Design and structural analysis of metallamacrocycles based on a combination of ethylene glycol bearing pyridine units with zinc, cobalt and mercury

Article abstract of DOI:10.1002/ejic.200300598

In the presence of MX₂ salts, ligand 1 (in a M/L ratio of 2:2, M = Zn, Hg, Co, X = Cl or I), based on the ethylene glycol fragment bearing two pyridine units as monodentate coordination sites, leads to isostructural square-shaped neutral metallamacrocycles as demonstrated by X-ray diffraction on single crystals. For all dinuclear complexes generated, the dicationic metal centre adopts a distorted tetrahedral coordination geometry and its coordination sphere is composed of the X₂N₂ set of coordinating atoms. For all complexes, the parallel packing of the cyclic structures generates channels which are occupied by solvent molecules. The solvent molecules, which behave as substrates, are positioned within the cavity of the metallamacrocycles. Control of the dimension of the macrocycles, by varying the size of the connecting metal centre, has also been demonstrated. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300598

SHORT COMMUNICATION
Design and Structural Analysis of Metallamacrocycles Based on a
Combination of Ethylene Glycol Bearing Pyridine Units with Zinc, Cobalt and
Mercury
[a]
[a]
[a]
[a]
´
Philippe Grosshans, Abdelaziz Jouaiti, Veronique Bulach, Jean-Marc Planeix,
Mir Wais Hosseini,*[a] and Nathalie Kyritsakas[b]
Keywords: Glycol / Pyridine / Zinc / Cobalt / Mercury / Metallamacrocycle
In the presence of MX2 salts, ligand 1 (in a M/L ratio of 2:2,
M = Zn, Hg, Co, X = Cl or I), based on the ethylene glycol
parallel packing of the cyclic structures generates channels
which are occupied by solvent molecules. The solvent
fragment bearing two pyridine units as monodentate coor- molecules, which behave as substrates, are positioned within
dination sites, leads to isostructural square-shaped neutral
metallamacrocycles as demonstrated by X-ray diffraction on
single crystals. For all dinuclear complexes generated, the
dicationic metal centre adopts a distorted tetrahedral coor-
dination geometry and its coordination sphere is composed
of the X2N2 set of coordinating atoms. For all complexes, the
the cavity of the metallamacrocycles. Control of the dimen-
sion of the macrocycles, by varying the size of the connecting
metal centre, has also been demonstrated.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
metal complexes and organic ligands. This has been pre-
viously demonstrated with metal halide complexes.[11,12] In-
Metallamacrocycles are finite entities composed of or- deed, in that case, the coordinating halide centres not only
ganic fragments and endocyclic metal centres.[1Ϫ11] These neutralise the cationic charge of the metal cation, but also,
species may be described as cyclic structures either resulting by occupying some of the coordination sites within the first
from the bridging of metal centres by organic ligands that coordination sphere around the metal, allow the disposition
possess at least two coordinating sites or from the intercon- of the remaining unoccupied sites to be controlled. This
nection of organic ligands by the metal centres. For the de- aspect has been demonstrated by us both in the case of
sign of metallamacrocycles, one must take into account the discrete metallamacrocycles[12] and for coordination
characteristics of the organic ligand (shape, rigidity, number networks.[13Ϫ20]
and disposition of the coordinating sites) as well as the ster-
Another important issue associated with the metallamac-
eochemical requirements of the metal centre (oxidation rocycles is the control of the nuclearity (i.e. the metal to
state, geometry, number and disposition of free coordi- ligand ratio). Indeed, depending on the nature of the bis-
nation sites).[3]
(monodentate) ligand (rigidity, positioning of the coordin-
The majority of metallamacrocycles reported to date are ating sites) and the metal cation used (number and dispo-
based on the combination of cis-protected cationic square- sition of coordination sites), different cyclic structures such
planar metal units such as diphosphane or ethylenediamine as [1.1] I, [2.2] II, [3.3] III, [4.4] IV etc. may be expected
complexes of PdII and PtII and often bis(pyridine) neutral (Figure 1).[3,21]
ligands.[2Ϫ4] For these cases, due to the neutral nature of the
Here, in the continuation of our investigations on the de-
ligands used, the metallamacrocycles formed are cationic sign of metallamacrocycles,[12,21Ϫ27] we describe the forma-
in nature and thus are associated with anions for charge tion of four new neutral metallamacrocycles based on the
neutrality purposes. In order to generate uncharged metal- use of the bis(monodentate) ligand 1 and neutral metal hal-
lamacrocycles, one may consider a combination of neutral ide complexes (MX2: M ϭ Zn, Hg, Co; X ϭ Cl or I).
