Synthesis, X-ray crystal structure, and properties of antipyrinium perchlorates, hexakis(antipyrine)thulium- and hexakis(antipyrine)ytterbium perchlorates. Quantum-chemical studies of ligands protonation

Article abstract of DOI:10.1134/S0036023614050143

Protonation of the bioactive ligand-antipyrine (AP, 2,3-dimethyl-1-phenyl- 3-pyrazolin-5-one) has been considered, the crystal packing specific features for the protonated antipyrine perchlorate compounds ([APH]ClO ₄·H₂O (1, 2) and [AP₂H]ClO₄ (3, 4)), as well as the crystal structure particularities for [Tm(AP) ₆](ClO₄)₃ (5) and [Yb(AP)₆](ClO ₄)₃ (6) have been elucidated. The protonation ability - complex formation ability relationship has been revealed for a number of organic ligands. Quantum-chemical calculations (DFT) and comparison with the experimental data allowed aligning some organic ligands in a row according to their ability to be protonated and to be incorporated into the inner coordination sphere of the complex.

Full text of DOI:10.1134/S0036023614050143

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2014, Vol. 59, No. 5, pp. 455–468. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © N.S. Rukk, D.V. Albov, R.S. Shamsiev, S.N. Mudretsova, R.A. Osipov, V.V. Zamalyutin, A.Yu. Skryabina, V.V. Kravchenko, 2014, published in Zhurnal
Neorganicheskoi Khimii, 2014, Vol. 59, No. 5, pp. 622–636.
COORDINATION COMPOUNDS
Synthesis, Xꢀray Crystal Structure, and Properties
of Antipyrinium Perchlorates, Hexakis(Antipyrine)Thuliumꢀ
and Hexakis(Antipyrine)Ytterbium Perchlorates.
QuantumꢀChemical Studies of Ligands Protonation1
N. S. Rukka, D. V. Albovb, R. S. Shamsieva, S. N. Mudretsovab, R. A. Osipova,
V. V. Zamalyutina, A. Yu. Skryabinaa, and V. V. Kravchenkoa
a M.V. Lomonosov Moscow University of Fine Chemical Technology (MITKhT)
b M.V. Lomonosov Moscow State University (MSU)
eꢀmail: roukkn@inbox.ru
Received October 7, 2013
Abstract—Protonation of the bioactive ligand—antipyrine (AP, 2,3ꢀdimethylꢀ1ꢀphenylꢀ3ꢀpyrazolinꢀ5ꢀone)
has been considered, the crystal packing specific features for the protonated antipyrine perchlorate comꢀ
pounds ([APH]ClO4
⋅
)
H2O (1, 2
and [Yb(AP)6](ClO4)3 (6)
)
and [AP2H]ClO4 (3, 4
)), as well as the crystal structure particularities for
[Tm(AP)6](ClO4)3 (
5
have been elucidated. The protonation ability—complex
formation ability relationship has been revealed for a number of organic ligands. Quantumꢀchemical calcuꢀ
lations (DFT) and comparison with the experimental data allowed aligning some organic ligands in a row
according to their ability to be protonated and to be incorporated into the inner coordination sphere of the
complex.
DOI: 10.1134/S0036023614050143
1
The design and structural particularities of well as the respective compounds with orthophosphoꢀ
supramolecular compounds is a very important ric [21] and salicylic acids [22] are known. But in the
research area due to the perspective of the new funcꢀ majority of cases no data on the antipyrinium comꢀ
tional material synthesis and application in electronꢀ
ics, catalysis, bioengineering, as well as due to their
potential usage as magneticꢀ, liquid crystallineꢀ, porous
materials [1]. Supramolecular compounds are formed as
a result of nonꢀcovalent interactions, first of all, hydrogen
bonding and cooperative interactions [2, 3]. It should be
mentioned that these interactions are determined by a
number of different factors including the presence of
some lanthanide aquated ions which are involved in
the synthetic procedure but are not incorporated into
the crystal lattice [4, 5].
Meanwhile, a number of organic ligands are weak
bases and these are coordinated by the central atom of
the complex via the ligand donor atom (mainly oxygen
with respect to lanthanides).
Antipyrine (2,3ꢀdimethylꢀ1ꢀphenylꢀ3ꢀpyrazolinꢀ
5ꢀone, AP), its derivatives and complexes with alkaꢀ
pounds crystal structure particularities are available in
the literature.
Interaction of the ligand molecules with those of
the solvent, for example, diꢀ2ꢀpyridylketone,
(py)2CO, with weakly acidic acetone under the basic
conditions, results in the intermediate formation of
CH3COCH2−
the
carbanion due to αꢀhydrogen
abstraction from acetone molecule in the presence of
the EtO– strong base with subsequent formation of
(py)2C(CH2COCH3)(O)– species involved in complex
formation with nickel(II) [23]. So, possible interacꢀ
tions between the ligand and solvent molecules,
including the acidꢀbase ones, should be taken into
consideration in the course of the complex formation
studies.
It is known that organic ligands often exhibit bioacꢀ
tivity which is determined by the scavenging activity
against free radicals (for example, against hydroxyl
radicals, as for 4ꢀaminoantipyrine and its derivatives)
[24] and antimicrobial properties as well [25]. Antioxꢀ
idant properties of antipyrine and its derivatives and
inhibition of human neutrophil oxidative burst by
pyrazolone derivatives have been considered in [26,
27], while the synergistic anaesthetic effect of antipyꢀ
lineꢀearth metals [6, 7], p elements [7, 8], d elements
[9–11], and lanthanides [12–15] are of considerable
importance because of their potentially beneficial
medicinal applications [15]. Antipyrine, being a weak
base [16], can be easily protonated with formation of
antipyrinium compounds. For example, antipyrinium
chloride [17], iodide [18], or perchlorate [19, 20], as
1
The article was translated by the first author.
455

