Synthesis and Characterization of Selenophosphatocavitands

Article abstract of DOI:10.1007/s10870-016-0635-1

Treatment of a series of substituted resorcin[4]arenes in pyridine with dichlorophenyl-phosphine followed by addition of selenium powder resulted in the formation of the corresponding selenophosphatocavitands [R₂CHC₆HR₁O

Full text of DOI:10.1007/s10870-016-0635-1

J Chem Crystallogr (2016) 46:124–127
DOI 10.1007/s10870-016-0635-1
ORIGINAL PAPER
Synthesis and Characterization of Selenophosphatocavitands
Yan-Jing Wang1 Nian-Nian Wang1 Ai-Quan Jia1 Qian-Feng Zhang1
•
•
•
Received: 28 September 2015 / Accepted: 4 February 2016 / Published online: 13 February 2016
Ó Springer Science+Business Media New York 2016
Abstract Treatment of a series of substituted resor-
cin[4]arenes in pyridine with dichlorophenyl-phosphine
followed by addition of selenium powder resulted in the
formation of the corresponding selenophosphatocavitands
[R2CHC6HR1O2PSePh]4 (R1 = H, R2 = CH2CH2Ph, 1;
R1 = CH3, R2 = CH3, 2; R1 = CH3, R2 = C2H5, 3) in
moderate yields. All compounds were spectroscopically
characterized, of which the structure of 3ÁCHCl3 has been
established by X-ray crystallography. The molecular
structure of 3 shows that the selenophosphato-cavitand
adopts C4v bowl-shaped conformation with four P=Se
bonds oriented toward the molecular cavity.
Graphical Abstract Three selenophosphatocavitands
[R2CHC6HR1O2PSePh]4 (R1 = H, R2 = CH2CH2Ph, 1;
R1 = CH3, R2 = CH3, 2; R1 = CH3, R2 = C2H5, 3) were
synthesized and spectroscopically characterized, of which
Keywords Resorcinarene Á Selenium Á
the structure of 3ÁCHCl3 has been established by X-ray
Phosphatocavitand Á Synthesis Á Structure
crystallography.
Introduction
Calix[4]resorcinarenes are cavity-containing macrocyclic
compounds that attract considerable interest in the field of
host–guest and supramolecular chemistry as three-dimen-
sional building blocks for the design of selective cation
receptors and carriers [1]. It is thus understood that the use
of calix[4]resorcinarenes for the chemo- and stereo-selec-
tive recognition of carbohydrates is particularly important,
of which phosphorus-containing calix[4]resorcinarenes
have been of increasing interest in the past decades, mainly
because of their ability to act as unusual multi-dentate
& Qian-Feng Zhang
zhangqf@ahut.edu.cn; ahutchang@yahoo.com
ligands [2, 3]. Quite
a few phosphorus-containing
1
Institute of Molecular Engineering and Applied Chemistry,
Anhui University of Technology, Ma’anshan 243002, Anhui,
People’s Republic of China
calix[4]resorcinarenes have been synthesized in which the
phosphorus atoms adopts various coordination numbers
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J Chem Crystallogr (2016) 46:124–127
125
and oxidation states. For examples, derivatives of
calix[4]resorcinarenes with Ph2P, PhP, (Et2N)2P(=O), and
(EtO)2P(=O) units show strong coordination ability with
transition metals such as gold(I), platinum(II), silver(I), and
copper(I), to give transition-metal rimmed bowl complexes,
which have the potential to accept small guest molecules and
ions [4–8]. The phosphoryl (P=O) or thiophosphoryl (P=S)
groups were attached to the calix[4]resorcinarene skeleton to
produce the typical phosphito- or thiophosphato-cavitand
which may be prepared by using a two-step synthetic route.
