New acyclic neutral phosphorus sulfides and sulfide oxides

Article abstract of DOI:10.1002/zaac.201300419

A great number of binary neutral phosphorus sulfides was discovered and investigated. However all stable representatives of this family of compounds adopt a polycyclic structure in contrast to their lighter homologues, the nitrogen oxides. Acyclic representatives can be stabilized by adduct formation with a nitrogen base. The bis(pyridine) adduct py₂P₂S ₅ of the unstable acyclic phosphorus sulfide P₂S ₅ is readily obtained stirring P₄S₁₀ in pyridine at ambient temperature. X-ray diffraction studies on single crystals of py₂P₂S₅·0.5 py (1b) show a N ₂O₅ like structure for the P₂S₅ framework. The long P-N distances of 1.86 A indicate only weak coordination of the pyridine molecules to phosphorus. Single crystal X-ray diffraction studies on py₂P₂S_4.34O _0.66 (2) reveal the presence of py₂P₂S ₄O (3) together with py₂P₂S₅ in the crystal. Compound 3 contains the mixed phosphorus oxide sulfide molecule P ₂S₄O stabilized as bis(pyridine) adduct. It is readily obtained from pyP₂S₅ by oxidation with KMnO₄ in pyridine. The oxygen atom occupies the bridging position between the two phosphorus atoms. Quantum chemical calculations at the MPW1PW91 level of theory as well as DTA/TG thermal analyses confirm the weak coordination of the pyridine molecules in py₂P₂S₅, py₂P ₂S₄O, and py₂P₂S₇ to phosphorus.

Full text of DOI:10.1002/zaac.201300419

ARTICLE
DOI: 10.1002/zaac.201300419
New Acyclic Neutral Phosphorus Sulfides and Sulfide Oxides
Stefanie Schönberger,[a] Christoph Jagdhuber,[a] Laura Ascherl,[a] Camilla Evangelisti,[a]
Thomas M. Klapötke,[a] and Konstantin Karaghiosoff*[a]
Keywords: Phosphorus; Sulfides; Molecular structure; Pyridine adduct; Quantum chemical calculations; Thermal analysis
Abstract. A great number of binary neutral phosphorus sulfides was
molecules to phosphorus. Single crystal X-ray diffraction studies on
discovered and investigated. However all stable representatives of this py2P2S4.34O0.66 (2) reveal the presence of py2P2S4O (3) together with
family of compounds adopt a polycyclic structure in contrast to their py2P2S5 in the crystal. Compound 3 contains the mixed phosphorus
lighter homologues, the nitrogen oxides. Acyclic representatives can
oxide sulfide molecule P2S4O stabilized as bis(pyridine) adduct. It is
be stabilized by adduct formation with a nitrogen base. The bis(pyri- readily obtained from pyP2S5 by oxidation with KMnO4 in pyridine.
dine) adduct py2P2S5 of the unstable acyclic phosphorus sulfide P2S5 The oxygen atom occupies the bridging position between the two phos-
is readily obtained stirring P4S10 in pyridine at ambient temperature.
X-ray diffraction studies on single crystals of py2P2S5·0.5 py (1b)
phorus atoms. Quantum chemical calculations at the MPW1PW91
level of theory as well as DTA/TG thermal analyses confirm the weak
show a N2O5 like structure for the P2S5 framework. The long P–N coordination of the pyridine molecules in py2P2S5, py2P2S4O, and
distances of 1.86 Å indicate only weak coordination of the pyridine py2P2S7 to phosphorus.
posed this molecule to be generated by refluxing P4O10 in
Introduction
pyridine but could not identify the product of this reaction by
Binary neutral phosphorus sulfides have been known for a
any means. In our group this experiment was repeated several
long time. It was Berzelius, who in 1843 was the first to inves-
times, however we were also not able to verify the existence
tigate the behavior of sulfur towards phosphorus and synthe-
of this molecule.
