Synthesis, spectroscopic characterization and structural studies of nickel complexes of O,O′-diaryl(dibenzyl) dithiophosphates: Crystal structures of Ni[S2P(OC6H4CH3-o) 2]2, Ni[S2P(OC6H4CH 3-m)2]2 and Ni[S2P(OCH 2Ph)2](2)

Article abstract of DOI:10.1016/j.poly.2005.10.022

Purple-coloured, tetra-coordinated Ni(II) complexes, Ni[S ₂P(OR)₂]₂ (R = o-, m-, p-OC₆H ₄Me, Ph and CH₂Ph) have been obtained by reaction of NiCl₂ with salts of corresponding O,O′-diaryl(dibenzyl) dithiophosphates and have been characterized by elemental analysis, UV, IR, ¹H, and ³¹P NMR spectroscopy. Trends in the data are discussed. The crystal structures of Ni[S₂P(OC₆H ₄Me-o)₂]₂, Ni[S₂P(OC ₆H₄Me-m)₂]₂ and Ni[S ₂P(OCH₂Ph)₂]₂ are also described. Ni[S₂P(OC₆H₄Me-o)₂]₂ crystallizes as monoclinic in the space group P2₁/n with cell parameters a = 9.069(2), b = 13.503(2), c = 23.735(4) ?, α = 90.00°, β = 90.11(1)°, γ = 90.00°, V = 2906.6(8) ?^-3, Z = 4, R = 0.0351, R_w = 0.0787, Ni[S ₂P(OC₆H₄CH₃-m)₂] ₂ as triclinic in the space group P1? with cell parameters a = 9.4675(4), b = 12.8568(5), c = 13.1174(6) ?, α = 88.810(4)°, β = 83.416(5)°, γ = 73.711(4)°, V = 1522.4(1) ?^-3,Z = 2, R = 0.0354, R_w = 0.0830, and Ni[S ₂P(OCH₂Ph)₂]₂ as triclinic in the space group P1? with cell parameters a = 10.887(2), b = 14.081(3), c = 16.238(3) ?, α = 72.70(3)°, β = 76.57(3)°, γ = 72.76(3)°, V = 2241.4(8) ?^-3, Z = 2, R = 0.0365, R _w = 0.0785. Each of these has a distorted square-planar geometry around nickel with MS₄ coordination environment.

Full text of DOI:10.1016/j.poly.2005.10.022

Polyhedron 25 (2006) 945–952
www.elsevier.com/locate/poly
Synthesis, spectroscopic characterization and structural studies of
nickel complexes of O,O0-diaryl(dibenzyl) dithiophosphates:
Crystal structures of Ni[S2P(OC6H4CH3-o)2]2,
Ni[S2P(OC6H4CH3-m)2]2 and Ni[S2P(OCH2Ph)2]2
a
b
a
c
c,
*
Ann L. Bingham , John E. Drake , Mark E. Light , Manisha Nirwan , Raju Ratnani
a
Department of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, UK
Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ont., Canada N9B 3P4
Department of Pure and Applied Chemistry, M.D.S. University, Jaipur Road, Ajmer 305 009, Rajasthan, India
b
c
Received 14 August 2005; accepted 22 October 2005
Available online 6 December 2005
Dedicated with affection and gratitude to Professor M.B. Hursthouse on the occasion of his ꢀretirementꢁ and J.E.D. wishes to thank
Mike Hursthouse for being such a good friend in deed at a time of need.
Abstract
Purple-coloured, tetra-coordinated Ni(II) complexes, Ni[S2P(OR)2]2 (R = o-, m-, p-OC6H4Me, Ph and CH2Ph) have been obtained by
reaction of NiCl2 with salts of corresponding O,O0-diaryl(dibenzyl) dithiophosphates and have been characterized by elemental analysis,
1
UV, IR, H, and 31P NMR spectroscopy. Trends in the data are discussed. The crystal structures of Ni[S2P(OC6H4Me-o)2]2, Ni[S2P-
(OC6H4Me-m)2]2 and Ni[S2P(OCH2Ph)2]2 are also described. Ni[S2P(OC6H4Me-o)2]2 crystallizes as monoclinic in the space groꢀu3p
˚
˚
P21/n with cell parameters a = 9.069(2), b = 13.503(2), c = 23.735(4) A, a = 90.00ꢀ, b = 90.11(1)ꢀ, c = 90.00ꢀ, V = 2906.6(8) A
,
ꢀ
Z = 4, R = 0.0351, Rw = 0.0787, Ni[S2P(OC6H4CH3-m)2]2 as triclinic in the space group P1 with cell parameters a = 9.4675(4), b =
12.8568(5), c = 13.1174(6) A, a = 88.810(4)ꢀ, b = 83.416(5)ꢀ, c = 73.711(4)ꢀ, V = 1522.4(1) Aꢀ3,Z = 2, R = 0.0354, Rw = 0.0830, and
˚
˚
ꢀ
˚
Ni[S2P(OCH2Ph)2]2 as triclinic in the space group P1 with cell parameters a = 10.887(2), b = 14.081(3), c = 16.238(3) A, a =
72.70(3)ꢀ, b = 76.57(3)ꢀ, c = 72.76(3)ꢀ, V = 2241.4(8) Aꢀ3, Z = 2, R = 0.0365, Rw = 0.0785. Each of these has a distorted square-planar
˚
geometry around nickel with MS4 coordination environment.
ꢁ 2005 Elsevier Ltd. All rights reserved.
Keywords: Nickel; o-, m-, p-tolyl; Dithiophosphates; Benzyl; Structure
1. Introduction
plexes with analogous aromatic ligands have been less stud-
ied. A survey of the literature confirms the importance of
nickel complexes with thio ligands where the main thrust
of research has been on the preparation of complexes hav-
ing varied applications in agriculture as pesticides [18], in
lubrication engineering as antiwear and extreme pressure
additives [19,20], and in industry as antioxidants of poly-
olefines [21] and as catalyst stabilizers [22].
