Polyhedron 20 (2001) 2231 2240

www.elsevier.com/locate/poly

Transition metal complexes with thiosemicarbazide-based ligands.

Part XLI. Two crystal structures of cobalt(III) complexes with
salicylaldehyde S-methylisothiosemicarbazone and theoretical study
on orientations of coordinated pyridines
Goran A. Bogdanovic a,1, Vesna B. Medakovic b, Ljiljana S. Vojinovic c,
Valerija I. C& esljevic c, Vukadin M. Leovac c, Anne Spasojevic-de Bire a,
Snezana D. Zaric b,*
Laboratoire de Structures, Proprietes et Modelisation des Solides (SPMS), UMR 8580 du CNRS, Ecole Centrale Paris,
Grande Voie des Vignes, 92295 Chatenay-Malabry Cedex, France
b
Department of Chemistry, Uni6ersity of Belgrade, Studentski trg 16, P.O. Box 158, 11001 Belgrade, Yugosla6ia
c
Institute of Chemistry, Faculty of Sciences, Uni6ersity of No6i Sad, Trg Dositeja Obrado6ica 3, 21000 No6i Sad, Yugosla6ia
a

Received 31 January 2001; accepted 26 April 2001

Abstract
Two compounds, [CoIII(L)(py)3][CoII(py)Cl3]EtOH and [CoIII(L)(py)3]I3 (H2L= salicylaldehyde S-methylisothiosemicarbazone,
py =pyridine), were synthesized and the crystal structures determined by single-crystal X-ray diffraction. In both structures the
geometries of the cation are very similar to a thiosemicarbazide-based ligand coordinated in the mer configuration. The axial
pyridines are in mutual perpendicular orientation, the angles between the planes being 85.3(2) and 82.5(2). The plane of the
equatorial pyridine is tilted with respect to the equatorial plane by about 40. The orientations of the pyridines were studied in
model systems by quantum chemistry calculations. It was shown that the interactions between axial and equatorial pyridines are
responsible for the orientation of pyridines in the complex cation; consequently, there are very similar geometries of the complex
cation in both crystal structures. The compounds were also characterized by elemental analysis, molar conductivity, magnetic
susceptibility and electronic absorption spectra. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Crystal structures; Thiosemicarbazide based ligands; DFT calculations; Co(III) complexes; Preferential pyridine orientation

1. Introduction
Because of their biological activity and analytical
application, thiosemicarbazides and thiosemicarbazones, as well as their metal complexes have been the
subject of many studies [1]. Numerous metal complexes
have been synthesized with S-alkylisothiosemicarbazide-based ligands and one of the most extensively
used ligands is salicylaldehyde S-alkylisothiosemicarbazone [2,3]. This ligand can coordinate to the metal in
* Corresponding author. Fax: + 381-11-638785.
E-mail address: szaric@chem.bg.ac.yu (S.D. Zaric).
1
Present address: Vinca Institute of Nuclear Sciences, Laboratory
of Theoretical Physics and Condensed Matter Physics, P.O. Box 522,
11001 Belgrade, Yugoslavia.

the monoanionic (resulting from deprotonation of the

phenolic hydroxyl) or dianionic form (formed by an
additional deprotonation of the 2NH group of the
isothiosemicabazide moiety).
In the cation complexes of CoIII presented in this
paper salicylaldehyde S-methylisothiosemicarbazone
ligand is ONN-tridentate coordinated, the three other
coordinated positions are occupied by three pyridines.
The orientations of histidines, axially ligated to heme,
are considered to have a strong influence on the function of heme cofactors in proteins. Different conformations can shift the redox potential [4] and they can
control the coordination of substrates to heme-proteins
[5]. Therefore, orientations of the axial ligand have
been studied in heme proteins [69]. From experimen-

0277-5387/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 1 ) 0 0 8 1 9 - 1

