Modified methods to synthesize of 1,8-bis[2-(diphenylphosphoryl)phenoxy]-3,6-dioxaoctane (L). Crystal structure and vibration spectra of [LiL]ClO4·2C6H6

Article abstract of DOI:10.1134/S1070363215040234

Abstract Modified methods to synthesize, 1,8-bis[2-diphenylphosphoryl)phenoxy]-3,6-dioxaoctane phosphoryl podand (L), an effective complexing agent for the lithium cation, is reported. The possibility to use the phase-transfer catalysis and microwave irradiation is shown. The crystal structure of coordination complex [LiL]ClO₄·2C₆H₆ is determined by X-ray diffraction analysis.

Full text of DOI:10.1134/S1070363215040234

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 4, pp. 899–905. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © V.E. Baulin, I.S. Ivanova, I.N. Polyakova, E.N. Pyatova, E.S. Krivorot’ko, A.Yu. Tsivadze, 2015, published in Zhurnal Obshchei
Khimii, 2015, Vol. 85, No. 4, pp. 659–665.
Modified Methods to Synthesize
of 1,8-Bis[2-(diphenylphosphoryl)phenoxy]-3,6-dioxaoctane (L).
Crystal Structure and Vibration Spectra of [LiL]ClO ·2C H
4
6
6
a,c
a,b
b
a,b
V. E. Baulin , I. S. Ivanova , I. N. Polyakova , E. N. Pyatova ,
a
a
E. S. Krivorot’ko , and A. Yu. Tsivadze
a
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
e-mail: mager1988@gmail.com
b
Kurnakov Institute of General and Inorganic Chemistry, Moscow, Russia
c
Institute of Physiologically Active Compounds, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
Received December 20, 2014
Abstract—Modified methods to synthesize, 1,8-bis[2-diphenylphosphoryl)phenoxy]-3,6-dioxaoctane phos-
phoryl podand (L), an effective complexing agent for the lithium cation, is reported. The possibility to use the
phase-transfer catalysis and microwave irradiation is shown. The crystal structure of coordination complex
4 6 6
[LiL]ClO ·2C H is determined by X-ray diffraction analysis.
Keywords: synthesis of phosphoryl podands, IR and NMR spectroscopy, crystallography, lithium coordination,
complex formation
DOI: 10.1134/S1070363215040234
Lithium compounds are used as components of
compact energy sources [1]; metal lithium is used as a
coolant in nuclear reactors, and isotope Li is the only
industrial solutions. However, only few complexing
organic compounds for the effective binding of lithium
cation are known. As a rule, they are crown ethers with
the cavity of small radius [3] and phosphoryl podands;
among the latter the most interesting are oligoethylene
glycol diphenyl ethers ortho-substituted with diphenyl-
phosphoryl I [4] or diphenylphosphorylmethyl groups II
[5] (Scheme 1).
6
industrial source of tritium which is necessary for
thermonuclear energetics. Lithium salts are used in
psychiatry for reductive therapy of manic states and
prevention of bipolar affective (manic-depressive)
disorders [2]. Organic coordination compounds which+
are able to effectively and selectively bind the Li
cation are used for its analytical determination in
technological and biological solutions and for practical
recovery and purification of lithium salts from
+
The plot of stability constant logarithms of M L
complexes of phosphoryl podand I and II with lithium
2,4-dinitrophenolate (log KLi+) in THF–chloroform
Scheme 1.
O
n
O
P
O
P
n
O
P
O
O
P
O
O
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
I
II
n = 1−5.
8
99

9
00
BAULIN et al.
phosphoryl phenolate with triethylene glycol ditosylate
1
in boiling dioxane [6] or DMF [7]. Podand L was
prepared by the analogous reaction of sodium
diphenylphosphorylmethyl phenolate with triethylene
glycol ditosylate in dioxane [8]. Anhydrous dioxane
appeared to be the universal solvent for the synthesis
1
of ligands L and L [9]. In the exaples mentioned
above the corresponding phenolates were synthesized
in a separate step [8, 9].