Among the variety of dithio ligating systems, nickel
complexes with O,O0-dialkyl dithiophosphates [1–11] and
O,O0-alkylene dithiophosphates [12–17] have consistently
retained interest for the last few decades. These ligands
exhibit versatile modes of coordination and are known to
exist in bidentate and monodentate forms. However, com-
Our interest in exploring the coordination and bonding
properties of thio ligands led us to work on O,O0-diaryl
dithiophosphate ligand moieties. Some of these nickel(II)
complexes have been reported [23,24] in a fragmented
*
Corresponding author. Tel.: +91 145 2640059.
E-mail address: ratnaniraju@yahoo.co.uk (R. Ratnani).
0277-5387/$ - see front matter ꢁ 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2005.10.022

946
A.L. Bingham et al. / Polyhedron 25 (2006) 945–952
manner. Therefore, a systematic, consolidated and compar-
ative discussion on complexes of this series may prove use-
ful. In continuation of our search for new nickel(II)
complexes has led to this paper in which we report synthe-
sis of nickel(II) complexes of the types, Ni[S2P(OR)2]2,
(R = o-, m-, p-C6H4Me, Ph, CH2Ph) and their character-
ization by various spectroscopic techniques. We also report
on the X-ray single crystal structures of Ni[S2P(OC6H4-
Me-o)2]2, Ni[S2P(OC6H4Me-m)2]2, and Ni[S2P(OCH2Ph)2]2.
ing vibrations, respectively. Bands due to m(P@S) or m(P–
S)asym and m(P–S) or m(P–S)sym observed at 690–670 and
595–540 cmꢀ1 in the ditolyl dithiophosphoric acids and
their ammonium salts, are shifted to lower frequency by
ca. 10–30 cmꢀ1 in the corresponding nickel(II) complexes,
indicating bidentate attachment of the ligand to the metal
atom. In addition, the bands characteristic of ortho substi-
tution can be seen in the region 1944–1733w cmꢀ1, 755s
cmꢀ1, those of meta substitution in 1952–1809w cmꢀ1
,
897, 778s cmꢀ1 and those of para substitution in 1884–
1745w cmꢀ1, 816s cmꢀ1. Similarly, mono substitution in
complexes 4 and 5 are observed in the region 1952–
1809w cmꢀ1 as well as two peaks at 695, 744s cmꢀ1 [30].
2. Results and discussions
Reactions of nickel(II) chloride with ammonium salts of
O,O0-ditolyl/diphenyl/dibenzyl dithiophosphates in 1:2 molar
ratio in aqueous solution yield nickel(II) complexes of the
types, Ni[S2P(OR)2]2
1
2.3. H NMR spectra
The spectra were recorded in CDCl3 solutions at room
temperature. The H NMR data of nickel(II) complexes
NiCl2 þ 2NH4S2PðORÞ2ꢀ! Ni½S2PðORÞ2ꢁ2 þ 2NH4Cl
(R = o-, m-, p-OC6H4Me, Ph and CH2Ph).
1
are remarkably similar to those of the salts of dithiophos-
phoric acids [31] probably due to the large separation
between the nickel and protons. Negligible shift for methyl
protons is observed in complexes 1–3 as compared to the
corresponding salts, showing a singlet in the range 2.24–
2.37 ppm. The phenyl protons appear in the region 6.85–
7.41 ppm in complexes 1–5, undergoing slight down field
shifts of ca. 0.1–0.2 ppm compared to their position in
the free ligand, presumably as a consequence of the coordi-
nation of the ligand.
The precipitated purple solid was separated by filtration
and repeatedly washed with benzene. All of these nickel(II)
complexes are purple, powdery solids, soluble in all com-
mon organic solvents and were characterized by elemental
1
analysis, IR, UV–Vis, H and 31P NMR spectroscopy.
2.1. Electronic absorption spectra
The electronic spectra of the nickel(II) complexes, recor-
ded in C6H6, show three bands in the region 681–690, 517–
530 and 390–395 nm in the visible region with a single
band at 320–322 nm in the near ultraviolet region. The first
2.4. 31P NMR spectra
1
1
1
1
The 31P NMR spectra of complexes 1–5, show a rela-
tively sharp, singlet in the region 79–94 ppm, indicating
that the phosphorous nuclei are equivalent and only one
type of phosphorous is present in each case in solution.
The 31P NMR chemical shifts for these complexes are
shifted approximately 20–25 ppm upfield from those of
the corresponding salts of dithiophosphoric acids.
three bands can be assigned to A1g ! A2g, A1g ! B2g,
1
1
and A1g ! Eg transitions, respectively. Almost identical
electronic transitions for open chain and cyclic dithiophos-
phate complexes were observed [25,26] indicating consis-
tent square-planar geometry.
2.2. IR spectra
The relevant assignments of the IR bands (Table 1) have
been made by comparisons with the spectra of the ammo-
nium salts of O,O0-ditolyl/diphenyl/dibenzyl dithiophos-
phates [27,28] and analogous nickel(II) O,O0-dialkyl
dithiophosphate complexes [25,29]. The two strong inten-
sity bands present in the 1043–985 and 835–770 cmꢀ1
regions are assigned to m[(P)–O–C] and m[P–O–(C)] stretch-
2.5. Molecular structures of Ni[S2P(OC6H4Me-o)2]2,
Ni[S2P(OC6H4Me-m)2]2 and Ni[S2P(OCH2Ph)2]2
Ni[S2P(OC6H4Me-o)2]2 (1) crystallizes in the space
group P21/n and Ni[S2P(OC6H4Me-m)2]2 (2) and Ni[S2P-
ꢀ
(OCH2Ph)2]2 (5) crystallize in the space group P1. The
ORTEP diagram in Fig. 1 shows the single molecule in
Table 1
IR spectral data (cmꢀ1) for the bis[O,O0-diaryl(dibenzyl)dithiophosphate]nickel(II) complexesa
No.
Compound
m [(P)–O–C]
m [P–O–(C)]
m (P@S)
m (P–S)
1
2
3
4
5
a
Ni[S2P(OC6H4CH3-o)2]2
Ni[S2P(OC6H4CH3-m)2]2
Ni[S2P(OC6H4CH3-p)2]2
Ni[S2P(OC6H5)2]2
1043m
1010s
1017m
1005m
985s
725m
718m
713m
723m
821m
659, 603s
622, 603s
665, 556s
667, 603s
654, 603s
560m
565m
535m
562m
565m
Ni[S2P(OCH2C6H5)2]2
Key: s = strong, m = medium, w = weak.

