Trans-bis[O-2,4-di-tert-butylphenyl(4-methoxyphenyl)dithiophosphonato- κ2S,S′]nickel(II)

Article abstract of DOI:10.1107/S0108270102008764

In the title compound, [Ni(C₂₁H₂₈O₂PS₂)₂], the Ni atom resides on an inversion centre and is coordinated in a square-planar array by four S atoms, with Ni-S and P-S bond lengths of 2.2336 (12)/2.2351 (13) and 1.9910 (16)/2.0010 (17) A, respectively. The two O-2,4-di-tert-butylphenyl and two 4-methoxyphenyl moieties adopt trans configurations about the central Ni atom.

Full text of DOI:10.1107/S0108270102008764

metal-organic compounds
the SÐNiÐS coordination planes is 88.70 (5)ꢀ, and the NiÐS
and SÐP bond lengths are 2.2336 (12)/2.2351 (13) and
Acta Crystallographica Section C
Crystal Structure
Communications
Ê
1.9910 (16)/2.0010 (17) A, respectively. These bond lengths
compare well with those found in other related NiII complexes
(Haiduc et al., 1984; Hoskins & Tiekink, 1985; Arca et al., 1997;
van Zyl et al., 1998; Hao, Fun et al., 2001; Hao, Jian et al., 2001;
ISSN 0108-2701
È
Ozcan et al., 2002).
trans-Bis[O-2,4-di-tert-butylphenyl
(4-methoxyphenyl)dithiophosphon-
ato-j2S,S0]nickel(II)
Á
a
a
b
È
Yusuf Ozcan, Semra Ide, * Mehmet KarakusÎ and Hamza
Yõlmazb
aDepartment of Engineering Physics, Hacettepe University, Beytepe 06532, Ankara,
Turkey, and bDepartment of Chemistry, Ankara University, Tandogan 06100,
Ä
Ankara, Turkey
Correspondence e-mail: side@hacettepe.edu.tr
Received 16 April 2002
Accepted 15 May 2002
Online 20 June 2002
In the the title compound, [Ni(C21H28O2PS2)2], the Ni atom
resides on an inversion centre and is coordinated in a square-
planar array by four S atoms, with NiÐS and PÐS bond
lengths of 2.2336 (12)/2.2351 (13) and 1.9910 (16)/
Ê
2.0010 (17) A, respectively. The two O-2,4-di-tert-butylphenyl
and two 4-methoxyphenyl moieties adopt trans con®gurations
about the central Ni atom.
Comment
The differences in the NiÐS and SÐP bond lengths are
Owing to their insecticide and antioxidant activities, dithio-
phosphonate compounds have been widely investigated in the
®elds of medicine, industry and agriculture. Despite this,
studies on the molecular structures of dithiophosphonate
complexes have not been reported adequately up until
recently. In recent years, NiII complexes of this type have
received increasing attention owing to their extensive appli-
cations 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 products are also useful in biological applications
(Hao, Fun et al., 2001). Consequently, the synthesis, physico-
chemical investigations and crystal structures of many similar
complexes and their adducts have been reported (You et al.,
1994; Huang et al., 1995; Hao, Fun et al., 2001; Hao, Jian
et al., 2001). A previous study involving a related NiII±di-
thiophosphonate complex, namely trans-bis[O-n-propyl
(p-methoxyphenyl)dithiophosphonato]nickel(II), has been
È
comparable with those found in our previous study (Ozcan et
al., 2002), where the values were 2.2251 (9)/2.2283 (9) and
Ê
2.004 (1)/2.008 (1) A, respectively. These differences were
explained by electron delocalization in the PÐS ꢀ-bonding in
È
reported (Ozcan et al., 2002). The title complex, (III), was
prepared and the structure determined in an extension of our
previous research studies.
The Ni atom lies on a crystallographic centre of symmetry
and the asymmetric unit consists of half of the nickel(II)
complex molecule (Fig. 1). The Ni atom is coordinated by four
S atoms and has a trans con®guration imposed by the ligands
in a square-planar environment. The dihedral angle between
Figure 1
An ORTEP-3 (Farrugia, 1997) drawing of (III), showing the atom-
numbering scheme and ellipsoids at the 40% probability level.
m388 # 2002 International Union of Crystallography
DOI: 10.1107/S0108270102008764
Acta Cryst. (2002). C58, m388±m389

