Synthesis and characterization of bis-and tris-(4-carboxybenzoyl)- alkaneamines

Article abstract of DOI:10.4067/S0717-97072012000300023

A practical and efficient protocol to obtain bis- and tris-(4- carboxybenzoyl)alkaneamines based on monoprotected 1,4-benzenedicarboxylic acid is reported here. N-(4-methoxycarbonylbenzoyloxy)succinimide was treated with aliphatic diamines and triamines to form aliphatic hydrocarbon-linked bis- and tris-amides 4a-4e. The yields ranged from good to very good and showed that choosing the right acylating agent is a key point in this synthesis. All the compounds were characterized by elemental analysis, FTIR, and 1H NMR.

Full text of DOI:10.4067/S0717-97072012000300023

J. Chil. Chem. Soc., 57, Nº 3 (2012)
SYNTHESIS AND CHARACTERIZATION OF BIS- AND TRIS-(4-CARBOXYBENZOYL)-ALKANEAMINES
L. GUARDA†, N. PARRA†, M. S. CHÁVEZ†, J. BELMAR†, C. A. JIMÉNEZ†*, J. PASÁN‡, C. RUIZ-PÉREZ‡
†Department of Organic Chemistry, Faculty of Chemical Sciences, University of Concepcion, Casilla 160-C, Concepción, Chile.
‡Laboratorio de Rayos X y Materiales Moleculares. Departamento de Física Fundamental II. Facultad de Física. Universidad de La Laguna. Avda. Astrofísico
Francisco Sánchez s/n, E-38204 La Laguna. Spain
(Received: April 19, 2012 - Accepted: June 25, 2012)
ABSTRACT
A practical and efficient protocol to obtain bis- and tris-(4-carboxybenzoyl)alkaneamines based on monoprotected 1,4-benzenedicarboxylic acid is reported
here. N-(4-methoxycarbonylbenzoyloxy)succinimide was treated with aliphatic diamines and triamines to form aliphatic hydrocarbon-linked bis- and tris-amides
4a–4e. The yields ranged from good to very good and showed that choosing the right acylating agent is a key point in this synthesis. All the compounds were
characterized by elemental analysis, FTIR, and 1H NMR.
Keywords: Acylating Agents, Ligands design, Amides.
RESULT AND DISCUSSION
INTRODUCTION
The Scheme 1 shows the synthetic route followed to the preparation of
the corresponding bis-amides. In the first place, the monomethyl ester of the
1,4-benzenedicarboxylic acid (1) is obtained in an almost quantitative yield
by an oxidation of methyl 4-formylbenzoate in acidic media, the temperature
must be carefully controlled to avoid the ester hydrolysis. The succinimide
ester 2 is also easily obtained and readily crystallized. Since 2 is a fairly stable
compound, it can be stored and used whenever needed. Then, the bis-amides
3a-e and 4a-e due to their high insolubility in water, can be easily purified by
successive washing. The physical characteristics and the analytical data that
confirm the compound structures are presented in the Experimental section.
Coordination compounds with infinite one-, two-, and three-dimensional
network structures have been intensively studied. Particularly compounds
with backbones constructed by metal ions as “nodes” and divergent polytopic
organic ligands as “linkers”, form a great family of polymers; which are called
“coordination polymers” (CPs).1 These kinds of materials have been studied
in ionic exchange,2 separation,3 chemisorption,4 gas storage,5 catalysis,6
magnetism,7 optoelectronic8 and luminescence.9 In the design and construction
of CPs the size, shape and functionalities in the connectors have become an
extremely important factor, because of the particular properties that they
give to the final material.10 The connectors in CPs can be separated in two
big families, rigid and flexible ligands. Compared with the rigid ligand, using
flexible ones to construct CPs is more difficult and developing systematic
methodologies to synthesize from prior designed structure for these systems is
still a great challenge. The most important advantage in final structures based
on flexible ligands is the sensitivity to many subtle factors. Flexible ligands can
adopt different conformations as a consequence of free rotations about their
single bonds, giving raise to low symmetry structures.11 On the other hand,
the “breathing” ability and adaptative recognitions properties can be achieved
using the flexibility as a feature in the design of new connectors.12 Developing
of CPs based on flexible ligands is a good opportunity to get a better insight
into the details of a self-assembly process and it is a way for raising some
signposts toward future research on predicted and pre-designed CPs.
