Cis- and trans-planar four-coordinated palladium(II) azo-5-pyrazolone (thione) complexes with N2O2- and N2S2-ligand environment: Synthesis and structure

Article abstract of DOI:10.1134/S0036023615120062

Three novel palladium(II) azo complexes (I-III), whose compositions and structures were established from C, H, N, S elemental analysis and IR and ¹H NMR spectroscopy, were synthesized by boiling palladium(II) acetate and some pyrazolazo derivat

Full text of DOI:10.1134/S0036023615120062

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2015, Vol. 60, No. 12, pp. 1481–1486. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © A.S. Burlov, A.I. Uraev, K.A. Lysenko, I.S. Vasil’chenko, S.A. Mashchenko, E.V. Korshunova, D.A. Garnovskii, E.D. Garnovskaya, G.S. Borodkin, 2015,
published in Zhurnal Neorganicheskoi Khimii, 2015, Vol. 60, No. 12, pp. 1621–1626.
COORDINATION COMPOUNDS
cisꢀ and transꢀPlanar FourꢀCoordinated Palladium(II)
Azoꢀ5ꢀPyrazolone (Thione) Complexes with N2O2ꢀ
and N2S2ꢀLigand Environment: Synthesis and Structure
A. S. Burlova, A. I. Uraeva, K. A. Lysenkob, I. S. Vasil’chenkoa, S. A. Mashchenkoa,
E. V. Korshunovaa, D. A. Garnovskiia, c, E. D. Garnovskayaa, and G. S. Borodkina
a Research Institute of Physical and Organic Chemistry, Southern Federal University,
pr. Stachki 194/2, RostovꢀonꢀDon, 344090 Russia
b Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia
c Southern Scientific Center, Russian Academy of Sciences, pr. Chekhova 41, RostovꢀonꢀDon, 344006 Russia
eꢀmail: garn@ipoc.rsu.ru
Received April 2, 2015
Abstract—Three novel palladium(II) azo complexes (I–III), whose compositions and structures were estabꢀ
1
lished from C, H, N, S elemental analysis and IR and H NMR spectroscopy, were synthesized by boiling
palladium(II) acetate and some pyrazolazo derivatives, namely, 2ꢀisoꢀpropyl(phenyl)ꢀ3ꢀmethylꢀ4ꢀ[(4ꢀmethꢀ
ylphenyl)diazenyl]ꢀ1Hꢀpyrazolꢀ5ꢀone and 1ꢀisoꢀpropylꢀ3ꢀmethylꢀ4ꢀ[(4ꢀmethylphenyl)diazenyl]ꢀ1Hꢀpyraꢀ
zolꢀ5ꢀthione (HL(a–c)) in an acetone/methanol (1 : 1) mixture. Xꢀray diffraction analysis was performed for
complexes
figuration for the PdN2O2 chelate ring, while the formation of the cisꢀplanar structure by the PdN2S2 chelate
ring was typical for complex III
I and III. Complex I with an N2O2ꢀligand environment was established to have a transꢀplanar conꢀ
.
DOI: 10.1134/S0036023615120062
Metal complexes based on aromatic and heterocyꢀ physicochemical properties. The structure of comꢀ
plexes I and III was confirmed by Xꢀray diffraction.
clic azo ligands are one of the most actively studied
class of coordination compounds in recent time [1–8]
due to their potential application as materials for
molecular electronics and photonics [3, 4]. Azo comꢀ
pounds and their complexes are photochromic [5, 6],
pH sensitive [7], and redox active [8]. At the same
time, metal chelates containing the –N=N– azo moiꢀ
ety represent a convenient model for studying the
effects of nature of the metal center and donating
Me
Me
N N
X
N N
X
Me
Me
H
Pd/2
N
N
N
R
N
R
nitrogen, oxygen, sulfur, and selenium atoms in ortho
ꢀ
position to the azo group and the steric effects of subꢀ
stituents in aromatic or heterocyclic fragment on the
formation of cisꢀ or transꢀcoordinated isomers [9–15].
