Molecular tectonics: Formation and structural studies on a 2-D directional coordination network based on a non-centric metacyclophane based tecton and zinc cation

Article abstract of DOI:10.1039/b917089h

The combination of tectons based on the [1111]metacyclophane backbone blocked the 1,3-alternate conformation bearing two imidazoly or pyrazolyl groups located on the same side with metal halide complexes leads to the formation of either discrete metallmacrobicycles or infinite 1-D coordination networks. The same backbone bearing two sets of two different coordinating poles composed of two pyridyl and two pyrazolyl units, owing to its non-centrosymmetric nature, forms a directional 2-D network packed in an anti-parallel fashion.

Full text of DOI:10.1039/b917089h

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Molecular tectonics: formation and structural studies on a 2-D directional
coordination network based on a non-centric metacyclophane based tecton
and zinc cation†
Je´roˆme Ehrhart, Jean-Marc Planeix,* Nathalie Kyritsakas-Gruber and Mir Wais Hosseini*
Received 18th August 2009, Accepted 3rd December 2009
First published as an Advance Article on the web 15th January 2010
DOI: 10.1039/b917089h
The combination of tectons based on the [1111]metacyclophane backbone blocked the 1,3-alternate
conformation bearing two imidazoly or pyrazolyl groups located on the same side with metal halide
complexes leads to the formation of either discrete metallmacrobicycles or infinite 1-D coordination
networks. The same backbone bearing two sets of two different coordinating poles composed of two
pyridyl and two pyrazolyl units, owing to its non-centrosymmetric nature, forms a directional 2-D
network packed in an anti-parallel fashion.
coordination patterns, which define the structural nodes of the
assembly, are translated into one direction of space, for 2-D, they
Introduction
In the area of crystal engineering,1,2 the control of directionality is
are translated into two directions of space. One of the possibilities
one of the most challenging tasks. Imposing a design of acentric
for the design of directional 2-D architectures can be based on an
orientation of the components which make up the crystal is of
acentric organic tecton offering four differentiated coordinating
interest for exploiting, for example, directional physical properties
sites located on a backbone and oriented in a divergent fashion
such as photon or electron transfer processes in the solid state.
(Fig. 1(a)). Within this category, one may consider a tecton
Let us restrict ourselves to crystals composed of coordination
bearing two different sets of two monodentate coordination poles
networks3 made up of organic tectons4 and metal centres. For 3-
(Fig. 1(a)).
D networks, the formation of crystals results from the mutual
interconnection of the organic and metallic parts in all three
dimensions of space,5 whereas for 1- and 2-D networks, the
generation of crystals may be described as resulting from the
formation of the network by interconnection of the organic parts
by metal centres and the packing of the networks in two and one
directions of space respectively.
We have previously reported the design and formation of direc-
tional 1-D networks in the crystalline phase.6-8 The design principle
explored was based on combinations of acentric tectons possessing
two differentiated coordination poles and metal cations.6 We have
also succeeded in obtaining a polar crystal based on the use
of a directional and chiral organic tecton.7 Furthermore, the
same construction principle was used for surface patterning by
directional 1-D networks.8
Fig. 1 Schematic representation of the formation of non-centric (b) and
centric (c) 2-D coordination networks formed upon combination of a
Here, we report on the design, formation and structural
analysis of a directional 2-D coordination network formed upon
combining an acentric tecton based on the [1111]metacyclophane
backbone bearing two pyrazolyl and two pyridyl units and ZnCl2.
non-centric tecton (a) bearing two different sets of two coordinating sites
with a metal centre offering two coordination sites and syn-parallel (d) and
anti-parallel (e) arrangements of the consecutive directional planes.
The combination of such a tecton (Fig. 1(a)) with a metal
centre offering two free coordination sites could lead to a
2-D network resulting from the bridging of consecutive organic
moieties by metal centres (Fig. 1(b) and 1(c)). For such a sheet-type
architecture, the directionality depends on the way the consecutive
organic tectons are oriented with respect to each other. For the
non-centrosymmetric arrangement, the 2-D network is directional
(Fig. 1(b)), whereas for the centrosymmetric organisation of
the tectons, owing to the presence of centres of symmetry, the
overall architecture is non-directional (Fig. 1(c)). For the three-
dimensional organisation of the 2-D networks, the packing may
occur either in a syn-parallel fashion leading thus to a directional
Results and discussion
Coordination networks are periodic architectures defined by their
dimensionality (1-, 2- or 3-D). Whereas for 1-D networks, the
Laboratoire de Chimie de Coordination Organique (UMR CNRS 7140),
Universite´ de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal, 67000 Stras-
bourg, France. E-mail: hosseini@chimie.u-strasbg.fr; Fax: 33 390241325;
Tel: 33 390241323
† CCDC reference numbers 744810–744821. For crystallographic data in
CIF or other electronic format see DOI: 10.1039/b917089h
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crystal (Fig. 1(d)) or in an anti-parallel mode generating a non-
directional crystal (Fig. 1(e)).
For the design of organic tectons schematically represented
in Fig. 1(a), the [1111]metacyclophane backbone is particularly
well suited. Indeed, this rigid unit adopts a thermally stable 1,3-
alternate conformation9 and can be readily tetra functionalised by
a variety of groups such as hydoxy,9 cyano,10 mercapto,11 pyridyl,12
bipyridyl13 and quinolinyl.13 Examples of disubstituted derivatives
have been also reported.14
Using the cyclophane backbone blocked in the 1,3-alternate
conformation, a series of four new tectons (compounds 9–12,
Scheme 1) bearing two different sets of coordinating sites have
been designed and synthesised (see experimental).
Scheme 2 Structures of compounds 1–8.