2232

G.A. Bogdano6ic et al. / Polyhedron 20 (2001) 22312240

tal data on heme model systems and from molecular

mechanics studies it was shown that the orientations of
axial ligands have an influence on the porphyrin ring
conformations. In complexes with parallel orientation
of two planar axial ligands, the porphyrin ring remains
planar. For porphyrin complexes, which have two planar axial ligands in perpendicular orientation, the porphyrin ring is almost invariably distorted from
planarity [712]. The DFT calculations on [Fe(por)(py)2] and [Fe(por)(py)2]+ showed that for the FeII
complex there is no difference in the preferential orientations (parallel or orthogonal) of axially coordinated
pyridines, but for the FeIII complex the orthogonal
orientation is more stable [11]. The calculations on
[Fe(por)(im)2] and [Fe(por)(im)2]+ showed that for both
complexes there is no difference in the preferential
orientations (parallel or orthogonal) of axially coordinated imidazoles [12].
Recently, [Fe(TMP)(5-MeHim)2]ClO4 has been obtained in two distinct crystalline forms with different
relative axial ligand orientations: one is almost parallel
and the other is almost perpendicular [13]. Hence, one
can conclude that the two conformational isomers are
energetically nearly equivalent.
In this work the synthesis and crystal structure determination of [Co(L)(py)3][Co(py)Cl3]EtOH (1) and
[Co(L)(py)3]I3 (2) (H2L = salicylaldehyde S-methylisothiosemicarbazone, py= pyridine) have been performed. Due to some ambiguities in the previous published structure of 1, a re-investigation of the structure
has been done [2]. Very similar geometries of the complex cation in both crystal structures, with perpendicular orientations of axial pyridines, indicated that there
are intramolecular interactions influencing the orientation of coordinated pyridines. Quantum chemistry calculations have been done on model systems in order to
find out factors influencing the orientation of the axially coordinated pyridines.

its effective magnetic moment is 4.28 mB. The substance

loses 3.42% in mass at 80C (calculated 2.99%). At
105C there is no further loss in mass.
Anal. Found: C, 46.74; H, 4.37; Co, 14.56; N, 12.10.
Calc. for Co2C31H35N7O2SCl3: C, 46.90; H, 4.44; Co,
14.85; N, 12.35%.

2.1.2. [Co(L)(py)3]I3 (2)

0.60 g (2.5 mmol) of CoCl6H2O was added to a
warm solution of 0.75 g (5.0 mmol) NaI in 5.0 cm3 of
EtOH. The reactants were dissolved by mild heating.
After 15 min of cooling at r.t., crystals of NaCl were
separated. 0.26 g (1.25 mmol) of H2L and 0.4 cm3 of
pyridine were added to the solution of CoI2. The reactants were dissolved again by mild heating. After 2 days
at r.t. crystals were filtered from a dark solution, and
washed out with EtOH and ether. The yield was 0.69 g
(55%).
The molar conductivity of a 1 10 3 mol dm 3
compound solution in DMF is 70.2 S cm2 mol 1.
Anal. Found: C, 7.25; H, 2.97; Co, 7.25; N, 9.71.
Calc. for CoC24H24N6OSI3: C, 32.60; H, 2.74; Co, 6.66;
N, 9.51%.
2.2. Physicochemical measurements
Elemental analysis was carried out by standard
micromethods.
Magnetic susceptibility measurements were made at
r.t. using a MSB-MKI magnetic susceptibility balance
(Sherwood Scientific Ltd, Cambridge, UK). The data
were corrected for diamagnetic susceptibilities. Molar
conductivities of freshly prepared 110 3 mol dm 3
solutions were measured on a Jenway 4010 conductivity
meter.
Electronic absorption spectra were taken on a Cary
219 spectrophotometer.

2.3. Crystal structure determinations

2. Experiments and results

2.1. Synthesis and physicochemical properties

2.1.1. [Co(L)(py)3][Co(py)Cl3] EtOH (1)
EtOH (5.0 cm3) and pyridine (0.4 cm3) were added to
a mixture of 0.60 g (2.5 mmol) of CoCl26H2O and 0.26
g (1.25 mmol) of salicylaldehyde S-methylisothiosemicarbazone (H2L). The reactants were dissolved by stirring and mild heating. After 24 h at room temperature
(r.t.) crystals were formed. The crystals were filtered
from the green solution and washed out with EtOH and
ether. The yield was 0.70 g (75%).
The molar conductivity of a 110 3 mol dm 3
compound solution in dimethyl formamide (DMF) is
41.3 S cm2 mol 1. The compound is paramagnetic and

Data were collected on an EnrafNonius CAD4 diffractometer [14] using Mo Ka radiation (u=0.71069 A, )
and 2q scans in the 1.2325.98 q range for complex
1 and 1.6427.97 q range for complex 2. Cell constants and an orientation matrix for data collection,
obtained from 24 centered reflections in the range
14.9717.98 for 1 and 13.0417.14 for 2, corresponded to a triclinic and monoclinic cell, respectively.
The dimensions are given in Table 1. The data were
corrected for Lorentz and polarization effects [15]. A
Gaussian-type absorption correction [16b] based on the
crystal morphology was applied (Tmin = 0.535, Tmax =
0.713 for 1; Tmin = 0.254, Tmax = 0.531 for 2).
The structures were solved by the heavy atom
method [17a] and difference Fourier methods and
refined on F 2 by a full-matrix least-squares method