While the phosphito- and thiophosphato-cavitands were
previously described and proved to be efficient extractants
for metal cations, however, the analogous selenophosphato-
cavitands have not been reported to date. As a part of our
interests on cavitand compound based upon calix[4]resor-
cinarenes, we have previously reported the tetrametallo-
phosphonitocavitand complexes and their optical properties
[9, 10]. In this paper, we wish to present synthesis and
characterization of selenophosphatocavitands, which is
expected to expand the pool of the supramolecular chemistry
of the chalcogeno-phosphato-cavitands.
For 1: Yield: 1.63 g, 57.6 %. 1H NMR (400 MHz,
CDCl3): d (ppm) 8.03 (dd, 8H, P(Se)PhHo), 7.58 (m,
4H ? 8H, P(Se)PhHm ? P(Se)PhHp), 7.28 (s, 4H, ArH),
7.22 (m, 20H, C6H5), 6.25 (s, 4H, ArHupper), 4.75 (t, 4H,
3J = 6.4 Hz, bridge CH), 2.34 (m, 16H, CH2CH2C6H5);
31P NMR (CDCl3, 162 MHz): d (ppm) 80.67 (s); selected
IR (KBr, cm-1): m(P–Ph) 1432.7, m(P–O) 1059.4, m(P=Se)
686.2. Anal. Calc. for C84H68O8P4Se4: C 61.32, H 4.17;
found: C 61.30, H 4.18 %.
For 2: Yield: 1.29 g, 48.2 %. 1H NMR (400 MHz,
CDCl3): d (ppm) 8.23 (dd, 8H, P(Se)PhHo), 7.54 (m,
4H ? 8H, P(Se)PhHm ? P(Se)PhHp), 7.17 (s, 4H, ArH),
4.88 (q, 4H, 4J = 7.8 Hz, bridge CH), 2.17 (s, 12H,
ArCH3), 1.25 (d, 12H, 2J = 6.4 Hz, CH3); 31P NMR
(CDCl3, 162 MHz): d (ppm) 79.39 (s); selected IR (KBr,
cm-1): m(P–Ph) 1478.3, m(P–O) 1113.4, m(P=Se) 694.5.
Anal. Calc. for C60H52O8P4Se4: C 52.75, H 3.91; found: C
52.73, H 3.96 %.
For 3: Yield: 1.83 g, 66.3 %. 1H NMR (400 MHz,
CDCl3): d (ppm) 8.21 (dd, 8H, P(O)PhHo), 7.60 (m,
4H ? 8H, P(Se)PhHm ? P(Se)PhHp), 7.15 (s, 4H, ArH),
4.75 (t, 4H, 3J = 6.0 Hz, bridge CH), 2.75 (s, 12H,
ArCH3), 2.15 (m, 8H, CH2CH3), 1.02 (t, 12H, 3J = 7.2 Hz,
CH2CH3); 31P NMR (CDCl3, 162 MHz): d (ppm) 75.03
(s); selected IR (KBr, cm-1): m(P–Ph) 1478.3, m(P–O)
1121.7, m(P=Se) 686.7. Anal. Calc. for (C64H60O8P4Se4)Á
(CHCl3): C 51.51, H 3.89; found: C 51.47, H 3.82 %.
Experimental
General
All reagents, unless otherwise stated, were purchased as
analysis grade and used without further purification.
Calix[4]resorcinarenes were prepared by a modification of
X-ray Crystallography
1
the literature method [11]. H NMR and 31P NMR spectra
X-ray diffraction intensity data for a single-crystal of
3ÁCHCl3 (0.11 mm 9 0.13 mm 9 0.17 mm) were col-
lected at 293(2) K on a Bruker SMART Apex 1000 area-
detecting diffractometer equipped with graphite monochro-
were recorded on a Bruker Avance-400 Fourier-transform
spectrometer with reference to SiMe4 and 85 % H3PO4,
respectively, infrared spectra on a Nicolet 6700 FT-IR
spectrophotometer. All elemental analyses were carried out
using a Perkin-Elmer 2400 CHN analyzer.
