ZnII complexes based on hybrid N-pyrazole, N′-imine ligands: Synthesis, X-ray crystal structure, NMR characterisation, and 3D supramolecular properties

Article abstract of DOI:10.1071/CH14344

The present report is on the synthesis of two new 3-imine-3,5-dimethylpyrazole ligands, N-[3-(3,5-dimethyl-1H-pyrazol-1-yl)propylidene]ethylamine (L1) and N-[3-(3,5-dimethyl-1H-pyrazol-1-yl)propylidene]propylamine (L2). These ligands form molecular complexes with the formula [ZnCl₂(L)] (L≤L1 (1) and L2 (2)) when the reacting with ZnCl₂ in a metal (M)/ligand (L) ratio of 1:1. These new Zn^II complexes have been characterised by elemental analyses, conductivity measurements, mass spectrometry, and infrared, ¹H and ¹³C{¹H} NMR spectroscopy techniques. The two crystalline structures of complexes 1 and 2 have been solved by X-ray diffraction methods. Finally, we have studied the self-assembly three-dimensional supramolecular structure through different intra- and intermolecular contacts. The application of these Zn^II complexes in supramolecular crystal engineering is interesting due to (1) the easy preparation and the high efficiency of this system and (2) the different bonding properties of the heteroatoms (N-pyrazole vs N-imine) present in the structure of the ligands.

Full text of DOI:10.1071/CH14344

CSIRO PUBLISHING
Aust. J. Chem. 2015, 68, 749–757
Full Paper
http://dx.doi.org/10.1071/CH14344
II
Zn Complexes Based on Hybrid N-Pyrazole, N9-imine
Ligands: Synthesis, X-Ray Crystal Structure, NMR
Characterisation, and 3D Supramolecular Properties
A
A
B
Miguel Guerrero, Lourdes Rivas, Teresa Calvet,
B
,
C
,
A D
Merc e` Font-Bardia,
and Josefina Pons
A
Departament de Qu ´ı mica, Universitat Aut o` noma de Barcelona, 08193-Bellaterra,
Barcelona, Spain.
B
Cristallografia, Mineralogia i Dip o` sits Minerals, Universitat de Barcelona, Mart ´ı i
Franqu e` s s/n, 08028-Barcelona, Spain.
C
Unitat de Difracci o´ de Raig-X, Centres Cient ´ı fics i Tecnol o` gics de la Universitat
de Barcelona (CCiTUB), Universitat de Barcelona, Sol e´ i Sabaris, 1-3,
08028-Barcelona, Spain.
D
Corresponding author. Email: Josefina.Pons@uab.es
The present report is on the synthesis of two new 3-imine-3,5-dimethylpyrazole ligands, N-[3-(3,5-dimethyl-1H-pyrazol-
-yl)propylidene]ethylamine (L1) and N-[3-(3,5-dimethyl-1H-pyrazol-1-yl)propylidene]propylamine (L2). These
1
ligands form molecular complexes with the formula [ZnCl (L)] (L ¼ L1 (1) and L2 (2)) when the reacting with ZnCl
2
2
II
in a metal (M)/ligand (L) ratio of 1 : 1. These new Zn complexes have been characterised by elemental analyses,
1
13
1
conductivity measurements, mass spectrometry, and infrared, H and C{ H} NMR spectroscopy techniques. The two
crystalline structures of complexes 1 and 2 have been solved by X-ray diffraction methods. Finally, we have studied
the self-assembly three-dimensional supramolecular structure through different intra- and intermolecular contacts. The
II
application of these Zn complexes in supramolecular crystal engineering is interesting due to (1) the easy preparation and
the high efficiency of this system and (2) the different bonding properties of the heteroatoms (N-pyrazole vs N-imine)
present in the structure of the ligands.
Manuscript received: 29 May 2014.
Manuscript accepted: 29 July 2014.
Published online: 14 October 2014.
Introduction
propylidene]propylamine (L2). The L1 and L2 ligands contain
one nitrogen pyrazole and one imine nitrogen as potential
[
1]
The construction of molecular architectures depends mostly
on the combination of several factors such as the coordination
geometry of the metal ions, nature of the organic ligands and
counterions, and ratio between the metal salts and ligands,
among others. One of the most interesting aspects of coordina-
tion chemistry is the design of hybrid ligands, which are able to
distinguish between different metals depending on the reaction
N-donor atoms (Scheme 1). We also describe the study of their
II
reactivity with Zn , isolating complexes [ZnCl (L)] (L ¼ L1 (1)
2
and L2 (2)). Complete characterisation of L1 and L2 and
II
their Zn complexes are reported, focusing on NMR studies
discussion, crystallographic structures, and self-assembly three-
dimensional (3D) arrangements.
[
2]
conditions. The complexes, including pyrazolic ligands, are
[3]
present in many pharmacologically important compounds,
Results and Discussion
[
macromolecular chemistry, and homogeneous catalysis.
4]
[5]
Synthesis and Characterisation of the Ligands
Particularly, group 12 metals (Zn, Cd, and Hg) are promising
due to their wide variety of coordination numbers and geome-
1
tries provided by the d configuration of the metal centre.
In the recent past years, our research group has focussed its
interest on the synthesis and characterisation of heterotopic
ligands containing a N-pyrazole group with other donor group
such as P-phosphine (N,P),
O-alcohol (N,O), S-thioether (N,S),
As an extension to these results, in the present paper, we
report the synthesis of new pyrazole-derived ligands with an
imine group: N-[3-(3,5-dimethyl-1H-pyrazol-1-yl)propylidene]
ethylamine (L1) and N-[3-(3,5-dimethyl-1H-pyrazol-1-yl)
New 3-imino-3,5-dimethylpyrazole ligands (L1 and L2) were
prepared following similar procedures as described in the litera-
0
[6]
[12]
ture.
The synthetic procedure for the preparation of the L1
and L2 ligands consists of two steps (Scheme 1). First, 3,5-
dimethylpyrazolewasreacted withacroleinindry dioxanetogive
[13]
the 3-(3,5-dimethyl-1H-pyrazol-1-yl)propanal (Scheme 1a).
[
7]
0
0
[8]
P -phosphinite (N,P ),
0
[9]
[10]
[11]
or N-amine (N,N ).
In the second step, the corresponding amine (ethylamine (L1) or
propylamine (L2)) dissolved in water was added to generate the
L1 and L2 ligands (Scheme 1b). The ligands were obtained as
pure products(62 % (L1) and 95 % (L2) yields). The ligandshave
been fully characterised by melting points, elemental analyses,
Journal compilation Ó CSIRO 2015
www.publish.csiro.au/journals/ajc

7
50
M. Guerrero et al.
(
a)
O
dry dioxane
0ЊC, 24 h
3
,5PzO
N
3
N
H
4
N
N
H
H
Acrolein
O
,5Pz
H
N
(
b)
L1
L2
H
N
N
N
N
N
H
CH Cl /H O
H
2
2
2
N
O
N
N
H
3
,5PzO
N
(
c)
ZnCl2
[
ZnCl (L)] (L ϭ L1 (1); L2 (2))
L1–L2
2
Ethanol
Scheme 1.
