Synthesis, characterization and spectral studies of nitrogen base adducts of bis(O,O′-ditolyldithiophosphato)nickel(II). Crystal structures of Ni[S2P(OC6H4Me-p)2] 2 · C10H8N

Article abstract of DOI:10.1016/j.poly.2007.01.003

Title full: Synthesis, characterization and spectral studies of nitrogen base adducts of bis(O,O′-ditolyldithiophosphato)nickel(II). Crystal structures of Ni[S₂P(OC₆H₄Me-p)₂] ₂ · C₁₀H₈

Full text of DOI:10.1016/j.poly.2007.01.003

Polyhedron 26 (2007) 2672–2678
www.elsevier.com/locate/poly
Synthesis, characterization and spectral studies of nitrogen base
adducts of bis(O,O0-ditolyldithiophosphato)nickel(II).
Crystal structures of Ni[S2P(OC6H4Me-p)2]2 Æ C10H8N2 and
Ni[S2P(OC6H4Me-o)2]2 Æ C14H12N2 Æ C6H6
a
b
a
Ann L. Bingham , John E. Drake , Michael B. Hursthouse ,
a
c
c,
*
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
b
c
Department of Pure and Applied Chemistry, MDS University, Ajmer 305 009, India
Received 18 December 2006; accepted 10 January 2007
Available online 14 January 2007
Abstract
Reactions of Ni[S2P(OR)2]2(R = o-, m- and p-C6H4Me) with nitrogen donor ligands, viz. pyridine (C5H5N or py), 2,20-bipyridyl
(C10H8N2 or bipy) and 2,9-dimethyl-1,10-phenanthroline (C14H12N2 or dmphen) were carried out in benzene to yield green paramagnetic
solids. These adducts were characterized by UV–visible and IR spectroscopy, magnetic measurements and, in two cases, by X-ray
crystallography, to indicate how the number of donor atoms and steric factors affect the Ni–S bonding. The molecular structures of
2,20-bipyridylbis {O,O0-di(p-tolyl)dithiophosphate}nickel(II), Ni[S2P(OC6H4Me-p)2]2 Æ C10H8N2 and 2,9-dimethyl-1,10-phenanthroline-
bis{O,O0-di(o-tolyl)dithiophosphate}nickel(II), Ni[S2P(OC6H4Me-o)2]2 Æ C14H12N2 Æ C6H6 are described. The geometry around nickel
in the bipyridyl adduct is distorted octahedral with NiS4N2 coordination, whereas in the 2,9-dimethyl-1,10-phenanthroline adduct it
is trigonal bipyramidal with NiS3N2 coordination in which one dithiophosphate moiety is bidentate and the other is monodentate.
ꢀ 2007 Elsevier Ltd. All rights reserved.
Keywords: Synthesis; Nickel adducts; Structure; 2,20-Bipyridyl; 2,9-Dimethyl-1,10-phenanthroline
1. Introduction
industry [13] and for their insecticidal activity [14]. Synthe-
ses, along with extensive spectroscopic studies, have been
reported for nickel(II) dithiophosphate adducts with
monodentate nitrogen base ligands such as pyridine (py),
4-picoline, and primary amines [9,15–17] as well as with
bidentate ligands such as bipyridyl (C10H8N2 or bipy), phe-
nanthroline (phen), 2,9-dimethyl-1,10-phenanthroline
(C14H12N2 or dmphen) and aromatic primary diamines
[8,16–20]. X-ray structures have been reported for Ni[S2P-
(OEt)2]2(py)2 [21], Ni[S2P(OPri)2]2(py)2 [22], Ni[S2P-
(OPri)2]2(2-aminopyridine-N)2 [23], Ni[S2P(OMe)2]2(phen)
[24], Ni[S2P(OBun)2]2(bipy) [25], Ni[S2P(OMe)2]2(dmphen)
[24], Ni[S2P(OCMe2CMe2O)2]2(dmphen) [26] and Ni[S2P-
(OC6H4Me-p)2]2(phen) [27].
The coordination chemistry of nickel with dialkyl(acy-
clic) [1–5] and alkylene(cyclic) [6–12] dithiophosphate
ligands has been explored extensively in the past three dec-
ades yielding several four coordinate square planar com-
plexes. These square planar complexes can be stabilized
by the formation of adducts with neutral donor ligands
to yield five and six coordinate adducts. Adducts of nickel
(II) dithiophosphate with nitrogen donor ligands have been
used as antioxidants and antiwear additives in the rubber
*
Corresponding author. Tel.: +91 11 145 2640059.
E-mail address: ratnaniraju@yahoo.co.uk (R. Ratnani).
0277-5387/$ - see front matter ꢀ 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2007.01.003

A.L. Bingham et al. / Polyhedron 26 (2007) 2672–2678
2673
The continuation of our interest in various dithiophos-
phate ligands led us to work on the reactions of aryl dithio-
phosphate nickel complexes with nitrogen donor moieties
to examine how the aromatic moiety influences coordina-
tion with the metal. Thus, we report the syntheses of nickel
(II) adducts of the general type Ni[S2P(OR)2]2 Æ nL (where
R = o-, m-, p-C6H4Me; n = 2, L = C5H5N; n = 1, L =
C10H8N2, C14H12N2) and their characterization by various
spectroscopic techniques. We also report the molecular
structures of Ni[S2P(OC6H4Me-p)2]2 Æ C10H8N2 and Ni[S2P-
(OC6H4Me-o)2]2 Æ C14H12N2 Æ C6H6.
the ligands. The presence of medium to weak bands in
the regions 380–362 and 344–324 cmꢂ1 have been assigned
to m(Ni–S) vibrations consistent with the metal sulfur bond-
ing. One or two peaks due to m(C–N) vibrations appears in
the region 1604–1579 cmꢂ1 suggests the formation of
adducts.