Quantumꢀchemical calculations performed within the
framework of density functional theory (DFT) for
squareꢀplanar palladium(II) complexes of oxyazo and
thioazo derivatives show that a transꢀstructure is more
preferable for the PdN2O2 chelate moiety, whilst the,
cisꢀgeometry is typical for the palladium complexes
with an N2S2ꢀdonor atoms set. Another characteristic
feature of azo complexes due to an ambidentate charꢀ
acter of the azo group is the possibility of existence of
fiveꢀ and/or sixꢀmembered chelate rings within one
complex molecule [15].
X = O, R = isoꢀPr (I);
X = O, R = Ph (II);
X = S, R = isoꢀPr (III)
X = O, R = isoꢀPr (HLа);
X = O, R = Ph (HLb);
X = S, R = isoꢀPr (HLc)
EXPERIMENTAL
1ꢀisoꢀPropyl(phenyl)ꢀ3ꢀmethylꢀ4ꢀparaꢀmethylpheꢀ
nylazopyrazolꢀ5ꢀones (HLа, HLb) and 1ꢀisoꢀpropylꢀ
3ꢀmethylꢀ4ꢀparaꢀmethylphenylazopyrazoleꢀ5ꢀthione
(HLc) were synthesized as described earlier [16, 17].
Synthesis of complexes I and II. To a boiling methꢀ
anol solution (50 mL) containing HLa (0.511 g,
2 mmol) or HLb (0.585 g, 2 mmol), a palladium aceꢀ
tate solution (0.220 g, 1 mmol) in hot acetone (10 mL)
Herein we report the synthesis of three novel pallaꢀ
dium complexes I–III on the basis of 4ꢀazoꢀ5ꢀ
hydroxy(mercapto)pyrazole (HL) and study their was slowly added. The reaction mixture was refluxed
1481

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BURLOV et al.
IR spectrum (KBr,
, cm–1): 1595 m, 1479 m, 1457 s,
1430 s, 1415 s, 1387 s, 1256 s, 1194 s, 1173 m, 846 m,
749 s, 686 s.
1H NMR spectrum, DMSOꢀ
d6 (ppm): 2.37 (s, 6H,
2CH3), 2.45 (s, 6H, 2CH3), 7.00–7.74 (mult, 18H,
2Ph + 2C6H4).
ν
Table 1. Selected crystallographic data and refinement
parameters for complexes
I
and III
Complex
I
III
Symmetry system
Space group
Triclinic
Monoclinic
P
1
P21/n
T
, K
120(2)
10.321(4)
11.805(4)
13.110(5)
106.858(7)
91.633(7)
113.315(7)
1385.0(8)
2 (1)
640
1.489
7.11
0.756/0.867
58
120(2)
a
b
, Å
, Å
13.748(2)
13.957(2)
16.820(2)
Complex III was synthesized by the above method
using HLc as the initial compound. The yield was 78%.
Complex III brown crystals with m.p. 265–266°C.
c
α
, Å
, deg
, deg
, deg
For C28H34N8S2Pd, anal. calcd. (%): C, 51.49; H,
5.25; N, 17.16; S, 9.82.
β
113.844(2)
γ
V
Z
F
, Å3
')
(000)
ρcalcd, g/cm–3
, cm–1
Tmin Tmax
θmax, deg
Measured reflections
Rint
2952.1(6)
4 (1)
1344
1.470
8.03
0.752/0.852
58
22371
(0.0548)
7593
Found (%): C, 51.52; H, 5.32; N, 17.12; S, 9.85.
(Z
IR spectrum (KBr,
, cm–1): 1595 m, 1495 m, 1457 s,
ν
1430 s, 1415 s, 1387 s, 1256 s, 1194 s, 1173 m, 846 m,
749 s, 686 s.
μ
1H NMR spectrum, DMSOꢀd6 (ppm): 1.52 (d,
/
i
ꢀPr), 3JHH = 6.5 Hz), 2.32 (s, 6H, 2CH3),
2
12H, 4CH3(
2.45 (s, 6H, 2CH3), 4.94 (septet, 2H, 2CH, JHH
6.5 Hz), 6.80–7.22 (m, 8H, 2C6H4).
3
15314
(0.0378)
7252
=
(
)
Independent reflections
Reflections with
C, H, N, and S elemental analysis was performed
on a Carlo Erba Instruments TCM 480.