sized the first representative of this class of compounds, the
Shortly after this publication Wolf patented the compounds
“P2S5”.[1] This molecule was later discovered to be the dimer
py2P2S5 and py2P2S4, which he claimed to have synthesized
P4S10. Since then many more phosphorus sulfides P4Sx (x = 3–
by refluxing P4S7 in pyridine.[6] Also in this case, however, no
10) have been discovered.[2] It is striking that all these neutral
proper characterization of the products was given.
compounds adopt a polycyclic structure. This occurs due to
In 2009 our group presented the crystal structures of
the problem of an unfavorable σ3λ5 bonding situation at the
py2P2S5 and py2P2S7 together with a full characterization of
phosphorus atom in acyclic representatives. In order to stabi-
these compounds.[7] The py2P2S7 was synthesized by refluxing
lize the σ3λ5-phosphorus in such a molecule the missing forth
stoichiometric amounts of P4S10 and elemental sulfur in pyr-
coordination partner might be provided by adduct formation,
idine. Two years later the swedish group of Prof. Bergman also
for example by coordination of a base like pyridine.
published the crystal structure of py2P2S5 and discussed its use
In fact 1967 Fluck and Binder were able to describe such a
as thionating agent.[8]
compound.[3] In the course of their investigations on perthio-
In the following an improved synthesis and the new struc-
phosphonic acid anhydrides they discovered, that on heating
ture of py2P2S5·0.5 py are presented. Quantum chemical calcu-
P4S10 in pyridine the bis(pyridine) adduct of the monomeric
lations at the MPW1PW91 level of theory using a polarized
unit P2S5 is formed. This system has been used as sulfur re-
double-zeta basis set (aug-cc-pVDZ) were accomplished to
moving agent in organic chemistry before. Fluck et al. de-
verify the 31P NMR spectroscopic properties and to enlighten
scribed the synthesis of the bis(pyridine) adduct of P2S5 and
the possible existence of a pyridine free acyclic phosphorus
reported its 31P NMR chemical shift.
sulfide P2S5. Also the question whether analogous mixed phos-
Meisel and co-workers used this compound as starting mate-
phorus sulfide oxide molecules can be stabilized by pyridine
rial to synthesize new betaines, containing pyridine and one
coordination will be discussed.
phosphorus atom.[4] In 1982 Wolf and Meisel attempted to syn-
thesize the structurally analogue adduct py2P2O5.[5] They pro-
Results and Discussion
* Prof. Dr. K. Karaghiosoff
Fax: +49-89-2180-77492
E-Mail: klk@cup.uni-muenchen.de
The Pyridine Adduct py2P2S5 (1a)
[a] Department of Chemistry
Ludwig-Maximilian University of Munich
In course of our investigations of py2P2S5 (1a), we found
that for its synthesis refluxing P4S10 in pyridine is not neces-
Butenandtstr. 5–13 (D)
81377 Munich, Germany
68
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New Acyclic Neutral Phosphorus Sulfides and Sulfide Oxides
sary. The yield of 1a can be improved by just stirring the start- Table 1. Details for X-ray data collection and structure refinement for
compounds 1b and 2.
ing material in pyridine at ambient temperature for a short
period of time. Refluxing only causes the formation of larger
amounts of py2P2S4O (3) as byproduct. This is shown in Fig-
ure 1, where the 31P NMR spectra of the respective reaction
solutions are compared. We observed the 31P NMR shift of
py2P2S5 at δ = 104.4 ppm and the one for py2P2S4O at δ =
98.5 ppm.
py2P2S5·0.5 py (1b)
12.5H12.5N2.5P2S5
py2P2S4,34O0,66 (2)
Formula
M /g·mol–1
Color, habit
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
β /°
C
C10H10N2P2 S4.25O0.75
368.40
419.99
colorless block
triclinic
¯
P1
colorless block
monoclinic
P21/c (No. 53)
14.564(1)
11.061(1)
9.884(1)
90
92.890(7)
90
1590.2(2)
4
1.539
0.346
4.20–25.00
17822
2893
8.976(2)
9.203(2)
12.672(2)
102.547(5)
90.241(4)
118.501(6)
890.870(10)
2
1.566
0.826
4.44–28.28
10688
4381
γ /°
V /Å3
Z
ρcalc /g·cm–3
μ /mm–1
θ range /°
Data collected
Data
Parameters
Rint
203
177
0.0759
0.0574
0.1401
0.1036
0.1514
1.017
0.0329
0.0370
0.0830
0.0537
0.0933
1.001
R1 [I Ͼ 2σ]
wR2 [I Ͼ 2σ]
R1 [all data]
wR2 [all data]
GOF on F2
Figure 1. 31P{1H} NMR spectrum of a solution of P4S10 in pyridine
before (top) and after (bottom) refluxing for 1 h at 120 °C.