A.L. Bingham et al. / Polyhedron 25 (2006) 945–952
947
Fig. 1. ORTEP plot of Ni{S2[P(OC6H4CH3-o)2]2}2. The non-hydrogen atoms are drawn with 50% probability ellipsoids. Hydrogen atoms omitted for
clarity.
the asymmetric unit of 1. In displaying the expanded two
molecules of the asymmetric unit of 2 (Fig. 2) and the
one and one-half molecules in the asymmetric unit of 5
(Fig. 3), the hydrogen atoms were omitted for clarity. Figs.
1–3 illustrate that the immediate environment about the Ni
atom is essentially distorted square-planar and that the two
dithiophosphate groups are bidentate in both complexes.
The average Ni–S distance is 2.2332(6) for 1, 2.236(6) for
Fig. 2. ORTEP plot of the expanded two independent molecule of Ni[S2P(OC6H4CH3-m)2]2. The non-hydrogen atoms are drawn with 50% probability
ellipsoids. Hydrogen atoms omitted for clarity.

948
A.L. Bingham et al. / Polyhedron 25 (2006) 945–952
Fig. 3. ORTEP plot of the two independent molecules of Ni[S2P(OCH2Ph)2]2. The non-hydrogen atoms are drawn with 50% probability ellipsoids. The
hydrogen atoms are omitted for clarity.
˚
both molecules in 2 and 2.235(7) A for those in 5, are
or obvious trends in the distances and bond angles as
the nature of R is changed in the Ni[S2P(OR)2]2 complexes
although in general the tolyl derivatives, Ni[S2P(OC6H4-
Me-o)2]2, Ni[S2P(OC6H4Me-m)2]2, Ni[S2P(OC6H4Me-p)2]2,
probably show the most similarities.
˚
similar to the average value of 2.232(4) A for Ni[S2P-
(OC6H4Me-p)2]2] [23]. This bond length is marginally
longer than found in dialkyl dithiophosphate analogue,
Ni[S2P(OEt)2]2 (2.21 A) [32,33] and Ni[S2P(OPri)2]2
˚
˚
(2.222(5) A) [34]. The average S–P distances are 1.9841(7)
in 1, 1.982(7) in 2 and 1.996(5) A in 5, which are compara-
˚
3. Experimental
ble to the values observed in Ni[S2P(OC6H4Me-p)2]2]
(1.976(2) A), Ni[S2P(OEt)2]2(1.97) and Ni[S2P(OPri)2]2
˚
Nickel chloride, benzyl alcohol, o-, m-, p-cresols were
purchased from E. Merck. Solvents (benzene, n-hexane,
diethyl ether) were dried by standard methods before use.
Stringent precautions were taken to exclude moisture dur-
ing experimental manipulations. Literature methods were
used for the preparation of O,O0-ditolyl [27] and O,O0-
diphenyl [28] dithiophosphoric acids. O,O0-dibenzyl dithio-
phosphoric acid was prepared by the reaction of P2S5 and
benzyl alcohol in 1:4 molar ratio. Ammonium salts of the
dithiophosphoric acids were prepared by the reaction of
parent acids with an equimolar amount of ammonia in
benzene.
˚
(1.992(1) A). The average P–O distances of 1.586(1) in 1,
˚
1.585(5) in 2 and 1.578(4) A in 5, lie between the values
reported for the analogues, Ni[S2P(OEt)2]2 (1.63) and
i
˚
Ni[S2P(OPr )2]2 (1.565(1) A) while that of 2 is identical to
˚
that of Ni[S2P(OC6H4Me-p)2]2] (1.585(2) A).
The S–Ni–S ligand bite angles are 88.39(2)ꢀ and
88.59(2)ꢀ in 1, are 88.79(2)ꢀ and 89.18(2)ꢀ in the two mole-
cules of 2, and range from 87.95(3)ꢀ to 88.52(3)ꢀ in 5; sim-
ilar to the values in Ni[S2P(OC6H4Me-p)2]2] (89.12(2)ꢀ) and
the two analogues, Ni[S2P(OEt)2]2 (88ꢀ) and Ni[S2P(O-
Pri)2]2 (88.10(4)ꢀ). The S–P–S bond angles vary from
103.32(3)ꢀ to 103.69(3)ꢀ in 1 and range from 104.18(4)ꢀ
to 104.80(4)ꢀ in 2, thus, having similar values as in the para
substituted analogue, Ni[S2P(OC6H4Me-p)2]2] (104.85(3)ꢀ).
The values are marginally smaller in the OCH2Ph deriva-
tive 5 (101.73(4)–102.81(4)ꢀ). The angles reported in Ni[S2-
P(OEt)2]2 and Ni[S2P(OPri)2]2 are 103ꢀ and 101.7(1)ꢀ,
respectively. The O–P–O bond angles are 99.37(7)–
99.24(7)ꢀ in 1, range from 99.83(9)ꢀ to 100.20(9)ꢀ in 2
and are 99.39(7)ꢀ in Ni[S2P(OC6H4Me-p)2]2. These values
are bracketed by those in 5 ranging from 95.22(8)ꢀ to
101.04(9)ꢀ. Thus, there appear to be no significant changes
3.1. Preparations
3.1.1. Ni[S2P(OC6H4Me-o)2] (1)
Typically, to an aqueous solution of NiCl2 Æ 6H2O
(0.287 g, 1.2073 mmol), was added an aqueous suspension
of NH4S2P(OC6H4Me-o)2 (0.801 g, 2.449 mmol) in 1:2
molar ratio with constant stirring.
A purple solid
was immediately obtained. After stirring for 3 h, the
precipitated Ni[S2P(OC6H4Me-o)2]2 was filtered off. The
compound was purified with repeated washing with dried

A.L. Bingham et al. / Polyhedron 25 (2006) 945–952
949
benzene. Purple powdery solid. Yield: 0.768 g, 94%; m.p.
