Coordinational compounds of 3d-metal phthalates with nicotinamide

Article abstract of DOI:10.1134/S1070363209060255

Complexes of iron(II), cobalt(II), nickel(II), copper(II), and zinc with nicotinamide were synthesized. The compounds obtained were characterized by means of chemical analysis, conductometry, thermogravimetry, and by means of the IR and the diffuse reflection spectroscopy.

Full text of DOI:10.1134/S1070363209060255

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 6, pp. 1175–1182. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © T.V. Koksharova, I.S. Gritsenko, I.V. Stoyanova, S.E. Samburskii, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79,
No. 6, pp. 1003–1010.
Coordinational Compounds of 3d-Metal Phthalates
with Nicotinamide
T. V. Koksharovaa, I. S. Gritsenkoa, I. V. Stoyanovab, and S. E. Samburskiia
a Mechnikov Odessa National University, ul. Dvoryanskaya 2, Odessa, 65026 Ukraine
e-mail:koksharova@farlep.net
b Bogatskii Physicochemical Institute, National Academy of Sciences of Ukraine, Odessa, Ukraine
Received January 12, 2009
Abstract—Complexes of iron(II), cobalt(II), nickel(II), copper(II), and zinc with nicotinamide were
synthesized. The compounds obtained were characterized by means of chemical analysis, conductometry,
thermogravimetry, and by means of the IR and the diffuse reflection spectroscopy.
DOI: 10.1134/S1070363209060255
Anions of o-phthalic acid, H2Pht, are interesting
objects from the point of view of complex formation.
Phthalate ligand exhibits broad variety in the structure
of H2Pht-containing complexes existing either as
polymeric or monomeric compounds with different
functions of two chemically equivalent carboxylic
groups [1]. Structural function of acid, and of its
monoation HPht– and dianion Pht2– is determined by
compromise between the steric hindrances determined
by two carboxylic groups in o-position and their
tendency to form the maximum number of the metal-
oxygen bonds while complex formation [2]. On the
basis of analysis of the great array of experimental and
reported data the workers [3] have distinguished
26 ways of coordination of o-phthalate anion with the
dentity varying from 1 to 7. The way of coordination
of phthalate anion in complexes with different ligands
is effected by sterical characteristics of co-ligands. The
Complexes, formed by the molecular nitrogen-containing
ligands, in detail, by pyridine and methylpyridines and
the phthalate anions are reported about [1, 2, 4]. But no
data on the products of the reaction of metal phthalates
with another organic molecules containing the pyridine
fragment were found by us. Due to that we have
chosen nicotinamide with the purpose of synthesis and
investigation of structure and properties of its
coordinational com-pounds with iron(II), cobalt(II),
nickel(II), copper(II), and zinc phthalates.
amide ratio. The composition of complexes appeared
to be independent of the reagent ratio for all the metals
under study. Results of chemical analysis (Table 1)
show that all the complex formers under study give the
compounds of the 1:2 metal–nicotinamide composition.
In the case of copper(II) the compound of the 1:4
composition was also obtained. Reaction of nickel(II)
with nicotinamide is accompanied by partial protona-
tion of the phthalate residue, and it enters the complex
as monoanion. Complexes of 3d-metal phthalates with
nicotinamide dissolve in water and DMF, and to some
extent lower in ethanol. For the compound with
sufficient solubility in water (above 0.01 mol l–1) the
values of molar electroconductivities were measured,
what permitted to establish the type of their ionic
decay (Table 1).
Structure of the compounds II, IV was evaluated by
means of the X-ray analysis [5, 6]. It was found that
structural units of compound II are [CoL2(H2O)4]2+
cations and the Pht2– anions. The Co atom is located in
the sufficiently regular octahedral surrounding of two
pyridine nitrogen atoms, two nicotinamide ligands, and
four oxygen atoms belonging to water molecules.
Structural units of the compound IV are linear chains
formed by means of the bridge phthalate anions and
the molecules of crystallization water.
