Cobalt(II) compounds with acetone isonicotinoyl hydrazone tautomers: Syntheses and crystal structures of complexes with free donor atoms

Article abstract of DOI:10.1016/j.ica.2016.03.045

Complexes with free donor atoms, as potential metalloligands, are important building blocks in crystal engineering of coordination polymers and metal organic frameworks. In this work, the possibility of formation of cobalt(II) complexes with free N-donor atoms based on acetone isonicotinoyl hydrazone (Hisn), is verified. Syntheses, X-ray crystal structures and spectroscopic properties of two new cobalt(II) compounds with this hydrazone, are reported. The structural studies reveal the formation of a cationic complex in [Co(Hisn)₂(H₂O)₂](NO₃)₂ (1) containing keto ligands (Hisn) as well as a neutral complex [Co(isn)₂(py)₂]_n (2), with the deprotonated hydrazone (isn) in its enolate form. Both complexes, with two various tautomers of the hydrazone, contain uncoordinated pyridyl groups that allows to regard them as potential N-donor metalloligands.

Full text of DOI:10.1016/j.ica.2016.03.045

Inorganica Chimica Acta 448 (2016) 86–92
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Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Cobalt(II) compounds with acetone isonicotinoyl hydrazone tautomers:
Syntheses and crystal structures of complexes with free donor atoms
⇑
Kornel Roztocki, Dariusz Matoga , Wojciech Nitek
Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
Complexes with free donor atoms, as potential metalloligands, are important building blocks in crystal
engineering of coordination polymers and metal organic frameworks. In this work, the possibility of for-
mation of cobalt(II) complexes with free N-donor atoms based on acetone isonicotinoyl hydrazone (Hisn),
is verified. Syntheses, X-ray crystal structures and spectroscopic properties of two new cobalt(II) com-
pounds with this hydrazone, are reported. The structural studies reveal the formation of a cationic com-
Received 17 November 2015
Received in revised form 30 January 2016
Accepted 30 March 2016
Available online 23 April 2016
plex in [Co(Hisn)
2 2 2 3 2
(H O) ](NO ) (1) containing keto ligands (Hisn) as well as a neutral complex [Co
Keywords:
Cobalt
Complex
Hydrazone
Isonicotinoyl
Tautomer
(
isn) (py) (2), with the deprotonated hydrazone (isn) in its enolate form. Both complexes, with two
2
2 n
]
various tautomers of the hydrazone, contain uncoordinated pyridyl groups that allows to regard them
as potential N-donor metalloligands.
Ó 2016 Elsevier B.V. All rights reserved.
1
. Introduction
In recent years, constructing metal-organic frameworks (MOFs),
from the propensity of divalent cobalt to be kinetically and oxida-
tion unstable as compared to cobalt(III) centers. For instance, such
an instability was observed in a series of cyanoacetylacetonate
metalloligands when the attempts to incorporate the cobalt(II)
metalloligand into a mixed-metal network, were unsuccessful [12].
The aim of this work was to synthesize and structurally charac-
terize cobalt(II) complexes with free N-donor atoms based on ace-
tone isonicotinoyl hydrazone (Hisn). Utilization of N-containing
heterocyclic molecules (present in Hisn and aimed to remain unco-
ordinated in its complexes) as bridging ligands in the successful
construction of coordination polymers with transition metal ions,
has been reviewed [13]. Our recent research on reactivity of the
aforementioned hydrazone (Hisn) with manganese(II) and copper
(II) centers led us either to a layered isonicotinate-based man-
ganese-organic framework [14] or to a copper complex with free
pyridyl groups [15], respectively. Additionally, we have demon-
strated the ability of acetone picolinoyl complexes to act as
N-donor metalloligands on the example of layered homometallic
i.e. crystalline coordination polymers with organic ligands and
potential voids, have become an increasingly popular area of mate-
rials chemistry [1–3]. The interest in these materials results mainly
from their designable assembly, tunable structures as well as a
variety of structure-dependent properties and applications such
as for instance gas storage, separations, catalysis, optoelectronic
devices, drug delivery, etc. [1–3]. MOFs are generally composed
of metal ions or clusters named nodes, and organic ligands named
linkers. The conceptual replacement of the latter for metalloligands
(i.e. non-polymeric complexes containing free donor atoms) in
these materials has been realized in practice with several two-step
syntheses leading to mixed-metal organic frameworks [4]. This
approach has also been useful for obtaining extended heterometal-
lic networks with coordinatively unsaturated metal centers that
significantly affect MOF properties such as for instance sorption
selectivity, sorption capacity and catalytic performance.
