(Dicyclohexyldithiophosphinato-S,S′)-[2-(2-pyridyl-N)phenyl] mercury(II)

Full text of DOI:10.1107/S0108270199015048

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Fig. 1 shows the molecular structure of (I) and the atom-
numbering scheme used. Selected interatomic distances and
angles are listed in Table 1. The Hg atom is strongly coordi-
ISSN 0108-2701
nated to C8, the carbon at position 2 of the phenyl group
Ê
[HgÐC8 = 2.088 (11) A], and to one of the dithiophosphinate
S atoms (S1). The C8ÐHgÐS1 fragment is almost linear
0
ꢁ
(
[
Dicyclohexyldithiophosphinato-S,S )-
2-(2-pyridyl-N)phenyl]mercury(II)
[
178.9 (3) ], as is usual in monoorganomercuric thiolate deri-
Ê
vatives (Casas et al., 1999). The HgÐS1 distance [2.365 (3) A]
lies in the range observed for other organomercury(II) di-
thiophosphates and dithiophosphinates (Zukerman-Schpector
et al., 1991; V a zquez-L o pez et al., 1992; Casas et al., 1994). The
a
b
Jos e S. Casas, * Eduardo E. Castellano, M. S. Garc Âõ a
a
a
a
Tasende, Agust Âõ n S a nchez, Jos e Sordo, Ezequiel M.
Ê
HgÐN distance of 2.694 (9) A is also shorter than the sum of
Ê
c
d
V a zquez-L o pez and Julio Zukerman-Schpector
the van der Waals radii (3.55 A; Casas et al., 1999; Bondi,
964); it is close to the values found in [Hg(PhPy)Cl] [2.63 (1)
1
and 2.67 (1) A; Constable et al., 1989], but is clearly shorter
a
Departamento de Qu Âõ mica Inorg a nica, Facultade de Farmacia, Universidade de
Ê
b
Santiago de Compostela, 15706 Santiago de Compostela, Galicia, Spain, Instituto
Ê
than in [Hg(PhPy)(AcO)] [2.727 (9) A; Casas et al., 1996] and
de Fisica de S Äa o Carlos, Universidade de S Äa o Paulo, Caixa Postal 369, CEP 13560
c
Ê
longer than in [Hg(PhPy)(Hstsc)] [2.576 (6) A; H
S Äa o Paulo, Brazil, Departamento de Qu Âõ mica Inorg a nica, Facultade de Ciencias-
2
stsc = 2-
formyl-(2-hydroxybenzene)thiosemicarbazone; Lobana et al.,
d
Qu Âõ mica, Universidade de Vigo, 36200-Vigo, Galicia, Spain, and Departamento de
Qu Âõ mica, Universidade Federal de S Äa o Carlos, Caixa Postal 676, 13565-905 S Äa o
Carlos, SP, Brazil
+
1
moiety in (I) are not coplanar but form a dihedral angle of
998]. The phenyl and pyridinyl rings of the [Hg(PhPy)]
Correspondence e-mail: qiscasas@usc.es
ꢁ
1
acetate derivative (Casas et al., 1996).
9.3 (6) , and the interplanar angle is narrower than in the
Received 9 November 1999
Accepted 22 November 1999
The other dithiophosphinato sulfur, S2, lies 3.336 (3) AÊ
from the Hg atom. This distance, too, is shorter than the sum
Ê
of the corresponding van der Waals radii (3.8 A; Casas et al.,
The crystal
[
structure
of
the
title
compound,
Hg(C H N)(C H PS )], consists of molecules in which
1
1
8
12 22
2
1
999; Bondi, 1964), and though longer than that observed in
the Hg atom is coordinated strongly to the C atom in position
of the phenyl group and to one of the dithiophosphinate S
Ê
HgPh (S PEt )] [3.182 (3) A; Casas et al., 1994], is within the
2 2
[
2
usual range for secondary HgÁ Á ÁS bonds in mono-
organomercury dithiophosphates and dithiophosphinates.
Taking this HgÁ Á ÁS interaction into account, the coordination
geometry around the Hg atom can be described as distorted
square planar [the largest displacement from the least-squares
atoms, and at longer distances to the pyridine N atom and the
other S atom. The CÐHgÐS fragment involving the S atom
more strongly bound to Hg is almost linear [CÐHgÐS =
ꢁ
1
78.9 (3) ].
Ê
plane through Hg/N/C8/S1/S2 is for N, which is 0.35 (1) A out
of the plane].