456
RUKK et al.
N
O
N
+ HClO4 + Ln(ClO4)3 ⋅ nH2O → (APH)ClO4 ⋅ H2O + (AP)2HClO4 + [Ln(AP)6](ClO4)3
(1
or
2)
(3
or
4)
(5, Ln = Tm; 6, Ln = Yb)
Fig. 1. Scheme of compounds preparation.
rine under its simultaneous application with chlorate polyhydrates in turn were used as reactants
lidocaine—in [28].
for synthesis of [Ln(AP)6](ClO4)3 (Ln = Tm, Yb)
which were prepared from an aqueous solution of
Ln(ClO4)3 ⋅ nH2O and AP taken in an AP : HClO4
molar ratio of 1 : 6. Isothermal (room temperature)
evaporation of the solvent for about 1–3 d yielded iniꢀ
tially small amount of colourless prismatic single crysꢀ
The aim of the present work is to study the antipyꢀ
rine protonation, to elucidate the structural particuꢀ
larities of antipyrinium perchlorates with different
composition, and to derive the protonation ability—
complex formation ability relationship for a number of
organic ligands. Quantumꢀchemical calculations of
protonation energy have been performed for some
organic ligands. Additionally, the goal of the current
work consists in elucidation of the synthetic procedure
specific features for preparation of antipyrine comꢀ
plexes of thuliumꢀ and ytterbium perchlorates with
subsequent studies of their bioactivity, similarly to
antipyrine complexes of lanthanide iodides [15].
tals of [APH]ClO4
then [Tm(AP)6](ClO4)3 (
⋅
H2O (
2
)
or [AP2H]ClO4 (
4) and
5)
or [Yb(AP)6](ClO4)3 (6),
respectively (Fig. 1).
Antipyrine derivatives, 3ꢀmethylꢀ1ꢀphenylꢀ2ꢀ
pyrazolinꢀ5ꢀone (AP–Me, “Fluka”) and 1ꢀ(4ꢀchloꢀ
rophenyl)ꢀ3ꢀmethylꢀpyrazolꢀ5ꢀone
(AP–Me–Cl,
Aldrich) were used without preliminary purification.
Our attempts to prepare lanthanide complexes with
these compounds were unsuccessful, because in all
cases the uncomplexed ligand precipitated. (! Because
lanthanide perchlorates combined with organic
ligands are potentially explosive they should be hanꢀ
dled in small quantities and with adequate precauꢀ
tions).
The lanthanide content in the prepared comꢀ
pounds was determined by the complexonometric
method (titration by EDTA solution in the presence of
xylenol orange as an indicator). Microanalyses (C, H,
N) were performed on a CHNS Flash EA1112
(Thermo Finnigan, Italy) elemental analyzer. The
antipyrine content was determined by back titration of
excess iodine by sodium thiosulfate solution. The relꢀ
ative error of determination equals to ca. 0.2–0.3 %
for C, H, N. Details are given in [29, 30]. Results of
chemical and elemental analyses are given in Table 1.
EXPERIMENTAL SECTION
Synthesis. Antipyrinium perchlorates [APH]ClO4
⋅
H2O ( and [AP2H]ClO4 ( were obtained from an
1)
3)
aqueous solutions of antipyrine (preliminary recrysꢀ
tallized from ethanol) and perchloric acid taken in an
AP : HClO4 molar ratio of 1 : 1 or 2 : 1, respectively. For
this purpose, aqueous solution of HClO4 (40%, 2 or
1 mL) was added dropwise to an aqueous solution of
antipyrine (1.88 g, 10 mmol). White crystalline comꢀ
pounds (1) and (3) were filtered off, washed with small
portions of cold water and dried in a desiccator over
sodium hydroxide. The yield of the compounds was in
the range of 70–90%. Single crystals of (1) and (3)
were obtained as colourless prisms from a filtrate as a
result of the solvent isothermal evaporation at room
temperature for about 2–3 d.
Compounds
2 and 4 were not analyzed because of
their very small amount.
Lanthanide carbonate trihydrates Ln2(CO3)3
3H2O (Ln = Tm, Yb) were used as reagents for prepaꢀ
ration of Ln(ClO4)3 ⋅ nH2O by a reaction of the respecꢀ potentiometric titration method at 30°C under Ar
⋅
Protonation constants were determined by the
tive carbonate with the stoichiometric amount of atmosphere (pH 340 pHꢀmeter, ESLKꢀ01.7ꢀ or
HClO4. The prepared thuliumꢀ and ytterbium perꢀ HI1179Bꢀcombined electrodes, ATPꢀ02 automatic
Table 1. Results of the elemental and chemical analyses for compounds 1, 3, 5, 6
Content (found/calculated), wt %
N
Compound
C
H
AP
Ln
[APH]ClO4 · H2O (
[AP2H]ClO4 (
[Tm(AP)6](ClO4)3 (
[Yb(AP)6](ClO4)3 (
1
)
53.84/43.08
54.97/55.41
5.23/4.92
5.13/5.28
11.18/9.18
11.36/11.75
–
–
–
–
3)
5
)
–
–
–
–
–
–
70.42/70.73
69.77/70.55
9.69/10.58
10.71/10.81
6)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 5 2014

SYNTHESIS, XꢀRAY CRYSTAL STRUCTURE, AND PROPERTIES
457
Table 2. Wavenumbers (cm–1) of the main vibration bands maxima in the IRꢀspectra of antipyrine and antipyrinium perꢀ
chlorates [18, 34]
1–4
AP
1
2
3
4
Assignment
(CCH)
(CCN)
(NCC)
460m
503m
590m
618m
428vw
488s
591m
464w
490m
604vs
430vw
490s
591m
447w
490s, 512w
591m
γ
γ
γ
γ
(CCC)(Ph)
−
621s
693s
626s
621s
693s
624s
693s
ν4(
)
ClO4
640m
700m
720m
737m
770s
815m
852m
913m
γ(CCν)
692m
721w
ρ
χ
ρ
(CH)(Ph)
(CCC)(Ph)
755w
770s
794m
(MeCC)(Ph)
768s
792s
766m
792w
861vw
770s
792s
ρ
(CH3)
882w
930w
884w
930w
874w
921w
984w
γ(CH)(Ph)
−
919w
ν1(
)
ClO4
988w
1025w
1055m
1080m
ρ
ρ
(NCO)
(CH)(Ph)
1016w
1043w
1018w
1018w
1046w
1035w
1093vs
−
1091vs
1091vs
1091vs
ν3(
)
ClO4
1111s
1146s
1100m
1136m
ν
ν
(CN)
(CC)
1162w
1192w
1244w
1289w
1324vw
1160w
1192w
1244w
1287w
1322w
1167w
1187m
1227m
1306s
1324s
1373m
1397s
1427w
1455m
1485s
1229w
1289vw
1320m
1231w
1289w
1313w
1358w
1410w
1433w
1460w
ν
δ
(CN)
(CH3)
ν(CC) +
δ(CCH)
δ(CH3)
δ(CH3)
1410m
1429w
1455m
1472m
1500s
1432m
1457w
1432m
1457w
1498s
1498s
1498s
ν
(CN) + ν(CC)
1524m
1546m
1578s
1550w
1591m
1608m
1592s
1665s
1608s
1598m
1608s
ν
Overtones
(CO)
1775w
1835w
1906w,
1968w
2039w
2362bm
2526bm
2608bm
1888vw
1912vw
1830w
1888vw
1901vw
2020w
2016w
2016w
ν
(O⋅⋅⋅H–OClO3)
2854w
2927w
3013w
3063w
3134w
2854w
2927w
3013w
3063w
3134w
ν
ν
(CH3)
(CH3) +
2970w
2990w
3098m
3150w
2932bm
3013bm
2959w
3045w
3063w
3135m
ν(CH)(Ph)
ν
(CH)(Ph)
3135bm
*
ν
—stretching vibrations;
δ
—inꢀplane bending vibrations; ρ—phenyl ring inꢀplane bending vibrations; γ—phenyl ring outꢀofꢀplane
bending vibrations;
χ— outꢀofꢀplane bending vibrations of the phenyl ring carbon atoms; m—medium; w—weak; vw—very weak; s—
strong; vs—very strong; b—broad.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 5 2014

