New metal complex systems as electrode active components of ion selective electrode membranes

Article abstract of DOI:10.1134/S1070328417110057

New donor-acceptor 3d-transition metal complexes were synthesized and the cobalt and nickel complexes were studied by X-ray diffraction; CIF files CCDC no. 1516693 (III(Ni)) and 1516694 (III(Co)). The crystal structure details of the reactants were discussed. The proposed compounds were tested as the active components of ion selective electrode membranes for determination of thiocyanate ions. The selectivity of the SCN-SE with metal complex-based membranes depends on the ligand structure and the central metal ion type. The proposed electrode is suitable for determination of thiocyanate ions in the presence of sulfate, chloride, nitrate, nitrite, bromide, and iodide ions.

Full text of DOI:10.1134/S1070328417110057

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2017, Vol. 43, No. 11, pp. 736–744. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © M.Yu. Nemilova, N.V. Shvedene, O.V. Mikhalev, I.V. Fedyanin, D.B. Shpakovsky, 2017, published in Koordinatsionnaya Khimiya, 2017, Vol. 43,
No. 11, pp. 668–675.
New Metal Complex Systems as Electrode Active Components
of Ion Selective Electrode Membranes
M. Yu. Nemilovaa, *, N. V. Shvedenea, O. V. Mikhaleva, **, I. V. Fedyaninb, and D. B. Shpakovskya
a Moscow State University, Moscow, 119991 Russia
b Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, 119334 Russia
*е-mail: mnemilova@mail.ru
**е-mail: mov@med.chem.msu.ru
Received May 26, 2017
Abstract—New donor-acceptor 3d-transition metal complexes were synthesized and the cobalt and nickel
complexes were studied by X-ray diffraction; CIF files CCDC no. 1516693 (III(Ni)) and 1516694 (III(Co)).
The crystal structure details of the reactants were discussed. The proposed compounds were tested as the
active components of ion selective electrode membranes for determination of thiocyanate ions. The selectiv-
ity of the SCN-SE with metal complex-based membranes depends on the ligand structure and the central
metal ion type. The proposed electrode is suitable for determination of thiocyanate ions in the presence of
sulfate, chloride, nitrate, nitrite, bromide, and iodide ions.
Keywords: donor–acceptor 3d-transition metal complexes, N-4-pyridylbenzamide, N-(5-quinolinyl)-3,5-
dinitrobenzamide, active components of ion selective electrode (ISE) membranes, thiocyanate-selective
electrodes
DOI: 10.1134/S1070328417110057
acceptor complexes of 3d transition metals,
INTRODUCTION
М2+(L)2(An–)2(H2O)n (I–IV; Scheme 1), for determi-
Cobalt(II), nickel(II), and zinc(II) complexes
nation of thiocyanate ions and to compare the crystal
ML2(An)2(H2O)n (L = N-(4-pyridinyl)benzamide, N-(5-
structures of some compounds studied by X-ray dif-
quinolinyl)3,5-dinitrobenzamide, N-(4-pyridinyl)3,5-
fraction: III(Co), III(Ni), and V(Ni).
dinitrobenzamide, N-(5-quinolinyl)benzamide, n = 2, 4)
For quantification of toxic thiocyanate ions, which
can occur in waste and surface waters and appear in
the human body, by ion measurements [12, 13], elec-
trode systems with solid membranes based on mix-
tures of Ag2S and AgX (X = halogen) are often used.
Electrodes with crystalline membranes based on an
AgSCN–Ag2S mixture can also be employed. How-
ever, the thiocyanate determination is markedly inter-
fered with by Br–, I–, S2–, and CN– ions and the limit
of detection (cmin) is ~10–5 mol/L [14].
were synthesized from aqua complexes containing the
benzamide or dinitrobenzamide acceptor moiety and N-
heterocycle (pyridine or quinoline) residues as donor
components. Depending on the conditions of complex-
ation (temperature, reaction time, solvent), it is possible
to obtain complexes of different composition
ML2(NO3)2(H2O)n(L")m either containing a solvent mol-
ecule (L") or, in some cases, anhydrous [1–6].