[a]
´
Universite Louis Pasteur, Laboratoire de Chimie de
Coordination Organique, Institut Le Bel,
4, rue Blaise Pascal, 67000 Strasbourg, France
Fax: (internat.) ϩ 33-3-90241325
Results and Discussion
E-mail: hosseini@chimie.u-strasbg.fr
The design of ligand 1 (Scheme 1) is based on the ethyl-
ene glycol fragment 2 as a spacer connecting two mono-
dentate pyridine derivatives. The connection between the two
[b]
´
Universite Louis Pasteur, Service Commun des Rayons X,
Institut Le Bel,
4, rue Blaise Pascal, 67000 Strasbourg, France
Eur. J. Inorg. Chem. 2004, 453Ϫ458
DOI: 10.1002/ejic.200300598
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
453

M. W. Hosseini et al.
SHORT COMMUNICATION
For the generation of metallamacrocycles under self-as-
sembly processes, the choice of the coordinating het-
eroatoms and the cationic metal centre is crucial. Indeed,
the self-assembly phenomena requires reversible coordi-
nation bond formation. Since ligand 1 contains two pyri-
dine units as coordinating sites, zinc(), mercury() and co-
balt() halides have been chosen because the binding of
pyridine to these metals in the oxidation state  is reversible.
Thus, although many different species may be formed in
solution, the selection of a metallamacrocycle with a given
nuclearity may be achieved by the crystallisation process. In
the present investigation, zinc(), mercury() and cobalt()
halides were combined with ligand 1 under crystallisation
conditions leading exclusively to four new metallamacro-
cycles 4Ϫ7, which were characterised by elemental analysis
and X-ray diffraction on single crystals (Table 1). All four
metallamacrocycles were found to be insoluble in common
solvents such as CH2Cl2, CHCl3, MeOH, EtOH, THF,
CH3CN and dioxane and for that reason they could not be
characterised by NMR spectroscopy. The metallamacro-
cycles 4Ϫ7 were slightly soluble in DMF and readily soluble
in DMSO. However, the 1H NMR solution study in DMSO
revealed that the chemical shifts observed for all signals
were identical to those observed for the free ligand in the
same solvent, probably implying that the metallamacro-
cycles are degraded in DMSO.
Figure 1. Schematic representations of the formation of metalla-
macrocycles of different nuclearity between a bis-monodentate
fragment and a metal centre possessing two free coordination sites
Treatment of ligand 1 with ZnI2, produced slightly yel-
lowish single crystals upon slow diffusion of a solution of
ZnI2 in EtOH into a solution of 1 in CHCl3. The X-ray
diffraction study of 4 (Table 1) revealed that the crystal (tri-
¯
clinic, P1) is composed of one ZnI2 dinuclear [2.2] complex
4 (Type II; Figure 1) and one disordered CHCl3 solvent
molecule. The solvent molecule is located within the cavity
of the metallamacrocycle of the cyclophane (there are four
edges, each defined by one pyridine unit), which leads to an
inclusive complex in the crystalline phase (Figure 2).
The shape of the metallamacrocycle is a very slightly dis-
Scheme 1
˚
˚
torted square (8.65 A ϫ 8.72 A) with the two ZnI2 units
˚
occupying diagonal corners (Zn···Zn distance 12.25 A). For
units is achieved through an ester group at the 4-position ligand 1, the ethylene glycol fragment adopts a gauche con-
of the pyridine ring. Although the straight forward syn- formation with the OϪCϪCϪO dihedral angles of Ϫ80.2°
thesis of 1 has been reported,[28] we used our own method- and ϩ80.3°. The plane of the two ester groups (average
˚
ology consisting of the condensation of ethylene glycol 2 CϪO and CϭO distances are approximately 1.32 A and
˚
with 3 in dry THF and in the presence of Et3N (see Exp. 1.19 A, respectively; the OϪCϪO angle lies between 123.6°
Sect.).
