Synthesis, crystal structure and thermal studies of bis(O,O′- dibenzyldithiophosphato)-(2,2′-bipyridine)nickel(II) complex

Article abstract of DOI:10.1081/SIM-200026301

The bis(O,O′-dibenzyldithiophosphato)Ni(II) adduct, [(PhCH ₂O)₂PS₂]₂ Ni(bpy), was synthesized by the reaction of [(PhCH₂O)₂PS₂]₂Ni with 2,2′-bipyridine in the solid state. Single crystals of the title compound as the dihydrate were obtained by recrystallization in ethanol-distilled water (v/v = 9:1). The structure characterization was performed by means of IR, elemental analyses, and single crystal x-ray analysis. The crystal of the title compound consists of two disconnected structural units, each of which includes two non-coordination water molecules. The coordination geometry of each Ni atom is a distorted octahedron. The thermogravimetric (TG) data indicate that thermal decomposition of the title compound takes place in four steps and the residue is Ni(OPS₂) ₂.

Full text of DOI:10.1081/SIM-200026301

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Synthesis, Crystal Structure
and Thermal Studies of
bis(O,O′‐Dibenzyldithiophosphat
Complex
Fangfang Jian a , Guoxia Zheng a & Hailian Xiao a
a New Materials & Function Coordination
Chemistry Laboratory , Qingdao University of
Science and Technology , Qingdao, Shandong,
266042, China
Published online: 16 Nov 2010.
To cite this article: Fangfang Jian , Guoxia Zheng & Hailian
Xiao (2004) Synthesis, Crystal Structure and Thermal Studies of
bis(O,O′‐Dibenzyldithiophosphato)‐(2,2′‐Bipyridine)nickel(II) Complex, Synthesis
and Reactivity in Inorganic and Metal-Organic Chemistry, 34:9, 1517-1528, DOI:
10.1081/SIM-200026301
To link to this article: http://dx.doi.org/10.1081/SIM-200026301
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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 34, No. 9, pp. 1517–1528, 2004
Synthesis, Crystal Structure and
Thermal Studies of bis(O,O0-
Dibenzyldithiophosphato)-(2,20-
Bipyridine)nickel(II) Complex
*
Fangfang Jian, Guoxia Zheng, and Hailian Xiao
New Materials & Function Coordination Chemistry Laboratory, Qingdao
University of Science and Technology, Qingdao, Shandong, China
ABSTRACT
The bis(O,O0-dibenzyldithiophosphato)Ni(II) adduct, [(PhCH2O)2PS2]2
Ni(bpy), was synthesized by the reaction of [(PhCH2O)2PS2]2Ni with
2,20-bipyridine in the solid state. Single crystals of the title compound
as the dihydrate were obtained by recrystallization in ethanol–distilled
water (v/v ¼ 9 : 1). The structure characterization was performed by
means of IR, elemental analyses, and single crystal x-ray analysis. The
crystal of the title compound consists of two disconnected structural
units, each of which includes two non-coordination water molecules.
The coordination geometry of each Ni atom is a distorted octahedron.
*
Correspondence: Fangfang Jian, New Materials & Function Coordination Chemistry
Laboratory, Qingdao University of Science and Technology, Qingdao, Shandong
266042, China; E-mail: ffj2003@163169.net.
1517
DOI: 10.1081/SIM-200026301
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