The known metal complexes with a similar struc-
ture such as Co[(NPBA)2(OAc)2(H2O)2] (NPBA =
N-(4-pyridinyl)benzamide) [7, 8] proved to be appli-
cable as sensors for colorimetric measurements; how-
ever, they have not been studied as active components
of electrochemical sensors.
The moderate selectivity to the accompanying halides
and pseudo-halides and insufficiently low limit of detec-
tion promoted the search for new electrode-active com-
pounds. Broad opportunities for this search are provided
At the laboratory of electrochemical methods of by the use of polymeric PVC membranes characterized
analysis of the Division of Analytical Chemistry, Mos- by a wider range in which the Nernst equation holds and
cow State University, the metal complexes that we a lower limit of detection than crystalline membranes
(cmin ~ 10–6–10–7 mol/L). There are known SCN-SE of
this type based on organic reagents such as polyiminopy-
ridines [15], crown ethers [16], calixarenes [17], and
prepared were used as active components of ion selec-
tive electrode PVC-membranes for determination of
nitrate and iodide ions in aqueous solutions [9–11].
This objective of this study was to evaluate the elec- polyamines [18] and metal complexes containing cobalt
trode activity of PVC membranes based on donor- [19], rhodium [20], manganese [21–23], zinc [24–26],
736

NEW METAL COMPLEX SYSTEMS AS ELECTRODE ACTIVE COMPONENTS
737
mercury [27, 28], copper [29–31], iron [32], cadmium
[33], and nickel [34–37] in various combinations with
these reagents. The ISE operation is considerably
affected by both the nature of the complexing metal and
ligand structure.
Thus, the synthesis of new ligands for metal com-
plexes and elucidation of the effect of these com-
pounds on the characteristics of polymeric mem-
brane-based electrodes is a promising task.
O
H2O
M2+
An
(I)
NH
N
N
NH
O
OH2
An
NO2
NO2
O
NH
H2O
An
An
(II)
N
M2+
N
NO2
NO2
OH2
NH
O
O2N
O2N
O
H2O
M2+
An
N
NO2
(III)
An2
N
NH
O
NH
An
O
H2
NO2
O
NH
H2O
An
M2+
An
(IV)
N
N
O
H2
NH
O
I: M = Co, Ni; L = N-(4-pyridinyl)benzamide; An =
−, OAc–; n = 0, 2
NO3
II: M = Co, Ni, L = N-(5-quinolinyl)3,5-dinitrobenzamide; An =
III: M = Co, Ni, L = N-(4-pyridinyl)3,5-dinitrobenzamide; An =
−, OAc–; n = 0, 2
NO3
−, OAc–; n = 0, 2, 4
−, OAc–; n = 0, 2.
NO3
IV: M = Co, Ni, L = N-(5-quinolinyl)benzamide; An = Cl–,
NO3
Scheme 1.
EXPERIMENTAL
and Ni(II) nitrates were used as received. 3,5-Dinitro-
benzoyl chloride was prepared by refluxing the initial
acid with thionyl chloride with the addition of 2 or
3 drops of DMF as the catalyst; the crude product was
crystallized from a minimum volume of hot toluene
The synthesis of metal complexes was performed as
described in our previous study [1] using commercially
available 4-aminopyridine, 5-aminoquinoline, and
3,5-dinitrobenzoic acid. The hexahydrates of Co(II) and dried [1–5].
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 43 No. 11 2017

738
NEMILOVA et al.
The structures of the products were confirmed by no. 1516693 (III(Ni)) and no. 1516694 (III(Co));
IR spectra, which were recorded on an IR 200 Fourier deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.
Transform IR spectrometer (Thermo-Nikolet). In uk/data_request/cif).
some cases, internal reflection spectroscopy was used
Membrane preparation. Polyvinyl chloride (PVC)
to avoid undesirable absorption in the region of
of C-70 brand and o-nitrophenyl octyl ether (Fluka)
3400 cm–1 (OH stretching vibrations).
plasticizer in 1 : 2 ratio and electrode active compounds
The reactions were monitored and the purity of (EAC), namely, metal complexes I–IV (2 wt %), were
compounds was determined by TLC on Silufol UV- dissolved in tetrahydrofuran (THF) (Khimmed), son-
254 plates with a toluene–acetone mixture (1 : 1) as icated for 10 min, and left for complete evaporation of
the eluent.
the solvent. In the preparation of the membrane with
a lipophilic additive, the ionic liquid 1,3-dihexade-
cylimidazolium nitrate (0.5 wt %) was also added.