The infrared spectra for 4a-e show a broad absorption from 3000 to 2500
cm-1 characteristic for acid OH stretching. A sharp absorption band close to
3300 cm-1 for NH stretching. Two C=O absorption are shown for 3a-e, one of
them is shifted to lower wavenumber for 4a-e, that account for the ester-acid
1
transformation. The H NMR spectra show two important low field signals,
the first, between 14 and 13 ppm for OH (2H), the second, below 9 ppm for
NH (2H).
Polytopic linkers such as carboxylate have allowed the synthesis of rigid
structures which do not collapse easily and can exhibit permanent porosity. In
addition, they are neutral networks that prevent counterion inclusion in CPs.13
On the other hand, the amide group has been described to be an important
synthon, both in organic crystals14 and coordination polymers.15 Although
the amide groups can also act like binding sites,16 their affinities towards the
metallic centers are much lower. In the synthesis of coordination polymers and
organic crystals, the amide groups have been involved in increasing the stability
through hydrogen bond interactions, being this, the most important contribution
to the supramolecular structures.17 In spite of the restricted rotation around C-N
amide bond, there is some flexibility associated to it. This restricted rotation
feature allows to be defined as a “weak point” (non-rigid area), important in
the solid to allow the breathing modes.18 The rational synthetic design of a
connector that integrates these important features should be kept in mind in the
process of developing new coordination polymers.
Our goal is to obtain ligands that combine these characteristics.
N-hydroxysuccinimide esters have been used to obtain bis- and tris-amides.
We described the synthesis of N,N – disubstituted - 3,5 – di – tert – butyl –
2 – hydroxyl - benzamides using the corresponding ester, some years ago.19
This procedure has resulted to be the best choice to synthesize amides, even
better than the obvious method using the chloride derivative of the acid and the
corresponding diamine. These esters are acylating agents which can be used
under very mild conditions, usually providing good yields. To our knowledge,
bis- and tris-(4-carboxybenzoyl)alkaneamines have never been described by
other authors before.
Scheme 1. (a) KMnO , H2SO , H2O, 10°C, 2 h (b) N-Hydroxysuccinimide,
DCC, 10°C, dioxane, 24 h4, r.t. (c)4di- or triamine, Et3N, DMF, DMPA, 12 h, r.t.
(d) KOH, MeOH/H2O, 3 h, reflux.
The NH signal is broad, but it is possible to observe the multiplicity
associated with the coupling with methylene of the alkyl chain. Signals
corresponding to the aromatic hydrogens can be identified without any doubt,
because they constitute an AA’BB’ spin system that gives rise to a doublet of
doublets centered close to 8.00 ppm in all cases (Figure 1).
The high field signals are characteristics to each compound depending on
the nature of the aliphatic chain. In the case of 4a (Figure 1), it is possible to
observe one signal that integrates by four hydrogens and presents a diffuse
multiplicity associated to NH to 8.79 ppm. The melting points, as expected for
amides, are high.
e-mail: cjimenez@udec.cl
1305

J. Chil. Chem. Soc., 57, Nº 3 (2012)
Figure 1. Selected areas of 1H-NMR of compounds 4a.
In order to examine the molecular structure of these connectors, as well as
the organization in the solid state, attempts to obtain single crystals were carried
out. By slow evaporation of dimethylsulphoxide solution, crystals suitable for
X-ray diffraction were obtained for 4a and 4e. Pertinent crystallographic details
were given in the Table 1. The crystal structures of 4a and 4e are different and
because of this they will be described separately. The asymmetric unit for 4a
contains half of the molecule, since it sits on an inversion center and the alkyl
chains exhibit a staggered conformation (Figure 2a). The molecules of 4a are
engaged in amide-to-amide hydrogen bonds (N-H•••O) which propagate in
the form of a b-sheet network along the a axis. Alongside, the benzoic acid
groups are linked via a double O-H•••O hydrogen bond in the classic synthon
for carboxylic acids along the [02-1] direction to build a supramolecular two-
dimensional network. (Figure 2b). The relevant parameters of the hydrogen
bonds discussed in the text are given in Table 2.
Figure 3. a) View of pseudo-calix conformation for 4e. Intermolecular
hydrogen bonds are drawn as grey broken lines. b) Perspective view of
hydrogen bonded 4e interactions. H atoms not involved in hydrogen bond and
O2W interactions have been omitted for clarity.
Table 1. Crystallographic data for 4a and 4e.