1
13
1
mass spectrometry, and infrared (IR), H, C{ H} NMR spec-
troscopy techniques. The NMR signals were assigned by refer-
1
Table 1. H NMR results: Chemical shifts (d) and H, H coupling
1
1
3
constants (J) for 1 and 2 measured in CDCl at 298K
[14]
ence to the literature and from the analysis of DEPT, COSY,
and HMQC spectra.
Compound
1
2
Elemental analyses, mass spectrometry, and all spectrosco-
pic data for L1 and L2 are consistent with the proposed
formulae. The positive ionisation spectra (ESI –MS; electro-
spray ionisation mass spectroscopy) of L1 and L2 ligands
d CH
d CH (9) [ppm]
2
(8) [ppm]
4.84
2.94
4.86
2.93
þ
2
2
J
J
J
J
8a,8b [Hz]
9a,9b [Hz]
ꢀ12.5
ꢀ12.3
2
3
3
þ
ꢀ12.5
ꢀ12.3
measured in acetonitrile display a peak attributable to [LþNa]
3
8a,9a [Hz]; J8b,9b [Hz]
7.18; 3.02
7.18; 3.02
7.20; 3.10
7.20; 3.10
(
L ¼ L1, L2). In the IR spectra of the two ligands, the charac-
3
8a,9b [Hz]; J8b,9a [Hz]
teristic absorptions measured using NaCl pellets observed at
1
ꢀ
1
ꢀ1
667 cm are attributed to n(C¼N ) (L1, L2), 1553 cm are
im
attributed to the pyrazolyl group [n(C¼C), n(C¼N)] (L1, L2),
pz
spectrum of complex 1 also shows another peak at m/z 218
100 %), corresponding to [ZnCl (L1)-3,5-Me pz]. Molecular
ꢀ1
and 773 cm are attributed to d(C–H) (L1, L2), confirming
oop
(
2
2
the presence of the imine group in the structure of the ligand.
The NMR spectra were recorded in CDCl for the ligands. In
peaks of the cations are observed with the same isotope
distribution as the theoretical ones. Moreover, conductivity
values in methanol for complexes 1 and 2 are in agreement
with the presence of non-electrolyte compounds because
3
1
the H NMR spectra, characteristic signals appear at 5.72 ppm
(
L1) and 5.74 ppm (L2), attributable to CH . Other signals are
pz
attributed to NpzCH CH CH¼N that appear at 7.65 ppm (L1,
ꢀ1
2
ꢀ1
ꢀ1
2
ꢀ1
2
2
im
reported values (59 O cm mol (1) and 61 O cm mol
1
3
1
L2). In the C{ H} NMR, the most important signals appear at
05.1 ppm (L1) and 105.0 ppm (L2), which correspond to CHpz,
ꢀ1
2
ꢀ1 [15]
(
2)) are lower than 80 O cm mol
The IR spectra of the two complexes in KBr pellets display
.
1
and 160.7 ppm (L1) and 161.1 ppm (L2), attributable to
NpzCH CH CH¼N .
absorptions of the 3-imine-3,5-dimethylpyrazole ligands. For all
complexes, the most characteristic bands are those attributable
2
2
im
ꢀ1
to the pyrazolyl group: [n(C¼C), n(C¼N)] at 1554 cm (1)
pz
Synthesis and Characterisation of the Complexes
ꢀ1
ꢀ1
and 1551 cm
(2), and d(C–H)
at 802 cm
794 cm (2), and other characteristic bands are those attribut-
(1) and
oop
ꢀ1
Complexes [ZnCl (L)] (L ¼ L1 (1) and L2 (2)) were obtained by
2
ꢀ
1
ꢀ1
[14 ]
treatment of the corresponding ligand (Scheme 1c) with ZnCl
able to n(C¼N ) at 1666 cm (1) and 1664 cm (2).
im
This
band is shifted to the lower frequencies relative to that of the free
ligand upon coordination of the nitrogen atoms.
2
in a 1 : 1 or 1 : 2 metal (M)/ligand (L) molar ratio in absolute
ethanol for 24 h. Interestingly, stoichiometry of the complexes
does not depend of the M/L molar ratio. Several techniques were
used for the characterisation of all complexes: elemental anal-
yses, mass spectrometry, conductivity measurements, and IR,
and one-dimensional (1D) and two-dimensional (2D) NMR
spectroscopy techniques. In addition, a full 3D structure deter-
mination for compounds 1 and 2 was performed through single-
crystal X-ray diffraction method.
1
The H, C{ H}NMR, DEPT, COSY, HMQC, and NOESY
13
1
spectra were recorded in CDCl for the two complexes are
3
1
13
1
discussed. H and C{ H} NMR spectra were consistent with
the proposed formulation and showed the coordination of the
ligands (L1 and L2) to the Zn atom. NMR spectroscopic data
are reported in the Experimental section. For compounds 1 and
2, the study of the Npz-CH -CH -CH¼N fragments as
2
2
im
0
0
The elemental analyses for compounds 1 and 2 are consistent
with the formula [ZnCl (L)]. The positive ionisation spectra
AA XX systems gave a set of coupling constants for each
compound. These constants were consistent with the simulated
spectra for compounds 1 and 2, obtained with the aid of the
2
þ
(
ESI –MS), in acetonitrile, of compounds 1 and 2 give a
þ
[16]
peak attributable to [ZnCl(L)] (L ¼ L1 (1), L2 (2)). The
gNMR program.
All these results are reported in Table 1.

3
D Supramolecular Structures Using Hybrid Ligands
751
H8a H9b
H8b
H9a
H
H C
3
H8
H9
N
N
N
CH3
Zn
Experimental
H C
3
Cl
Cl
5.100
5.000
4.900
4.800
4.700
4.600
4.500
3.300
3.200
3.100
3.000
2.900
2.800
2.700
2.600
Simulated
1
Fig. 1. 250 MHz H NMR data obtained at 298 K and the simulated g NMR spectra for the H8 and H9 protons of the Npz-CH
fragment of [ZnCl (L1)] (1).
2
-CH
2
-CH¼Nim
2
C7
Fig. 1 shows the experimentally determined and simulated
spectra for 1.
C5
C8
1
In the H NMR spectra of 1 and 2 at room temperature, the
C6
methylene protons for Npz-CH -CH -CH¼N chain appear as
2
2
im
C3
two bands. One is a well-defined band (doublet of doublet of
doublets) at d ¼ 4.84 ppm (1) and 4.86 ppm (2) and other is a
broad band at d ¼ 2.94 ppm (1) and 2.93 ppm (2). This suggests
that at 298 K, there is a fluxional process in which, with ring-
N2
N3
C9
C10
flipping, the two hydrogens of each CH are interconverted and
2
only one signal can be observed. HMQC spectra were used to
assign the signals of protons H-8 and H-9.
N1
C2
Cl1
Zn
As observed from the NOESY spectra, the methyl linked to
the pyrazole at d ¼ 2.28 ppm (1) and (2) shows NOE interactions
with d ¼ 4.84 ppm (1) and 4.86 ppm (2), but not with the ones at
d ¼ 2.94 ppm (1) and 2.93 ppm (2). The other signal is attribut-
able to Npz-CH -CH -C¼N , which appears at 7.95 ppm in
C1
C4
Cl2
2
2
im
both complexes.
