Synthesis, vibrational spectra, and crystal and molecular structure of 1,5-bis[2-(dihydroxyphosphinyl)phenoxy]-3-oxapentane dihydrate [(HO) 2(O)P(C6H4)(OCH2CH2) 2O(C6H4</sub

Article abstract of DOI:10.1134/S0036023611080043

A modified method of synthesis of a phosphoryl podand, 1,5-bis[2- (dihydroxyphosphinyl)phenoxy]-3-oxapentane (L), has been developed. The IR spectra of this podand and its dehydrate (L [L ? H₂O] ? H₂O (I) have been studied, the struc

Full text of DOI:10.1134/S0036023611080043

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2011, Vol. 56, No. 8, pp. 1222–1231. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.E. Baulin, L.Kh. Minacheva, I.S. Ivanova, E.N. Pyatova, A.V. Churakov, D.V. Baulin, V.S. Sergienko, A.Yu. Tsivadze, 2011, published in Zhurnal
Neorganicheskoi Khimii, 2011, Vol. 56, No. 8, pp. 1293–1302.
COORDINATION
COMPOUNDS
Synthesis, Vibrational Spectra, and Crystal and Molecular
Structure of 1,5ꢀBis[2ꢀ(dihydroxyphosphinyl)phenoxy]ꢀ3ꢀ
oxapentane Dihydrate
[(HO)2(O)P(C6H4)(OCH2CH2)2O(C6H4)P(O)(OH)2(H2O)] · H2O
V. E. Baulina, L. Kh. Minachevab, I. S. Ivanovab, E. N. Pyatovab, A. V. Churakovb,
D. V. Baulinc, V. S. Sergienkob, and A. Yu. Tsivadzec
a Institute of Physiologically Active Substances, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
b Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
c Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
Received March 29, 2010
Abstract—A modified method of synthesis of a phosphoryl podand, 1,5ꢀbis[2ꢀ(dihydroxyphosphinyl)pheꢀ
noxy]ꢀ3ꢀoxapentane (L), has been developed. The IR spectra of this podand and its dehydrate (L [L . H2O] .
H2O (
orthorhombic,
Pna21, = 0.0512 for 3016 reflections with
I
)
have been studied, the structure of
= 9.4006(19) Å, = 25.494(5) Å,
> 2
I
has been determined by Xꢀray crystallography. The crystals are
= 8.4264(17) = 4, space group
V = 2019.5(7) Å3,
. Compound is a host–guest molecular complex. Phosꢀ
a
b
c
)
Å,
Z
R
I
σ
(I
I
phoryl podand L acts as a host molecule, and one of the water molecules (H2O(11)) is a guest. This molecule
forms one donor and one acceptor intramolecular hydrogen bond with hydroxyl groups of two phosphoryl
groups (O(8)H(4) and O(3)H(2)) and combines them into an 18ꢀmembered macrocyclic ring, acting as a
kind of “lock.” The H2O(11) molecule forms a second donor intramolecular hydrogen bond with the O(5)
ether atom. The neutral molecular complexes are linked by hydrogen bonds directly and through the second
water molecule (H2O(10)) into chains running along the
c
axis.
DOI: 10.1134/S0036023611080043
Systematic conductometric [1] and calorimetric
The structures of molecular phosphoryl podands
[2, 3] studies of podands (acyclic crown ether anaꢀ [11, 12] and their lithium [13], sodium [14], zinc and
logues) with phosphorylꢀcontaining terminal groups cadmium [15], and barium and mercury complexes
have shown that these compounds are efficient recepꢀ [16] have been determined by IR spectroscopy and
tors for binding alkali metal cations. According to liqꢀ Xꢀray crystallography. In addition, pentaꢀ and hexavaꢀ
uid extraction data, phosphoryl podands can be comꢀ lent actinide complexes with phosphorylꢀcontaining
ponents of extraction systems for isolation and conꢀ podands derived from triethylene glycol have been
centration of platinum from hydrochloric acid synthesized and structurally characterized [17]. Availꢀ
solutions [4], scandium from chloride solutions [5], able data have demonstrated that the complexing abilꢀ
and uranium and thorium from both chloride [6] and ity of phosphorylꢀcontaining podands with respect to
nitric acid solutions [7]. The can be used for extraction alkali metal cations is mainly determined by the strucꢀ
of gold traces [8] and lanthanide nitrates [9]. Phosꢀ ture of the terminal moiety, which is consistent with
phoryl podands are as good as crown ethers for binding the general terminal group concept [18]. Therefore,
of amine picrates. In addition, they can recognize priꢀ one of the methods of control of the efficiency and
mary amines in the presence of secondary and ternary selectivity of phosphorylꢀcontaining podands in difꢀ
amines. In these reactions, 3ꢀoxapentane derivatives ferent reactions is to change the structure of these terꢀ
with three oxygen atoms in the polyether chain and minal moieties. However, all aboveꢀmentioned studies
rather conformationally rigid terminal groups—resiꢀ have dealt with phosphine oxide derivatives, neutral
dues of
оꢀphosphorylꢀcontaining phenols—exhibit phosphoryl podands, whereas acidꢀtype podands—
the best efficiency and selectivity. These molecules phosphonic acid derivatives—have been almost
bind amino groups in the optimal way through two entirely ignored. Only some pyrocatechol derivatives
outer ether oxygen atoms and two most basic phosꢀ [19] and 1,5ꢀbis(dihydroxyphosphinyl)phenoxyꢀ3ꢀ
phoryl oxygen atoms [10].
oxapentane (L) [20] have been studied.
