Synthesis, complexing properties, and selectivity of bis(diphenylphosphorylmethyl) ethers of oligoethylene glycols. Crystal structure of 1,3-bis(diphenylphosphoryl)-2-oxapropane

Article abstract of DOI:10.1134/S107036321711010X

A convenient method of synthesis of phosphoryl-substituted podands with dipehnylphosphorylmethyl end groups of the general formula Ph₂P(O)CH₂O(CH₂CH₂O)_nCH₂P(O)Ph₂ (Lⁿ, n = 0–6) is described. The stability constants of the complexes of the podands with alkali metal 2,4-dinitrophenolates were determined by conductometry. The ion-selective properties of the podands with respect to alkali and alkaline-earth metal cations were assessed by ionometry. The crystal structure of 1,3-bis(diphenylphosphoryl)-2-oxapropane was established by X-ray diffraction analysis.

Full text of DOI:10.1134/S107036321711010X

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 11, pp. 2574–2581. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © I.S. Ivanova, V.E. Baulin, I.N. Polyakova, E.N. Pyatova, E.S. Krivorot’ko, E.N. Galkina, A.Yu. Tsivadze, 2017, published in Zhurnal
Obshchei Khimii, 2017, Vol. 87, No. 11, pp. 1833–1840.
Synthesis, Complexing Properties, and Selectivity
of Bis(diphenylphosphorylmethyl) Ethers
of Oligoethylene Glycols. Crystal Structure
of 1,3-Bis(diphenylphosphoryl)-2-oxapropane
I. S. Ivanovaa,b*, V. E. Baulinb,c, I. N. Polyakovaa, E. N. Pyatovaa,b,
E. S. Krivorot’kob, E. N. Galkinaa, and A. Yu. Tsivadzeb
a Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
*e-mail: isivanova@mail.ru
b Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russia
c Institute of Physiologically Active Substances, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
Received June 26, 2017
Abstract―A convenient method of synthesis of phosphoryl-substituted podands with dipehnylphos-
phorylmethyl end groups of the general formula Ph2P(O)CH2O(CH2CH2O)nCH2P(O)Ph2 (Ln, n = 0–6) is
described. The stability constants of the complexes of the podands with alkali metal 2,4-dinitrophenolates were
determined by conductometry. The ion-selective properties of the podands with respect to alkali and alkaline-
earth metal cations were assessed by ionometry. The crystal structure of 1,3-bis(diphenylphosphoryl)-2-
oxapropane was established by X-ray diffraction analysis.
Keywords: organophosphorus podands, stability constants, complex formation, alkali metals, ion-selective
properties, XDR analysis
DOI: 10.1134/S107036321711010X
Synthetically available acyclic analogs of crown
ethers (podands) are potent complexing agents for
alkali and alkaline-earth metal cations. They have
found application as active components of extraction
systems extraction chromatographic materials, and
plasticized membranes of ion-selective electrodes [1].
Of considerable interest are podands containing the
phosphoryl group, which is easily polarized and
possesses a high coordinating ability. The stability of
complexes with phosphoryl-substituted podands and
the selectivity of their formation depends on many
factors, including the number and donor power of the
coordinating centers and the rigidity of the ligand. We
showed that phosphoryl-substituted podands with
Scheme 1.
O
O
O
n
O
n
P
P
O
O
Ph
P
Ph
O
P
Ph
Ph
O
Ph
Ph
Ph
Ph
n
Lign
Lig1
n = 1–5.
2574

SYNTHESIS, COMPLEXING PROPERTIES, AND SELECTIVITY
Scheme 2.
2575
tion products were isolated and used to synthesize
unsymmetrical phosphoryl-substituted podands [13].
Podand L1 was also synthesized in 33% yield in a
nonaquoeus biphasic liquid–solid system. The solid
phase was a mixture of KOH and K2CO3 powders, the
liquid phase was a solution of diphenylphosphinous
acid and 1,2-bis(chloromethoxy)ethane in benzene,
and the phase-transfer catalyst was 18-crown-6.
However, attempted synthesis of longer chain ethylene
glycols by the reaction of diphenylphosphinous acid
with bis(chloromethyl) ethers did not lead to a success
[13]. The synthesis of some podands by the reaction of
(chloromethyl)diphenylphosphine oxide with lithium
glycolates was also reported [14, 15].