4a
4e
C36H32N6O16
626.61
Monoclinic
P21/c
Formula
F.W.
C18H16N2O6
356.33
Crystal System
Space group
a (Å)
Triclinic
P-1
4.9952(10)
5.0381(12)
16.148(3)
98.371(3)
96.288(4)
90.592(3)
399.49(15)
1
11.3070(8)
13.8360(11)
18.9020(17)
-
b (Å)
Figure 2. a) View of 4a molecule with numering scheme, b) Packing
diagram showing the b-sheet network and dimeric synthon for carboxylic acid.
H atoms not involved in hydrogen bond have been omitted.
c (Å)
a (deg)
The asymmetric unit in 4e contains three molecules, one tris-amide
molecule and two crystallization water molecules. The tris-amide is found in
its zwitterion form, with the amine nitrogen protonated and one carboxylate
arm deprotonated. Although the three amidobenzoic groups are free to rotate
in solution; remarkably, in the solid state they are bent to the same direction
to give the molecule a pseudo-calix form (Figure 3a). This calix conformation
is supported by intramolecular N-H•••O interaction (Table 2). Each molecule
is connected to two adjacent tris-amide molecules through O-H•••O hydrogen
bonds. The carboxylic moieties act as single hydrogen bond donors, but the
carboxylate moiety acts as a double acceptor of hydrogen bond (Figure 3b).
Additionally, each unit is further linked through p•••p interaction and hydrogen
bond involving the water molecules.
b (deg)
101.582(7)
-
g (deg)
V (Å3)
2896.9(4)
4
Z
m (mm-1)
rcal (g cm-3)
R1 (I>2s(I))
wR2 (on F2 all data)
0.113
0.111
1.481
1.437
0.1118
0.0596
0.1275
0.3752
1306

J. Chil. Chem. Soc., 57, Nº 3 (2012)
was DMSO-d6, except when otherwise stated. Melting points were obtained on
a Kofler microscope and are uncorrected. Elemental analyses were obtained in
a FISON EA 1108 Analyzer. Chemical shifts for NMR spectra (d) are quoted in
ppm. Infrared values (n) are quoted in reciprocal centimeters (cm-1).
Table 2. Relevant Hydrogen Bond Parameters in 4a/4e.
Comp.
4a
typea
H•••A (Å)
2.08(4)
1.63(4)
1.89(2)
2.06(2)
2.37(3)
2.57(3)
1.60(3)
1.60(3)
1.82(3)
1.90(3)
2.07(2)
D•••A (Å)
2.873(7)
2.614(7)
2.751(2)
2.860(3)
3.094(3)
3.242(3)
2.555(2)
2.581(3)
2.799(3)
2.777(4)
3.067(4)
D-H•••A (°)
152(1)
173(3)
157(1)
154(1)
141(1)
136(1)
172(3)
169(3)
170(2)
144(3)
170(2)
N(1)-H•••O(3a)
O(1)-H•••O(2b)
N(1)-H•••O(4)
N(3)-H•••O(1wc)
N(4)-H•••O(4)
N(4)-H•••O(1)
O(5)-H•••O(3d)
O(9)-H•••O(2e)
O(1w)-H•••O(7)
O(1w)-H•••O(2wf)
O(2w)-H•••O(3)
Synthesis of Bis- and Tris-(4-carboxybenzoyl)alkaneamines.
Synthesis of 4-(methoxycarbonyl)benzoic acid. (1)
4e
In a 500 ml three-necked round-bottomed flask methyl 4-formylbenzoate
(15.0 g, 0.091mol) were suspended in 150 ml of water and 10 ml of concentrated
H2SO4. The mixture was cooled to 10°C and KMnO4 (10.3 g, 0.065mol) was
slowly added. The reaction mixture was stirred for 2 h at the same temperature.
Then NaHSO3(s) was added until the MnO2 was fully reduced. The white
solid resulting was filtered and recrystallized from ethanol. Yield: 61%; M.
P: 222-224°C. Anal. Elem. C9H8O4: Calcd. C, 60.0; H, 4.5. Found. C, 59.8;
1
H, 4.6. H-NMR: 8.82 (s, 1H, OH), 8.03 (d, 2H, Har, J= 8.3Hz), 7.96 (d, 2H,
Har J=8.4Hz), 3.87 (s, 3H, OCH3). FTIR: 3300-2500(OH), 2959(Csp2-H),
2816(Csp3-H), 1700(C=O ester), 1689(C=O acid.), 1570(C=C).