Molecular Structure of py2P2S5·0.5 py (1b)
Colorless block-shaped single crystals of py2P2S5·0.5 py
(1b) were isolated after refluxing a pyridine solution of
py2P2S5 and investigated by X-ray diffraction. Compound 1b
¯
crystallizes in the triclinic space group P1 with one molecule
of py2P2S5 and half a molecule of pyridine in the asymmetric
unit (Table 1). Figure 2 shows the molecular structure of 1b
together with selected atom distances and bond angles.
The distance of the phosphorus atoms to the single coordi-
nated sulfur atoms is with an average value of 1.939(1) Å
Figure 2. Molecular structure of 1b in the crystal. Thermal ellipsoids
are set at 50% probability level. Selected atom distances /Å and
angles /°: P1–S1/P2–S1 2.107(2)/2.121(2), P1–S2/P1–S3 1.931(2)/
1.947(2), P2–S4/P2–S5 1.933(2)/1.945(2), P1–N1/P2–N2 1.863(2)/
1.855(2); S1–P1–S2/S1–P2–S4 116.2(1)/114.7(1), S1–P1–S3/S1–P2–
S5 103.6(1)/102.0(1), S2–P1–S3/S4–P2–S5 122.63(4)/124.5(1), P1–
S1–P2 111.8(1).
within the range expected for
a P–S double bond
[1.922(14) Å].[9] The distance between the phosphorus atoms
and the bridging sulfur atom is averagely 2.114(1) Å, which is
in good accordance with the one expected for a single bond
(2.11 Å[2a]). The P–N distances are with an average value of anion [1.906(2) Å],[10] in which a similar bonding situation is
1.859 Å around 0.2 Å longer than expected for a P–N single found.
bond [1.652(24) Å],[9] which indicates only weak coordination
The phosphorus atoms are surrounded distorted tetrahedrally
of the pyridine molecule to phosphorus. Similar strongly elon- by three sulfur atoms and one pyridine molecule. The largest
gated P–N distances have been reported for the solvent free values for S–P–S angles are found between the phosphorus
py2P2S5 [1.862(6) Å and 1.865(3) Å],[7] py2P2S7 [1.869(3) Å and the two single coordinated sulfur atoms with 123.6°. The
–
and 1.865(3) Å],[7] and also for the pyridine adduct of the PS3
angles involving the bridging sulfur atom are smaller with val-
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K. Karaghiosoff et al.
ARTICLE
ues around 102.8°. The P1–S1–P2 angle has a value of 111.9°.
The phosphorus atoms are again surrounded distorted tetra-
Although only a slight distortion of the tetrahedral environ- hedrally by two single coordinated sulfur atoms, one molecule
ment around the phosphorus atom might be expected, the sum of pyridine, and the bridging sulfur or oxygen atom, complet-
of the S–P–S angles indicates with a value of 341.8° a strong ing the tetrahedron. The oxygen atom can be found with 66%,
deviation towards a planar PS3 arrangement. A similar situa- while the sulfur is occupying the bridging position with 34%.
tion is found for solvent free py2P2S5[7], py2P2S7[7] and for the Because of the different P–O and P–S distances and the devia-
pyridine adduct of the PS3– anion[10] with values of 341°, 344°, tion in the angles at the bridging chalcogen atoms, the posi-
and 347°, respectively. This provides further evidence for an tions of the two atoms could be identified and the atoms re-
only weak coordination of the pyridine to the phosphorus.
fined anisotropically. The distances between the phosphorus
and the single coordinated sulfur atoms differ with a value of
1.930(2) Å only slightly from the distance expected for a P–S
double bond [1.922(14) Å[9]). Due to the disorder in the crystal
all values are afflicted with higher standard uncertainties.