1222

SYNTHESIS, VIBRATIONAL SPECTRA
1223
For the latter, the dissociation and stability conꢀ
stants of complexes with Ca2+, Mg2+, Cd2+, Ni2+,
Cu2+ and Zn2+ cations [21]. It has been recently
shown that 1,5ꢀbis(hydroxyethoxyphosphinyl)pheꢀ
noxyꢀ3ꢀoxapentane (L1) and its 4,4'ꢀdiꢀtertꢀbutyl
analogue (L2)
O
P
O
O
P
O
O
HO OHHO OH
L
O
P
O
O
P
O
P
O
O
P
O
O
O
O
EtO OHHO OEt
EtO OHHO OEt
L1
L2
are promising compounds for selective extraction of
thorium(VI) in the presence of uranium(VI) and lanꢀ
thanum(III) from nitric acid media and are of interest
as component components of porous sorbents used for
concentration, separation, and isolation of products of
spent nuclear fuel treatment [22].
EXPERIMENTAL
Synthesis of compounds L and C (Scheme 1) was
carried out with the use of butyllithium in a dry argon
atmosphere. For column chromatography, silica gel L
(100–160
μ
m) and Chloroform as an eluent were
In the present paper, we describe a modified
method of synthesis of compound L and preparation
used. Melting points were measured on a Boetius
PHMK 05 microscope plate (uncorrected) and therꢀ
mogravimetrically. Commercially available solvents
were additionally purified by known methods.
of its dihydrate [L
⋅
H2O] H2O (I) and report their IR
⋅
and NMR spectra and results of Xꢀray crystallographic
study.
O
O
EtO P OEt
O
EtO P OEt
O
OLi
Li
1. LiN(iꢀPr)
T
⋅ THF
2
O
P
T
= 20°C
= –78°C
OEt
EtO
A
B
1.
TsO
2. HCl
O
OTs
1. Me SiCl,NaBr,
3
O
O
O
P
O
O
P
O
P
CH CN, 80°C
3
2. H O
2
O
O
O
O
P
OEt
HO OHHO OH
EtO
EtO
OEt
L
C
Yield 90%
Yield 65%
Scheme 1.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

1224
BAULIN et al.
1,5ꢀBis[2ꢀdiethoxyphosphinyl)phenoxy]ꢀ3ꢀoxapenꢀ
tane (C). To a solution containing 1.11 g (0.011 mol) diisoꢀ Instruments Qꢀ500 derivatograph in the temperature
propylamine in 25 mL of dry tetrahydrofuran (THF) range 20–500 in platinum crucibles at a heating rate
cooled to –78 (internal thermometer), 9.17 mL of 5 K/min.
(0.011 mol) of 1.2 N
ane was added dropwise. The reaction mixture was
stirred for 30 min at –78 10 , then a solution conꢀ
Thermogravimetric studies were carried out on a TA
°C
°С
n
ꢀbutyllithium solution in hexꢀ
IR absorption spectra were recorded as mineral oil
mulls on a Bruker Vertex 70 spectrophotometer in the
range 400–4000 cm–1.
°С
taining 2.30 g (0.01 mol) of phenyl diethyl phosphate
(A) in 10 mL of dry THF was added, and the resulting
mixture was stirred for 1 h at –78 10
the solution was heated to 20 in 1 h and stirred for
another 1 h. Then, 2.07 g (0.005 mol) of diethylene
glycol ditosylate was added, the solution was heated
and refluxed under stirring for 8 h, and the solvent was
vacuum distilled off. Then, 50 mL of water was added
to the residue, and the mixture was extracted with
3 × 30 mL). The extract was washed with
water ( × × 25 mL) and dried by sodium sulfate, and
chloroform was removed under vacuum. The residue
was applied to a column packed with silica gel L (100–
160 m). Chloroform and chloroform–isopropanol
(20 : 1) were used for elution. The yield of compound
C (viscous oil) was 1.72 g (65%).
For C24H36O9P2 anal. calcd. (%): C, 54.34; H,
6.84; P, 11.68.
Xꢀray crystallography. Crystals of
by recrystallization for a 50% ethanol. Crystals of
C16H24O11P2 (FW = 454.29) are orthorhombic,
9.4006(19) Å, = 25.494(5) Å, = 8.4264(17) Å,
= 2019.5(7) Å3, ρcalc = 1.494 g/cm3,
Мо ) =
0.273 mm–1
(000) = 952, = 4, space group Рna21
Experimental reflection intensities (4933 reflecꢀ
tions, 3016 of them were unique, (int) 0.0565) were
collected at 150(2) K from a colorless crystal 0.25
0.20 0.10 mm in size on a Bruker SMART APEX II
automated diffractometer (Мо 0.71073 Å, graphiꢀ
scan).Corrections for absorpꢀ
I were obtained
°С. After that,
a
=
°С
b
c
V
μ
(
К
α
,
F
Z
.
R
×
chloroform (
×
3
К
,
λ
α
te monochromator,
ψ
tion were applied on the basis of measured intensities
of equivalent reflections [23]. Reflections were colꢀ
μ
lected in the index ranges –9
9 (2.55°≤ θ ≤ 24.96 ; coverage on
The structure was solved by direct methods
≤
h
≤
10, –30
≤
k
≤
21,
⎯
7
≤
l
≤
°
θ
= 96.5%).