Each copper atom is coordinated by two pyridine
nitrogen atoms of two nicotinamide ligands, by two
oxygen atoms of different phthalate anions, and the
oxygen atom of water molecule. Coordination number
The complexes were synthesized by addition of
crystalline 3d-metal phthalate to the nicotinamide
aqueous solution in the 1:2 and 1:4 metal–nicotin-
1175

1176
KOKSHAROVA et al.
Table 1. Elemental analysis, molar electroconductivity in water, and coloration of products I–VI of the reaction of 3d-metal
phthalates with nicotinamide
Found, %
Calculated, %
Comp.
no.
Λm,
Color
Brown
Formula
Ω
–1 cm2 mol–1
M
N
12.2
9.4
M
N
12.4
10.2
8.8
C20H16FeN4O6 [FeL2Pht]
12.1
10.3
12.1
9.7
Poorly soluble
I
Reddish pink
Greenish light blue
Blue
C20H16CoN4O6·6H2O [CоL2Pht.6H2O]
C28H22N4NiO10·2H2O [NiL2(HPht)2·2H2O]
C20H16CuN4O6·1.5H2O [CuL2Pht·1.5H2O]
C32H28CuN8O8 [CuL4Pht]
91
253
II
8.1
11.1
15.2
11.2
8.8
12.8
8.9
8.4
11.2
15.6
11.0
III
IV
V
13.2
8.9
Poorly soluble
Poorly soluble
74
Light blue
White
12.6
C20H16N4O6Zn·2H2O [ZnL2Pht.2H2O]
12.8
VI
is completed to six by the second (chelating) distant
atom of carboxy group. Coordinational polyhedron of
copper atom is the elongated tetragonal bipyramide.
between the oxygen atom of the amide group and the
central atom. Absorption bands νring at 1600 and at
1000 cm–1 in the IR spectra of complexes undergo the
high frequency shift as compared to the spectrum of
free nicotinamide what corresponds to coordination of
nicotinamide with the central atom through the
nitrogen atom of the pyridine ring. Such character of
shifts of the above-mentioned absorption bands is
observed also for the complexes characterized by the
X-ray data what shows that the proposals concerning
the type of coordination are true.
Conclusions concerning the character of ligand
coordination and the coordination polyhedrons of the
rest substances I, III, V, and VI were made on the
basis of spectral data. Attribution of frequencies of the
main absorption bands in the IR spectra of
nicotinamide and the complexes synthesized was
carried out on the basis of the reported data [7–9] and
presented in Table 2. Frequencies of some bands in the
IR spectrum of nicotinamide are significantly in-
fluenced by the association of its molecules in the solid
state due to formation of H-bonds. This effect is more
significant for the spectra of crystalline amides, while
in the spectra of crystalline complexes of metals with
amides the effect of H-bonding is insignificant if the
amino group nitrogen atom of nicotinamide does not
take part in bonding. Spectral and X-ray data of the
large number of complexes tell in favor of this fact [8].
That is why for the correct attribution of shifts of the
absorption bands of nicotinamide while complex
formation we suggested it necessary to obtain IR
spectra of the ligand in KBr pellets as well as in the
suspension in vaseline oil. In the case of metal
phthalates and complexes the IR spectra of samples in
vaseline oil are not informative because the absorption
bands of oil overlap partially with the absorption bands
of carboxylic group. Hence, comparison of the
absorption bands of nicotinamide in vaseline oil and of
metal phthalates and complexes synthesized in KBr
pellets was most convenient for interpretation of the IR
spectra.
It is established that IR spectroscopy is the reliable
method for identification of the mode of coordination
of carboxylate ligands, in detail of dicarboxylates [10].
For the diagnostics of the coordination model of
carboxylic group Δν(COO–) (νas – νs) value, that is the
difference between νas and νs frequencies is used [11].
