Bis(O,O′-di-p-tolyldithiophosphato-S,S′)(1,10-phenanthroline-N, N′)-nickel(II)

Full text of DOI:10.1107/S0108270101005522

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
NiN2S4 chromophore. Crystals of this compound are
composed of discrete molecules.
Communications
ISSN 0108-2701
Bis(O,O0-di-p-tolyldithiophosphato-
S,S0)(1,10-phenanthroline-N,N0)-
nickel(II)
Qingli Hao,a Hoong-Kun Fun,b* Suchada
Chantrapromma,b² Ibrahim Abdul Razak,b Fangfang Jian,a
Xujie Yang,a Lude Lua and Xin Wanga
The NiÐS distances of the title complex (Table 1) are in
good agreement with similar distances found in the six-coor-
dinate complex [Ni{(C4H9O)2PS2}2(bipy)] [2.466 (2) and
aMaterials Chemistry Laboratory, Nanjing University of Science and Technology,
Nanjing 210094, People's Republic of China, and bX-ray Crystallography Unit,
School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
Correspondence e-mail: hkfun@usm.my
Ê
2.524 (2), 2.463 (2) and 2.522 (2) A; You et al., 1986].
However, the distances are much longer than those in four-
coordinate compounds, such as [Ni(S2COPh-4-tBu)2]
Ê
[2.219 (4) and 2.213 (6) A; Chen & Fackler, 1978], [Ni{(iso-
Ê
C3H7O)2PS2}2] [2.227 (1) and 2.216 (1) A; Hoskins & Tiekink,
1985] and [Ni{(OC2H5)(4-CH3OPh)PS2}2] [2.1297 (8) and
Received 14 February 2001
Accepted 29 March 2001
Ê
2.2225 (8) A; Arca et al., 1997]. This probably re¯ects the
change from octahedral coordination in the title compound to
square-planar or tetrahedral coordination.
The NiÐN distances of the title compound (Table 1) are in
good agreement with similar distances found in [Ni-
Ê
{(C4H9O)2PS2}2(bipy)] [2.089 (4) and 2.088 (4) A] and [Ni-
The title coordination complex, [Ni(C14H14O2PS2)2(C12H8N2)]
or [Ni(pMePh-dtp)2(phen)] (phen is 1,10-phenanthroline; dtp
is diaryldithiophosphate), has a non-crystallographic twofold
axis of symmetry through the Ni atom and the phen moiety.
Two O,O-di-p-tolyldithiophosphate (dtp) ions act as bidentate
ligands. The central metal atom is coordinated by four S atoms
from two dtp groups and two N atoms from the phen ligand.
The title compound displays distorted octahedral geometry
around the central Ni atom.
Ê
{(C2H5O)CS2}2(phen)]Á3H2O [2.074 (4) and 2.076 (4) A;
Xiong et al., 1997].
The distances between P1 and the two S atoms (Table 1) are
nearly equal. However, the distances between P2 and the
other two S atoms are different. It is noteworthy that all the
Comment
Ê
PÐS bonds lengths are intermediate between single (2.09 A)
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 (Harrison & Kikabhai, 1987; Kovtun et al., 1992).
Additionally, the adducts and their formation reactions have
also been found useful in a variety of ways, such as in biolo-
gical applications and as both ultraviolet absorbers and anti-
oxidants. In addition to their syntheses and various
physicochemical investigations, the crystal structures of many
nickel(II) complexes and their adducts with nitrogen bases
have been reported (Huang et al., 1995; You et al., 1994). Metal
complexes of the [M(LL)3] ion type, where LL is either 1,10-
phenanthroline (phen) or a modi®ed phen ligand, are parti-
cularly attractive species for developing new diagnostic and
therapeutic agents that can recognize and cleave DNA
(Barton, 1986; Naing et al., 1995). Thus, the crystal structure of
[Ni(pMePh-dtp)2(phen)], (I), was determined.
A perspective view of the title complex with the atomic
numbering scheme is shown in Fig. 1. In the title complex, the
NiII atom lies in the centre of the octahedral geometry of the
Figure 1
The structure of (I) showing 50% probability displacement ellipsoids and
the atom-numbering scheme.
² Permanent address: Department of Chemistry, Prince of Songkla University,
Hat-Yai, Songkhla 90112, Thailand.
ꢀ
Acta Cryst. (2001). C57, 717±718
# 2001 International Union of Crystallography
Printed in Great Britain ± all rights reserved 717