G.A. Bogdano6ic et al. / Polyhedron 20 (2001) 22312240

[17b]. All H atoms were placed at the calculated positions except the H atoms from the isothiosemicarbazide
moiety, which were determined from difference Fourier
synthesis and freely refined. Idealized H atoms were
refined with isotropic displacement parameters set to
1.2 (1.5 for methyl groups) times the equivalent
isotropic U value of the parent atom.
Special attention has to be given to the refinement of
complex 1. In a previous paper [2] the reported structure did not contain any solvent molecule. Nevertheless,
a precise analysis of the structure with the PLATON
program [16,18] has shown that solvent accessible voids
exist in the crystal lattice with a volume of 208.8 A, 3.
Theoretical volumes for EtOH dimer as solvent
molecules fit very well with the calculated space. Ethanol molecules can be expected in the crystal lattice since
synthesis is done in that solvent. Moreover, the experimental density of 1 is 1.48 Mg m 3, and calculated
densities are 1.493 and 1.406 Mg m 3 with and without
EtOH, respectively. The elemental analysis is also in
agreement with the presence of solvent molecules in the
crystal lattice.
In order to take into account the presence of EtOH
molecules in the crystal, two different refinements have
been performed on the new dataset:

2233

1. The positions of non-hydrogen atoms of EtOH were

determined from the difference Fourier map. However, because of the very high disorder of the
molecule, these atoms were refined with isotropic
thermal parameters (quoted as refinement 1a).
2. Using the SQUEEZE procedure [16b] a new reflection
file was formed, where the disordered solvent contribution (as determined in the previous step) is subtracted from the observed data. Further refinements
of the whole complex were done using this new file
(quoted as refinement 1b).
Crystallographic data and refinements parameters for
complexes 1 and 2 are summarized in Table 1. The
maximum and minimum peaks on the final difference
Fourier map are located within 0.5 A, of the Cl and Co
atoms. The structure of complex 1 obtained from the
two refinement strategies (1a and 1b) are very similar;
therefore, Tables 24 present the results deduced from
procedure 1b compared to the structure of complex 2.
Figs. 1 and 2 present the structures of complexes 1 and
2, respectively.

2.4. Computational methods

The calculations were performed on three different
model systems of the complex cation [CoIII(L)(py)3]+.

Table 1
Crystal data, data collection and structural refinement details

Empirical formula
Color; habit
Size (mm)
Temperature (K)
Crystal system
Space group
Unit cell dimensions
a (A, )
b (A, )
c (A, )
h ()
i ()
k ()
V (A, 3)
Z
Dcalc (Mg m3)
Absorption coefficient (mm1)
Data collection limits
Reflections collected
Empirical formula
Independent reflections
Data for [I\2|(I)]/restraints/parameters
Goodness-of-fit on F 2
R1 , wR2 [I\2|(I)]

Complex 1aa

Complex 1bb

Complex 2c

C31H35Cl3Co2N7O2S
green; prism
0.290.500.58
293(2)
triclinic
P1(

C29H29Cl3Co2N7OS
green; prism
0.290.500.58
293(2)
triclinic
P1(

C24H24CoI3N6OS
brown; prism
0.180.360.50
293(2)
monoclinic
P21/n

9.024(5)
11.844(3)
16.923(4)
100.91(2)
92.29(6)
95.11(6)
1766(2)
2
1.493
1.265
h, 9k, 9l
7370
C31H35Cl3Co2N7O2S
6910 [Rint =0.0231]
5531/0/404
1.073
0.0667, 0.1990

9.024(5)
11.844(3)
16.923(4)
100.91(2)
92.29(6)
95.11(6)
1766(2)
2
1.406
1.265
h, 9 k, 9 l
7370
C29H29Cl3Co2N7OS
6910 [Rint =0.0223]
5537/0/392
1.078
0.0654, 0.2011

14.646(3)
12.513(2)
16.622(2)
90.00
106.100(10)
90.00
2926.8(8)
4
2.005
3.850
h, k, 9 l
7827
C24H24CoI3N6OS
7046 [Rint =0.0267]
5114/0/323
1.037
0.0366, 0.0941

R = Fo Fc /F o2, Rw = [(w(Fo 2F c2)]/[w(F o2)2]0.5.

a
For 1a: w = 1/[| 2(F o2)+(0.1346P)2+3.1230P] where P= (F o2+2F c2)/3.
b
For 1b: w =1/[| 2(F o2)+(0.1480P)2+1.4970P] where P= (F o2+2F c2)/3.
c
For 2: w = 1/[| 2(F o2)+(0.0465P)2+4.4300P] where P= (F o2+2F c2)/3.