In the present work, alkylation of 2-(diphenyl-
phosphoryl)phenol with ditosylates and more synthe-
tically accessible polyethylene glycol dichlorides was
investigated under various reaction conditions. In order
to optimize the method to synthesize of podand L, the
preliminary preparation of sodium 2-(diphenyl-
phosphoryl)phenolate was excluded; the latter was
obtained in situ by adding NaH (as a suspension in
vaseline oil) to a solution of 2-(diphenylphosphoryl)-
phenol in dioxane. When reactive triethylene glycol
ditosylate was used, the yield of phosphoryl podand L
reached 80% (Scheme 2, method a).
n
Fig. 1. Plot of the stability constant logarithms of complexes
+
M L of phosphoryl podands I, II with lithium 2,4-dinitro-
phenolate in THF–chloroform (4 : 1) mixtures vs the
number of ethylene glycol units n.
(
4 : 1, vol) mixtures vs the number of the ethylene
glycol units (n) obtained earlier by conductometry
[
4, 5] is given in Fig. 1.
The data of the plot show that triethylene glycol
1
derivatives of I and II (n = 3) (L and L , respectively),
exhibit the maximum ability to bind lithium cation.
The logarithms of the stability constants measured
under the same conditions for the the lithium
complexes of phosphoryl podand L (log K 7.0) and its
close structural analogue L (log K 6.7) are higher than
those for the known crown ethers (12C4, 15C5, 18C6,
B18C6, and DB18C6) [4, 5].
The possibility to prepare podand L using phase-
transfer catalysis was studied. The alkylation of 2-
(
diphenylphosphoryl)phenol with 1,8-dichloro-3,6-
dioxaoctane in a two-phase system (40% aqueous
solution of NaOH, toluene, 16 h, 100°C) in the
presence of tetrabutyl-ammonium bromide (TBAB)
afforded compound L in 51% yield; in the absence of
TBAB the yield was equal to 48%. Apparently,
compound L formed at the initial stage of synthesis is
able to act as a phase-transfer catalyst. After the
1
For the first time, phosphoryl podand L was syn-
thesized by the reaction of sodium 2-diphenyl-
Scheme 2.
O
O
O
O
OH
P
(
а)−(d)
O
O
O
P
P
Ph
Ph Ph
L
Ph
Ph
Ph
(
а): NaH, Ts(OCH
h, 48–51%; (c): NaOHsolid, dioxane, Cl(CH
CH CH Cl, 100°C, 16 h, 94%.
2
CH
2
)
3
OTs, dioxane, 100°C, 8 h, 80%; (b): 40% NaOH, toluene, Ts(OCH
2
CH
2
)
3
OTs,TBAB, 100°C, 16
2
CH O) ·
2
CH O) CH CH Cl, 100°C, 16 h, 84%; (d): Cs CO3solid, dioxane, Cl(CH
2
2
2
2
2
2
2
2
2
O
O
O
O
ONa
Ts(OCH CH ) OTs
2
2 3
O
O
O
MW, 50 W
0.6 h
P
P
P
Ph
Ph Ph
L (94%)
Ph
Ph
Ph
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 4 2015

MODIFIED METHODS TO SYNTHESIZE
901
reaction was completed, the signals of the starting 2-
diphenylphosphoryl)phenol and the target L product
(
3
1
were registered in the P NMR spectrum of the
reaction mixture. The decrease of the product yield is
probably caused by the concurrent hydrolysis of 1,8-
dichloro-3,6-dioxaoctane. The application of an-hyd-
rous two-phase systems appeared to be more effect-
tive. Thus, alkylation of 2-(diphenylphosphoryl)phenol
with 1,8-dichloro-3,6-dioxaoctane in a two-phase
system under anhydrous conditions (NaOHsolid, an-
hydrous dioxane, vigorous stirring, 12 h, 100°C)
provided podand L in 84% yield. The use of phase-
transfer system containing Cs CO
and anhydrous
2
3solid
dioxane allows one to increase the yield of the target
product to 94%.
