Synthesis and X-ray structure of new molecular clips based on diphenylglycoluril

Article abstract of DOI:10.3184/030823409X465231

A pair of new molecular clips based on diphenylglycoluril and 1, 2-dihydroindazol-3-one have been synthesised. Their structures and conformations were confirmed by single crystal X-ray diffraction.

Full text of DOI:10.3184/030823409X465231

418 RESEARCH PAPER
JULY, 418-419
JOURNAL OF CHEMICAL RESEARCH 2009
Synthesis and X-ray structure of new molecular clips based on
diphenylglycoluril
Hu Sheng-Lia,b,Wu Yan-Dongb, Li Jingb, Wang Kun-Rub and Wu An-Xinb*
aDepartment of Chemical and Enviromental
Engineering,
Hubei Normal University, Huangshi 435002, P. R. China
bKey Laboratory of Pesticide Chemical Biology, Ministry of Education, Central China Normal University, Wuhan 430079, P. R. China
&
A
pair of new molecular clips based on diphenylglycoluril
and 1, 2-dihydroindazol-3-one
have been synthesised.
Their structures and conformations were confirmed by single crystal X-ray diffraction.
Keywords: diphenyl glycoluril, molecular clip, 1, 2-dihydro-indazol-3-one
The design and synthesis of novel receptors with different
molecular cavities is one of the major challenges in host-
guest chemistry.! Glycoluril is an important building block
for supramolecular chemistry, and its derivatives have
been used as the basis for various molecular clips.2-4 Most
molecular clips based on diphenylglycoluril have been
derived from benzene, hydroquinone and their relatives.
They possess good symmetry with the aromatic walls and
show good binding properties for aromatic guests, especially,
for dihydroxybenzene, by hydrogen bonding, i t - i t stacking
interactions and a so-called 'cavity-effect'.5,6
Cl
We now report the synthesis and X-ray structure of a pair
of new molecular clip from diphenylglycoluril and 1, 2-
dihydroindazol-3-one. The deep U-shaped cavity in their
structures provides great potential for binding aromatic guest
molecules.
The synthesis of the title clip molecules 4a and 4b is shown
in Scheme 1. The structures and conformations of compound
4a and 4b were further elucidated by their single crystal X-ray
diffraction, as shown in Figs 1 and 2.
The crystals of 4a and 4b were obtained by slow evaporation
of their solution in chloroform/methanol (20:1, v/v) mixtures.
The crystal structures of 4a and 4b clearly revealed that they
Fig.
1
The crystal structure of 4a.
have well-defined geometry due to the rigidity that the fused
rings confer on the molecule. The distance between the two
carbonyl oxygens (02-03) of the glycoluril ring in 4a and
4b amounts to 5.341 A and 5.461 A, respectively, which
indicates that two carbonyl groups of glycoluril ring are good
hydrogen-acceptors for 1, 3-dihydroxy-substituted aromatic
guests.2 The dihedral angle between two phenyl rings of the
sidewalls in 4a and 4b are 58.01° and 29.11°, and the distance
between the centroids of two phenyl rings of the sidewalls in
4a and 4b are 7.838 A and 6.845 A, respectively. These values
are suitable for the complexation of an aromatic ring by i t - i t
stacking interactions.7
In conclusion, a pair of new molecular clips derived from
diphenylglycoluril have been synthesised. Their structures
and conformations were confirmed by single crystal X-ray
diffraction. Both have great potential to bind aromatic guest
5NH
Q-NH
3
Scheme
1
* Correspondent.E-mail:hushengli168@126.com

JOURNAL OF CHEMICAL RESEARCH 2009 419
4b. M.p. >300°C (dec.). TLC (CHCliCHpH,
20:1), Rf 0.24.
IR (KEr, cm-I): 3064, 1730, 1667, 1620, 1460, 1384, 1260, 1154,
874,750. OH (400 MHz, DMSO-d6) 7.60-7.50 (m, 4 H, ArH), 7.42-
7.39(m, 2 H), 7.25-7.15(m, 10 H, ArH), 7.07-7.02(m, 2 H), 6.20 (d,
J = 14.8,2 H, NCH2N), 6.03 (d, J = 15.2, 2 H, NCH2N), 4.85 (d,
J = 15.2,2 H, NCH2N), 4.73 (d, J = 14.8,2 H, NCH2N). MS (EI): m/z
= 611.3 [M + H]+. Anal. Calcd for C34H26N804(610.21): C, 66.88; H,
4.29; N, 18.35. Found: C, 66.55; H, 4.24; N, 17.88%.
X-ray diffraction study of 4a and 4b
A white crystal of the title compound 4a and 4b were each mounted
on a glass fibre in a random orientation at 295(2) K, respectively.
The determination of the unit cell and the data collection were
performed with MoKa radiation (ic = 0.71073 A) on a Bruker Smart
Apex-CCD diffactometer with a '!'-(j) scan mode. The structure was
solved by direct methods with SHELXS-97 program and expanded
by Fourier technique. The non-hydrogen atoms were refined
anisotropically, and the hydrogen atoms were placed at the calculated
positions.
Crystal data for 4a: C36H28C16N804,M = 849.36, Triclinic, space
groupP-I,a=9.6598(9), b= 13.2119(12),c= 15.3667(14)A, a=97.875(2),
~ = 97.643(2), y = 104.726(2)°, V= 1849.8(3) A3, Z = 2, Dc= 1.525 g
cm-3, Reflections collected: 17111, independent reflections: 7205
[Rint= 0.0656] Final R indices [1>26(1)]: RI = 0.0622, wR2 = 0.1584.
R indices (all data): RI = 0.0995, wR2 = 0.1812. CCDC 294988.
Crystal datafor 4b: C34H26N80S,M= 634.63, Monoclinic, space
group C/c, a = 11.2685(10), b = 24.869(2), c = 21.381(2)A, a = 90,
~ = 100.407(2), Y = 90°, V = 5893.3(9) A3, Z = 8, Dc = 1.431 g cm-3,
Reflections collected: 21072, independent reflections: 5188 [Rint
= 0.0360], Final R indices [1>26(1)]: RI = 0.0578, wR2 = 0.1590.
R indices (all data): RI = 0.0798, wR2 = 0.1770. CCDC 279808.
c'"
Fig. 2 The crystal structure of 4b.
molecules. Further studies on their binding properties are
m progress.
Experimental
General
All reagents obtained from commercial sources were of AR grade.
Melting points were determined with XT4A micromelting point
apparatus and were uncorrected. The IH NMR was recorded on a
Mercury Plus-400 spectrometer with TMS as internal reference and
CDCI3 as solvent. IR were recorded on a Perkin-Elmer PE-983
IR spectrometer as KBr pellets with absorption in cm-I. MS were
obtained with Finnigan Trace MS instrument using EI method.
Elemental analyses were carried out on a Vario EL III instrument.
We thank the Central China Normal University, the National
Natural Science Foundation of China (Grant No. 20672042)
for financial support.
Synthesis
Diphenylglycolurill,
as the literature method.
Received 11May 2009; accepted 27 May 2009
Paper 09/0581 doi: 10.3184/030823409X465231
Published online: 10 July 2009
8 and glycoluril cyclic ether 29 were prepared
General procedure for preparation of 4a and 4b
Anhydrous MeS03H (IOmL) was added to
a flask contammg
References
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