5491
5094
[
I
> 2
Refined parameters
1 with [ > 2 )]
σ
(I)]
360
360
IR spectra of samples were recorded on a Nicolet
Impactꢀ400 spectrometer in KBr pellets in the region
of 4000–400 cm–1.
R
I
σ(I
0.0474
0.1189
1.001
0.0452
0.0935
1.096
wR2 (all reflections)
GOOF
Melting temperatures were measured on a Kofler
table.
Residual electron density 1.172/–0.760 0.791/–0.469
ρmax
/
ρmin, e Å–3
1H NMR spectra 1H NMR spectra were measured
on a Varian Unity 300 spectrometer at ambient temꢀ
perature in DMSOꢀd6 with the signal of residual 2H of
the solvent as the internal reference.
on a water bath for 1 h and cooled to room temperaꢀ
ture. The formed precipitates of complexes were filꢀ
tered off, washed with hot isoꢀpropanol three times,
dried in a vacuum, and crystallized from a methaꢀ
nol/chloroform (2 : 1) mixture. The yield was 76% for
Xꢀray diffraction analysis of complexes I and III.
Xꢀray diffraction experiments were carried out on a
complex
Complex
For C28H34N8O2Pd, anal. calcd. (%): C, 54.15; H, equipment. The structures were solved by direct methꢀ
I
and 80% for complex II
.
Bruker SMART 1000 diffractometer (Mo
K radiation,
α
graphite monochromator,
ω
ꢀscans) at 120 K using a
I
brown crystals with m.p. 240–241°C.
Cryostream (Oxford Cryosystems) lowꢀtemperature
5.52; N, 18.04.
ods and refined by the leastꢀsquares technique in the
2
anisotropic fullꢀmatrix approximation on
Hydroꢀ
Fhkl.
Found (%): C, 54.25; H, 5.54; N, 18.16.
gen atoms were located from te difference electron
density syntheses and refined in the isotropic approxiꢀ
IR spectrum (KBr,
, cm–1): 1592 m, 1498 m, 1463 s,
ν
1430 s, 1422 s, 1393 c, 1274 s, 1185 s, 1164 m, 849 m,
764 s, 691 s.
mation. Selected crystallographic data for complexes
I
and III and some refinement parameters are given in
Table 1. All the calculations were performed using the
SHELXTL PLUS software [18].
1H NMR spectrum, DMSOꢀd6 (ppm): 1.07 (d,
12H, 4CH3(i
ꢀPr), 3JHH = 6.7 Hz), 2.26 (s, 6H, 2CH3),
2.39 (с, 6H, 2CH ), 3.54 (s, 6H, 2CH3), 3.54 (septet,
2H, 2CH, JHH = 6.7 Hz), 7.17–7.36 (mult, 8H,
2C6H4).
The Xꢀray diffraction data for complexes I and III
were deposited with the Cambridge Structure Dataꢀ
base (nos. 1012994 and 1012995).
3
3
Complex II redꢀbrown crystals with m.p. 275–
276°C.
RESULTS AND DISCUSSION
For C34H30N8O2Pd, anal. calcd. (%): C, 59.26; H,
4.39; N, 16.26.
Azo compounds HL(a–c) were synthesized by the
published methods [16] for HLa,b (scheme 1) and [17]
for HLc (scheme 2).
Found (%): C, 59.35; H, 4.28; N, 16.36.
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CISꢀ AND TRANSꢀPLANAR FOURꢀCOORDINATED PALLADIUM(II)
Tolꢀn
1483
Me
Me
N
N
EtOH
0°C
+ nꢀTolN+2Cl–
H
N
N
O
O
N
R
N
R
R = isoꢀPr, Ph
Scheme 1.