˚
mated MoKa radiation (k = 0.71073 A) by using an x
scan technique (2.37° \ h \ 27.55°). The collected frames
were processed with the software SAINT [12]. The data were
corrected for absorption using the program SADABS [13].
Structures were solved by Direct Methods and refined by
full-matrix least-squares on F2 using the SHELXTL software
package [14]. All non-hydrogen atoms were refined
anisotropically. The positions of all hydrogen atoms
Synthesis
General Synthesis of Selenophosphato-cavitand Compound
To
a
solution of substituted calix[4]resorcinarene
attached on carbon were generated geometrically [C(sp3)–
(1.52 mmol) in 20 mL dry pyridine, dichlorophenylphos-
phine (0.85 mL, 6.08 mmol) was added slowly at room
temperature. After stirring for 3 h at 80 °C, selenium
powder (540 mg, 6.84 mmol) was added and the mixture
was continuously stirred for 6 h. The solvent was removed
under vacuum and the crude product was washed with
water and dried under vaccum. Analytical pure product was
obtained as white solid by recrystallization from acetone or
chloroform.
2
˚
˚
H = 0.96 A and C(sp )–H = 0.93 A] and allowed to ride
on adjacent carbon atoms before the final cycle of refine-
ment. One carbon atom C(40) was treated with disorder.
The final refined values of the multiplicities are 0.5 for
C(40) and 0.5 for C(40a). The crystallographic data and
details of the structure refinement are given in Table 1.
Selected bond lengths and bond angles of 3ÁCHCl3 are
given in Table 2.
123

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J Chem Crystallogr (2016) 46:124–127
˚
Table 1 Crystallographic data for selenophosphato-cavitand com-
pound 3ÁCHCl3
Table 2 Selected bond lengths (A) and bond angles (°) for 3ÁCHCl3
Se(1)–P(1)
Se(2)–P(2)
Se(3)–P(3)
Se(4)–P(4)
P(1)–O(1)
P(1)–O(8)
P(1)–C(41)
P(2)–O(2)
P(2)–O(3)
P(2)–C(47)
P(3)–O(5)
P(3)–O(4)
P(3)–C(53)
P(4)–O(7)
P(4)–O(6)
P(4)–C(59)
2.051(3)
2.051(3)
2.050(3)
2.055(3)
1.616(6)
1.621(6)
1.792(9)
1.607(6)
1.609(6)
1.757(10)
1.613(6)
1.617(6)
1.774(9)
1.601(5)
1.605(6)
1.785(9)
O(1)–P(1)–Se(1)
O(8)–P(1)–Se(1)
C(41)–P(1)–Se(1)
O(2)–P(2)–O(3)
O(2)–P(2)–C(47)
O(3)–P(2)–C(47)
O(2)–P(2)–Se(2)
O(3)–P(2)–Se(2)
C(47)–P(2)–Se(2)
O(5)–P(3)–Se(3)
O(4)–P(3)–Se(3)
C(53)–P(3)–Se(3)
O(7)–P(4)–Se(4)
O(6)–P(4)–Se(4)
C(59)–P(4)–Se(4)
C(1)–O(1)–P(1)
115.1(2)
114.9(2)
119.4(3)
104.4(3)
101.3(4)
100.3(5)
114.8(2)
115.2(2)
118.6(4)
115.7(2)
115.5(2)
119.6(3)
116.0(2)
115.4(2)
119.4(3)
121.6(4)
Compound
3ÁCHCl3
Empirical formula
Formula weight
Crystal system
Space group
C65H60O8Cl3P4Se4
1515.20
Monoclinic
P21/n
˚
a, A
15.856(11)
18.610(13)
23.785(16)
90
˚
b, A
˚
c, A
a, °
b, °
c, °
107.413(11)
90
3
˚
V, A
6697(8)
Z
4
T
293
l(MoKa), mm-1
Dc, g cm-3
2.458
1.503
Reflections collected
Independent reflections/R(int)
Final R1, wR2 [I C 2r(I)]
[all data]
34,195
11,761/0.1332
0.0755, 0.1714
0.2203, 0.2297
0.975
about 7.20 ppm, which is similar to that in related thio-
phosphorylated cavitand [8]. The 31P NMR spectra of 1–3
showed a singlet at d 80.67, 79.39, and 75.03 ppm,
respectively, indicative of the same environment of the
four phosphorous atoms. The FT-IR spectra of 1–3 showed
the characteristic peaks for P–O and P=Se stretching
vibrations at around 1110 and 690 cm-1, respectively, and
the P–Ph stretching vibrations were observed at about
1470 cm-1, indicating of P(V) moieties in 1–3.