CHCl3 in the presence of SnCl4.14 Precursor 3 was obtained in 30%
yield upon treatment of the dichloro compound 2 by mesitylene
in nitroethane and in the presence of SnCl4.14 Finally, compound
2 was prepared in 84% yield by reacting bromomesitylene 1 with
CH3OCH2Cl in CH2Cl2 in the presence of SnCl4.14
Intermediates 7 and 8 have been obtained in 81 and 79% yields
respectively in DMF and in the presence of catalytic amounts of
NaI upon nucleophilic displacement reactions between compound
4 and sodium imidazolate or pyrazolate. The desired compounds
9–12 have been synthesised using the Suzuki coupling reaction
in DMF and in the presence of Cs2CO3 using Pd(PPh3)4 as the
catalyst. It is worth noting that for this reaction, we have found
Scheme 1 The black dots indicate the position of connection of the coor-
dinating units to the cyclophane backbone in 1,3-alternate conformation.
For these four tectons 9–12, in order to impose the non-
centrosymmetry, the north and south parts are differentiated by
both the nature of the coordinating sites and the type of junction
(direct connection through an Ar–Ar junction for north and
attachment through a methylene group for south).
◦
the use of microwaves (120 W) at 130 C particularly useful for
obtaining the desired compounds in acceptable yields and in rather
short reaction times (ca. 30 min). Thus, the reaction of boronic
ester 5 with compound 7 or 8 afforded tectons 9 and 11, possessing
in common the PhSMe group and differentiated by the presence
of either two imidazolyl (9) or two pyrazolyl (11) groups, in 22
and 38% yields respectively. On the other hand, the same type of
coupling using the 4-pyridyl-boronic ester 6 afforded compounds
10 and 12 in 28 and 32% yields respectively.
It is interesting to note that the two intermediates 7 and 8 bearing
two imidazolyl or two pyrazolyl coordinating groups on the same
side of the cyclophane mean plane may also be of interest for the
formation of either discrete species of the metallamacrocyclic type
or infinite 1-D networks. Thus, they have been also combined with
metal centres.
The two 5-membered ring heterocycles, imidazole15 and
pyrazole,16 have been selected because of their propensity to form
complexes with a variety of metal centres. Furthermore, being
positional isomers, their use allows exploring the role played by
the orientation of the coordinating N atoms once attached to the
cyclophane backbone. The choice of imidazole17 and pyrazole18
was also based on our previous studies on metacyclophane
derivatives bearing four such heterocycles. The choice of the
methylene spacer connecting the two aromatic moieties located
on the same side of the cyclophane skeleton to heterocycles
through a C–N bond was based on synthetic reasons and for
introducing rotational flexibility. For the other coordinating pole,
two pyridines or thioether groups were used.
Since compounds 7–12 are neutral species, in order to generate
neutral coordination networks, they were combined with neutral
metal halide MX2 type complexes offering two free coordination
sites.
Tectons 9 and 10 have in common the imidazolyl group and
differ by the nature of the other coordinating sites (PhSMe for
9 and pyridyl for 10). The same holds for tectons 11 and 12
except that the two common imidazolyl groups are replaced by
two pyrazolyl units (Scheme 1).
The synthesis of compounds 9–12 requires the differentiation
of the north and the south parts of the cyclophane blocked in 1,3-
alternate conformation. We thought that this could be achieved by
using two different coupling reactions, one based on the classical
nucleophilic displacement of halides centres and the other one
the Suzuki Ar–Ar coupling reaction. Thus, compound 4 bearing
two Ar–Br groups and two ArCH2Cl moieties appeared as the
intermediate of choice (Scheme 2).
Structural investigations
For all compounds 7–12, although the [1111]metacyclophane
backbone imposing the 1,3-alternate conformation because of
steric reasons between CH3 groups is intrinsically rigid, the use
of the methylene group between two of its phenyl group and either
the two imidazolyl or pyrazolyl units introduces some rotational
flexibility. Indeed, compounds 7–12 can display three extreme
conformers based on the orientation of the heterocycles with
respect to centre of the cyclophane backbone. These rotamers
The synthesis of 4 was achieved in 87% yield by a chloromethy-
lation reaction of the dibromo derivative 3 using CH3OCH2Cl in
2138 | Dalton Trans., 2010, 39, 2137–2146
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((ii), (io) and (oo)) are depicted in Fig. 2 for the dibromo
intermediates 7 and 8.
Fig. 2 Schematic representation of the three possible extreme rotamers
(ii), (io) and (oo); i (in) and o (out) for the disubstituted compounds 7 and
8 corresponding to the orientation of the coordinating sites with respect
to the centre of the cyclophane backbone.
Schematic representations of the extreme rotamers for the dif-
ferentiated compounds 9–12 are given in Fig. 3. It is worth noting
that for the other sets of coordinating sites, since the junction
between the cyclophane backbone and PhSMe and pyridyl units
are achieved using position 4, no rotational conformer may be
expected.
Fig. 4 Schematic representation of the formation of a discrete metal-
lamacrobicycle (b) by the (ii) rotamer (a) of compound 7 and different
infinite 1-D networks ((d)–(g)) by the (oo) rotamer (c) of tecton 8 differing
by different orientation of the cyclophane backbone.
and Hg; X = Cl or Br) afforded a series of crystalline materials
(see experimental) that were structurally investigated in the solid
state by X-ray diffraction on single-crystals (see Table 4 in
experimental).
For all cases, the same type of metallamacrobicycle (Fig. 4(b))
is formed (Fig. 5). For 7-CoX2 (X = Cl or Br) (Fig. 5(a) and (b)),
7-ZnBr2 (Fig. 5(c)), 7-CuBr2 (Fig. 5(d)) and 7-HgBr2 (Fig. 5(e))
¯
complexes, the crystal system is triclinic with P1 as the space
group. All complexes studied crystallise with solvent molecules
(H2O in the case of 7-CoCl2 and CHCl3 for the other complexes,
see experimental). Although the five cases are isostructural, as
Fig. 3 Schematic representation of the three possible extreme rotamers
(ii), (io) and (oo); i (in) and o (out) for the tetrasubstituted compounds 9–12
corresponding to the orientation of the imidazolyl or pyrazolyl groups with
respect to the centre of the cyclophane backbone.
