Ionothermal synthesis of new cobalt and chromium thiophosphate anions [Co(Co(P3S8)2)2]4- and [Cr(P3S9)2]3-

Article abstract of DOI:10.1016/j.poly.2016.02.015

Two new metal thiophosphate anions, [Co(Co(P₃S₈)₂)₂]^4- and [Cr(P₃S₉)₂]^3-, have been isolated as single crystals of EMIM (1-ethyl-3-methylimidazolium) salts from ionothermal reaction of the elements in [EMIM][CF₃SO₃]. The former compound is structurally unique from known thiophosphate anions, contains three cobalt ions in two different coordination environments and oxidation states, and has bridging, polydentate P₃S₈^3- groups that coordinate to the cobalt ions through both S and P ions. The chromium thiophosphate anion contains octahedrally-coordinated Cr ions and is structurally similar to the known ion [Ni(P₃S₉)₂]^4-. The structures of both salts were determined by single-crystal X-ray diffraction. Both compounds were characterized by EDX and IR spectroscopies.

Full text of DOI:10.1016/j.poly.2016.02.015

Polyhedron xxx (2016) xxx–xxx
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Ionothermal synthesis of new cobalt and chromium thiophosphate
4
À
3À
anions [Co(Co(P S ) ) ] and [Cr(P S ) ]
3
8 2 2
3 9 2
⇑
Jason A. Cody , Lauren M. Dalecky, Christian A. Juillerat, Grant C.B. Alexander, Luke C. Shylanski
Department of Chemistry, Lake Forest College, 555 N. Sheridan Rd., Lake Forest, IL 60045, United States
a r t i c l e i n f o
a b s t r a c t
4
À
3À
9 2
Article history:
3 8 2 2 3
Two new metal thiophosphate anions, [Co(Co(P S ) ) ] and [Cr(P S ) ] , have been isolated as single
Received 30 September 2015
Accepted 8 February 2016
Available online xxxx
crystals of EMIM (1-ethyl-3-methylimidazolium) salts from ionothermal reaction of the elements in
EMIM][CF SO ]. The former compound is structurally unique from known thiophosphate anions, con-
tains three cobalt ions in two different coordination environments and oxidation states, and has bridging,
groups that coordinate to the cobalt ions through both S and P ions. The chromium
thiophosphate anion contains octahedrally-coordinated Cr ions and is structurally similar to the known
[
3
3
3
À
polydentate P
3
S
8
Keywords:
Ionothermal
Ionic liquid
Thiophosphate
Crystal structure
Mixed-valence cobalt(II/III) complexes
4À
ion [Ni(P
S
3 9
2
) ]
. The structures of both salts were determined by single-crystal X-ray diffraction. Both
compounds were characterized by EDX and IR spectroscopies.
Ó 2016 Elsevier Ltd. All rights reserved.
1
. Introduction
regardless of widely ranging reagent proportions, heating schemes,
2
À
etc. yielded only the [Ni(P
S
2 8
)
2
]
anion [13]. Recently, we
Ionic liquids (ILs) have been extensively studied because of
expanded the technique to include chromium and cobalt. For a
more lengthy introduction to the process and importance of this
approach, please see this earlier article.
their high thermal stability, negligible vapor pressure, ability to
dissolve a variety of materials, reusability, and wide liquid-phase
range [1]. Renewed interest has been spurred by their unique prop-
erties that enable them to be employed in a wide-range of applica-
tions including environmental air and soil purifiers [2], electrolytes
in photovoltaic cells and batteries [3,4], and synthesis of useful
materials including electrodes [5], aluminophosphates, organic-
inorganic hybrids, metal organic frameworks, and zeolites [6,7].
The low vapor pressure and ability to dissolve a variety of materi-
als have made ILs ideal for replacing environmentally harmful con-
ventional organic solvents [8]. Ionothermal synthesis methods use
ILs as the solvent that can often double as a structure directing
agent, in high temperature synthesis [9]. Ionothermal methods
have employed ILs to synthesize zeolites [10], metal-organic
frameworks [11], and polyoxometalates [12].