The nitrogen atom of the pyridine molecule has a distance
of 1.853(4) Å to the phosphorus atom, which is elongated com-
pared to the expected 1.652(24) Å[9] for a P–N single bond. So
this indicates again only a weak coordination of the pyridine
molecules to the phosphorus. This is further supported by the
sum of the S–P–S(O) angles of 341.0(5)° and 344.3(4)° respec-
tively, which again show a deviation towards a planar sur-
rounding of phosphorus by the chalcogen atoms.
Crystal Structure of py2P2S4.34O0.66 (2)
Crystals of py2P2S4.34O0.66 suitable for X-ray diffraction
were obtained from the reaction of P4S3 with elemental sulfur
in pyridine. The structure was solved in the monoclinic space
group P21/c (Table 1).
The crystal contains both, the compound py2P2S5 and the
related oxygen derivative py2P2S4O, with the oxygen atom in
the bridging position. The two molecules occupy the same po-
sitions in the crystal except for the bridging O1 and S5 be-
tween the two phosphorus atoms, which results in a disorder
in this position. Figure 3 shows the molecular structure and
contains selected atom distances and bond angles.
The Pyridine Adduct py2P2S4O (3)
The bis(pyridine) adduct py2P2S4O (3) (n = 1) is the first
member of a series of pyridine stabilized mixed phosphorus
sulfide oxides P2S5–nOn (n = 1–4), which fill the gap between
py2P2S5 and the still unknown adduct py2P2O5. Compound 3
can be obtained by stirring 1a and KMnO4 in pyridine for 2 d
at ambient temperature. It is identified by the 31P NMR signal
at δ = 98.5 ppm (Figure 4), which fits the one predicted by
quantum chemical calculations (see below).
Figure 4. 31P{1H} NMR spectrum of 3 in pyridine.
Figure 3. Molecular structure of 2 in the crystal (two different viewing
directions). Thermal ellipsoids are set at 50% probability level. Se-
lected atom distances /Å and angles /°: P1–S1/P1–S2 1.928(2) /
1.925(2), P1–S5/P2–S5 1.968(9)/2.013(9), P1–O1/P2–O1 1.687(11)/
1.695(11), P1–N1/P2–N2 1.852(4)/1.854(4); S1–P1–S2/S3–P2–S4
123.0(1)/123.7(1), S1–P1–S5/S4–P2–S5 92.5(3)/93.2(3), S2–P1–S5/
S3–P2–S5 125.2(3)/124.1(3), S1–P1–O1/S4–P2–O1 109.7(5)/
109.9(5), S2–P1–O1/S3–P2–O1 110.0(5)/110.7(4).
Quantum Chemical Calculations
The compounds py2P2S5 and py2P2S7 can be viewed as
loose pyridine adducts of the acyclic phosphorus sulfides P2S5
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New Acyclic Neutral Phosphorus Sulfides and Sulfide Oxides
and P2S7. It is interesting to investigate how the coordination
of pyridine influences the atom distances and the structures of
the free P2S5 and P2S7 molecules. In order to give an answer
to this question quantum chemical calculations at the
MPW1PW91 level of theory using a polarized triple-zeta basis
set (aug-cc-pVTZ) for py2P2S5 and a polarized double-zeta ba-
sis set (aug-cc-pVDZ) for the free P2S5 were carried out.
Furthermore energy values for both molecules were deter-
mined on the level of CBS-4M and the 31P NMR spectroscopic
data for py2P2S5 and py2P2S4O were calculated.
The optimized structure of the P2S5 molecule is shown in
Figure 5. The calculated atom distances and bond angles
within the py2P2S5 molecule correspond very well to those ob-
served for 1b in the crystal (Table 2). Remarkably the calcu-
lated atom distances and bond angles for the pyridine free sulf-
ide P2S5 also do not differ much from the calculated and exper-
imentally determined values for py2P2S5. Obviously adduct
formation has little influence on the bonding situation within
the P2S5 framework. Coordination of pyridine affects mainly
the arrangement around the phosphorus atom causing a slight
deviation from planarity for the PS3 moiety.