Dealing with the disubstituted compounds 7 and 8, based on our
previous investigations on the tetrakis imidazolyl derivative,17 for
the (ii) rotamer (Fig. 4(a)) of the bisimidazole based compound
7, we expect the formation of a discrete metallamacrobicycle19
(Fig. 4(b)) in the presence of metal halides MX2. Again based
on our previous observations for the tetrakis pyrazolyl based
tecton,18 for the (oo) rotamer (Fig. 4(c)) we predict the formation
of 1-D coordination networks (Fig. 4(d)–(g)) in the presence of
metal halides serving as bridging inorganic tectons. The four
schematically represented 1-D networks in Fig. 4(d)–(g) possess
the same connectivity mode but differ only by the orientation of
the cyclophane backbone.
Fig. 5 The solid-state structure of the discrete metallamacrobicycles
formed upon associating compound 7 with CoCl2 (a); CoBr2 (b); ZnBr2
(c); CuBr2 (d); HgBr2 (e). For clarity, H atoms and solvent molecules are
omitted. For bond distances and angles see text.
The combination in solution (mixture of CHCl3–MeOH) of
ligand 7 with different metal halides MX2 (M = Co, Zn, Cu
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◦
˚
Table 1 Average bond distances (A) and angles ( ) for 7-CoX2 (X = Cl
or Br), 7-ZnBr2, 7-CuBr2 and 7-HgBr2
M
X
Co
Cl
Co
Br
Zn
Br
Cu
Br
Hg
Br
dN–M
dX–M
NMN
XMX
NMX
2.00
2.25
113.2
123.8
105.0
2.01
2.39
115.2
123.9
104.6
2.01
2.38
112.5
123.2
105.3
1.96
2.39
138.5
134.7
97.8
2.30
2.54
106.6
135.7
102.9
expected, the metrics (bond distances and angles) are different
for each complex (Table 1). The metallamacrobicycles are formed
by simultaneous binding of MX2 centres by both imidazolyl
groups located on the same face of the molecule ((ii) rotamer,
Fig. 4(a)) through two M–N bonds (dM–N in the range of 1.96–
˚
2.30 A). In all cases, the metal centre, adopting a distorted
tetrahedral coordination geometry (for bond angles see Table 1), is
tetracoordinated and its coordination sphere is composed of two
˚
N and two X atoms (dM–N in the range of 2.24–2.54 A).
The bond distances and angles observed here are similar to
those obtained for the metallamacrotricyclic analogues previously
formed by reacting the tetraimidazolyl derivative with MX2 type
complexes.17
The ability of pyrazolyl-based tecton 8 to generate infinite
coordination networks was also investigated by combining 8 with
metal halides (MX2, M = Co2+ and Zn2+; X= Cl- and Br-).
Whereas for 8-CoX2 (X = Cl or Br) and 8-ZnCl2 similar neutral
1-D networks are obtained (Fig. 6), in the case of 8-ZnBr2,
although again a 1-D network is observed, the consecutive tectons
8, adopting a different conformation, are differently arranged
(Fig. 7). In all four cases, the crystals contained solvent molecules.
Except in the case of CoCl2 for which CHCl3 molecules could
be localised, for all other three cases, the solvent molecules
were disordered and the SQUEEZE command20 was used (see
crystallographic Table 5 in experimental).
For the first type, the 1-D networks are similar but not
isostructural (see crystallographic Table 5 in experimental). They
are generated by bridging of consecutive tectons 8, adopting
the (oo) conformation (Fig. 4(c)), by CoCl2 (Fig. 6(a)), CoBr2
(Fig. 6(b)) or ZnCl2 (Fig. 6(c)).
Fig. 6 Portion of the 1-D coordination network (view perpendicular to
the network axis) generated upon combining the tecton 8 with CoCl2 (a);
CoBr2 (b); ZnCl2 (c) and the packing of consecutive 1-D networks (d)
(view along the network axis) for (8-CoCl2)n. For the other two cases, the
same packing is observed. H atoms and solvent molecules are omitted for
clarity. For bond distances and angles see text.
In all three cases, the bridging takes place between Co and
Zn centres and consecutive tectons through M–N bonds (dM–N in
The packing of consecutive 1-D networks perpendicular to the
network axis is given in Fig. 6(d).
Again, the bond distances and angles observed here are
similar to those obtained for infinite networks previously ob-
tained by combining MX2 type complexes with the tetrapyrazolyl
analogue.18
Rather surprisingly, for the combination of 8 with ZnBr2, the or-
ganic tecton adopts the (io) conformation (Fig. 2). Consequently,
the type of 1-D network obtained is different in geometry (Fig. 7).
The crystal (orthorhombic, Pbca), in addition to 8 and ZnBr2,
contains disordered solvent molecules).
˚
the range of 2.01–2.06 A, Table 2). Both metal centres adopt a
distorted tetrahedral coordination geometry (for bond angles see
Table 2). Their coordination spheres are composed of two N and
˚
two X atoms (dM–N in the range of 2.22–2.37 A).
Within each 1-D network, the consecutive tectons 8 are tilted
by ca. 90◦ (see Fig. 4(g)).