(SHELXSꢀ97 [24]) and refined by leastꢀsquares calꢀ
culations on F2 (SHELXLꢀ97 [25]) in the fullꢀmatrix
Found (%): C, 54.22; H, 6.69; P, 11.28.
1H NMR
(
δ,
ppm, С6D6): 1.13 t, 12H, anisotropic approximation for all nonꢀhydrogen
4СН3СН2О), 3.80–3.90 (m, 8Н, 2ОСН2СН2), 4.13 atoms. The positions of the hydrogen atoms of both
(m, 8H, 4СН3СН2О), 6.73–7.21 (m, 6H, Ar–H).
31Р NMR (
, ppm, С6D6): 17.03.
water molecules and two of the four hydroxyl groups at
the phosphorus atoms were determined experimenꢀ
tally from difference electron density maps and refined
isotropically. The other hydrogen atoms were introꢀ
duced in geometrically calculated positions and
refined as riding on their bonded carbon or oxygen
atoms with isotropic temperature factors UH equal to
δ
1,5ꢀBis[2ꢀ(dihydroxyphosphinyl)phenoxy]ꢀ3ꢀoxapꢀ
entane (L). To a solution of 1.72 g (0.0032 mol) of comꢀ
pound C in 25 mL of dry acetonitrile, 2.00 g (0.019 mol)
of freshly calcined sodium bromide and 2.17 g (0.020
mol) of trimethylchlorosilane were added. The resultꢀ
ing suspension was refluxed for 6 h, and the solvent was
removed under vacuum. Then 30 mL of distilled water
was added to the residue, and the mixture was allowed
to stand at room temperature for 20 h. The precipitate
was filtered off, washed on a filter with 50 mL of disꢀ
1.2
U
C or 1.5
The final residuals were
and GOOF = 0.964 for 2092 reflections with
= 0.0846 and wR = 0.0934 for all unique reflecꢀ
UO.
R
1 = 0.0512, wR
2
= 0.0835,
> 2 );
I
σ
(I
R1
2
tions. The total number of refined parameters was 287,
the extinction coefficient was 0.0013(4), and the absoꢀ
lute structure parameter was 0.14(14). The Δρmax and
Δρmin were 0.261 and –0.235 е А–3, respectively.
tilled water, and vacuum dried (4 h, 80
The yield of L was 1.34 g (90%), mp 208–213
°
С, 10 mmHg).
°
С. The
melting point of the analytical sample obtained by
recrystallization from an alcohol–water (1 : 1) mixture
The atomic coordinates and thermal parameters
for structure
lengths and angles are listed in Table 2.
The structural data for were deposited with the
I are summarized in Table 1, and bond
and vacuum dried at 80
213 [17]).
For C16H20O9P2 anal. calcd. (%): C, 45.94; H, 4.82;
P, 14.81.
Found (%): C, 45.84; H, 4.58; P, 14.58.
1H NMR (
, ppm, DMSO): 3.92 (m, 4H,
°С
was 212–213°С (lit.: 212–
°С
I
Cambridge Crystallographic Data Centre (CCDC
no. 768236).
δ
OCH2CH2), 4.18 (m, 4H, OCH2CH2) 7.04–7.68 (m,
8H, Ar–H), 5.96 (s, 4H, 4P–OH).
RESULTS AND DISCUSSION
An approach to the synthesis of phosphoryl
podands is based on the Williamson reaction, the reacꢀ
31P NMR (
, ppm): 12.30.
δ
1H and 31P NMR spectra were recorded on a tion of orthoꢀphosphorylated phenol phenolates with
Bruker CXPꢀ200 spectrometer. The 1H and 31P NMR dihalide and ditosyl derivatives of ethylene glycols.
chemical shifts were referenced to TMS (internal) and Previously, L was obtained from oꢀdiethoxyphosphiꢀ
85% Н3РО4 (external), respectively.
nylphenol, which was converted into a sodium derivaꢀ
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

SYNTHESIS, VIBRATIONAL SPECTRA
1225
Table 1. Atomic coordinates (
×
104, for H atoms,
,
×
103) and
I*
tive by the reaction with sodium hydrate [20]. In the
thermal parameters Ueq/Uiso
(
Å2
×
103) in structure
present work, we developed a scheme of synthesis of
1,5ꢀbis(dihydroxyphosphinyl)phenoxyꢀ3ꢀoxapentane
(L) bypassing the special stage of obtaining phenolate
(Scheme 1). The initial compound was phenyl diethyl
phosphate (A), which reacts with lithium diisopropyꢀ
Atom
P(1)
x
y
z
Ueq/Uiso
1690(1)
767(1)
6185(1)
3879(1)
5996(1)
6476(1)
5725(2)
8223(2) 28(1)
8284(2) 26(1)
9422(4) 35(1)
6838(4) 37(1)
7471(4) 33(1)
P(2)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
lamide to give the lithium salt of oꢀdiethoxyphosphiꢀ
nylphenol (B) [26]. The resulting salt was immediately
used without isolation in the reaction with diethylene
glycol ditosylate, which yields the intermediate comꢀ
pound tetraethyl diphosphonate (C).