2
1
copper-organic framework built of acetone nicotinoyl
l-j ,j
A considerable number of metalloligands based on various
metal centers and organic ligands have been obtained and further
successfully utilized as linkers in heterometallic MOFs so far [2b,5].
In this group; however, MOFs with incorporated cobalt(II) based
metalloligands are few and far between [6–11]. This may come
linkers [15]. Other picolinoyl-bridged homometallic [16] and
heterometallic [17] coordination polymers with networks of higher
dimensionalities (2D or 3D) have also been reported. All these
findings underscore the feasibility of the approach to use picolinoyl
moieties (with or without metals) as building blocks for the
construction of metal-organic framework materials.
For cobalt, the literature survey shows an earlier report on
cobalt(II) complexes with acetone isonicotinoyl hydrazone,
obtained from cobalt(II) chloride [18]. However, their formulae
⇑
Corresponding author.
E-mail addresses:
D. Matoga).
matoga@chemia.uj.edu.pl,
dariusz.matoga@uj.edu.pl
(
http://dx.doi.org/10.1016/j.ica.2016.03.045
020-1693/Ó 2016 Elsevier B.V. All rights reserved.
0

K. Roztocki et al. / Inorganica Chimica Acta 448 (2016) 86–92
87
and characterization are mainly based on elemental analysis and
equipped with a Mo K
a
radiation source, graphite monochromator
spectroscopic measurements, without X-ray structures. Herein
we present syntheses, X-ray structures and spectroscopic proper-
ties of two new cobalt(II) monomeric complexes with acetone
isonicotinoyl hydrazone. The complexes have been obtained from
either acetate or nitrate cobalt salts and their single-crystal X-ray
structures unequivocally confirm the diversity of hydrazone
ligands in these compounds. Both complexes possess uncoordi-
nated pyridyl groups that make them potential metalloligands
with rare cobalt(II) centers.
and Oxford CryoJet system for measurements at low temperature.
Diffraction data for single crystal 2 were collected at 293 K on the
Oxford Diffraction SuperNova four-circle diffractometer, using a Cu
Ka radiation source and graphite monochromator. For both com-
pounds positions of all non-hydrogen atoms were determined by
direct methods using SIR-97 [19]. All non-hydrogen atoms were
refined anisotropically using weighted full-matrix least-squares
2
on F . Refinement and further calculations were carried out using
SHELXL-97 [20]. The hydrogen atom of the keto form of the ligand
in compound 1 (H(9) bound to N(9)) was located from the differ-
ence Fourier map. The other hydrogen atoms joined to carbon
atoms were positioned with an idealized geometry and refined
using a riding model. The crystal data and details of data collection
and structure refinement parameters are summarized in Table 1.
2
. Experimental
2.1. Materials and methods
All reagents and solvents were of analytical grade (Sigma
Aldrich, Alfa Aesar, Polmos, Fluka) and were used without further
purification. Carbon, nitrogen, and hydrogen were determined by
conventional microanalysis using an Elementar Vario MICRO Cube
elemental analyzer. IR spectra were recorded on a Thermo Scien-
tific Nicolet iS5 FT-IR spectrophotometer equipped with an iD5
diamond ATR attachment. Magnetic susceptibility measurements
were carried out at 22 °C on a Sherwood Scientific Magway MSB
MK1 balance. Powder X-ray diffraction (PXRD) patterns were
recorded at room temperature (295 K) on a Rigaku Miniflex 600
3
. Results and discussion
3.1. Synthesis
The preparation of both compounds 1 and 2 involved condensa-
tion reaction between acetone and isonicotinoyl hydrazide as the
first step that was carried out in ethanol without isolation of the
resulting acetone isonicotinoyl hydrazone (Hisn). Subsequently,
cobalt(II) salts (nitrate or acetate) were directly added to the
hydrazone solution in a 1:2 molar ratio (Scheme 1). The use of a
more basic acetate salt caused deprotonation of the hydrazone
and lead, after recrystallization from pyridine, to the neutral mono-
meric complex 2 with deprotonated enol tautomer of Hisn, i.e. ace-
tone isonicotinoyl hydrazonate (isn). Before the final
crystallization step, an intermediate precipitate of 2a was isolated.