МALDI mass spectra were measured on an Auto-
flex II Bruker instrument (FWHM resolution of
18000). The samples were deposited on polished steel
substrates. The spectra were recorded in the positive
and negative ion modes.
The plasticized membranes formed as films and
cut-out as circles 10 mm in diameter were attached by
a special tip and a coupling nut to a cylindrical Teflon
electrode body, which was filled with a 1 × 10–4
М
The 1H NMR spectra of solutions in CD3OD were
recorded in a Bruker Avance 400 DPX spectrometer
(400 MHz) with TMS as an internal standard.
solution of KCl. A silver wire coated by a silver chlo-
ride layer served as the internal reference electrode. An
ESSR 10103 silver chloride electrode filled with a 3 М
solution of KCl was used as the external reference elec-
trode. Prior to investigation of electrode properties,
the membrane PVC electrodes were preconditioned in
a 0.1–0.01 М solution of KSCN for at least 5–7 days.
The X-ray diffraction study of III(Ni) (An = NO3–)
was carried out on a Bruker Apex DUO CCD auto-
mated diffractometer (λ(CuKα) = 1.54178 Å, 2θ <
144°), that of III(Co) (An =
−) was performed on
NO3
Preparation of solutions. The initial 1 × 10–1
М
a Bruker Smart Apex II CCD automated diffractome-
ter (λ(MoKα) = 0.71073 Å, 2θ < 60°). The empirical
absorption corrections and systematic error correc-
tions for both structures were applied using the SAD-
ABS program package. The structures were solved by
the direct method and refined by full-matrix least
2
solutions of KSCN for studying the electrode charac-
teristics were prepared by dissolving weight portions of
reagent grade and analytical grade dry substances in dis-
tilled water. More dilute working solutions (1 × 10–2–1 ×
10–6 М) were prepared by successive dilution. Solu-
tions containing foreign anions for investigating the
potentiometric selectivity were prepared by dissolving
weight portions of the corresponding reagent grade
and analytical grade alkali metal salts in water.
squares on
with anisotropic thermal parameters
Fhkl
for all non-hydrogen atoms. The hydrogen atoms
attached to carbon atoms were placed into calculated
positions and included in the refinement in the riding
model with Uiso(H) = 1.2 Ueq(C), and the hydrogens of
coordinated water molecules were found from differ-
ence Fourier maps and refined in the isotropic
approximation.
Potentiometric measurements were carried out on
an Expert 001 ion meter (Russia) and on a HI 2211
HANNA рH/ORP-meter (Germany). The potential
was recorded with not more than 1 mV/min drift.
Crystallographic parameters and final R factors for
III(Ni) (C24H24NiO20N10, M = 831.24): at T = 120 K,
light green crystals, monoclinic, space group P21/c,
a = 8.56210(10), b = 14.8957(2), c = 12.2736(2) Å, β =
91.7390(10)°, V = 1564.64(4) Å3, Z = 2 (Z' = 0.5),
ρ(calcd.). = 1.764 g/cm3, R1 = 0.0290 (for 2806 reflec-
tions with I > 2σ(I) out of 3043 unique reflections),
wR2 = 0.0763, GOOF = 1.049; for III(Co)
(C24H24CoO20N10, M = 831.46): at T = 120 K, brown
crystals, monoclinic, space group P21/c, a =
8.6104(4), b = 14.9748(7), c = 12.2327(5) Å, β =
91.6150(10)°, V = 1576.65(12) Å3, Z = 2 (Z' = 0.5),
ρ(calcd.) = 1.751 g/cm3, R1 = 0.0319 (for 3777 reflec-
tions with I > 2σ(I) out of 4591 unique reflections),
wR2 = 0.0808, GOOF = 1.044.
pot
The potentiometric selectivity coefficients (
)
ki
j
were determined by the method of separate solutions,
with concentrations of the target and foreign ions
being 1 × 10–2 mol/L.