Tolꢀn
Tolꢀn
Tolꢀn
N
N
N
Me
Me
N
Me
3
reflux, 12 h
N N
Cl
POCl
Na S
2
DMSO, 4 h
H
H
N
N
N
O
S
N
N
N
isoꢀPr
isoꢀPr
Scheme 2.
isoꢀPr
The earlier published IR, UV, 1H NMR, and Xꢀray center as typical of palladium complexes with other
diffraction data [19, 20] obtained for similar pyrazoleꢀ
containing azo derivatives reveal the realization of
oxoꢀ and thiohydrazone tautomers for this class of
ligands [21]. The coordination cores of complexes
and III have different geometries. The transꢀarrangeꢀ
ment of N2O2 donating atoms is typical of complex
and cisꢀconfiguration of the PdN2S2 coordination
core is observed in complex III (Figs. 1 and 2).
I
I,
1
compounds (schemes 1 and 2). Thus, the H NMR
spectrum of compounds HL(a–c) exhibits singlet signal
from the hydrazone proton at 13.48 (HLa), 13.63
(HLb), and 16.76 (HLc), respectively.
Palladium(II) azo chelates I–III were synthesized
by refluxing azo derivatives HL(a–c) and palladium aceꢀ
tate in a methanol–acetone solution at a ratio of 2 : 1
(scheme 3).
Table 2. Selected bond lengths (
complex
d
) and bond angles (
ω
) in
I
Bond
d
, Å
Bond , Å
d
Pd(1)–O(1) 2.004(2)
Pd(1)–N(4) 2.032(3)
Pd(1)–O(1')
Pd(1)–N(4')
O(1)–C(1')
N(1)–C(1')
N(1')–N(2')
N(1')–C(4')
C(1')–C(2')
N(2')–C(3')
C(2')–N(3')
C(2')–C(3')
N(3')–N(4')
C(3')–C(7')
N(4')–C(8')
1.998(2)
2.056(2)
1.287(3)
1.339(4)
1.396(3)
1.473(4)
1.423(4)
1.318(4)
1.345(4)
1.441(4)
1.294(3)
1.488(4)
1.443(3)
Me
Me
O(1)–C(1)
N(1)–C(1)
N(1)–N(2)
N(1)–C(4)
C(1)–C(2)
N(2)–C(3)
C(2)–N(3)
C(2)–C(3)
N(3)–N(4)
C(3)–C(7)
N(4)–C(8)
1.281(3)
1.344(4)
1.407(3)
1.469(4)
1.431(4)
1.316(4)
1.345(4)
1.438(4)
1.283(3)
1.479(4)
1.453(4)
Me
N
Me
N
N
N
Pd(OAc)
2
H
Pd/2
N
N
X
X
N
R
N
R
Scheme 3.
The 1H NMR spectra confirm an N2O2ꢀ and N2S2
coordination surrounding of the metal center in comꢀ
plexes II, and III, respectively. No singlet signals
from the hydrazone NH protons are observed in the
1H NMR spectra of complexes I–III in comparison
with the nonꢀcoordinated HL(a–c) spectra recorded in
ꢀ
I,
Angle
ω
, deg
Angle
ω
, deg
O(1)Pd(1)N(4) 93.29(9) O(1')Pd(1)N(4')
93.55(9)
C(1)O(1)Pd(1) 118.4(2) C(1')O(1')Pd(1) 118.6(2)
O(1)C(1)N(1) 123.5(3) O(1')C(1')N(1') 123.8(3)
O(1)C(1)C(2) 131.0(3) O(1')C(1')C(2') 130.0(3)
N(1)C(1)C(2) 105.5(2) N(1')C(1')C(2') 106.1(2)
N(3)C(2)C(1) 128.7(3) N(3')C(2')C(1') 129.4(3)
N(3)C(2)C(3) 125.8(3) N(3')C(2')C(3') 125.0(3)
C(1)C(2)C(3) 105.2(3) C(1')C(2')C(3') 105.0(3)
N(4)N(3)C(2) 119.7(2) N(4')N(3')C(2') 120.6(2)
N(3)N(4)C(8) 112.3(2) N(3')N(4')C(8') 111.4(2)
N(3)N(4)Pd(1) 128.71(2) N(3')N(4')Pd(1) 126.0(2)
C(8)N(4)Pd(1) 118.97(2) C(8')N(4')Pd(1) 122.5(2)
DMSOꢀd6. Hence, compounds HL(a–c) interact with
the palladium ion in the monodeprotonated form (L–) to
form chelate complexes Pd(L(a–c))2 (I–III), in which
bidentate coordination occurs via the nitrogen atom of
the azo moiety and the oxygen atom in complexes
and II and through the sulfur atom in complex III
The final conclusion about the structure of the synꢀ
thesized complexes was made on the basis of Xꢀray difꢀ
fraction results obtained for complexes
ray diffraction analysis shows that palladium chelates
and III have a nearly planar surrounding of the metal
I
.