The unique properties of ILs and the nearly endless cation/anion
combinations provide a wide variety of experimental conditions to
produce novel inorganic compounds [1]. The combination of the
cation and anion changes the solvent properties. In the recent
example of four nickel thiophosphate anions that precipitated as
EMIM salts using ILs, the non-precipitating anion of the solvent
determined the nature of the isolated salts [13]. All four were iso-
There are few known ternary cobalt thiophosphate compounds:
CoPS
3
3
[14] and CoPS [15]. The CoPS structure has staggered
ethane-like P
2 6
S
units that bridge two six-coordinate, octahedral
cobalt ions making two-dimensional sheets. The cubic CoPS struc-
ture is highly condensed with octahedrally coordinated cobalt ions
and disordered, tetrahedrally coordinated phosphorus and sulfur
ions.
There are few cobalt structures that contain cobalt ions with
both 2+ and 3+ oxidation states, and all of the known compounds
contain cobalt ions that are octahedrally coordinated to nitrogen or
oxygen ions [16–18]. The most interesting of these, Co
3
(l-Hda-
trz) (H O) (Hdartz = 3,5-diamino-1,2,4-triazole)
6
2
6
]Á(NO
3
)
8
Á4H
2
O
[19], contains three cobalt ions, two of which are 3+ and one that
is 2+, similar to the title compound.
In all three of the known simple chromium thiophosphates,
CrPS
is octahedrally coordinated to sulfur ions. The two-dimensional
sheets found in CrPS comprise one-dimensional chains of CrS
octahedra linked by PS groups. The CrP 9.24 structure contains
chromium ions octahedrally coordinated to PS groups bridged
by disulfur linkages and single sulfur ions. All of the phosphorus
4 3 2 4 3 3
[20], K Cr (PS ) [21], and CrP S9.24 [22], the chromium ion
4
6
4
3
S
4
4 3 3
lated from [EMIM][BF ], but all reactions in [EMIM][CF SO ],
ions are tetrahedrally coordinated to sulfur ions in the CrP
3 9.24
S
compound.
⇑
Corresponding author.
E-mail address: cody@lakeforest.edu (J.A. Cody).
http://dx.doi.org/10.1016/j.poly.2016.02.015
277-5387/Ó 2016 Elsevier Ltd. All rights reserved.
0
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2
J.A. Cody et al. / Polyhedron xxx (2016) xxx–xxx
Herein we present the structures of the new metal thiophos-
phates [EMIM] [Co(Co(P ] and [EMIM] [Cr(P ].
The structure of the chromium compound was obtained using
Nonius CCD diffractometer with a molybdenum source (see
Table 1). A set of 200 frames was collected with a rotation of
4
3
8
S )
2
)
2
3
3 9
S )
2
2
.000% per frame and an exposure time of 600 s; the crystal to
2
. Material and methods
A total mass of 1.25 g of elemental transition metal, phospho-
detector distance was 29.60 mm. Refinements were done with the
SHELXTL-97 [27] software package; absorption correction was made
with the program JANA2006 [28] using the program X-SHAPE [29].
Refinement of the inorganic portion of the structure [Cr
rus, and sulfur were combined and ground together in a nitro-
gen-filled MBraun Lab Master 130 glovebox. Pyrex tubes were
charged with 125 mg of the elemental mixture and then trans-
ferred to a nitrogen-filled glovebag wherein a 1.25 mL aliquot of
3À
(P
3 9
S )
2
]
was straightforward whereas the refinement of the
+
organic EMIM cations was not. Both unique cations are disor-
dered; the first is disordered over two overlapping, planar loca-
tions, sharing two common carbon ions. The occupancy of the
two positions was refined to a value of 0.673(10) for the major part
and 0.327(10) for the minor part. The second unique EMIM cation
is disordered over a center of inversion and therefore was refined
as 50% occupied for the original and 50% occupied for the symme-
try-generated version of the molecule. Both cations were refined
anisotropically and hydrogen ions were fixed in a riding model.
[
3 3
EMIM][CF SO ] was added. The IL was synthesized according to
the procedure shown in Fig. 1 [23]. The tubes were vacuum-sealed
and heated in a temperature-controller-equipped drying oven.
After the heating profile was complete, the solids in the reaction
tubes were filtered in the glovebag and kept under nitrogen before
analysis. The IL filtered off was stored under nitrogen and reused
for reactions with similar conditions.