The comparison of the convection and microwave
heating of the reaction mixture showed that in the
procedures of 2-(diphenylphosphoryl)phenol alkyla-
tion with both triethylene glycol ditosylate and 1,8-
dichloro-3,6-dioxaoctane, the yield of compound L did
not depend on the heating, but the microwave
irradiation reduced the reaction time to 0.4–0.6 h. The
microwave synthesis was performed in hermetically
closed 10 mL ampoules, as well as in 75–100 mL glass
flasks charged with significantly larger amounts of the
reagents.
+
Fig. 2. General view of complex cation [LiL] (for the
terminal phenyl rings, only the carbon atoms connected
with the phosphorus atoms are shown).
4
5
О and О oxygen atoms bound to it are half-occupied.
The other part of ClO anion is disordered around the
In order to find the cause of the high stability
constant of phosphoryl podand L with respect to the
–
4
0
(
0z axis over three closely located positions
+
Li cation, single crystals of [LiL]ClO ·2С Н were
2
6
7
8
9
3
10 11 12 13
4
14 15 16 17
4
6
6
Cl O O O O , Cl O O O O , and Cl O O O O )
grown and their structure was investigated by the X-
ray diffraction analysis.
with the occupancy ratio 0.125 : 0.050 : 0.075.
In the structure, the complex cations recur at half-
+
According to the XRD data, the [LiL] cation is
–
translations along axes 2. Anions ClO and benzene
4
located on the two-fold rotation axis (Fig. 2). All six
oxygen atoms of ligand L are included in the Li
environment. In accord with different electron
donating abilities of the phosphoryl (O ), ether (O ),
and anisole (O ) oxygen atoms, the lengths of the Li–O
bonds are significantly different [1.865(4), 2.115(5),
and 2.639(2) Å, respectively]. The polyhedron of the
Li atom has an irregular shape which can be described
as a distorted flattened tetrahedron, whose О О О
and О О О faces are centered by atoms О and О ,
molecules are located in the cavities of the loose
packing. Taking into account that in the structure the
1
–
4
Cl O anion can adopt two orientations, it is
1
3
impossible to describe the crystal topology un-
ambiguously. In the case that the anion retains its
orientation in a layer, perpendicular to the z axis, the
2
+
С–Н···О hydrogen bonds between cations [LiL] and
1
–
4
anions Cl O form chains running (depending on the
1
1а
3
anion orientation) along the x or y axis (Table 1). The
layers of x- and y-chains can alternate arbitrarily. With
1
1а 3а
2
2а
1
1
1a
respectively. The dihedral angle between the Li O O
1
–
4
the Cl O anion disordered over the structure, only
1
3
3a
and Li O O planes which characterizes the flattening
of the tetrahedron, is equal to 64.4°. The positions of
the perchlorate anion are located on two crystallo-
fragments of chains are formed. Some of the benzene
22
27
molecules (С –С ) form weak hydrogen bonds with
4
–
4
the Cl О anion.
1
graphically independent four-fold axes. The Cl atom
occupies completely a position on the axis with
The assignment of the main vibration frequencies in
coordinates 1/2 1/2 z, and the general positions of the
the IR spectrum of podand L and complex [LiL]ClO ·
4
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 4 2015

9
02
BAULIN et al.
–
1
Table 1. Geometric characteristics of theС–Н···О hydrogen
Table 2. Assignment of the main vibration frequencies (cm )
6 6
in the IR spectra of podand L and complex [LiL]ClO ·2С Н
bonds in the structure of [LiL]ClO
Symmetry
4
·2С
6
Н
6
4
Assignment
L
4 6 6
[LiL]ClO ·2С Н
d, Å
DHA,
deg
D–H···A
transformation
for atom A
ν(Р–Ph)
1438
1377
1446
1377
H···A D···A
ω(СН2)
ν(Р–Ph)
1
1
11А
4
1
365
C –H ···О
y, 1 – х, z
y, 1 – х, z
–y, х, z
2.37 3.212(7) 148
2.29 3.125(6) 147
1
326
1350
1287
12
12А
5
C –H ···О
1285
1272
1245
1179
1140
25
25А
14
16
C –H ···О
2.54 3.272
2.36 3.155
134
141
ν(PhO)
ν(Ph=O)
δ(Ph)
1256
1180
1140
1120
1095
26
26А
С –H ···О
x, –y, 0.5 + z
1
120
2
С Н (Table 2) was done based on the structural and
6 6
ν
as(COC), ν(ClO
4
)
1102
spectral investigations [10–12].