Synthesis of N-(4-methoxycarbonylbenzoyloxy)succinimide. (2)
4-(Methoxycarbonyl)benzoic acid (1) (5.3 g, 0.029 mol) and
N-hydroxysuccinimide (3.7 g, 0.032 mol) were dissolved in 100 ml of dry
dioxane. The solution was cooled to 10°C and dicyclohexylcarbodiimide (5.7
g, 0.028 mol) dissolved in 80 ml of the same solvent, was slowly dropped.
The reaction mixture was stirred for 24 h at room temperature. The urea was
separated by filtration and the filtrate evaporated to dryness. The white solid
was recrystallized from ethanol. Yield: 62%, M.P.: 175-177ºC. Anal. Elem.
Symmetry operators: (a) = x-1, y, z; (b) = -x, -y-1, -z+1; (c) = x, -y+½, z+½;
(d) = -x+2, -y, -z+1; (e) = -x+2, y+½, -z+½; (f) = x-1, -y+½, z-½.
CONCLUSIONS
1
C H11NO6: Calcd. C, 56.3; H, 4.0; N, 5.1. Found. C, 56.2; H, 3.8; N, 5.2. H
N1M3 R: 8.24 (d, 2H, Har J=7.2Hz), 8.21 (d, 2H, Har J=8.4), 3.93 (s, 3H, OCH3),
2.92 (s, 4H). FTIR: 1780(C=O), 1734(C=O).
We have described a convenient procedure to obtain di- and tricarboxilic
linkers. According to our experience, the coupling reaction using
N-hydroxysuccinimide ester remains as the most efficient procedure to carry
out the synthesis of bis- and tris-amides in good yields (65%).
The new ligands herein reported combine: (a) carboxylate coordination
moieties, (b) carboxamide thermal stable groups, and (c) aliphatic flexible
chains. These features are attractive to be incorporated in the construction of
coordination polymers.
Synthesis of N,N`-bis-(4-methoxycarbonylbenzoyl) alkaneamines (3a-e).
General Procedure.
To a solution of N-(4-methoxycarbonylbenzoyloxy) succinimide (2) (1.0
g, 3.61 mmol) and the corresponding diamine or triamine (1.81 or 1.2 mmol) in
15 ml of DMF, 5 ml of Et N and a catalytic amount of DMPA were added. The
reaction mixture was stirr3ed for 12 h at room temperature and then poured into
ice/10% HCl. The solid was filtered and washed with water and then diethyl
ether.
The crystal structures have been determined in two cases, showing the
remarkably calix conformation of 4e. More research is currently carried out to
obtain new crystalline coordination polymers.
N,N`-bis-(4-methoxycarbonylbenzoyl)-1,2-ethanediamine. (3a). Yield:
93%. M.P.: 309ºC. Anal. Elem. C20H20N2O6: Calcd. C, 62.5; H, 5.2; N, 7.3.
Found. C, 62.1; H, 4.8; N, 7.2. H NMR: 8.83 (s, 2H, NH), 8.03 (d, 4H, Har
J=6.0Hz), 7.97 (d, 4H, Har, J=6.0Hz), 3.87 (s, 6H, OCH ), 3.47 (s, 4H). FTIR:
3298(NH), 3076(Csp2-H), 2953(Csp3-H), 1723(C=O este3r), 1637(C=O amide),
1548 (C=C).
EXPERIMENTAL
1
Crystal Structure Determination
The crystallographic data collection of 4a was carried out in the BM16
beamline of the ESRF (Grenoble, France) with l = 0.7385 Å at 100(2) K with a
CCD detector (ADSCq210r) making phi (j) scans of one degree per frame. Two
orientations of the crystal were measured in order to achieve the desired data
completeness. Data were indexed, integrated and scaled using the HKL2000
program.20 The X-ray data collection of 4e was performed on a Bruker-Nonius
KappaCCD diffractometer using graphite-monochromated Mo Ka radiation
(l = 0.71073 Å) at 293(2) K. Orientation matrix and lattice parameters were
obtained by least-squares refinement of the reflections obtained by q-c scan
(Dirax/lsq method). Data collection and data reduction were carried out with
the COLLECT21 y EVALCCD22 programs. The indexes of data collection were
-6 ≤ h ≤ 6, -6 ≤ k ≤ 6 and -20 ≤ l ≤ 20 for 4a, and -14 ≤ h ≤ 14, -16 ≤ k ≤ 17
and -24 ≤ l ≤ 19 for 4e. Of the 1660 (4a) and 6048 (4e) measured independent
reflections 1583 (4a), and 1889 (4e) have I ≥ 2s(I). The structures were solved
by direct methods and refined with full-matrix least-squares technique on F2
using the SHELXS-97 and SHELXL-97 programs.23 All non-hydrogen atoms
were refined anisotropically. The hydrogen atoms were set on geometrical
positions except those of the carboxylic groups and the water molecules.