O
P
O
P
O
P
O
P
n
n
O
O
O
O
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
n
L1
Ln
n
n = 1–5 (L1 ), 0–6 (Ln).
ortho-phosphorylated phenol fragments (Lign and
Lig1 ) as end groups exhibit a high coordinating power
n
In the present work we obtained compounds L0–L6
in yields of 71–85% by the reaction of (hydroxy-
methyl)diphenylphosphine with corresponding glycol
ditosylates or dichlorides in the biphasic Cs2CO3–
dioxane system at 100°С (Scheme 3). Reaction prog-
ress was monitored by TLC and 31Р NMR. The yield
of the target products was almost independent on
whether the phase-transfer catalyst (18-crown-6 or
tetrabutylammonium bromide) was present or absent.
With solid NaOH or anhydrous K2CO3 as the bases,
the yields of short-chain podands L1–L3 and long-
chain podands L4–L6 decreased to reduced to 30–45%
and 15%, respectively. The yields of compounds L4–
L6 was strongly increased by the addition to the
reaction mixture of equivalent quantities of CsOH or
Cs2CO3. Therewith, by the end of the reaction, the 31Р
NMR spectrum of the reaction mixture showed, along
with the signal of the final product, a signal 0.25 ppm
apart from and 15% as intense as this signal. We
suggest that this signal belonged to a complex of the
ligand with Cs+, because it disappeared after the
reaction mixture had been treated with dilute HCl.
Apparently, here we faced template assembly of a
polydentate organic ligand on the cesium cation, a
phenomenon which is not infrequently observed in the
synthesis of cyclic polyethers [1]. Tsvetkov et. [13]
described podands L2 and L3 as oily substances. By
contrast, we obtained these products in the crystalline
state, and compound L1 had a much higher melting
point. Attempted synthesis of phosphoryl-substituted
podands by the reaction of О,О-dipentyl (hydroxy-
methyl)phosphonate or (2-hydroxyethyl)diphenylphos-
phine oxide with diethylene glycol ditosylate at varied
reaction conditions failed: No other products but
decomposition products of the starting reagents were
detected in the reaction mixture.
with respect to alkali metal cations (Scheme 1).
The stability constants of the complexes of such
podands not infrequently compare or even higher than
the stability constants of similar complexes with crown
ethers [2, 3]. In [4, 5] we determined the crystal
n
structure of the complexes of Lign and Lig1 with some
alkali metal cations and correlated the structures and
stability constants of the complexes. Earlier Baulin and
co-workers [6, 7] made an attempt to correlate the
structure of phosphoryl-substituted podands Lign, Lig1n,
and L1n and their Li/Na selectivity, taking into account
the relative fraction of the phosphoryl groups in the
podand, its conformational rigidity, and ethylene
glycol chain length, but the resulting data proved
controversial (Scheme 2).
Proceeding with research into the dependence of
the structure of podands and their complexing
properties and selectivity, in the present work we
studied phosphoryl-substituted podands Ln (n = 0–6)
having diphenylphosphorylmethyl end groups.
Earlier some compounds of the Ln series were
tested as extractants for europium and americium from
nitric acid media [8] and for platinum from hydro-
chloric acid media [9]. Evidence showing that such
compounds favor removal of strontium from mice was
reported [10]. Podands Ln were also used in plasticized
membranes for ion-selective electrodes for the deter-
mination of octylammonium [11] and guanidinium
cations [12].
The first representatives of the Ln series were
synthesized by the reaction of (chloromethyl)diphenyl-
phosphine oxide with sodium mono- and (hydroxy-
methyl)diphenylphosphine oxide with diethylene glycol
dithosylate in boiling toluene. A series of monoalkyla-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 11 2017

2576
IVANOVA et al.
Scheme 3.
O
OH
P
(1) Cs2CO3
O
O
(2) Ph2P(O)CH2OTs
O
P
P
dioxane, 100oС, 10 h
Ph
Ph
Ph
Ph
Ph
Ph
85%
L0
O
O
P
(2) TsOCH2(CH2OCH2)mCH2OTs
On
Ph
dioxane, 100oС, 10 h
O
OH
P
m = n _
1
P
Ph
O
Ph
Ph
(1) Cs2CO3
L1_3
Ph
Ph
O
O
(3) ClCH2(CH2OCH2)nCH2Cl
n
dioxane, 100oС, 10 h
O
O
P
P
Ph
Ph
Ph
Ph
L4_6
The logarithms of the stability constants of
phosphoryl-substituted podands Ln (n = 0–6) with
alkali metal 2,4-dinitrophenolates, obtained by con-
ductometry in a THF–СНCl3 binary solvent (4 : 1 v/v),
are listed in Table 1. As seen, the stability constants
are rather low, and, therefore, podands Ln, except for
L1, rank below their conformationally more flexible
podand L3 are 4.8 and 4.5. In going to Cs+ is almost
leveled: log KCs+ = 3.8 and 3.7 for podands Lig3 [3, 13]
and L3, respectively. In general, podands Ln are also
less efficient than isodentate crown ethers [2, 3].