Compared to the spectrum of podand L, in the IR
δ(Ph)
(COC) + ν(CC)
δ(Ph)
ν(CO) + ν(CC) + ρ
CH
1073
1043
spectrum of [LiL]ClO ·2С Н ν(Р=О) frequency
4
6
6
ν
s
–
1
(
1180 cm ) is almost the same as in the spectrum of
podand L (1179 cm ), and the band ν(Рh–О) band is
shifted to the high-frequency region by 11 cm . A
different alteration of frequencies was observed for
complexes of lithium with podand L [12]: the ν(Р=О)
997
954
931
867
833
804
761
753
734
718
–
1
–
1
954
931
875
859
804
765
(
2
)
1
–
1
was increased by 5–7 cm and the position of the ν
Рh–О) band remained unchanged. The low-frequency
ν(РС)
δ(Ph)
(
region of the spectrum includes the vibrations that
depend on the conformation of the ethylene glycol
748
–
1
–1
738
units {1090–1120 cm [ν (СОС)], 1000–800 cm
as
721
713
695
[
ν(СО), ρ(СН ), ν(СС)]} or on the mutual orientation
2
–1
–1
of the benzene rings {800–700 cm [δ(Ph)], ~500 cm ,
δ(PhРО), δ(СРО)]} [12]. This range of the IR
spectrum of podand L contains two bands: : the intense
band near 1120 cm due to vibrations of the benzene
rings connected with the phosphorus atom and the
697
[
δ(СОС),
δ(ClO4)
619
–
1
624
δ(PhРО)
552, 526,
517
558, 533, 506, 480
–
1
medium-intensity band near 1102 cm due to the
ν (СОС) vibrations. In the IR spectrum of [LiL]ClO ·
as
4
–
1
2
C H , the intense broad band of the stretching
517 cm ), whereas in the spectrum of [LiL]ClO ·
6
6
4
–
–1
–1
vibrations of the СlО anion appears near 1095 cm .
2С Н a strong band appears near 558 cm and three
4
6
6
In the IR spectrum of [LiL]ClO ·2C H , the number of
significantly weaker bands appear at 553, 506, and 480
cm .
4
–
6
6
1
–1
bands in the range 1000–800 cm is the same as in the
spectrum of starting podand L, but the ratio of their
intensities changes.
As noted above, the stability constant of the lithium
complex with 1,8-bis[2-(diphenylphosphoryl)methyl-
1
Relatively significant distinctions between the
spectra caused by the conformational rebuilding of the
phenoxy]-3,6-dioxaoctane L was somewhat lower
than that of the complex with podand L. In the
–
1
1
podand are observed only in the region 550–500 cm ,
where the absorption bands of bending vibrations of
the terminal phosphoryl-containing groups appear. The
absorption in this spectral range is significantly
affected by the mutual position of the benzene rings at
the phosphorus atom. Thus, in the IR spectrum of free
podand L there are three strong bands (552, 526, and
structure of [LiL ]I·H O [10] the nearest tetrahedral
2
environment of the lithium atom includes two
phosphoryl and two ether oxygen atoms like in
+
complex [LiL] , however, the anisole oxygen atoms
were located at distances of 2.82 and 2.90 Å from Li,
that is, too far to form Li–O bonds. In this complex the
tetrahedron of the lithium atom is flattened to a smaller
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 4 2015

MODIFIED METHODS TO SYNTHESIZE
903
+
degree with respect to that in [LiL] : the corresponding
Table 3. Crystallographic data and refinement parameters of
the structure of [LiL]ClO
Parameter
4 6 6
·2С Н
dihedral angle is 74.1°. Note that, the structure of
LiL ]I·H O was determined with low accuracy. The
1
[
Value
2
Li–O bond lengths with both phosphoryl oxygen atoms
are 1.8(1) Å; the bonds with ether oxygens are 2.28(7)
and 2.32(7) Å. It is believed that, some weakening of
the bonds between lithium and the oxygen atoms of the