and 125.0°) is slightly tilted with respect to the connected
Compound 1, which is of the bis(monodentate) type, may pyridine unit (CϪCϪCϪO dihedral angles of 2.3° and
either behave as a ligand and thus lead to metallamacro- 6.2°). The coordination sphere around the metal is com-
cyclic complexes or act as a tecton and generate coordi- posed of two IϪ anions and two N atoms belonging to two
nation networks in the presence of appropriate metal pyridine units of two different ligands (1) with average
centres.[29,30] We have previously demonstrated the latter ZnϪN and ZnϪI bond lengths of approximately 2.06 A
˚
˚
case using analogous oligoethylene glycol based tectons, and 2.54 A, respectively (Figure 2). The metal centre adopts
which lead to the formation of double-helical infinite net-
a
distorted tetrahedral coordination geometry with
works when combined with silver cations.[31,32] Ligand 1 has NϪZnϪN and IϪZnϪI angles of 102.8° and 121.0°,
also been used for the formation of 1D coordination net- respectively. The NϪZnϪI angle varies between 106.4° and
works in the presence of copper bromide.[33] The formation 107.4°. The slightly distorted square metallamacrocycles are
of coordination networks based on an analogous com- packed in a parallel fashion thus generating channels occu-
pound for which the ethylene glycol unit is replaced by an pied by solvent molecules. In one direction of space, the
ethylene diamine fragment has also been reported.[34]
metallamacrocycles probably interact through stacking be-
454
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org Eur. J. Inorg. Chem. 2004, 453Ϫ458

Design and Structural Analysis of Metallamacrocycles
Table 1. X-ray data for metallamacrocycles 4Ϫ7 formed between ligand 1 and metal halides
SHORT COMMUNICATION
4:1-ZnI2
5:1-ZnCl2
6:1-HgCl2
7:1-CoCl2
Chemical Formula
Molecular mass
Crystal system
Space group
C29H25Cl3I4N4O8Zn2
1302.23
C29H24Cl7N4O8Zn2
935.45
monoclinic
P21/c
9.6818(4)
18.9516(13)
10.2085(7)
90.00
98.198(5)
90.00
C15H13Cl4HgN2O4
627.68
monoclinic
P21/c
10.0469(2)
19.3318(4)
10.3355(2)
90.00
98.814(5)
90.00
C15H13Cl4CoN2O4
486.024
monoclinic
P21/c
10.030(2)
18.899(5)
10.112(2)
90.00
98.85(3)
90.00
1894.0(8)
1.70
triclinic
¯
P1
˚
a (A)
9.860(2)
10.042(3)
10.228(3)
81.30(2)
81.81(2)
86.97(2)
990.4(4)
2.184
˚
b (A)
˚
c (A)
α (°)
β (°)
γ (°)
3
˚
V (A )
1854.0(2)
1.676
1983.70(7)
2.10
Dcalcd. (gcmϪ3
)
Z
1
2
4
4
blue
Colour
colourless
0.37 ϫ 0.21 ϫ 0.08
4.580
colourless
0.40 ϫ 0.20 ϫ 0.15
1.850
colourless
0.20 ϫ 0.15 ϫ 0.06
8.320
Crystal size (mm)
0.15 ϫ 0.07 ϫ 0.01
1.494
173
µ(Mo-Kα) (mmϪ1
T (K)
)
173
173
173
Data collected
Obsd. data [I Ͼ 3σ(I)]
R1
5760
4916
0.039
0.129
5399
3785
0.050
0.113
10139
3570
0.029
0.046
34078
3341
0.043
0.156
wR2
GooF
CCDC No
1.116
216069
1.035
216070
1.008
216071
1.114
216073
Figure 2. Solid-state structure of the dinuclear zinc metallamacro-
cycle 4 obtained upon reacting ligand 1 with ZnI2; the cavity of the
square macrocycle is occupied by a disordered CHCl3 molecule
(top) and in one direction of space; the metallamacrocycles interact
through stacking between pyridine units (bottom); H atoms are not
represented for clarity; for bond lengths and angles see text
Figure 3. The solid-state structure of the dinuclear zinc metalla-
macrocycle 5 (top) obtained upon reacting ligand 1 with ZnCl2;
the square macrocycle forms an inclusive complex with a CHCl3
molecule (disordered) and the packing of consecutive units (bot-
tom); H atoms are not represented for clarity; for bond lengths and
angles see text
tween pyridine units disposed in an anti-parallel manner
(shortest distance between carbon atoms of two pyridines that is, gauche conformation of the ethylene glycol fragment
belonging to two consecutive metallamacrocycles is ca. (OϪCϪCϪO dihedral angles Ϫ77.2° and ϩ77.2°). The