2.2. UV–visible spectra
The spectra of the adducts of bis(O,O0-ditolyl dithio-
phosphato)nickel(II) recorded in CH2Cl2 (Table 2) show
3
three absorption bands corresponding to 3A2g ! T2g,
3
3
3
2. Results and discussion
3A2g ! T1g(F), A2g ! T1g(P) transitions expected for
octahedral nickel species [16,18]. The first band correspond-
3
3
Reactions of bis (O,O0-ditolyldithiophosphato)nickel(II)
complexes were carried out with pyridine or 2,20-bipyridyl
or 2,9-dimethyl-1,10-phenanthroline in benzene
ing to A2g ! T2g transition is obtained in the range of
3 3
1102–1130 nm. The second absorption A2g ! T1g(F) is
observed in the range 727–735, 654–658 for pyridine and
bipyridyl adducts, respectively but split in two absorptions
in the range 676–686 and 866–886 nm for 2,9-dimethyl-
1,10-phenanthroline adducts. This split is probably due to
Ni½S2PðORÞ2ꢀ2 þ nL ! Ni½S2PðORÞ2ꢀ2 ꢁ nL
ð1Þ
(R = o-, m-, p-C6H4Me; n = 2, L = C5H5N; n = 1, L =
C10H8N2, C14H12N2)
The purple colour changed on addition of nitrogen base
to give a consistent green colour on addition of a slight
excess of base. In each case a green powder (yield, 67–
78%), soluble in organic solvents, was obtained.
1
3
spin-orbit coupling of E(D) with T1g. The third band,
3
3A2g ! T1g is seen in the range of 447–451, 416–422 and
423–441 nm for pyridine, bipyridyl and 2,9-dimethyl-1,10-
phenanthroline adducts, respectively.
2.3. Magnetic moments measurements
2.1. IR spectra
The magnetic measurements (Table 2) for nitrogen base
adducts of bis(O,O0-ditolyldithiophosphato)nickel(II)
obtained in the range of 3.20–3.26 BM at 298 K indicate
the presence of two unpaired electrons. Similar values are
found in the literature for a number of other bis(O,O0-di-
tolyldithiophosphato)nickel(II) adducts [16].
The IR spectra of the nitrogen base adducts of bis(O,O0-
ditolyl dithiophosphato)nickel(II) were measured over the
range of 4000–200 cmꢂ1. The assignments of the relevant
IR bands (Table 1) were made by comparisons with the
spectra of the corresponding nickel(II) O,O0-ditolyldithio-
phosphate complexes [28]. The two strong intensity bands
present in the 1168–1123 and 841–790 cmꢂ1 regions are
assigned to m[(P)–O–C] and m[P–O–(C)] stretching vibra-
tions, respectively. Bands due to m(P–S)asym and m(P–S)sym
observed at 693–656 and 568–516 cmꢂ1 in adducts 1–9,
indicate a slight change in the bonding patterns of the
dithiophosphate moieties upon adduct formation. How-
ever, in case of dmphen adducts, 7–9 additional bands cor-
responding to m(P–S)asym and m(P–S)sym are also observed
suggesting the S-mondentate and S,S-chelating nature of
2.4. Molecular structures of Ni[S2P(OC6H4Me-p)2]2 Æ
C10H8N2 (6) and Ni[S2P(OC6H4Me-o)2]2 Æ
C14H12N2 Æ C6H6 (7)
Ni[S2P(OC6H4Me-p)2]2 Æ C10H8N2 (6) and Ni[S2P-
(OC6H4Me-o)2]2 Æ C14H12N2 Æ C6H6 (7), crystallize as
ꢀ
triclinic and monoclinic in space groups P1 and P21/c,
respectively. The ORTEP diagrams in Figs. 1 and 2 illus-
trate that in 6 the nickel atom lies at the centre of a
Table 1
IR spectral data (cmꢂ1) for the nitrogen base adducts of bis(O,O0-ditolyldithiophosphate)nickel(II) complexesa
No.
Compound
m(C–N)
m[(P)–O–C]
m[P–O–(C)]
m(P–S)asym.