2
Fig. 2. ORTEP drawing of [ZnCl (L1)] (1), showing all non-hydrogen
atoms and the atom numbering scheme; 50 % probability amplitude dis-
placement ellipsoids are shown.
Crystal Structures of the Complexes [ZnCl (L)]
2
(
L 5 L1 (1), L 5 L2 (2))
[
17]
For complexes 1 and 2, it has been possible to obtain colourless
monocrystals suitable for X-ray analyses through crystallisation
from dichloromethane/diethyl ether (1 : 1) mixture.
N –Zn–Cl (101.38–122.98), N –Zn–Cl (102.98–120.08),
pz
im
[18]
ꢀ
and Cl Zn–Cl (112.08–116.18). The Zn–N , Zn–N , and
pz im
Zn–Cl distances in both complexes are in the known range
˚
for tetrahedral species: Zn–Npz (1.94–2.17 A), Zn–N (1.98–
II
The structures consist of discrete Zn molecules linked by
im
[17,18]
˚ ˚
2.09 A), and Zn–Cl (2.18–2.37 A).
diverse intermolecular interactions. It is important to mention
that complex 2 contains two symmetrically independent mole-
cules and two water solvent molecules in the unit cell. The
The ligands adopt an E-, Z-configuration in these
complexes. The angle between the planes Zn–N1–N2–C6 and
Zn-N3–C8–C7–C6 is 58.938 for 1, and those between planes
Zn1–N11–N12–C16 and Zn1–N13–C18–C17–C16, and planes
Zn2–N21–N22–C26 and Zn2–N23–C28–C27–C26 are 56.098
and 54.358, respectively, for 2. All these values indicate the
V-shaped form of the complexes studied here. The [ZnCl (N )
II
environment around the Zn centre in both complexes consists
of two chlorine atoms and one ligand L (L1 (1) or L2 (2))
coordinated by (N , N ), building a seven-membered metallo-
cycle whose conformation can be described as deformed half
pz
im
II
chair (Figs 2 and 3, respectively). The Zn centre adopts a
pseudo tetrahedral coordination, where the tetrahedron is some-
2
pz
[
19]
(N )] core is present in two complexes in the literature.
im
As
ꢀ
what distorted by larger Cl Zn–Cl, N–Zn–Cl, and N–Zn–N
seen in Table 2, the Zn–Nim distances are significantly longer
than the Zn–Npz distances. The numbers of parameters refined
and other details regarding the refinement of the crystal struc-
tures of complexes 1 and 2 are gathered in Table 3.
angles in comparison with the tetrahedral value (Table 2). The
values of the angles for complexes 1 and 2 are in agreement
with the values reported in the literature for tetrahedral species

7
52
M. Guerrero et al.
Cl21
Cl22
C24
Zn2
C211
C15
C17
O1W
C210
C21
C29
N23
N21
C18
C22
C16
N13
C13
N22
N12
C110
C23
C12
C19
C28
C26
N11
C11
C27
Zn1
C111
C25
O2W
Cl12
C14
Cl11
2
Fig. 3. ORTEP drawing of [ZnCl (L2)] (2), showing all non-hydrogen atoms and the atom numbering scheme; 50 % probability
amplitude displacement ellipsoids are shown.
together stabilise the 3D supramolecular network (Fig. 5).
Moreover, it is interesting to find that all the methyl groups are
located on the external parts of the layer, generating important
hydrophobic interactions (Fig. 5). Among the non-covalent
interactions, hydrophobic interactions, usually existing among
alkyl chains of biological macromolecules, are difficult to be
observed from a crystallographic perspective.
The two independent (not symmetrically related) molecules
of 2 are alternately packed forming chains along the direction
[010]. Inside these chains, the molecules are linked by hydrogen
bonding between the oxygen atoms of two water molecules and
the four chloride atoms of the complexes (Fig. 6, Table 4).
Furthermore, these chains are connected by weak interactions
C–HꢁꢁꢁCl between molecules related by symmetry of the neigh-
bouring chains. Additionally, p–p interactions can be observed
between pyrazole rings of the two alternated molecules along
the [100] direction (Fig. 7).
˚
Table 2. Selected bond lengths [A] and bond angles [8] for 1 and 2
1
Zn–N(1)
2.031(2)
2.099(3)
Zn–N3
[20]
Zn–Cl1
2.231(2)
Zn–Cl2
2.2356(14)
100.53(10)
113.56(8)
108.72(8)
111.02(8)
107.30(9)
114.54(5)
N1–Zn–N3
N1–Zn–Cl1
N3–Zn–Cl1
N1–Zn–Cl2
N3–Zn–Cl2
Cl1–Zn–Cl2
2
Zn1–N11
2.028(4)
2.074(4)
Zn2–N21
2.070(4)
2.067(5)
2.227(2)
2.184(2)
Zn1–N13
Zn2–N23
Zn1–Cl11
2.243(2)
Zn2–Cl21
Zn1–Cl12
2.275(2)
Zn2–Cl22
Conclusions
N11–Zn1–N13
N11–Zn1–Cl11
N13–Zn1–Cl11
N11–Zn1–Cl12
N13–Zn1–Cl12
Cl11–Zn1–Cl12
100.96(18)
112.20(14)
108.38(13)
110.44(13)
109.49(13)
114.46(7)
N21–Zn2–N23
N21–Zn2–Cl21
N23–Zn2–Cl21
N21–Zn2–Cl22
N23–Zn2–Cl22
Cl21–Zn2–Cl22
102.3(2)
We have presented the reactivity of the new ligands 3-imino-
108.74(14)
103.83(15)
111.63(14)
109.57(14)
119.19(7)
3
of the coordination of these ligands to Zn has revealed the
,5-dimethylpyrazole (L1 and L2) towards ZnCl . The study
2
II
formation of molecular complexes [ZnCl (L)] (L ¼ L1 (1)
2
and L2 (2)). NMR studies have shown to be very useful in
the determination of the configuration of ligands in these
complexes in solution; also, the single-crystal X-ray diffrac-
tion method has allowed confirmation of the structures
in solid state. Finally, we have studied the 3D supramolecular
structure through different intra- and intermolecular contacts
leading to an easy approach to obtain supramolecular crystal
structures with different bonding properties of the hetero-
atoms (N-pyrazole vs N-imine) present in the structure of
the ligands.
Extended Structures of the Complexes [ZnCl (L)]
2
(
L 5 L1 (1), L 5 L2 (2))
In compound 1, the molecular units are further linked with 2
equivalent units (Fig. 4) through intermolecular hydrogen
´
˚
bond bridges (R
1
¼ 2.913(2) A; angle of
bond¼
C–HꢁꢁꢁCl
C–HꢁꢁꢁCl
66.96(3)8) to form undulating mono-dimensional chains
Fig. 4a) along the a-axis leading to intermolecular ZnꢁꢁꢁZn
(
˚
distances of 7.809(2) A (ꢀ1 þ x, y, z). Furthermore, complex 1
Experimental
shows the cooperative intermolecular interaction C–HꢁꢁꢁCl
˚
General Details
between adjacent chains in the c-axis (R
¼ 2.819(2) A;
C–HꢁꢁꢁCl
angle of
c) and p intermolecular interaction between C9–H9B and the
bond¼ 150.78(2)8; x, 1/2 ꢀ y, 1/2 þ z) (Fig. 4b,
The reactions were carried out under nitrogen atmosphere using
vacuum line and Schlenk techniques. All reagents were of
commercial grade and used without further purification. All
solvents were dried and distilled by standard methods.