Exceptions are podands L1 and L2, which more
efficiently than isodentate crown ethers bind
Li+ [log KLi+ = 5.7 (L1), 2.8 (benzo-12-crown-4),
5.2 (L2), 4.6 (15-crown-5)] and compare with or
slightly better in binding efficiency than their analogs
Lig1 and Lig2 (log KLi+ = 5.8 and 4.6, respectively).
In worth mentioning that phosphoryl-substituted
podand L1 has a high lithium/sodium selectivity
coefficient.
n
analogs L1 in the efficiency of binding alkali metal
cations [6, 7]. With respect to lithium and sodium
cations, podands Ln even rank below less confor-
mationally flexible podands Lign. For example, the
log KLi+ and log KNa+ for podand Lig3 are 7.0 and 6.1,
respectively [3, 13], and the respective values for
Table 1. Stability constants of the complexes of podands Ln (n = 0–6)withalkali metal2,4-dinitrophenolates in a THF–CHCl3
binary solvent (4 : 1 v/v)
log K
Podand
KLi/KNa
Li+
4.2
5.7
5.2
4.8
4.6
4.6
4.6
Na+
3.2
3.6
4.2
4.5
5.2
5.2
5.1
K+
2.7
3.2
3.8
4.4
5.0
5.4
5.1
Rb+
2.4
2.9
3.5
4.2
4.6
5.2
–
Cs+
2.1
2.7
3.2
3.7
4.2
4.7
–
L0
L1
L2
L3
L4
L5
L6
10.0
125.9
10.0
2.0
–
–
–
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SYNTHESIS, COMPLEXING PROPERTIES, AND SELECTIVITY
2577
The lower stability constants of the complexes of
conformationally flexible podands Ln compared to
n
their less flexible analogs Lign and Lig1 affect the ion
selectivity of the former: none of the synthesized
podands Ln showed potentiometric selectivity to
lithium cations. Study of the membrane-active pro-
perties with respect to alkali and alkaline-earth metal
cations established that podands Ln all, unlike Lign and
n
Lig1 , are, to a greater or lesser degree, are selective to
Cs+ (Fig. 1). Figure 2 presents the electrode
characteristics of cesium-selective electrodes on the
basis of podands with two (L2, Fig. 2a) and five (L5,
Fig. 2b) ethylene glycol units, a dibutyl phthalate
plasticizer, and a potassium tetrakis(4-chlorophenyl)-
borate lipophilic additive (50% with respect to the
electrode-active component) in the presence of some
interfering alkali and alkaline-earth metal cations.
Fig. 1. Potentiometric selectivity coefficients for cesium-
selective electrodes on the basis of ligands L0–L3 and L5
with a dibutyl phthalate plasticizer and a potassium tetrakis-
(4-chlorophenyl)borate lipophilic additive (50% with respect
to the electrode-active component).
Podand L3 showed the best electroanalytical
characteristics with respect to Cs+, even the stability
constants of the corresponding complex is not the
highest (Tables 1 and 2). The same correlation between
stability constants and potentiometric selectivity constants
was previously observed for the less flexible podands
which form strong bonds with Li+, Na+, and K+
contribute much to the stability of the complexes. The
relative contribution of the phosphoryl groups into the
stability of the complexes decreases in the order Li+ >
Na+ > K+ due to the equalization of the cation bond
lengths with the phosphoryl and ether oxygen atoms
and increase of the number of ether oxygens.
Unfortunately, we failed to isolate crystalline alkali
metal complexes of podands Ln. It can also be
suggested that in going from Li+ to Cs+ the con-
tributions of the phosphoryl and ether oxygen atoms in
the stability of the complexes, too, equalize, and the
stability constants gradually increase with increasing
number of coordinating centers.
3
Lig3 and Lig1 and Li+ [4, 5]. The highest potentio-
metric selectivity with respect to alkali metal cations
was displayed by podand L3 and with respect to alkaline-
earth metal cations, its shorter-chain analog L1 (Fig. 1).