The calculation was performed by the formula:
⎛
⎞
⎟
⎠
Zi
S
Zi
Z j
gkipot
=
E − E + 1 −
logai,
(
)
j
j
i
⎜
⎝
where Ei, Ej are the electrode potentials measured in
solutions of the target and foreign ions (mV), Zi and Zj
are ion charges, is the target ion activity in the solu-
tion, S is the slope of the electrode function for a singly
ai
charged ion [3].
The effect of рH was studied by measuring the elec-
trode potential in a 1 × 10–3 М solution of KSCN
(30 mL); рH was decreased by adding a dilute solution
of H2SO4 and increased by adding solid LiOH.
The structure solution and refinement were carried
out using the SHELX program package, version
2014/7 [38]. The structures are deposited with the
Cambridge Crystallographic Data Centre (CCDC
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NEW METAL COMPLEX SYSTEMS AS ELECTRODE ACTIVE COMPONENTS
739
Table 1. Effect of the nature of the complexing ion on the electrode characteristics of PVC-membranes based on reagent I
in KSCN solutions
Slope of the electrode
function, mV/decade
Linearity range,
mol/L
Central ion
Limit of detection, mol/L
Co2+
Ni2+
Zn2+
5 × 10–5–0.1
1 × 10–4–0.1
1 × 10–3–0.1
8.7 × 10–6
2.0 × 10–5
3.3 × 10–4
50
39
37
RESULTS AND DISCUSSION
coordinated water molecules (O(1wA) and O(2wA))
form an extensive hydrogen bond network with
nitrate anions and carbonyl oxygen atoms (O(5) and
O(5A)). The hydrogen atom of the N(1) and N(1A)
amide moiety also forms a hydrogen bond with the
nitrate anion.
In order to elucidate the effect of the metal nature
on the electrode properties of membranes based on
proposed compounds, we studied the electrode char-
acteristics of PVC membranes based on EAC I con-
taining various complexing ions (М = Co2+, Ni2+,
Zn2+) in solutions of potassium thiocyanate (Table 1).
A comparison of the obtained results showed that
the highest electrode response of 53 mV/decade, an
extended linearity range of 5 × 10–5–0.1 mol/L, and a
low limit of detection of 5.6 × 10–6 mol/L were char-
acteristic of the cobalt-containing reagent I (Table 1).
For the membranes with nickel(II)- and zinc(II)-
based EAC, the slope of the ISE electrode function
did not correspond to the theoretical value and the
limit of detection was much higher.
It follows from X-ray diffraction data for the
crystalline forms of tetraaqua-bis[4-(3,5-dinitro-
benzamido)pyridine]cobalt(II) nitrate (III(Co))
and tetraaqua-bis[4-(3,5-dinitrobenza-mido)pyri-
dine]nickel(II) nitrate (III(Ni)) that the synthe-
sized complexes, similar in the structure to reported
complexes [7, 8], have a different solvation shell
structure, because the metal atom in them is sur-
rounded by four H2O molecules rather than by two
−
The interactions of various natures are expected to
weaken metal–anion bonds and increase the lability of
the anion involved in the ion exchange at the mem-
brane–aqueous solution interface.
Furthermore, the results of X-ray diffraction
demonstrated that the metal–ligand bond in the Co
complex is longer than that with Ni; hence, it is less
strong, which may facilitate ion exchange near the
coordination sphere.
Hence, according to the results of potentiometric
measurements and X-ray diffraction data for metal
complexes, it is expedient to study the electrode char-
acteristics only for membranes with various cobalt-
containing ligands.