C–HꢁꢁꢁCl
´
˚
pyrazole ring (R
C–HꢁꢁꢁCl
156.66(2)8; –x, –y, –z). All the intermolecular interactions
¼ 2.790(2) A; angle of
bond¼
C–HꢁꢁꢁCl

3
D Supramolecular Structures Using Hybrid Ligands
753
Table 3. Crystallographic data for compounds 1 and 2
1
2
Formula
C
10
2
H17Cl N
3
Zn
22 4 6 2
C H40Cl N OZn
Formula weight
Temperature [K]
˚
Wavelength [A]
315.53
293(2)
0.71073
677.14
293(2)
0.71073
System, space group
Unit cell dimensions
Monoclinic, P2
1
/c
Orthorhombic, Pna2
1
˚
a [A]
˚
b [A]
˚
c [A]
8.596(6)
14.933(7)
12.869(7)
121.95(4)
1495.7(15)
4
23.177(10)
8.481(5)
15.229(5)
90
b [8]
˚
3
V [A ]
2993(2)
4
Z
ꢀ
3
D
c
[g cm
]
1.500
1.502
ꢀ
1
]
m [mm
F(000)
3
Crystal size [mm ]
2.112
1.986
652
1400
0.2 ꢂ 0.09 ꢂ 0.08
0.2 ꢂ 0.1 ꢂ 0.1
h, k, l ranges
–12 # h # 12, ꢀ22 # k # 20, ꢀ17 # l # 17 –34 # h # 34, ꢀ12 # k # 12, ꢀ22 # l # 20
2y range [8]
2.311 to 32.351
12674/4152 (Rint ¼ 0.0827)
94.6
1.757 to 32.401
26213/9183 (Rint ¼ 0.0646)
99.3
Reflections collected/unique/ (Rint
)
Completeness to y [%]
Absorption correction
Empirical
Empirical
Max. and Min. transmission
Data/restrains/parameters
0.5 and 0.5
4152/2/145
1.158
0.82 and 0.79
9183/28/334
0.835
2
Goodness-of-fit on F
Final R indices (I .2s(I))
R indices (all data)
˚
Largest difference peak and hole [e A
R
R
1
¼ 0.0555, wR
¼ 0.1014, wR
2
¼ 0.1167
¼ 0.1307
R
R
1
¼ 0.0477, wR
¼ 0.1244, wR
2
¼ 0.0862
¼ 0.1022
1
2
1
2
ꢀ3
]
þ0.459, ꢀ0.362
þ0.975, ꢀ0.597
(
a)
2
.913 Å
Cl1
H4C
(
b)
(c)
2
Fig. 4. Views of 1- and 2D layered supramolecular architectures of [ZnCl (L1)] (1) along the a-direction, generated by
C–HꢁꢁꢁCl intermolecular interactions.
Elemental analyses (C, H, N) were carried out by the staff
Barcelona on a Tensor 27 (Bruker) spectrometer, equipped
with an attenuated total reflectance (ATR) accessory model
MKII Golden Gate with diamond window in the range of
of Chemical Analyses Service of the Universitat Aut o` noma de
Barcelona on a Euro Vector 3100 instrument. Conductivity
measurements were performed at room temperature (r.t.) in
ꢀ
1
1
13
1
4000–600 cm . H NMR, C{ H} NMR, COSY, HMQC,
and NOESY spectra were recorded on a NMR-FT Bruker
250 MHz spectrometer in CDCl solution at room temperature.
ꢀ
3
1
(
0
M methanol solution, employing a Ciber-Scan CON 500
Euthech Instruments) conductometre. IR spectra were run on a
Perkin–Elmer FT spectrophotometer, series 2000 as NaCl
3
All chemical shifts values (d) are given in ppm relative to
TMS as internal standard. Mass spectra were obtained on an
Esquire 3000 ion trap mass spectrometer from Bruker Daltonics.
ꢀ
1
disks in the range of 4000–100 cm , and also recorded at the
Chemical Analysis Service of the Universitat Aut o` noma de

7
54
M. Guerrero et al.
3
according to published methods.
-(3,5-Dimethyl-1H-pyrazol-1-yl)propanal was synthesised
[
This solution was placed in a water bath at 408C for 24 h.
After the reaction concluded, the solvent was removed under
vacuum. The product was purified by flash chromatography
13]
Synthesis of 3-(3,5-Dimethyl-1H-pyrazol-1-yl)propanal
˚
(
silica gel 60 A) with a mixture of ethyl acetate/dichloromethane
(1 : 1) (R
¼ 0.3) as eluent, generating a yellow oil (5.78 g,
76 %). nmax (NaCl)/cm 3082 (n(C–H)ar), 2921 (n(C–H)al),
Acrolein (C H O; 0.07 mol, 5 mL) was added to 3,5-dimethyl-
3
F
4
ꢀ1
pyrazole (0.05 mol, 4.85 g) dissolved in 40 mL of dry dioxane.
...
Table 4. Supramolecular interactions C–H X (X 5 Cl or C)
parameters for complexes 1 and 2
Complex
D–HꢁꢁꢁA
HꢁꢁꢁA [ A˚ ]
DꢁꢁꢁA [ A˚ ]
D–HꢁꢁꢁA [8]
1
2
(L1)
(L2)
C4–H4BꢁꢁꢁCl2C4–
H4CꢁꢁꢁCl1
2.819,
2.913
2.835
2.633,
2.323
3.688,
3.755
3.800
3.071,
3.372
150.78,
166.96
133.33
122.11,
121.64
C9–H9Bꢁꢁꢁpz ring
Cl2ꢁꢁꢁH–O1–Hꢁꢁꢁ
Cl22Cl11ꢁꢁꢁ
H–O2–HꢁꢁꢁCl12
3.853 Å
Fig. 7. View of p–p intermolecular interaction between adjacent pyrazole
Fig. 5. View of 3D supramolecular architecture of [ZnCl
2
(L1)] (1).
2
rings of [ZnCl (L2)] (2).
Cl22
O1
Cl21
N23
O2
Cl11
Fig. 6. Views of 1D supramolecular chain of [ZnCl
2
(L2)] (2) along the [010] direction, generated by O–HꢁꢁꢁCl intermolecular
interactions.