Scheme 1. Dissociation of py2P2S5 in P2S5 and pyridine.
Furthermore quantum chemical calculations on the level of
CBM-4M were carried out to compare the enthalpy values of
1 and the pyridine free compound P2S5 (Scheme 1).
The difference in the enthalpies resulting from the calcula-
tions is 0.10 kJ·mol–1. Thus the composition according to the
reaction in Scheme 1 is slightly endothermic. This small differ-
ence of enthalpy fits well to the experimentally determined
strongly elongated P–N distance in the bis(pyridine) adduct
1b. Both suggest that the P–N bonds in 1 should be cleaved
easily at higher temperatures generating free P2S5, which
should be stable in the gas phase.
A similar situation is found for the bis(pyridine) adduct of
P2S7. The results of a quantum chemical study of the bonding
situation in this compound compared to free P2S7 (Figure 6)
have been discussed in detail.[7b]
Table 2. Calculated and experimentally observed distances /Å and
bond angles /° of 1 (average values).
For the dissociation of py2P2S7 in free P2S7 and pyridine
(Scheme 2) an enthalpy difference of 1.3 kJ·mol–1 was calcu-
lated. This result suggests that in this case it might also be
py2P2S5 (obs.) P2S5 (calcd.)
py2P2S5 (calcd.)
Distances /Å
P–N
P–Ssc
1.86
1.93
2.12
–
1.92
2.13
1.86
1.94
2.12
P–Stc
S–S
Angles /°
Ssc–P–Ssc
Ssc–P–Stc
Stc–Stc–Stc
P–Stc–P
123
104/115
134
107/118
128
103/115
112
113
112
a) sc = single coordinated; tc = twofold coordinated.
Scheme 2. Dissociation of py2P2S7 in P2S7 and pyridine.
Figure 5. Optimized structure of P2S5 (three different orientations).
Figure 6. Optimized structure of P2S7 (three different orientations).
Z. Anorg. Allg. Chem. 2014, 68–75
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71

K. Karaghiosoff et al.
ARTICLE
Figure 7. Computed C2 structures of [(py)PS2]2S (left) and [(py)PS2]2O (right) at MPW1PW91/aug-cc-pVDZ level of theory.
possible to promote the dissociation thermally as depicted in possibility of generating the pyridine free phosphorus sulfides
the Scheme above and thus to generate free acyclic P2S7 in the and sulfide oxides DTA/TG thermal analyses were performed.
gas phase.
For this purpose the compounds were heated up to 400 °C in
steps of 5 °C·min–1. In the thermograms (Figure 8, Figure 9,
Figure 10, and Figure 11) the dashed curve shows the weight
signal, while the black one represents the heat flow signal,
which indicates changes in the energy at a certain temperature.
The thermal analysis of the bis(pyridine) adduct of P2S5 1a
is shown in Figure 8. The endothermic heat flow signal at
168 °C derives from the two pyridine molecules leaving the
solid, while the sharp peak at 261 °C quotes the melting point
of the resulting P,S material. The melting point of P4S10 is
reported to be 288 °C[13] and thus differs by 27 °C from that
observed for the P,S material obtained. The resulting material
almost immediately starts to decompose releasing volatile
products.
NMR Spectroscopy
In order to estimate the 31P NMR chemical shift of
[(py)PS2]2S (1) and [(py)PS2]2O (3), the isotropic magnetic
shielding was computed using the GIAO (Gauge-Independent
Atomic Orbital) method implemented in G03.[11,12] The struc-
tures were optimized in C2 symmetry (Figure 7) and the fre-
quencies calculated (NIMAG = 0) at MPW1PW91/aug-cc-
pVDZ level of theory. Subsequently, the NMR shielding ten-
sors were calculated at the same level of theory using the
GIAO method.[11,12] Table 3 summarizes the computed iso-
tropic magnetic shielding and relative 31P NMR chemical
shifts (ppm) referenced to H3PO4.