m(P–S)sym
m(Ni–S)
1
2
3
4
5
6
7
8
9
a
Ni[S2P(OC6H4Me-o)2]2(C5H5N)2
Ni[S2P(OC6H4Me-m)2]2(C5H5N)2
Ni[S2P(OC6H4Me-p)2]2(C5H5N)2
Ni[S2P(OC6H4Me-o)2]2 Æ N2C10H8
Ni[S2P(OC6H4Me-m)2]2 Æ N2C10H8
Ni[S2P(OC6H4Me-p)2]2 Æ N2C10H8
Ni[S2P(OC6H4Me-o)2]2 Æ N2C14H12
Ni[S2P(OC6H4Me-m)2]2 Æ N2C14H12
Ni[S2P(OC6H4Me-p)2]2 Æ N2C14H12
1585 m
1584 s
1598 m
1581, 1603 m
1590 m
1595, 1604 m
1579 m
1590 m
1142 s
1123 s
1162 m
1130 s
1130 s
1153 m
1167 s
1139 m
1168 s
820 s
824 s
822 s
831 s
831 s
812 m
790 m 674 m,
841 m 680 m,
790 s
682 s
687 s
693 m
681 s
685 s
555 m
568 m
535 s
565 m
564 m
556 m
549 sh
560 sh
550 m, 516 m
370 w, 324 w
365 w, 325 w
370 w, 333 w
367 w, 344w
362 w, 327w
377 w, 328 w
380 m, 330 m
377 w, 328 w
378 w, 325 w
680 s
657 m
665 m
672 s, 656,m
1580, 1592 m
Key: s = strong, m = medium, w = weak, sh = shoulder.

2674
A.L. Bingham et al. / Polyhedron 26 (2007) 2672–2678
Table 2
in the two bidentate dithiophosphate ligands and in the
range of other analogous six-coordinated compounds,
Electronic spectra and magnetic moments for the nitrogen base adducts of
bis(O,O0-ditolyldithiophosphate)nickel(II) complexes
n
˚
Ni[S2P(OBu )2]2(bipy) (2.463(2)–2.524(2) A) [25], Ni[S2-
S. no. Compound
Kmax (nm)
leff (BM)
˚
P(OMe)2]2(phen) (2.47(1)–2.52(1) A) [24] and Ni[S2P-
˚
1
2
3
4
5
6
7
8
9
Ni[S2P(OC6H4Me-o)2]2(C5H5N)2
1120, 735, 451 3.20
1110, 727, 447 3.19
1130, 734, 449 3.22
1130, 658, 418 3.23
(OC6H4Me-p)2]2(phen) (2.486(1)–2.532(1) A) [27]. The
Ni[S2P(OC6H4Me-m)2]2(C5H5N)2
Ni[S2P(OC6H4Me-p)2]2(C5H5N)2
Ni[S2P(OC6H4CH3-o)2]2 Æ N2C10H8
distances are significantly larger and cover a larger range
than in the four-coordinate precursors Ni[S2P(OC6H4Me-
˚
p)2]2 (average 2.332(2) A) [29] and Ni[S2P(OC6H4Me-o)2]2
Ni[S2P(OC6H4CH3-m)2]2 Æ N2C10H8 1114, 656, 416 3.21
Ni[S2P(OC6H4CH3-p)2]2 Æ N2C10H8 1102, 654, 422 3.23
Ni[S2P(OC6H4CH3-o)2]2 Æ N2C14H12 1105, 676, 430 3.25
Ni[S2P(OC6H4CH3-m)2]2 Æ N2C14H12 1125, 676, 441 3.23
Ni[S2P(OC6H4CH3-p)2]2 Æ N2C14H12 1110, 686, 423 3.24
˚
(average 2.233(8) A) [28]. By contrast, in Ni[S2P(OC6H4-
Me-o)2]2 Æ (C14H12N2) Æ C6H6 (7), the bidentate dithiophos-
phate ligand, with Ni–S bond lengths of 2.352(1) and
˚
2.539(1) A, might more accurately be defined as anisobi-
dentate, while the second dithiophosphate ligand is clearly
˚
distorted octahedral, NiN2S4, chromophore whereas in 7
the geometry around nickel is that of a distorted trigonal
bipyramidal, NiN2S3 chromophore. Solvent benzene
molecules are also incorporated into the crystal of the lat-
ter. In 6 the square planar structure of Ni[S2P(OC6H4Me-
p)2]2 [29] has readily accommodated the introduction of
bipy while maintaining the integrity of the two bidentate
S2P(OC6H4Me-p)2 ligands, as was also found for Ni[S2-
monodentate with Ni(1)–S(3) at 2.386(1) A and Ni(1)–S(4)
˚
at 5.462(2) A. The closest approach of this pendant S atom
to the Ni atom of the nearest adjacent molecule is
7.208(2) A. Similar behavior is seen in the analogous five-
coordinate complexes, Ni[S2P(OMe)2]2(dmphen) [24] and
Ni[S2P(OCMe2CMe2O)2]2(dmphen) [26], with the monod-
entate Ni–S bonds 2.42(1) and 2.398(3) A, respectively,
and the (aniso)bidentate ligands having Ni–S distances
ranging from 2.30(1) to 2.58(1) A. The Ni–N bond lengths
are similar in 6 (2.060(1) and 2.079(1) A) and 7 (2.010(1)
˚
˚
˚
P(OC6H4Me-p)2]2(phen) [27]. By contrast, in
7 the
˚
analogous distorted square planar structure of Ni[S2-
P(OC6H4Me-o)2]2 [28] with two bidentate ligands is not
maintained in the presence of dmphen because the cleavage
of one Ni–S bond results in the formation of a monoden-
tate ligand. The presence of methyl groups in 7 on the
nitrogen base, dmph increases the crowding near Ni atom
resulting the cleavage of one Ni–S bond. Hence one of
the ligand is rendered as monodentate and other as biden-
tate. The cis orientation of the nitrogen donor atoms is also
responsible for this cleavage.