The workers [10] showed that Δν value about 200 cm–1
for the phthalate anion in copper(II) complexes with
nitrogen-containing ligands is the bordering between
the monodentate and the bidentate–chelate coordina-
tion. One of the oxygen atoms of COO– forms strong
coordination bond with the complex-forming ion while
the second one takes part in the considerably weaker
binding with the same ion or the adjacent one to form
the linear polymeric chain. Just the same picture is
observed in our case for the CuL2PHt·1.5H2O complex
IV: Δν for this compound is just equal to 200 cm–1,
and the X-ray analysis showed that Cu–O distances are
1.964 and 2.235 Å for two oxygen atoms of different
phthalate anions bound with one atom of copper, and
2.587 Å for another (chelating) oxygen atom of one of
the carboxy groups [5]. We consider that more
convenient for the interpretation of the IR spectra of
carboxylate complexes is not the Δν = νas – νs value,
but Δν(COO–), the difference between Δν(COO–)
values of the mixed-ligand complex and starting
carboxylate. According to the reported data on the X-
Comparison of the absorption bands of nicotin-
amide on the one hand, and of the complexes obtained
on the other showed that in all the cases the frequency
of ν(C=O) (“amide I”) absorption band increases in
complexes what is caused by the absence of bonding
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COORDINATIONAL COMPOUNDS OF 3d-METAL PHTHALATES
1177
Table 2. IR spectral data for nicotinamide L, 3d-metal phtalates and the reaction products I–VI
Absorption bands (cm–1) of COO– group
Absorption bands of nicotinamide and phthalate anion (cm–1)
Compound
L (KBr pellets ) 3376, 3300, 3170 [ν(NH)], 3090, 3035, 2970, 2960, 2910, 2890, 2820 [ν(CH)],
1687 [ν(C=О)], 1627 [δ(NH2)], 1580 (νring), 1380, 1360, 1340 [δ(CСН)], 1290,
1250, 1205 [δ(CСН), δ(ССС)], 1160, 1134 [δ(NH2), δ(CСН)], 1030, 1005
(νring), 890, 835, 760 [ν(CС), δ(ССС)], 702 [δ(CСN)ring], 635, 610
[δ(СNC)ring], 550 [δ(CСN), δ(ССС)]
L (suspension in 3350, 3145 [ν(NH)], 1665 [ν(C=О)], 1610 [δ(NH2)], 1585, 1560 (νring), 1365,
vaseline oil)
1330 [δ(CСН)], 1295, 1195 [δ(CСН), δ(ССС)], 1145, 1120 [δ(NH2), δ(CСН)],
1020, 965 (νring), 880, 820, 765 [ν(CС), δ(ССС)], 710 [δ(CСN)ring], 635, 615 [δ
(СNC)ring], 595, 500 [δ(CСN), δ(ССС)]
FePht·2H2O
1570
1569
1408
1409
162
160
3368, 3180 [ν(NH)], 3064 [ν(CH) (L)], 1672 [ν(C=О)], 1611 [δ(NH2)], 1575
(νring), 1491 [δ(CСН)], 1298 [δ(CСН), δ(ССС)], 1150 [δ(NH2), δ(CСН)], 1090,
1043 (νring), 863, 830, 792 [ν(CС), δ(ССС)], 754 [δ(ОСО)], 698
[δ(CСN)ring], 669, 652 [δ(СNC)ring], 586 [δ(CСN), δ(ССС)]
–2
I
CоPht·2H2O
1558
1535
1398
1385
160
150
3340 [ν(ОH)], 3175 [ν(NH)], 3005, 2820, 2795 [ν(CH) (L)], 1705 [ν(C=О)],
1660 [δ(NH2)], 1620 [νring (L)], 1435 [δ(CСН)], 1305 [δ(CСН), δ(ССС)], 1150
[δ(NH2), δ(CСН)], 1080, 1065 [νring(L)], 890, 830 [ν(CС), δ(ССС)], 765 [δ
(ОСО)], 690 [δ(CСN)ring(L)], 635 [δ(СNC)ring(L)], 550 [δ(CСN),
δ(ССС)]
–10
II
NiPht·2H2O