˚
3.80 A).
plane of the two ester groups (average CϪO and CϭO dis-
˚
˚
As expected, when ZnI2 was replaced by ZnCl2 under the tances are ca. 1.32 A and 1.19 A, respectively; the OϪCϪO
same conditions, the X-ray diffraction study (Table 1) again angle lies between 124.6° and 125.2°) is again slightly tilted
revealed a similar metallamacrocycle 5 (Figure 3). The crys- with respect to the connected pyridine unit (CϪCϪCϪO
tal structure (monoclinic, P21/c) is again composed of one dihedral angles of Ϫ0.8° and ϩ10.2°). The coordination
ZnCl2 dinuclear complex 5 and one disordered CHCl3 sol- sphere around the metal centre is composed of two ClϪ
vent molecule. The latter, as mentioned above, is located anions and two N atoms belonging to two pyridine units of
within the cavity of the metallamacrocycle (Figure 3). The two different ligands (1) with ZnϪN and ZnϪCl average
metallamacrocycle adopts a similarly distorted square form bond lengths of approximately 2.05 A and 2.21 A, respec-
as above with almost identical dimensions (8.64 A ϫ 8.73 tively (Figure 2). The metal centre adopts a distorted tetra-
A, Zn···Zn distance is 12.36 A). Ligand 1 presents the same hedral coordination geometry with NϪZnϪN and
characteristics as those observed for the ZnI2 complex 4, ClϪZnϪCl angles of 101.6° and 121.5°, respectively. The
˚
˚
˚
˚
˚
Eur. J. Inorg. Chem. 2004, 453Ϫ458
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
455

M. W. Hosseini et al.
SHORT COMMUNICATION
NϪZnϪCl angle varies between 105.9° and 111.4°. Again, respectively. The NϪHgϪCl angle varies between 97.0° and
as for the previous case mentioned above, the square metal- 104.7°. As for the previous cases mentioned above, the
lamacrocycles are packed in a parallel fashion generating square metallamacrocycles are packed in a parallel fashion
channels. Also, in one direction of space, the metallamacro- with stacking interactions (shortest distance between car-
cycles probably interacts through stacking between pyridine bon atoms of two pyridines belonging to two consecutive
˚
units disposed in an anti-parallel fashion (shortest distance metallamacrocycles ca. 3.60 A) in one direction of space
between carbon atoms of two pyridines belonging to two between consecutive metallamacrocycles 6 (Figure 4).
˚
consecutive metallamacrocycles is ca. 3.67 A). Comparison
Finally, ligand 1 was allowed to react with CoCl2 under
of structures 4 and 5 shows that changing the steric demand crystallisation conditions. The slow diffusion of a solution
of the halogen atoms coordinated to the metal centre has of CoCl2·6H2O in EtOH into a solution of 1 in C2H2Cl4
almost no effect on the size of the metallamacrocycle.
afforded blue crystals (Table 1). The crystal structure
In order to increase the dimensions of the metallamacro- (monoclinic, P21/c) is composed of one CoCl2 dinuclear
cycle, that is, the size of the endocyclic cavity, it may be complex 7 and one tetrachloroethane solvent molecule.