Goodness-of-fit on F2
-3
˚
Residual q, e A
?1.117/-0.693
Results and Discussion
The molecular structure of 3 is shown in Fig. 1a. The
packing mode of 3 shows its alternating configuration
(Fig. 1b). Complex 3 crystallizes in monoclinic space
group P21/n with one molecule of selenophosorylated
cavitand and a solvent molecule of CHCl3 in the unit cell.
In the solid state, the molecule adopts C4v bowl-shaped
conformation with four P=Se bonds oriented toward the
molecular cavity. The P=Se bonds and the phenyl sub-
stituents are in the axial and equatorial positions,
Treatment of series substituted resorcin[4]arene in pyridine
solution with dichlorophenylphosphine followed by addi-
tion of selenium powder resulted in the formation of the
phosphorylated (P=Se) cavitand in moderate yields (see
Scheme 1). These complexes are air stable in both the solid
and solution. The chemical shifts of the bridging CH in 1–3
appeared at around 4.80 ppm, and the upper aryl proton in
compound 1 showed a singlet at 6.25 ppm, while the lower
aryl proton in compounds 1–3 also showed a singlet at
Ph
R
R
R
1
Se
P
1
1
Ph
O
O
HO
OH
Ph
O
O
P
Se
P
Ph
R
P
O
O
OH
R
O
HO
O
R
R
R
R
R
2
py / PhPCl
toluene, reflux
R
2
2
2
2
2
2
Se powder
toluene, reflux
R
R
1
1
1
R
R
1
1
1
R
R
R
R
R
2
R
2
2
OH
O
2
2
2
HO
O
O
O
P
Se
P
Ph
P
P
Se
HO
O
O
O
OH
O
Ph
Ph
R
R
1
1
R
1
Ph
R = H, R = CH CH Ph
1
2
3
1
2
2
2
R = CH , R = CH
1
3
2
3
R = CH , R = C H
2 5
1
3
2
Scheme 1 Syntheses of selenophosphatocavitands 1–3
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J Chem Crystallogr (2016) 46:124–127
127
Three selenophosphatocavitands with different sub-
stituents are synthesized and characterized. Single-crystal
diffraction analysis of 3 shows that the selenophosphato-
cavitand adopts C4v bowl-shaped conformation with four
P=Se bonds oriented toward the molecular cavity. The
˚
P=Se bond lengths ranging from 2.050(3) to 2.055(3) A
and only one 31P NMR signal was observed for the three
compounds, indicating their symmetrical structures.
Supplementary Material
Crystallographic data for 3ÁCHCl3 have been deposited
with the Cambridge Crystallographic Data Centre as sup-
plementary publication no. CCDC 1405666. Copies of the
data can be obtained free of charge on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax:
(?44)1233-336-033; e-mail: deposit@ccdc.cam.ac.uk].
Acknowledgments This project was supported by the Natural Sci-
ence Foundation of China (90922008).
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Fig. 1 a Molecular structure of compound 3; b p-packing mode of
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˚
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˚
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˚
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˚
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8.99° for Se3–P3–C53–C54 and the largest observed tor-
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forming claw-like squareness conformation.
123