458
RUKK et al.
Table 3. Crystallographic parameters, details of Xꢀray diffraction experiment and structure refinement for 1–4
2
4
Compound
1
3
(new polymorph)
(new polymorph)
Empirical formula
FW
C11H15ClN2O6
306.70
C11H15ClN2O6
306.70
C22H25ClN4O6
476.91
C22H25ClN4O6
476.91
Crystal system
Space group
Monoclinic
Monoclinic
Triclinic
Monoclinic
P
21/
c
P
21/
a
P21/a
P
1
a
b
c
α
β
γ
V
Z
, Å
, Å
, Å
, deg
, deg
, deg
11.153(6)
7.759(3)
18.558(8)
90
113.96(4)
90
12.502(10)
9.986(8)
13.475(13)
90
116.81(8)
90
1501(2)
4
1.357
9.107(6)
10.671(7)
13.618(9)
108.09(4)
93.82(4)
109.47(4)
1164.5(13)
2
19.316(14)
7.975(7)
30.884(19)
90
92.19(10)
90
4754(6)
8
1.333
, Å3
1467.5(11)
4
ρcalcd, g/cm3
μ
1.388
2.565
1.360
0.116
, mm–1
2.507
1.809
Crystal colour, shape and Colourless prism,
size, mm
range, deg
Colourless prism,
Colourless prism,
Colourless prism,
0.20
×
0.20
×
0.20
0.30
× 0.30 × 0.30
0.10
×
0.10
×
0.10
0.50
× 0.50 × 0.50
θ
4.34–69.93
3.68–67.94
1.26–19.99
1.43–69.97
Index ranges
–13
–9
–22
≤
≤
≤
h
k
l
≤
≤
13
0
–14
0
≤
≤
≤
h
k
l
≤
≤
≤
13
12
16
–11
–13
0
≤
≤
≤
h
k
l
≤
≤
≤
11
12
16
–23
0
≤
≤
≤
h
k
l
≤
≤
23
8
≤
12
0
0
≤
37
Measured reflections
Refinement method
Parameters under refineꢀ
ment
2703
2727
4404
8593
Full matrix least squares on F2
195
194
306
609
GOOF
1.057
0.910
0.861
0.950
R
Δρmax
1/wR2
[I
≥
2
σ
(I
)]
0.0748/0.2331
0.402/–0.276
0.0669/0.1733
0.278/–0.236
0.0534/0.1262
0.189/–0.189
0.0696/0.2013
0.359/–0.299
/
Δρmin, e/Å3
titrator, TZhTSꢀ02 thermostat). Standard buffer soluꢀ CuKα radiation λ = 1.5418 Å, graphite monochromator,
tions
(
КНС2О4/Н2С2О4, рН 1.68, 25
°
С),
2θ
range from 10° to 80°, step of 0.02°).
Thermal analysis (TGꢀDSC). Thermal Analysis
(КН2РО4/Nа2НРО4, рН 6.86, 25
°С), and HCl soluꢀ
tion with precise concentration were used for elecꢀ
trode calibration. Titration of antipyrine solution
(50 mL, 0.01 M in the outer thermostat with thermoꢀ
stated water jacket) was performed using continuous
agitating with a magnetic stirring bar in the pH value
range from 6.5 to 2.0. The data processing was done on
(TGꢀDSC) was carried out on the Simultaneous
Thermal Analyser STAꢀ409 (Netzsch, Germany) in
the capped alumina crucibles under He flow, the
temperature was ramped from 20 up to 300°C at a
heating rate of 10 degree/min. An empty alumina
crucible was used as the reference. The applied senꢀ
sor was a sensitive contact platform on the basis of
PtꢀRh thermocouple (the relative error of temperaꢀ
the basis of the Wolfram Mathematica
7 software [31] (see
Appendix). Previously we have obtained the preliminary
results concerning the formation constants logβ1, logβ2
,
ture measurement equals to 0.02°С). The sensor
logβ1/2 for antipyrinium species such as [APH]+,
was calibrated with the following reference subꢀ
stances: In, Sn, Zn, Al, Ag, Au. Samples of the
compounds under studies were prepared from single
crystals.
Single crystal XRD analysis 1–6. Experimental
intensities of diffraction reflections were collected at
293(2) K using EnrafꢀNonius CAD–4 diffractometer
[APH2]2+, [AP2H]+ [32, 33]. In the present work we have
obtained more definite results (logβ1= 2.0(1), logβ2
=
4.3(1), logβ1/2 = 3.9(1)), the value of β1 being in good
agreement with literature data (logβ1 = 2.2 [16]).
IRꢀspectra (4000–400 cm–1 and 600–50 cm–1,
Table 2) were recorded on the IR–Fourier spectromeꢀ
ter EQUINOX 55 (BRUKER, Germany) with samꢀ
ples prepared as suspensions with Nujol or as KBr pelꢀ
lets.
(for
1
,
2
, and
: AgKα radiation,
chromator, or
tion correction was taken into account by the
4
:
CuKα radiation,
= 0.56087 Å; graphite monoꢀ
scan mode) [35]. An absorpꢀ
scan
λ = 1.54184 Å; for 3,
5,
6
λ
ω/2θ
ω
/θ
ꢀ
Ψ
Powder XRD analysis. The samples phase purity and method for particular reflections. The unit cell paramꢀ
identity were confirmed by the powder Xꢀray diffraction eters were determined and refined for 25 reflections.
(XRD) analysis (Shimadzu XRDꢀ6000 diffractometer, The main experimental parameters and the comꢀ
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 5 2014