In our previous work [4] we analyzed the structures
and stability constants of the complexes of alkali
n
metals with podands Lign and Lig1 , and isostructural
crown ethers to show that the phosphoryl groups
(a)
(b)
20 mV
20 mV
pCs+, M
pCs+, M
Fig. 2. Electrode characteristics of cesium-selective electrodes on the basis of podands (a) L2 and (b) L5 with a dibutyl phthalate
plasticizer and a potassium tetrakis(4-chlorophenyl)borate lipophilic additive (50% with respect to the electrode-active component)
in the presence of some single- and double-charged ions. a: (1) Rb+, (2) Ca2+, (3) Mg2+, (4) Na+, (5) Li+, and (6) Cs+; b: (1) Ba2+, (2)
Rb+, (3) K+, (4) Sr2+, (5) Ca2+, (6) Li+, (7) Mg2+, (8) Na+, and (9) Cs+.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 11 2017

2578
IVANOVA et al.
Table 2. Electrode characteristics of the Cs+-selective electrodes
on the basis of podands Ln (n = 0–3, 5)
The molecule of podand L0 in an open con-
figuration can form a bridge between metal atoms. On
the other hand, this molecule can also act as a chelating
ligand similarly to podand L1 with a longer ethylene
glycol chain in a crystal of [Nd2(NO3)6L13], where it
fulfills both bridging and chelating functions [16].
Slope of the
Linear range of the
Podand electrode function,
electrode
function,
mB/pCs+
Detection
limit, М
М
L0
L1
L2
L3
L5
10–4–10–1
10–4–10–1
10–4–10–1
10–4–10–1
10–4–10–1
54±1
55±1
51±1
52±1
50±1
6.0×10–4
3.4×10–4
7.6×10–5
4.0×10–5
5.0×10–5
The bond lengths and bond angles in the molecule
of podand L0 are close to standard values. The lengths
of analogous bonds Р1=О1 and Р2=О2 [1.484(2) and
1.479(2) Å], as well as О3–С25 and О3–С26 [1.422(3)
and 1.421(3) Å] are equal within the experimental
error; the С25О3С26 bonds is 112.6(2)°.
The ether О3 atoms forms two weak intramolecular
С–Н···О hydrogen bond, and the phosphoryl О1 atom
forms two intramolecular hydrogen bonds (Table 4),
one of which joins the molecules into centrosymmetric
dimers, and the other joins the dimers into chains. The
О2 atom of the other phosphoryl group is involved in a
weaker, directed binding with the phenyl ring of the
neighboring chain.
The crystals of 1,3-bis(diphenylphosphoryl)-2-oxa-
propane (L0) suitable of X-ray diffraction (XRD)
analysis were obtained by recrystallization from a 1 : 1
benzene–hexane mixture. The general view of the
molecule of podand L0 in crystal is shown in Fig. 3.
The principal crystal data, experimental details, and
structure refinement parameters are listed in Table 3.
The central fragment O1–P1–C25–O3–C26–P2–O2 is
flattened; the rms deviation of the seven atoms from
the mean plane is 0.092 Å. All bonds in the fragment
have a trans configuration. The C1–C6 and C19–C24
phenyl ring planes form a dihedral angle in 22.7°. The
other dihedral angles between phenyl ring planes are
72.5°–81.9°.
Thus, we developed a fairly facile synthesis of
phosphoryl-substituted
podands
Ph2P(O)CH2O
(CH2CH2O)nCH2P(O)Ph2 and thus made these
compounds more accessible. The stability constants of
the complexes of the synthesized podands with alkali
metal 2,4-dinitrophenolates were determined. It was
shown that the plasticized polymer membranes of ion-
selective electrodes podands Ln (n = 0–4) as an active
component are selective to the cesium cation. The
crystal structure of 1,3-bis(diphenylphosphoryl)-2-
oxapropane was established by XRD analysis.
EXPERIMENTAL
1
The H and 31Р NMR spectra were recorded on a
Bruker СХР-200 spectrometer against TMS and 85%
Н3РО4, respectively. The melting points were measured
on a Boetius PHMK 05 hot stage. Syntheses with
CsCO3 were performed under dry argon. Column chro-
matography was performed on Silica L (100–160 µm),
eluent chloroform.
1,3-Bis(diphenylphosphoryl)-2-oxapropane (L0).