Table 3. Computed isotropic magnetic shieldings (GIAO method[11,12]
,
MPW1PW91/aug-cc-pVDZ) and relative 31P chemical shifts /ppm ref-
erenced to H3PO4.
py2P2S5
py2P2S4O
H3PO4
–E/ a.u.
3170.462064 2847.464794 644.135802
NIMAG
0
0
0
p.g.
C2
249.9
C2
260.8
C3
364.3
δ = 31P , calcd. isotr.
shielding
δ = 31P , calcd.
(ref. to H3PO4)
δ = 31P , exptl.,
(ref. to H3PO4)
114.3
104.4
103.5
98.5
0.0
0.0
The calculated 31P NMR chemical shifts for py2P2S5 and
the oxygen derivative py2P2S4O compare well to the experi-
mentally observed values. Introduction of oxygen in the bridg-
ing position in place of sulfur causes only a small shift of δ31P
to higher field.
Figure 8. Thermogram of py2P2S5 (1a).
The thermal behavior of the bis(pyridine) adduct of P2S5 1b
is particularly interesting as it contains an additional free pyr-
idine molecule in the crystal. Its thermogram is depicted in
Figure 9. The first endothermic heat flow signal can be as-
signed to the free pyridine being released. This temperature is
in accordance to the melting point of py2P2S5·0.5 py 1b
Thermal Analyses
In order to gain further insight into the thermal stability of (115 °C). The other three signals correspond very well to those
the pyridine adducts 1a, 1b, 2, and py2P2S7 and investigate the observed for the adduct py2P2S5 1a.
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New Acyclic Neutral Phosphorus Sulfides and Sulfide Oxides
Figure 9. Thermogram of py2P2S5·0.5 py (1b).
Figure 11. Thermogram of py2P2S7 (4).
The thermogram of py2P2S4.34O0.66 2 (Figure 10), which in
fact contains py2P2S5 1 and py2P2S4O 3, shows a slightly dif-
ferent behavior. The two pyridine molecules leave the solid
already at 148 °C. The resulting material, which in addition to
phosphorus and sulfur now contains also oxygen, undergoes a
further transformation at 226 °C and melts at 300 °C, followed
by decomposition and release of volatile products.
ambient temperature. Single crystal X-ray diffraction studies
on py2P2S5·0.5 py (1) confirm stabilization of the P2S5 frame-
work by weak coordination of the pyridine molecules to phos-
phorus. X-ray diffraction studies on py2P2S4.34O0.66 (2) pro-
vide first evidence for the existence of py2P2S4O, a bis(pyrid-
ine)adduct of the mixed phosphorus sulfide oxide P2S4O with
oxygen bridging the two phosphorus atoms. These results point
to a general concept of stabilizing reactive phosphorus species
containing σ2λ5 phosphorus atoms by weak coordination of a
nitrogen base to phosphorus. It should be possible to extend
this concept to other small molecules with three coordinated
phosphorus(V) atoms. Thermogravimetric investigations on
py2P2S5, py2P2S4.34O0.66, and py2P2S7 confirm the weak coor-
dination of pyridine to phosphorus and indicate, that these ad-
ducts might be of interest as precursors for the generation of
gaseous acyclic phosphorus sulfides and sulfide oxides.
Experimental Section
General Conditions: All reactions were carried out in an inert gas
atmosphere using Argon (Messer), purity 4.6 in 50 L steel cylinder)
and working with Schlenk techniques. The glass vessels used were
stored in a 130 °C drying oven. Before filling they were flame dried
in vacuo at 10–3 mbar. Elemental sulfur was used as received (Acros
Organics). P4S10 and P4S3 were commercially obtained (Honeywell
Riedel-de Haën). The pyridine used was dried with commonly known
methods and freshly distilled before use.
Figure 10. Thermogram of py2P2S4.34O0.66 (2).