˚
and 2.009(1) A) which is in good agreement with the
distances found in the six-coordinate analogues, Ni[S2P-
n
˚
(OBu )2]2(bipy) (2.088(4) and 2.089(4) A) [25], Ni[S2P-
˚
(OMe)2]2(phen) (2.08(1) and 2.09(1) A) [24] and Ni[S2-
P(OC6H4Me-p)2]2(phen) (2.082(3) and 2.086(3) A) [27] as
well as in the five-coordinate analogues Ni[S2P-
(OMe)2]2(dmphen) (1.97(1) and 2.03(1) A) [24] and Ni[S2P-
˚
˚
˚
(OCMe2CMe2O)2]2(dmphen) (2.005(8) and 2.015(7) A)
[26]. Although the differences are small, the trend of
slightly shorter Ni–N bonds in the five coordinate com-
plexes is clear and suggestive of slightly stronger bonding
In Ni[S2P(OC6H4Me-p)2]2(C10H8 N2) (6), all four Ni–S
˚
bond lengths are fairly similar (2.4757(7) to 2.5096(6) A)
Fig. 1. ORTEP plot of the molecule Ni[S2P(OC6H4Me-p)2]2 Æ C10H8N2. The non-hydrogen atoms are drawn with 50% probability ellipsoids.

A.L. Bingham et al. / Polyhedron 26 (2007) 2672–2678
2675
Fig. 2. ORTEP plot of Ni[S2P(OC6H4Me-o)2]2 Æ C14H12N2 Æ C6H6. The non-hydrogen atoms are drawn with 25% probability ellipsoids and the benzene
molecule is omitted for clarity.
when accommodation has been made to incorporate the
bulkier nitrogen ligand by the cleavage of an Ni–S bond
and reorientation of the resulting monodentate sulfur
ligand. The average lengths of the four P–S bonds in 6
are the same as in Ni[S2P(OC6H4Me-p)2]2 (average
Ni[S2P(OMe)2]2 Æ phen and Ni[S2P(OC6H4Me-p)2]2 Æ phen
(average 79.4(3)ꢁ) and five coordinate analogues Ni[S2P-
(OCMe2CMe2O)2]2 Æ dmphen and Ni[S2P(OMe)2]2 Æ dm-
phen (average 82.5(0.3)ꢁ), respectively. In 6, the least
deviation from 180ꢁ involves the two shorter (stronger)
Ni–S bonds in the bidentate ligands (S(1)–N(1)–S(4)
(173.09(2)ꢁ), while those involving the donor and the longer
Ni–S bonds are slightly more deviated with N–Ni–S angles
of 171.63(4)ꢁ and 168.03(4)ꢁ. The three cis S–Ni–S angles,
other than the ligand bite angles, cover the range 91.33–
93.53ꢁ, whereas the six involving S–Ni–N angles range
from 88.41(4)ꢁ to 97.18(4)ꢁ. In 7, the axial positions of
the distorted trigonal bipyramid are occupied by the
Ni–S bond of the monodentate ligand and the longer Ni–
S bond of the (aniso)bidentate ligand (S(2)–Ni(1)–S(3)
167.05(5)ꢁ). The sum of the three angles in the trigonal
plane (S(1)–Ni(1)–N(1) 134.3(1)ꢁ, S(1)–Ni(1)–N(2)
142.1(1)ꢁ and N(1)–Ni(1)–N(2) 82.6(2)ꢁ) is 359.1ꢁ. The
dmphen group is also essentially in the equatorial plane.
Similar corresponding angles have been reported for Ni[S2-
POCMe2CMe2O)2]2 Æ dmphen (axial S–Ni–S 169.1(1)ꢁ;
equatorial S–Ni–N 131.1(3)ꢁ, S–Ni–N 144.3(2)ꢁ and N1–
Ni–N 82.5(3)ꢁ) [26] and Ni[S2P(OMe)2]2 Æ dmphen (axial
S–Ni–S 165.8(1)ꢁ; equatorial S–Ni–N 130.2(3)ꢁ,
S–Ni–N 145.7(2)ꢁ and N1–Ni–N 82.4(43)ꢁ) [24].
˚
1.973(6) A) which suggests that the competitive chelation
of sulfur and nitrogen donor atoms has no significant influ-
ence on the partial double bond character of these P–S
bonds. In 7, the P(2)–S(4) bond of the pendant, non-inter-
˚
acting sulfur atom is by far the shortest (1.941(2) A), with
the P(1)–S(2) bond associated with the much longer Ni(1)–
S(2) bond in the anisobidentate ligand being somewhat
˚
longer (1.969(2) A). The P(1)–S(1) associated with the
shorter Ni(1)–S(1) anisobidentate bond and the P(1)–S(3)
associated with the monodentate Ni(1)–S(3) bond are
˚
longer and essentially the same, 1.997(2) and 1.995(2) A,
respectively.
