Crystal structure of 25,27-bis[(2-cyanophenyl)methoxy] calix[4]arene

Article abstract of DOI:10.1023/A:1014355506343

The crystal structure of 25,27-bis[(2-cyanophenyl)methoxy] calix[4]arene (C₄₄H₃₄N₂O₄) was determined by X-ray crystallographic analysis. It possesses space group R3, with a = b = 35.993(8) A, c = 13.842(3) A, α

Full text of DOI:10.1023/A:1014355506343

C
Journal of Chemical Crystallography, Vol. 31, No. 6, June 2001 ( 2002)
Crystal structure of 25,27-bis[(2-cyanophenyl)methoxy]
calix[4]arene
Chuan-Ming Jin,(1) Guo-Yuan Lu,(1)* Yan Xu,(1) Qian Li,(1) Fang Liu,(1)
and Xiao-Zeng You(1)
Received November 20, 2000
The crystal structure of 25,27-bis[(2-cyanophenyl)methoxy] calix[4]arene (C44H34N2O4)
¯
was determined by X-ray crystallographic analysis. It possesses space group R3, with a =
= 90 , = 120 , and D = 1.260 mg/cm3
˚
˚
b = 35.993(8) A, c = 13.842(3) A,
=
calc
for Z = 18. Crystal data indicate that Compound 1 exists in a pinched-cone conformation
with intramolecular hydrogen bonds.
KEY WORDS: Functionalized calix[4]arene; tweezers; crystal structure.
Introduction
is a crucial one because it is not only the syn-
thetic intermediate for the preparation of Com-
Calixarenes are a class of macrocyclic host
pounds 2, 3, and 4 but also a possibly good
host compound for some metal cations.13,14 Re-
cently, single crystals of Compound 1 were ob-
tained from its acetone solution and subjected to
X-ray crystallographic structure analysis. The re-
sult indicates that the Tweezer molecule 1 ex-
ists as a pinched-cone conformation. In this
paper, we report the synthesis and crystal struc-
ture of Compound 1. The details on the syn-
theses of other compounds will be published
elsewhere.
compounds that is attracting increasing interest
owing to their potential for forming host–guest
complexes and acting as enzyme mimics, espe-
cially if appropriately functionalized.1 Our in-
6
terest lies in the syntheses and possible appli-
cations of functionalized calixarenes that have
the ability to catch ions or neutral molecules.7
9
Recently, a series of functionalized calixarenes
have been prepared in our laboratory (Scheme 1).
In these calix[4]arenes, two functional groups
such as cyano, amino, carboxylic, or guanidinium
groups have been introduced to each calix[4]arene
molecule under suitable conditions to form the
Experimental
12
so-called tweezer molecules,10
which can
bind some metal cations or organic molecules.
Among these tweezer molecules, Compound 1
Preparation of Compound 1
The calix[4]arene was prepared according
to the literature.15 The calix[4]arene (0.57 g,
1.35 mmol) and 2-cyanobenzyl bromide (0.53 g,
2.7 mmol) were dissolved in 10 mL of anhydrous
acetonitrile, and the solution refluxed for 42 h in
(1) Department of Chemistry, State Key Laboratory of Coordina-
tion Chemistry, Nanjing University, 210093 Nanjing, People’s
Republic of China.
*To whom correspondence should be addressed; e-mail: nnj.lugy@
jonline.com.
301
C
1074-1542/01/0600-0301/0 2002 Plenum Publishing Corporation