◦
˚
Table 2 Average bond distances (A) and angles ( ) for (8-MX2)n (M =
Co or Zn, X = Cl or Br)
M
X
Co
Cl
Co
Br
Zn
Cl
Zn
Br
The neutral network, of the type schematically presented in
Fig. 4(e), is again generated by bridging of consecutive tectons
dN–M
dX–M
NMN
XMX
NMX
2.02
2.23
104.6
120.8
107.6
2.02
2.37
105.6
111.0
110.1
2.06
2.23
98.2
121.3
108.7
2.01
2.35
98.6
120.5
108.9
8 by ZnBr2 through the formation of two Zn–N bonds (dZn–N
=
2.01 A). Zn2+ cation again adopts a distorted tetrahedral geometry
˚
˚
and is surrounded by two N and two Br atoms (dZn–Br = 2.35 A).
Within the 1-D network, the consecutive tectons 8 are parallel and
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Fig. 8 Portions of the structure of 1-D networks obtained upon com-
bining 11 with CoX2. (X = Cl (a) and X = Br (c)) and a view along the
network axis for 11-CoCl2 (b). H atoms and solvent molecules are omitted
for clarity.
◦
˚
Table 3 Average bond distances (A) and angles ( ) for (11-CoX2)n (X =
Cl or Br)
M
X
Co
Cl
Co
Br
dN–M
dX–M
NMN
XMX
NMX
2.01
2.22
100.1
115.8
109.8
2.02
2.35
100.2
113.8
110.4
Fig. 7 A portion of the 1-D coordination network (view perpendicular to
the axis of the network (a)) and packing of two consecutive networks (b)
generated upon combining the tecton 8 with ZnBr2. H atoms and solvent
molecules are omitted for clarity. For bond distances and angles see text.
CoCl2 and CoBr2 respectively). The metal centre adopts a distorted
tetrahedral geometry (see Table 3 for angles).
Thus, compound 11 behaves as a tecton bearing two coordi-
nating sites located on the same face of the cyclophane backbone
(analogue of tecton 8) and the isostructural 1-D networks formed
in the presence of CoX2 are of the type schematically represented
in Fig. 4(d)).
Finally, the combination of the acentric tecton 12, bearing two
pyrazolyl groups on one face of the backbone and two pyridyl units
on the other face, with ZnCl2 afforded the desired directional 2-D
network (Fig. 9(a)).
tilted by 180◦. Consequently, the network is of the zigzag type. The
packing of consecutive 1-D networks is given in Fig. 7(b)).
Much to our surprise, despite many attempts consisting in
using different metal halides (variation of both metal and halide),
different tecton/metal ratio, solvent systems and crystallisation
techniques, no crystalline materials could be obtained using
tectons 9 and 10 having in common two imidazolyl groups.
The first attempt to generate directional architecture using the
acentric tecton 11 bearing two PhSMe and two pyrazolyl units
and MX2 complexes failed. Indeed, X-ray diffraction studies on
single crystals containing 11 and either CoCl2 (Fig. 8(a) and (b))
or CoBr2 (Fig. 8(c)) revealed the formation of isostructural 1-D
networks. Both crystals (monoclinic, P21/c) contained disordered
solvent molecules which could not be localised and thus the
SQUEEZE command was used for solving their structures (see
crystallographic Table 6 in experimental).20 Unexpectedly, none
of the two PhSMe groups behave as a coordinating site. This is
probably due to the weak binding ability of the thioether group.
The 1-D networks are thus formed by the bridging of con-
secutive CoX2 centres by tecton 11 through the formation of
The crystal (monoclinic, C2/c) in addition to tecton 12 and
ZnCl2 contains MeOH and H2O solvent molecules.
Bridging of consecutive tecton 12 by ZnCl2 complexes gen-
erates the 2-D network. The bridging mode takes place in a
non-centrosymmetric fashion. Indeed, the coordination node
is composed of a Zn2+ cation, two Cl- anions, one pyridyl
and one pyrazolyl unit (Fig. 10). The translation of the above
mentioned node into two directions of space generates the sheet-
type architecture.
The organic tecton 12, adopts the (oo) conformation (Fig. 3),
however the coordinating N atoms of both pyrazolyl groups
are outwardly oriented. The Zn2+ cation is tetracoordinated
and adopts a distorted tetrahedral coordination geometry
(NpyrazZnNpy, ClZnCl, ClZnNpyraz and ClZnNpy angles of 102.3,
122.6, 106.8 and 108.0◦ respectively). The coordination sphere
around Zn2+ is composed of two Cl- anions (dZnCl of 2.195 and
˚
˚
Co–N bonds (dCo–N of 2.01 A and 2.02 A for CoCl2 and CoBr2
respectively). The Co(II) is surrounded by two N atoms belonging
to two consecutive tectons 11 (coordinating N atom of pyrazolyl
˚
˚
unit) and two halide anions (dCo–X of 2.22 A and 2.35 A for
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In conclusion, the functionalised [1111]metacyclophane deriva-
tives 7 and 8 bearing two imidazolyl or two pyrazolyl groups
behave as a ligand and a tecton respectively. In the presence of a
variety of MX2 complexes, whereas compound 7 leads to discrete
metallamacrobicycles, compound 8 generates neutral analogous
infinite 1-D coordination networks. The acentric compound 11,
bearing two different sets of coordinating poles (two PhSMe and
two pyrazolyl), owing to the weak binding ability of the thioether
group behaves as an analogue of the disubstituted tecton 8 and
forms 1-D coordination networks in the presence of MX2 centres.
Finally, the combination of ZnCl2 with the acentric tectons 12,
composed of two pyrazolyl and two pyridyl groups, led to the
formation of neutral directional 2-D networks resulting from
the unsymmetrical nature of the coordination node composed of
Zn2+ cation, two Cl- anions and one pyrazolyl and one pyridyl
moieties. However, the packing of consecutive sheets takes place
in an antiparallel fashion leading thus to a non-directional 3-D
organisation.