658(4)
992(3)
2533(4)
3502(3)
3616(4)
2856(3)
–110(3)
1639(4)
–137(3)
10010(5)
3472(4)
2912(5)
3116(5)
4128(6)
4981(6)
4809(5)
3783(5)
4122(6)
3348(5)
3035(6)
3557(6)
2973(5)
3934(5)
3964(6)
3029(6)
2090(5)
2020(5)
73
It is worth noting that the use of the less “alkaline”
lithium ion rather than the sodium cation and the
6031(1) 10965(4) 38(1)
5002(1) 12334(4) 36(1)
3997(1) 10882(4) 35(1)
replacement of dioxane with a boiling point of 100
°
С
by lowꢀboiling THF (64 ) have almost no effect on
°
С
the reaction yield. The resulting ester (C), after purifiꢀ
cation by column chromatography, reacted with trimꢀ
4087(1)
4319(1)
3591(1)
4916(2)
5001(2)
6645(2)
7130(2)
7479(2)
9609(4) 31(1)
7488(4) 31(1)
7047(4) 35(1)
5930(5) 43(1)
9128(5) 33(1)
9014(6) 28(1)
8298(7) 33(1)
8860(7) 41(2)
ethylbromosilane (prepared in situ in the trimethylꢀ O(8)
chlorsilane–sodium bromide–acetonitrile system) to
give the corresponding tetrasilyl ether, which was
hydrolyzed under mild conditions into tetrabasic
diphospjonic acid L. The lack of separate stages of isoꢀ
lation of оꢀdiethoxyphosphinylphenol and preparaꢀ
tion of its phenolate as described in [20] considerably
reduces the reaction time, simplifies the synthesis of
L, and makes the product cheaper.
O(9)
O(10)
O(11)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
Recrystallization of L from an ethanol–water (1 : 1)
7330(2) 10101(7) 41(2)
6852(2) 10846(7) 37(1)
6509(2) 10311(6) 31(1)
5919(2) 12483(6) 41(2)
5470(2) 13193(8) 39(1)
4556(2) 13116(8) 42(1)
4071(2) 12379(6) 45(2)
3516(2) 10182(6) 29(1)
3136(2) 10667(7) 38(1)
mixture leads to the formation of its [LН2О]
with a melting point of 209
Compound is a neutral host–guest molecular
⋅
H2O (I)
°С.
I
complex [27], where L acts as a host and one of the
water molecules is a guest (Fig. 1). The second water
molecule of crystallization is involved only in hydrogen
bonds between [LН2О] molecular complexes (Fig. 2).
In complex I, the guest molecule Н2О(11) forms
one donor and one acceptor intramolecular hydrogen
bond with the O(8)H(4) and O(3)H(2) hydroxyl
(bonds 7 and 2, Table 3) and links two ends of the
podand chain to form three H rings—an 18ꢀmemꢀ
bered macrocyclic ring and two 11ꢀmembered C(13)
2656(2)
2534(2)
2917(2)
3410(2)
626
9955(7) 40(2)
8758(6) 39(2)
8226(8) 33(1)
8949(6) 25(1)
(O(11)H(2)O(3)P(1)C(1)C(6)O(4)C(7)C(8)O(5)H(8)
and O(11)H(7)O(8)P(2)C(16)C(11)O(6)C(10)C(9)
O(5)H(8) rings—acting as a kind of “lock.” The
H2O(11) molecule forms a second donor intramolecꢀ
ular hydrogen bond with the O(5) ether atom (bond 8,
Table 3).
C(14)
C(15)
C(16)
H(1)
616
55
H(2)
269(5)
546(2)
460(3)
526(3)
466(3)
470(3)
502(2)
377
815(7) 46(16)
683(8) 100(30)
539(9) 110(30)
522(8) 90(30)
870(8) 110(30)
1011(7) 60(20)
Podand L in
I has a Cꢀlike conformation with an
approximate plane passing through the central ether
m
H(4)
H(5)
H(6)
H(7)
114(8)
oxygen atom. Correspondingly, the two gauche О–
СН2–СН2–О moieties of the diethylene glycol chain
have opposite signs of torsion angles. The podand has
gauche conformation with respect to the C–C bonds
and a trans conformation with respect to C–O (Table 4).
1006(8)
973(7)
a
275(8)
Thus, the ethylene glycol chain is composed of two H(8)
357(6)
units with the same TGT conformation (beginning
with the O(4) atom). Both phosphoryl oxygen atoms
H(3)
–22
625
52
* The coordinates of the hydrogen atoms involved in hydrogen
bonds are given.
face point into the podand molecule, which favors
their possible coordination to metal atoms.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

1226
BAULIN et al.