(Diphenylphosphoryl)methanol, 6.0 g (26.0 mmol),
and 10.0 g (26.0 mmol) of (diphenylphosphoryl)-
methyl p-toluenesulfonate were added to a suspension
of 8.4 g (26.0 mmol) of finely ground anhydrous
Cs2CO3 in 30 mL of anhydrous dioxane [17]. The
mixture was stirred under reflux for 10 h and eva-
porated in a vacuum. The residue was mixed with
Fig. 3. General view of the molecule of 1,3-bis(diphenyl-
phosphoryl)-2-oxapropane (L0) in
a
crystal (thermal
ellipsoids are given at a 50% probability level).
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SYNTHESIS, COMPLEXING PROPERTIES, AND SELECTIVITY
2579
Table 3. Principal crystal data, experiment details, and structure refinement parameters for podand L0
Parameter
Formula
Value
Parameter
dcalc, g/cm3
µMo, mm–1
Value
C26H24O3P2
446.39
150(2)
1.344
0.223
M
T, K
F(000)
936
λ, Å
0.71073
Monoclinic
P21/n
Crystal dimensions, mm
Tmin, Tmax
0.14×0.04×0.02
0.6143, 0.7452
2.103–25.464
Crystal system
Space group
Z
θ range, deg
4
Number of reflections:
Measured unique
(N) [Rint]
18417
4094 [0.1077]
2531
with I > 2σ(I) (N0)
a, Å
11.0924(12)
Number of refined
parameters
352
b, Å
11.8590(13)
17.2761(19)
103.919(2)
2205.8(3)
R1, wR2 at N0
R1, wR2 at N
S
0.0482, 0.0829
0.1004, 0.0984
1.003
c, Å
β, deg
V, Å3
Δρmax /Δρmin, е/Å3
0.268/–0.264
Table 4. С–Н···О interactions in the crystal of podand L0
d, Å
Symmetry transformations
С–H···O
CHO angle, deg
of the О atom
C–H
H···O
2.59(3)
2.57(3)
2.41(3)
2.50(3)
2.68(3)
C···O
C12–H12···O3
C14–H14···O3
C21–H21···O1
C22–H22···O1
C5–H5···O2
x, y, z
0.94(3)
0.94(3)
1.01(3)
0.95(3)
0.97(3)
3.269(4)
3.252(4)
3.203(4)
3.238(4)
3.366(4)
130(2)
130(2)
135(2)
135(2)
128(2)
x, y, z
–x, –y, –z + 1
x – 0.5, –y + 0.5, z – 0.5
–x + 1, –y, –z + 1
75 mL of a double dilute HCl, and the mixture was
extracted with CHCl3 (5×50 mL). The extract was
washed with a double dilute HCl (3×50 mL) and water
(3×50 mL), and the solvent was removed in a vacuum.
The residue was recrystallized from benzene–hexane
(1 : 1). Yield 85%, mp 134–136°С. 1H NMR spectrum
methanol, 100.0 mmol, and 50.0 mmol of tetraethylene
glycol dichloride were added to a suspension of
100.0 mmol of a finely ground anhydrous Cs2CO3 in
80 mL of anhydrous dioxane. The mixture was stirred
under reflux for 8 h and evaporated in a vacuum. The
residue was mixed with 100 mL of a double dilute
HCl, and the mixture was extracted with CHCl3 (3×
75 mL). The extract was washed with a double dilute
HCl (5×50 mL) and water (5×50 mL) and the solvent
was evaporated in a vacuum. The residue was chromato-
graphed on a silica column and recrystallized from
2
(CDCl3), δ, ppm: 4.50 d (4Н, СН2Р, JHH = 7.5 Hz),
7.33–7.75 m (20Н, Ar-H). 31Р NMR spectrum
(CDCl3): δР 27.50 ppm. Found, %: С 69.70, 69.90; Н
5.00, 4.90; Р 13.40, 13.60. C26H24O3P2. Calculated, %:
С 70.00; Н 5.40; Р 13.90.
1
ethyl methyl ketone. Yield 70%, oil. H NMR spec-
Podands L1–L3 were synthesized as described in [5].
trum (CDCl3), δ, ppm: 3.40–3.74 m (16Н, СН2СН2О),
4.34 d (4Н, СН2Р, 2JHH = 7.0 Hz), 7.41 m (12Н, Ar-H),
7.80 m (8Н, Ar-H). 31Р NMR spectrum (CDCl3): δР
1,15-Bis(diphenylphosphoryl)-2,5,8,11,14-penta-
oxapentadecane (L4). (Diphenylphosphoryl)-
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2580
IVANOVA et al.