Comment
In the reaction of [2-(2-pyridyl)phenyl]mercury(II) acetate,
[Hg(PhPy)(OAc)], with diphenyldithiophosphinic acid,
HS PPh , the CÐHg bond is broken to afford phenylpyridine
2
2
and [Hg (S PPh ) ] (Casas et al., 1997). The reaction of di-
2
2
2 4
cyclohexyldithiophosphinic acid, HS PCy , with an appro-
2
2
+
priate mole ratio of the TlPh2 cation in chloroform likewise
produces protodemetallation (i.e. the loss of one or more alkyl
or aryl groups from the metal with formation of an alkane
3
+
or arene), affording Tl species and benzene (Casas et al.,
995). To explore this type of process further, we reacted
Hg(PhPy)(OAc)] with HS PCy . At room temperature, the
1
[
2
2
reaction afforded a black solid which probably contains HgS,
but near 273 K, in an ice bath, it yielded a product from which
colourless crystals of the title organomercury dithio-
phosphinate, [Hg(PhPy)(S PCy )], (I), were isolated, showing
Figure 1
A view of the molecule of compound (I) (ZORTEP; Zsolnai & Huttner,
1994) showing the atom-numbering scheme. Displacement ellipsoids are
2
2
drawn at the 30% probability level and H atoms are shown as spheres of
arbitrary radii.
that no protodemetallation process had occurred.
82 Jos e S. Casas et al. ꢀ [Hg(C11
1
8 2
H N)(C12H22PS )]
Acta Cryst. (2000). C56, 182±183

metal-organic compounds
Secondary HgÁ Á ÁS bonds in monoorganomercury dithio-
phosphates and dithiophosphinates are generally inter-
molecular, organizing the molecules into centrosymmetric
dimers, as in [HgMe(S PPh )] (Zukerman-Schpector et al.,
Table 1
Selected geometric parameters (A, ).
Ê
ꢁ
2
2
HgÐC8
HgÐS1
HgÐN
HgÐS2
2.088 (11)
2.365 (3)
2.694 (9)
3.336 (3)
PÐC111
PÐC121
PÐS2
1.839 (9)
1.843 (8)
1.963 (4)
2.066 (4)
1
991) and [HgPh{S P(OEt) }] (V a zquez-L o pez et al., 1992), or
2 2
into linear chains of identically oriented monomers, as in
HgPh(S PEt )]. In the case of (I), these possibilities are
PÐS1
[
2
2
probably prevented by steric hindrance. The structure of (I) is
probably most similar to that of 2-formyl-(2-hydroxy-
benzene)thiosemicarbazonate, [Hg(PhPy)(Hstsc)] (Lobana et
al., 1998). The lattices of these compounds consist of mol-
ecules which have no intermolecular interactions and in which
the Hg atom has two primary bonds [HgÐC8, HgÐS1 and
C8ÐHgÐS1 in the dithiophosphinate complex, (I) (Table 1);
C8ÐHgÐS1
C8ÐHgÐN
S1ÐHgÐN
C8ÐHgÐS2
S1ÐHgÐS2
NÐHgÐS2
C111ÐPÐC121
178.9 (3)
72.7 (4)
C111ÐPÐS2
C121ÐPÐS2
C111ÐPÐS1
C121ÐPÐS1
S2ÐPÐS1
112.8 (3)
113.0 (3)
104.6 (3)
104.8 (3)
115.24 (17)
74.18 (11)
99.12 (13)
106.9 (2)
109.5 (3)
70.99 (8)
171.8 (2)
105.5 (4)
PÐS2ÐHg
PÐS1ÐHg
Ê
HgÐC = 2.083 (7) and HgÐS = 2.357 A, and CÐHgÐS =
ꢁ
Data collection: CAD-4 EXPRESS (Enraf±Nonius, 1994); cell
re®nement: CAD-4 EXPRESS (Enraf±Nonius, 1994); data reduction:
XCAD-4 (Harms & Wocadlo, 1996); program(s) used to solve
structure: SHELX97 (Sheldrick, 1997); program(s) used to re®ne
structure: SHELX97; software used to prepare material for publi-
cation: SHELX97.
1
77.7 (2) in the thiosemicarbazonate] and two secondary
bonds [HgÐN and HgÐS2 in (I) (Table 1); two HgÐN bonds
Ê
with distances 2.576 (6) and 3.126 (6) A in the thio-
�
semicarbazonate]. Finally, the S PCy ligand is more aniso-
2
2
bidentate in (I) (see Table 1) than in [TlPh (S PCy )] [TlÐS1 =
2
2
2
Ê
.789 (3) and TlÐS2 = 2.816 (3) A; Casas et al., 1995]. In
2
keeping with this, the PÐS1 bond, corresponding to S strongly
coordinated to metal, is longer and the PÐS2 bond shorter in
This work was supported by the Spanish Ministry of
Education and Culture.
(
I) (Á/ꢀ = 18.2) than in the latter compound.
Experimental
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: NA1445). Services for accessing these data are
described at the back of the journal.