Elemental analysis, IR spectroscopy and powder X-ray diffraction
have clearly shown that 2a, with a composition corresponding to
diffractometer with Cu K
from 3° to 70° with a 0.05° step at a scan speed of 3° min
a
radiation (k = 1.5418 Å) in a 2h range
À1
.
2
2
.2. Syntheses
2 2 2 3 2
.2.1. Synthesis of [Co(Hisn) (H O) ](NO ) (1)
Isoniazid (274 mg, 2.00 mmol) and acetone (700
l
l, 9.52 mmol)
were dissolved in ethanol (40 mL) and heated under reflux for
approximately 15 min. Co(NO O (291 mg, 1.00 mmol) was
3
)
2
Á6H
2
added into colorless solution and the heating under reflux was con-
tinued for 15 min. The red mixture was left under ambient condi-
tions and yellow precipitate of 1 was obtained after 24 h (yield:
[
2 2
Co(isn) (H O)] formula, is different from complex 2 (Fig. 1). The
insolubility of 2a in most common organic solvents may indicate
its polymeric nature with coordinated pyridyl groups, similarly
as it was observed for copper(II) MOF based on acetone nicotinoyl
hydrazone [15]. The behavior of pyridine, capable of dissolving 2a,
is unique since it acts as a base that, being in large excess, substi-
tutes monodentately bound ligands of 2a, and at the same time
does not attack bidentate enolate ligands (isn), keeping them
4
78 mg, 83.5%). The precipitate was washed with a small amount
of ethanol and dried in air. Orange crystals of 1 suitable for sin-
gle-crystal X-ray diffraction were obtained after crystallization in
an H-tube at room temperature. One arm of the H-tube was filled
with an isoniazid/acetone solution in ethanol (ca. 3 mL; concentra-
tion the same as in the main synthesis); second arm was filled with
Co(NO
3
)
2
Á6H
2
O dissolved in ethanol (ca. 3 mL; concentration the
same as in the main synthesis); approx. 6 mL of ethanol was slowly
added on top of both arms. Single crystals of 1 suitable for X-ray
analysis were obtained after approx. one week. Anal. Calc. for
Table 1
Crystal data and structure refinement parameters for [Co(Hisn)
Co(isn) (py) ] (2).
2
2
(H O)
2
](NO
3
)
2
(1) and
[
2
2
CoC18
H
26
N
8
O10: C, 37.70; H, 4.57; N, 19.54. Found: C, 37.80; H,
1
2
4
.80; N, 19.46%. eff = 4.4 B.
l
l
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C
18
H
26CoN
8
O
10
C
28
H
30CoN
8
O
2
573.40
monoclinic
P2 /c
7.0130(2)
19.8350(3)
8.9090(2)
90
98.8780(10)
90
1224.42(5)
2
569.53
triclinic
P1ꢀ
2
.2.2. Synthesis of [Co(isn)
The synthetic procedure was analogous to that of 1 except that
Co(CH COO) O (249 mg, 1.00 mmol) was used instead of Co
Á4H
Á6H O. The beige precipitate of 2a (with a composition of
Co(isn) (H O)]) was filtered and dried in air (yield: 375 mg,
7.3%). Anal. for 2a: Calc. for CoC18 : C, 50.35; H, 5.16; N,
9.57. Found: C, 50.85; H, 4.83; N, 19.51%. eff = 4.5 B. Orange
2 2
(py) ] (2)
1
8.584(5)
9.324(5)
9.470(5)
97.737(5)
102.935(5)
94.858(5)
726.8(7)
1
3
2
2
b (Å)
c (Å)
(
[
NO
3
)
2
2
2
2
a
(°)
b (°)
(°)
8
1
22 6 3
H N O
c
l
l
3
V (Å )
crystals of 2 suitable for single-crystal X-ray diffraction were
Z
crystallized from pyridine solution of 2a. Anal. for 2: Calc. for
T (K)
100(2)
1.555
0.770
5424
2791 [Rint = 0.0118]
293(2)
1.301
4.943
12110
3036 [Rint = 0.0283]
3
CoC28
H, 5.40; N, 19.62%.