1560
1604 a
1405
1393
155
211
3365, 3159 [ν(NH)], 1699 [ν(C=О)], 1630 [ν(СООН)], 1615 [δ(NH2)], 1604a
(νring), 1436 [δ(CСН)], 1320 (δОН), 1285 a (δОН), 1255, 1198 [δ(CСН),
δ(ССС)], 1136 [δ(NH2), δ(CСН)], 1054, 1036 (νring), 946 (γОН), 850, 830, 811,
762 [ν(CС), δ(ССС)], 730 [δ(ОСО)], 696 [δ(CСN)ring], 668, 654
[δ(СNC)ring], 584 [δ(CСN), δ(ССС)]
56
III
CuPht·H2O
1530
1560
1410,
1350
120,
180
3445, 3425 [ν(ОH)], 3370, 3350, 3320, 3290 [ν(NH)], 3065, 3050, 3030
[ν(CH) (L)], 1705 [ν(C=О)], 1650 [δ(NH2)], 1605 [νring(L)], 1440, 1425
[δ(CСН)], 1280 [δ(CСН), δ(ССС)], 1180 [δ(NH2), δ(CСН)], 1060, 1045 [νring (L)],
870, 845, 810 [ν(CС), δ(ССС)], 745 [δ(ОСО)], 710 [δ(CСN)ring(L)], 680, 635
[δ(СNC)ring(L)], 515 [δ(CСN), δ(ССС)]
1360
200
80, 20
54, –6
IV
3346, 3180, 3114 [ν(NH)], 3073 [ν(CH) (L)], 1695 [ν(C=О)], 1632 [δ(NH2)],
1604 (νring), 1326 [δ(CСН)], 1297, 1251, 1203 [δ(CСН), δ(ССС)], 1148
[δ(NH2), δ(CСН)], 1085, 1060, 1035 (νring), 853, 841, 792, 775 [ν(CС),
1557
1383
174
V
δ(ССС)], 724 [δ(ОСО)], 700 [δ(CСN)ring], 690, 650 [δ(СNC)ring
]
ZnPht·2H2O
1616
1541
1394
1395
222
146
3342, 3226, 3123 [ν(NH)], 3070 [ν(CH) (L)], 1694 [ν(C=О)], 1671 [δ(NH2)],
1629 (νring), 1436 [δ(CСН)], 1202 [δ(CСН), δ(ССС)], 1146 [δ(NH2),
δ(CСН)], 1086, 1054, 975 (νring), 842, 824 [ν(CС), δ(ССС)], 770 [δ(ОСО)],
708 [δ(CСN)ring], 656, 646 [δ(СNC)ring], 550 [δ(CСN), δ(ССС)]
–76
VI
a Absorption band is contributed by nicotinamide and the phthalate anion.
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1178
KOKSHAROVA et al.
ray analysis of copper(II) phthalate monohydrate [12]
carboxy groups of the phthalate ion are bound with
copper in different manner. One of them forms a
bridge connecting two atoms of copper while another
one in fact occupies one coordination site, but it is
bound with two metal atoms through one atom of
oxygen in its turn bound with the bridge molecule of
water. Evidently due to that the IR spectrum of
CuPht·H2O contains one band νas(COO–) at 1530 cm–1
and two νs(COO–) bands at 1410 and 1350 cm–1.
Hence in the case of starting copper(II) phthalate
Δν(COO–) has two values, 120 and 180 cm–1. From
that it follows that ΔΔν(COO–) also acquires two
meanings. The largest one, 80 cm–1, relates to the
transformation of the bidentate bridge carboxy group
to that occupy-ing one coordination place. Smaller
value, 20 cm–1, corresponds to the carboxylic group
occupying one coordination site in the starting
phthalate as well. Presence of one more distant bond
between copper and the carboxylic group oxygen is not
reflected in the IR spectrum. For the compounds II, V,
and VI (COO–) values acquire negative meanings. For
the compound CoL2Pht·6H2O II it was established by
means of the X-ray studies that phthalate ion is located
in the outer sphere, and under these conditions not an
increase but a decrease in difference between νas(COO–)
and νas(COO–) by 10 cm–1 takes place. That means that
Δν(COO–) for the complex obtained by us is negative.