nearest environment and the loss of the bonds with the
Empirical formula
C
54
H
52ClLiO10
P
2
M
965.28
T, K
150(2)
λ, Е
α
MoK , 0.71073
1
+
distant anisole oxygen atoms in complex [LiL ] as
Space group, Z
P4cc, 4
16.4877(6)
17.9974(7)
4892.5(4)
1.310
+
compared to [LiL] results in the decrease of the
a, Å
c, Å
stability constant. Apparently, ligand L is com-
+
plementary to the Li cation to a greater degree than
1
3
ligand L . The ligand contour of L is shorter than that
V, Å
1
–3
of L by two CH -groups. The smaller size of the
2
dcalc, g cm
pseudomacrocyclic cavity ensures the coordination of
–1
µ
Mo, mm
0.203
+
Li by all six oxygen atoms. The comparison of the
+
1 +
T
min, Tmax
0.6603, 0.7461
2024
structure and stability of complexes [LiL] and [LiL ]
illustrates the principle of geometric conformity of the
spatial arrangement of the coordination centers of an
organic ligand and a cation and the principle of
cooperativity of multiple interactions [13].
F(000)
Crystal size, mm
0.32 × 0.20 × 0.20
2.471–30.764
θ range, deg
Reflections:
In the length of the coordination contour the
phosphoryl podand L corresponds to the 18C6 crown
ether. In the Cambridge database [14], the data on
several lithium complexes with 18C6 are available, but
only in two of them other ligands are not included in
metal coordination. In compound [Li(18C6)]{Nd[(1,3-
Me Si) Cp] (SO CF ) } [15], the lengths of six Li–O
collected
independent (N) [Rint
with I > 2σ(I) (N0)
47487
7599 [0.0369]
6565
]
R
R
S
1
, wR
2
2
by N
0
0.0406, 0.1150
0.0506, 0.1248
0.942
1
, wR
by N
3
2
2
3
3 2
3
Δρmax /Δρmin, e/Å
0.315/–0.425
lie within the range 2.056–2.216 Å. In [Li(18C6)]·
Li(THF)(18C6)][Fe(Pc)], where H Pc is phthalo-
[
2
cyanine [16], two independent lithium atoms form five
bonds each (2.039–2.108 and 2.057–2.475 Å) with
oxygen atoms of 18C6 molecules. The environment of
the latter atom includes additionally the oxygen atom
of a THF molecule. The comparison of the length
Li–O bond lengths demonstrates that the phosphoryl
groups are responsible for greater stability of complex
points were determined by means of a short Anschutz
thermometer.
Focused microwave synthesis was performed on a
DISCOVER type installation (CEM Corp., USA,
maximal capacity 300 W, frequency 2450 MHz)
equipped with temperature and pressure sensors.
+
+
[LiL] with respect to [Li(18C6)] .
1
,8-Bis[2-(diphenylphosphoryl)phenoxy]-3,6-di-
oxaoctane (L). a. A suspension of 1.4 g (32.7 mmol)
of NaH in vaseline oil was added to a suspension of
9.6 g (32.7 mmol) of 2-(diphenylphosphoryl)phenol
[6] in 60 mL of anhydrous dioxane. The mixture was
stirred for 0.5 h at 100°С. Then a solution 7.5 g
(16.4 mmol) of triethylene glycol ditosylate in 100 mL
of anhydrous dioxane was added, and the mixture was
refluxed for 8 h. After removing the solvent 45 mL of
dilute HCl (1 : 1) was added to the residue. The reac-
EXPERIMENTAL
NMR spectra were registered on a Bruker-СPX-200
and a Bruker-DXР-200 (200 МHz) spectrometers with
1
31
tetramethylsilane ( H) or 85% Н РО ( P) as
3
4
references. IR spectra were recorded on a Bruker
Vertex 70 instrument in the range 4000–400 cm
suspensions in vaseline oil). TLC analysis was
–
1
(
performed using Silufol plates, detecting with iodine
vapor. Column chromatography was done with the use
of silica gel of the L grade (100–160 μm), eluent
СHCl or a 20 : 1СHCl –i-PrOH mixture. Melting
tion product was extracted with CHCl (3 × 35 mL).
