Bis(benzenethiolato-S)(2,9-dimethyl-1,10-phenanthroline-N,N′) cadmium(II)

Full text of DOI:10.1107/S0108270101015906

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
gate fully the structure±property relationships in analogous
CdII complexes for comparison with these ZnII systems, we
have investigated the reactions of monothiolate complexes of
CdII with substituted 1,10-phenanthroline ligands.
ISSN 0108-2701
Bis(benzenethiolato)(2,9-dimethyl-1,10-phenanthroline)-
cadmium(II), (I), is monomeric, in contrast to related 1,2-
benzenedithiolate complexes which are dinuclear (Lowther et
al., 2001; Gronlund, Wacholtz & Mague, 1995). The elongated
displacement ellipsoid of atom S2 is evidence of positional
disorder in this atom, but attempts to model this by two or
even three partially occupied sites were unsuccessful. It was
evident from these attempts that no simple disorder model
would be suf®cient to describe alternate positions for this
atom. It appears from Fig. 3 that the whole molecule is
disordered over several slightly different conformations
involving libration about a point near the center of the chelate
ring. This is effectively an `inversion' about this point and
evidently the several conformations existing over the whole of
the crystal vary considerably more in the locations of atom S2
and its attached phenyl ring than in the locations of the
Bis(benzenethiolato-S)(2,9-dimethyl-
1,10-phenanthroline-N,N0)-
cadmium(II)
William F. Wacholtza and Joel T. Magueb*
aDepartment of Chemistry, University of Wisconsin Oshkosh, Oshkosh, WI 54901,
USA, and bDepartment of Chemistry, Tulane University, New Orleans, LA 70118,
USA
Correspondence e-mail: joelt@tulane.edu
Received 4 July 2001
Accepted 27 September 2001
The title compound, [Cd(C6H5S)2(C14H12N2)], exists as
monomeric molecules with offset ꢀ-stacking interactions
between the phenanthroline ligands in adjacent molecules.
Comment
Highly colored and luminescent complexes can be formed
when ZnII or CdII is coordinated in a heteroleptic ®eld
containing N,N-heterocyclic and either one dithiolate or two
monothiolate ligands. This visible transition has been
described as a metal-mediated ꢀ±ꢀ* ligand-to-ligand charge-
transfer (LLCT) transition (Koester, 1975; Crosby et al., 1985;
Truesdell & Crosby, 1985; Kutal, 1990; Burt & Crosby, 1994)
and is observed for a large variety of mono- and dithiolate plus
N,N-heterocyclic ligand sets (Muresan & Muresan, 1979;
Fernadez & Kisch, 1984; Crosby et al., 1985; Highland &
Crosby, 1985; Highland et al., 1986; Reddy et al., 1992; Galin et
al., 1993; Gronlund, Burt & Wacholtz, 1995; Gronlund,
Wacholtz & Mague, 1995; Halvorsen et al., 1995; Zemskova et
al., 1998; Yam et al., 1999; Wang et al., 2000). A number of
recent studies have indicated that unusual multinuclear ZnII
and CdII complexes are obtained when the mixed ligand set is
Figure 1
A perspective view of (I). Displacement ellipsoids are drawn at the 40%
probability level and H atoms have been omitted for clarity.
a planar N,N-heterocyclic ligand in combination with a di-
thiolate ligand (Halvorsen et al., 1995; Gronlund, Wacholtz &
Mague, 1995; Wang et al., 2000; Lowther et al., 2001). However,
when substituents are attached to the periphery of 1,10-
phenanthroline ligands, only mononuclear complexes tend to
be observed. In one ZnII system, two different crystal forms
are obtained for very subtle conformational changes in the
monothiolate ligands (Jordan et al., 1991). In order to investi-
Figure 2
View of the ꢀ-stacking interaction in (I). The molecule containing primed
atoms is related to the other by the operation
1
2
x, 12 + y, z.