4 3 8 2 2
2.1. Synthesis of [EMIM] [Co(Co(P S ) ) ]
2.4. EDX
In an attempt to make a 1:6:18 ratio, an undergraduate research
student inadvertently prepared a 1:22:4 ratio (8.5 mg: 98.1 mg:
8.5 mg) of cobalt, phosphorus and sulfur that was loaded as
Energy dispersive X-ray analysis (EDX) provides semi-quantita-
tive micro-elemental analysis from the use of a scanning electron
microscope (SEM) that analyses characteristic X-rays emitted from
atoms when stimulated with a beam of electrons [30]. The chem-
ical composition of needles of both compounds were analyzed by
an EDX-equipped SEM (Hitachi S-3400N-II). This was preformed
with the crystal mounted on double-sided conducting tape on an
aluminum stub.
The observed molar ratio of cobalt, phosphorus, sulfur averaged
over several spot and area analyses of several crystals was
:4.66:11.4, in good agreement with the molar ratio determined
from the crystal structure solution (1:4:10.7). Synthesis from this
molar ratio was attempted, but the lack of success implies the
excess phosphorous is needed to produce the Co crystals.
The observed molar ratios of chromium, phosphorus, sulfur
averaged 1:7.1:22.1, in an acceptable agreement with the ratio
determined from the crystal structure solution (1:6:18). The ratio
of sulfur to phosphorus averaged 3.1:1.
1
described above and heated in an oven at 150 °C for 72 h. This error
was fortuitous; based on the compounds previously isolated with
nickel [13], such a large phosphorous loading might never have
been attempted. The tube was then quickly cooled to 70 °C and
slowly cooled at a rate of 0.5 °C/h from 70 °C to 30 °C. After com-
pletion of the heating profile, the tube was opened, filtered, and
the crystals were separated by hand. The few isolated crystals were
red needles surrounded by gray powder (EDX indicates a 1:2.2
ratio of phosphorus to sulfur). The red needles slowly decompose
in air with no visible change in appearance.
1
3 3 9 2
2.2. Synthesis of [EMIM] [Cr(P S ) ]
A 1:6:18 ratio (8.0 mg: 28.7 mg: 90.6 mg), of chromium, phos-
phorus, and sulfur was used in an attempt to prepare an analog
of nickel thiophosphate anion with the same ratios [13]. The mix
was prepared as described above and heated in an oven at 150 °C
for 72 h. The tube was then cooled to 30 °C at 0.5 °C/h, opened, fil-
tered, and contents sorted by hand. The isolated solids were orange
plates of the product surrounded by a byproduct of black powder.
The color of the plates varies from yellow to red as the thickness
increases. The orange plates are also air sensitive.
2
.5. FT-IR
The IR stretches of both compounds were recorded on a Thermo
Nicolet Avatar 360 FT-IR spectrometer in pressed KBr disks.
The observed stretches for [EMIM] [Co(Co(P ] were
[Co(Co (P
13 (sh), 746 (sh), 735 (w), 720 (sh), 618 (sh), 558 (sh), 493 (m),
4
3
S
8
)
2
)
2
m
+
À1
4À
(
8
4
EMIM ) 668 (vw) and 623 (w) cm
,
m
3 8
S ) ) ] 824 (w),
2 2
2.3. X-ray crystallography
À1
À1
3
73 (sh), 458 (sh), and 449 (m) cm
3
, m(CF SO ) 758 (w), 640
À1
(
s), 571 (m), 520 (w) cm
.
The structure of the cobalt compound was determined by sin-
The observed stretches for [EMIM]
3
[Cr(P
3
S
9
)
2
] were FT-IR:
m
gle-crystal X-ray diffraction data collected on a Bruker KAPPA
APEX-II single crystal X-ray diffractometer with a molybdenum
source (see Table 1). The structure was solved and refined using
+
À1
(
(
6
EMIM ) 846 (vw), 701 (vw), 668 (vw), and 616 (w) cm
,
m
[(Cr
3
À
P S ) ] 965 (vw), 818 (w), 807 (w), 734 (w), 706 (sh), 673 (sh),
3 9 2
58 (s), 590 (sh), 580 (m), 522 (sh), 494 (s), 459 (sh), 419 (vw),
SHELXL-14 [24] in the OLEX 2 GUI [25,26]. The inorganic anion was
refined anisotropically and the EMIM cations were refined isotrop-
À1
and 402 (w) cm . The IR spectrum of the nickel analog shares sim-
À1
ilar stretches to those at 658 (s) and 494 (s) cm [13].
+
ically. One of the EMIM cations is disordered over two overlapping
positions with refined occupancies of 0.6 and 0.4 for the two orien-
tations. All of the EMIM cations in the Co structure were refined
using restraints.