possible to increase the size of the metal centre. For that Again the solvent molecule is located within the cavity of
reason, ligand 1 was treated with HgCl2. Upon slow dif- the metallamacrocycle 7 (Figure 5), which adopts a slightly
˚
fusion of a solution of HgCl2 in EtOH into a solution of 1 distorted square shape with similar dimensions (8.63 A ϫ
˚
˚
in C2H2Cl4, colourless crystals were obtained (Table 1). The 8.71 A, Co···Co distance is ca. 12.22 A) close to those ob-
crystal structure (monoclinic, P21/c) is composed of one served for the Zn complexes 4 and 5. Ligand 1 presents
neutral metallamacrocycle 6 and one tetrachloroethane sol- the same characteristics as those observed for the dinuclear
vent molecule. The solvent molecule is again located within metallamacrocycles 4Ϫ6 which were obtained with zinc and
the cavity of the metallamacrocycle 6 (Figure 4). The struc- mercury, that is, gauche conformation of the ethylene glycol
ture again adopts a slightly distorted square form with fragment (OϪCϪCϪO dihedral angles Ϫ77.8° and
˚
˚
larger dimensions, as expected (8.98 A ϫ 9.05 A, the ϩ77.9°). The plane of the two ester groups (average CϪO
˚
˚
˚
Hg···Hg distance is 13.29 A). Ligand 1 presents the same and CϭO distances are ca. 1.33 A and 1.19 A, respectively;
characteristics as those observed for the dinuclear metalla- OϪCϪO angles lie between 124.2° and 125.0°) is again
macrocycles 4 and 5 obtained with zinc, that is, gauche con- tilted with respect to the connected pyridine unit
formation of the ethylene glycol fragment (OϪCϪCϪO di- (CϪCϪCϪO dihedral angles of Ϫ1.5° and ϩ9.9°). Interest-
hedral angles Ϫ81.8° and ϩ81.8°). The plane of the two ingly, the coordination sphere around the Co2ϩ cation is
ester groups (average CϪO and CϭO distances are ca 1.33 only composed of two ClϪ anions and two N atoms belong-
A and 1.19 A, respectively, the OϪCϪO angle lies between ing to two pyridine units of two different ligands (1) with
123.6° and 123.8°) is again slightly tilted with respect to the CoϪN and CoϪCl average bond lengths of approximately
connected pyridine unit (CϪCϪCϪO dihedral angles of 2.04 A and 2.22 A, respectively. The metal centre adopts a
Ϫ1.2° and Ϫ8.9°). The coordination sphere around the distorted tetrahedral coordination geometry with
Hg2ϩ cation is composed of two ClϪ anions and two N NϪCoϪN and ClϪCoϪCl angles of 105.7° and 120.4°,
atoms belonging to two pyridine units of two different li- respectively. The NϪCoϪCl angle varies between 105.4°
gands (1) with HgϪN and HgϪCl average bond lengths of and 110.2°. This coordination geometry around CoII with
˚
˚
˚
˚
˚
˚
approximately 2.39 A and 2.36 A, respectively. The metal the (X2N2) set of coordinating centres differs from the pre-
centre adopts a distorted tetrahedral coordination geometry viously observed octahedral geometry with the same type
with NϪHgϪN and ClϪHgϪCl angles of 97.0° and 141.7°, of donor sites (pyridine and ClϪ).[13Ϫ18] Once again, as for
Figure 5. The solid-state structure of the dinuclear cobalt metalla-
Figure 4. The solid-state structure of the dinuclear mercury metal-
macrocycle 7 (top) obtained upon reacting ligand 1 with CoCl2;
lamacrocycle 6 (top) obtained upon reacting ligand 1 with HgCl2; the CoII centre adopts a distorted tetrahedral coordination ge-
the square macrocycle forms an inclusive complex with tetrachloro- ometry; the square macrocycle forms an inclusive complex with
ethane molecule; the packing of consecutive units generates chan- tetrachloroethane molecule; the packing of consecutive units gener-
nels (bottom); H atoms are not represented for clarity; for bond
lengths and angles see text
ates channels (bottom); H atoms are not represented for clarity; for
bond lengths and angles see text
456
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 453Ϫ458

Design and Structural Analysis of Metallamacrocycles
SHORT COMMUNICATION
C2H2Cl4 solution (1 mL) of 1 (5 mg) into a EtOH (2 mL) solution
of ZnI2, ZnCl2, HgCl2 or CoCl2·6H2O (1.5 mg); 4:
C14H12O4N2·ZnI2 (591.45): calcd. C 28.43, H 2.05, N 4.74; found
C 28.38, H 2.12, N 4.68; 5: C14H12N2O4·ZnCl2 (408.55): calcd. C
41.16, H 2.96, N 6.86; found C 41.33, H 3.08, N 6.90; 6:
C14H12N2O4·HgCl2 (543.76): calcd. C 30.92, H 2.22, N 5.15; found
C 30.89, H 2.32, N 5.46; 7: C14H12N2O4·CoCl2 (410.10): calcd. C
41.82, H 3.10, N 6.97; found C 41.88, H 3.06, N 6.99.
the previous cases mentioned above, the slightly distorted
square metallamacrocycles are packed in a parallel fashion
with stacking interactions (shortest distance between car-
bon atoms of two pyridines belonging to two consecutive
˚
metallamacrocycles is ca. 3.60 A) are in one direction of
space between consecutive metallamacrocycles of 7.