G.A. Bogdano6ic et al. / Polyhedron 20 (2001) 22312240

2234

Table 2
Selected geometric parameters (A, , ) for [CoIII(L)(py)3]+
Complex 1 [2]

Complex 1b

Complex 2

MS1

MS2a

MS2b

MS3

Bond lengths
Co1O1
Co1N1
Co1N3
Co1N6
Co1N5
Co1N4
SC1
SC1S
C1N2
C1N3
N1C2
N1N2
O1C4

1.893(7)
1.911(8)
1.889(9)
1.963(7)
1.953(7)
1.960(8)
1.76(1)
1.80(1)
1.33(1)
1.34(1)
1.27(1)
1.40(1)
1.35(1)

1.884(4)
1.884(3)
1.902(5)
1.976(4)
1.970(3)
1.980(4)
1.766(5)
1.802(5)
1.319(6)
1.321(6)
1.285(6)
1.387(5)
1.315(5)

1.880(2)
1.879(3)
1.891(4)
1.991(3)
1.963(3)
1.974(3)
1.763(4)
1.779(3)
1.313(6)
1.314(6)
1.279(4)
1.411(5)
1.316(5)

1.870
1.885
1.915
1.971
1.974
2.022

1.865
1.867
1.913
2.025
1.960
2.031

1.854
1.869
1.908
2.000
1.977
2.040

1.873
1.879
1.911
1.965
1.992
2.012

1.355
1.397
1.359
1.475
1.347

1.361
1.391
1.355
1.476
1.347

1.365
1.381
1.355
1.477
1.347

1.359
1.391
1.355
1.474
1.343

Bond angles
O1Co1N1
O1Co1N3
N1Co1N3
O1Co1N6
N1Co1N6
N3Co1N6
O1Co1N5
N1Co1N5
N3Co1N5
N6Co1N5
O1Co1N4
N1Co1N4
N3Co1N4
N6Co1N4
N5Co1N4
O1Co1N4C1a
C1bN5N6C1c

95.4(5)
176.8(5)
81.6(6)
89.8(5)
90.2(6)
89.1(6)
88.9(5)
90.1(6)
92.2(6)
178.6(6)
88.6(5)
175.9(6)
94.4(6)
90.4(6)
89.4(6)
34(1)
84(1)

95.1(2)
176.1(2)
81.4(2)
89.2(2)
89.8(2)
88.9(2)
88.4(2)
89.9(2)
93.4(2)
177.6(2)
88.5(2)
176.3(2)
95.0(2)
91.0(2)
89.5(2)
34.0(4)
83.8(4)

95.8(1)
177.4(1)
81.6(2)
90.0(1)
87.8(2)
90.3(2)
87.1(1)
90.6(1)
92.5(2)
176.5(1)
88.2(1)
175.0(2)
94.3(2)
89.4(1)
92.4(1)
37.4(3)
86.3(3)

97.1
178.2
83.5
89.5
88.9
88.8
88.8
91.2
92.9
178.3
86.9
174.7
92.4
87.7
92.3

97.9
178.6
82.9
88.7
89.8
91.2
88.4
90.6
92.8
176.0
89.1
173.0
90.2
89.4
90.7

70.5

4.8

96.4
178.6
82.6
90.6
90.1
90.5
87.6
89.2
91.3
178.0
87.6
175.8
93.3
91.0
89.8
37.9
87.3

96.1
177.7
82.7
90.7
89.1
91.3
88.4
89.1
89.5
177.9
87.7
176.2
93.4
91.3
90.6
35.2

Table 3
Total puckering amplitudes and torsion angles for six-membered chelate rings

QT (A, )
O1CoN1C2 ()
CoN1C2C3 ()
N1C2C3C4 ()
C2C3C4O1 ()
CoO1C4C3 ()
N1CoO1C4 ()

Complex 1

Complex 2

MS1

MS2a

MS2b

MS3

0.1545(5)
11.0(4)
3.7(6)
4.3(7)
0.1(6)
11.5(6)
14.8(3)

0.1627(1)
8.0(3)
0.9(5)
5.5(6)
4.0(6)
16.7(5)
16.6(3)

0.05
4.1
3.0
1.5
4.2
1.9
1.7

0.12
5.1
1.4
3.7
3.9
12.7
11.6

0.02
0.6
1.3
0.1
2.1
2.7
1.3

0.10
8.5
5.3
2.4
4.5
1.4
6.5

The geometries for different conformers of the three

model systems were optimized and energies were calculated using the B3LYP method. These B3LYP calculations have been carried out with the GAUSSIAN-98
program [20]. In the B3LYP geometry optimizations,
STO-3G basis sets were chosen for the carbon, nitrogen, oxygen and hydrogen atoms and LANL2DZ for
the cobalt atom. The DFT method is used as it gives
good results for all transition metal complexes includ-

ing transition metal complexes of the first row

[11,12,21]. In cases where conformers were not stationary points some torsion angles were fixed in order to
keep the desired orientations of pyridines. Starting
with these optimized structures, the B3LYP single
point energy calculations were made using the 6-31G
basis sets. The partial charges, which are presented in
the article, are charges calculated with 6-31G basis
sets.