1518
Jian, Zheng, and Xiao
The thermogravimetric (TG) data indicate that thermal decomposition of
the title compound takes place in four steps and the residue is Ni(OPS2)2.
Key Words: Crystal structure; Solid state reaction; Dithiophosphato
Ni(II) complexes; 2,20-Bipyridine adduct; TG.
INTRODUCTION
Dialkyldithiophosphate complexes of transition metals have received
increasing attention in recent years owing to their extensive applications in
lubrication engineering and in the plastics industry.[1,2] In addition to their
syntheses and various physico-chemical investigations, the crystal structures
of many of these compounds and their adducts with nitrogen bases have
been reported.[3,4] Metal chelates in which the metal ion is coordinately unsa-
turated can act as electron acceptors and yield adducts with neutral molecules
being electron donors.[5] In recent years, adducts of nickel(II) dithiophosphate
with neutral nitrogen ligands have received increasing attention owing to their
extensive applications as both antioxidants and antiwear additives in the
rubber industry and in lubrication engineering.[6,7] Additionally, the adducts
and their formation reactions have also been found useful in a variety of
ways, such as in biological applications and as both ultraviolet absorbers
and antioxidants. The crystal structures of many nickel(II) complexes and
their adducts with nitrogen bases have been reported.[8,9] Furthermore, the
amines in lubricating oil have a great influence on the properties of nickel(II)
dialkyldithiophosphate additives.[10] It is of interest to investigate further
the interaction between metal dialkyldithiophosphate and amines. In this
paper, we report the thermal analyses and structure of bis(O,O0-
dibenzyldithiophosphato)(2,20-bipyridine)nickel(II) inclusion compounds
with water molecules.
EXPERIMENTAL
Reagents and Instruments
All chemicals were of analytical reagent grade and used directly without
further purification. (PhCH2O)2PS2Na was prepared according to the literature
method.[11] Elemental analyses were determined with a Perkin–Elmer 1400C
analyzer. IR spectra (4000–400 cm21), as KBr pellets, were recorded on a
Nicolet FT-IR 170X spectrophotometer. TG and DTG curves were recorded

Dialkyldithiophosphate Complexes
1519
on a Netzsch-TG209 GmbH thermoanalyzer in a flow of N2, in the tempera-
ture range from 20 to 1000 8C, with a heating rate of 10 8C/min.
Preparation of Complexes
Synthesis of [(PhCH2O)2PS2]2Ni
.
Stoichiometric amounts of nickel(II) nitrate (Ni(NO3)2 6H2O, 3.0 g,
10 mmol) and sodium O,O0-dibenzyldithiophosphate [(PhCH2O)2PS2Na,
3.3 g, 10 mmol] in deionized water (50 mL) were stirred together for 20 min.
The formed deep green precipitate was collected by filtration, washed with
water, and then dried over P4O10. Yield, 3.3 g (97%); m.p. 135–1378C.
Anal. Calcd: for C28H28NiO4P2S4 (FW 677.17): C, 49.62; H, 4.13. Found:
C, 49.13%; H, 4.05%.
Synthesis of [(PhCH2O)2PS2]2Ni(bpy) (Solid State Reaction)
bis(O,O0-Dibenzyldithiophosphate)Ni(II), prepared as above, (3.3 g,
4.9 mmol) and 2,20-bipyridine (7.8 g, 53 mmol) were mixed and ground in
an agate mortar to get the best possible homogeneity. The mixture was
heated at 50 8C for 2 hr in a round-bottom flask. The color of the mixture
changed from deep green to light green. Afterwards the product was
washed with petroleum ether (b.p. 60–90 8C), and dried in vacuum. Yield,
4.0 g (98%), m.p. 130–132 8C.
Synthesis of [(PhCH2O)2PS2]2Ni(bpy) (Wet Method)
When we prepared the above complex by the wet method we obtained
solid [(PhCH2O)2PS2]2Ni(bpy) in 85% yield. bis(O,O0-Dibenzyldithio-
phosphate)Ni(II) (3.40 g, 5.0 mmol) was dissolved in hot EtOH (50 mL),
stirred, and the warm solution of bpy (0.40 g, 5.2 mmol) in EtOH (50 mL)
was added. The mixture was refluxed for 20 min. The solution was filtered.
The filtrate concentrated, when a green crystalline solid appeared which
was separated by filtration to give solid [(PhCH2O)2PS2]2Ni(bpy) (3.5 g).
Anal. Calcd. for C38H36N2NiO4P2S4 (FW 833.58): C, 54.75; H, 4.32; N,
3.36. Found: C, 54.56%; H, 4.11%; N, 3.26%.