27.97 ppm. Found, %: С 65.10, 65.40; Н 6.30, 6.20; Р
9.90, 9.70. C34H40O7P2. Calculated, %: С 65.60; Н
6.50; Р 10.00.
Radelkis ОР-0820Р silver chloride electrode. The
electroanalytical parameters of the membrane were
determined, according to the IUPAC recommenda-
tions, at pH 5‒7 [20]. The potentiometric selectivity
coefficient were determined in mixed and in individual
solutions [21].
1,18-Bis(diphenylphosphoryl)-2,5,8,11,14,17-hexa-
oxaoctadecane (L5) was synthesized in a similar way.
1
Yield 71%, oil. H NMR spectrum (CDCl3), δ, ppm:
3.48–3.80 m (20Н, СН2СН2О), 4.38 d (4Н, СН2Р, 2JHH
=
The electrode functions were measured in aqueous
solutions of CsNO3 with concentrations of 1×10–6–
1×10–1 М. Dibutyl phthalate or o-nitrophenyl octyl
ether were used plasticizers and potassium tetrakis(4-
chlorophenyl)borate (50% with respect to the electrode-
active component) as a lipophilic additive. The detec-
tion limits of the membranes, which differed from
other only by the nature of the additive, were within
one order of magnitude.
7.0 Hz), 7.48 m (12Н, Ar-H), 7.85 m (8Н, Ar-H). 31Р
NMR spectrum (CDCl3): δР 27.94 ppm. Found, %: С
64.50, 64.60; Н 6.50, 6.70; Р 9.00, 9.80. C36H44O8P2.
Calculated, %: С 64.90; Н 6.70; Р 9.30.
1,21-Bis(diphenylphosphoryl)-2,5,8,11,14,17,20-
heptaoxaicosan (L6) was synthesized in a similar way.
1
Yield 77%, oil. H NMR spectrum (CDCl3), δ, ppm:
3.47–3.75 m (24Н, СН2СН2О), 4.35 d (4Н, СН2Р, 2JHH
=
7.5 Hz), 7.48 m (12Н, Ar-H), 7.85 m (8Н, Ar-H). 31Р
NMR spectrum (CDCl3): δР 27.93. Found, %: С 64.0;
Н 6.6; Р 8.6. C38H48O9P2. Calculated, %: С 63.9; Н
6.7; Р 8.7.
X-ray diffraction study. The XRD pattern of the
crystal of podand L0 was obtained on a Bruker APEX-
II CCD automated diffractometer (MoKα, graphite
monochromator, ω scanning) at the Center for Collec-
tive Use, Kurnakov Institute of General and Inorganic
Chemistry, Russian Academy of Sciences. The
structure was solved by a direct method. Absorption
was included applied empirically using equivalent
reflections. All hydrogen atoms were located by
Fourier difference synthesis. The nonhydrogen atoms
were refined by least squares on F2hkl with anisotropic
thermal parameters. The coordinates of H atoms were
refined independently, the isotropic thermal parameters
U(H) were set at 1.2Uequiv(С).
Conductometric measurements were performed
in THF–СНСl3 (4 : 1, v/v) by the procedure described
in [18]. Alkali metal 2,4-dinitrophenolates were used
as salts. The random error (+2s, where s is the rms
deviation) in the log K values for the complexes of the
ligands with alkali metal cations was less than +0.1 log
units. The concentrations of ionogenic impurities in the
ligands were controlled by conductometry.
Ionometric measurements. The plasticized polymer
membranes for the ion-selective electrodes containing
podands Ln (n = 0–4) as active components were
prepared as described in [19]. A solution of podand Ln
in an organic solvent (plasticizer) was added to a
solution of polyvinyl chloride in cyclohexanone. The
amounts of the starting materials were chosen so that
to obtain the desired polymer composition. The mem-
branes contained the same compositions, wt %: active
component 1–2%, polyvinyl chloride 30–33%, plas-
ticizer 65–69%, and lipophilic additive [potassium
tetrakis(4-chlorophenyl)borate] 0–2%. The plasticizers
were dibutyl phthalate or ortho-nitrophenyl octyl ether.
The content of the lipophilic additive was varied from
0 to 100% with respect to the electrode-active component.
Data collection and processing were performed
using APEX2, SAINT, and SADABS [22]. The
structure was solved using SIR-92 [23] and refined
using SHELXL-2014/7 [24]. The resulting crystal data
were deposited in the Cambridge structural database
(CCDС 1557290).
ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project nos. 15-03-
02995 and 15-03-02635) and Russian Science
Foundation (project no. 14-13-01286).
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