G.A. Bogdano6ic et al. / Polyhedron 20 (2001) 22312240

2235

Table 4
Interligand contacts (A, ) in crystal structures and model systems of complex cations
Complex 1

Complex 2

MS1

MS2a a

MS2b b

MS3

AHB system
A =O1, B= C1a (or N4)
A =O1, B= C5b (or N5)
A =O1, B= C5c (or N6)

2.44(1)
2.44(1)
2.60(1)

2.38(1)
2.55(1)
2.48(1)

2.42
2.81 d
2.55 d

2.47 c
2.53
2.34

2.60 c
2.50
2.43

2.47
2.41
2.67

AHHB system
A = C1a (or N4), B=C5b (or N5)
A =C1a (or N4), B= C5c (or N6)

3.35(1)
3.32(1)

3.30(1)
3.41(1)

2.55 d
2.65 d

2.45 c
2.49 c

2.41 c
2.42 c

3.43
3.33

Model system 2 with perpendicular orientations of axial pyridines.

Model system 2 with parallel orientations of axial pyridines.
c
The distances are with H of NH3 in equatorial position.
d
The distances are with H of NH3 in axial position.
b

3. Discussion

3.1. Synthesis and physicochemical properties

The reaction of warm EtOH solutions of CoX26H2O
(X = Cl, I) with salicylaldehyde S-methylthiosemicarbazone (H2L), synthesized according to Ref. [22], and
pyridine in a mole ratio 2:1:5 in the presence of the air
oxygen resulted in complexes 1 and 2. A common
characteristic of both compounds is that the same
octahedral complex cation of cobalt(III) is coordinated
with the dianion of the tridentate ONN isothiosemicarbazone and with three pyridine molecules. In the case
of complex 1, the cation is stabilized by the tetrahedral
[CoIICl3Py] anion. In contrast, the reaction with CoI2
yielded no [CoIII3Py], obviously less stable, and complex 2 presents I3 as the anion. Therefore, complex 2
is diamagnetic and complex 1 paramagnetic, with a
value veff =4.28 mB, which is in the range characteristic
of the tetrahedral CoII complexes [23].
The complexes are highly soluble in DMF, less soluble in MeOH, EtOH, and Me2CO, and insoluble in
H2O and Et2O.
The molar conductivity (uM) of the freshly prepared
DMF solution of complex 2 corresponds to the 1:1 type
of electrolyte [24], whereas uM of complex 1, probably
because of the presence of the voluminous anion, is
lower. In any case, DMF solutions of these complexes
are not stable. In both cases, after several days, the
brown complex of the non-electrolyte type
[CoIII(HL)L], described earlier [25], is formed. In contrast to the DMF solutions, the Me2CO solutions are
more stable, which in the case of complex 1 is also
observed as the preservation of its green color.
The electronic absorption spectra of the DMF and
Me2CO solutions of both complexes are characterized
by the presence of the absorption maxima at : 400 nm
(m =900022 000 dm3 mol 1 cm 1) which can be ascribed to the octahedral CoIII ion [26]. The spectrum of
complex 1 in both solvents contains additional weaker

absorption bands (m= 640 900 dm3 mol 1 cm 1) with

a maxima in the range of 600675 nm, which undoubtedly belong to the tetrahedral anion.

3.2. Re-in6estigation of the structure of 1

The re-investigation of the structure of complex 1
leads us to the following results: (i) The position of the
solvent molecule has been determined; the observed

Fig. 1. ORTEP [19] drawing of [CoIII(L)(py)3][CoII(py)Cl3] with the

atom numbering scheme. The thermal ellipsoids correspond to 50%
probability.

Fig. 2. ORTEP [19] drawing of [CoIII(L)(py)3]I3 with the atom numbering scheme. The thermal ellipsoids correspond to 50% probability.

2236

G.A. Bogdano6ic et al. / Polyhedron 20 (2001) 22312240

geometry is a dimer exhibiting mutual H-bonds between oxygen lone pairs and hydrogen atoms from CH2
groups (I). (ii) The cation complex structure remains
globally the same [2], but as expected the values are
more accurate (Table 2). (iii) The main discrepancy is
observed in the salicylaldehyde S-methylisothiosemicarbazone ligand. After final full-matrix least-squares
refinement with anisotropic temperature factors for
non-H atoms, there was no suitable peak indicating the
presence of a hydrogen atom near the N2 atom.