1520
Jian, Zheng, and Xiao
Synthesis of Hydrated Complex and Single Crystal of
.
[((PhCH2O)2PS2)2Ni(bpy)] 2H2O
The anhydrous complex [(PhCH2O)2PS2]2Ni(bpy) (0.20 g, 0.24 mmol)
was dissolved in an ethanol–distilled water (v/v ¼ 9 : 1) mixture (30 mL) at
room temperature. The green solution was filtered, and the filtrate was left
to stand undisturbed at room temperature. Upon slow evaporation at room
temperature, a deep-green crystalline solid appeared several days later and
was separated by filtration. Single crystals suitable for x-ray analysis were
obtained. The yield was 2.0 g (96%), m.p. 128–130 8C. Anal. calcd. for
C38H40N2NiO6P2S4 (FW 869.61): C, 52.48; H, 4.64; N, 3.22. Found: C,
52.25%; H, 4.56%; N, 3.03%.
X-Ray Crystal Structure Determination
.
The selected crystal of [((PhCH2O)2PS2)2Ni(bpy)] 2H2O was mounted
on a four-circle CAD4 automatic diffractometer using Mo-Ka radiation
˚
(l ¼ 0.71073 A, T ¼ 293 K) graphite monochromation. The structure was
solved by direct methods[12] and all non-hydrogen atoms were refined on F2
anisotropically by a full-matrix least squares method.[13] Hydrogen atoms
were located from the difference Fourier map and added to the structure cal-
culations, but their positions were not refined. The contributions of these
hydrogen atoms were included in structure–factor calculations. A summary
of the key crystallographic information is given in Table 1.
RESULTS AND DISCUSSION
Synthesis
The reaction of benzyl alcohol with solid phosphorus pentasulfide (P2S5) at
about 165 8C yields O,O0-dibenzyldithiophosphoric acid, (PhCH2O)2PS2H. This
acid reacts with solid sodium hydroxide in the molar ratio 1 : 1 at room temp-
erature with stirring to form sodium O,O0-dibenzyldithiophosphate, (PhCH2O)2-
PS2Na. The nickel(II) complex of O,O0-dibenzyldithiophosphate was obtained
by the reaction of nickel nitrate and sodium O,O0-dibenzyldithiophosphate in
deionized water. We obtained the complex [(PhCH2O)2PS2]2 Ni(bpy) by
solid phase synthesis. Because there are many advantage in solid–solid phase
synthesis, such as not needing crystallization, filtration, and separation, which
can increase the yield of the reaction product.[14] A well-ground mixture of
[(PhCH2O)2PS2]2Ni and 2,20-bipyridine, was put into a round-bottom flask