All of them were refined with a riding model except those of the carboxylic
groups. The final Fourier-difference maps showed maximum and minimum
height peaks of 0.524 and -0.480 eÅ-3 (4a), and, 0.217 and -0.206 eÅ-3 (4e). The
final geometrical calculations and the graphical manipulation were carried out
with PARST9724 and DIAMOND25 and MERCURY26 programs, respectively.
Crystallographic data (excluding structure factors) for the compounds 4a and
4e have been deposited at the Cambridge Crystallographic Data Centre with
CCDC reference numbers 876558 (4a) and 876559 (4e).
N,N`-bis-(4-methoxycarbonylbenzoyl)-1,3-propanediamine. (3b).Yield:
87%. M.P.: >330°C. Anal. Elem. C21H22N2O6: Calcd. C, 63.3; H, 5.6; N, 7.0.
Found. C, 63.2; H, 5.2; N, 6.9. 1H NMR: 9.04 (t, 2H, NH, J=8.0Hz), 7.96 (d,
4H, Har, J=13.2Hz), 7.88 (d, 4H, Har, J=13.6 Hz), 3.88 (s, 6H, OCH3), 3.74 (c,
4H), 3.55 (q, 2H). FTIR: 3302(NH), 3072(Csp2-H), 2958(Csp3-H), 1723(C=O
ester), 1637(C=O amide), 1544(C=C).
N,N`-bis-(4-methoxycarbonylbenzoyl)-1,4-butanediamine. (3c). Yield:
99%. M.P.: >330ºC. Anal. Elem. C22H24N2O6: Calcd. C, 64.1; H, 5.9; N, 6.8.
1
Found. C, 63.9; H, 5.6; N, 6.8. H NMR: 8.24 (d, 4H, Har, J=8.3Hz), 8.19
(d, 4H, Har, J=8.3Hz), 8.06(s, 2H, NH), 3.92 (s, 6H, OCH3), 3.08 (m, 4H),
1.18 (t, 4H). FTIR: 3300(NH), 3020(Csp2-H), 2950(Csp3-H), 1721(C=O ester),
1630(C=O amide), 1538(C=C).
N,N’,N’’-tris-(4-methoxycarbonylbenzoyl)-1, 1, 1-tris-(amino methyl)
ethane (3d). Yield: 51%. M.P.: 223-225ºC. Anal. Elem. C32H33N3O9: Calcd. C,
63.7; H, 5.5; N, 7.0. Found. C, 63.4; H, 5.4; N, 6.8. 1H NMR: 8.82 (t, 3H, NH),
8.11-8.00 (d,d, 12H, Harom), 3.89 (s, 9H, OCH3), 3.29 (d, 6H, CH ), 0.91 (s,
3H, CH3). FTIR: 3321(NH), 1724(C=O ester), 1648(C=O amide), 12538(C=C).
N,N’,N’’-tris-(4-methoxycarbonylbenzoyl)-tris-(2-amino ethyl) amine
(3e). Yield: 89 %. M.P.: 239-241ºC. Anal. Elem. C33H36N4O9: Calcd. C, 62.6;
H, 5.7; N, 8.9. Found. C, 62.5; H, 5.5; N, 8.6. 1H NMR: 9.07 (s, 3H, NH), 7.95
(d, 6H, Har, J= 8.0Hz), 7.91 (d, 6H, Har, J=8.0Hz), 3.88 (s, 9H, OCH ), 3.73 (m,
6H), 3.54 (m, 6H). FTIR: 3248 (NH), 2956 (Csp3-H), 1723(C=O e3ster), 1670
(C=O amide), 1641 (C=C).
Synthetic Characterizations
All chemicals were obtained from commercial sources. Compounds
were characterized by FTIR (Nicolet, Magna 550) KBr discs and H NMR
1
(BrukerBioSpinGmbH 400 MHz) using TMS as internal standard. The solvent
1307

J. Chil. Chem. Soc., 57, Nº 3 (2012)
Hydrolysis Procedure. Bis- and Tris-amides (4a-e).