8.28; S, 18.53. Found: Ni, 8.12; S, 18.60%. 1H NMR
(CDCl3): d 7.23–7.32 (dm, OC6H5), 31P NMR (CDCl3): d
84.59 ppm. UV/Vis electronic absorption spectral data
[kmax, nm(A)] in benzene 688, 525, 394, 321.
90 ꢀC. Calc. for C28H28O4S4P2Ni: Ni, 8.71; S, 18.90.
1
Found: Ni, 8.75; S, 18.72%. H NMR (CDCl3): d 2.25 (s,
Me), 7.04–7.41 (m, OC6H4), 31P NMR (CDCl3): d
84.10 ppm. UV/Vis electronic absorption spectral data
[kmax, nm(A)] in benzene 685, 520, 392, 322.
3.1.5. Ni[S2P(OCH2Ph)2]2 (5)
3.1.2. Ni[S2P(OC6H4CH3-m)2]2 (2)
Method as above gave a purple powdery solid. Yield:
0.668 g, 86%; m.p. 125 ꢀC. Calc. for C28H28O4S4P2Ni: Ni,
8.71; S, 18.90. Found: Ni, 8.64; S, 18.78%. 1H NMR
(CDCl3): d 5.22 (s, OCH2), 6.99–7.33 (bs, C6H5), 31P
NMR (CDCl3): d 93.66 ppm. UV/Vis electronic absorption
spectral data [kmax, nm(A)] in benzene 683, 527, 390, 320.
Method as above gave a purple powdery solid. Yield:
0.807 g, 93%; m.p. 106 ꢀC. Calc. for C28H28O4S4P2Ni: Ni,
8.71; S, 18.90. Found: Ni, 8.60; S, 18.98%. 1H NMR
(CDCl3): d 2.38 (s, Me), 7.07–7.29 (dm, OC6H4), 31P
NMR (CDCl3): d 84.95 ppm. UV/Vis electronic absorption
spectral data [kmax, nm(A)] in benzene 690, 517, 394, 320.
3.1.3. Ni[S2P(OC6H4CH3 ꢀ p)2]2 (3)
3.2. Physical measurements
Method as above gave a pale purple powdery solid. Yield:
0.797 g, 89%; m.p. 171 ꢀC. Calc. for C28H28O4S4-P2Ni: Ni,
8.71; S, 18.90. Found: Ni, 8.47; S, 18.88%. 1H NMR
(CDCl3): d 2.31 (s, Me), 6.85–7.37 (m, OC6H4), 31P NMR
(CDCl3): d 79.10 ppm. UV/Vis electronic absorption spec-
tral data [kmax, nm(A)] in benzene 681, 530, 395, 322.
Sulfur was estimated gravimetrically as barium sulfate
(Messengerꢁs method) and Nickel as dimethylglyoximate.
IR spectra were recorded on a Perkin–Elmer 577 spectro-
photometer in KBr pellets in the range 4000–200 cmꢀ1
.
Electronic spectra in the range 200–800 nm were recorded
on UV visible spectrophotometer-2201 in C6H6. 1H
NMR spectra were recorded on a Bruker DRX300
(300MHzFT NMR) spectrometer in CDCl3 using TMS
as an internal standard.
3.1.4. Ni[S2P(OPh)2]2 (4)
Method as above gave a purple powdery solid. Yield:
0.759 g, 91%; m.p. 122 ꢀC. Calc. for C24H24O4S4P2Ni: Ni,
Table 2
Crystal data and structure refinement for NiS2[P(OC6H4CH3-o)2]2 (1), NiS2[P(OC6H4CH3-m)2]2 (2), and Ni[S2P(OCH2Ph)2]2 (5)
Empirical formula
Formula weight
Temperature (K)
C
677.39
120(2)
28H28O4P2S4Ni
C28H28O4P2S4Ni
677.39
120(2)
C42H42O1.5P3S6Ni1.5
1016.90
120(2)
˚
Wavelength (A)
0.71073
0.71073
0.71073
Crystal system
Space group
a (A)
monoclinic
P21/n
9.093(2)
13.529(2)
23.779(4)
90.00
90.17(1)
90.00
2925.3(8)
4
1.548
triclinic
triclinic
ꢀ
ꢀ
P1
P1
˚
9.4675(4)
12.8568(5)
13.1174(6)
88.810(4)
83.416(5)
73.711(4)
1522.4(1)
2
1.478
1.049
700
0.50 · 0.30 · 0.14
2.99–27.54
ꢀ12 6 h 6 12,
ꢀ16 6 k 6 16,
ꢀ17 6 l 6 17
28956
10.887(2)
14.081(3)
16.238(3)
72.70(3)
76.57(3)
72.76(3)
2241.4(8)
2
1.506
1.069
1050
0.10 · 0.08 · 0.08
2.91–27.47
ꢀ14 6 h 6 14,
ꢀ18 6 k 6 18,
ꢀ21 6 l 6 21
47686
˚
b (A)
˚
c (A)
a (ꢀ)
b (ꢀ)
c (ꢀ)
3
˚
Volume (A )
Z
Dcalc (g/cm3)
Absorption coefficient (mmꢀ1
F(000)
)
1.099
1400
Crystal size (mm3)
0.10 · 0.10 · 0.05
2.98–27.48
ꢀ11 6 h 6 10,
ꢀ14 6 k 6 17,
ꢀ24 6 l 6 30
23640
h Range for data collection (ꢀ)
Index ranges
Reflections collected
Independent reflections (Rint
Maximum and
)
6621 (0.0418)
0.9471 and 0.8980