metal-organic compounds
Ê
and the double bond (1.87 A) values, resulting from substan-
Table 1
Selected geometric parameters (A, ).
ꢁ
Ê
tial delocalization of electrons throughout the two NiS2P four-
membered rings. This is similar to that found for analogous dtp
complexes, e.g. [Ni{(C2H5O)2PS2}2(C9H7N)2] (Huang et al.,
1995), [Ni{(C4H9O)2PS2}2(py)2] (Liu et al., 1987), [Ni{(C4H9-
O)2PS2}2(bipy)] and [M2{(i-C3H7O)2PS2}4], M = Zn or Cd
(Byrom et al., 2000).
NiÐN1
NiÐN2
NiÐS2
NiÐS4
NiÐS1
NiÐS3
S1ÐP1
2.082 (3)
2.086 (3)
2.486 (1)
2.488 (1)
2.505 (1)
2.532 (1)
1.976 (1)
S2ÐP1
S3ÐP2
S4ÐP2
O1ÐC13
O2ÐC20
O3ÐC27
O4ÐC34
1.977 (1)
1.965 (1)
1.972 (1)
1.417 (4)
1.406 (4)
1.398 (4)
1.405 (4)
The CÐO distances are much shorter than those found in
Ê
[Ni{(C2H5O)2PS2}2(C5H6N2)2] [1.446 (5) and 1.430 (5) A].
This is probably a result of the electronic effect of the benzene
rings.
N1ÐNiÐN2
S2ÐNiÐS1
S4ÐNiÐS3
79.8 (1)
81.13 (3)
81.57 (3)
S1ÐP1ÐS2
S3ÐP2ÐS4
110.37 (6)
112.81 (5)
The SÐNiÐS bond angles (Table 1) are similar to those
found in [Ni{(C4H9O)2PS2}2(bipy)] [81.40 (7) and 81.63 (7)ꢁ].
The N1ÐNiÐN2 bond angle (Table 1) is also similar to that
found in [Ni{(C4H9O)2PS2}2(bipy)] [79.5 (2)ꢁ].
The phen ligand and Ni atom are also coplanar; the mean
After checking their presence in the difference map, all H atoms
were geometrically ®xed and allowed to ride on their attached atoms
(CH3 with AFIX 137 in SHELXTL).
Ê
Data collection: SMART (Siemens, 1996); cell re®nement: SAINT
(Siemens, 1996); data reduction: SAINT and SADABS (Sheldrick,
1996); program(s) used to solve structure: SHELXTL (Sheldrick,
1997); program(s) used to re®ne structure: SHELXTL; molecular
graphics: SHELXTL; software used to prepare material for publi-
cation: SHELXTL and PLATON (Spek, 1990).
deviation from the best plane is 0.065 (1) A. The two planes
Ê
through Ni, P and S2 form a dihedral angle of 89.18 (4) A. The
dihedral angles between the plane of the phen ligand and
Ê
these two NiS2P planes are 89.21 (7) and 74.92 (7) A. This
indicates that the structure of NiN2S4 is obviously a distorted
octahedron.
The authors would like to thank the Malaysian Government
and Universiti Sains Malaysia for research grant R&D No.
305/PFIZIK/610942.
Experimental
The title compound was prepared by mixing a solution of nickel(II)
bis(O,O0-di-p-tolyldithiophosphate) (0.1 mmol) in acetone (50 ml)
and phen (0.1 mmol) with heating. The solution was cooled to room
temperature and was then ®ltered. Green prismatic single crystals
suitable for X-ray analysis were obtained upon slow evaporation of
the solvent.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1464). Services for accessing these data are
described at the back of the journal.
Crystal data
References
[Ni(C14H14O2PS2)2(C12H8N2)]
Mr = 857.60
Triclinic, P1
Z = 2
Dx = 1.401 Mg m
Mo Kꢀ radiation
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3
Ê
a = 11.1819 (2) A
Cell parameters from 8192
re¯ections
Ê
b = 12.0934 (2) A
c = 17.2860 (2) A
ꢃ = 1.3±28.3ꢁ
ꢄ = 0.80 mm
T = 293 (2) K
Ê
1
ꢀ = 107.693 (1)ꢁ
ꢁ = 96.349 (1)ꢁ
ꢂ = 109.896 (1)ꢁ
Prismatic slab, green
0.40 Â 0.24 Â 0.16 mm
3
Ê
V = 2033.41 (5) A
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Data collection
Siemens SMART CCD area-
detector diffractometer
! scans
Absorption correction: empirical
(SADABS; Sheldrick, 1996)
Tmin = 0.739, Tmax = 0.882
11570 measured re¯ections
7040 independent re¯ections
5007 re¯ections with I > 2ꢅ(I)
Rint = 0.055
ꢃ
max = 25.0ꢁ
h = 12 ! 13
k = 14 ! 11
È
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany.
l = 20 ! 19
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Wisconsin, USA.
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Inc., Madison, Wisconsin, USA.
Spek, A. L. (1990). Acta Cryst. A46, C-34.
Intensity decay: negligible
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.048
wR(F2) = 0.120
S = 0.93
7040 re¯ections
482 parameters
H-atom parameters constrained
w = 1/[ꢅ2(Fo2) + (0.0346P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢅ)max = 0.001
Xiong, R. G., Liu, C. M., Zuo, J. L., Li, H. Z., You, X. Z., Fun, H. K. &
Sivakumar, K. (1997). Polyhedron, 16, 2315±2319.
You, X. Z., Xiong, R. G., Dong, J. X. & Huang, X. Y. (1994). Polyhedron, 13,
2763±2765.
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154±158.
3
Ê
Áꢆmax = 0.40 e A
3
Ê
0.77 e A
Áꢆmin
=
ꢀ
718 Qingli Hao et al.
[Ni(C14H14O2PS2)2(C12H8N2)]
Acta Cryst. (2001). C57, 717±718