In the case of the bis(pyridine) adduct of P2S7 (4), in the
thermogram (Figure 11) only two endothermic transformations
can be observed. The first one occurs at 161.6 °C and is as-
signed to the loss of pyridine. Thus a material of the composi-
tion P2S7 remains. At a temperature of 242.4 °C it melts and
begins to decompose releasing volatile products. Decomposi-
tion is complete at 298 °C.
The results of the thermal analysis of the adducts 1–4 show,
that all adducts release pyridine at temperatures between
140 °C and 170 °C before melting, thus confirming the rela-
tively weak coordination of pyridine to phosphorus.
X-ray Crystallography: The single crystal X-ray diffraction data
were collected with an Oxford Xcalibur3 diffractometer equipped with
a Spellman generator (voltage 50 kV, current 40 mA), Enhance
molybdenum Kα radiation source (λ = 71.073 pm), Oxford Cryosys-
tems Cryostream cooling unit, four circle kappa platform and a Sap-
phire CCD detector. Data collection and reduction were performed
with CrysAlisPro.[14] The structures were solved with SIR97[15], re-
fined with SHELXL-97,[16] and checked with PLATON,[17] all inte-
grated into the WinGX software suite.[18] The finalized CIF files were
checked with checkCIF.[19] Intra- and intermolecular contacts were an-
alyzed with DIAMOND (version 3.2i), plots are shown with thermal
ellipsoids at the 50% probability level. Details for data collection and
Conclusions
The bis(pyridine) adduct of the acyclic binary phosphorus
sulfide P2S5 is readily obtained by stirring P4S10 in pyridine at structure refinement are summarized in Table 1.
Z. Anorg. Allg. Chem. 2014, 68–75
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73

K. Karaghiosoff et al.
ARTICLE
Crystallographic data (excluding structure factors) for the structures in wards sulfur (192.4 mg, 0.75 mmol) was added to the yellow reaction
this paper have been deposited with the Cambridge Crystallographic mixture and refluxed for 1 h at a temperature of 120 °C. Colorless
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. crystals of py2P2S4.34O0.66 were obtained while cooling the solution to
Copies of the data can be obtained free of charge on quoting the de- ambient temperature. The precipitate was separated from the solution
pository numbers CCDC-937614 (1b) and CCDC-940974 (2) and dried in vacuo (Yield: 299.4 mg, 43%). 31P{1H} NMR (pyridine):
(Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk, http://
www.ccdc.cam.ac.uk)
δ (ppm) = 104.3 (s). Elemental analysis (py2P2S4.34O0.66): calcd. C
32.49, N 7.58, H 2.73, S 37.57%; found C 32.60, N 8.48, H 3.61, S
33.74%. Mass (DEI+) m/z = 379.8 (MS = [C10H10N2P2S5]+), 363.6
(MO = [C10H10N2P2S4O]+), 347.9 ([MS–S]+), 299.9 ([MS–py]+),
284.7 ([MO–py]+), 252.8 ([MO–pyS]+), 221.9 ([M–py2]+), 188.8
([MO–pyPS2]+), 128.0 ([PS3]+), 63.0 ([PS]+). Raman (200 mW, room
temp.): ν˜ = 3068 (25), 1604 (46), 1182 (53), 1031 (55), 1015 (100),
472 (84) cm–1. IR (200 mW, room temp.): ν˜ = 3009 (w), 2510 (w),
2124 (w), 1629 (w), 1602 (m), 1596 (w), 1517 (m), 1484 (m), 1476
(s), 1447 (s), 1390 (w), 1323 (w), 1252 (w), 1187 (m), 4481 (m),
1159 (m), 1129 (m), 1051 (m), 1023 (w), 1041 (m), 1014 (m), 998 (m),
896 (br., vs), 767 (m), 743 (s), 731 (m), 718 (m), 675 (vs) cm–1.
NMR Spectroscopy: NMR spectra were recorded with a Jeol EX 400
Eclipse instrument operating at 161.997 MHz (31P). Chemical shifts
are referred to 85% H3PO4 as external standard. All spectra were mea-
sured, if not mentioned otherwise, at 25 °C.