3
D Supramolecular Structures Using Hybrid Ligands
755
1
720 (n(C¼O)), 1553 (n(C¼C), n(C¼N)) , 1461 (d(C¼C),
solvent. The mixture was stirred for 18 h. The solution was
reduced to 5 mL and the precipitate appeared. The solid was
filtered, washed with 5 mL of diethyl ether, and recrystallised
with dichloromethane.
pz
d(C¼N)) , 1423 (d(CH ) ), 1387 (d(CH ) ), 1021 (d(C–H) ),
pz
3 as
3 s
ip
3
7
N CH CH CHO), 5.73 (1H, s, CH ), 4.22 (2H, t, J 6.6,
79 (d(C–H) ). d (CDCl , 250 Mz) 9.78 (1H, t, J 0.9,
oop H 3
3
pz
2
2
pz
3
N CH CH CHO), 3.02 (td, 2H, J 6.6, 0.9, N CH CH CHO),
ꢀ3
1: Yield: 0.25 g (39 %). Conductivity (2.4 ꢂ 10 M in meth-
pz
2
2
pz
2
2
1
3
.24, 2.16 (3H, s, CH (pz)). C{ H} NMR (CDCl , 63 MHz)
1
ꢀ1
2
ꢀ1
ꢀ1
2
1
anol): 59 O cm mol . n
(neat)/cm 3020 (n(C–H)ar),
3
3
max
99.9 (N CH CH CHO), 147.9, 139.2 (CCH ), 105.1 (CH
3
2973, 2922 (n(C–H) ), 1666 (n(C¼N )), 1554 (n(C¼C),
pz
2
2
al
im
(pz)), 43.8 (N CH CH CHO), 41.4 (N CH CH CHO), 13.6,
2
n(C¼N)) , (d(C¼C)), 1469 (d(C¼N)) , 1449 (d(CH ) ),
3 s ip oop H
pz
2
2
pz
2
pz pz 3 as
þ
þ
1
1.1 (CCH ). m/z (ESI ) 175 (100 %, C H N O þ Na ). Anal.
1392, 1381 (d(CH ) ), 1057 (d(C–H) ), 802 (d(C–H) ). d
(CDCl , 250 MHz) 7.95 (1H, br, N CH CH CH¼N ), 5.94
3
8
12
2
Calc. for C H N Oꢁ0.5H O (161.2): C 59.61, H 8.12, N 17.38.
8
12
2
2
3
pz
2
2
im
Found: C 59.22, H 8.21, N 17.69 %.
(1H, s, CH ), 4.84 (2H, m, N CH CH CH¼N ), 3.93 (2H, q,
pz
pz
2
2
im
3
J 7.4, N CH CH ), 2.94 (2H, m, N CH CH CH¼N ), 2.49,
im
2
3
pz
3
2
2
im
2
.28 (3H, s, CH (pz)), 1.43 (3H, t, J 7.4, N CH CH ). d
3 im 2 3 C
Synthesis of N-[3-(3,5-Dimethyl-1H-pyrazol-1-yl)
propylidene]ethylamine (L1) and N-[3-(3,5-Dimethyl-1H-
pyrazol-1-yl)propylidene]propylamine (L2)
(
(
CDCl , 63 MHz) 169.5 (N CH CH CH¼N ), 151.6, 141.6
3
pz
2
2
im
CCH ), 107.6 (CH(pz)), 57.7 (N CH CH ), 41.8 (N CH
3 im 2 3 pz 2
CH CH¼N ), 35.7(N CH CH CH¼N ), 16.1(N CH CH ),
2
im
pz
2
2
im
im
2
3
The synthesis consists of the reaction between 3-(3,5-dimethyl-
1
þ þ
3.7, 11.3 (CCH ). m/z (ESI ) 278 (69 %, ZnCl(L1) ), 218
3
1
H-pyrazol-1-yl)propanal (10 mmnol, 1.52 g) in CH Cl
2 2
(
(
100%, ZnCl (L1)-3,5-Me pz). Anal. Calc. C H Cl N Zn
2 2 10 17 2 3
(
7.5 mL) and 10 mmol of the appropriate amine (L1: ethylamine
0 %, 0.80 mmol or L2: propylamine 99 %, 0.83 mmol) in water
7.5 mL). The mixture was stirred at room temperature for 3 h
and extracted three times with 5 mL of CH Cl . The organic
315.6): C 38.06, H 5.43, N 13.32. Found: C 38.13, H 5.45,
7
(
N 13.30 %.
. Yield: 0.30 g (46 %). Conductivity (2.5 ꢂ 10 M in meth-
ꢀ3
2
2
2
ꢀ1
2
ꢀ1
ꢀ1
anol): 61 O cm mol . n
(neat)/cm 3032 (n(C–H)ar),
max
phase was collected and dried overnight with anhydrous
Na SO . The solution was filtered off and the solvent was
removed under vacuum. The L1 and L2 ligands were obtained
2
966, 2932 (n(C–H) ), 1664 (n(C¼N )), 1551 (n(C¼C), n
al
im
2
4
(C¼N)) , 1468 (d(C¼C), d(C¼N)) , 1449 (d(CH ) ), 1384
3 s ip oop H 3
pz pz 3 as
(
d(CH ) ), 1055 (d(C–H) ), 794 (d(C–H) ). d (CDCl ,
as white solids.
2
CH ), 4.86 (2H, m, N CH CH CH ), 3.93 (2H, t, J 7.3,
50 MHz) 7.95 (1H, br, N CH CH CH¼N ), 5.94 (1H, s,
pz im 2 2 3
ꢀ1
pz
2
2
im
L1: Yield: 1.11 g (62 %), mp 40–428C. nmax (NaCl)/cm
121 (n(C–H) ), 2967, 2928, 2869 (n(C-H) ), 1667 (n(C¼
3
3
ar
al
N CH CH CH¼N ), 2.93 (2H, m, N CH CH CH¼N ),
pz
2
2
im
pz
2
2
im
N )), 1553 (n(C¼C), n(C¼N)) , 1461 (d(C¼C), d(C¼N)) ,
3
3
im
pz
pz
2
.50, 2.28 (3H, s, CH (pz)), 1.92 (2H, td, J 7.4, J 5.3,
3
1423 (d(CH ) ), 1384 (d(CH ) ), 1022 (d(C–H) ), 773 (d(C–
H)oop). dH (CDCl3, 250 MHz) 7.65 (1H, t,
3
3
as
3 s
ip
N CH CH CH ), 0.94 (3H, t, J 7.4, N CH CH CH ). d
im C
3
2
2
3
im
2
2
3
J 4.1,
3
(
(
(
(
CDCl , 63 MHz) 169.7 (N CH CH CH¼N ), 152.0, 141.7
3
pz
2
2
im
N CH CH CH¼N ), 5.72 (1H, s, CH ), 4.17 (2H, t, J 7.3,
pz
2
2
im
pz
CCH ), 107.8 (CH(pz)), 65.4 (N CH CH CH¼N ), 42.1
3
3
pz
2
2
im
N CH CH CH¼N ), 3.30 (2H, q, J 7.4, N CH CH ), 2.69
pz
2
2
im
im
2
3
N CH CH CH ),
35.8
N CH CH CH ), 13.9, 11.9 (CCH ), 11.6 (N CH CH CH ).
(N CH CH CH¼N ),
23.8
3
3
im
2
2
3
pz
2
2
im
(
td, 2H, J 7.3, J 4.1, N CH CH CH¼N ), 2.19, 2.17 (3H, s,
pz
2
2
im
3
im
2
2
3
3
im
2
2
3
CH (pz)), 1.13 (3H, t, J 7.4, N CH CH ). d (CDCl , 63 MHz)
1
þ
þ
3 im 2 3 C 3
m/z (ESI ) 292 (100 %, ZnCl(L2) ). Anal. Calc. for
C H Cl N Zn (329.6): C 40.09, H 5.81, N 12.75. Found: C
60.7 (N CH CH CH¼N ), 147.6, 138.9 (CCH ), 105.1 (CH
pz
2
2
im
3
1
1
19
2 3
(
(
(
pz)), 55.7 (N CH CH ), 45.3 (N CH CH CH¼N ), 36.3
im 2 3 pz 2 2 im
4
0.11, H 5.92, N 12.82 %.