In Ni[S2P(OC6H4Me-p)2]2(C10H8 N2) (6), the S–Ni–S
ligand bite angles of 81.33(2) and 81.99(2)ꢁ are similar to
the values observed in Ni[S2P(OBun)2]2(bipy) (81.40(7)
and 81.63(7)ꢁ) [25], Ni[S2P(OMe)2]2(phen) (81.3(2)ꢁ and
81.6(2)ꢁ) [24] and Ni[S2P(OC6H4Me-p)2]2(phen) (81.13
and 81.57(2)ꢁ) [27]. The bite angle of the chelating ligand
in Ni[S2P(OC6H4Me-o)2]2 Æ C14H12N2 Æ C6H6 (7) is similar
(82.05(4)ꢁ) and comparable to that in Ni[S2P(OMe)2]2 Æ dm-
phen (81.7(1)ꢁ [24] and Ni[S2POCMe2CMe2O)2]2 Æ dmphen
(82.1(1)ꢁ) [26]. The N–Ni–N bite angles of 79.10(5)ꢁ in 6
and 82.6(2)ꢁ in 7, are typical of the values found in
the corresponding six-coordinate, Ni[S2P(OBun)2]2 Æ bipy,
In 6 the S–P–S bond angles for the bidentate ligands
are 110.34(2)ꢁ and 112.53(3)ꢁ as was reported for the
six-coordinate analogues Ni[S2P(OC6H4Me-p)2]2 Æ phen
(110.37(6)–112.81(5)ꢁ) [27] and Ni[S2P(OMe)2]2 Æ phen

2676
A.L. Bingham et al. / Polyhedron 26 (2007) 2672–2678
(110.8(2)–111.6(2)ꢁ) [24]. In 7, the two angles differ con-
siderably with the S–P–S bond angle of 116.1(1)ꢁ for the
monodentate ligand being considerably larger than that
of the (aniso)bidentate ligand (108.27(8)ꢁ). These values
are similar to those found in the analogous five-coordi-
nated complexes, Ni[S2P(OMe)2]2 Æ dmphen (116.9(2)ꢁ
and 111.1(2)ꢁ) [24] and Ni[S2P(OCMe2CMe2O)2]2 Æ dm-
phen (117.2(2)ꢁ and 108.0(2)ꢁ) [26].
3.1.8. Ni[S2P(OC6H4Me-m)2]2 Æ C14H12N2 (8)
Yield: 0.321 g, 71.9%. Anal. Calc. for C42H40O4N2-
S4P2Ni: Ni, 6.84; S, 14.96. Found: Ni, 6.81; S, 14.90%.
3.1.9. Ni[S2P(OC6H4Me-p)2]2 Æ C14H12N2 (9)
Yield: 0.426 g, 73.4%. Anal. Calc. for C42H40O4N2-
S4P2Ni: Ni, 6.84; S, 14.96. Found: Ni, 6.79; S, 14.87%.
3.2. Physical measurements
3. Experimental
Sulfur was estimated gravimetrically as barium sulfate
(Messengers method) and nickel as dimethylglyoximate.
IR spectra were recorded in the range 4000–200 cmꢂ1 on
a Perkin–Elmer 983G spectrophotometer (Nujol mull).
Electronic spectra in the range 200–1200 nm were recorded
on a Perkin Elmer UV/VIS/NIR spectrometer-Lambda 19
in CH2Cl2. The magnetic measurements at 298 K were
determined using the Evans NMR method [32].
Solvents (benzene, dichloromethane, n-hexane, diethyl
ether) were dried by standard methods before use. All reac-
tions were carried out in pre-dried glassware under anhy-
drous conditions. Literature methods were used for the
preparation of bis(O,O0-ditolyldithiophosphato)nickel(II)
[28] and ammonium salts of O,O-ditolyldithiophosphoric
acids [30,31].
3.1. Preparations
Table 3
3.1.1. Ni[S2P(OC6H4Me-o)2]2 Æ 2C5H5N (1)
Crystal data and structure refinements for Ni[S2P(OC6H4Me-p)2]2 Æ
C10H8N2 and Ni[S2P(OC6H4Me-o)2]2 Æ C14H12N2 Æ C6H6
Ni[S2P(OC6H4Me-o)2]2 (0.489 g, 0.723 mmol) was dis-
solved in dry benzene (20 ml). Pyridine was added until
the purple colour of the solution changed to green. The
solution was concentrated under vacuo. Diethylether was
added to the concentrated solution to obtain a green pre-
cipitate. The adduct was recrystallized using a dichloro-
methane/ether mixture (1:2 v/v). Yield: 0.328 g, 67%.
Anal. Calc. for C38H38O4N2S4P2Ni: Ni, 7.02; S, 15.35.
Found: Ni, 6.83; S, 15.17%.
Empirical formula
Formula weight
Temperature (K)
C38H36O4N2P2S4Ni C48H46O4N2P2S4Ni
833.58
120(2)
963.76
120(2)
˚
Wavelength (A)
0.71073
triclinic
0.71073
monoclinic
P21/c
13.950(1)
22.697(2)
14.4965(7)
Crystal system
Space group
ꢀ
P1
˚
a (A)
10.8219(7)
12.035(3)
16.737(3)
70.73(1)
75.004(9)
70.752(8)
1915.1(5)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
90.050(6)
3.1.2. Ni[S2P(OC6H4Me-m)2]2 Æ 2C5H5N (2)
3
˚
Method as above gave a green powdery solid. Yield:
0.401 g, 73%. Anal. Calc. for C38H38O4N2S4P2Ni: Ni,
7.02; S, 15.35. Found: Ni, 6.94; S, 15.48%.