3.3. Crystal structure of complexes 1 and 2. General

beha6ior
Globally, the two compounds differs from their
counter anions. In complex 1, the anion is [CoIICl3Py].
The Co2 atom is in a tetrahedral environment formed
by three Cl atoms [2.282(2) 2.313(3) A, ] and one pyridine N atom [2.053(5) A, ]. The crystal structure of the
complex 2 anion consists of the tri-iodide anion, which
is almost linear with the I1I2I3 angle of 175.86(2).
The I1I2 and I2I3 bond lengths are 2.9330(6),
2.8867(6) A, , respectively.
The Co atom in complex cations lies in an octahedral
environment with salicylaldehyde S-methylisothiosemicarbazone coordinated in the mer configuration. In all
previously published compounds [3] the salicylaldehyde
S-methylisothiosemicarbazone (H2L) is coordinated to
transition metals as a planar tridentate NNO ligand
forming fused five- and six-membered chelate rings.
The same trend is observed in the structure of complexes 1 and 2 (Figs. 1 and 2). However, this ligand can
be coordinated as a monoanionic (HL) or dianonic
(L) ligand. As observed for complex 1 (vide supra)
there is no hydrogen atom near the N2 atom. The
structure quality of complex 2 is good enough to allow
the detection of all hydrogen atoms and therefore one
can conclude that the salicylaldehyde S-methylisothiosemicarbazone is coordinated in both complexes as a
dianion. This means that both octahedral coordinated
atoms have an oxidation state of + 3, instead of + 2,
as previously published [2] for complex 1. This high
oxidative state is in agreement with the electronic spectra of complexes. It can be confirmed by re-investigating the structure [2] in which the distance between the
dummy hydrogen atom bonded to N2 nitrogen and
the hydrogen atom from the methyl group bonded to S
is 1.8 A, . Such a short distance is physically meaningless

due to the steric hindrance. This steric hindrance could

be avoided by a cis position of the methyl group with
respect to N3 nitrogen, which is the case in some
complexes with coordinated salicylaldehyde Smethylisothiosemicarbazone as a monoanion [3ac,f,g].
In the crystal packing, there are a few hydrogen
bonds of N3H group: N3H(N3) = 1.030 A, ,
H(N3)Cl2 = 2.370 A, ,
N(3)H(N3)Cl2 =166.1
and N3H(N3) = 1.030 A, , H(N3)I3 = 2.916 A, ,
N3H(N3)I3 =174.1 for structures 1 and 2, respectively [27]. These H-bonds do not have an important
influence on the structure of the cation.
The complex cations in both structures are very
similar, which is clear when comparing the bond distances and angles (Table 2). It is interesting to notice
that both complex cations are stereochemically almost
identical (conformations of chelate rings, mutual orientations of axial ligands, orientation of equatorial ligand). It means that different anions, and different
packing do not have any influence on the conformation
of the [CoIII(L)(py)3]+ complex cation; the conformation of the cation is determined by intramolecular
interactions in the cation. In order to investigate these
mutual ligands influences, quantum chemical calculations on different conformers of model systems of the
complex cation were performed.

3.4. Geometries of complex cations in the crystal

structures and in the calculated model systems
The quantum chemical calculations have been done
on the model systems with the equatorial chelate ligand
smaller than in the real molecule (Fig. 3). In order to
investigate mutual influence of coordinated pyridines
three different model systems were used. In model
system 1, two NH3 groups are coordinated at axial
positions and one pyridine is coordinated in equatorial
position. In model system 2, one NH3 is coordinated in
equatorial position and two pyridines are coordinated
in axial positions. In model system 3, three pyridines
are coodinated, one in equatorial and two in axial
positions. The geometries for a few different conformers of each of the three model systems were obtained.
However, Tables 24 contain only geometric data of
stationary point conformers, obtained with full optimization. In model system 1, the conformer with the
equatorial pyridine (MS1) is tilted by about 40 with
respect to the equatorial plane; in model system 2, there
are two conformers, with perpendicular (MS2a) and
with parallel orientations of axial ligands (MS2b); and
in model system 3, the conformer has the axial ligands
in perpendicular orientation (MS3).
Table 2 gives geometric parameters for the crystal
structures of the complex cation and for the optimized
geometries of the model systems. There are slight differences between experimental and calculated bond

G.A. Bogdano6ic et al. / Polyhedron 20 (2001) 22312240

2237

Fig. 3. Perspective view of the model systems: (a) model system 1 (MS1); (b) model system 2 (MS2a); and (c) model system 3 (MS3).