302
Jin, Lu, Xu, Li, Liu, and You
Scheme 1
the presence of anhydrous potassium carbonate
(0.21 g, 1.5 mmol). The solvent was evaporated
in vacuo and the residue was dissolved in 20 mL
of dichloromethane, washed with 1.0 mol/L HCl
solution (20 mL) and water (20 mL), respec-
tively, dried over anhydrous magnesium sulfate.
The solvent was evaporated in vacuo to dryness
and the residue was recrystallized from chloro-
form and methyl alcohol to give 1 (610 mg,
= 8.32 (d, J = 7.5 Hz, 2H, 2 3HArCN),
7.72 (d, J = 7.3 Hz, 2H, 2 6HArCN), 7.47
(m, 4H, 2 4,5HArCN), 7.38 (s, 2H, 2 ArOH),
7.06 (d, J = 7.4 Hz, 4H, 2 3,5HArOH), 6.86
(d, J = 7.5 Hz, 4H, 2 3,5HAr), 6.75 (t, J =
7.5 Hz, 2H, 2 4HAr), 6.68 (t, J = 7.4 Hz,
2H, 2 4HArOH), 5.28 (s, 4H, 2 ArCH2O),
4.23 (d, J = 12.5 Hz, 4H, 4 endo-ArCHAr),
3.30 (d, J = 12.5 Hz, 4H, 4 exo-ArCHAr);
Anal. for C44H34N2O4. Calcd: C, 80.71; H,
5.23; N, 4.28. Found: C, 80.66; H, 5.44;
N, 4.26.
69%), white needle crystal, m.p. > 300 C; IR
1
(
max, cm ); 3415.5 (OH), 2227.9 (CN), 1593.8,
1531.6, 1475.7(Ar);1HNMR(500MHz, CDCl3):

Crystal structure of calix[4]arene
303
Table 2. Non-Hydrogen Atomic Coordinates ( 104) and Equivalent
Isotropic Displacement Parameter (A
Crystal structure determination
2
103) for Compound 1
˚
Colorless single crystals were obtained
by slow evaporation of the acetone solution
of Compound 1, and a single crystal with
dimensions of 0.30 0.26 0.26 mm was
mounted on a Siemens P4 four-circle diffrac-
tometer with graphite monochromated Mo K
a
Atom
x
y
z
Ueq
O(1)
O(2)
O(3)
O(4)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
8400(1)
9325(1)
8730(1)
9106(1)
9524(2)
9530(2)
9744(2)
9954(2)
9950(2)
9741(2)
9725(2)
9299(2)
9180(2)
8782(2)
8487(2)
8584(2)
8998(2)
9389(2)
9158(2)
9181(2)
8970(3)
8738(3)
8705(2)
8915(2)
8890(2)
8233(2)
7912(2)
7501(2)
7192(2)
7305(2)
7708(2)
8007(2)
7825(2)
8099(2)
7924(2)
8177(3)
8611(2)
8808(2)
8541(2)
9290(2)
8751(2)
8959(2)
9064(2)
9255(2)
9343(2)
9242(2)
9047(2)
8951(2)
8861(3)
8874(2)
705(1)
1420(1)
727(1)
1229(1)
1824(2)
1897(2)
2307(2)
2646(2)
2572(2)
2163(2)
2075(2)
1965(2)
2275(2)
2181(2)
1763(2)
1437(2)
1555(2)
1239(2)
1081(2)
1373(2)
1231(3)
803(4)
496(3)
643(2)
340(3)
976(2)
791(2)
727(2)
539(2)
428(2)
489(2)
669(2)
375(2)
772(2)
990(2)
1361(2)
1530(2)
1326(2)
937(2)
1515(2)
407(2)
207(2)
300(2)
106(2)
179(2)
278(2)
84(2)
1208(2)
1971(2)
3075(2)
68(2)
2332(4)
3334(4)
3661(5)
3036(6)
2066(5)
1693(4)
613(4)
188(4)
112(4)
203(4)
437(4)
384(3)
108(3)
829(4)
1778(4)
2457(5)
3333(5)
3506(6)
2869(5)
1979(5)
1288(6)
587(4)
72(1)
69(1)
64(1)
62(1)
58(2)
64(2)
82(2)
92(2)
84(2)
62(2)
69(2)
62(2)
75(2)
78(2)
64(2)
54(1)
51(1)
67(2)
60(2)
87(2)
116(3)
124(3)
100(2)
72(2)
90(2)
63(2)
53(2)
70(2)
82(2)
75(2)
58(2)
55(1)
78(2)
58(2)
73(2)
74(2)
73(2)
64(2)
56(2)
74(2)
67(2)
56(2)
65(2)
76(2)
79(2)
80(2)
59(2)
65(2)
134(3)
94(2)
˚
( = 0.71073 A) radiation, using –2 scan
mode (range 4 < 2 < 50 ), variable from 5.0
1
to 50.0 min in ω. The data were corrected
for Lorentz and Polarization effects during data
reduction using XSCANS.16 The structure was
solved by direct methods and all non-hydrogen
atoms were refined anisotropically on F2 by full-
matrix least squares using SHELXTL.17 All the
H atoms were placed in the calculated positions
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(37)
C(38)
C(39)
C(40)
C(41)
C(42)
C(43)
C(44)
N(1)
˚
˚
---- ==
---- ==
(C H 0.96 A, O H 0.85 A), assigned fixed
isotropic displacement parameters 1.2 times the
equivalent isotropic U value (1.5 times for OH)
of the attached atom, and allowed to ride on
their respective parent atoms. Crystallographic
data and non-hydrogen atomic coordinates are
summarized in Tables 1 and 2, respectively.
208(4)
85(4)
808(5)
Table 1. Crystal Data and Summary of Intensity Data Collection and
Structure Refinement
1668(4)
1825(4)
1079(4)
2796(4)
3419(4)
3885(4)
4380(4)
4429(4)
4000(4)
3524(4)
4013(4)
3652(4)
3087(4)
2121(4)
1618(5)
2069(5)
3043(5)
3543(4)
4544(5)
737(5)
Color/shape
Colorless/needle
CCDC deposit no.
Chemical formula
Formula weight
CCDC-1003/6021
C
44H34N2O4
654.73
Temperature, K
293(2)
Crystal system
Space group
Rhombohedral
R3
¯
˚
˚
Unit cell dimensions (7038
reflections in full range)
a = 35.993(8) A
b = 35.993(8) A
˚
c = 13.842(3) A
3
˚
Volume, A
15530(6)
Z
18
1.260
Siemens P4
Density (calculated), Mg/cm3
Diffractometer
range for data collection, deg
Independent reflections
Data/restraints/parameters
Goodness of fit on F2
Final R indices [I > 2 (I)]
R indices (all data)
1.96–25.00
5836 (Rint = 0.1064)
5836/24/452
0.988
R1 = 0.0821, wR2 = 0.1500
R1 = 0.2404, wR2 = 0.2139
XSCANS
172(2)
94(2)
237(2)
N(2)
5350(4)
Computer programs
Structure solution
aUeq is defined as one-third of the trace of the orthogonalized
Ui j tensor.
SHELXTL