Volume (A )
4589.8(5)
4
1.395
0.721
Z
Density (calculated) (g/cm3) 1.446
Absorption coefficient
(mmꢂ1
F(000)
Crystal size (mm3)
0.851
)
3.1.3. Ni[S2P(OC6H4Me-p)2]2 Æ 2C5H5N (3)
Yield: 0.205 g, 69%. Anal. Calc. for C38H38O4N2S4P2Ni:
Ni, 7.02; S, 15.35. Found: Ni, 7.10; S, 15.51%.
864
2008
0.20 · 0.14 · 0.07
3.06–25.08
0.20 · 0.10 · 0.10
h Range for data collection 3.30–27.55
(ꢁ)
Index ranges
ꢂ14 6 h 6 13,
ꢂ16 6 h 6 16,
ꢂ26 6 k 6 27,
ꢂ17 6 l 6 15
41699
3.1.4. Ni[S2P(OC6H4Me-o)2]2 Æ C10H8N2 (4)
Yield: 0.263 g, 78.2%. Anal. Calc. for C38H36O4N2-
S4P2Ni: Ni, 7.04; S, 15.39. Found: Ni, 7.25; S, 15.52%.
ꢂ15 6 k 6 15,
ꢂ21 6 l6 21
40064
Reflections collected
Independent reflections
8756 [0.0289]
8062 [0.1040]
[Rint
Max. and min. transmission 0.9197 and 0.8483
]
3.1.5. Ni[S2P(OC6H4Me-m)2]2 Æ C10H8N2 (5)
Yield: 0.349 g, 74%. Anal. Calc. for C38H36O4N2S4P2Ni:
Ni, 7.04; S, 15.39. Found: Ni, 7.25; S, 15.72%.
0.9513 and 0.8693
Full-matrix least-
squares on F2
8062/0/551
Refinement method
Full-matrix least-
squares on F2
8756/0/461
1.037
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [F2 > 4r(F2)] R1 = 0.0277,
wR2 = 0.0703
1.019
3.1.6. Ni[S2P(OC6H4Me-p)2]2 Æ C10H8N2 (6)
Yield: 0.357 g, 77.5%. Anal. Calc. for C38H36O4N2-
S4P2Ni: Ni, 7.04; S, 15.39. Found: Ni, 7.11; S, 15.48%.
R1 = 0.0590,
wR2 = 0.1083
R1 = 0.1097,
wR2 = 0.1260
R indices (all data)
R1 = 0.0328,
wR2 = 0.0730
0.0029(5)
3.1.7. Ni[S2P(OC6H4Me-o)2]2 Æ C14H12N2 (7)
Yield: 0.288 g, 69.7%. Anal. Calc. for C42H40O4N2-
S4P2Ni: Ni, 6.84; S, 14.96. Found: Ni, 6.75; S, 14.72%.
Extinction coefficient
Largest differencꢂe3in peak
0.489 and ꢂ0.390
0.738 and ꢂ0.564
˚
and hole (e A
)

A.L. Bingham et al. / Polyhedron 26 (2007) 2672–2678
2677
Table 5
Bond lengths (A) and angles (ꢁ) for Ni[S2P(OC6H4Me-o)2]2 Æ
14H12N2 Æ C6H6
3.3. Crystal structure determination
˚
C
A translucent green, block crystal of Ni[S2P(OC6H4Me-
p)2]2 Æ C10H8N2 (6) and a green prism crystal of Ni[S2-
P(OC6H4Me-o)2] Æ C14H12N2 Æ C6H6 (7) were mounted on
a glass fibre. Data were collected on a Bruker-Nonius
Kappa CCD area detector diffractometer, with / and x
scans chosen to give a complete asymmetric unit. Cell
refinement [33] gave cell constants corresponding to a tri-
clinic cell for 6 and a monoclinic cell for 7 whose dimen-
sions are given in Table 3 along with other experimental
parameters. The crystal of 7 was a monoclinic pseudo
merohedral twin with beta approximately 90ꢁ emulating
orthorhombic. An absorption correction was applied [34].
The structures were solved by direct methods [35] and
refined using the WinGX version [36] of SHELX-97 [37].