Hence, it can be proposed that some equalization of
bonds in the phthalate anion takes place. Such picture
is most probably caused by the fact that due to the
interaction of starting salt with nicotinamide phthalate
anion is not bound with cobalt what relates to its
displacement in the outer sphere of complex. Negative
ΔΔν(COO–) value for the copper(II) compound of the
1:4 com-position also permits to propose that phthalate
anion is located in the outer sphere though this
compound as well as copper(II) complex of the 1:2
composition has two ΔΔν(COO–) meanings. As it was
shown above, that means that starting copper(II)
phthalate contains differently bound groups. The outer
sphere location of phthalate anion is confirmed by
molar electrocon-ductivity measurements in water
(Table 1). According to [13] compounds CoL2Pht·
6H2O II and ZnL2Pht· 2H2O VI can be regarded as
electrolytes of the 1:1 type while the compound NiL2
(HPht)2·2H2O III is a three-ionic electrolyte. For the
latter one specific features in the IR spectrum are also
observed. The workers [3] have described complexes
with 1-methyl-imidazole of the composition M(1-
MeIm)6(HPht)2· 2H2O (M = Co, Ni). IR spectra of
these compounds contain absorption bands at 1634
cm–1 [ν(COOH)], at 1290 cm–1 [ν(OH)], and at 939–
937 cm–1 [γ(OH)]. That means that o-phthalic acid
presents here in a form of monoanion. IR spectra of
NiL2(HPht)2·2H2O ob-tained by us contain analogous
bands at 1630 (shoulder), 1285, and 946 cm–1 what
also tells in favor of presence of the monoprotonated
phthalate anion. Hence, conductometric as well as
spectroscopic data confirm that nickel complex
contains monoanions of phthalic acid in the outer
sphere. For the iron(II) complex (compound I) ν(COO–)
shows no alterations after the reaction with nicotin-
amide. It permits to propose that phthalate anion does
not change its symmetry in the course of complex
formation, but remains the bidentate ligand in the com-
position of the inner sphere of the iron(II) complex.
Table 3. Diffuse reflection spectra of complexes of 3d-metal
phthalates with nicotinamide I–VI
Data of the diffuse reflection spectroscopy are
listed in Table 3. Analysis of the band location permits
to propose that the compounds I and III have
tetrahedral structure, while the compound V is pseudo-
tetrahedral [14].
Comp. no.
λmax, nm
2471.8
479
Assignment
5E → 5T2
I
4T1g(F) → 4T1g(P)
4T1g(F) → 4A2g
4T1g(F) → 4T2g
3T1 → 3T1(P)
3Т1 → 3A2
II
Table 4 presents the data concerning thermogravimetric
studies of the compounds synthesized. Thermal stab-
ility of analogous comlexes depending on the complex
forming metal decreases in the following series:
1120.2
1968
592.8
1224
III
Fe2+ > Cu2+ > Zn2+ > Ni2+ > Co2+.
This series of thermal stability of d-metal phthalate
complexes with nicotinamide is analogous to the series
obtained for metal valerates and benzoates [15]. Note
that the compounds IV and V having the same
complex former copper(II), but differing in the
740.5
736.4
1981.6
IV
V
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COORDINATIONAL COMPOUNDS OF 3d-METAL PHTHALATES
1179
metal:nicotinamide stoichiometric ratio exhibit large
difference of the decomposition temperatures. In this
case higher thermal stability of CuL2Pht·1.5H2O IV as
compared to CuL4Pht V arises evidently from the
polymeric structure of the compound having 1:2 ratio
of metal to ligand. The same reason explains lower
solubility of compound IV as compared to V, because
crystallization of the first product and its isolation from
the solution in the course of synthesis proceeds much easier.
the crystallization water. First endoeffect is accom-
panied by the 6% loss of mass, while for the second
one this value is 13.6%. Theoretical calculations show
that loss of two molecules of water gives the value of
6.26%, while four water molecules give 12.52%.
These data are in good agreement with the experi-
mental results. Hence, at lower temperature the
liberation of two molecules from the outer sphere
water takes place, while further heating leads to the
liberation of four intraspheric water molecules. On the
basis of the results obtained following structures can
be offered for the compounds I–IV.