SYNTHESIS, XꢀRAY CRYSTAL STRUCTURE, AND PROPERTIES
Table 4. Hydrogen bonding parameters for
459
1–4
1
D–H⋅⋅⋅
O5–H5⋅⋅⋅O6
O6–H61⋅⋅⋅O2i
A
D–H
H
⋅⋅⋅
A
D
⋅⋅⋅
A
D–H⋅⋅⋅
A
0.74(5)
0.89(2)
0.89(2)
1.81
1.95
2.80
2.552
2.797
3.687
2.900
+ 1/2]
174
158
175
166
O6 –H61⋅⋅⋅Cl1ii
O6 –H62⋅⋅⋅O1iii
Symmetry codes: (i) [
0.88(2)
2.03
x, –y
+ 1/2,
z
– 1/2]; (ii) [
x, –y
+ 1/2,
z
– 1/2]; (iii) [–x, y + 1/2, –z
2
D–H⋅⋅⋅
A
D–H
H⋅⋅⋅
A
D⋅⋅⋅
A
D–H⋅⋅⋅
A
O5–H5⋅⋅⋅O1
0.96
1.04
1.04
1.04
0.92
1.64
1.96
2.57
2.74
1.93
2.561
2.968
3.392
3.749
2.828
160
162
136
163
164
O1–H1A⋅⋅⋅O13
O1–H1A⋅⋅⋅O12
O1–H1A⋅⋅⋅Cl1
O1–H1B⋅⋅⋅O14i
Symmetry codes: (i) [–x + 1/2, y + 1/2, –z + 2]
3
D–H⋅⋅⋅
A
D–H
1.12
H
⋅⋅⋅
A
D
⋅⋅⋅
A
D–H⋅⋅⋅
A
O25–H1⋅⋅⋅O5
1.33
2.430
166
4
D–H⋅⋅⋅
A
D–H
H⋅⋅⋅
A
D⋅⋅⋅
A
D–H⋅⋅⋅
A
O65–H5⋅⋅⋅O5
O25–H25⋅⋅⋅O45
1.27
1.26
1.28
1.26
2.435
2.451
144
153
Table 5. Crystallographic parameters, details of Xꢀray diffraction experiment and structure refinement for
5
and
6
Compound
Empirical formula
5
6
C66H72Cl3N12O18Tm
1596.64
C66H72Cl3N12O18Yb
1600.75
FW
System
Sp. gr.
Trigonal;
Trigonal
R3
R3
a
, Å
13.910(9)
32.29(2)
5411(6)
3
13.937(7)
32.351(18)
5442(5)
c
, Å
V
, Å3
Z
3
ρcalcd, g/cm3
, mm–1
Crystal colour, shape and size, mm
1.470
1.465
μ
0.761
0.795
Colourless prism
Colourless prism
0.30
×
0.30
×
0.30
0.30
× 0.30 × 0.30
θ
range, degree
1.42–19.98
1.42–19.50
Index ranges
–16
0
≤
≤
≤
h
k
l
≤
≤
≤
8
16
39
–16
0
≤
≤
≤
h
k
l
≤
≤
≤ 38
8
16
0
0
Measured reflections
Refining method
Parameters under refinement
GOOF
2283
Fullꢀmatrix least squares method on F2
160 160
1.088
2129
1.064
R
Δρmax
1/wR2
[
I
≥
2
σ
(
I
)]
0.0374/0.0967
0.828/–0.682
0.0354/0.0887
0.665/–0.457
/
Δρmin, e/Å3
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 5 2014

460
RUKK et al.
С(7)
O(4)
O(1)
С(3)
С(6)
Cl(1)
O(3)
H(62)
С(4)
N(2)
C(9)
N(1)
C(12)
H(5)
C(5)
O(6)
H(61)
O(2)
O(5)
C(13)
C(8)
C(11)
C(10)
C(11)
H(61)
O(6)
O(5)
C(4)
C(10)
O(2)
C(13)
C(5)
H(5)
C(9)
N(2)
C(12)
N(1)
O(3)
C(11)
H(62)
C(3)
O(1)
O(4)
Fig. 2. Fragment of packing for compound 1. Selected interatomic distances (Å): O(6)–H(61) 0.89(2); O(6)–H(62) 0.88(2);
O(5)–H(5) 0.74(5); C(5)–O(5) 1.325(5); N(1)–C(5) 1.326(5); N(1)–N(2) 1.370(5); N(2)–C(3) 1.336(5); C(3)–C(4) 1.366(6);
C(4)–C(5) 1.355(5); N(1)–C(8) 1.437(5); C(8)–C(9) 1.365(6); C(9)–C(10) 1.383(6); C(10)–C(11) 1.349(7); C(11)–C(12)
1.366(8); C(12)–C(13) 1.367(7); C(8)–C(13) 1.375(6); Cl(1)–O(3) 1.342(5); Cl(1)–O(1) 1.368(6); Cl(1)–O(2) 1.391(5);
Cl(1)–O(4) 1.393(5).
C(11)
C(12)
C(10)
C(11)
C(12)
C(13)
C(9)
C(8)
C(10)
C(13)
C(9)
C(8)
O(11)
N(1)
C(6)
O(5)
C(5)
O(12)
O(13)
N(2)
N(1)
O(11)
C(6)
O(5)
C(5)
H(5)
H(1A)
O(1)
O(12)
Cl(1)
O(14)
C(3)
C(4)
N(2)
C(7)
H(5)
C(11)
O(13)
O(14)
H(1B)
C(3)
C(4)
H(1A)
O(1)
H(1B)
C(7)
O(14)
H(1B)
O(13)
C(11)
H(1A)
O(1)
O(12)
O(11)
Fig. 3. Fragment of packing for compound 2. Selected interatomic distances (Å): C(5)–O(5) 1.318(4); C(4)–C(5) 1.397(5);
C(3)–C(4) 1.394(5); N(2)–C(3) 1.320(4); N(1)–N(2) 1.363(3); N(1)–C(5) 1.319(4); N(1)–C(8) 1.451(5); C(8)–C(9)
1.338(6); C(9)–C(10) 1.382(7); C(10)–C(11) 1.398(9); C(11)–C(12) 1.302(9); C(12)–C(13) 1.421(7); C(8)–C(13) 1.355(6);
Cl(11)–O(12) 1.315(5); Cl(1)– O(13) 1.383(4); Cl(1)–O(14) 1.394(5); Cl(1)–O(11) 1.408(4).
pounds crystallographic characteristics are given in refined on F2 by the full matrix least squares method in
Tables 3–5. The primary processing of the experimenꢀ the anisotropic approximation for nonꢀhydrogen
tal data array was performed by the WinGX program atoms. Hꢀatoms bound to O atoms were found indeꢀ
package [36]. All subsequent calculations were perꢀ pendently on the basis of the differential Fourier synꢀ
formed in the framework of the SHELXꢀ97 program theses. Other hydrogen atoms were introduced into
package [37]. The crystal structures of the comꢀ the calculated positions and refined in the isotropic
pounds (1–6) were determined by direct method and approximation by the riding model method. Visualizaꢀ
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 5 2014