Dialkyldithiophosphate Complexes
1521
Table 1. Crystal data and structure refinement for the title compound.
Empirical formula
Formula weight
Unit cell dimensions
C38H40N2NiO6P2S4
869.61
˚
a ¼ 10.980(2) A a ¼ 76.14(3)8
˚
b ¼ 18.161(4) A b ¼ 108.02(3)8
˚
c ¼ 20.187(4) A g ¼ 78.34(3)8
3
˚
Volume
3826.3(13) A
Z, Calculated density
Absorption coefficient
F(0 0 0)
4, 1.510 Mg/m3
0.859 mm21
1808
Crystal size
u Range for data collection
Limiting indices
0.25 ꢂ 0.20 ꢂ 0.15 mm
1.04–25.808
0 ꢃ h ꢃ 13, 221 ꢃ k ꢃ 21,
224 ꢃ l ꢃ 24
Reflections collected/unique
Completeness to u ¼ 24.97
Refinement method
14,672/13,874 [Rint ¼ 0.0364]
94.2%
Full-matrix least-squares on F2
13874/0/935
1.055
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I . 2s (I)]
R indices (all data)
Largest different peak and hole
R1 ¼ 0.0648, wR2 ¼ 0.1700
R1 ¼ 0.1526, wR2 ¼ 0.2092
23
˚
0.604 and 20.607 e A
and heated at 508C for 2 hr. After that the product was washed with petroleum
ether (b.p. 60–908C), and dried in vacuum, the solid bis(O,O0-
dibenzyldithiophosphato)(2,20-bipyridine)Ni(II) complex, [(PhCH2O)2PS2]2-
Ni(bpy), was obtained at higher yield than by the solution reaction. The
general equations for the formation of the complexes are given below.
P2S5 þ 4PhCH2OH ꢀ! 2ðPhCH2OÞ2PS2H þ H2S
ðPhCH2OÞ2PS2H þ NaOH ꢀ! ðPhCH2OÞ2PS2Na þ H2O
ð1Þ
ð2Þ
2ðPhCH2OÞ2PS2Na þ NiðNO3Þ2 ꢀ! ½ðPhCH2OÞ2PS2ꢁ2Ni þ 2NaNO3 ð3Þ
½ðPhCH2OÞ2PS2ꢁ2Ni þ bpy ꢀ! ½ðPhCH2OÞ2PS2ꢁ2NiðbpyÞ
ðbpy ¼ 2;20-bipyridineÞ
ð4Þ
Single crystals suitable for x-ray measurements of bis(O,O0-dibenzyl–
dithiophosphato)(2,20-bipyridine)Ni(II) dihydrate were obtained by recrystal-
lization with a mixture of ethanol and distilled water (9 : 1) at room
temperature. From the data of the elemental analyses, it can be seen that
there are two water molecules which enter the crystal lattice of the

1522
Jian, Zheng, and Xiao
bis(O,O0-dibenzyldithiophosphato)(2,20-bipyridine)nickel(II) complex to
form an inclusion compound with water molecules. This result was also
confirmed by x-ray, IR, and thermal analysis described below.
Single Crystals Structure
Figure 1 shows a perspective view of the title compound [((PhCH2O)2
.
PS2)2Ni(bpy)] 2H2O with the atomic numbering scheme. Figure 2 shows a
perspective view of the crystal packing in the unit cell. Selected bond dis-
tances and angles are listed in Table 2. The structure of the title complex con-
tains a pair of independent, disconnected [(PhCH2O)2PS2]2Ni(bpy) structural
units [named Ni(1) and Ni(2), see Fig. 1], each of which consists of two non-
coordination solvent water molecules. Each Ni(II) atom is located in the centre
of the octahedral NiN2S4 chromophore. Two bis(O,O0-dibenzyldithio-
phosphato) ligands are coordinated to the central nickel atom by their two
sulfur atoms, forming four-membered chelate rings, and one 2,20-bipyridine
ligand is coordinated to the nickel atom with its two nitrogen atoms
forming a five-membered chelate ring. The range of the Ni–S distances in
the two independent parts of the molecule are nearly the same, 2.439(2)–
˚
˚
2.521(2) A for Ni(1) and 2.433(2)–2.523(2) A for Ni(2), which are in
good agreement with similar distances found in six-coordinated complexes,
such as [(BuO)2PS2]2Ni(bpy)[15] [2.463(2)–2.524(2) A] and [(EtO)2PS2]2
˚
Figure 1. Molecular structure with the atomic numbering scheme for the title compound.