H
32
N
8
O
2
: C, 58.84; H, 5.64; N, 19.61. Found: C, 58.82;
eff = 4.5 B.
Dcalc (Mg/m )
À1
l
(mm
)
l
l
Reflections measured
Reflections unique
Reflections observed [I > 2
2.3. Crystallographic data collection and structure refinement
r(I)]
2619
2892
R indices [I > 2r(I)]
R
wR
1
0.0299
0.0762
0.0350
0.0924
Diffraction data for single crystal of 1 were collected at 100 K
using the Bruker-Nonius Kappa CCD four-circle diffractometer,
2

8
8
K. Roztocki et al. / Inorganica Chimica Acta 448 (2016) 86–92
Scheme 1. Synthetic route to cobalt(II) complexes with acetone isonicotinoyl hydrazone: (a) cationic complex with the keto tautomer (1); (b) neutral complex with the
deprotonated enol tautomer (enolate) (2).
intact. This process leads to the formation of compound 2, [Co
isn) (py) ], with two pyridine ligands coordinated to the cobalt
center.
compound 1 show significant differences (Table 2) as compared
to the corresponding bonds in compound 2, which indicates that
the C@N–N(H)–C@O moiety exists in 1, whereas the conjugated
(
2
2
À
In contrast to basic acetate, when cobalt(II) nitrate was utilized
as a starting salt, the hydrazone remained in its keto form during
the synthesis, and nitrates were incorporated in the resulting pro-
duct 1 to balance the positive charge of cobalt ions. The as-synthe-
sized bulk product 1 is identical with single crystals grown in the
H-tube for X-ray analysis (Fig. 2). Similarly, bulk material of 2, after
reaction of 2a with pyridine, is the same as the single-crystal used
for X-ray structure determination (Fig. 2).
C@N–N@C–O moiety is present in 2. The negative charge arising
from the O8–H enolic group deprotonation, delocalized over the
À
C@N–N@C–O moiety, causes the decrease of Co(1)–O(8) bond
length (2.031(2) Å in 2) as compared to analogous Co(1)–O(8) bond
in 1 (2.115(2) Å). Furthermore, the distance between C(7)–O(8) in
compound 1 is shorter than in 2 whereas the length of Co(1)–N
(10) bond shows an inverse relationship (Table 2). Also, the hydra-
zone deprotonation in 2, that leads to a formation of the conju-
gated system and electron delocalization, makes the enolate
ligand more planar than its keto analog in complex 1. For example,
the torsion angles O(8)–C(7)–N(9)–N(10); C(7)–N(9)–N(10)–Co(1);
N(9)–C(7)–O(8)–Co(1) are 3.0(2); -18.9(2); 15.5(2)° for 1 and À1.7
3.2. X-ray crystal structures
Single-crystal X-ray diffraction reveals that both monomeric
(
3); À3.1(2); 5.9(2)° for 2, respectively.