ꢀ
1400 # 2001 International Union of Crystallography
Printed in Great Britain ± all rights reserved
Acta Cryst. (2001). C57, 1400±1402

metal-organic compounds
Data collection
remaining atoms. This is likely to be the reason for the CdÐS
distances (Table 1), particularly CdÐS2, appearing shorter
Enraf±Nonius CAD-4
diffractometer
ꢂ/2ꢂ scans
Absorption correction: empirical
via scans (North et al., 1968)
Tmin = 0.734, Tmax = 0.836
2388 re¯ections with I > 2ꢄ(I)
ꢂmax = 26.0ꢁ
Ê
than the usual values of around 2.50 A. The two phenyl rings
h = 0 ! 17
are inclined at an angle of 56.2 (1)ꢁ (Fig. 1). The phenyl ring
involving C7 is nearly parallel to the mean plane of the
phenanthroline ligand [dihedral angle 9.1 (2)ꢁ], while the
k = 0 ! 14
l = 0 ! 34
2 standard re¯ections
frequency: 120 min
intensity decay: <1%
4548 measured re¯ections
4548 independent re¯ections
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.035
wR(F2) = 0.102
S = 1.02
4548 re¯ections
w = 1/[ꢄ2(Fo2) + (0.0374P)2
+ 2.7120P]
where P = (Fo2 + 2Fc2)/3
(Á/ꢄ)max = 0.002
3
Ê
Áꢅmax = 0.45 e A
3
Ê
0.51 e A
282 parameters
H-atom parameters constrained
Áꢅmin
=
Table 1
Selected geometric parameters (A, ).
ꢁ
Ê
CdÐN1
CdÐN2
2.341 (4)
2.341 (3)
CdÐS2
CdÐS1
2.4189 (16)
2.4321 (14)
N1ÐCdÐN2
N1ÐCdÐS2
N2ÐCdÐS2
71.64 (12)
106.22 (10)
104.21 (10)
N1ÐCdÐS1
N2ÐCdÐS1
S2ÐCdÐS1
105.80 (9)
109.59 (9)
139.08 (5)
Figure 3
View of (I) perpendicular to the plane of the phenanthroline ligand,
showing the apparent librational motion.
other phenyl ring makes an angle of 64.3 (2)ꢁ with this mean
plane. Fig. 2 depicts the offset ꢀ-stacking between phenan-
throline ligands of neighboring molecules. The rings in ques-
tion are virtually parallel, with a distance between the centers
The H atoms were included in calculated positions (CÐH = 0.93±
Ê
0.96 A) as riding, with isotropic displacement parameters 1.2 times
those of the attached C atom.
Ê
of gravity of the two rings of 3.62 (1) A and a perpendicular
distance from the center of gravity of one ring to the mean
Data collection: CAD-4 Software (Enraf±Nonius, 1989); cell
re®nement: CAD-4 Software; data reduction: XCAD4 (Harms, 1996);
program(s) used to solve structure: SHELXS97 (Sheldrick, 1990);
program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997);
molecular graphics: SHELXTL (Bruker, 1997).
Ê
plane of the other of 3.55 (1) A.
Experimental
We thank the Chemistry Department of Tulane University
for support of the X-ray laboratory and anonymous UW
Oshkosh donors for funding to establish the Emission Spec-
troscopy Laboratory.
Benzenethiol (0.21 ml, 2.1 mmol) in hot ethanol (10 ml) was added
dropwise to a hot solution of cadmium acetate dihydrate (266.5 mg,
1.0 mmol) in a 1:1 (v/v) mixture (50 ml) of ethanol and dimethyl-
formamide. The solution was brought to re¯ux and 2,9-dimethyl-1,10-
phenanthroline monohydrate (226.3 mg, 1.0 mmol) dissolved in hot
ethanol (25 ml) was added slowly with stirring. A ¯occulent golden
yellow precipitate formed immediately and the reaction was
continued for an additional 30 min. The mixture was cooled to room
temperature, allowed to stand for 24 h and the solid collected by
suction ®ltration (yield 94%). Yellow crystals were obtained by slow
evaporation of a dimethylformamide solution of the complex in air.