lengths. The bond angles around Co1 show that the

upper pyridine is slightly bent towards O1. In the
crystal structures and in the calculated model systems
with axial pyridines (MS2 and MS3) the O1Co1N5
angle is smaller than 90, the N3Co1N5 angle is
larger than 90, and the N6Co1N5 angle is smaller
that 180. The values of these angles indicate that there
is an attraction between hydrogen atoms on C1b and
O1 due to some weak CHO hydrogen bonds (Table
4) , caused by substantial positive charge on the hydrogen atom (calculated to be around 0.2) and negative
charge on the oxygen atom (calculated to be around
0.6).
In the crystal structures and in the calculated model
systems (MS1 and MS3) the equatorial pyridine is tilted
by about 40 to the equatorial plane (Table 2). This
orientation of the equatorial pyridine is a compromise
between two effects: one is the attraction between hydrogen atom on C1a of the pyridine and O1, and the
other is the repulsion of the hydrogen atom on N3
(with calculated positive charge of 0.28) and the hydrogen atom on C5a (with calculated positive charge of
0.22). Because of these interactions the O1Co1N4
angle is smaller than 90 and the N3Co1N4 angle is
larger than 90. Relevant interligand interactions are
given in Table 4.
The six-membered chelate rings in both crystal structures are very similar (Table 3) and they are almost
planar. The conformation of these rings can be described as half-chair. Non-planar conformation of the
chelate ring is a probable consequence of an attraction
between the hydrogen of the C1a atom and the O1
atom.
In the model systems six-membered chelate rings are
even more planar than in the crystal structures, they
have smaller total puckering amplitudes (Table 3).
Since there is no condensed aromatic ring, there is
better delocalization of electrons in the chelate ring.
The ring is the most planar when there are no axial
pyridines (MS1) or for parallel orientation of axial

pyridines (MS2b). The torsion angles in six-membered

chelate rings show that non-planarity behavior is very
similar in different structures (Table 3). For the conformer of MS3 when axial pyridines are parallel, the
equatorial pyridine falls in the equatorial plane, and the
equatorial chelate ligand is planar. The orientation of
equatorial pyridine and planarity of the equatorial
chelate ligand is caused by the steric interactions, which
are equivalent above and below the equatorial plane.
The planarity of the equatorial ligand when the axial
ligands are in mutual parallel orientation has already
been observed in cases of porphyrinato complexes [7
12], and shows analogy of our complexes with porphyrinato complexes.
Similarity of the bonding angles around Co1 and of
the conformations of six-membered rings in the crystal
structures and in the calculated structures indicates that
our model systems are suitable for investigation of
factors that influence the orientations of axial ligands in
complexes 1 and 2.

3.5. Preferential orientations of the pyridines in the

calculated cation complexes
The calculations on different conformers, even with
fixed torsion angles, of the model systems described
above were performed in order to investigate the factors that have influence on the orientations of coordinated pyridines.

3.5.1. Orientation of the equatorial pyridine in the

absence of axial pyridine
Calculations on model system 1 (Fig. 3(a)), with two
NH3 in axial positions and pyridine in equatorial position, were performed in order to show what the preferred orientation of the equatorial pyridine is
independent of interactions with axial pyridines. The
geometries and the energies were calculated for three
conformers. In the first conformer the structure was
fully optimized and the pyridine was in a similar posi-

G.A. Bogdano6ic et al. / Polyhedron 20 (2001) 22312240

2238

tion to the crystal structure, the angle between the

plane of the ring and the equatorial ligand being
35.2. In the other two conformers, which are not
minima, the pyridine was fixed in the equatorial plane
(torsion angle O1Co1N4C1a =0.0) and fixed to be
perpendicular to the equatorial plane (torsion angle
O1Co1N4C1a = 90.0) (Table 5). The first conformer, fully optimized, is the most stable. Hence, the
orientation of the equatorial pyridine with an angle of
about 40 to the equatorial plane is the preferable
orientation of the equatorial pyridine. The structure
with the pyridine in the equatorial plane and the structure with the pyridine perpendicular to the equatorial
plane are less stable by 0.79 and 8.38 kcal mol 1,
respectively.

there is steric hindrance of hydrogens on pyridines,

H(C1a) and H(C1c), and the H(N3) from the five-membered equatorial ring, since there is substantial positive
charge on these hydrogen atoms, around 0.18 on
H(C1b) and H(C1c) and around 0.29 on H(N3). These
calculations show that the axial pyridines do not prefer
perpendicular orientation if the equatorial pyridine is
not present. The results are very similar to the results of
calculations on FeII complexes with porphyrine and
axial pyridines or imidazoles, where it was found that
the structures with perpendicular and parallel orientations of axial ligands had almost the same stability
[11,12]. These show that for the same d6 metal systems
there is no important influence of chelate equatorial
ligands on the orientation of the axially coordinated
pyridines.

3.5.2. Orientation of the axial pyridines in the absence

of equatorial pyridine
In order to see what the preferable orientations of
axial pyridines in the absence of the equatorial pyridine
are, calculations were performed on model system 2
(Fig. 3(b)), with two axial pyridines and the NH3 in the
equatorial position. The geometries and energies were
calculated for three conformers: with two pyridines
perpendicular to each other, with parallel pyridines
above the six-membered ring, and with parallel pyridines above the five-membered ring. The structures with
perpendicular pyridines and with parallel pyridines
above the five-membered ring have very similar energies, the second one being only 0.67 kcal mol 1 more
stable. The structure with the parallel pyridines above
the six-membered ring is less stable by 4.02 kcal mol 1.
Since that structure is not a stationary point, it was
necessary to fix torsion angles to keep axial pyridines in
parallel position. This structure has higher energy since