Fig. 9 A portion (perpendicular view to network axis) of the structure
of the 2-D networks formed by combining tecton 12 with ZnCl2 (a) and
a portion of the structure showing the centric packing of two consecutive
planes (b). For clarity, the two consecutive networks are differentiated by
the colour of C atoms. H atoms and solvent molecules are omitted for
clarity.
We are currently attempting to generate new coordination
networks by combining tectons 9–12 with other metal centres and
metal complexes.
Experimental
General: all reagents were purchased from commercial sources and
used without further purification. 1H NMR spectra were recorded
at room temperature on a Bruker (300 MHz) NMR spectrometer.
Microanalyses were performed by the Service de Microanalyses de
la Fe´de´ration de Recherche de Chimie, Universite´ de Strasbourg,
Strasbourg.
Synthesis
Fig. 10 Schematic representation of the directional 2-D coordination
network formed upon combining the acentric tecton 12 with ZnCl2.
Compound 4. To a solution of compound 3 (1.5 g, 2.19 mmol)
and chloromethyl-methylether (0.5 ml, 6.55 mmol) dissolved in
35 ml of CHCl3, at -10 ◦C anhydrous SnCl4 (0.75 ml) was added
drop wise. After complete addition, the solution was stirred for
˚
2.200 A) and two N atoms, one belonging to the pyridine unit
˚
(dZn–Npy = 2.032 A) and the other to pyrazole moiety (dZn–Npyraz
=
◦
60 min at -10 C and overnight at RT. To the reaction mixture,
˚
2.049 A) of consecutive tectons 12 (Fig. 9(a)). Owing to the un-
symmetrical nature of the assembling node, the 2-D architecture,
oriented along the b axis, is directional (Fig. 10).
20 ml of an aqueous HCl solution (10%) was added drop wise.
The organic phase is separated and washed with water (25 ml) and
then with an aqueous solution of NaOH (25 ml, 1M). The organic
phase was dried over MgSO4. After filtration and removal of the
solvent, the residue was dissolved in a minimum of CH2Cl2 and
100 ml of Et2O are added. The precipitate was filtered affording
pure compound 4 in 87% yield (1.49 g) as a white powder. M. P. >
300 ◦C. 1H-NMR (CDCl3, 300 MHz, 25 ◦C) d (ppm): 1.06 (s, 6H,
p-CH3); 1.14 (s, 6H, p-CH3); 2.45 (s, 12H, o-CH3); 2.59 (s, 12H,
o-CH3); 4.05 (s, 8H, Ar-CH2-Ar); 4.72 (s, 4H, CH2Cl); 13C-NMR
(CDCl3, 75 MHz, 25 ◦C) d (ppm): 18.2; 18.5; 21.7; 22.2; 34.3; 46.2;
130.8; 131.1; 133.6; 133.9; 134.6; 135.3; 133.3; 139.2.
Unfortunately and as often observed, the packing of consecutive
directional 2-D networks takes place in the centrosymmetric
fashion thus leading to a non-polar 3-D organisation (Fig. 9(b)).
The parallel packing of sheets, of the ABA type, generates p–
p interactions between the aromatic moieties of the cyclophane
backbones belonging to consecutive sheets with 3.58 A distance
between them. The overall 3-D structure exhibits two sorts of
channels along the c axis (Fig. 9(b)) with different dimensions,
one small (4 A ¥ 11 A) and one large (7 A ¥ 15 A). The H2O and
MeOH solvents molecules are located within the large channels.
The percentage of the potential accessible volume calculated using
the PLATON software is 23%.
Unfortunately, except for crystals composed of discrete met-
allamacrobicyclic units obtained with ligand 7, all other solid
materials were found to lose their structural integrity upon release
of solvent molecules. In particular, for crystals composed of tecton
12 and ZnCl2 offering channels, X-ray diffraction study on powder
revealed the complete loss of crystalline order upon release of H2O
and MeOH molecules.
˚
˚
˚
˚
˚
Compound 7. To a solution of sodium imidazolate (234 mg,
2.6 mmol) dissolved in 30 ml of dry DMF, compound 4 (500 mg,
0.64 mmol) and a spatula of NaI were added. The solution was
stirred for 24 h at 95 ◦C. After cooling to RT, the solvent was
removed and the residue dissolved in 50 ml of CH2Cl2 and washed
with 50 ml of an aqueous saturated solution of NaHCO3 and then
with 50 ml of water. The organic layer was separated and dried over
MgSO4. After filtration and removal of the solvent, the residue
was dissolved in 10 ml of CH2Cl2. Addition of 2 ml of MeOH
2142 | Dalton Trans., 2010, 39, 2137–2146
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and 50 ml of Et2O followed by cooling to 0 ◦C generated a white
precipitate which was filtered and washed with small portions of
Et2O affordin◦g 0.44 g of compound 7 (81% yield) as◦a white solid.
removed under reduced pressure. The residue thus obtained was
dissolved in CH2Cl2 (20 ml) and washed with an aqueous solution
of NaOH (1M) (25 ml) and then with water (25 ml). The organic
phase was dried over MgSO4. After filtration and removal of
the solvent, the mixture was purified by column chromatography
(SiO2, CH2Cl2). Compounds 11 and 12 were obtained in 32 and
38% yields respectively.
1
M. P. > 300 C. H-NMR (CDCl3, 300 MHz, 25 C), d (ppm):
1.11 (s, 6H, p-CH3); 1.19 (s, 6H, p-CH3); 2.33 (s, 12H, o-CH3); 2.59
(s, 12H, o-CH3); 4.06 (s, 8H, Ar-CH2-Ar); 5.21 (s, 8H, CH2-Im);
6.78 (bs, 4H, H-Im); 7.05 (bs,◦4H, H-Im); 7.22 (bs, 4H, H-Im). 13C-
NMR (CDCl3, 75 MHz, 25 C), d (ppm): 17.2; 18.0; 19.1; 22.6;
34.2; 46.8; 118.6; 128.3; 128.9; 129.3; 133.5; 133.6; 134.2; 136.4;
136.7; 138.1; 138.8. Calc (%) for C48H54Br2N4 (mw = 846.78): C
68.08; H 6.43; N 6.62; found: C 67.92; H 6.21; N 6.76.