SYNTHESIS, XꢀRAY CRYSTAL STRUCTURE, AND PROPERTIES
461
O(3)
O(4)
O(1)
Cl(1)
C(27)
O(2)
C(23)
C(7)
C(26)
C(3)
C(24)
N(22)
C(28)
C(6)
N(2)
C(4)
C(29)
N(21)
C(25)
C(13)
C(12)
N(1)
C(5)
O(5)
H(1)
C(30)
C(33)
C(8)
O(25)
C(31)
C(9)
C(11)
C(32)
C(10)
Fig. 4. Structure of the compound 3. Selected interatomic distances (Å): O(5)–C(5) 1.283(3); C(4)–C(5) 1.393(4); C(3)–C(4)
1.374(4); N(2)–C(3) 1.337(4); N(1)–N(2) 1.377(3); N(1)–C(5) 1.363(4); N(1)–C(8) 1.427(4); C(8)–C(9) 1.354(4); C(9)–
C(10) 1.387(5); C(10)–C(11) 1.353(5); C(11)–C(12) 1.363(5); C(12)–C(13) 1.382(5); C(8)–C(13) 1.370(5); O(25)–C(25)
1.289(4); Cl(1)–O(1) 1.352(3); Cl(1)–O(2) 1.389(3); Cl(1)–O(3) 1.328(4); Cl(1)–O(4) 1.408(5).
O(7)
C(51)
C(52)
Cl(2)
O(9)
O(8)
C(66)
C(67)
N(62)
C(53)
C(63)
C(50)
O(3)
O(4)
C(49)
C(48)
C(27)
N(22)
O(6)
C(64)
C(23)
C(24)
C(73)
N(61)
C(65)
Cl(1)
O(1)
O(45)
N(41)
C(72)
C(71)
C(25)
C(10)
C(11)
C(68)
C(46)
N(42)
O(2)
H(25)
C(45)
C(9)
C(26)
O(25)
O(65)
C(69)
C(70)
H(5)
C(44)
C(43)
O(5)
N(21)
C(12)
C(8)
C(13)
C(33)
C(28)
C(5)
C(29)
C(47)
N(1)
C(6)
N(2)
C(3)
C(4)
C(31)
C(30)
C(32)
C(7)
Fig. 5. Structure of the compound 4. Selected interatomic distances (Å): C(5)–O(5) 1.292(4); N(1)–C(5) 1.323(4); N(1)–N(2)
1.379(4); N(2)–C(3) 1.363(5); C(3)–C(4) 1.347(5); C(4)–C(5) 1.419(5); N(1)–C(8) 1.428(4); C(8)–C(9) 1.388(5); C(9)–
C(10) 1.359(5); C(10)–C(11) 1.333(6); C(11)–C(12) 1.386(7); C(12)–C(13) 1.371(6); C(8)–C(13) 1.380(5); C(65)–O(65)
1.256(4); Cl(1)–O(1) 1.326(4); Cl(1)–O(2) 1.376(4); Cl(1)–O(3) 1.422(5); Cl(1)–O(4) 1.336(4).
tion of the compounds
performed using the MERCURY program [38].
Crystallographic data for the compounds
1–6 structure (Figs. 2–8) was charge on request: http://www.ccdc.cam.ac.uk/
data_request/cif; eꢀmail: deposit@ccdc.cam.ac.uk).
1–6
have
Quantumꢀchemical calculations were performed
been deposited in the Cambridge Crystallographic with the Priroda package [39] in the framework of the
Data Centre (the depository numbers CCDC 928893– Density Functional Theory (DFT) (PBE exchangeꢀ
928896 for compounds
1–4, 943633 (compound 5), correlation functional [40], TZDP basis set). The
943632 (compound ); copies can be obtained free of geometry optimization was performed without restricꢀ
6
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 5 2014