) in structure I
Table 2. Selected bond lengths (
d
) and bond angles (
ω
Bond
d
, Å
Bond
d, Å
P(1)–O(1)
P(1)–O(2)
P(1)–O(3)
P(1)–C(1)
P(2)–O(7)
P(2)–O(9)
P(2)–O(8)
P(2)–C(16)
O(4)–C(6)
O(4)–C(7)
O(5)–C(8)
O(5)–C(9)
O(6)–C(11)
O(6)–C(10)
Angle
1.481(3)
1.531(3)
1.549(4)
1.772(5)
1.486(4)
1.532(3)
1.543(3)
1.770(5)
1.364(6)
1.435(6)
1.419(6)
1.423(6)
1.366(5)
1.435(6)
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
C(7)–C(8)
C(9)–C(10)
C(11)–C(12)
C(11)–C(16)
C(12)–C(13)
C(13)–C(14)
C(14)–C(15)
C(15)–C(16)
Angle
1.389(7)
1.409(7)
1.385(7)
1.371(8)
1.381(7)
1.376(6)
1.482(7)
1.467(7)
1.387(7)
1.398(6)
1.364(7)
1.374(7)
1.390(7)
1.399(7)
ω
, deg
ω
, deg
O(1)P(1)O(2)
O(1)P(1)O(3)
O(2)P(1)O(3)
O(1)P(1)C(1)
O(2)P(1)C(1)
O(3)P(1)C(1)
O(7)P(2)O(9)
O(7)P(2)O(8)
O(9)P(2)O(8)
O(7)P(2)C(16)
O(9)P(2)C(16)
O(8)P(2)C(16)
P(1)O(3)H(2)
C(6)O(4)C(7)
C(8)O(5)C(9)
C(11)O(6)C(10)
P(2)O(8)H(4)
P(2)O(9)H(9C)
H(5)O(10)H(6)
H(7)O(11)H(8)
C(2)C(1)C(6)
C(2)C(1)P(1)
113.4(2)
111.7(2)
105.9(2)
112.5(2)
104.1(2)
108.8(2)
112.03(18)
111.18(19)
110.40(19)
111.9(2)
105.1(2)
105.9(2)
114(3)
C(6)C(1)P(1)
120.4(4)
121.2(6)
119.0(5)
121.5(5)
119.6(5)
124.8(5)
114.8(4)
120.4(5)
108.3(4)
110.9(5)
110.3(5)
109.3(5)
123.5(5)
116.3(4)
120.2(5)
120.7(5)
120.8(5)
119.0(5)
121.4(6)
117.8(5)
120.0(4)
122.2(4)
C(3)C(2)C(1)
C(4)C(3)C(2)
C(3)C(4)C(5)
C(6)C(5)C(4)
O(4)C(6)C(5)
O(4)C(6)C(1)
C(5)C(6)C(1)
O(4)C(7)C(8)
O(5)C(8)C(7)
O(5)C(9)C(10)
O(6)C(10)C(9)
O(6)C(11)C(12)
O(6)C(11)C(16)
C(12)C(11)C(16)
C(13)C(12)C(11)
C(12)C(13)C(14)
C(13)C(14)C(15)
C(14)C(15)C(16)
C(15)C(16)C(11)
C(15)C(16)P(2)
C(11)C(16)P(2)
117.4(4)
111.6(4)
117.5(4)
120(4)
109.5
110(6)
117(5)
118.3(5)
121.1(4)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

SYNTHESIS, VIBRATIONAL SPECTRA
1227
C(9)
C(8)
C(7)
O(5)
C(10)
O(6)
O(4)
C(12)
C(5)
C(11)
C(6)
C(13)
C(4)
H(8)
O(7)
O(1)
H(7)
O(11)
H(2)
O(3)
C(16)
P(2)
C(14)
C(15)
C(3)
C(1)
P(1)
C(2)
O(8)
O(9)
O(2)
H(4)
H(1)
H(3)
Fig. 1. Structure of the podand in structure I.
O(1)
O(9)
O(10)
O(7)
O(2)
O(8)
Fig. 2. A fragment of the chain of structure I along the c axis.
No information is currently available on the strucꢀ bonds and occupies the position analogous to the
tures of podands or their complexes with terminal water molecule position in
. The third donor bond of
the ammonium cation also involves the ether oxygen
atom of podand II. As in , both phosphoryl oxygen
atoms point into the podand molecule, which has a Cꢀ
shaped conformation, pseudosymmetry plane , and
I
hydroxyl substituents in the phosphoryl groups. Only
compounds with phenyl substituents at the phosphorus
atoms have been studied. For example, the host–guest
complex of 1,5ꢀbis(diphenylphosphinyl)phenoxyꢀ3ꢀ
I
m
opposite signs of the О–СН2–СН2–О angles in the
diethylene glycol chain.
oxapentane (II) with DLꢀphenylglycine ethyl ester trifluꢀ
.
oromethanesulfonate II H3N+CH(Ph)C(O)OEt
⋅
−) (III) [28] has been studied [28]. The podands
F3CSO3
The geometric parameters of phosphoryl podand L
are close to common values. Both phosphorus atoms
have a distorted tetrahedral coordination. The P=O
in and III differ only in the substituents at the phosꢀ
phorus atoms (two OH groups in and two Ph rings in
III). In III, the ammonium cation of DLꢀphenylglyꢀ
I
I
and P–C bond lengths are equal to each other with
3σ
cine ethyl ester (guest) binds the phosphoryl groups of (av. 1.483(4) and 1.771(5) Å, respectively). Their valꢀ
the podand through two N–H···О donor hydrogen ues are consistent with the corresponding distances for
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

1228
BAULIN et al.