3
The extract was washed consecutively with 10%
solution of KOH (2 × 30 mL), dilute HCl (2 × 30 mL),
3
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 4 2015

9
04
BAULIN et al.
and water (3 × 35 mL) and evaporated in a vacuum.
The residue was purified by chromatography. Yield
The residue was purified by chromatography. Yield
3.3 g (94%).
9
.3 g (80%), mp 201–202°С (benzene–hexane, 1 : 1).
e. A mixture of 3.2 g (10.1 mmol) of sodium 2-
diphenylphosphoryl) phenolate [10] and 0.93 g
5.0 mmol) of 1,8-dichloro-3,6-dioxaoctane in 7 mL of
anhydrous dioxane was placed into the laboratory
system with focused microwave heating in herme-
tically closed glass vial. The mixture was heated at
1
Н NMR spectrum (СDCl ), δ, ppm: 3.20 m (4Н,
СН СН О), 3.30 s (4Н, СН СН О), 3.90 m (4Н,
СН СН О), 6.90 m (2Н, ArH), 7.08 m (2Н, ArH), 7.45
m (14Н, ArH), 7.90 m (10Н, ArH). Р NMR spectrum
3
(
(
2
2
2
2
2
2
3
1
(СDCl ): δ 26.92 ppm. Found, %: С 72.20, 72.53; Н
3 Р
5
7
.73, 5.79; Р 8.51, 8.43. C H O P . Calculated, %: С
42 40 6 2
1.96; Н 6.04; 8.63.
1
50°C (50 W) for 0.6 h. After cooling, the reaction
mixture was poured into 50 mL of water, acidified
with conc. HCl to pH 1, and extracted with СHCl3
b. A mixture of 3.0 g (10.0 mmol) of 2-(di-
(
(
3 × 30 mL). The extract was washed with dilute HCl
2 × 30 mL), and water (3 × 35 mL), and evaporated in
phenylphosphoryl)phenol, 0.02 g (0.06 mmol) of
tetrabutylammonium bromide, 1.0 g (5.0 mmol) of 1,8-
dichloro-3,6-dioxaoctane, 20 mL of toluene, and
0 mL of 40% solution of NaOH was stirred for 16 h
at 100°C. Then the organic layer was separated,
consecutively washed with 10% solution of NaOH
a vacuum. To the residue 20 mL of diethyl ether was
added, and the precipitate was filtered off. The filtrate
was chromatographed. Yield 3.2 g (91%).
1
Complex [LiL]ClO ·2С Н . Preliminarity filtered
4
6
6
(
2
5
3 × 10 mL), dilute HCl (2 × 10 mL), and water (3 ×
0 mL), and evaporated in a vacuum. To the residue
0 mL of water was added, and the mixture was
solutions of lithium perchlorate in methanol and
podand L in acetonitrile (М : L = 2 : 1) were mixed at
room temperature and left standing in air approxi-
mately for 7 days. Crystalline precipitate was filtered
off, washed with ethanol, and recrystallized from a
extracted with CHCl (3 × 30 mL). The extract was
3
washed with 10% KOH solution (2 × 30 mL), dilute
HCl (2 × 30 mL), and water (3 × 35 mL), and
evaporated in a vacuum. The residue was purified by
column chromatography. Yield 1.8 g (51%).
CHCl –С Н (1 : 1) mixture.
