6
4
) ] moiety in the crystal structure of -
modification of (H O)
3
3
Pd(SbF
6
)
5
(thermal ellipsoids are drawn at the 50% probability level).
IV
Fig. 4. Part of the crystal structure of (H
3
O)
3
[Cr (SbF
6
)
6
](Sb F11)·HF showing discrete
2
2
–
[
Cr(SbF
6
) ] group (thermal ellipsoids are drawn at the 50% probability level).
6
1
7

6
71
2
92
2
75
3
05
5
96 552
213 119
900
700
500
300
1
100
-
Wavenumber (cm )
Fig. 5. Raman spectrum of H
3
OMg(SbF
6
3
) .
1
8

Table 1
IV
11)·HF.a
11)·HF
Summary of crystal data and refinement results for H
3
OMg(AsF
6
)
3
, (H
3
O)
3
M(SbF
6
)
5
(M = Mn, Pd) and (H
3
O)
3
[Cr (SbF
6
)
6
](Sb F
2
IV
Formula
Fw
H
750.58
200
3
OMg(SbF
6
)
3
(H
1290.76
200
3
O)
3
Mn(SbF
6
)
5
LT-(H
3
O) Pd(SbF
3
6
)
5
HT-(H O) Pd(SbF
1342.27
293
3
3
6
)
5
(H
3
O)
3
[Cr (SbF
6
)
6
](Sb F
2
1342.27
200
1995.70
150
T (K)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
orthorhombic
Pnma
10.6330(7)
14.6887(11)
9.60007(7)
90
monoclinic
triclinic
P1
monoclinic
C 2/c
15.3036(3)
15.3901(3)
22.7805(5)
90
108.188(2)
90
5097.29(18)
8
monoclinic
P2
1
/m
P 2 /m
1
10.5743(3)
21.7430(5)
10.8011(3)
90
91.463(2)
90
10.7217(2)
10.7563(2)
22.7684(5)
102.766(2)
102.673(2)
90.538(2)
2493.86(9)
4
9.9725(2)
22.4411(6)
17.6694(4)
90
90.035(2)
90


(deg)
(deg)
90
90
γ (deg)
3
V (Å )
1499.49(19)
4
2482.55(11)
4
3954.29(17)
4
Z
λ (Å)
0.71069
5.598
3.325
0.0446
0.1082
1.298
0.71069
6.085
3.453
0.035
0.0727
1.058
0.71069
6.273
3.575
0.0405
0.0904
0.71069
6.138
3.511
0.024
0.055
0.71069
5.872
3.296
0.046
0.1240
1.072
-
1
μ (mm )
D
calcd (g/cm3)
b
R
1
c
wR
2
d
GOF indicator
1.417
1.058
a
Unit cells of H
3
OM(SbF
6
3
) (M = Zn, orthorhombic at 200 K: 10.6775 Ǻ, 14.6424 Ǻ, 9.5462 Ǻ; M = Co, orthorhombic at 200 K: 10.8360Ǻ,
b
1
wR
4.4746Ǻ, 9.6268 Ǻ) and (H
3
O)
o
3
Cd(SbF
6
)
5
(tetragonal at 200 K: 10.797(14) Ǻ, 10.797(14) Ǻ, 43.25(3) Ǻ). R
1
= Σ׀׀F
o
׀– ׀F
c
׀Σ/׀׀F ׀for I > 2σ(I).
o
c
2
2 2
2 2 1/2 d
2
2 2
1/2
2
= [Σ[w(F
o
–F
c
) ]/ Σ(w(F
) ]
.
GOF = [Σw(F
o
– F
c
) /(N
o
– N
p
)] , where N
o
= no. of reflns and N
p
= no. of refined parameters.
1
9