Analysis calculated for C26H22CdN2S2: C 57.93, H 4.12, N 5.20%;
found: C 57.9, H 4.1, N 5.2%.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: DA1203). Services for accessing these data are
described at the back of the journal.
References
Bruker (1997). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wis-
consin, USA.
Burt, J. A. & Crosby, G. A. (1994). Chem. Phys. Lett. 220, 493±496.
Crosby, G. A., Highland, R. G. & Truesdell, K. A. (1985). Coord. Chem. Rev.
64, 41±52.
Enraf±Nonius (1989). CAD-4 Software. Enraf±Nonius, Delft, The Nether-
lands.
Fernadez, A. & Kisch, H. (1984). Chem. Ber. 117, 3102±3111.
Galin, A. M., Razskakovsky, V. & Mel'nikov, M. Y. (1993). J. Photochem.
Photobiol. A: Chem. 72, 35±40.
Crystal data
[Cd(C6H5S)2(C14H12N2)]
Mr = 538.98
Orthorhombic, Pbca
Mo Kꢁ radiation
Cell parameters from 25
re¯ections
Ê
a = 14.164 (2) A
ꢂ = 11.1±15.8ꢁ
1
Ê
b = 12.034 (2) A
ꢃ = 1.12 mm
T = 293 (2) K
Ê
c = 27.648 (3) A
Ê
V = 4712.5 (13) A
3
Column, pale orange
0.48 Â 0.28 Â 0.16 mm
Z = 8
Dx = 1.519 Mg m
Gronlund, P. J., Burt, J. & Wacholtz, W. F. (1995). Inorg. Chim. Acta, 234,
13±18.
3
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Acta Cryst. (2001). C57, 1400±1402
Wacholtz and Mague [Cd(C6H5S)2(C14H12N2)] 1401

metal-organic compounds
Gronlund, P. J., Wacholtz, W. F. & Mague, J. T. (1995). Acta Cryst. C51, 1540±
1543.
Halvorsen, K., Wacholtz, W. F. & Crosby, G. A. (1995). Inorg. Chim. Acta, 228,
81±88.
Harms, K. (1996). XCAD4. University of Marburg, Germany.
Highland, R. G., Brummer, J. G. & Crosby, G. A. (1986). J. Phys. Chem. 90,
1593±1598.
Muresan, N. & Muresan, V. (1979). Rev. Roum. Chim. 24, 1123±1128.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351±
359.
Reddy, H. K., Zhang, C., Schlemper, E. O. & Schrauzer, G. N. (1992). Inorg.
Chem. 31, 1673±1677.
Sheldrick, G. M. (1990). Acta Cryst. A46, 467±473.
È
Sheldrick, G. M. (1997). SHELXL97. University of Gottingen, Germany.
Highland, R. G. & Crosby, G. A. (1985). Chem. Phys. Lett. 119, 454±458.
Jordan, K. J., Wacholtz, W. F. & Crosby, G. A. (1991). Inorg. Chem. 30, 4588±
4593.
Truesdell, K. A. & Crosby, G. A. (1985). J. Am. Chem. Soc. 107, 1787±1788.
Wang, Q., Long, D., Hu, H., Cui, Y. & Huang, J. (2000). J. Coord. Chem. 49,
201±209.
Koester, V. J. (1975). Chem. Phys. Lett. 32, 575±580.
Kutal, C. (1990). Coord. Chem. Rev. 99, 213±252.
Lowther, M. D., Wacholtz, W. F. & Mague, J. T. (2001). J. Chem. Crystallogr. In
the press.
Yam, V. W., Pui, Y. & Cheung, K. (1999). New J. Chem. 23, 1163±1169.
Zemskova, S. M., Prashad, G., Glinskaya, L. A., Klevtsova, R. F., Durasov,
V. B., Tkachev, S. V., Gromilov, S. A. & Larionov, S. V. (1998). Zh. Neorg.
Khim. 43, 1644±1650.
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1402 Wacholtz and Mague
[Cd(C6H5S)2(C14H12N2)]
Acta Cryst. (2001). C57, 1400±1402