complexes 1 and 2 possess a six-coordinate cobalt(II) center sur-
rounded by two bidentate isonicotinoyl hydrazones in the trans
mode (Figs. 3 and 4) as well as two additional monodentate
ligands. The water and pyridine molecules are axially connected
to cobalt(II) centers saturating coordination spheres in compounds
As also revealed by X-ray diffraction, the intermolecular inter-
actions within crystal structure of compound 1 are dominated by
relatively strong hydrogen bonds involving three groups of atoms
(
Table 3): nitrates oxygen atoms and hydrogen atoms of water
molecules (O(14)–H(14B)Á Á ÁO(17)#5 = 2.685(2) Å; angle = 165
3)°); nitrates oxygen atoms and hydrogen atoms of the hydrazone
1
and 2, respectively. The cobalt(II) centers in both complexes
(
adopt octahedral geometry with deviations from ideal geometry
group (N(9)–H(9)Á Á ÁO(17) = 2.762(2) Å; angle = 160(2)°); pyridine
nitrogen atoms and hydrogen atoms of water molecules (O(14)–
H(14A)Á Á ÁN(1)#4 = 2.748(2) Å; angle = 180(3)°). On the other hand,
compound 2 is stabilized by relatively weak hydrogen bonds
between hydrogen atoms of aromatic rings and nitrogen atoms
of pyridyl rings or oxygen atoms of hydrazonate groups (Table 3).
mainly imposed by the O(8)–Co(1)–N(10) bite angles (1: 75.60
(
(
4)°; 2: 77.09(6)°) and additionally by various bonds distances
Table 2); axial shortening is observed for 1 and axial elongation
for 2. The trans geometry observed for pyridine ligands in complex
is different from that of analogous hydrazone complex: cis-[Co
LL) (py) ] (where LL is acetone naphthoyl hydrazonoate) also
2
(
2
2
There is no p–p stacking between aromatic rings as the distances
between their centroids are within the 4.54–5.88 Å range.
obtained through recrystallization from pyridine [21].
In compound 2 the organic ligands have undergone tautomer-
ization and deprotonation in order to compensate the charge of
metal center. The different situation is in [Co(Hisn)
2
(H O)
2 2
]
3.3. IR, UV–Vis spectroscopy and magnetic moments
(
NO (1) where positive metal charge is compensated by two
3 2
)
nitrate counterions. The deprotonation of the organic ligand in 2
has influence on bond lengths within the hydrazone group and
the coordination sphere of this complex. The enolate form of the
ligand in compound 2 can be confirmed by both crystallographic
and spectroscopic data (Section 3.3). The corresponding C–N,
N–N and C–O bond distances in the C@N–N(H)–C@O moiety in
The infrared spectra of the obtained complexes exhibit several
characteristic absorptions of acetone isonicotinoyl hydrazone
(Fig. 5). The appearance of bands at 1608 m (for 1), 1606 s (for 2)
À1
and 1596 s cm (for 2a) can be ascribed to
m(C@N) vibrations
and confirms the presence of azomethine groups. The band at
À1
1267 cm , observed for 2 and 2a only, indicates the presence of

K. Roztocki et al. / Inorganica Chimica Acta 448 (2016) 86–92
89
Fig. 2. PXRD patterns of the as-synthesized bulk materials (as) compared with
PXRD patterns calculated from the single-crystal structures (calc) for [Co(Hisn) (-
2
Fig. 1. PXRD patterns (top) and IR spectra (bottom) of the recrystallized 2 and as-
synthesized 2a. PXRD pattern given for 2 is calculated from the single-crystal
structure.
2 2 3 2 2 2
H O) ](NO ) (1) (top) and [Co(isn) (py) ] (2) (bottom).
1
430 cm–1 that was ascribed to asymmetric stretching vibrations
enolate C–O groups and is in agreement with the crystallographic
of inorganic nitrates [22].
data for 2. In contrast, the appearance of a strong band at
The room-temperature magnetic susceptibility measurements
À1
1
622 cm in the spectrum of compound 1, corresponding to the
of 1,
2
and 2a gave the effective magnetic moments
½
C@O stretching vibration, confirms the presence of the keto form
M B
[leff = (8v T) ] 4.4, 4.5 and 4.5 l , respectively. These are
of the hydrazone (Hisn). The methyl groups are easily recognizable
by their absorptions in the 2840–3000 cm region, and the aro-
reasonable values for a high-spin configuration (S = 3/2) for
cobalt(II) centers in a tetragonal distorted environment with
strong orbital contributions [23]. The spin state of these cobalt(II)
compounds is in conformity with the moderate ligand field
À1
matic C–H stretching vibrations of pyridine rings appear as rela-
À1
tively weak bands within 3050–3100 cm
.