3
. Results and discussion
3
3
.1. [EMIM] [Co(Co(P S ) ) ]
4
3 8 2 2
.1.1. Crystal structure
The compound, [EMIM]
4
3 8 2 2
[Co(Co(P S ) ) ] contains three cobalt
ions in two different coordination environments (octahedral and
tetrahedral) and two different oxidation states,+3 and +2 (See
Fig. 2).
3 3
Fig. 1. Synthesis of [EMIM][CF SO ].
Please cite this article in press as: J.A. Cody et al., Polyhedron (2016), http://dx.doi.org/10.1016/j.poly.2016.02.015

J.A. Cody et al. / Polyhedron xxx (2016) xxx–xxx
3
phosphate ligand; none have S and P coordinating from the same
ligand. In the following compounds the cobalt ion is octahedrally
coordinated to three organic bidentate ligands attached to the
metal by the sulfur or phosphorus ions: [Co(C
2
H
5
OCS
(dppe = 1,2-bis
{(Ph PO) BF }]
dtc = N,N-dimethyldithiocarbamate) [35], and [Co(S PMe (Me
CH PMe )]BF [36]. The other three examples contain two
bidentate organic ligands attached to the metal by a sulfur and
2 2 6 16 2
) (C H P )]
[
(
(
B(C
6
H
5
)
4
]
[33],
[Co(dppe)(EtOCS
[34],
2
)(COS
2
)]
diphenylphosphino)ethane)
[Co(dtc)
2
2
2
2
2
2
)
2
2
-
PCH
2
2
2
4
+
two phosphines: trans- and cis-[Co(dtc)
2
(PMe3-nPh
n
2
) ]
(n = 0, 1,
2
or 3) [37], [Co(dtc)
Ph ]+ (n = 0–2) complexes [39].
The charge of the [Co(Co(P
2
(PHPh
2
)
2
]BF
4
) [38], and [Co(dtc)
2
{P(OMe)3-n-
n 2
}
S
)
8 2
)
2
]4 anion was determined
À
3
+
from the number of [EMIM] cations observed in the crystal struc-
ture. This overall charge of 4À, combined with all S ions (2À each
for a total À64), the reasonably-assigned +3 and +5 for the phos-
phine and sulfur-surrounded phosphorus ions (sum = +52), bal-
ances all but eight positive charges for the three Co ions. Thus,
they are reasonably assigned +2 for the central Co ion and +3 for
the two octahedrally-coordinated Co ions. The observed Co–S dis-
tances are consistent with this assignment; the Co(II)–S distances
of 2.326(3)–2.332(4) are slightly longer than those of Co(III)–S
Fig. 2. Thermal ellipsoid plot of the cobalt thiophosphate anion from the salt
EMIM] [CoS (Co(P ]. Cobalt ions are indigo, phosphorus magenta, and sulfurs
3 7 2 2
yellow. Bond distance ranges: [CoS (Co(P S ) ) ] , Co1–S 2.326(3)–2.332(4),
[
4
4
3 7 2 2
S ) )
4À
4
Co2,3-S 2.272(4)–2.319(3), Co2,3-P 2.224(4)–2.248(3) Å. (Color online.)
2
3
3
.272(4)–2.319(3).
.2. [EMIM] [Cr(P S ) ]
3
3 9 2
.2.1. Crystal structure
The first instance of the P
3
À
3
S
9
appearing as a tridentate ligand in
[Ni(P ] [13]. The prior
to this, the anion appeared as a multi-metal bidentate ligand, coor-
dinating to three Ga ions in (t-Bu) Ga [40], and as coordina-
[41]. In neither case does P
a mono-metal complex was in [EMIM]
2
3 9 2
S )
6
3 3 9
P S
3
À
tion polymer with Cu in K
act as a tridentate ligand.
2
CuP
3
S
9
3 9
S
Within crystallographic databases when chromium is found
coordinated to sulfur it is most often found with three bidentate
ligands, such as S
coordinated metallocubane structures such as [Cp
NEt }]. Although sulfur and phosphorus have both been used as
CC
2 6
H
6
[42] or S COC H
2 2 5
[43], or within highly
6 8 8
Cr S {C(S)
2 2
)
Fig. 3. Thermal ellipsoid plot of the chromium thiophosphate anion from the salt
coordination method of many organic ligands, strictly triphos-
phates have not been found coordinated to Cr(III) [44].