DTA/TG: Thermal analytic measurements were carried out with a
Thermoanalyzer TG-DTA-92 (Setaram) in an inert gas atmosphere
(He). The compound was heated in a corundum melting pot up to a
temperature of 750 °C in steps of 5 °C·min–1.
Mass Spectrometry: Mass spectra were obtained with an MStation
JMS 700 (Jeol) using the ionization method DEI+/EI+.
py2P2S4O (4): To KMnO4 (41.7 mg, 0.264 mmol) a solution of 1
(46.8 mg) in pyridine (5 mL) was added and stirred for 48 h at room
temperature. The precipitate was filtered and the solvent was removed
from the yellow solution in vacuo (Yield: 44 mg, 98%). 31P{1H} NMR
(pyridine): δ (ppm) = 98.0 (s). Elemental analysis for py2P2S4O: calcd.
C 32.96, N 7.69, H 2.77, S 35.20%; found C 37.42, N 8.71, H 3.48,
S 28.24%. Mass (EI+) m/z = 363.9 ([C10H10N2P2S4O]+), 331.9
([M–S]+), 284.7 ([M–py]+), 252.9 ([M–pyS]+), 205.0 ([M–py2]), 190.0
([M–pyS2]+), 173.0 ([M–pyPS2O]+), 128.0 ([PS3]+), 63.0 ([PS]+). Ra-
man (200 mW, room temp.): ν˜ = 3062 (49), 1615 (48), 1016 (100),
470 (60), 385 (52) cm–1. IR (200 mW, room temp.): ν˜ = 3056 (vw),
2397 (w), 1631 (w), 1593 (w), 1532 (w), 1484 (m), 1444 (w), 1385
(vw), 1248 (w), 1211 (w), 1151 (w), 1051 (w), 1033 (vw), 1021 (vw),
998 (w), 868 (br., vs), 743 (s), 680 (vs), 666 (s) cm–1.
IR Spectroscopy: The spectra were recorded with a Perkin-Elmer
Spektrum one FT-IR instrument (KBr pellets) equipped with a
Diamant-ATR Dura Sampler at 25 °C (neat). Raman spectra were re-
corded with a Bruker RAMII Raman instrument (λ = 1064 nm,
200 mW, 25 °C) equipped with a D418-T Detector at 200 mW at
25 °C.
py2P2S5 (1a): P4S10 (889.2 mg, 2 mmol) was stirred in pyridine
(40 mL) for 1 h. Colorless needles of 1a crystallized overnight and
were separated by filtration and dried in vacuo. (Yield: 1415.4 mg,
93%). 31P{1H} NMR (pyridine): δ (ppm) = 104.2 (s). Elemental analy-
sis for py2P2S5: calcd. C 31.57, N 7.36, H 2.65, P 16.28, S 42.14%;
found C 32.92, N 7.69, H 3.30, S 31.78%. Mass (EI+) m/z = 379.8
([C10H10N2P2S5]+), 347.8 ([M–S]+), 299.9 ([M–py]+), 221.9 ([M–
py2]+), 191.9 ([M–py2S]+), 160.0 ([M–py2S2]+), 128.0 ([PS3]+), 96.0
([PS2]+), 63.0 ([PS]+). Raman (200 mW, room temp.): ν˜ = 3066 (31),
1609 (36), 1567 (29), 2000 (43), 1014 (100), 468 (50), 448 (37)
cm–1. IR (200 mW, room temp.): ν˜ = 1087 (s), 3060 (m), 1633 (vw),
1606 (m), 1532 (vw), 1484 (vw), 1471 (vw), 1452 (vs), 1330 (vw),
1262 (vw), 1194 (w), 1154 (vw), 1093 (vw), 1053 (m), 1044 (s), 1011
(m), 762 (m), 734 (vs), 673 (vs), 655 (w), 642 (w), 575 (vs), 461 (w),
454 (w), 423 (w) cm–1.
Acknowledgements
Financial support by the Department of Chemistry, University of
Munich, is gratefully acknowledged. Stefanie Schedlbauer is thanked
for her help with the syntheses.
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74
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Received: August 20, 2013
Published Online: October 15, 2013
Z. Anorg. Allg. Chem. 2014, 68–75
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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