For the compound CoL2Pht·6H2O (II) first two
endoeffects are connected evidently with the loss of
O
N
C
O
O
Fe
C
O
O
NH2
C
N
O
C
NH2
I
O
C
NH2
N
H2O
H2O
OH2
OH2
Co
N
C6H4(COO)2 2 H2O
H2N
C
O
II
O
C
NH2
N
H
H
H
[C6H4(COO)(COOH)]2
O
Ni
N
O
H
H2N
C
O
III
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 6 2009

1180
KOKSHAROVA et al.
O
O
C
C
NH2
NH2
N
N
O
C
O
O
O
n/2 H2O
Cu O
C
H
O
Cu O
C
H
C O
O
N
O
H
N
H
H2N
O
H2N
C
C
O
n
IV
O
O
C
C
NH2
NH2
O
N
C
N
H2N
H
O
H
H
C6H4(COO)2
Zn
N
O
C6H4(COO)2
N
C
N
Cu
N
H
C
O
NH2
H2N
H2N
O
C
O
VI
V
Table 4. Results of derivatographic studies of thermal
stability of the 3d-metal phthalate complexes with nicotin-
amide I–VI
Comparison of the results presented in this work
with the previously reported data on the analogous
complexes of 3d-metal valerates and benzoates with
nicotinamide [15–19] shows that phthalate anion as
compared to the above-mentioned monocarboxylate
ones is more inclined to driving in the outer sphere. In
some cases it leads to decrease in the coordination
number of the central ion.
General
Endoeffects
Exoeffects
T, °C Δm, %
Comp.
no.
loss of
mass, %
80.5
T, °C
Δm, %
285–450(385) 70.0
150–287(242) 33.4
I
70–112(100)
6.0
52.9
75.4
76.0
84.4
II
112–150(130) 13.6
93–178(112) 13.5
EXPERIMENTAL
225–292(260) 22.2
292–450(428) 31.7
225–350(300) 53.8
350–445(418) 17.3
190–280(230) 56.9
280–455(385) 10.8
455–500(480) 10.8
180–290(228) 67.4
III
IV
V
IR spectra were recorded on a Perkin-Elmer
SPECTRUM BX II FT-IR spectrometer in KBr pellets.
Diffuse reflection spectra were obtained on a Perkin-
Elmer Lambda-9 spectrophotometer against MgO
(βMgO 100%). Thermogravigrams were measured on a
Paulik–Paulik–Erdey derivatograph in air, heating rate
10 deg min–1.
150–190(170)
100–180(150)
4.6
8.9
Iron(II), cobalt(II), nickel(II), copper(II) and zinc
chlorides, phthalic acid, and nicotinamide of the “pure
for analysis” grade were used.
80.3
VI
380–475(442)
4.0
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COORDINATIONAL COMPOUNDS OF 3d-METAL PHTHALATES
1181
Metal content in the compounds obtained was
measured complexonometrically [20], nitrogen content
was evaluated by means of the Dumas method [21].
with small amount of water, and dried in a dessicator
over CaCl2 until the constant mass.
REFERENCES
Complex I. Nicotinamide, 0.005 mol, was dis-
solved in 5 ml of water, and 0.0025 mol of dry metal
phthalate was added in portions under constant stirring.
After the addition was complete, the mixture obtained
was heated to boil and then stirred with a magnetic
stirrer until the alteration in the coloration of
precipitate. The crystals formed were filtered off on a
Schott filter, washed with small amont of water and
dried in a dessicator over CaCl2 until the constant
mass.
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Complex II. Nicotinamide, 0.61 g, was dissolved
in 5 ml of water, and 0.65 g of crystalline CoPht·2H2O
was added in portions under permanent stirring.
Obtained pink solution was left on cold, and after 3 h
pink crystals were formed. The precipitate was filtered
from the mother liquor and dried in a dessicator over
CaCl2 until the constant mass.
5. Sadikov, G.G., Koksharova, T.V., Antsyshkiha, A.S.,
Gritsenko, I.S., and Sergienko, V.S., Kristallografiya,
2008, vol. 53, no. 4, p. 668.
Complex III. Nicotinamide, 0.61 g, was dissolved
in 5 ml of water, and 0.65 g of the crystalline NiPht·
2H2O was added in portions under permanent stirring.