In summary, the rather simple ligand 1, composed of an
ethylene glycol unit bearing two pyridines as monodentate
coordination sites, leads in the presence of metal halides
(MX2: M ϭ Zn, Hg, Co; X ϭ Cl or I) in a M/L ratio of
2:2 to isostructural square-shape neutral metallamacro-
cycles. The metallamacrocyclic structures offer rather large
cavities of the cyclophane type which are occupied by sol-
vent molecules. In the crystal, the square-cyclic units are
packed in a parallel fashion, thus generating channels occu-
pied by solvent molecules. In one direction of space, the
metallamacrocycles probably interact with each other
through stacking of the pyridine units belonging to con-
secutive units and are disposed in an anti-parallel manner.
Since the solvent molecules included in the cavity of the
metallamacrocycles may play a template role and thus de-
fine the nuclearity of the complex, we are currently evaluat-
ing this aspect. The formation of other types of finite metal-
lamacrocycles using ligand 1, other metal centres and the
generation of infinite coordination networks are currently
under investigation. The ability of the analogous ligand for
which the pyridine units are connected at the 3-position to
generate metallamacrocycles and/or coordination networks
with a variety of metal complexes is also currently being in-
vestigated.
Crystal Structure Characterisation: X-ray diffraction data was car-
ried out on a Kappa CCD diffractometer equipped with an Oxford
Cryosystem liquid N2 device, with graphite-monochromated Mo-
Kα radiation (Table 1). In the case of 6, diffraction data were cor-
rected for absorption and analysed using the OpenMolen pack-
age,[35] whereas for the other three metallamacrocycles 4, 5 and 7,
NoniusϪMaxus Package 4.3 was used. All non-H atoms were re-
fined anisotropically. CCDC-216069 to -216071 and -216073 con-
tain the supplementary crystallographic data for this paper. These
data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html or from the Cambridge Crystallographic data Cen-
tre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: (internat.)
ϩ44-1223/336-033; E-mail: deposit@ccdc.cam.ac.uk.
Acknowledgments
´
Thanks to Universite Louis Pasteur and the Ministry of Research
and Technology for financial support and a scholarship to P. G.
[1]
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1
used without further purification. H and 13C NMR spectra were
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´ ´
´
de Microanalyses de la Federation de Recherche Chimie, Universite
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Synthesis of Ligand 1: A solution of 3 as its hydrochloride salt
(2.15 g, 12 mmol) in dry THF (30 mL) was added to ethylene glycol
2 (0.3 g, 4.8 mmol) under argon. The mixture was stirred before
Et3N (5 mL) was added and stirred at room temperature for a
further 12 hours. The brownish solution was evaporated to dryness
under reduced pressure. A saturated aqueous hydrogenocarbonate
solution (50 mL) was added to the residue and the mixture was
extracted with CH2Cl2 (3 ϫ 50 mL). The organic solvent was re-
moved and the residue purified by column chromatography (SiO2,
CH2Cl2-0-2 % MeOH) affording the pure compound 1 (0.66 g, 51
%) as a slightly yellowish oil. C14H12N2O4 (272.26): calcd. C 61.76,
H 4.44, N 10.29; found C 61.59, H 4.53, N 9.96. 1H NMR (CDCl3,
300 MHz, 25 °C): δ ϭ 4.71 (s, 4 H, CH2O), 7.84 (dd, 4 H, J ϭ 1.65
and 4.41 Hz), 8.79 (dd, J ϭ 1.6, 4.4 Hz, 4 H) ppm. 13C NMR
(CDCl3; 300 MHz; 25 °C): δ ϭ 63.2, 122.8, 136.7, 150.7, 164.9
ppm.
[8]
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