Dialkyldithiophosphate Complexes
1523
Figure 2. A view of the crystal packing down the a axis for [((PhCH2O)2PS2)2
.
Ni(bpy)] 2H2O.
[16]
˚
[2.486(1)–2.511(1) A]. However, the distances are much longer
Ni(Py)2
than those in four-coordinate compounds, such as (4-Bu-PhOCS2)2Ni[17]
[9]
[2.219(4) and 2.213(6) A] and [(EtO)(4-CH3OPh)PS2]2Ni [2.1297(8) and
˚
˚
2.2225(8) A]. This probably reflects the change from octahedral coordination
in the title compound to square-planar or tetrahedral coordination. The range
of the Ni–N distances in the two independent parts are all nearly the same,
˚
2.054(5)–2.073(5) A for Ni(1) and 2.055(5)–2.063(5) A for Ni(2), which
˚
are also in good agreement with similar distances found in [(BuO)2PS2]2
[18]
Ni(bpy)[15] [2.089(4) and 2.088(4) A] and [((EtO)CS2)2Ni(Phen)] 3H2O
˚
.
˚
[2.074(4) and 2.076(4) A]. The S–Ni–S bond angles are larger than those
found in [(BuO)2PS2]2Ni(bpy)[15] [81.40(7) and 81.63(7)8], while the
N–Ni–N bond angles are similar to that of [(BuO)2PS2]2Ni(bpy).
˚
Table 2. Selected bond length (A) and bond angles (8) for the title compound.
Ni(1)–N(1)
Ni(1)–S(3)
2.054(5)
2.439(2)
2.452(2)
2.055(6)
2.433(2)
2.469(2)
79.0(2)
Ni(1)–N(2)
Ni(1)–S(2)
2.073(5)
2.443(2)
2.521(2)
2.063(6)
2.446(2)
2.523(2)
90.03(7)
91.19(8)
90.72(8)
80.89(8)
Ni(1)–S(1)
Ni(2)–N(4)
Ni(1)–S(4)
Ni(2)–N(3)
Ni(2)–S(5)
Ni(2)–S(7)
Ni(2)–S(8)
Ni(2)–S(6)
N(1)–Ni(1)–N(2)
S(2)–Ni(1)–S(1)
N(4)–Ni(2)–N(3)
S(8)–Ni(2)–S(7)
S(3)–Ni(1)–S(2)
S(2)–Ni(1)–S(4)
S(5)–Ni(2)–S(7)
S(5)–Ni(2)–S(6)
83.23(7)
78.3(3)
83.08(7)

1524
Jian, Zheng, and Xiao
. . .
There are some potentially weak C–H Y hydrogen bonds (Y ¼ O and
S), intermolecular interactions and p–p stacking interactions in the
lattice.[19,20] The O(6) atom with the C(75) atom in the bipyridine ring form
. . .
potentially weak C–H O intermolecular interactions, the donor and accep-
˚
tor distance is 3.3036 A for C(75)–H(75A). . .O(6) (symmetry code:
2 2 x, 1 2 y, 2 z). S(2), S(5), and S(6) with the C atom in benzyl, S(8),
. . .
with the C atoms in the bipyridine ring form potentially weak C–H S inter-
. . .
molecular interactions, the donor and acceptor distances are C(62) S(2)
˚
. . .
. . .
˚
3.7438
3.6391(1) A [symmetry code: 2 2 x, 1 2 y, 2z], C(42) S(6) 3.7251 A [sym-
A
[symmetry code: 1 2 x, 1 2 y, 1 2 z]; C(65) S(5)
. . .
˚
˚
. . .
metry code: 2 2 x, 2y, 2z] and C(73) S(8) 3.6383 A [symmetry code:
1 2 x, 1 2 y, 2z]. The other feature of intermolecular interaction is due to
the type of p–p stacking interactions between the molecules in the crystal
lattice. The center-to-center distance between the adjacent bipyridine for
˚
Ni(2) is 3.924 A. The shortest interplanar distance between the parallel bipyr-
˚
idine ring planes is 3.351 A. It is obvious that they form a slightly stronger
p–p stacking interaction.[21,22] In the solid state, all of the above extensive
hydrogen bonds in this structure form a two-dimensional hydrogen bond
network which stabilizes the crystal structure.
Infrared Spectra
The IR spectrum exhibits characteristic strong bands at 1601 (C55C),
1454, 1442 (C55N), 744 cm21 [n(C–H) pyridine ring] for the coordinated
bipyridine ligands.[23] The significant change in the ligand bands upon
complex is the decrease in n(C–Npy). The shift to lower frequencies in the
spectra of the complexes suggests delocalization of the p-election density
around the nitrogen atoms and a lower C55N stretching force due to the coordi-
nation through nitrogen of the pyridine ring [free ligand n(C55N) at 1515 and
1452 cm21].[24] The IR spectra of the title compound also exhibit the charac-
teristic absorptions of [(RO)2PS2]2Ni, n(P–O–C) at 1021 and 988 cm21, and
n
asym(PS2) at 697 and 677 cm21, as well as nsym(PS2) at 604 and 536 cm21
,
respectively.[25] A medium absorption band at 1620 cm21 may be assigned
to non-coordinated water, consistent with the results of the crystal structure
determination mentioned above and the TG analysis data below.
Thermal Studies
The TG/DTG curves of the title compound, [((PhCH2O)2PS2)2
.
Ni(bpy)] 2H2O, are presented in Fig. 3. From Fig. 3, we can see that there