After the addition was complete resulting mixture was
stirred with a magnetic stirrer until the complete
dissolution of crystals. The emerald-colored solution
obtained was placed in the porcelain cup for the partial
evaporation of solvent. After some time green
precipitate was formed. It was filtered off on a Schott
filter, washed with small amount of water, and dried in
a dessicator over CaCl2 until the constant mass.
6. Koksharova, T.V., Antsyshkina, A.S., Sadikov, G.G.,
Sergienko, V.S., and Gritsenko, I.S., Abstracts of
Papers, XVII Ukr. Conf. on Inorganic Chemistry with
the Participation of Foreign Scientists, Heads of the
Reports, Lviv, 2008, p. 165.
7. Tsivadze, A.Yu., Tsyntsadze, G.V., Kharitonov,
Yu.Ya., and Gverdtsiteli, L.V., Zh. Neorg. Khim., 1978,
vol. 23, no. 2, p. 447.
8. Tsyntsadze, A.Yu., Shaftvaladze, M.V., and Tsivad-
ze, A.Yu., Koord. Khim., 1990, vol. 16, no. 12, p. 1666.
9. Shabilalov, A.A., Borisova, N.N., and Azizov, M.A.,
Koord, Khim., 1987, vol. 13, no. 9, p. 1227.
Complexes IV, V. Nicotinamide, 0.61 g, was
dissolved in 5 ml of water, and 0.00125 mol of crystal-
line CuPht·H2O was added in portions with stirring.
Resulting mixture was heated to boil. Dissolution of
starting phthalate was accompanied by formation of
new precipitate. After stirring for an hour, light blue
precipitate of compound IV was separated on a Schott
filter and crystallized from water. After some time the
crystals of compound V precipitated from the filtrate.
10. Subramanian, P.S ., Dave Paresh, C., Borich, Vinod, P.,
and Srivinas, D., Polyhedron, 1998, vol. 17, no. 4,
p. 443.
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13. Kukushkin, Yu.N., Khimiya koordinatsionnykh soe-
dinenii (Chemistry of Coordinational Compounds),
Moscow: Vysshaya Shkola, 1985.
Complex VI. Nicotinamide, 0.61 g, was dissolved
in 5 ml of water, and 0.66 g of crystalline ZnPht·2H2O
was added in portions under permanent stirring.
Resulting mixture was heated to boil until the complete
dissolution of precipitate of the starting salt. The
mixture obtained was stirred on a magnetic stirrer until
the formation of white precipitate. The crystals
obtained were filtered off on a Schott filter, washed
14. Liver, E., Elektronnaya spektroskopiya neorga-
nicheskikh soedinenii (Electronic Spectroscopy of
Inorganic Compounds), Moscow: Mir, 1987, vol. 2.
15. Koksharova, T.V., Gritsenko, I.S., and Stoyanova, I.V.,
Zh. Obshch. Khim., 2007, vol. 77, no. 9, p. 1564.
16. Antsyshkina, A.S., Koksharova, T.V., Sadikov, G.G.,
Gritsenko, I.S., Sergienko, V.S., and Egorova, O.A., Zh.
Neorg. Khim., 2006, vol. 51, no. 6, p. 972.
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17. Antsyshkina, A.S., Sadikov, G.G., Koksharova, T.V.,
Gritsenko, I.S., and Sergienko, V.S., Zh. Neorg. Khim.,
2006, vol. 51, no. 10, p. 1671.
2007, vol. 52, no. 5, p. 847.
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metricheskoe titrovaniye (Complexonometric Titration),
Moscow: Khimiya, 1970.
21. Klimova, V.A., Osnovnye mikrometody analiza
organicheskikh soedinenii (Essential Micromethods for
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18. Koksharova, T.V., Sadikov, G.G., Antsyshkina, A.S.,
Gritsenko, I.S., Sergienko, V.S., and Egorova, O.A., Zh.
Neorg. Khim., 2006, vol. 51, no. 6, p. 966.
19. Sadikov, G.G., Antsyshkina, A.S., Koksharova, T.V.,
Gritsenko, I.S., and Sergienko, V.S., Kristallografiya,
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