N CH CH CH¼N ), 16.2 (N CH CH ), 13.7, 11.2
pz 2 2 im im 2 3
þ
þ
CCH ). m/z (ESI ) 202 (100 %, L1 þ Na ). Anal. Calc. for
3
C H N ꢁ0.5H O (188.3): C 63.80, H 9.64, N 22.32. Found:
1
0
17
3
2
X-Ray Crystal Structures for Compounds 1 and 2
C 63.58, H 9.37, N 21.93 %.
Tests with several solvents were conducted, but it was not
possible to obtain single crystals of suitable quality. Although
with some indications of being slightly twinned in the case of
compound 2, eventually, crystals of compounds 1 and 2 were
selected through recrystallisation from CH Cl and diethyl ether
ꢀ
1
L2: Yield: 1.83 g (95 %), mp 45–478C. nmax (NaCl)/cm 3121
n(C–H) ), 2958, 2928, 2873 (n(C–H) ), 1667 (n(C¼N ),
(
1
ar
al
im
553 (n(C¼C), n(C¼N)) , 1461 (d(C¼C), d(C¼N)) , 1423
pz
pz
(d(CH ) ), 1384 (d(CH ) ), 1022 (d(C–H) ), 773 (d(C–H) ).
3 as 3 s ip oop
3
2
2
d (CDCl , 250 MHz) 7.65 (1H, t, J 4.1, N CH CH CH¼N ),
H
3
pz
2
2
im
mixture.
3
5.74 (s, 1H, CH ), 4.18 (t, 2H, J 7.1, N CH CH CH ), 3.31 (td,
pz im 2 2 3
Data for 1 and 2 were collected on a MAR 345 diffractometer
with an image plate detector. Unit cell parameters were deter-
mined from 890 reflections for compound 1 and 121 reflections
for 2 (38 , y , 318), and refined by least-squares method. Inten-
sities were collected with graphite monochromatised MoKa
radiation using v/2y scan technique. For 1, 12674 reflections
were measured in the range of 2.318 # y # 32.358; 4152 of which
were non-equivalent by symmetry (Rint (on I) ¼ 0.082). Lorentz
polarisation and absorption corrections were made; and 2598
reflections were assumed as observed by applying the condition
I $ 2s(I). For 2, 26213 reflections were measured in the range of
3
4
3
2
H, J 6.9, J 0.9, N CH CH CH¼N ), 2.72 (2H, td, J 6.9,
pz
2
2
im
3
J 4.1, N CH CH CH¼N ), 2.21, 2.18 (3H, s, CH (pz)),
pz 2 2 im 3
3
1
J
.57 (2H, sx,
J 7.1, N CH CH CH ), 0.84 (3H, t,
im 2 2 3
3
7.1, N CH CH CH ). dC (CDCl3, 63 MHz) 161.1
im 2 2 3
(
6
N CH CH CH¼N ), 147.5, 138.9 (CCH ), 105.0 (CH(pz)),
pz
2
2
im
3
3.4 (N CH CH CH¼N ), 45.2 (N CH CH CH ), 36.3
pz
2
2
im
im
2
2
3
(
(
N CH CH CH¼N ), 23.9 (N CH CH CH ), 13.6, 11.7
þ
3 im 2 2 3
pz 2 2 im im 2 2 3
CCH ), 11.1 (N CH CH CH ). m/z (ESI ) 225 (100 %, L2 þ
þ
Na ). Anal. Calc. for C H N ꢁ0.5H O (202.3): C 65.29, H 9.98,
11
19
3
2
N 20.77. Found: C 65.52, H 9.79, N 20.58 %.
1
.768 # y # 32.408; 9183 of which were non-equivalent by
Synthesis of the Complexes [ZnCl (L)] (L 5 L1 (1); L2 (2))
2
symmetry (Rint (on I) ¼ 0.064); and 4616 reflections were
assumed as observed by applying the condition I $ 2s(I).
Both structures were solved by direct methods using
SHELXS computer program (SHELXS-97) and refined by full
matrix least-squares method with SHELXL-97 computer
A solution of 2.0 mmol of the corresponding ligand (L1: 0.38 g;
L2: 0.40 g) dissolved in 20 mL of absolute ethanol was added to
a solution of 2.0 mmol (0.28 g) of ZnCl and 4 mL of triethyl
2
orthoformate (for dehydration purposes) in 10 mL of the same

7
56
M. Guerrero et al.
program using 12674 reflections for 1 and 987 for 2. For 1, the
2
(e) J. M. Lehn, Science 1993, 260, 1762. doi:10.1126/SCIENCE.
8511582
2 2
2
minimised function was Sw||F | ꢀ |F | | , where w ¼ [s (I) þ
o
c
2
ꢀ1
2
2 2
(
f) C. A. Mirkin, M. A. Ratner, Annu. Rev. Phys. Chem. 1992, 43, 719.
(
0.00449P) ] and P ¼ (|F | þ 2|F | ) /3. For 2, the minimised
2 ꢀ1
o c
o
2 2
c
2
2
doi:10.1146/ANNUREV.PC.43.100192.003443
[5] (a) J. P e´ rez, L. Riera, Eur. J. Inorg. Chem. 2009, 4913. doi:10.1002/
EJIC.200900694
function was Sw||F | ꢀ |F | | , where w¼ [s (I)þ (0.00488P) ]
2
2 2
and P¼ (|F | þ 2|F | ) /3. The H atoms were included in the
o
c
calculated position and constrained for compound 1, and mixed
(
b) M. Guerrero, J. Pons, J. Ros, J. Organomet. Chem. 2010, 695, 1957.
doi:10.1016/J.JORGANCHEM.2010.05.012
c) V. Montoya, J. Pons, V. Branchadell, J. Garc ´ı a-Ant o´ n, X. Solans,
[21]
2
for compound 2. The final R(F) factor and R (F )values as well
w
as the number of parameters refined and other details regarding the
refinement of the crystal structures are gathered in Table 3.
(
M. Font-Bard ´ı a, J. Ros, Organometallics 2008, 27, 1084. doi:10.1021/
OM7009182
Crystallographic Data
(d) J. Y. Lee, O. K. Farha, J. Roberts, K. Scheidt, S. T. Nguyen,
J. T. Hupp, Chem. Soc. Rev. 2009, 38, 1450. doi:10.1039/B807080F
Crystallographic data for the structural analyses have been
deposited with the Cambridge Crystallographic Data Centre,
CCDC reference numbers 1000672 and 1000673 for compounds
(
e) D. Peral, F. G o´ mez-Villarraga, X. Sala, J. Pons, J. C. Bay o´ n, J. Ros,
M. Guerrero, L. Vendier, P. Lecante, J. Garc ´ı a-Ant o´ n, K. Philippot,
Catal. Sci. Technol. 2013, 3, 475. doi:10.1039/C2CY20517C
(f) S. Ojwach, J. Darkwa, Inorg. Chim. Acta 2010, 363, 1947.
doi:10.1016/J.ICA.2010.02.014
[ZnCl (L1)] (1) and [ZnCl (L2)] (2), respectively. Copies of
2 2
this information may be obtained free of charge from www.
ccdc.cam.ac.uk/data_request/cif or from the Director, CCDC,
[6] (a) J. Yang, B. Wu, F. Y. Zhuge, J. J. Liang, C. D. Jia, Y. Y. Wang,
N. Tang, X. J. Yang, Q. Z. Shi, Cryst. Growth Des. 2010, 10, 2331.
doi:10.1021/CG100093N
1
0
2 Union Road, Cambridge, CB2 1EZ, UK; fax: þ44 1223 236
33; email: deposit@ccdc.cam.uc.uk.