The logarithms of the potentiometric selectivity
coefficients to thiocyanate ions in the presence of
some anions (
ISE based on cobalt-containing membrane (I); the
) were calculated for the
− log KSCN X
−
molecules, while the
counterions occur in the resulting values are summarized in Table 2. No inter-
NO3
outer sphere, but are not directly bound to the metal fering effect of the foreign ions on the SCN-selective
atom as in [7, 8] (Fig. 1). In the structures that we electrode potential was found; however, in the pres-
studied by X-ray diffraction, the hydrogen atoms of ence of iodide and salicylate ions, the potentiometric
O(4)
O(1A)
O(2A)
O(3)
N(5)
O(5)
O(2wA)
O(1w)
N(3A)
C(12A)
C(5)
C(6)
C(1)
C(3A)
C(2A)
N(1A)
C(11)
C(13A)
C(10)
C(7)
Ni(1)
N(2A)
C(9A)
C(4A)
C(5A)
N(1)
N(2)
C(9)
C(13)
C(7A)
C(10A)
C(4)
C(2)
C(1A)
O(3A)
N(5A)
O(4A)
C(11A)
C(3)
N(3)
O(1)
C(6A)
C(12)
O(1wA)
O(2w)
O(5A)
O(2)
Fig. 1. General view of the cation of tetraaqua-bis[4-(3,5-dinitrobenzamido)pyridine]nickel(II) nitrate complex (III).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 43 No. 11 2017

740
NEMILOVA et al.
Table 2. Effect of foreign ions on the potentiometric
response of SCN-SE based on reagent I
For electrodes based on active components II and
III, electrode responses close to theoretical ones were
obtained, 55.5 and 60.9 mV/decade, respectively, the
lowest limit of detection being observed for the mem-
brane based on II (4.9 × 10–6 mol/L).
A comparison of the structures of reagents used in
membranes as electrode-active components with the
determined electrode characteristics in thiocyanate
solutions shows that the best response and the lowest
limit of detection are inherent in the membrane based
on the ligand with several terminal nitro groups and
quinoline as the donor moiety.
An important characteristic of the electrode behav-
ior of the membrane is the рH range in which the
potential is invariable. SCN-SE potential measure-
ments in solutions of thiocyanate ions at various рH
showed that the structure of the EAC ligand affects the
stability of the electrode potential in thiocyanate solu-
tions. Figure 2 shows the potentials of the SCN elec-
trode based on cobalt-containing metal complexes II
and III plotted vs. the solution acidity. It was found
that the electrode potential for the membrane based
on III does not change in acid media as рH increases
from 2 to 4. In the рH range above 4, the electrode
potential loses stability and first increases and then (at
рH > 6) substantially decreases.
Conversely, the potential of the SCN electrode
with the membrane based on compound II, which dif-
fers from III by the presence of quinoline moiety in
the ligand, barely depends on the medium acidity. It
changes only slightly as рH increases from 2 to 10.
While evaluating the differences in the structures of
these two metal complexes present in the membrane,
it is noteworthy that according to X-ray diffraction
data, quinoline-containing structures are prone to
intermolecular stacking interactions and hydrogen
bonding, which may affect in different ways the
behavior of the membranes based on them upon vari-
ation of the acidity.
Ion (X–)
− log KSCN X−
SO24−
F–
Cl–
2.74
2.54
2.57
2.74
CH3COOH–
Br–
2.59
2.71
NO2−
NO3−
2.15
I–
1.06
2.36
1.08
С6Н5СОО–
С6Н4ОНСОО–
selectivity coefficients were an order of magnitude
lower than in the presence of other ions.
The effect of the ligand structure on functioning of
SCN electrodes was elucidated by investigating the
electrode properties of PVC membrane electrodes also
on the basis of cobalt reagents II–IV. Table 3 presents
the key characteristics of all of the studied SCN-ISE.
A comparison of experimental results showed that
the slope of the electrode function and the limit of
detection for PVC-ISE in potassium thiocyanate solu-
tions depend on the structure of ligands in the metal
complexes. The lowest electrode response
(34.8 mV/decade) and the highest limit of detection
(6.1 × 10–4 mol/L) were inherent in compound IV
devoid of terminal nitro groups.
Thus, the best electrode characteristics and the
largest pH range of functioning are inherent in the
SCN-SE based on the cobalt-containing complex II.
Since the best characteristics were found for the
membrane electrodes based on II and III, the selectiv-
The electrodes based on compound I possess
somewhat better characteristics: the slope of the elec-
trode function is 50.0 mV/decade, which is, however,
lower than the theoretical value, and the limit of
detection is 8.7 × 10–6 mol/L.