Table 3. Geometries of hydrogen bonds in structure
I
Distance, Å
No. D–H⋅⋅⋅A contact
DHA angle, deg
Atom A coordinates
–x –y + 1, z – 1/2
D–H
H···A
D···A
1
2
3
4
5
6
7
8
O(2)–H(1)···O(7)
O(3)–H(2)···O(11)
O(8)–H(4)···O(10)
O(9)–H(3)···O(1)
O(10)–H(5)···O(7)
O(10)–H(6)···O(1)
O(11)–H(7)···O(8)
O(11)–H(8)···O(5)
0.82
1.69
2.506(4)
171
,
0.91(5)
1.02(8)
0.82
1.60(6)
1.54(8)
1.70
2.477(5)
2.527(5)
2.498(4)
2.775(5)
2.724(6)
2.811(5)
2.704(5)
162(5)
164(7)
164
x, y, z
x – 1, –y + 1,
z
–x –y + 1, z – 1/2
,
0.98(7)
0.92(7)
1.08(8)
0.84(6)
1.80(7)
1.84(7)
1.76(8)
1.87(6)
174(7)
159(6)
163(5)
173(6)
–x + 1,–y + 1, z – 1/2
–x + 1, –y + 1, z – 1/2
x
x
,
,
y
,
,
z
z
y
the Ph3P=O modifications: 1.483(2)–1.494(2) and along the
с
axis. Figure 2 shows a fragment of this
1.787(2)–1.808(2) Å, respectively [29–31]. The P– chain, and Fig. 3 shows the projection of the structure
OH bonds in L vary within the range 1.531(3)– along the
b axis.
1.549(4) Å (av. 1.539(3) Å). In the РО3С tetrahedra,
In the course of our study, we recorded the IR specꢀ
tra of L and compound obtained by recrystallization
of L from 50% ethanol. It turned out that, although the
spectral pattern is retained and positions of some
bands remain unaltered, there are rather significant
differences caused by symmetry features of molecules
the OPC and OPO angles are within 104.1(2)
112.5(2) and 105.1(2) –113.4(2) , respectively.
°
–
I
°
°
°
The average bond lengths and bond angles of the
ОСН2СН2О moieties in the L molecule have comꢀ
mon values: O–C(sp3) 1.428(5), O–C(sp2) 1.365(5),
C(sp3)–C(sp3
117.4(4)
C(sp3) 109.7(5)
)
1.475(7)
, C(sp3)–О–C(sp3) 111.6(4)
. The С(sp3)–С(sp3
bond lengths in I
Å
,
C(sp2)–О–C(sp3
, О–C(sp3)–
)
)
of L and I. To interpret the IR spectra, we used the
°
°
results of our previous works, where a comprehensive
assignment of vibrational spectra and Xꢀray crystalloꢀ
graphic data were reported for some neutral phosphorylꢀ
containing podands and their complexes [12–16, 33].
°
are considerably smaller than the common value
(1.530(15) Å [32]), which is typical of podands and
crown ethers [27]. The phenyl rings in the podand are
The C–H and C–C stretching and bending vibraꢀ
tions of the benzene rings and methylene groups are in
their typical frequency ranges, and the corresponding
at an angle of 43.5
°
to each other.
, the neutral host–guest comꢀ
In the crystal of
I
plexes are linked directly through intermolecular
hydrogen bonds 1 and 4 (Table 3). Here, the acceptors
are the O(1) and O(7) phosphoryl atoms, and the
donors are the hydroxyl groups. The complexes are
also combined by three hydrogen bonds involving the
second water molecule Н2О(10): two donor bonds (5
and 6) and one acceptor bond (3). Thus, the above
intermolecular hydrogen bonds form a chain running
bands in the IR spectra of L and
quencies (Table 5). Below 1250 cm–1, the vibrational
spectra of L and are considerably different. However,
I have the same freꢀ
I
the stretching vibration frequency for the Ph–O bond
adjacent to the ethylene glycol chain remains unalꢀ
tered.
In the IR spectrum of L, the important analytical
ν
(Р=О) frequency, determined by the electronegativity
of the substituents at the phosphorus atom, is 1217 cm–1
(1195 cm–1 for Ph3P=O, CH3OPhP(O)Ph2, and neuꢀ
tral phosphorylꢀcontaining podands [12–16]).
Table 4. Torsion angles in structure
I
Angle
ω
, deg
–6.1
The IR spectra of phosphorylꢀcontaining
podands below 1125 cm–1 show absorption bands at
frequencies depending either on the conformation
of ethylene glycol units (νas(COC) = 1090–1125,
P(1)C(1)C(6)O(4)
C(1)C(6)O(4)C(7)
C(6)O(4)C(7)C(8)
O(4)(7)(8)O(5)
–166.5
162.5
68.4
ρ
(СН2) = 800–1000 cm–1) or, as demonstrated in
[14], on the mutual orientation of the benzene rings at
(7)C(8)O(5)C(9)
172.3
–169.1
–74.2
–166.4
165.0
1.9
the phosphorus atom ( (Ph),
δ
δ
(PhPO) 400–500 cm–1).
C(8)O(5)C(9)C(10)
O(5)C(9)C(10)O(6)
C(9)C(10)O(6)C(11)
(10)O(6)C(11)C(16)
O(6)C(11)C(16)P(2)
The IR spectrum of II with a known structure [33],
which is structurally very similar to L, shows two bands
at 1120 and 1104 cm–1 in the νas(COC) region. Inasꢀ
much as Xꢀray crystallography shows that the ethylene
glycol chain in II is composed of onlyTGT units, the
band at ~1104 cm–1 is due to νas(COC) of two TGТ
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

SYNTHESIS, VIBRATIONAL SPECTRA
1229
a
b
c
0
Fig. 3. Projection of structure I along the b axis.
units [33].The band at 1120 cm–1 is due to the
vibration.