All of the non-hydrogen atoms were treated anisotropi-
cally. 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
Ni(1)–S(1)
Ni(1)–S(2)
Ni(1)–N(1)
S(1)–P(1)
2.352(1)
2.539(1)
2.010(4)
1.997(2)
1.969(2)
1.604(4)
1.596(4)
1.437(7)
1.401(7)
1.363(7)
1.325(7)
Ni(1)–S(3)
Ni(1)ꢁ ꢁ ꢁS(4)
Ni(1)–N(2)
S(3)–P(2)
2.386(1)
5.462(2)
2.009(5)
1.995(2)
1.941(2)
1.607(4)
1.610(4)
1.411(8)
1.385(8)
1.366(7)
1.330(7)
S(2)–P(1)
S(4)–P(2)
P(1)–O(1)
P(1)–O(2)
O(1)–C(1)
O(2)–C(8)
N(1)–C(29)
N(1)–C(33)
P(2)–O(3)
P(2)–O(4)
O(3)–C(15)
O(4)–C(22)
N(2)–C(35)
N(2)–C(41)
S(1)–Ni(1)–S(2)
N(1)–Ni(1)–S(1)
N(2)–Ni(1)–S(1)
N(1)–Ni(1)–S(2)
N(2)–Ni(1)–S(2)
P(1)–S(1)–Ni(1)
P(1)–S(2)–Ni(1)
S(1)–P(1)–S(2)
O(1)–P(1)–S(1)
O(2)–P(1)–S(1)
O(1)–P(1)–S(2)
O(2)–P(1)–S(2)
O(1)–P(1)–O(2)
C(1)–O(1)–P(1)
C(8)–O(2)–P(1)
82.05(4)
134.3(1)
142.1(1)
89.9(1)
N(1)–Ni(1)–N(2)
S(1)–Ni(1)–S(3)
S(2)–Ni(1)–S(3)
N(1)–Ni(1)–S(3)
N(2)–Ni(1)–S(3)
P(2)–S(3)–Ni(1)
82.6(2)
85.17(5)
167.05(5)
100.6(1)
97.3(1)
91.6(1)
87.06(6)
82.60(6)
108.27(8)
113.0(2)
112.7(2)
114.2(2)
114.8(2)
93.6(2)
113.28(7)
S(3)–P(2)–S(4)
O(3)–P(2)–S(3)
O(4)–P(2)–S(3)
O(3)–P(2)–S(4)
O(4)–P(2)–S(4)
O(3)–P(2)–O(4)
C(15)–O(3)–P(2)
C(22)–O(4)–P(2)
116.1(1)
111.0(2)
105.2(2)
112.8(2)
113.2(2)
96.5(2)
Table 4
˚
Bond lengths (A) and angles (ꢁ) for Ni[S2P(OC6H4Me-p)2]2 Æ C10H8N2
120.9(3)
122.4(3)
127.6(4)
125.0(4)
Ni(1)–S(1)
Ni(1)–S(2)
Ni(1)–N(1)
S(1)–P(1)
S(2)–P(1)
P(1)–O(1)
P(1)–O(2)
O(1)–C(1)
2.4757(7)
2.5049(4)
2.060(1)
1.9788(5)
1.9751(6)
1.602(1)
1.604(1)
1.406(2)
1.406(2)
1.352(2)
1.340(2)
81.33(2)
173.09(2)
93.53(2)
79.10(5)
92.73(4)
95.17(4)
92.33(4)
171.63(4)
84.50(2)
83.79(2)
126.2(1)
115.1(1)
92.19(6)
110.34(2)
112.77(5)
113.46(5)
113.25(5)
113.84(5)
121.48(9)
123.38(9)
118.7(1)
119.5(1)
119.4(1)
119.0(1)
118.7(1)
121.5(1)
115.1(1)
122.7(2)
Ni(1)–S(3)
Ni(1)–S(4)
Ni(1)–N(2)
S(3)–P(2)
S(4)–P(2)
2.4814(7)
2.5096(6)
2.079(1)
1.9727(6)
1.9645(6)
1.609(1)
1.605(1)
1.404(2)
1.401(2)
1.351(2)
1.339(2)
81.99(2)
93.46(2)
91.33(2)
C(2)–C(1)–O(1)
C(6)–C(1)–O(1)
C(9)–C(8)–O(2)
C(29)–N(1)–Ni(1)
C(33)–N(1)–Ni(1)
C(29)–N(1)–C(31)
N(1)–C(29)–C(35)
N(1)–C(29)–C(30)
N(1)–C(33)–C(32)
N(1)–C(33)–C(34)
119.9(6)
116.4(5)
119.8(6)
112.2(4)
128.1(4)
119.7(5)
116.4(5)
122.6(6)
120.4(5)
118.6(5)
C(16)–C(15)–O(3)
C(20)–C(15)–O(3)
C(23)–C(22)–O(4)
C(35)–N(2)–Ni(1)
C(41)–N(2)–Ni(1)
C(35)–N(2)–C(41)
N(2)–C(35)–C(29)
N(2)–C(35)–C(36)
N(2)–C(41)–C(40)
N(2)–C(41)–C(42)
116.8(6)
119.5(6)
120.9(7)
112.0(4)
129.2(4)
118.9(5)
116.8(5)
123.8(5)
120.6(6)
117.1(5)
P(2)–O(3)
P(2)–O(4)
O(3)–C(15)
O(4)–C(22)
N(2)–C(34)
N(2)–C(38)
S(3)–Ni(1)–S(4)
S(1)–Ni(1)–S(4)
S(2)–Ni(1)–S(4)
O(2)–C(8)
N(1)–C(29)
N(1)–C(33)
S(1)–Ni(1)–S(2)
S(1)–Ni(1)–S(3)
S(2)–Ni(1)–S(3)
N(1)–Ni(1)–N(2)
N(1)–Ni(1)–S(1)
N(1)–Ni(1)–S(2)
N(1)–Ni(1)–S(3)
N(1)–Ni(1)–S(4)
P(1)–S(1)–Ni(1)
P(1)–S(2)–Ni(1)
C(33)–N(1)–Ni(1)
C(29)–N(1)–Ni(1)
O(1)–P(1)–O(2)
S(1)–P(1)–S(2)
O(1)–P(1)–S(1)
O(1)–P(1)–S(2)
O(2)–P(1)–S(1)
O(2)–P(1)–S(2)
C(1)–O(1)–P(1)
C(8)–O(2)–P(1)
C(6)–C(1)–O(1)
C(2)–C(1)–O(1)
C(13)–C(8)–O(2)
C(9)–C(8)–O(2)
C(33)–N(1)–C(29)
N(1)–C(29)–C(30)
N(1)–C(29)–C(34)
N(1)–C(33)–C(32)
cycle of full-matrix least-squares refinement was based on
8756 observed reflections (7822 for F2 > 4r(F2)) and 461
variable parameters for 6 and 8062 observed reflections
(5543 for F2 > 4r(F2)); and 551 variable parameters for 7
and converged (largest parameter shift was 0.001 times its
esd).