metal-organic compounds
Table 1
Selected geometric parameters (A, ).
our previous work. Similar observations have also been made
in the present and related studies (Ooi & Fernando, 1968;
Arora et al., 1978; Hoffmann et al., 1979; Hoskins & Tiekink,
1985; Hao, Fun et al., 2001; Hao, Jian et al., 2001). Small
differences in the geometric parameters around the central Ni
atom may also be explained by the steric effect of different
molecular groups attached to the P atom in related complexes.
The mean NiÐSÐP angle in (III) (Table 1) is in good
agreement with similar angles found in bis(butyldithio-
phosphato)bis(4-aminopyridine)nickel(II) [82.83 (5)ꢀ; You et
al., 1994] and [Ni{(C4H9O)2PS2}(pyridine)2] [82.57ꢀ; Liu et al.,
1987]. The CÐO distance in the O-2,4-di-tert-butylphenyl
(O-dtb) group is much longer than the range found in
bis(di-p-tolyldithiophosphato)(1,10-phenanthroline)nickel(II)
ꢀ
Ê
NiÐS2
NiÐS1
NiÐP1
P1ÐO1
2.2336 (12)
2.2351 (13)
2.7942 (14)
1.598 (3)
P1ÐS2
P1ÐS1
O1ÐC8
1.9910 (16)
2.0010 (17)
1.423 (5)
S2ÐNiÐS1
S2ÐP1ÐS1
P1ÐS1ÐNi
P1ÐS2ÐNi
88.70 (5)
102.98 (7)
82.34 (6)
82.60 (6)
O1ÐP1ÐC5
O1ÐP1ÐS2
C5ÐP1ÐS1
100.53 (18)
113.63 (13)
112.16 (16)
H atoms bonded to C atoms were placed geometrically and all H
Ê
atoms were treated as riding, with CÐH distances of 0.93 and 0.96 A,
and Uiso(H) values of 1.2Ueq(C).
Ê
Data collection: CAD-4 EXPRESS (Enraf±Nonius, 1993); cell
re®nement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms &
Wocadlo, 1995); program(s) used to solve structure: SHELXS97
(Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97
(Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997);
software used to prepare material for publication: WinGX (Farrugia,
1999).
[1.398 (4)±1.47 (1) A; Hao, Fun et al., 2001] and is probably
the result of electronic effects from the aromatic ring. All
other structural parameters have normal values. The
methoxyphenyl group and the main part of the O-dtb group
(atoms O1, C8±C14 and C18) are individually planar and the
dihedral angle between these planes is 62.6 (1)ꢀ.
The authors acknowledge the purchase of the CAD-4
diffractometer under grant DPT/TBAG1 of the Scienti®c and
Technical Research Council of Turkey.
Experimental
Lawesson's reagent, (I) (1.48 g, 3.53 mmol), was treated with 2,4-di-
tert-butylphenol (1.45 g, 7.07 mmol) in hot benzene (25 ml), yielding
the O-di-tert-butylphenyl ester of dithiophosphonic acid, (II). The
title compound, (III), was prepared by the reaction of (II) with
nickel(II) acetate in a 1:1 mixture of benzene and acetic acid. The
compound crystallizes directly from the reaction medium and these
crystals were used for the X-ray study. The purple-coloured
compound (III) melts at 515±516 K, is stable well over its melting
point, and recrystallizes, upon cooling, just below the melting
temperature without any observable change in its colour. IR (KBr,
cm 1): 552 (PS, symmetric), 670 (PS, asymmetric); 1028 (POC).
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GG1114). Services for accessing these data are
described at the back of the journal.
References
Arca, M., Cornia, A., Devillona, F. A., Fabretti, A. C., Isaia, F., Lippolis, V. &
Verani, G. (1997). Inorg. Chim. Acta, 262, 81±84.
Arora, S. K., Hayes, D. M. & Fernando, Q. (1978). Acta Cryst. B34, 3355±3357.
Enraf±Nonius (1993). CAD-4 EXPRESS. Version 1.1. Enraf±Nonius, Delft,
The Netherlands.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837±838.
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Dumitrescu, L. I. (1984). J. Mol. Struct. 114, 467±470.
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Crystal data
3
[Ni(C21H28O2PS2)2]
Mr = 873.76
Monoclinic, P21/c
Dx = 1.275 Mg m
Mo Kꢂ radiation
Cell parameters from 4916
re¯ections
Ê
a = 8.1782 (18) A
ꢃ = 9.9±18.0ꢀ
ꢄ = 0.72 mm
T = 293 (2) K
Ê
b = 32.060 (12) A
1
Ê
c = 8.709 (3) A
ꢁ = 94.68 (3)ꢀ
V = 2275.8 (12) A
Z = 2
3
Ê
Prism, violet
0.30 Â 0.25 Â 0.20 mm
Data collection
Enraf±Nonius CAD-4
diffractometer
!±2ꢃ scans
Absorption correction: scan
(North et al., 1968)
Tmin = 0.814, Tmax = 0.870
4916 measured re¯ections
4611 independent re¯ections
2618 re¯ections with I > 2ꢅ(I)
Rint = 0.045
max = 26.3ꢀ
ꢃ
Hoskins, B. F. & Tiekink, E. R. T. (1985). Acta Cryst. C41, 322±324.
Huang, X.-Y., Xiong, R.-G., Dong, J.-X. & You, X.-Y. (1995). Acta Cryst. C51,
598±600.
Kovtun, G. A., Zhukovskaya, G. B., Kratko, G. A. & Sukhoveev, V. V. (1992).
Neftepererab. Neftekhim. Kiev, 43, 39±41.
h = 10 ! 10
k = 0 ! 39
l = 10 ! 0
4916 standard re¯ections
frequency: 120 min
intensity decay: 0.9%
Liu, S. X., Lin, C. C., Xu, Z., Yu, Y. P. & You, X. Z. (1987). Chin. J. Org. Chem.
5, 369±373.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351±
359.
Ooi, S. & Fernando, Q. (1968). Inorg. Chem. 6, 1558±1562.
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.050
wR(F2) = 0.141
S = 0.99
4611 re¯ections
w = 1/[ꢅ2(Fo2) + (0.0613P)2
+ 0.9574P]
È
Ozcan, Y., Ide, S., KarakusÎ, M. & Yõlmaz, H. (2002). Anal. Sci. In the press.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of
where P = (Fo2 + 2Fc2)/3
(Á/ꢅ)max < 0.001
È
Gottingen, Germany.
You, X. Z., Xiong, R. G., Dong, J. X. & Huang, X. Y. (1994). Polyhedron, 13,
3
Ê
2763±2766.
Zyl, W. E. van, Stables, R. J. & Fackler, J. P. (1998). Inorg. Chem. Commun. 1,
51±54.
Áꢆmax = 0.53 e A
3
Ê
0.35 e A
241 parameters
H-atom parameters constrained
Áꢆmin
=
ꢁ
È
Acta Cryst. (2002). C58, m388±m389
Yusuf Ozcan et al. [Ni(C21H28O2PS2)2] m389