δ
(Ph) ~48 cm lower than the
ν
(Р=О) frequency in the specꢀ
trum of L (Table 5). This decrease in
ν
(Р=О) is
The IR spectrum of L in the range of 1000–1125 cm–1
shows only one band of moderate intensity at ~1125 cm–1,
which is most likely a superposition of two bands
explained by the fact that, according to Xꢀray diffracꢀ
tion, both phosphoryl oxygen atoms form strong
hydrogen bonds with neighboring podand molecules
(Table 3).
νas(COC) and (Ph). According to the correlations in
δ
[13, 14], the band at 1125 cm–1 can be due to vibraꢀ
tions of ethylene glycol units with an approximate TGG
conformation. Therefore, we can assume that the ethꢀ
ylene glycol chain of the L podand molecule is built of
two TGG units.
In the range of νas(СОС), the IR spectrum of
I
shows two bands of approximately equal intensity at
1122 and 1104 cm–1. The former can be due to bendꢀ
ing vibrations of the benzene rings (~1120 cm–1 in the
spectrum of II), and the latter, in accord with Xꢀray
crystallographic data, is caused by νas(СОС) of the
TGT ethylene glycol units. In another conformationꢀ
ally important range of 800–1000 cm–1, the spectra of
L and O are also different (Table 5). As mentioned
above, the IR spectrum of L in this range shows two
strong, broad bands of P–OH bending vibrations. In
In the range 800–1000 cm–1, the IR spectrum of L
shows two strong, broad bands with maxima at 986,
936, 921, and 904 cm–1. According to [34], the band at
~986 cm–1 arises from bending vibrations
(РОН).
δ
The strong band at 904 cm–1 and the weak band at
830 cm–1 can be can be assigned to the possible presꢀ
ence of two TGG units in the L molecule.
the IR spectrum of I, these vibrations are observed as
one strong broad band with maxima at 1041, 1018, and
961 cm–1, which is caused by the involvement of both
the H and O atoms of the POH groups in various intraꢀ
and intermolecular hydrogen bonds.
The presence of absorption bands at 3293 and
1710 cm–1 in the IR spectrum of L allowed us to
assume that there are strong hydrogen bonds or some
number of hydration water molecules in the L moleꢀ
cule. Thermogravimetric study of L showed that no
weight loss was observed on heating of the compound
Taking into account the fact that both ОСН2СН2О
units in the molecule of I have the same TGT conforꢀ
mation and using the known correlations [14], we can
assign the bands at 961 and 867 cm–1 to composite
stretching–bending vibrations of the TGT units.
up to the melting point (209
the decomposition of the compound, which was
accompanied by exothermal events at 240 and 250
°С). Further heating led to
°С.
Thus, we can state that podand L does not contain
hydration water molecules, and the broad bands at
3293 and 1710 cm–1 are due to strong hydrogen bonds.
In the range of water stretching vibrations, the specꢀ
trum of
which, according to Xꢀray crystallography data, can be
I
shows the wellꢀdefined bands at ~3522 cm–1,
In the IR spectrum of
I
, P=O stretching vibrations assigned to the presence of the outerꢀsphere water
give rise to the moderate band at 1169 cm–1. This is molecule in
I
. The broad band at 3312 cm–1 arises
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

1230
BAULIN et al.
Table 5. Assignment of basic vibrational frequencies (cm–1) in
from stretching vibrations of the coordinated Н2О
molecule.
the IR spectra of L and
I
Thermogravimetric studies of
outerꢀsphere water molecule is removed at 93
the innerꢀsphere water molecule is removed at 111
(the temperatures correspond to the even maxima).
The overall water weight loss is 7.31% (calculated,
I
showed that the
Assignment
L
I
°
С
, and
ν
ν
ν
ν
(H2O),
3522
3312
°
С
(O–H···O),
(H–O···H)
(P–OH)
3293
7.92%). The melting point of compound
and the decomposition temperature is 260 С.
I
is 200 С,
°
2360
°
δ
δ
ν
(O–H···O),
(H–O···H)
(Ph)
1710
ACKNOWLEDGMENTS
1599
1575
1482
1593
1576
1480
This work was supported by the Presidium of the
Russian Academy of Sciences (program “Developꢀ
ment of Methods of Synthesis of Chemical Substances
and Design of New Materials”) and by the Russian
Foundation for Basic Research (project nos. 11ꢀ03ꢀ
00589_a and 11ꢀ03ꢀ00509_a).
δ
(CH2),
(P–Ph)
1457
1450
1463
1443
ν
ω
(CH2)
1378
1360
1377
ν
(Ph)
1278
1286
1249
REFERENCES
ν
(Ph–O),
1249
1239
1. V. I. Evreinov, V. E. Baulin, Z. N. Vostroknutova, et al.,
Izv. Akad. Nauk SSSR, Ser. Khim., No. 9, 1990 (1989).
τ(CH2)
2. L. V. Govorkova, O. A. Raevskii, V. P. Solov’ev, et al.,
Izv. Akad. Nauk SSSR, Ser. Khim., No. 3, 575 (1991).
3. V. P. Solov’ev, V. E. Baulin, N. N. Strakhova, and
L. V. Govorkova, Izv. Akad. Nauk, Ser. Khim., No. 9,
1581 (1994).