[
3 3 9 2
EMIM] [Cr(P S ) ]. The chromium ion is indigo, phosphorus magenta, and sulfur
yellow. Bond distance ranges: Cr–S 2.4082(15)–2.4108(17) Å. (Color online.)
The chromium ion is octahedrally coordinated to the sulfur ions
3
À
in the P
S
3 9
tridentate ligand (see Fig. 3). The coordination com-
[Ni(P ] [13] com-
plex is analogous to that found in the [EMIM]
2
3 9 2
S )
The central, tetrahedrally-coordinated Co ion bridges two Co
+
pound, but the crystal structure varies since an additional [EMIM]
cation is needed to balance the charge, thus resulting in a new
structure.
3 8 2
(P S ) units through four S atoms; each of the S atoms belongs
3
À
3À
3 8
to one of the four P
3
S
8
ligands. In turn, each of these P
S
groups
coordinates to their respective Co ions through one P(III) ion and
two S ions, creating an octahedral coordination environment for
the Co ions. The presence of both phosphorus- and sulfur-ion
bonding modes for thiophosphates is rare and has only been
4. Conclusions
7
À
3À
3 8
reported previously in Ni
4
P
13
S
32 [13]. The P
S
ligands also con-
The new cobalt and chromium thiophosphate compounds pre-
sented herein demonstrate the applicability of ionothermal syn-
thesis to two new metals in the thiophosphate system. The
tain two P(V) ions tetrahedrally-coordinated to S ions. All P–S,
Co–P, and Co–S distances are consistent with previous structural
studies.
4
À
structurally unique anion [Co(Co(P
3
8
S )
)
2 2
]
has rare coordination
These coordination geometries for Co(II) and Co(III) are not new,
but the combination of both in the same structure with only one
type of ligand is unique. In the literature there are several exam-
of P ions to a metal ion from a thiophosphate ligand and contains
Co ions in both tetrahedral and octahedral coordination. The syn-
thesis of the chromium analog of the original nickel thiophosphate
2
À
ples of tetrahedral CoS
bidentate sulfur-containing ligands such as in [Co(C
or four monodentate sulfur-containing ligands as in [Co
S) ](ClO [32]. In all of these examples, when the oxida-
4
groups including those containing two
anion, [Ni(P
S
3 9
)
2
]
demonstrates the reactivity of another transi-
2À
3
5
S )
2
]
[31],
tion metal with thiophosphate ligands. Both syntheses demon-
strate the versatility of ionothermal synthesis for preparing new
thiophosphate compounds.
(
5
C H
12
N
2
4
4 2
)
tion state was assigned to the central, tetrahedrally coordinated
cobalt ion it is 2+ [32].
Acknowledgements
There are seven reported structures of a cobalt ion octahedrally
coordinated to two phosphorus ions and four sulfur ions, all of
which contain two bidentate sulfur ligands and one bidentate
This work made use of the EPIC facility (NUANCE Center-North-
western University), which has received support from the MRSEC
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4
J.A. Cody et al. / Polyhedron xxx (2016) xxx–xxx
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Formula
[EMIM]
4
[Co(Co
]
3
[EMIM] [Cr
(
(
P
S )
3 8 2
)
2
(P
1148.40
monoclinic
P2 /c
3 9 2
S ) ]
[
M
2019.02
orthorhombic
Pna2
(
Crystal system
Space group
a (Å)
b (Å)
c (Å)
1
1
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17.6238(11)
19.2860(12)
21.2766(14)
90
90
90
7231.8(8)
4
1.854
12.735(3)
10.150(2)
18.316(4)
90
100.80(3)
90
2325.6(9)
2
1.640
1.287
1170
0.0672
28259
5084
a
(°)
b (°)
(°)
c
3
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D
l
calc (g cm
(mm
)
À1
)
1.90
[
[
[
F(000)
4068.0
0.1206
141596
21128
11209
0.055, 0.1216
100
1
R
int
Total reflections
Unique reflections
(
I > 2
, wR
T (K)
r
(I)
3455
0.0689, 0.1779
293
2.006, À0.669
R
1
2
I > 2
r
(I)
Maximum, minimum electron
density (e/Å )
1.33, À1.29
3
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Please cite this article in press as: J.A. Cody et al., Polyhedron (2016), http://dx.doi.org/10.1016/j.poly.2016.02.015