◦
1
Compound 9. M. P. > 300 C. H-NMR (CDCl3, 300 MHz,
25 ◦C), d (ppm): 1.24 (s, 3H, p-CH3); 1.31 (s, 6H, p-CH3); 2.06
(s, 12H, o-CH3); 2.37 (s, 12H, o-CH3); 4.06 (AB, 8H, J = 18 Hz,
Ar-CH2-Ar); 5.24 (s, 4H, CH2-Im); 6.81 (s, 2H, H-Im); 7.06 (s, 4H,
H-Pyridine); 7.08 (s, 2H, H-Im), 8.68 and 8.71 (d, 2H, J = 5,8 Hz,
H-Pyridine); 13C-NMR (CDCl3, 75 MHz, 25 ◦C), d (ppm): 17.2;
18.2; 18.3; 19.3; 29.7; 33.0; 47.1; 118.8; 124.9; 125.2; 128.6; 128.8;
128.9; 130.7; 133.6; 135.1; 136.2; 136.8; 137.7; 138.4; 138.5; 150.0;
150.1; 151.9. Calc (%) for C58H62N6 (mw = 843,15): C 82.62; H
7.41; N 9.97; found: C 82.56; H 7.70; N 10.13.
Compound 8. Under argon atmosphere and at RT, to a
suspension of sodium hydride (60% in oil) (60 mg, 2.5 mmol)
in 30 ml of dry DMF, pyrazole (177 mg, 2.6 mmol) was added
in small portions. The solution was stirred for 2 h at RT before
compound 4 (500 mg, 0.64 mmol) and a spatula of NaI were
added. The solution was stirred for 24 h at 95 ◦C. After cooling to
RT, the solvent was removed and the residue dissolved in 50 ml of
CH2Cl2. The organic phase was washed with 50 ml of an aqueous
saturated solution of NaHCO3 and then with 50 ml of water. The
organic layer was separated and dried over MgSO4. After filtration
and removal of the solvent, the residue was dissolved in 10 ml of
CH2Cl2 and upon addition of 2 ml of MeOH and 50 ml of Et2O
a precipitate was obtained which was filtrated and washed with
small portions of Et2O affording 0.43 mg of the pure compound
8 (79% yield) as a white solid. M. P. > 300 ◦C. 1H-NMR (CDCl3,
300 MHz, 25 ◦C), d (ppm): 1.15 (s, 6H, p-CH3); 1.21 (s, 6H, p-
CH3); 2.35 (s, 12H, o-CH3); 2.62 (s, 12H, o-CH3); 4.09 (s, 8H,
Ar-CH2-Ar); 5.45 (s, 8H, CH2-Pyr); 6.16 (t, 2H, J1 = 2,0 Hz, J2 =
1,5 Hz, H-Pyr); 6.88 (d, 2H, J = 2 Hz, H-Pyr); 7.57 (d, 2H, J =
1,5 Hz, H-Pyr); 13C-NMR (CDCl3, 75 MHz, 25 ◦C), d (ppm): 17.2;
18.1; 19.0; 22.6; 34.2; 51.7; 105.1; 127.6; 128.3; 129.4; 133.6; 133.9;
134.3; 136.5; 138.0; 138.9; 139.4. Calc (%) for C48H54Br2N4 (mw =
846.78): C 68.08; H 6.43; N 6.62; found: C 68.10; H 6.46; N 6.80.
Compound 10. M. P. > 300 ◦C. 1H-NMR (CDCl3, 300 MHz,
25 ◦C), d (ppm): 1.25 (s, 6H, p-CH3); 1.31 (s, 6H, p-CH3); 2.05
(s, 12H, o-CH3); 2.36 (s, 12H, o-CH3); 3.99 and 4.10 (AB, 8H,
J = 18 Hz, Ar-CH2-Ar); 5.45 (s, 8H, CH2-Pyr); 6.16 (t, 2H, J1 =
2,0 Hz, J2 = 2,2 Hz, H-Pyr); 6.87 (d, 2H, J = 2,2 Hz, H-Pyr); 7.08
(d, 4H, J = 5,5 Hz, H-Pyridine); 7.54 (d, 2H, J = 2 Hz, H-Pyr);
8.67 (bs, 4H, H-Pyridine); 13C-NMR (CDCl3, 75 MHz, 25 ◦C) d
(ppm): 17.2; 18.1; 18.4; 19.3; 29.7; 33.2; 51.8; 105.0; 126.6; 127.6;
129.3; 130.0; 130.2; 131.7; 133.8; 134.4; 136.2; 136.8; 137.5; 138.5;
139.3; 140.3; 140.6. Calc (%) for C58H62N6 (mw = 843,15): C 82.62;
H 7.41; N 9.97; found: C 82.76; H 7.19; N 10.04.
Compound 11. M. P. > 300 ◦C. 1H-NMR (CDCl3, 300 MHz,
25 ◦C), d (ppm): 1.23 (s, 6H, p-CH3); 1.33 (s, 6H, p-CH3); 2.08 (s,
12H, o-CH3); 2.36 (s, 12H, o-CH3); 2.56 (s, 12H, S-CH3); 4.02 and
4.10 (AB, 8H, J = 18 Hz, Ar-CH2-Ar); 5.25 (s, 8H, CH2-Pyr); 6.83
(s, 2H, H-Pyr); 7.00 (dd, 2H, J1 = 8,7 Hz, J2 = 1,8 Hz, H-Ph); 7.04
(dd, J1 = 8,7 Hz, J2 = 1,8 Hz, 2H, H-Ph); 7.08 (s, 2H, H-Pyr); 7.24
(s, 2H, H-Pyr); 7.34 (m, 4H, H-Ph); 13C-NMR (CDCl3, 75 MHz,
25 ◦C), d (ppm): 17.0; 17.2; 18.1; 18.6; 19.7; 29.9; 32.9; 53.2; 105.7;
127.0; 127.8; 129.3; 130.1; 130.5; 131.7; 134.0; 134.8; 137.2; 136.4;
137.2; 138.8; 139.0; 140.9; 142.8. Calc (%) for C62H68N4S2 (mw =
933.36): C 79.78; H 7.34; N 6.00; found: C 80.13; H 7.12; N 6.03.