4. A. N. Turanov, V. E. Baulin, A. V. Kharitonov, and
E. N. Tsvetkov, Zh. Neorg. Khim. 39 (8), 1394 (1994).
5. A. N. Turanov, N. K. Evseeva, V. E. Baulin, and
ν
δ
δ
(Ph=O)
1217
1150
1125
1169
1151
(Ph)
(Ph), νas(COC)
1122
1104
δ
(Ph)
1084
1046
1089
νs(COC) +
ν
(CC)
1061
1041
E. N. Tsvetkov, Zh. Neorg. Khim. 40 (5), 861 (1995).
6. A. N. Turanov, V. K. Karandashev, V. E. Baulin, and
E. N. Tsvetkov, Radiokhimiya, No. 2, 140 (1995).
7. A. N. Turanov, V. K. Karandashev, and V. E. Baulin,
Radiokhimiya 40 (1), 36 (1998) [Radiochemistry 40
(1), 39 (1998)].
δ
δ
(Ph),
(POH)
1018
1005n
986
ν
(CO) +
(CH2)
ν(CC) +
961
947
ρ
8. A. N. Turanov, V. K. Karandashev, V. E. Baulin, and
E. N. Tsvetkov, Zh. Neorg. Khim. 40 (11), 1926 (1995).
936
921
904
9. A. N. Turanov, V. K. Karandashev, and V. E. Baulin,
Zh. Neorg. Khim. 51 (11), 1942 (2006) [Russ. J. Inorg.
Chem. 51 (11), 1829 (2006)].
867
847
10. S. G. Dmitrienko, I. V. Pletnev, V. E. Baulin, and
E. E. Tsvetkov, Zh. Anal. Khim. 49 (8), 804 (1994).
830
807
11. L. Kh. Minacheva, I. S. Ivanova, A. Yu. Tsivadze, and
V. S. Sergienko, Dokl. Akad. Nauk 377 (1), 57 (2001)
[Dokl. Chem. 377 (1–3), 65 (2001)].
12. L. Kh. Minacheva, V. E. Baulin, and V. G. Sakharova,
Koord. Khim. 21 (3), 236 (1995).
13. L. Kh. Minacheva, I. S. Ivanova, I. K. Kireeva, et al.,
801
ν
(P–C),
δ
(Ph)
776
769
741
726
698
765
736
723
704
Koord. Khim. 19 (3), 185 (1993).
14. I. S. Ivanova, L. Kh. Minacheva, I. K. Kireeva, et al.,
Zh. Neorg. Khim. 37 (10), 2185 (1992).
15. L. Kh. Minacheva, I. S. Ivanova, I. K. Kireeva, et al.,
Zh. Neorg. Khim. 39 (7), 1143 (1994).
16. I. S. Ivanova, I. K. Kireeva, V. E. Baulin, et al.,
Zh. Neorg. Khim. 40 (5), 792 (1995).
17. I. A. Charushnikova, V. E. Baulin, A. M. Fedoseev,
δ
δ
(COC),
(PhPO)
614
556
539
516
502
486
613
559
514
482
et al., Koord. Khim. 36 (2), 1 (2010).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

SYNTHESIS, VIBRATIONAL SPECTRA
1231
18. F. Vogtle and E. Weber, Angew. Chem. Int. Engl., 26. L. S. Melvin, Tetrahedron Lett. 22 (35), 3375 (1981).
No. 18, 753 (1979).
19. A. N. Bovin, A. N. Degtyarev, and E. N. Tsvetkov,
27. Host–Guest Complex Chemistry: Macrocycles, Ed. by
F. Vögtle and E. Weber (Springer, Berlin, 1985; Mir,
Moscow, 1988).
Zh. Obshch. Khim. 57 (1), 82 (1987).
20. V. E. Baulin, V. Kh. Syundyukova, and E. N. Tsvetkov,
Zh. Obshch. Khim. 59 (1), 62 (1989).
21. T. I. Ignat’eva, V. E. Baulin, O. A. Raevskii, and E. N. Tsvetꢀ
28. A. H. Alberts, K. Timmer, I. Y. Noltes, et al., J. Am.
Chem. Soc. 101 (12), 3375 (1979).
29. Y. Ruban and V. Zabel, Cryst. Struct. Commun.
671 (1976).
5 (3),
kov, Zh. Obshch. Khim. 60 (7), 1503 (1990).
22. V. E. Baulin, D. V. Baulin, A. N. Usolkin, et al., Proꢀ
ceedings of VI Russian Conference of Radiaochemistry,
Radiochemistryꢀ2009, p. 18.
23. G. M. Sheldrick, SADABS, Program for Scaling and
Correction of Area Detector Data, Univ. of Göttingen,
Germany (1997).
24. G. M. Sheldrick, SHELXSꢀ97, Program for the Soluꢀ
tion of Crystal Structures, Univ. of Göttingen, Gerꢀ
many (1997).
30. C. P. Brock, W. B. Schweizer, and J. D. Dunitz, J. Am.
Chem. Soc. 107 (24), 6964 (1985).
31. A. L. Spek, Acta Crystallogr., Sect. C 43 (6), 1233
(1987).
32. F. H. Allen, O. Kennard, D. Y. Watson, et al., J. Chem.
Soc., Perkin Trans. 2, No. 12, S1 (1987).
33. A. N. Chekhlov, Izv. Akad. Nauk SSSR, Ser. Khim.,
No. 3, 624 (1992).
25. G. M. Sheldrick, SHELXLꢀ97, Program for the 34. L. J. Bellamy, The Infrared Spectra of Complex Moleꢀ
Refinement of Crystal Structures, Univ. of Göttingen, cules (Wiley, New York, 1958; Inostrannaya Literatura,
Germany (1997). Moscow, 1963).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011