(
b) H. Fleischer, Y. Dienes, B. Mathiasch, V. Schmitt, D. Schollmeyer,
Inorg. Chem. 2005, 44, 8087. doi:10.1021/IC050814M
c) M. Guerrero, J. Pons, M. Font-Bardia, T. Calvet, J. Ros, Polyhe-
Acknowledgements
(
This work has been supported by MAT2011–27225 and the 2009SGR76
projects are acknowledged. L. R. also acknowledges the Universitat
Aut o` noma de Barcelona for their pre-doctoral grant.
dron 2010, 29, 1083. doi:10.1016/J.POLY.2009.11.018
7] (a) S. Mu n˜ oz, J. Pons, J. Ros, C. A. Kilner, M. A. Halcrow, J. Orga-
[
nomet. Chem. 2011, 696, 2736. doi:10.1016/J.JORGANCHEM.2011.
0
4.019
References
(
b) G. Esquius, J. Pons, R. Y a´ n˜ ez, J. Ros, R. Mathieu, N. Lugan,
[
1] (a) L. E. Kreno, K. Leong, O. K. Farha, M. Allendorf, R. P. Van Duyne,
B. Donnadieu, J. Organomet. Chem. 2003, 667, 126. doi:10.1016/
S0022-328X(02)02156-3
J. T. Hupp, Chem. Rev. 2012, 112, 1105. doi:10.1021/CR200324T
(
b) A. A. Talin, A. Centrone, A. C. Ford, M. E. Foster, V. Stavila, P.
(c) G. Esquius, J. Pons, R. Y a´ n˜ ez, J. Ros, R. Mathieu, B. Donnadieu,
N. Lugan, Eur. J. Inorg. Chem. 2002, 2999. doi:10.1002/1099-0682
(200211)2002:11,2999::AID-EJIC2999.3.0.CO;2-A
Haney, R. A. Kinney, V. Szalai, F. Gabaly, H. P. Yoon, F. L e´ onard, M.
D. Allendorf, Science 2014, 343, 66. doi:10.1126/SCIENCE.1246738
2] (a) P. Cordier, F. Tournilhac, C. Soulie-Zikovic, L. Liebler, Nature
[
[8] (a) S. Mu n˜ oz, M. Guerrero, J. Ros, T. Parella, M. Font-Bard ´ı a, J. Pons,
Cryst. Growth Des. 2012, 12, 6234. doi:10.1021/CG3014333
(b) S. Mu n˜ oz, J. Pons, J. Garc ´ı a-Ant o´ n, X. Solans, M. Font-Bard ´ı a,
J. Ros, J. Coord. Chem. 2009, 62, 3940. doi:10.1080/
00958970903208292
2
008, 451, 977. doi:10.1038/NATURE06669
b) H. J. Schneider, R. M. Strongin, Accounts Chem. Res. 2009, 42,
489. doi:10.1021/AR800274U
c) N. N. Adarsh, P. Dastidar, Chem. Soc. Rev. 2012, 41, 3039.
doi:10.1039/C2CS15251G
d) N. Robertson, L. Cronin, Coord. Chem. Rev. 2002, 227, 93.
doi:10.1016/S0010-8545(01)00457-X
e) E. Lindler, T. Schneller, F. Auer, H. A. Mayer, Angew. Chem., Int.
Ed. 1999, 38, 2155.
f) V. V. Grushin, Chem. Rev. 2004, 104, 1629. doi:10.1021/
CR030026J
g) A. L. Gavrilova, B. Bosnich, Chem. Rev. 2004, 104, 349.
(
1
(
(c) S. Mu n˜ oz, J. Pons, X. Solans, M. Font-Bard ´ı a, J. Ros, J. Organomet.
Chem. 2008, 693, 2132. doi:10.1016/J.JORGANCHEM.2008.03.010
(d) R. Trib o´ , S. Mu n˜ oz, J. Pons, R. Y a´ n˜ ez, A. Alvarez-Larena, J. F.
Piniella, J. Ros, J. Organomet. Chem. 2005, 690, 4072. doi:10.1016/
J.JORGANCHEM.2005.05.047
(
(
(
[9] (a) M. Guerrero, J. A. P e´ rez, M. Font-Bard ´ı a, J. Pons, J. Coord. Chem.
2013, 66, 3314. doi:10.1080/00958972.2013.837895
(b) J. A. P e´ rez, V. Montoya, J. A. Ayll o´ n, M. Font-Bard ´ı a, T. Calvet,
J. Pons, Inorg. Chim. Acta 2013, 394, 21. doi:10.1016/J.ICA.
2012.07.027
(
doi:10.1021/CR020604G
3] (a) J. Pons, J. Ros, M. Llagostera, J. A. P e´ rez, M. Ferrer, Spanish
[
Patent 01494 2003.
(c) M. Guerrero, J. Pons, J. Ros, M. Font-Bard ´ı a, O. Vallcorba, J. Rius,
V. Branchadell, A. Merko c¸ i, CrystEngComm 2011, 13, 6457.
doi:10.1039/C1CE05626C
(d) S. Mu n˜ oz, J. Pons, J. Ros, M. Font-Bard ´ı a, C. A. Kilner, M. A.
Halcrow, Inorg. Chim. Acta 2011, 373, 211. doi:10.1016/J.ICA.2011.
04.027
(
b) R. W.-Y. Sun, D. L. Ma, E. L.-M. Wong, C. M. Che, Dalton Trans.
007, 4884.
c) A. Satake, T. Nakata, J. Am. Chem. Soc. 1998, 120, 10391.
doi:10.1021/JA982269C
d) C. Navarro-Ranninger, L. L o´ pez-Solera, V. M. Gonz a´ lez, J. M.
2
(
(
P e´ rez, A. Alvarez-Valdes, A. Mart ´ı n, P. R. Raithby, J. R. Massager,
(e) C. Luque, J. Pons, T. Calvet, M. Font-Bard ´ı a, J. Garc ´ı a-Ant o´ n,
J. Ros, Inorg. Chim. Acta 2011, 367, 35. doi:10.1016/J.ICA.2010.
11.041
C. Alonso, Inorg. Chem. 1996, 35, 5181. doi:10.1021/IC960050Y
(
e) K. Sakai, Y. Tomita, T. Ue, K. Goshima, M. Ohminato,
T. Tsubomura, K. Matsumoto, K. Ohmura, K. Kawakami, Inorg.
Chim. Acta 2000, 297, 64. doi:10.1016/S0020-1693(99)00287-X
4] (a) M. Guerrero, J. Pons, V. Branchadell, T. Parella, X. Solans,
M. Font-Bard ´ı a, J. Ros, Inorg. Chem. 2008, 47, 11084. doi:10.1021/
IC8013915
(f) V. Montoya, J. Pons, X. Solans, M. Font-Bard ´ı a, J. Ros, Inorg.