Dialkyldithiophosphate Complexes
1525
Figure 3. TG/DTG curves of the title compound.
are four steps of weight loss, and the decomposition events take place at 178.4,
250.9, 296.0, and 444.8 8C with four heat-absorption peaks, respectively. The
compound shows no decomposition below 178 8C; but, at 178.4 8C, decompo-
sition occurs. On the basis of weight changes, the first process of the weight
loss corresponds to the loss of water (found: 3.70%; calcd.: 4.14%), with a
weak endothermic phenomenon; then, the second event of weight loss may
be related to the loss of one benzyl moiety (found: 10.74%; calcd.:
10.48%), also an endothermic phenomenon. There is one intense endothermic
peak in the DTG curve at 296.0 8C, and about 30.93% weight loss in the TG
curve between 290 and 340 8C, which is attributed to the loss of the other three
benzyl groups (found: 30.93%; calcd.: 31.43%). In the temperature range of
340–660 8C, there is a small weak endothermic peak at 444.8 8C, with
about 18.68% weight loss, which is attributed to the loss of the 2,20-bipyridine
group (found: 18.68%; calcd.: 17.94%). Then, at 660 8C , T , 860 8C, the
4.97% weight loss in the TG curves may be related to the loss of two
oxygen atoms (found: 4.97%; calcd.: 3.68%). Finally, at T . 860 8C, the
residual weight of 31.97% suggests that the residue may be Ni(S2PO)2
(found: 31.91% calcd.: 32.28%). No structural transitions were found in this
compound, which imply a high thermal stability. It is interesting to note
that at about 178.4 8C only the release of water molecules takes place, the
temperature of the loss of water molecules is higher than that of similar
inclusion complexes forming a lattice inclusion compound with water

1526
Jian, Zheng, and Xiao
molecules trapped in channels reported before,[26] suggesting that the water
molecules are firmly clathrated in the crystal lattice which is confirmed by
the x-ray crystal structural determination described above.
From the TG analysis above, the decomposition process may be described
as follows:
ꢀ2H2O
½ððPhCH2OÞ2PS2Þ2Ni(bpy)ꢁ ꢄ 2H2O ꢀꢀꢀꢀꢀꢀ!½ðPhCH2OÞ2PS2ꢁ2Ni(bpy)
176–250 8C
ꢀPhCH2
250–296 8C
ꢀPhCH2
296–340 8C
ꢀꢀꢀꢀꢀꢀ!½ð3=2PhCH2ÞO2PSꢁ2Ni(bpy) ꢀꢀꢀꢀꢀꢀ!ðO2PS2Þ2Ni(bpy)
ꢀbpy
ꢀO2
660–860 8C
ꢀꢀꢀꢀꢀꢀ!ðO2PS2Þ2Ni ꢀꢀꢀꢀꢀꢀ!ðOPS2Þ2Ni
340–660 8C
ACKNOWLEDGMENT
The authors would like to thank Natural Science Foundation of Shandong
Province (No.Y2002B06).
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Received July 7, 2003
Accepted April 20, 2004