R. Heddy, J. Li., Angew. Chem. Int. Ed., 45, 616, (2006).
To a solution of 3a-e (1.3 mmol) in 20 ml of methanol/water 2:1 mixture,
KOH (0.29 g, 5.1 mmol) was added. The resulting mixture was refluxed with
stirring during 3 h and then poured into 250 ml of an ice-10% HCl mixture,
stirred and filtered. The white solid was filtered and washed with water and
diethyl ether.
4
5
O. M. Yaghi, H. Li, T. L. Groy, J. Am. Chem. Soc., 118, 9096, (1996).
(a) S.-I. Noro, S. Kitagawa, M. Kondo, K. Seki, Angew. Chem., Int.
Ed., 39, 2082, (2000). (b) M. Kondo, T. Okubo, A. Asami, S.-I. Noro,
T. Yoshitomi, S. Kitagawa, T. Ishii, H. Matsuzaka, K. Seki, Angew.
Chem., Int. Ed., 38, 140, (1999). (c) M. Kondo, T. Yoshitomi, K. Seki, H.
Matsuzaka, S. Kitagawa, Angew. Chem., Int. Ed. Engl., 36, 1725, (1997).
a) L. Pan, H. Liu, X. Lei, X. Huang, D. H. Olson, N. J. Turro, J. Li,
Angew. Chem., Int. Ed., 42, 542, (2003). (b) M. Fujita, Y. J. Kwon, S.
Washizu, K. Ogura, J. Am. Chem. Soc., 116, 1151, (1994).
(a) G. H. Halder, C. J. Kepert, B. Moubaraki, K. S. Murray, J. D. Cashion,
Science, 298, 1762, (2002). (b) S. Sain, T. K. Maji, G. Mostafa, T.-H. Lu,
N. Ray Chaudhuri, New. J. Chem., 27, 185, (2003). (c) M.-H. Zeng, W.-X.
Zhang, X.-Z. Sun, X.-M. Chen, Angew. Chem., Int. Ed., 44, 3079, (2005).
(d) T. K. Maji, S. Sain, G. Mostafa, T.-H. Lu, J. Ribas, M. Monfort, N.
Ray Chaudhuri, Inorg. Chem., 42, 709, (2003).
(a) W. Lin, Z. Wang, L. Ma, J. Am. Chem. Soc., 121, 11249, (1999). (b)
O. R. Evans, R. Xiong, Z. Wang, G. K. Wong, W. Lin, Angew. Chem., Int.
Ed., 38, 536, (1999).
(a) J. Tao, X. Yin, Z.-B. Wei, R.-B. Huang, L.-S. Zheng, Eur. J. Inorg.
Chem., 125, (2004). (b) J. Luo, M. Hong, R. Wang, R. Cao, L. Han, Z.
Lin, Eur. J. Inorg. Chem., 2705, (2003). (c) H.-K. Fun, S. S. Sundara Raj,
R.-G. Xiong, J.-L. Zuo, Z. Yu, X.-Z. You, J. Chem. Soc., Dalton Trans.,
1915, (1999).
N,N`-bis-(4-carboxybenzoyl)-1,2-ethanediamine. (4a). Yield: 98%. M.P.:
>330ºC. Anal. Elem. C18H16N2O6: Calcd. C, 60.7; H, 4.5; N; 7.9. Found. C,
6
7
1
60.2; H, 4.5; N; 7.9. H NMR: 13.19 (s, 1H, OH), 8.78 (t, 2H, NH), 8.01 (d,
4H, Har, J=6.8Hz), 7.94 (d, 4H, Har, J=6.8Hz), 3.46 (d, 4H). FTIR: 3303(NH),
3300-2500(OH acid), 3066(Csp2-H), 2931(Csp3-H), 2668 and 2554(Fermi),
1694(C=O acid), 1637(C=O amide), 1540(C=C).
N,N`-bis-(4-carboxybenzoyl)-1,3-propanediamine. (4b). Yield: 98%.
M.P.: >330ºC. Anal. Elem. C19H18N2O6: Calcd. C, 61.6; H, 4.9; N; 7.6. Found.