I and III. Xꢀ
I
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 12 2015

1484
BURLOV et al.
C(14')
C(11')
C(10')
C(12')
C(9')
C(8')
C(5)
C(6)
C(13')
C(4)
N(1)
N(3')
O(1)
N(4')
C(7')
C(1)
C(2')
N(2)
C(3')
C(3)
Pd(1)
N(4)
N(2')
C(2)
C(1')
C(7)
N(1')
O(1')
N(3)
C(8)
C(9)
C(5')
C(4')
C(13)
C(6')
C(10)
C(12)
C(11)
C(14)
Fig. 1. General view of complex I with atoms shown as thermal ellipsoids (50% probability).
Selected bond lengths and angles in complexes
I and the deviation from the average ring plane is maximal
III are listed in Tables 2 and 3. Complex possesses a for the C(1) atom and equals 0.028 Å. The conformaꢀ
I
squareꢀplanar geometry of the coordination unit, tion of the Pd(1)O(1')C(1')C(2')N(3')N(4') ring is a
whereas PdN2S2 in complex III is tetrahedrally disꢀ flattened bath; the Pd(1) and C(2') atoms are, respecꢀ
torted. The dihedral angles between the tively, 0.255 and 0.053 Å out of the plane of other
O(1)Pd(1)N(4)/O1')Pd(1)N(4') and S(1)Pd(1)N(4)/ atoms. The bent angles in the above chelate rings are
S(1')Pd(1)N(4') planes are 2.2° and 13.8°, respectively. 0.95° and 11.4° along the Pd(1)…C(2) and Pd(1)…C(2')
metallocycles in complex
complex III
I
are more planar than in lines and 0.77° and 4.2° along the O(1)…N(4) and
O(1')…N(4') lines, respectively. The dihedral angle
.
between
the
C(1)C(2)N(3)N(4)
and
The coordination polyhedron of the pallaꢀ
dium(II) ion in complex is a squareꢀplanar; the
dihedral angle between the N(4)O(1)Pd(1) and
Pd(1)O(1')C(1')C(2') planes is 12.88°. These conforꢀ
mational distinctions between these chelate rings lead
to slight changes in bond lengths.
I
Pd(1)N(4')O(1') planes is 2.22°. The sixꢀmembered
chelate rings in complex
Pd(1)O(1)C(1)C(2)N(3)N(4) ring is nearly planar; Pd(1)S(1)C(1)C(2)N(3)N(4)
I
are nonꢀequivalent. The
In
complex
III
,
the
sixꢀmembered
and
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 12 2015

CISꢀ AND TRANSꢀPLANAR FOURꢀCOORDINATED PALLADIUM(II)
1485
C(14)
C(11)
C(12)
C(10)
C(14')
C(13)
C(10')
C(11')
C(9')
C(8)
C(9)
C(12')
N(4)
C(7')
N(3)
C(8')
N(4')
N(3')
C(2')
C(7)
C(3')
C(2)
C(13')
Pd(1)
C(3)
N(2')
C(1')
N(1')
N(2)
C(1)
C(6')
N(1)
S(1)
S(1')
C(4')
C(4)
C(5)
C(6)
C(5')
Fig. 2. General view of complex III with atoms shown as thermal ellipsoids (50% probability).
Pd(1)S(1')C(1')C(2')N(3')N(4') chelate rings are A decrease in O(1')…C(8) distance is likely due to the
strongly distorted. The Pd(1) and N(4) atoms in the distortion of the Pd(1)O(1')C(1')C(2')N(3')N(4') sixꢀ
first of them are 1.127 and 0.314 Å out of the average membered chelate ring. The distinction between the
plane of the other ring atoms, and the Pd(1) and N(4') conformations of the tolyl fragments is probably due to
atoms in the second ring are, respectively, 1.158 and intermolecular contacts.