Table 3. Effect of the EAC ligand on the PVC-ISE characteristics based on cobalt reagents I–IV in KSCN solution
Slope of the electrode
function, mV/decade
cmin, mol/L
EAC
Linearity range, mol/L
1 × 10–1–5 × 10–5
1 × 10–1–1 × 10–5
1 × 10–1–1 × 10–4
1 × 10–1–1 × 10–3
8.7 × 10–6
4.9 × 10–6
8.8 × 10–5
6.1 × 10–4
I
50.0
54.5
60.9
34.8
II
III
IV
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NEW METAL COMPLEX SYSTEMS AS ELECTRODE ACTIVE COMPONENTS
741
E, mV
300
250
1
200
2
150
100
50
0
2
4
6
8
10 pH
Fig. 2. Effect of рH on the potentials of thiocyanate SE membrane electrodes based on (2) II and (1) III in KSCN solutions.
ity of these electrodes in the presence of some anions nent and the target ion than anion exchange processes
was studied (Table 4).
based only on electrostatic interactions. Examples of
such interactions include donor-acceptor or stacking
interactions including intermolecular hydrogen bond-
ing in the ligand. In turn, the thiocyanate ion can also
be incorporated in this intricate and flexible system of
interactions at various stages of passage through the
membrane, which should increase the ISE selectivity.
Note that the found selectivity coefficients are
rather low for both electrodes; however, in most cases,
the electrode based on cobalt reagent II with a ligand
containing terminal nitro groups and a quinoline
donor moiety was more selective.
Relying on the above data, all the tested SCN elec-
trodes exhibited non-Hofmeister type selectivity. This
suggests that some stronger and more complex inter-
actions occur between the membrane active compo-
To study the effect of the ionogenic lipophilic addi-
tive on the electrode characteristics of SCN-ISE
based on II, we prepared membranes additionally
containing a hydrophobic component, an ionic liquid,
for example, 1,3-dihexadecylimidazolium nitrate
(Table 5). It was shown that the electrode response of
this membrane is 55 mV/decade, the linearity range is
0.1–1 × 10–5 M KSCN, and the limit of detection is
5 × 10–6 mol/L, which almost coincides with mem-
brane characteristics without an additive.
Table 4. Effect of the EAC nature on the selectivity of the
SCN electrode
− log KSCN−
X−
X–
membrane
membrane
It was found that SCN-SE with addition of ionic
liquid, which increases both the membrane polarity
and hydrophobicity, is selective to the thiocyanate ion
in the presence of foreign anions, but the selectivity
coefficients are higher than those for the electrode
without the additive. It can be concluded that the
introduction of a lipophilic additive somewhat impairs
the selectivity of the metal complex-based electrode
towards the SCN ion. This may indicate that the
SCN-SE selectivity cannot be improved by mere
increase in the overall hydrophobicity of the mem-
brane upon introduction of a lipophilic additive and
that without the additive, the active component acts as
a charged carrier.
based on II
based on III
SO24−
3.85
3.00
CH3COO–
F–
2.56
3.22
3.18
2.54
1.65
2.25
3.70
2.10
Cl–
Br–
NO2−
2.55
1.55
NO3−
1.86
0.59
2.77
0.62
1.60
0.70
2.90
0.10
Thus, as a result of this study, we developed a thiocy-
anate-selective PVC electrode based on cobalt-contain-
ing metal complex, Co(II)[(N-(5-quinolinyl)-3,5-dini-
trobenzamide)2(CH3COO)2(H2O)2], possessing a res-
ponse in the thiocyanate ion concentration range of 1 ×
10–1–1 × 10–5 mol/L (cmin = 4.9 × 10–6 mol/L) and
operating at рH 2–10.
I–
С6Н5СОО–
С6Н4ОНСОО–
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 43 No. 11 2017

742
NEMILOVA et al.
Table 5. Effect of the lipophilic additive on the selectivity of
Note also that we isolated and characterized the
SCN-SE based on II
anhydrous Ni(II) complex, V(Ni), with the same
ligand, but with a geometry fundamentally differing
from that described in [8] (Fig. 3).