Selected distances and bond angles are given in Tables 4
and 5 for molecules 6 and 7, respectively and the molecules
are displayed as ORTEP diagrams in Figs. 1 and 2.
N(2)–Ni(1)–S(1)
N(2)–Ni(1)–S(2)
N(2)–Ni(1)–S(3)
N(2)–Ni(1)–S(4)
P(2)–S(3)–Ni(1)
P(2)–S(4)–Ni(1)
C(38)–N(2)–Ni(1)
C(34)–N(2)–Ni(1)
O(3)–P(2)–O(4)
S(3)–P(2)–S(4)
88.41(4)
168.03(4)
97.18(4)
95.45(4)
81.71(2)
81.13(2)
126.6(1)
114.1(1)
97.02(6)
112.53(3)
112.20(5)
114.10(5)
107.01(4)
112.81(5)
125.33(9)
125.19(9)
118.0(4)
119.9(1)
123.1(1)
116.0(1)
118.4(1)
121.9(2)
115.4(1)
122.5(2)
O(3)–P(2)–S(3)
O(3)–P(2)–S(4)
O(4)–P(2)–S(3)
O(4)–P(2)–S(4)
4. Concluding comments
We have successfully prepared and characterized the fol-
lowing complexes, Ni[S2P(OR)2]2 Æ nL ((R = o-, m-, p-
C6H4Me; n = 2, L = C5H5N; n = 1, L = C10H8N2,
C14H12N2). The IR, UV–visible and magnetic measure-
ments of all of these nickel adducts and molecular
structures of two representative complexes, Ni[S2-
P(OC6H4Me-p)2]2 Æ C10H8N2 and Ni[S2P(OC6H4Me-o)2]2 Æ
C14H12N2 Æ C6H6 suggest the distorted octahedral for com-
plexes 1–6 and distorted trigonal bipyramidal environ-
C(15)–O(3)–P(2)
C(22)–O(4)–P(2)
C(20)–C(15)–O(3)
C(16)–C(15)–O(3)
C(27)–C(22)–O(4)
C(23)–C(22)–O(4)
C(38)–N(2)–C(34)
N(2)–C(34)–C(35)
N(2)–C(34)–C(29)
N(2)–C(38)–C(37)

2678
A.L. Bingham et al. / Polyhedron 26 (2007) 2672–2678
[10] C.P. Bhasin, R.C. Mehrotra, J. Indian Chem. Soc. 79 (4) (2002) 336.
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(1987) 195.
[12] C.P. Bhasin, G. Srivastava, R.C. Mehrotra, Inorg. Chim. Acta 144 (2)
(1988) 157.
ments around nickel for complexes 7–9 and are consistent
with the proposed structures for the analogous complexes
Ni[S2P(OMe)2]2 Æ phen, Ni[S2P(OMe)2]2 Æ dmphen and
Ni[S2POCMe2CMe2O)2]2 Æ dmphen.
[13] J.A. McCleverty, S. Gill, R.S.J. Kowalski, N.A. Bailey, H. Adams,
K.W. Lumbard, M.A. Murphy, J. Chem. Soc., Dalton Trans. (1982)
493.
Acknowledgements
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2293.
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Acta 77 (1983) L131.
[18] R. Micu-Semeniuc, L. Silaghi-Dumitreschu, I. Haiduc, Inorg. Chim.
Acta 17 (1976) 5.
One of us (M.N.) is grateful to CSIR, New Delhi for
financial support and Department of Chemistry, University
of Southampton for spectroscopic facilities. M.B.H. thanks
EPSRC for support of the X-ray facilities at Southampton
University. J.E.D. wishes to thank the University of Wind-
sor for financial support.
Appendix A. Supplementary material
[19] M.J. Hynes, P.F. Brannick, J. Chem. Soc., Chem. Comm. (1977)
642.
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25 (2000) 715.
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[23] Q. Hao, F. Jian, X. Wang, I.A. Razak, S.S.S. Raj, H.K. Fun, Acta
Cryst. Commun. C57 (2001) 160.
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cock, Inorg. Chim. Acta 164 (1989) 11.
CCDC 630576 and 630577 contain the supplementary
crystallographic data for Ni[S2P(OC6H4Me-p)2]2 Æ C10H8
N2 and Ni[S2P(OC6H4Me-o)2]2 Æ C14H12N2 Æ C6H6. These
data can be obtained free of charge via http://www.ccdc.ca-
m.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit
@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at doi:10.1016/
j.poly.2007.01.003.
[27] Q. Hao, H.K. Fun, S. Chantrapromma, I.A. Razak, F. Jian, X. Yang,
L. Lu, X. Wang, Acta Crystallogr. 57 (2001) 717.
[28] A.L. Bingham, J.E. Drake, M.E. Light, M. Nirwan, R. Ratnani,
Polyhedron 25 (2006) 945.
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