Table 2
Experimental conditions for the reactions between MO (Be, Mg, Ca, Sr, Ti, V, Nb, Mn, Ni, Cu, Zn, Pd, Hg, Sn, Pb) and SbF
5
in aHF and
observed reaction and crystallization products.
Starting compounds
MO
V
aHF
Time of Observed
reaction products
Time of
Observed single crystals
SbF
5
crystallization pon the crystallization
/
mg
/ mmol
0.8
1.04
0.83
1.18
0.5
0.57
0.55
1.37
1.36
0.96
1.03
1.09
0.7
/ mg / mmol / ml
/ d
after reaction
BeO
OMg(SbF
Ca(SbF /H
Sr(SbF /H
/TiF
/ d
/
70
28
f reaction products
/
a
b
BeO
MgO
CaO
SrO
TiO
VO
NbO
MnO
NiO
NiO
CuO
ZnO
PdO
PdO
20
42
47
123
32
38
60
97
102
72
82
89
85
85
650
1000 4.61
700 3.23
1000 3.00
3.00
4
4
4
3
3
4
4
4
4
3
4
4
4
4
3
1
1
1
c
H
3
6
)
3
H
H
/
3
OMg(SbF
6
)
3
c
6
)
2
3
OSbF
OSbF
/TiF
6
3
OSbF /H OSb
6
3
2 11
F
c
b
6
)
2
3
6
/
/
/
/
/
/
d
b
480
480
550
2.2
2.2
2.52
20
24
24
H
3
H
3
H
3
OSbF
OSb
OSbF
6
3
4
/
/
/
/
d
d
b
2
F11/VF
3
b
6
/H
3
OSb
2
F11/H
3
ONbF
6
c
b
1400 6.46
500 3.69
1000 4.61
900 4.15
1000 4.61
8
5
3
1
1
3
Mn(SbF
6
)
2
/H
3
OSb
2
F
11
c
b
H
3
H
3
H
3
H
3
ONi(SbF
ONi(SbF
OCu(SbF
OZn(SbF
6
)
)
3
3
/
c
6
19
20
21
yellow powder
stacked plates
c
6
)
3
c
6
)
3
H
/
3
6 3
OZn(SbF )
a
b
600
600
2.77
2.77
PdO
/
e
0.7
1
Pd(SbF
6
)
2
/H
3
OSbF
6
19
(H
3
O) Pd(SbF
3
6
)
5
/H
3
OSbF /
6
Pd(SbF
/
white powder
/
6 2
)
HgO
SnO
PbO
99
90
103
0.46
0.67
0.46
1100 5.07
800 3.69
1400 6.46
3
4
3
1c
Hg(SbF
6
)
2
/H
3
OSbF
6
/b
c
1
Sn(SbF
Pb(SbF
6
)
)
2
2
/H
/H
3
OSb
OSb
2
F
F
11
67
c
b
1
6
3
e
2
11
/
a
b
c
d
Undissolved. Crystallization wasn't attempted. Clear solution. Partly dissolved. After addition of F
2
clear green solution formed.
2
0

Table 3
Experimental conditions for the reactions between H
crystallization products
3
OSbF
6
and M(SbF
6
2
) , (M = Ca, Cr, Mn, Fe, Co Ni, Ag, Cd, Sn) and observed reaction and
Starting compounds
V
Time of Observed
reaction products
Time of
rystallization
Observed single crystals
upon the crystallization
of reaction products
M(SbF
6
)
2
H
3
OSbF
6
aHF
/ ml
3
/
mg / mmol
/ mg / mmol
/ d
after reaction
Ca(SbF /H
/ d
68
35
55
35
34
30
19
a
Ca(SbF
6
)
2
247
263
263
263
393
464
554
85
0.48
0.5
0.5
128
127
255
383
194
223
261
40
0.50
0.50
1.00
1.50
0.76
0.88
1.03
0.16
0.18
0.45
2
3
3
3
1
9
1
6
)
2
3
OSbF
6
H
3
OSbF
6
/H
3
2 11
OSb F
b
a
Mn(SbF
Mn(SbF
Mn(SbF
6
6
6
)
)
)
2
2
2
3
Mn(SbF
Mn(SbF
Mn(SbF
6
6
6
)
)
)
2
2
2
/H
/H
/H
)
6
3
3
3
OSb
OSbF
OSbF
2
F
6
11
(H
(H
(H
3
3
3
O)
O)
O)
3
3
3
Mn(SbF
Mn(SbF
Mn(SbF
6
6
6
)
)
)
5
5
5
a
3
3
3
2
2
5
5
5
2
a
0.5
6
/ H
3
OSbF
6
c
Fe(SbF
Co(SbF
6
)
2
0.74
8.88
1.05
0.16
0.18
0.15
0.90
H
3
H
3
H
3
/
OFe(SbF
OCo(SbF
ONi(SbF
6
3
stacked plates
OCo(SbF
yellow powder
a
6
)
2
)
3
H
3
)
6 3
a
Ni(SbF
Cr(SbF
6
)
)
2
2
6 3
)
d,e
IV
6
/
/
/
40
24
(H
Ag
(H
white powder
3
O)
(SbF
O) Cd(SbF
3
[Cr (SbF
/H OSbF
/H
6
)
6
](Sb F11)·HF
6
2
e
Ag(SbF
Cd(SbF
Sn(SbF
6
)
2
105
88
46
/
/
3
6
)
4
3
e
6
)
2
115
230
30
3
3
6
)
5
3
OSbF
6
c
6
)
2
533
0.90
4
Sn(SbF
6
)
2
/H
3
OSbF
6
19
a
b
c
d
e
Clear solution. 200 mg of SbF
5
was added. Partly dissolved. Clear colourless solution above green solid. Direct crystallization without prior
isolation and characterization of reaction products.
2
1