C, 59.9; H, 4.7; N; 7.5. 1H NMR: 8.65 (t, 2H, NH), 8.01 (d, 4H, H , J=4.4Hz),
7.99 (d, 4H, Har, J= 4.4 Hz), 3.34 (m, 4H), 1.81 (q, 2H), 1.58 (m, a2r H). FTIR:
3307(NH), 3300-2500(OH acid), 2950(Csp2-H), 2864(Csp3-H), 2672 and 2557
(Fermi), 1696(C=O acid), 1635(C=O amide), 1534 (C=C).
8
9
N,N`-bis-(4-carboxybenzoyl)-1,4-butanediamine. (4c). Yield: 99%. M.P.:
>330ºC. Anal. Elem. C20H20N2O6: Calcd. C, 62.5; H, 5.2; N, 7.3. Found. C,
1
61.6; H, 5.1; N, 7.3. H NMR: 8.62 (t, 2H, NH), 8.00 (d, 4H, Har, J=8.4Hz),
7.93 (d, 4H, H , J=8.4 Hz), 3.32 (m, 4H), 1.59 (s, 4H). FTIR: 3329(NH),
3300-2500(OH aracid), 2946(Csp2-H), 2871(Csp3-H), 2661 and 2541 (Fermi),
1681(C=O acid), 1638 (C=O amide), 1531 (C=C).
10 J.-P. Zhang, Y.-B., Zhang, J.-B. Lin, X.-M. Chen Chem. Rev. 112, 1001,
(2012)
11 T. Liu, J. Lü, R. Cao, CrystEngComm 12, 660 (2010).
12 S. Kitagawa, K. Uemura, Chem. Soc. Rev. 34, 109 (2005).
13 M. Eddaoudi, D. B. Moler, H. Li, B. Chen, T. M. Reineke, M. O’keeffe,
O. M. Yaghi, Acc. Chem. Res., 34, 319, (2001)
14 (a) L. Rajput, S. Singha, K. Biradha, Cryst. Growth & Des., 7, 2788,
(2007). (b) M. Sarkar, K. Biradha, Cryst. Growth & Des., 6, 202, (2006).
15 (a) L. Rajput, K. Biradha, Polyhedron, 27, 1248, (2008). (b) D. K. Kumar,
Inorg. Chim. Acta, 362, 1767, (2009).
N,N’,N’’-tris-(4-carboxybenzoyl)-1, 1, 1-tris-(aminomethyl) ethane (4d).
Yield: 76%. M.P.: 313-315ºC. Anal. Elem. C29H27N3O9: Calcd. C, 62.0; H, 4.8;
N, 7.5. Found. C, 60.9; H, 4.6; N, 7.5. 1H NMR: 8.80 (t, 3H, NH), 8.17 (d, 6H,
Har), 8.10 (d, 4H, Har), 3.40 (d, 6H, CH2), 2.60 (broad signal, 3H, OH), 1.01 (s,
3H, CH3). FTIR: 3286(NH), 3300-2500(OH acid), 3173(Csp2-H), 1712(C=O
acid), 1640(C=O amide), 1540(C=C).
N,N’,N’’-tris-(4-carboxybenzoyl)-tris-(2-amino ethyl) amine (3e). Yield:
93%. M.P.: >330ºC. Anal. Elem. C30H30N4O9: Calcd. C, 61.0; H, 5.1; N, 9.5.
Found. C, 60.7; H, 5.0; N, 9.4. H NMR: 13.14 (s, 2H, OH), 8.56 (s, 3H,
NH), 7.94 (d, 6H, Har, J=8.0Hz), 7.87 (d, 6H, Har, J=8.4Hz), 3.32 (s, 6H), 2.77
(s, 6H). FTIR: 3356(NH), 3300-2500(OH acid), 3057(Csp2-H), 2623(Fermi),
1715(C=O acid), 1646(C=O amide), 1541 (C=C).
16 (a) T. J. Collins, R. D. Powell, C. Slebodnick, E. S. Uffelman, J. Am.
Chem. Soc., 112, 899, (1990). (b) A. K. Patra, R. Mukherjee, Inorg. Chem.,
38, 1388, (1999). (c) J. M. Rowland, M. Olmstead, P. K. Mascharak,
Inorg. Chem., 40, 2810, (2001). (d) T. C. Harrop, M. M. Olmstead, P. K.
Mascharak, Inorg. Chim. Acta, 338, 189, (2002).