6973 (0.0383)
0.8670 and 0.6220
10182 (0.0536)
0.9193 and 0.9006
minimum transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [F2 > 4r(F2)]
R indices (all data)
full-matrix least-squares on F2
6621/0/356
full-matrix least-squares on F2
6973/0/355
full-matrix least-squares on F2
10182/0/571
1.036
1.031
1.035
R1 = 0.0351, wR2 = 0.0787
R1 = 0.0456, wR2 = 0.0843
0.356 and ꢀ0428
R1 = 0.0354, wR2 = 0.0830
R1 = 0.0503, wR2 = 0.0899
0.563 and ꢀ0.573
R1 = 0.0365, wR2 = 0.0785
R1 = 0.0545, wR2 = 0.0857
0.322 and ꢀ0.467
Largest difference
peak and hole (e A
ꢀ3
˚
)

950
A.L. Bingham et al. / Polyhedron 25 (2006) 945–952
Table 3
Table 4
a
˚
˚
Bond lengths (A) and angles (ꢀ) for Ni{S2[P(OC6H4CH3 -o)2]2}2 (1)
Selected bond lengths (A) and angles (ꢀ) for NiS2[P(OC6H4CH3-m)2]2 (2)
Ni(1)–S(1)
Ni(1)–S(2)
S(1)–P(1)
2.2415(6)
2.2241(6)
1.9839(7)
1.9850(7)
1.578(1)
1.595(1)
1.420(2)
1.418(2)
1.380(3)
1.388(3)
1.388(3)
1.387(3)
1.383(3)
1.391(3)
1.494(3)
1.384(3)
1.393(3)
1.395(3)
1.379(3)
1.382(3)
1.379(3)
1.493(3)
Ni(1)–S(3)
Ni(1)–S(4)
S(3)–P(2)
S(4)–P(2)
P(2)–O(3)
P(2)–O(4)
2.2353(6)
2.2318(6)
1.9854(7)
1.9820(7)
1.592(1)
1.579(1)
1.411(2)
1.419(2)
1.389(3)
1.390(3)
1.394(3)
1.375(3)
1.384(3)
1.383(3)
1.495(3)
1.372(3)
1.391(3)
1.394(3)
1.380(3)
1.380(3)
1.391(3)
1.498(3)
Molecule 1
Ni(1)–S(1)
Ni(1)–S(1)0
Ni(1)–S(2)
Ni(1)–S(2)0
S(1)–P(1)
Molecule 2
Ni(2)–S(3)
Ni(2)–S(3)00
Ni(2)–S(4)
Ni(2)–S(4)00
S(3)–P(2)
S(4)–P(2)
P(2)–O(3)
P(2)–O(4)
O(3)–C(15)
O(4)–C(22)
C(15)–C(20)
C(15)–C(16)
C(16)–C(17)
C(17)–C(18)
C(18)–C(19)
C(19)–C(20)
C(17)–C(21)
C(22)–C(27)
C(22)–C(23)
C(23)–C(24)
C(24)–C(25)
C(25)–C(26)
C(26)–C(27)
C(24)–C(28)
2.2421(6)
2.2421(6)
2.2310(6)
2.2310(6)
1.9884(8)
1.9778(8)
1.589(2)
1.579(2)
1.418(3)
1.417(3)
1.375(3)
1.381(3)
1.394(3)
1.395(4)
1.388(4)
1.393(4)
1.504(3)
1.376(3)
1.379(3)
1.394(3)
1.385(4)
1.388(4)
1.387(4)
1.516(4)
2.2430(6)
2.2430(6)
2.2286(6)
2.2286(6)
1.9849(8)
1.9774(8)
1.591(2)
1.582(2)
1.420(3)
1.420(3)
1.371(3)
1.384(3)
1.395(3)
1.391(4)
1.386(4)
1.391(4)
1.507(3)
1.381(4)
1.371(4)
1.394(4)
1.398(4)
1.376(4)
1.390(4)
1.498(4)
S(2)–P(1)
P(1)–O(1)
P(1)–O(2)
O(1)–C(1)
O(2)–C(8)
C(1)–C(6)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
C(2)–C(7)
C(8)–C(9)
C(8)–C(13)
C(9)–C(10)
C(10)–C(11)
C(11)–C(12)
C(12)–C(13)
C(9)–C(14)
O(3)–C(15)
O(4)–C(22)
C(15)–C(16)
C(15)–C(20)
C(16)–C(17)
C(17)–C(18)
C(18)–C(19)
C(19)–C(20)
C(16)–C(21)
C(22)–C(27)
C(22)–C(23)
C(23)–C(24)
C(24)–C(25)
C(25)–C(26)
C(26)–C(27)
C(23)–C(28)
S(2)–P(1)
P(1)–O(1)
P(1)–O(2)
O(1)–C(1)
O(2)–C(8)
C(1)–C(6)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
C(3)–C(7)
C(8)–C(13)
C(8)–C(9)
C(9)–C(10)
C(10)–C(11)
C(11)–C(12)
C(12)–C(13)
C(10)–C(14)
S(1)–Ni(1)–S(2)
S(1)–Ni(1)–S(3)
S(1)–Ni(1)–S(4)
Ni(1)–S(1)–P(1)
Ni(1)–S(2)–P(1)
S(1)–P(1)–S(2)
88.39(2)
178.51(2)
92.04(2)
83.86(3)
84.30(3)
103.32(3)
99.37(7)
108.82(6)
116.03(6)
114.41(6)
115.31(6)
126.4(1)
123.1(1)
123.0(2)
120.9(2)
116.1(2)
116.8(2)
121.9(2)
119.6(2)
120.1(3)
118.7(2)
121.7(2)
121.6(2)
122.8(2)
117.5(2)
119.5(2)
116.3(2)
121.9(2)
120.3(2)
119.7(2)
119.0(2)
122.6(2)
121.1(2)
S(3)–Ni(1)–S(4)
S(2)–Ni(1)–S(4)
S(2)–Ni(1)–S(3)
Ni(1)–S(3)–P(2)
Ni(1)–S(4)–P(2)
S(3)–P(2)–S(4)
O(3)–P(2)–O(4)
O(3)–P(2)–S(3)
88.59(2)
178.00(2)
91.03(2)
83.57(3)
83.74(3)
103.69(3)
99.24(7)
113.64(6)
115.39(6)
109.03(6)
116.29(6)