Both insolubility of 2a in several organic solvents and the pres-
ence of a strong band at 695 cm in the IR spectrum of 2a (Fig. 5),
x
strengths for N O6Àx donor sets (x = 2–4). The UV–Vis spectra of
1, 2 and 2a support the magnetic observation.
À1
attributable to the in-plane pyridine ring deformation vibrations
The electronic spectra of all compounds in the solid state are
dominated by strong bands in the UV region ascribable to intra-
ligand charge-transfer transitions (at 267, 212 nm for Hisn in 1;
[
(
22] and positively shifted from the band of the free Hisn ligand
660 cm ) [15], indicate the polymeric nature of this compound
À1
À
À
with coordinated pyridyl groups, as opposed to complex 2 with
at 242, 220 nm for py and isn in 2; at 220 nm for isn in 2a) as
well as to mlct transitions observed only for enolate complexes
approx. at 318, 304 nm for 2 and at 311, 304 nm for 2a (Fig. 6).
The visible region contains much weaker and less pronounced
absorptions associated with d–d transitions. The observed lowest
energy bands and shoulders (approx. at 520sh, 487 for 1, at 550,
520sh for 2, at 560sh, 520sh for 2a, positions in nm; sh = shoulders,
found as minima on the corresponding first derivative curves) can
free N-donor atoms. The lack of a characteristic amide N–H stretch-
À1
ing vibrations (ꢀ3300–3500 cm ) confirms the enolization and
deprotonation of the Schiff base in compounds 2 and 2a. In con-
trast, the spectrum of 1 contains bands of relatively high intensity
À1
at 3154 and 3181 cm indicating the presence of NH groups in the
keto tautomer of the hydrazone. Their lowered positions are asso-
ciated with the involvement of NH groups in hydrogen bonds.
4
4
4
4
Additionally, the spectrum of compound 1 has a strong band at
1 1 1 2
be assigned to spin-allowed T (F) ? T (P) and T ? A transi-
À1
À
7
1
298 cm
associated with symmetric stretching vibrations of
ions, accompanied by an intense band centered at ca.
tions for high-spin cobalt(II)-d complexes in an octahedral field.
the NO
3
The increased number of other less pronounced shoulders

9
0
K. Roztocki et al. / Inorganica Chimica Acta 448 (2016) 86–92
2 2 2 3 2
Fig. 3. X-ray crystal structure of [Co(Hisn) (H O) ](NO ) (1): (a) cationic complex with selected atom labeling scheme and 30% displacement ellipsoids; (b) packing pattern
viewed along the a axis; (c) packing pattern viewed along the c axis with strong hydrogen bonds indicated as dotted lines between donors and acceptors (d(DÁ Á ÁA) < 2.8 Å).
Hydrogen atoms are omitted for clarity.
Fig. 4. X-ray crystal structure of [Co(isn)
the c axis.
2 2
(py) ] (2): (a) coordination sphere with atoms labeling scheme and 30% displacement ellipsoids; (b) packing pattern viewed along

K. Roztocki et al. / Inorganica Chimica Acta 448 (2016) 86–92
91
Table 2
Selected bond lengths (Å) and angles (°) for [Co(Hisn)
(H
2 2
O)
2
](NO
3
)
2
(1) and [Co
2 2
(isn) (py) ] (2) with estimated standard deviations in parentheses.