462
RUKK et al.
(a)
6.397
3.977
4.002
(b)
Fig. 7. Fragment of packing for 3.
C(7)
O(21)
Cl(2)
C(6)
C(3)
O(22)
O(22)
N(2)
N(1)
O(22)
C(4)
C(13)
C(12)
C(5)
C(9)
C(8)
O(1)
O(11)
O(12)
O(12)
C(11)
O(12)
O(12)
C(10)
Cl(1)
Tm(1)
Fig. 6. Fragment of packing for 4: (a) mutual position of
O(11)
O(12)
rings (perchlorateꢀions are not drawn for clarity, angle
between planes of benzeneꢀ and pyrazolone rings equals to
21.84 Å); (b) view along axis b.
tions on the molecular symmetry. The stationarity of
the minima determined was confirmed by the absence
of the wavenumbers imaginary values in the calculated
vibrational spectra. The solvatation energy values were
calculated using The Polarized Continuum solvent
Model (PCM) with the Gaussian 09 program [41] (the
solvent is water). For comparison calculations were
performed using PCMꢀUFF [42] and PCMꢀSMD
[43] models taking into account both electrostatic and
nonꢀelectrostatic interactions (Table 6, Fig. 9, 10).
Fig. 8. Structure of [Ln(AP) ](ClO ) . Selected interꢀ
6
4 3
atomic distances (Å): Ln = Tm (5). Tm(1)–O(1) 2.190(3);
O(1)–C(5) 1.240(4);C(5)–C(4) 1.401(5); C(3)–C(4)
1.368(7); C(3)–N(2) 1.336(7); N(2)–N(1) 1.388(4);
N(1)–C(5) 1.379(5); N(1)–C(8) 1.419(5); C(8)–C(9)
1.368(6); C(9)–C(10) 1.380(7); C(10)–C(11) 1.304(12);
C(11)–C(12) 1.378(12); C(12)–C(13) 1.383(10); C(8)–
C(13) 1.375(7); Cl(2)–O(22) 1.319(8); Cl(2)–O(21)
1.342(9). Ln = Yb (6). Yb(1)–O(1) 2.180(3); O(1)–C(5)
1.255(5); C(5)–C(4) 1.395(6); C(3)–C(4) 1.365(7);
C(3)–N(2) 1.336(7); N(2)–N(1) 1.394(4); N(1)–C(5)
1.372(5); N(1)–C(8) 1.419(5); C(8)–C(9) 1.385(6);
C(9)–C(10) 1.379(7); C(10)–C(11) 1.327(12); C(11)–
C(12) 1.360(12); C(12)–C(13) 1.405(10); C(8)–C(13)
1.372(7); Cl(2)–O(22) 1.312(7); Cl(2)–O(21) 1.353(9).
RESULTS AND DISCUSSION
IRꢀspectra of 1–4 (Table 2) are characterized by
the absence of the absorption bands at 1665–1667 cm–1
(corresponding to C=O group stretching vibrations for
pure antipyrine) and by the presence of the absorption
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SYNTHESIS, XꢀRAY CRYSTAL STRUCTURE, AND PROPERTIES
463
Table 6. Protonation energy calculated values (*—calculations have been done for different conformers differing in the H
atom position; NH tautomer: H atom is at N; OHꢀtautomer, H atom is at O; CHꢀtautomer, H atom is at C; ** see Fig. 10)
Δ
E
0, kcal/mol
ΔE0, kcal/mol
p
Ka
Entry
Compound
4ꢀDMAAP
+H 2+/PCMꢀUFF +H 2+/PCMꢀSMD
(H2O)
5O 5O
1
2
4.84 [16]
5.20 [45]
–17.7 –7.4
AP
2.2 [16]
–19.5
–8.5
1.51 [50]
1.62 [45]
3
4
5
4ꢀAAP
4.44 [45]
1.66 [45]
0.66 [45]
–17.5
–17.0
–7.5
4ꢀOHAP
4ꢀAAAP
– 6.8
–15.9(anti(O))**
–21.7(syn(O))
–7.3(anti(O))
–12.6(syn(O))
6
7
APꢀMe*
–
–
(CH) –11.8
(NH) –17.2
(OH) –4.9**
(CH) –2.3
(NH) –8.0
(OH) 1.0
APꢀMe–Cl*
(CH) –7.8
(NH) –14.8
(OH) –3.6**
(CH) 0.2
(NH) –5.6
(OH) 1.7
8
9
Ur
0.18 [50]
0.96 [50]
1.4 [50]
–
–21.0
–16.5
–18.2
–11.0
–11.1
–6.6
–9.0
–5.2
ThioUr
AA
10
11
H2O
bands in the area of 3300–3500 cm–1 due to
H⋅⋅⋅O = C
phase transition with subsequent melting. For comꢀ
pound : endoꢀeffect at 116.8–120.0 C ( Htr = 3.07 J/g,
or 0.94 kJ/mol) and at 135.2 C ( Hm = 9.15 J/g, or
2.81 kJ/mol). For compound : endoꢀeffect at
Htr = 4.23 J/g, or 2.02 kJ/mol) and at
Hm = 6.83 J/g, or 3.26 kJ/mol).
2
°
Δ
4
Δ
hydrogen bonding formation with the participation of
the antipyrinium cations, water molecules and perꢀ
chlorateꢀions (compounds 1 and 2
). Unbonded ClO–4
ions show a Td symmetry which is manifested by the
occurrence of individual ν1 (920–930 cm–1) and ν3
(1091–1093 cm–1) bands [34] (Table 2). IRꢀspectra of
°
110.8
°
C (
C (
Δ
Δ
123.1
°
Particularities of the crystal packing for
more symmetrical one for ) (Figs. 2, 3) define the
compound higher dense (Table 3). Threeꢀcompoꢀ
1 and 2 (1
1
3
and 4 are similar. Wide absorption bands of low
1
intensity due to the OHꢀgroup stretching vibrations in
the area of 2200–3500 cm–1 are an indication of
hydrogen bonding (HB) formation and complete proꢀ
tonation of the carbonylꢀgroup oxygen atoms for all
antipyrine molecules [18] which is confirmed by the
single crystal XRD analysis (Tables 3, 4, Figs. 4, 5).
nent splitting in the IRꢀspectrum of 2 (1091, 1111, and
1146 cm–1, Table 2) confirms the more pronounced
distortion of its crystal lattice as well as the higher
degree of the Cl–O bond length scattering (Figs. 2, 3).
As for
4 (Figs. 5, 6), consideration of mutual location
of approximately parallel 5ꢀ and 6ꢀmembered aroꢀ
The absorption bands at 1613 and 1611 cm–1, matic rings of different molecules (the angle between
respectively, in the IRꢀspectra of and should be the planes equals to 21.84
, the respective interplanar
interpreted as the shifted band at 1665 cm–1 (stretchꢀ distance—3.977–4.002 Å, Fig. 6) demonstrates the
ing vibrations of carbonyl group for pure antipyrine). existence of
interaction as nonꢀcovalent contact
It confirms its incorporation into the coordination between
ꢀsystems [44]. It should be mentioned that
sphere of the thuliumꢀ and ytterbium complexes.
aromatic nitrogenꢀcontaining heterocycles are more
suited for interaction because of their lower elecꢀ
5
6
°
π–π
π
π–π
Thermograms of antipyrinium perchlorates ( ) and
1
tron density. When both rings are more electronꢀrich,
the π–π interaction is significantly weaker or is absent
(
3) are characterized by the presence of one endoꢀ
effect due to melting at 121.1 Hm = 17.8 J/g or
°C (Δ
at all (as it takes place for , Fig. 7).
3
5.46 kJ/mol) for
8.69 kJ/mol) for
1
3
and at 126.1°C (Δ
Hm = 18.23 J/g or
Compounds and were prepared in the presence
2 and 4 are characterized by the of thuliumꢀ and ytterbium cations, respectively, which
.
2
4
Thermograms of
presence of two endoꢀeffects possibly related with the have a specific influence on the crystallization process
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 5 2014