3 6 6
Single-crystal X-ray diffraction study of [LiL]
ClO · 2С Н was done at the Centre of Shared
4
6
6
Equipment of the Kurnakov Institute of General and
Inorganic Chemistry on a Bruker SMART APEX2
automated diffractometer. The structure was solved by
the direct method followed by the calculation of the
c. A mixture of 3.0 g (10.0 mmol) of 2-(diphenyl-
phosphoryl)phenol, 0.4 g (10 mmol) of crushed NaOH,
and 25 mL of anhydrous dioxane was stirred for 0.5 h
at 100°C. Then 0.93 g (5.0 mmol) of 1,8-dichloro-3,6-
dioxaoctane was added, and the mixture was stirred for
1
4
5
difference Fourier syntheses. The Cl , О , and О
atoms of the more regular perchlorate anion were
refined in anisotropic approximation under geometric
8
h for 100°C followed by evaporation in a vacuum.
To the obtained residue 50 mL of CHCl was added,
3
2
3
4
restraints. The Cl , Cl , and Cl atoms of the
perchlorate anion disordered over three positions were
refined isotropically under the restraint of equal
thermal parameters. Their bonds with the O atoms
were accepted to be 1.41 Å. Because of the low site
and the resulting solution was consecutively washed
with 30% NaOH solution (3 × 10 mL), dilute HCl
(
15 mL), and water (3 × 20 mL), and evaporated in a
vacuum. To the residue 20 ml of diethyl ether was
added, and the precipitate was filtered off. Yield 2.9 g
6
17
occupancy, atoms О –О were refined within the
riding model with thermal parameters exceeding the
Uiso of the Cl atoms by a factor of 1.5. The non-
(
84%).
d. A mixture of 3.0 g (10.0 mmol) of 2-(diphenyl-
phosphoryl)phenol, 3.3 g (10 mmol) of crushed
+
hydrogen atoms of the complex cation [LiL] and
benzene molecule were refined anisotropically. The
positions of the hydrogen atoms were calculated and
Сs CO , 0.93 g (5.0 mmol) of 1,8-dichloro-3,6-
2
3
dioxaoctane, and 30 mL of anhydrous dioxane was
stirred for 8 h at 100°C. Then the mixture was poured
into 70 mL of water, carefully acidified with conc. HCl
refined within the riding model with Uiso = 1.2U of
eq
the corresponding C atom.
to pH 1, and extracted with СHCl (3 × 25 mL). The
extract was consecutively washed with dilute HCl
Reflections were collected and prosseced by the
APEX2, SAINT, and SADABS software [16]. The
structure was solved and refined by means of SIR-92
[17] and SHELXL-2013 [18] packages, respectively.
The main crystallo-graphic data , parameters of data
3
(
2 × 20 mL), and water (3 × 20 mL), and evaporated in
a vacuum. To the residue 25 mL of anhydrous diethyl
ether was added and the precipitate was filtered off.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 4 2015

MODIFIED METHODS TO SYNTHESIZE
905
collection, and characteristics of structure refinement
are given in Table 3.
Chim. Acta, 1985, vol. 100, no. 2, p. 235. DOI: 10.1016/
S0020-1693(00)85291-3.
8
9
. Evreinov, V.I., Vostroknutova, Z.N., Baulin, V.E., Bon-
darenko, N.A., Syundyukova, V.Kh., and Tsvetkov, E.N.,
Zh. Obshch. Khim., 1989, vol. 59, no. 1, p. 67.
. Baulin, V.E., Cand. Sci. (Chem.) Dissertation,
Chernogolovka, 1988.
The crystallographic data have been deposited at the
Cambridge Structural Database (CCDС no. 1026871).
ACKNOWLEDGMENTS
1
1
0. Minacheva, L.Kh., Baulin, V.E., and Sakharova, V.G.,
Koord. Khim., 1995, vol. 21, no. 3, p. 236.
1. Minacheva, L.Kh., Ivanova, I.S., Tsivadze, A.Yu., and
Sergienko, V.S., Dokl. Chem., 2001, vol. 377, no. 1,
p. 65.
The work was financially supported by the Russian
Science Foundation (project no. 14-13-01286).
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