Chim. Acta 2007, 360, 625. doi:10.1016/J.ICA.2006.08.058
(g) A. Boixassa, J. Pons, X. Solans, M. Font-Bard ´ı a, J. Ros, Inorg.
Chim. Acta 2004, 357, 733. doi:10.1016/J.ICA.2003.06.015
(h) A. Boixassa, J. Pons, X. Solans, M. Font-Bard ´ı a, J. Ros, Inorg.
Chim. Acta 2003, 355, 254. doi:10.1016/S0020-1693(03)
00346-3
[
(
b) A. de Le o´ n, M. Guerrero, J. Garc ´ı a-Ant o´ n, J. Ros, M. Font-Bard ´ı a,
J. Pons, CrystEngComm 2013, 15, 1762. doi:10.1039/C2CE26687C
c) J. J. Neuman, M. Suri, G. Frank, Angew. Chem., Int. Ed. Engl. 2010,
9, 7790. doi:10.1002/ANIE.201002389
d) M. Guerrero, J. A. P e´ rez, T. Calvet, M. Font-Bard ´ı a, J. Pons, Aust.
J. Chem. 2013, 66, 685. doi:10.1071/CH13021
(
4
(i) A. Boixassa, J. Pons, X. Solans, M. Font-Bard ´ı a, J. Ros, Inorg.
Chim. Acta 2002, 340, 49. doi:10.1016/S0020-1693(02)01052-6
[10] (a) J. Garc ´ı a-Ant o´ n, J. Pons, X. Solans, M. Font-Bard ´ı a, J. Ros, Inorg.
Chim. Acta 2004, 357, 571. doi:10.1016/J.ICA.2003.08.013
(

3
D Supramolecular Structures Using Hybrid Ligands
757
(
b) J. Garc ´ı a-Ant o´ n, J. Pons, X. Solans, M. Font-Bard ´ı a, J. Ros, Inorg.
Chim. Acta 2003, 355, 87. doi:10.1016/S0020-1693(03)00333-5
c) J. Garc ´ı a-Ant o´ n, J. Pons, X. Solans, M. Font-Bard ´ı a, J. Ros, Eur. J.
Inorg. Chem. 2003, 2992. doi:10.1002/EJIC.200300035
(b) U. K o¨ hn, M. Klopfleisch, H. G o¨ rls, E. Anders, Tetrahedron:
Asymmetry 2006, 17, 811. doi:10.1016/J.TETASY.2006.02.009
(c) U. K o¨ hn, M. Schulz, H. G o¨ rls, E. Anders, Tetrahedron: Asymmetry
2005, 16, 2125. doi:10.1016/J.TETASY.2005.04.023
(d) M. Amirnasr, A. H. Mahmoudkani, A. Gorji, S. Dehghanpour,
H. R. Bijanzadeh, Polyhedron 2002, 21, 2733. doi:10.1016/S0277-
5387(02)01277-9
(
[
11] (a) M. C. Castellano, J. Pons, J. Garc ´ı a-Ant o´ n, X. Solans, M. Font-
Bard ´ı a, J. Ros, Inorg. Chim. Acta 2008, 361, 2923. doi:10.1016/J.ICA.
2
008.02.059
(
b) J. Pons, J. Garc ´ı a-Ant o´ n, M. Font-Bard ´ı a, T. Calvet, J. Ros, Inorg.
[18] (a) S. Bieller, A. Haghiri, M. Bolte, J. W. Bats, M. Wagner, H. W.
Lerner, Inorg. Chim. Acta 2006, 359, 1559. doi:10.1016/J.ICA.2005.
10.034
Chim. Acta 2009, 362, 2698. doi:10.1016/J.ICA.2008.12.009
12] A. Simion, C. Simion, T. Kanda, S. Nagashima, Y. Mitoma,
T. Yamada, K. Mimura, M. Tashiro, J. Chem. Soc., Perkin Trans 1
[
[
[
(b) A. M. Schuitema, M. Engelen, I. A. Koval, S. Gorter, W. L.
Driessen, J. Reedijk, Inorg. Chim. Acta 2001, 324, 57. doi:10.1016/
S0020-1693(01)00500-X
(c) C. J. Tokar, P. B. Kettler, W. B. Tolman, Organometallics 1992, 11,
2737. doi:10.1021/OM00044A001
2
001, 2001, 2071. doi:10.1039/B102749M
13] O. S. Attaryan, S. K. Antanosyan, F. S. Kinoyan, R. A. Tamazyan,
G. A. Panosyan, S. G. Matsoyan, Russ. J. Org. Chem. 2006, 42, 1868.
doi:10.1134/S1070428006120220
14] (a) E. Pretsh, T. Clerc, J. Seibl, W. Simon, Tables of Determination of
(d) M. Guerrero, J. Pons, T. Parella, M. Font-Bard ´ı a, T. Calvet, J. Ros,
Inorg. Chem. 2009, 48, 8736. doi:10.1021/IC900908N
[19] (a) U. K o¨ hn, M. Schulz, H. G o¨ rls, E. Anders, Tetrahedron: Asymmetry
2005, 16, 2125. doi:10.1016/J.TETASY.2005.04.023
(b) U. K o¨ hn, M. Schulz, H. G o¨ rls, E. Anders, Tetrahedron: Asymmetry
2006, 17, 811. doi:10.1016/J.TETASY.2006.02.009
[20] (a) A. Ustinov, H. Weissman, E. Shirman, I. Pinkas, X. B. Zuo,
B. Rybtchinski, J. Am. Chem. Soc. 2011, 133, 16201. doi:10.1021/
JA2066225
1
3
1
Organic Compounds. C NMR, H NMR, IR, MS, UV/Vis, Chemical
Laboratory Practice 1989 (Springer-Verlag: Berlin, Germany).
(b) D. H. Williams, I. Fleming, Spectroscopic Methods in Organic
Chemistry 1995 (McGraw-Hill: London, UK).
15] (a) L. K. Thompson, F. I. Lee, E. J. Gabe, Inorg. Chem. 1988, 27, 39.
doi:10.1021/IC00274A010
[
(
8
b) W. J. Geary, Coord. Chem. Rev. 1971, 7, 81. doi:10.1016/S0010-
545(00)80009-0
[
16] P. H. M. Butzelaar, g NMR ver. 4.0. IvorySoft 1997 (Cherwell
Scientific: Oxford, UK).
(b) B. Bhayana, C. S. Wilcox, Angew. Chem., Int. Ed. 2007, 46, 6833.
doi:10.1002/ANIE.200700932
[21] G. M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr. 2008,
[
17] (a) C. Y. Wang, Acta Crystallogr., Sect.E: Struct. Rep. Online 2011,
67, m1085. doi:10.1107/S1600536811027085
64, 112. doi:10.1107/S0108767307043930