3.5.3. Mutual orientations of the three pyridines

Calculations on model system 3, with three pyridines,
were done for the perpendicular mutual orientation of
axial pyridines and for two parallel orientations of axial
pyridines, above the five-membered ring and above the
six-membered ring. The conformation with a perpendicular orientation of axial pyridines is the most stable
(Table 5). This is a fully optimized structure where the
torsion angle between two pyridines is 87.3, and the
angle of the plane of the equatorial pyridine to the
equatorial plane is 38.0. The structures with parallel
axial pyridines are not stationary points and the torsion
angle was fixed. These structures are less stable by 4.45
and 7.00 kcal mol 1 than the structure with a perpendicular orientation of axial pyridines. Again, the structures with parallel axial pyridines above the
five-membered equatorial ring is more stable than the
structure with parallel axial pyridines above the sixmembered ring.

Table 5
Relative energies of calculated conformers of model systems a
Label in Section 3.4

O1Co1N4C1a
Model system 1

MS1

Model system 2

MS2a
MS2b

Model system 3

MS3

DE (kcal mol1) b

Torsion angle ()
C1bN5N6C1c

35.2
0.0 c
90.0 c

38.0
11.5
6.4

4.8 d
70.5
0.0e,f
87.3
0.9d,f
0.0e,f

Model systems are shown in Fig. 3.

Relative energies with respect to the most stable conformer of the particular model system.
c
In these structures orientations of equatorial pyridine with respect to equatorial plane is fixed.
d
Parallel pyridines are situated above the five-membered ring.
e
Parallel pyridines are situated above the six-membered ring.
f
In these structures orientations of axial pyridines with respect to equatorial ligand are fixed.
b

0.0
0.79
8.38
0.0
0.67
4.02
0.0
4.45
7.00

G.A. Bogdano6ic et al. / Polyhedron 20 (2001) 22312240

These studies on model systems show that axial

pyridines, in the absence of an equatorial pyridine, can
be in perpendicular or parallel orientation. The equatorial pyridine, in the absence of axial pyridines, prefers
to be tilted with respect to the equatorial plane by
about 40. In model systems with three pyridines the
most stable structure has a tilted equatorial pyridine,
and axial pyridines in normal mutual orientation. These
orientations of three pyridines are the most stable because there is no steric crowding between axial pyridines and the equatorial one (Table 4). That is, there is
substantial positive charge on the hydrogen atoms on
a-C of coordinated pyridine molecules, of around 0.2.
In the structures where axial pyridines are parallel
there is much more steric crowding. These steric interactions are responsible for a large instability of parallel
structures. That is, in the absence of axial pyridines, the
tilted orientation of the equatorial pyridine in only
more stable by 0.79 kcal mol 1 than the orientation in
the equatorial plane. However, in presence of axial
pyridines, the tilted orientation is more stable by 4.45
kcal mol 1; hence, the difference of 3.66 kcal mol 1 is
a consequence of interactions of axial pyridines with
the equatorial one.
4. Conclusions
The crystal structures of two compounds,
[CoIII(L)(py)3][CoII(py)Cl3]EtOH and [CoIII(L)(py)3]I3,
show that the geometries of the complex cations are
almost the same, with perpendicular orientation of axial
ligands, regardless of different anions and lattice packing. This indicates that intramolecular interactions in
the complex cation are responsible for the orientations
of coordinated ligands.
The DFT calculations on the model systems show
that the equatorial pyridine, because of interactions
with the chelate equatorial ligand, prefers to be tilted
by about 40 with respect to the equatorial plane. Axial
pyridines, in the absence of an equatorial pyridine, do
not prefer to be perpendicular, the calculations showing
that parallel and perpendicular orientations are almost
equally stable. This result is similar to the calculations
on the porphyrinato Fe complexes, indicating that in d6
systems chelate equatorial ligands do not have an important influence on the orientation of axially coordinated pyridines. However, in presence of a tilted
equatorial pyridine the perpendicular orientation of
axial pyridines is more stable, because in this orientation there are no steric constraints among coordinated
pyridines.
In the crystal structures and in the calculated structures of complex cations there are attractive electrostatic interactions of hydrogen atoms on a-C of
pyridine and the coordinated oxygen atom of the equatorial chelate ligand.

2239

5. Supplementary material
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC Nos. 154792 and 154793 for complexes 1 and 2, respectively. Copies of this information
may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
(fax:
+ 44-1223-336033;
e-mail:
deposit@ccdc.
cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
Acknowledgements
We would like to thank Professor E.W. Knapp for
useful discussions. This work was supported by the
Ministry for Science and Technology of the Republic of
Serbia (Grant No. 02E09). The calculations were carried out at the computer center of the Free University
of Berlin.
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