0.353 Å out of the average plane of the other atoms.
It is obvious that the replacement of sulfur for oxyꢀ
The S(1)C(1)C(2)N(3) and S(1')C(1')C(2')N(3')
gen atoms in the coordination core leads to the shortꢀ
moieties are nearly planar.
ening of bonds with tolyl substituents. As a result, the
The bent angles along the S(1)…N(4) and
S(1')…N(4') lines are 34.7° and 34.4°, respectively. The
dihedral angle between the Pd(1)C(1)C(2)N(3) and
Pd(1)C(1')C(2')N(3') planes is 20.4°.
bent angle along the S(1)…N(4) bond line considerably
increases, thus leading to the destabilization of the
transꢀconfiguration and its rearrangement into the cis
ꢀ
structure. It is noteworthy that some contacts in the
The observed distinctions between the structures of cisꢀconfiguration are also shortened (S(1)…S(1')
the chelate rings in complex
are most likely explained 3.087(1), С(8)…С(8') 3.085(2) Å) probably due to tetꢀ
by the steric interaction between oxygen and the tolyl rahedral distortion in the planar surrounding of the
substituent at the nitrogen atom. The conformations palladium atom. The complexes of ꢀhydroxyazo aroꢀ
I
о
of the tolyl rings at N(4) and N(4') are nonꢀequivalent matics realize only sixꢀmembered chelate rings [13],
(the C(9)C(8)N(4)N(3) and C(9')C(8')N(4')N(3') whereas the formation of two fiveꢀmembered chelate
torsion angles are 96.4° and 48.3°, respectively), thus rings or one fiveꢀ and one sixꢀmembered chelate rings
leading to the difference between the O(1)…C(8
′) and is observed in similar mercapto derivatives [13, 22, 23].
O(1')…C(8) molecular contacts (2.868(3) and 2.680(3) Å). In contrast to the earlier published data [13, 22, 23],
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 12 2015

1486
BURLOV et al.
) and bond angles ( ) in
Table 3. Selected bond lengths (
d
ω
REFERENCES
complex III
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,
Ed. by Y. A. McCleverty and T. Y. Meyer (Elesevierꢀ
Pergamon, Amsterdam/OxfordNew York, 2003).
Bond
d
, Å
Bond , Å
d
Pd(1)–S(1)
2.293(1)
Pd(1)–S(1')
Pd(1)–N(4')
S(1')–C(1')
N(1')–C(1')
N(1')–N(2')
N(1')–C(4')
C(2')–C(1')
N(2')–C(3')
N(3')–C(2')
C(2')–C(3')
N(4')–N(3')
C(3')–C(7')
N(4')–C(8')
2.2817(9)
2.080(3)
1.713(3)
1.350(4)
1.385(4)
1.469(5)
1.407(5)
1.315(5)
1.361(4)
1.422(4)
1.269(4)
1.489(5)
1.457(4)
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C(1)–C(2)
N(2)–C(3)
N(3)–C(2)
C(2)–C(3)
N(3)–N(4)
C(3)–C(7)
N(4)–C(8)
1.705(3)
1.355(4)
1.388(3)
1.461(4)
1.419(5)
1.313(4)
1.348(4)
1.422(4)
1.278(3)
1.487(5)
1.438(4)
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C(2)C(1)S(1)
N(1)C(1)C(2)
N(3)C(2)C(1)
N(3)C(2)C(3)
C(1)C(2)C(3)
99.6(1) C(1')S(1')Pd(1)
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ACKNOWLEDGMENTS
T. Y. Meyer
(ElesevierꢀPergamon,
Amsterꢀ
dam/Oxford/New York, 2003).
This work was supported by the Ministry of Educaꢀ
tion and Science of the Russian Federation within the
state task (base part) on project no. 1895 using the
equipment of the “Molecular Spectroscopy” Shared
Facility Center of the Southern Federal University.
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Coord. Chem. 34, 12 (2008).
Translated by E. Glushachenkova
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 12 2015