464
RUKK et al.
Δ
E0, kcal/mol
AP–Me–Cl
AP–Me
–4
–6
–8
–10
–12
–14
–16
ThioUr
4ꢀAAAP
Ur
4ꢀOHAP
4ꢀAAP
4ꢀDMAAP
–18
–20
–22
–24
AP
AA
–4 –3 –2 –1
0
1
2
3
4
5
6
7 pKa
Fig. 9. Dependence of the protonation energy upon p
K of ligands (pK values for AP–Me and AP–Me–Cl ligands were evaluꢀ
a a
ated according to [52, 53]), calculation of the protonation energy was performed in accordance with the PCMꢀUFF model [42]
taking into account both an electrostatic and nonꢀelectrostatic interactions. Abbreviations: 4ꢀDMAAP—(4ꢀdimethyꢀ
lamino)antipyrine, AP—antipyrine, 4ꢀAAP—4ꢀaminoantipyrine, 4ꢀOHAP—4ꢀhydroxyantipyrine, 4ꢀAAAP—4ꢀacetamiꢀ
doantipyrine; APꢀMe—3ꢀMethylꢀ1ꢀphenylꢀ2ꢀpyrazolinꢀ5ꢀone, APꢀMeꢀCl—1ꢀ(4ꢀchlorophenyl)ꢀ3ꢀmethylꢀpyrazolꢀ5ꢀone;
Ur—urea; ThioUr—thiourea; AA—acetamide.
[4, 5]. It results in different mode of packing (Figs. 2 nation energy for the nonꢀforming complexes AP–Me
and 3; 6 and 7) and in the existence of two endoꢀeffects and AP–Me–Cl. Ligands such as urea (Ur), AA and
in the respective thermograms related with the phase antipyrine (AP), which have the protonation energy
transition with subsequent melting.
below –18.2 kcal mol–1, form complexes stable both in
solution and in the solid state [11, 29, 45–48]. Ligands
with the protonation energy absolute value below that
of acetamide and above that of water molecules (area
between the two horizontal lines on Fig. 9) form comꢀ
plexes in solution [11, 45], but lanthanide complexes
with participation of ligands such as 4ꢀOHAP, 4ꢀ
DMAAP, 4ꢀAAP, 4ꢀAAAP were not structurally charꢀ
acterized. It was found that ThioUr molecules are not
coordinated by the lanthanide central atom but are
incorporated into an outer coordination sphere of the
complex, while water molecules are located in its inner
coordination sphere [48]. If the protonation energy
absolute value is small (above the higher horizontal
line on Fig. 9) the complexes are not formed (AP–Me
and AP–Me–Cl). The same tendency has been found
in the course of the protonation energy calculation
using the PCM–SMD model [43], while boundary
values are slightly deviated (Table 6).
The D–A distances (2.552 and 2.561 Å for 1, 2,
2.430 and 2.435, 2.451 Å for
confirm more loose packing of
(or ), calculated density being equal to 1.388
(1.357) g/cm3 and 1.360 (1.333) g/cm3 for compounds
and (Table 3).
3,
4
, respectively, Table 4)
2
(or ) with respect to
4
1
3
1
(2)
3 (4)
Isostructural crystals (
5) and (
6), similar to the
respective iodides [15], are of the cationꢀanion type
and contain octahedral [Ln(AP)6]3+ (Ln = Tm, Yb)
cations and tetrahedral perchlorate ions one of which
is disordered (Fig. 8), as it takes place for
[Tb(C11H12N2O)6](ClO4)3 [14]. The central atom has
an octahedral environment built from six oxygen
atoms of antipyrine molecules. The Ln–O bond
length demonstrate slight shortening (due to lanꢀ
thanide contraction) in going from 5 to 6: 2.190(3) (Ln =
Tm) and 2.180(3) Å (Ln = Yb) (Fig. 8). The Ln–O
bond length is somewhat higher for perchlorate comꢀ
plexes in comparison with the respective iodides:
2.176(3) (Ln = Tm) and 2.166 Å (2) (Ln = Yb) [15].
The elucidated regularities make themselves eviꢀ
dent in the dependence of the complexꢀforming
atom—the ligand donor atom bond length as a funcꢀ
Results of quantumꢀchemical calculations (Table 6) tion of the ligand type and the element sequence numꢀ
demonstrate (Figs. 9, 10) that the protonation energy ber for some lanthanide iodide complexes [15, 29, 46–
absolute values for ligands AP–Me and AP–Me–Cl 49]. Single crystal XRD data are in accordance with
are the minimal ones in comparison with those of the results of quantumꢀchemical calculations (Table 6,
other ligands incorporated into the real complexes. Fig. 9), as well as with the results of studies on protoꢀ
Thiocarbamide (ThioUr) forms adducts and takes an nation and complex formation for a number of polyarꢀ
intermediate position with respect to other ligands, omatic chelate ligands in nonꢀaqueous solvent [50].
absolute value of its protonation energy being lower On the basis of the studies performed the following raw
than 18.2 kcal mol–1 (–18.2 kcal mol–1—protonation of ligands can be written as their ability to be protoꢀ
energy for acetamide, AA), but higher than the protoꢀ nated and to be incorporated into the complex comꢀ
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 5 2014

SYNTHESIS, XꢀRAY CRYSTAL STRUCTURE, AND PROPERTIES
H3C
465
H3C
N
CH3
N
CH3
CH3
N
N
N
H3C
CH3
CH3
O
N
N
O
O
N
N
N
O
8
1
2
3
H3C
O
N
CH3
CH3
H
N
N
N
N
CH3
O
O
O
CH3
N
N
H
S
N
CH3
9
N
O
6
H
CH3
H3C
N
CH3
4
N
N
O
O
N
N
CH3
O
N
O
CH3
10
Cl
5
7
Fig. 10. Structures of molecules (the structure number is the entry number in the Table 6).
[APH22 +
]
pounds decreases: AP, AA, Ur > 4ꢀOHAP, 4ꢀDMAAP,
4ꢀAAP, 4ꢀAAAP >> ThioUr > APꢀMe, APꢀMeꢀCl.
(2)
β2 =
.
[AP][H+]2
It should be underlined that some complexes conꢀ
tain water molecules in their composition [46, 47].
For the case when one proton is bonded with two
antipyrine molecules:
2AP + [H+] ꢀ [AP2H+],
[AP2H+]
APPENDIX
FORMULA DERIVATION FOR CALCULATION
(3)
β1 2
=
.
In an acidic aqueous solution antipyrine molecules
are able to be protonated and to exist in a number of
[AP]2[H+]
species such as: [APH]+, [APH2]2+, [(AP)2H]+
.
Hence, during hydrochloric acid addition to an
aqueous solution of antipyrine the following equation
(the electroneutrality equation) should be obeyed,
AP + [H+] ꢀ [APH+],
[APH+]
where
stands for HCl concentration:
CCl−
(1)
β1 =
.
[AP][H+]
CCl− = [H+] + [APH+] + 2[APH22+] + [AP2H+].
(4)
For doubleꢀprotonated antipyrine molecule:
From (4), taking into consideration (1)–(3), we
obtain:
AP + 2[H+] ꢀ [APH22+] ,
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 5 2014