1
2
X = O
X = N
Bond lengths
Co(1)–X(14)
Co(1)–O(8)
Co(1)–N(10)
C(7)–O(8)
C(7)–N(9)
N(9)–N(10)
N(9)–H(9)
2.043(2)
2.115(2)
2.157(2)
1.247(2)
1.335(2)
1.407(2)
0.86(2)
2.208(2)
2.031(2)
2.174(2)
1.280(2)
1.304(2)
1.410(2)
–
N(10)–C(11)
1.291(2)
1.286(2)
Bond angles
O(8)–Co(1)–N(10)
O(8)–Co(1)–X(14)
X(14)–Co(1)–N(10)
75.60(4)
89.82(5)
90.47(5)
77.09(6)
90.54(6)
90.78(6)
Symmetry transformations used to generate equivalent atoms: #1 Àx, Ày, Àz (for
); #2 Àx + 1, Ày + 1, Àz + 1 (for 2).
1
Fig. 6. UV–Vis diffuse reflectance (after Kubelka-Munk transformation) of 1, 2 and
Table 3
2a.
2 2 2 3 2 2 2
Hydrogen bonds for [Co(Hisn) (H O) ](NO ) (1) [Co(isn) (py) ] (2) with estimated
standard deviations in parentheses (lengths in Å and angles in °).
D–HÁ Á ÁA
1
d(D–H)
d(HÁ Á ÁA)
d(DÁ Á ÁA)
<(DHA)
structures of 1 and 2 that show their tetragonal distortions from
symmetry: axial shortening and elongation, respectively
(Table 2).
O
h
C(5)–H(5)Á Á ÁO(16)
C(6)–H(6)Á Á ÁO(16)#2
C(12)–H(12B)Á Á ÁO(18)#3
C(13)–H(13A)Á Á ÁO(8)#1
N(9)–H(9)Á Á ÁO(17)
O(14)–H(14A)Á Á ÁN(1)#4
O(14)–H(14B)Á Á ÁO(17)#5
0.95
0.95
0.98
0.98
0.86(2)
0.83(3)
0.78(3)
2.51
2.53
2.56
2.36
1.94(2)
1.92(3)
1.93(3)
3.355(2)
3.391(2)
3.506(2)
3.314(2)
2.762(2)
2.748(2)
2.685(2)
148.3
151.3
161.0
164.2
160(2)
180(3)
165(3)
4
. Conclusion
In conclusion, two new cobalt(II) complexes with acetone ison-
icotinoyl hydrazone have been obtained. Combinations of initial
cobalt salts with ligand precursors led to cationic and neutral com-
plexes containing various tautomeric forms (keto or enolate) of the
hydrazone. The structural diversity of these new compounds has
been confirmed by single-crystal X-ray diffraction and infrared
spectroscopy. Both complexes feature free nitrogen donor atoms
that may potentially be further utilized as building blocks in the
construction of mixed-metal organic frameworks.
2
C(6)–H(6)Á Á ÁN(1)#2
C(12)–H(12A)Á Á ÁO(8)#1
C(15)–H(15)Á Á ÁO(8)
C(18)–H(18)Á Á ÁN(1)#3
C(19)–H(19)Á Á ÁO(8)#1
0.93
0.96
0.93
0.93
0.93
2.68
2.24
2.53
2.70
2.53
3.503(3)
3.173(3)
3.089(3)
3.521(4)
3.075(3)
147.4
164.4
118.7
148.3
118.1
Symmetry transformations used to generate equivalent atoms:
1 Àx, Ày, Àz; #2 x, Ày + 1/2, z À 1/2; #3 x + 1, Ày + 1/2, z + 1/2; #4 Àx À 1, Ày,
#
Àz À 1; #5 Àx À 1, Ày, Àz (for 1).
#
1 Àx + 1, Ày + 1, Àz + 1; #2 Àx, Ày + 2, Àz + 2; #3 x, y À 1, z À 1 (for 2).
Acknowledgements
We thank the National Science Centre (Poland) for financial
support (Grant no. 2012/07/B/ST5/00904). The research was car-
ried out partially with the equipment purchased thanks to the
European Regional Development Fund (Polish Innovation Economy
Operational Program, contract no. POIG.02.01.00-12-023/08).
Appendix A. Supplementary material
CCDC 980980 and 940620 contain the supplementary crystallo-
graphic data for compounds 1 and 2. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif. Supplementary data
associated with this article can be found, in the online version, at
http://dx.doi.org/10.1016/j.ica.2016.03.045.
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