304
Jin, Lu, Xu, Li, Liu, and You
Fig. 1. ORTEP drawing of Compound 1 (dashed lines indicate the H-bonding interaction).
1
Result and discussion
In the H NMR spectra of Compound 1 in
CDCl3, the peaks of the ArCH2Ar protons ap-
As shown in Fig. 1, Compound 1 exists
in a cone conformation in the crystal, which is
stabilized by intramolecular hydrogen bonds be-
tween the phenol hydroxy groups and ether oxy-
peared as doublets at 4.23 (Hendo) and 3.30 (Hexo
)
ppm, and the chemical shift difference of H
endo
and Hexo is about 1.0. This fact also indicates that
Compound 1 exists in the cone conformation in
solution.7,18,19
---- ----
----
gen atoms (
O
H
O
), and the geometric
data of the hydrogen bonds are given as fol-
In conclusion, the calix[4]arene moiety of
Compound 1 adopts a cone conformation both
in the crystal and in the solution. The two func-
tional units attached at the lower rim may be able
to form face-to-face tweezer structures and bind
metal cations.
˚
˚
----
lows: O(1) O(4), 2.889(3) A, O(1)
----
----
H
H
O(4),
O(3),
----
164 ; O(2) O(3), 2.793(3) A, O(2)
163 . There is a pseudo C2 symmetrical axis in
the calix[4]arene moiety of 1. Two phenolic ring
planes of the calix[4]arene make an angle of 15.9
with the respective pseudo C2 axis, and so they are
nearly parallel to each other, whereas the other
two phenyl planes with (2-cyanophenyl)methoxy
make an angle of 50.9 with the pseudo C2
axis. Therefore, the calix[4]arene moiety of
Compound 1 adopts a pinched-cone conformation
inthecrystalthoughthetwo2-cyanophenylplanes
attached at the lower rim of calix[4]arene make a
dihedral angle of 61.2 to each other.
Acknowledgments
We are grateful to the National Natural Science
Foundation of People’s Republic of China for finan-
cial support (Grant No. 29872014). We also thank
Dr Chunying Duan and Mr Yongjiang Liu who are
at state key Laboratory of Coordination Chemistry

Crystal structure of calix[4]arene
305
in Nanjing University for the crystallographic data
collection.
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