122.1(1)
124.3(1)
123.4(2)
118.3(2)
118.1(2)
115.7(2)
122.6(2)
119.8(2)
120.2(2)
118.4(2)
122.1(2)
122.2(2)
122.9(2)
120.6(2)
116.4(2)
116.9(2)
121.4(2)
120.1(2)
120.1(2)
118.8(2)
121.4(2)
121.8(2)
S(1)–Ni(1)–S(2)
S(1)0–Ni(1)–S(2)0
S(1)–Ni(1)–S(1)0
S(2)–Ni(1)–S(2)0
S(1)0–Ni(1)–S(2)
S(1)–Ni(1)–S(2)0
Ni(1)–S(1)–P(1)
Ni(1)–S(2)–P(1)
S(1)–P(1)–S(2)
O(1)–P(1)–O(2)
O(1)–P(1)–S(1)
O(1)–P(1)–S(2)
O(2)–P(1)–S(2)
O(2)–P(1)–S(1)
C(1)–O(1)–P(1)
C(8)–O(2)–P(1)
C(2)–C(1)–C(6)
C(6)–C(1)–O(1)
C(2)–C(1)–O(1)
C(1)–C(2)–C(3)
C(2)–C(3)–C(4)
C(3)–C(4)–C(5)
C(4)–C(5)–C(6)
C(5)–C(6)–C(1)
C(2)–C(3)–C(7)
C(4)–C(3)–C(7)
C(9)–C(8)–C(13)
C(13)–C(8)–O(2)
C(9)–C(8)–O(2)
C(8)–C(9)–C(10)
C(9)–C(10)–C(11)
C(10)–C(11)–C(12)
C(11)–C(12)–C(13)
C(12)–C(13)–C(8)
C(9)–C(10)–C(14)
C(11)–C(10)–C(14)
a
88.79(2)
88.79(2)
180.00
S(3)–Ni(2)–S(4)
89.18(2)
89.18(2)
180.00
S(3)00–Ni(2)–S(4)00
S(3)–Ni(2)–S(3)00
S(4)–Ni(2)–S(4)00
S(3)00–Ni(2)–S(4)
S(3)–Ni(2)–S(4)00
Ni(2)–S(3)–P(2)
O(1)–P(1)–O(2)
O(1)–P(1)–S(1)
O(1)–P(1)–S(2)
O(2)–P(1)–S(2)
O(2)–P(1)–S(1)
C(1)–O(1)–P(1)
C(8)–O(2)–P(1)
C(2)–C(1)–C(6)
C(6)–C(1)–O(1)
C(2)–C(1)–O(1)
C(1)–C(2)–C(3)
C(2)–C(3)–C(4)
C(3)–C(4)–C(5)
C(4)–C(5)–C(6)
C(5)–C(6)–C(1)
C(1)–C(2)–C(7)
C(3)–C(2)–C(7)
C(9)–C(8)–C(13)
C(13)–C(8)–O(2)
C(9)–C(8)–O(2)
C(8)–C(9)–C(10)
C(9)–C(10)–C(11)
C(10)–C(11)–C(12)
C(11)–C(12)–C(13)
C(12)–C(13)–C(8)
C(8)–C(9)–C(14)
C(10)–C(9)–C(14)
180.00
180.00
91.21(2)
91.21(2)
82.95(3)
83.47(3)
104.18(4)
100.20(9)
113.01(7)
115.74(7)
108.70(7)
115.39(7)
120.9(1)
124.9(1)
122.9(2)
118.5(2)
118.6(2)
119.4(2)
118.3(2)
121.3(2)
120.1(2)
117.9(2)
120.1(2)
121.5(2)
122.7(2)
119.6(2)
117.5(2)
119.6(2)
118.3(2)
121.1(2)
120.7(2)
117.6(2)
120.0(2)
121.6(2)
90.82(2)
90.82(2)
82.41(3)
82.95(3)
104.80(4)
99.83(9)
113.63(7)
115.05(7)
108.64(7)
115.17(7)
119.9(1)
123.1(2)
122.7(2)
118.5(2)
118.7(2)
119.3(2)
118.4(2)
121.2(2)
120.3(2)
118.0(2)
120.2(2)
121.4(2)
122.9(2)
120.0(2)
117.0(2)
120.0(2)
117.5(3)
121.6(3)
120.8(3)
117.2(2)
120.6(3)
121.9(3)
O(3)–P(2)–S(4)
O(4)–P(2)–S(4)
O(4)–P(2)–S(3)
Ni(2)–S(4)–P(2)
S(3)–P(2)–S(4)
O(3)–P(2)–O(4)
O(3)–P(2)–S(3)
O(3)–P(2)–S(4)
O(4)–P(2)–S(4)
O(4)–P(2)–S(3)
C(15)–O(3)–P(2)
C(22)–O(4)–P(2)
C(16)–C(15)–C(20)
C(20)–C(15)–O(3)
C(16)–C(15)–O(3)
C(15)–C(16)–C(17)
C(16)–C(17)–C(18)
C(17)–C(18)–C(19)
C(18)–C(19)–C(20)
C(19)–C(20)–C(15)
C(15)–C(16)–C(21)
C(17)–C(16)–C(21)
C(23)–C(22)–C(27)
C(27)–C(22)–O(4)
C(23)–C(22)–O(4)
C(22)–C(23)–C(24)
C(23)–C(24)–C(25)
C(24)–C(25)–C(26)
C(25)–C(26)–C(27)
C(26)–C(27)–C(22)
C(22)–C(23)–C(28)
C(24)–C(23)–C(28)
C(15)–O(3)–P(2)
C(22)–O(4)–P(2)
C(16)–C(15)–C(20)
C(20)–C(15)–O(3)
C(16)–C(15)–O(3)
C(15)–C(16)–C(17)
C(16)–C(17)–C(18)
C(17)–C(18)–C(19)
C(18)–C(19)–C(20)
C(19)–C(20)–C(15)
C(16)–C(17)–C(21)
C(18)–C(17)–C(21)
C(23)–C(22)–C(27)
C(27)–C(22)–O(4)
C(23)–C(22)–O(4)
C(22)–C(23)–C(24)
C(23)–C(24)–C(25)
C(24)–C(25)–C(26)
C(25)–C(26)–C(27)
C(26)–C(27)–C(22)
C(23)–C(24)–C(28)
C(25)–C(24)–C(28)
3.3. X-ray diffraction analysis
A translucent purple, block crystal of Ni[S2P(OC6H4-
Me-o)2]2, a brown/purple, slab crystal of NiS2[P(OC6H4-
Me-m)2]2 and a pink/purple block crystal of Ni[S2-
P(OCH2-Ph)2]2 were mounted on glass fibres. Data were
collected on a Bruker-Nonius Kappa CCD area detector
Symmetry equivalent positions (x + 1, ꢀy + 1, ꢀz) given by a prime
and (ꢀx, ꢀy, ꢀz) by a double prime.