466
RUKK et al.
CCl− −[H+] = [APH+] + 2[APH22+] + [AP2H+]
= β1[AP][H+] + 2β2[AP][H+]2 + β1 2[AP]2[H+].
β1[AP]aH+
[APH+] =
[APH22+] =
,
(1a)
(2a)
(3a)
(4a)
(5)
γ1
2
β2[AP](aH+
)
The material balance equation:
,
γ2
CAP = [AP] + β1[AP][H+]
+ β2[AP][H+]2 + 2β1 2[AP]2[H+].
β1 2[AP]2aH+
(6)
[AP2H+] =
,
γ1
On the basis of equations (1)–(6), the averagedꢀ
ligand number nB nB stands for the Bjerrum function)
is calculated as follows:
⎛
⎞
aH+
β1aH+ 2β2(aH+ )2 β1 2[AP]aH+
+ +
(
CCl−
−
= [AP]
.
⎜
⎟
⎟
⎠
⎜
γ1
γ1
γ2
γ1
⎝
CCl− −[H+]
Transformation of (4a) gives (4b):
nB =
CAP
β1 2aH+
2β2aH+
+
⎛
⎞
β1
[AP]2
+[AP]aH+
(7)
⎜
⎝
⎟
⎠
β1[H+] + 2β2[H+]2 + β1 2[AP][H+]
1 + 2β1 2[AP][H+] + β1[H+] + β2[H+]2
γ1
γ
γ2
1
(4b)
=
.
aH+
+
− CCl− = 0,
γ1
Taking into consideration the activity coefficients
and equations (1a)—(3a), we obtain expression (4a):
Solving equation (4b) with respect to [AP] gives (4c)
2
β1aH+ 2β2(aH+ )2
2β2aH+
β1 2aH+
a
⎛
⎞
H+
⎛
⎛
⎞⎞
⎛
⎞
β1
−
+
+
a
H+
+
− 4
− CCl−
⎜
⎜
⎝
⎟
⎟
⎠
⎜
⎝
⎜
⎝
⎟⎟
⎠⎠
⎜
⎝
⎟
⎠
γ1
γ2
γ
γ2
γ1
γ
1
1
(4c)
(4d)
AP =
.
[
]
2β1 2aH+
γ1
Multiplying the equation (4b) by the activity coefꢀ
ficient and taking into account that
2β2a γ1
H+
⎛
⎞
[AP]2β1 2a + [AP]aH+ β1 +
H+
γ1
⎜
⎝
⎟
⎠
γ2
CH0 ClVH0Cl
+ aH+ − γ1CCl− = 0,
CCl−
=
,
VM
equation (4e) is the solution of (4d):
equation (4d) is obtained:
2
2β2(aH+ )2γ1
2β2(aH+ )2γ1
⎛
⎞
⎛
⎞
− β a
+
+
β a
+
− 4β1 2aH+
a
H+
− γ1CCl−
H+
H+
⎜
⎟
⎟
⎠
⎜
⎜
⎝
⎟
⎟
⎠
(
)
1
1
⎜
γ2
γ2
⎝
AP =
,
(4e)
[
]
2β1 2aH+
or
2
2β2(aH+ )2γ1
2β2(aH+ )2γ1
γ2
CH0 ClVH0Cl
⎛
⎞
⎛
⎞
⎛
⎞
− β a
+
+
β a
H+
1
+
− 4β1 2aH+
a
H+
⎜
⎝
−
γ1
H+
⎜
⎟
⎟
⎠
⎜
⎜
⎝
⎟
⎟
⎠
1
⎟
⎠
⎜
⎝
γ2
VM
(4f)
AP =
,
[
]
2β1 2aH+
or
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 5 2014

SYNTHESIS, XꢀRAY CRYSTAL STRUCTURE, AND PROPERTIES
467
100
80
60
40
20
0
APH22+
AP
APH+
AP2H+
0
0.02
0.04
0.06
Clꢀ, mol/L
0.08
0.10
C
Fig. A1. Distribution curves for species with different composition.
0
0
2
⎛
⎞
CHClVHCl
− β a γ + 2β (a )2γ + β a γ + 2β (a )2γ + 4β a γ
H+
2
γ1γ2 − a γ2
H+
⎟
H+
H+
H+
H+
(
)
(
)
1
2
2
1
1
2
2
1
1 2
⎜
⎝
VM
⎠
(4g)
AP =
.
[
]
2β1 2aH+ γ2
Taking into consideration the activity coefficients,
the equation (7) after transformations will be as folꢀ
lows:
The data processing was done on the basis of the
Wolfram Mathematica 7 software [31]. For this purꢀ
pose the special program was written for searching the
minimum of functional which is a function of three
aH+
aH+
aH2 +
aH+
variables β1
,
β2,
β1/2, and equals to the sum of squared
CCl−
−
β1
+ 2β2
+ β1 2[AP]
γ1
γ1
γ2
γ1
deviations of
and
The NelderꢀMeadꢀ
nB(calcd).
nB(exp)
(8)
,
nB =
=
aH+
aH+
aH2 +
CAP
and the Differential Evolution Methods were used for
searching the functional conventional minimum.
1 + 2β1 2[AP]
+ β1
+ β2
γ1
γ1
γ2
We have used, as the initial data set, the averaged
pH values for a large number of parallel experiments,
that’s why the program averaging of the final results
was not done. Distribution curves for antipyrine and
the respective protonated species are given on Fig. A1.
As can be seen from Fig. A1, the antipyrine concentraꢀ
tion decreases, while that of doubleꢀprotonated speꢀ
cies increases upon acid addition.
and stand for the activity coefficients of the sinꢀ
γ1
γ2
gleꢀ or double charged ions, respectively, and
I
is the
ionic strength. The Debye–Hückel zero approach was
used due to the ionic strength small values.
logγ1 = −0.509 I,
logγ2 = −0.509 × 4 I,
I =
Zi2Ci,
1
2
∑
ACKNOWLEDGMENTS
concentration and charge of the species.
Ci, Zi
The authors are very grateful to Professor V. A. Mikhaiꢀ
lov (1930–2012), M.V. Lomonosov Moscow Univerꢀ
sity of Fine Chemical Technology (MITKhT), for
interesting ideas and valuable discussions.
We assume that
CH0 ClVH0Cl
I = CHCl
=
.
VM
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 5 2014

468
RUKK et al.
29. N. S. Rukk, L. D. Iskhakova, and S. U. Kreingol’d,
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