− log KSCN−
X−
X–
In anhydrous complex V(Ni), the coordination
polyhedron of nickel is a highly distorted octahedron
in which the pyridine nitrogen atoms of two ligand
molecules occupy the axial positions (as in III(Ni)),
while the other four coordination sites are occupied by
the pyridine nitrogen atom of the third ligand, two
oxygen atoms of one nitrate ion, and one oxygen
atom of the second nitrate ion (Fig. 2). The amide
hydrogen atoms in the crystal of V(Ni) are hydrogen-
membrane
based on II on II with an additive
membrane based
SO24−
CH3COO–
F–
3.50
3.36
2.56
3.22
3.18
2.54
3.20
3.02
2.78
2.10
...
bonded to coordinated nitrate anions (N O
Cl–
2.849(3)–3.084(3) Å), while the oxygen atoms of the
nitro groups are not involved in hydrogen bonding,
like in the aqua complexes considered below. Table 6
summarizes the geometric parameters of the metal
coordination polyhedra in III(Ni), III(Co), and
V(Ni). Unfortunately, complex V(Ni) (M = Ni; n = 0)
could not be used for membrane preparation because
of its low solubility.
Br–
NO2−
2.55
2.33
NO3−
1.86
0.59
2.77
0.62
1.72
0.41
2.51
0.50
I–
Thus, the patterns identified in the study of the key
electrode characteristics of the PVC SCN-membrane
are actually confirmed by X-ray diffraction studies of
some donor-acceptor metal complex compounds
based on cobalt and nickel ions.
C6H5COO–
C6H4OHCOO–
O(3B)
O(4B)
O(2B)
O(1B)
C(4B)
N(3B)
C(5B)
N(5B)
C(6B)
C(1B)
C(3B)
C(2B)
O(5B)
N(1B)
C(7B)
O(4A)
N(5A)
C(9B)
C(10B)
C(8B)
O(1)
C(3)
O(3A)
C(12B)
C(12) C(11)
N(3)
C(6A)
O(5A)
N(2B)
O(2)
O(6N)
C(5A)
C(4A)
O(4N)
C(9A)
C(10A)
C(11B)
C(7A)
C(8A)
C(2)
C(1)
C(7)
O(5)
Ni(1)
C(8)
N(1)
C(1A)
C(2A)
N(2A)
C(11A)
N(2)
C(4)
N(2N)
C(3A)
N(1A)
O(5N)
O(1N)
C(12A)
O(2N)
N(1N)
O(2A)
C(10)
C(9)
C(5)
N(3A)
C(6)
O(1A)
O(3)
O(3N)
N(5)
O(4)
Fig. 3. General view of the tris[4-(3,5-dinitrobenzamido)pyridine]nickel(II) nitrate (V(Ni)) accordng to X-ray diffraction data.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 43 No. 11 2017

NEW METAL COMPLEX SYSTEMS AS ELECTRODE ACTIVE COMPONENTS
743
Table 6. Geometric parameters of the coordination polyhedra of metal atoms in the complexes
Bond
M(1)–O(1w)
III(Ni)
III(Co)
V(Ni)
2.0702(11)
2.0785(12)
2.0785(12)
2.0888(11)
2.1109(11)
2.1289(12)
M(1)–O(2w)
M(1)–N(2)
2.084(2)
2.090(2)
M(1)–N(2w)
M(1)–N(2B)
M(1)–O(1N)
M(1)–O(2N)
M(1)–O(4N)
2.055(2)
2.2099(18)
2.1353(18)
2.0868(18)
International Participation “Problems of Solvation and
Complexation in Solutions. From Solution Effects to
New Materials”), Ivanovo, 2015, p. 96.
ACKNOWLEDGMENTS
This work was supported by the Russian Founda-
tion for Basic Research (project no. 17-03-01070 and
16-03-00743).
12. Vrednye khimicheskie veshchestva. Neorganicheskie
soedineniya I−IV grupp: sprav. izd. (Hazardous Chemi-
cals. Inorganic Compounds of Group I–IV Elements.
A Handbook), Filov, V.A. et al., Eds., Lenigrad:
Knimiya, 1988.
13. Sbornik sanitarno-gigienicheskikh normativov i metodov
kontrolya vrednykh veshchestv v ob’ektakh okruzhayush-
chei sredy (Collection of Sanitary Standards and Meth-
ods for the Control of Hazardous Chemicals in the
Environment), Moscow, 1991, p. 512.
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No. 11
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