[
2-(2-Pyridyl)phenyl]mercury acetate (21.6 mg, 0.052 mmol) and
dicyclohexyldithiophosphinic acid (13.7 mg, 0.052 mmol) were
dissolved in chloroform at 273 K. Slow evaporation in the refrigerator
gave colourless crystals suitable for X-ray analysis.
References
Crystal data
�
3
Alcock, N. W. (1970). Crystallographic Computing, edited by F. R. Ahmed,
S. R. Hall & C. P. Huber, pp. 271-278. Copenhagen: Munksgaard.
Bondi, A. (1964). J. Phys. Chem. 68, 441±451.
Casas, J. S., Castellano, E. E., Casti nÄ eiras, A., S a nchez, A. Sordo, J., V a zquez-
L o pez, E. M. & Zukerman-Schpector, J. (1995). J. Chem. Soc. Dalton Trans.
pp. 1403±1409.
Casas, J. S., Castellano, E. E., Garc Âõ a-Tasende, M. S., S a nchez, A., Sordo, J.,
V a zquez-L o pez, E. M. & Zukerman-Schpector, J. (1996). J. Chem.
Crystallogr. 26, 123±126.
[
M
Hg(C11
H
8
N)(C12
H
22PS
2
)]
D
x
= 1.758 Mg m
r
= 616.16
Mo Kꢂ radiation
Cell parameters from 25
re¯ections
Monoclinic, P2 =n
1
Ê
a = 14.923 (2) A
Ê
b = 9.9557 (10) A
ꢁ
ꢃ = 8±15
ꢄ = 6.87 mm
T = 293 (2) K
Ê
� 1
c = 15.728 (2) A
ꢁ
V = 2327.5 (5) A
Z = 4
ꢁ
Ê
= 95.088 (10)
3
Block, colourless
0.25 Â 0.25 Â 0.15 mm
Casas, J. S., Casti nÄ eiras, A., S a nchez, A., Sordo, J. & V a zquez-L o pez, E. M.
(
1994). J. Organomet. Chem. 468, 1±6.
Data collection
Casas, J. S., Garc Âõ a-Tasende, M. S., S a nchez, A., Sordo, J. & V a zquez-L o pez,
E. M. (1997). Inorg. Chim. Acta, 256, 211±216.
Casas, J. S., Garc Âõ a-Tasende, M. S. & Sordo, J. (1999). Coord. Chem. Rev. 193±
Enraf±Nonius CAD-4 diffract-
ometer
ꢅ-geometry diffractometer
Non-pro®led !/2ꢃ scans
Absorption correction: analytical
2272 re¯ections with I > 2ꢀ(I)
R
int = 0.060
ꢁ
ꢃmax = 24.97
195, 283±359.
h = � 17 ! 17
Constable, E. C., Leese, T. A. & Tocher, D. A. (1989). J. Chem. Soc. Chem.
Commun. pp. 570±571.
Enraf±Nonius (1994). CAD-4 EXPRESS. Version 5.1/1.2. Enraf±Nonius,
Delft, The Netherlands.
Harms, K. & Wocadlo, S. (1996). XCAD-4. University of Marburg, Germany.
Lobana, T. S., S a nchez, A., Casas, J. S., Casti nÄ eiras, A., Sordo, J. & Garc Âõ a-
Tasende, M. S. (1998). Polyhedron, 17, 3701±3709.
Sheldrick, G. M. (1997). SHELX97. University of G oÈ ttingen, Germany.
V a zquez-L o pez, E. M., Casti nÄ eiras, A., S a nchez, A., Casas, J. S. & Sordo, J.
(1992). J. Crystallogr. Spectrosc. Res. 22, 403±409.
k = 0 ! 11
(Alcock, 1970)
l = 0 ! 18
Tmin = 0.428, Tmax = 0.709
1 standard re¯ection
frequency: 30 min
intensity decay: � 3%
4
4
252 measured re¯ections
094 independent re¯ections
Re®nement
2
Re®nement on F
R(F) = 0.039
H-atom parameters constrained
2
2
2
w = 1/[ꢀ (F
where P = (F
(Á/ꢀ)max < 0.001
o
) + (0.0266P) ]
2
wR(F ) = 0.103
S = 0.961
2 2
+ 2F
c
o
)/3
Zsolnai, L. & Huttner, G. (1994). ZORTEP. University of Heidelberg,
Germany.
Zukerman-Schpector, J., V a zquez-L o pez, E. M., S a nchez, A., Casas, J. S. &
Sordo, J. (1991). J. Organomet. Chem. 405, 67±74.
Ê
� 3
4
2
094 re¯ections
53 parameters
Áꢆmax = 0.67 e A
Áꢆmin = � 0.712 e AÊ
� 3
Jos e S. Casas et al. ꢀ [Hg(C11
Acta Cryst. (2000). C56, 182±183
8 2
H N)(C12H22PS )] 183