Compounds 9 and 10. A solution of compound 7 (203 mg,
0.24 mmol) and anhydrous Cs2CO3 (156.0 mg, 0.48 mmol)
in dry DMF (20 ml) was degassed for 20 min with argon.
Under argon, Pd(PPh3)4 (27.8 mg, 0.024 mmol) and either 4-
(methylthio)phenylboronic ester 5 (180.1 mg, 0.72 mmol) or 4-
pyridineboronic ester 6 (148.0 mg, 0.72 mmol) were added. The
mixture thus obtained was placed in a microwaves oven (120 W)
and was stirred at 130 ◦C for 30 min. The solution was filtered and
the solvent removed under vacuum. The residue was dissolved
in CH2Cl2 (20 ml) and washed with an aqueous solution of
NaOH (1 M) (25 ml) and then with water (25 ml). The organic
phase was dried over MgSO4. After filtration and removal of
the solvent, the mixture was purified by column chromatography
(SiO2, CH2Cl2). Compounds 9 and 10 were obtained in 28 and
22% yields respectively.
Compound 12. M. P. > 300 ◦C. 1H-NMR (CDCl3, 300 MHz,
25 ◦C), d (ppm): 1.29 (s, 6H, p-CH3); 1.37 (s, 6H, p-CH3); 2.12 (s,
12H, o-CH3); 2.40 (s, 12H, o-CH3); 2.57 (s, 12H, S-CH3) 3.99 and
4.10 (AB, 8H, J = 18 Hz, Ar-CH2-Ar); 5.49 (s, 8H, CH2-Pyr); 6.17
(t, 2H, J1 = 2,0 Hz, J2 = 2,2 Hz, H-Pyr); 6.90 (d, 2H, J = 2,2 Hz,
H-Pyr); 7.05 (m, 8H, H-Ph); 7.37 (m, 8H, H-Ph); 7.6 (d, 2H, J =
2 Hz, H-Pyr); 13C-NMR (CDCl3, 75 MHz, 25 ◦C), d (ppm): 16.9;
17.2; 18.1; 18.4; 19.3; 29.7; 33.2; 51.8; 105.0; 126.6; 127.6; 129.3;
130.0; 130.2; 131.7; 133.8; 134.4; 136.2; 136.8; 137.5; 138.5; 139.3;
140.3; 140.6. Calc (%) for C62H68N4S2 (mw = 933.36): C 79.78; H
7.34; N 6.00; found: C 80.02; H 7.33; N 6.15.
Procedure for 11 and 12. A solution of compound 8 (210 mg,
0.25 mmol) and anhydrous Cs2CO3 (162.5 mg, 0.5 mmol) in
dry DMF (20 ml) was degassed for 20 min with argon. Under
argon atmosphere, Pd(PPh3)4 (28.8 mg, 0.025 mmol) and either
4-(methylthio)phenylboronic ester 5 (187.6 mg, 0.75 mmol) or
4-pyridineboronic ester 6 (154.2 mg, 0.75 mmol) were added. The
mixture was placed in a microwaves oven (120 W) and stirred
at 130 ◦C for 30 min. The solution was filtered and the solvent
Crystallisation
All discrete complexes 7-MX2: (M = Co; Zn; Cu; Hg; X= Cl
or Br) have been prepared as crystalline materials and have
been characterised by X-ray diffraction on single crystal and by
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Table 4 Crystallographic parameters for discrete metallamacrobicycles obtained upon combining compound 7 with MX2 (M = Co, Zn, Cu and Hg,
X = Cl or Br)
CoCl2
CoBr2
ZnBr2
CuBr2
HgBr2
Formula
C96H118Br4Cl4Co2N8O5
2043.28
Triclinic
¯
P1
C49H55Br4Cl3CoN4
1184.89
Triclinic
¯
P1
C49H55Br4Cl3N4Zn
1191.33
Triclinic
¯
P1
C49H55Br4Cl3CuN4
1189.50
Triclinic
¯
P1
C49H55Br4Cl3HgN4
1326.55
Triclinic
¯
P1
Formula weight
Crystal system
Space group
˚
a/A
11.8253(9)
14.3000(11)
15.6345(12)
92.834(4)
99.430(3)
107.919(4)
2467.5(3)
1
1.375
2.117
33 489
0.0485
11.5480(2)
14.7042(3)
15.2422(3)
92.5061(9)
92.9050(8)
110.0702(10)
2422.73(8)
2
1.624
3.857
38 997
0.0399
11.5652(2)
14.7038(4))
15.2283(4)
92.5000(10)
92.9650(10)
110.0270(10)
2424.56(10)
2
1.632
4.007
48 230
0.0450
11.4322(3)
14.6136(3)
15.3801(4)
91.8790(10)
93.1620(10)
109.7170(10)
2411.54(10)
2
1.638
3.972
35 032
0.0453
11.4429(6)
14.9630(9)
15.3162(11)
92.715(2)
90.510(2)
110.905(2)
2446.1(3)
2
1.801
6.615
45 948
0.0604
˚
b/A
˚
c/A
a/◦
b/◦
a/◦
3
˚
V/A
Z
s calcd/g cm-3
m/mm-1
No. of reflections
R(int)
No. of data I > 2s(I)
Final R indices [I > 2s(I)]
10 866
11 105
10 879
11 055
11 001
R1 = 0.0820
wR2 = 0.2357
R1 = 0.1285
wR2 = 0.2717
1.050
R1 = 0.0542
wR2 = 0.1209
R1 = 0.0854
wR2 = 0.1349
1.021
R1 = 0.0646
wR2 = 0.1422
R1 = 0.0861
wR2 = 0.1594
1.072
R1 = 0.0539
wR2 = 0.1131
R1 = 0.0868
wR2 = 0.1300
1.011
R1 = 0.0564
wR2 = 0.1317
R1 = 0.0935
wR2 = 0.1576
1.009
R indices (all data)
GoF
Table 5 Crystallographic parameters for 1-D coordination networks obtained upon combining the compound 8 with MX2 (M = Co, Zn; X = Cl or Br).