A.L. Bingham et al. / Polyhedron 25 (2006) 945–952
951
diffractometer, with / and x scans chosen to give a com-
plete asymmetric unit. Cell refinement [35] gave cell con-
stants corresponding to a monoclinic for 1 and triclinic
cells for 2 and 5 whose dimensions are given in Table 2
along with other experimental parameters. An absorption
correction was applied [36].
The structure was solved by direct methods [37] and was
refined using the WINGX version [38] of SHELXL97 [39]. All
of the non-hydrogen atoms were treated anisotropically.
Hydrogen atoms were included in idealized positions with
isotropic thermal parameters set at 1.2 times that of the
carbon atom to which they were attached. The final cycle
Table 5
a
˚
Bond lengths (A) and angles (ꢀ) for Ni[S2P(OCH2Ph)2]2
Molecule 1
Molecule 2
Ni(1)–S(1)
Ni(1)–S(2)
S(1)–P(1)
2.233(1)
2.2343(8)
1.9900(9)
1.999(1)
1.583(2)
1.571(2)
1.471(3)
1.466(3)
1.505(3)
1.385(3)
1.387(3)
1.390(3)
1.383(4)
1.384(4)
1.385(3)
1.507(3)
1.388(3)
1.388(3)
1.389(3)
1.380(4)
1.388(4)
1.385(3)
Ni(1)–S(3)
Ni(1)–S(4)
S(3)–P(2)
S(4)–P(2)
P(2)–O(3)
P(2)–O(4)
2.227(1)
2.2469(8)
1.9934(9)
1.993(1)
1.577(2)
1.583(2)
1.475(3)
1.464(2)
1.502(3)
1.382(3)
1.390(3)
1.390(3)
1.381(3)
1.381(4)
1.391(3)
1.498(3)
1.388(3)
1.393(3)
1.391(3)
1.382(3)
1.382(3)
1.391(3)
Ni(2)–S(5)
Ni(2)–S(6)
S(5)–P(3)
S(6)–P(3)
P(3)–O(5)
P(3)–O(6)
2.236(1)
2.2313(8)
2.0026(9)
1.996(1)
1.575(2)
1.579(2)
1.472(3)
1.475(3)
1.498(3)
1.383(3)
1.385(3)
1.386(3)
1.388(4)
1.374(4)
1.391(4)
1.494(3)
1.392(3)
1.394(3)
1.384(3)
1.389(4)
1.379(4)
1.388(3)
S(2)–P(1)
P(1)–O(1)
P(1)–O(2)
O(1)–C(1)
O(2)–C(8)
C(1)–C(2)
C(2)–C(7)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
C(6)–C(7)
C(8)–C(9)
C(9)–C(10)
C(9)–C(14)
C(10)–C(11)
C(11)–C(12)
C(12)–C(13)
C(13)–C(14)
O(3)–C(15)
O(4)–C(22)
C(15)–C(16)
C(16)–C(21)
C(16)–C(17)
C(17)–C(18)
C(18)–C(19)
C(19)–C(20)
C(20)–C(21)
C(22)–C(23)
C(23)–C(28)
C(23)–C(24)
C(24)–C(25)
C(25)–C(26)
C(26)–C(27)
C(27)–C(28)
O(5)–C(29)
O(6)–C(36)
C(29)–C(30)
C(30)–C(31)
C(30)–C(35)
C(31)–C(32)
C(32)–C(33)
C(33)–C(34)
C(34)–C(35)
C(36)–C(37)
C(37)–C(38)
C(37)–C(42)
C(38)–C(39)
C(39)–C(40)
C(40)–C(41)
C(41)–C(42)
S(1)–Ni(1)–S(2)
S(1)–Ni(1)–S(3)
S(1)–Ni(1)–S(4)
Ni(1)–S(1)–P(1)
Ni(1)–S(2)–P(1)
S(1)–P(1)–S(2)
O(1)–P(1)–O(2)
O(1)–P(1)–S(1)
O(1)–P(1)–S(2)
O(2)–P(1)–S(2)
O(2)–P(1)–S(1)
C(1)–O(1)–P(1)
C(8)–O(2)–P(1)
O(1)–C(1)–C(2)
C(7)–C(2)–C(3)
C(7)–C(2)–C(1)
C(3)–C(2)–C(1)
C(2)–C(3)–C(4)
C(5)–C(4)–C(3)
C(4)–C(5)–C(6)
C(5)–C(6)–C(7)
C(2)–C(7)–C(6)
O(2)–C(8)–C(9)
C(10)–C(9)–C(14)
C(10)–C(9)–C(8)
C(14)–C(9)–C(8)
C(9)–C(10)–C(11)
C(12)–C(11)–C(10)
C(11)–C(12)–C(13)
C(14)–C(13)–C(12)
C(13)–C(14)–C(9)
a
88.52(3)
178.39(2)
92.86(3)
84.10(3)
83.86(3)
102.81(4)
101.04(9)
115.07(7)
112.30(7)
115.14(7)
111.00(7)
118.9(1)
121.9(1)
108.1(2)
119.3(2)
119.8(2)
120.8(2)
120.5(2)
119.7(2)
120.1(2)
120.1(2)
120.3(2)
108.7(2)
119.1(2)
120.3(2)
120.6(2)
120.4(2)
120.4(2)
119.4(2)
120.4(3)
120.4(2)
S(3)–Ni(1)–S(4)
S(2)–Ni(1)–S(4)
S(2)–Ni(1)–S(3)
Ni(1)–S(3)–P(2)
Ni(2)–S(4)–P(2)
S(3)–P(2)–S(4)
O(3)–P(2)–O(4)
O(3)–P(2)–S(3)
88.00(3)
178.24(2)
90.66(3)
84.61(3)
84.09(3)
102.44(4)
95.22(8)
114.76(7)
114.12(7)
115.83(7)
115.19(7)
119.2(1)
120.7(1)
107.4(2)
119.4(2)
119.6(2)
121.0(2)
120.5(2)
119.6(2)
120.2(2)
120.0(2)
120.2(2)
108.6(2)
118.7(2)
120.0(2)
121.3(2)
120.4(2)
120.1(2)
120.1(2)
119.6(2)
121.1(2)
S(5)–Ni(2)–S(6)
87.95(3)
180.00
S(5)–Ni(2)–S(5)00
S(5)–Ni(2)–S(6)00
Ni(2)–S(5)–P(3)
92.05(3)
84.73(3)
85.00(3)
101.73(4)
96.56(9)
115.38(7)
115.89(7)
114.23(7)
113.82(7)
121.2(1)
119.4(1)
109.9(2)