17 (a) B.-C. Tzeng, H.-T. Yeh, Y.-L. Wu, J.-H. Kuo, G.-H. Lee, S.-M. Peng,
Inorg. Chem., 45, 591, (2006). (b) C. A. Jiménez, J. B. Belmar, F. S.
Delgado, M. Julve, C. Ruiz-Pérez, CrystEngComm, 9, 746, (2007).
18 G. Férey, C. Serre, Chem. Soc. Rev., 38, 1380, (2009).
19 C. A. Jiménez, J. B. Belmar, Tetrahedron, 61, 3938, (2005).
20 Z. Otwinowski, M. Minor. Macromolecular Crystallography, A, Methods
in Enzymology. Academic Press, New York. 276, 307-326 (1997).
21 R. W. W. Hooft, COLLECT. Nonius BV, Delft, (1999).
22 A. J. M. Duisenberg, L. M. J. Kroon-Batenburg, A. M. M. Schreurs, J.
Appl. Crystallogr., 36, 220, (2003) (EVALCCD).
1
ACKNOWLEDGMENTS
Financial support was provided by the Chilean National Research
Council, Fondecyt (Grant 11080179). An International cooperative
funding, PCIA/02644/09.MAE-AECI, MAT2010-16981 and “Factoría de
Cristalización” Consolider-Ingenio2010 CSD2006-00015.
REFERENCES AND NOTES
23 G. M. Sheldrick, SHELX97, Programs for Crystal Structure Analysis
(Release 97-2), Institut fur Anorganische Chemie der Universitat:
Gottingen, Germany, (1998).
24 M. Nardelli, J. Appl. Crystallogr., 28, 659, (1995).
25 DIAMOND 2.1d, Crystal Impact GbR, CRYSTAL IMPACT, K,
Brandenburg & H. Putz GbR, Bonn, Germany, (2000).
26 Mercury: visualization and analysis of crystal structures C. F. Macrae,
P. R. Edgington, P. McCabe, E. Pidcock, G. P. Shields, R. Taylor, M.
Towler, J. van de Streek, J. Appl. Crystallogr., 453, 39, (2006).
1
(a) G. R. Desiraju, Angew. Chem. Int. Ed. 34, 2311,(1995). (b) J.-M.
Lehn, Supramolecular Chemistry; VCH: Weinheim, (1995). (c) J.
Bernstein, R. E. Davis, L. Shimoni, N.-L. Chang, Angew. Chem., Int
Ed. 34, 1555, (1995). (d) M. W. Hosseini, A. DeCian, Chem. Commun.
727, (1998). (e) B. Kesanli, Y. Cui, M. R. Smith, E. W. Bitner, B. C.
Bockrath, W. Lin, Angew. Chem. Int. Ed. 44, 72, (2005). (f) N. L. Rosi,
M. Eddaoudi, J. Kim, M. O’Keeffe, O. M. Yaghi, Angew. Chem. 114,
294, (2002). (g) F. S. Delgado, J. Sanchiz, C. Ruiz-Pérez, F. Lloret, M.
Julve, Inorg. Chem. 42, 2938, (2003). (h) B. Chen, W. O. Ockwig, A. R.
Millward, D. S. Vontreras, O. M. Yaghi, Angew. Chem. Int. Ed. 44, 4745,
(2005). (i) D. Li, T. Wu, X. Zhou, R. Zhou, X. Huang, Angew. Chem. Int.
Ed. 44, 4175, (2005). (j) K. Biradha, C. Seward, M. J. Zaworotko, Angew.
Chem. Int. Ed., 38, 492, (1999). (k) K. Biradha, A. Mondal, B. Moulton,
M. J. Zaworotko, J. Chem. Soc., Dalton Trans., 3837, (2000).
2
3
(a) L. Pan, E. B. Woodlock, X. Wang, K.-C. Lam, A. L. Rheingold,
Chem. Commun., 1762, (2001). (b) K. S. Min, M. P. Suh, J. Am. Chem.
Soc., 122, 6834, (2000).
(a) D. N. Dybtsev, H. Chun, S. H. Yoon, D. Kim, K. Kim, J. Am. Chem.
Soc., 126, 32, (2004). (b) S. M. Kuznicki, V. A. Bell, S. Nair, H. W.
Hillhouse, R. M. Jacubinas, C. M. Braunbarth, B. H. Toby, M. Tsapatsis,
Nature, 412, 720, (2001). (c) L. Pan, D. H. Olson, L. R. Ciemnolonsky,
1308