119.4(2)
120.1(2)
120.4(2)
120.5(2)
119.9(3)
119.9(2)
120.2(3)
120.1(2)
108.3(2)
118.7(2)
119.8(2)
121.5(2)
120.8(2)
119.8(2)
120.1(2)
120.1(2)
120.5(2)
Ni(2)–S(6)–P(3)
S(5)–P(3)–S(6)
O(5)–P(3)–O(6)
O(5)–P(3)–S(5)
O(5)–P(3)–S(6)
O(6)–P(3)–S(6)
O(6)–P(3)–S(5)
O(3)–P(2)–S(4)
O(4)–P(2)–S(4)
O(4)–P(2)–S(3)
C(15)–O(3)–P(2)
C(22)–O(4)–P(2)
O(3)–C(15)–C(16)
C(21)–C(16)–C(17)
C(21)–C(16)–C(15)
C(17)–C(16)–C(15)
C(18)–C(17)–C(16)
C(19)–C(18)–C(17)
C(18)–C(19)–C(20)
C(19)–C(20)–C(21)
C(16)–C(21)–C(20)
O(4)–C(22)–C(23)
C(28)–C(23)–C(24)
C(28)–C(23)–C(22)
C(24)–C(23)–C(22)
C(25)–C(24)–C(23)
C(26)–C(25)–C(24)
C(27)–C(26)–C(25)
C(26)–C(27)–C(28)
C(23)–C(28)–C(27)
C(29)–O(5)–P(3)
C(36)–O(6)–P(3)
O(5)–C(29)–C(30)
C(31)–C(30)–C(35)
C(31)–C(30)–C(29)
C(35)–C(30)–C(29)
C(30)–C(31)–C(32)
C(31)–C(32)–C(33)
C(34)–C(33)–C(32)
C(33)–C(34)–C(35)
C(30)–C(35)–C(34)
O(6)–C(36)–C(37)
C(38)–C(37)–C(42)
C(38)–C(37)–C(36)
C(42)–C(37)–C(36)
C(39)–C(38)–C(37)
C(38)–C(39)–C(40)
C(41)–C(40)–C(39)
C(40)–C(41)–C(42)
C(41)–C(42)–C(37)
Symmetry equivalent positions (ꢀx + 1, ꢀy, ꢀz + 1) given by a double prime and equivalent distances and angles not listed are Ni(2)–S(5)00 2.236(1),
Ni(2)–S(6)00 2.2313(8) A; S(6) –Ni(2)–S(5) 87.95(3)ꢀ, S(6)–Ni(2)–S(6)00 180.00ꢀ, S(6)–Ni(2)–S(5)00 92.05(3)ꢀ.
00
00
˚

952
A.L. Bingham et al. / Polyhedron 25 (2006) 945–952
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(for 1), 6973 (for 2) and 10182 (for 5), observed reflections
(5515 (for 1), 5651 (for 2) and 7969 (for 5) for F2 > 4r(F2))
and 356 (for 1), 355 (for 2) and 571 (for 5) variable param-
eters and converged (largest parameter shift was 0.001
times its esd).
Selected distances and bond angles are given in Tables
3–5 for molecules 1, 2 and 5, respectively, and ORTEP dia-
gram are displayed in Figs. 1–3.
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4. Concluding comments
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We have successfully prepared and characterized the fol-
lowing complexes, Ni[S2P(OC6H4Me-o)2]2, Ni[S2P(OC6H4-
Me-m)2]2, Ni[S2P(OC6H4CH3-p)2]2, Ni[S2P(OC6H5)2]2 and
1
Ni[S2P(OCH2Ph)2]2. The IR, UV–Vis and H NMR spec-
tra of all of these nickel complexes are consistent with
the proposed structure. The molecular structures of Ni[S2P-
(OC6H4Me-o)2]2, Ni[S2P(OC6H4Me-m)2]2 and Ni[S2P-
(OCH2Ph)2]2 were all determined to have a distorted
square-planar environment around nickel, as has been
found for the structures reported for the analogues, com-
plexes Ni[S2P(OEt)2]2 and Ni[S2P(OPri)2]2.
5. Supplementary material
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Additional material available from the Cambridge Crys-
tallographic Data Centre (CCDC Nos. 280426, 280427, and
280706 for Ni[S2P(OC6H4Me-o)2]2, Ni[S2P(OC6H4Me-m)2]2,
and Ni[S2P(OCH2Ph)2]2, respectively, comprises the final
atomic coordinates for all atoms, thermal parameters,
and a complete listing of bond distances and angles). Cop-
ies of this information may be obtained free of charge on
application to The Director, 12 Union Road, Cambridge
CB2 2EZ, UK (fax: +44 1223 336033; email: deposit@
ccdc.cam.ac.uk or http://www.ccdc. cam.ac.uk).
Acknowledgements
One of us (M.N.) is grateful to CSIR, New Delhi for
financial support. M.E.L. thanks the UK Engineering
and Physical Sciences Council for support of the X-ray
facilities at Southampton University. J.E.D. wishes to
thank the University of Windsor for financial support.
We are thankful to RSIC, CDRI, Lucknow for the spectral
analyses.
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