For (8-CoBr2)n, (8-ZnCl2)n and (8-ZnBr2)n the solvents are disordered and the Squeeze command was used
CoCl2
CoBr2
ZnCl2
ZnBr2
Formula
C48H54Br2Cl2CoN4
976.60
Monoclinic
P21/n
13.0585(9)
26.0298(18)
16.2349(11)
90
101.517(2)
90
5407.3(6)
4
1.200
1.926
2004
0.0637
12 429
R1 = 0.0768
wR2 = 0.1960
R1 = 0.1490
wR2 = 0.2146
1.032
C48H54Br4CoN4
1065.52
Orthorhombic
Pca21
18.3656(4)
16.0416(4)
17.5199(6)
90
90
90
5161.6(2)
4
1.371
3.462
23 482
0.0540
9338
R1 = 0.0951
wR2 = 0.2445
R1 = 0.1267
wR2 = 0.2672
1.256
C48H54Br2Cl2N4Zn
983.04
Orthorhombic
Pbca
21.629(2)
18.9786(18)
34.265(3)
90
90
90
14065(2)
8
0.928
1.586
70 819
0.1083
15 804
R1 = 0.1077
wR2 = 0.2648
R1 = 0.2206
wR2 = 0.2901
1.091
C48H54Br4N4Zn
1071.96
Orthorhombic
Pbca
21.8030(10)
19.3128(9)
33.4302(14)
90
Formula weight
Crystal system
Space group
˚
a/A
˚
b/A
˚
c/A
a/◦
b/◦
a/◦
90
90
3
˚
V/A
14076.7(11)
8
1.012
2.644
130 795
0.0845
16 242
R1 = 0.0867
wR2 = 0.1729
R1 = 0.2001
wR2 = 0.1911
1.020
Z
s calcd/g cm-3
m/mm-1
No. of reflections
R(int)
No. of data I > 2s(I)
Final R indices [I > 2s(I)]
R indices (all data)
GoF
elemental analysis. These compounds are insoluble in common
solvents and for that reason were not further characterised.
7-MX2: in a crystallisation tube (15 cm height, 0.4 cm diameter),
single-crystals were obtained at room temperature after ca. 3 days
upon slow diffusion of 1.5 ml of a MeOH solution containing 3 mg
of the metallic salt into 1 ml of a CHCl3 solution containing 1 mg
of compound 7.
7-ZnBr2: calc. for C56H64Br6N8Zn (MW = 1072.00): C 53.78; H
5.08; N 6.10; found C 54.01; H 5.15; N 5.88.
7-CuBr2: calc. for C56H64Br6CuN8 (MW = 1070.13): C 53.87; H
5.09; N 5.24; found C 53.78; H 5.11; N 5.54.
7-HgBr2: calc. for C56H64Br6HgN8 (MW = 1207.18): C 47.76; H
4.51; N 4.64; found C 47.79; H 4.63; N 4.90.
(8-MX2)n: in a crystallisation tube (15 cm height, 0.4 cm
diameter), single-crystals were obtained at room temperature after
ca. 3 days upon slow diffusion of 1.5 ml of a MeOH solution
containing 3 mg of the metallic salt into 1 ml of a CHCl3 solution
containing 1 mg of the compound 8.
7-CoCl2: calc. for C48H54Br2Cl2CoN4 (MW = 976.62): C 59.03;
H 5.57; N 5.74; found C 58.83; H 5.76; N 6.00.
7-CoBr2: calc. for C56H64Br6CoN8 (MW = 1065.52): C 54.40; H
5.11; N 5.26; found C 54.56; H 5.02; N 5.55.
2144 | Dalton Trans., 2010, 39, 2137–2146
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Table 6 Crystallographic parameters for coordination networks obtained upon combining 11 with MX2 (X = Cl or Br) and tecton 12 with ZnCl2. For
(11-CoCl2)n and (11-CoBr2)n the solvents are disordered and the Squeeze command was used
(11-CoCl2)n
(11-CoBr2)n
(12-ZnCl2)n
Formula
C62H68Cl2CoN4S2
1063.15
Monoclinic
P21/c
15.8582(6)
13.8304(6)
32.7069(12)
90
91.618(2)
90
7170.6(5)
4
C62H68Br2CoN4S2
1152.07
Monoclinic
P21/c
16.0135(18)
14.0197(13)
32.858(4)
90
92.339(3)
90
7370.7(13)
4
1.038
1.406
58 445
16 440
0.0685
R1 = 0.0970
wR2 = 0.2566
R1 = 0.1446
wR2 = 0.2766
1.068
C234H260Cl16N24O4Zn8
4562.82
Monoclinic
C2/c
12.6081(13)
32.110(4)
13.8506(15)
90
94.815(4)
90
5587.6(11)
1
1.356
1.095
42 137
6425
0.0471
R1 = 0.0910
wR2 = 0.3180
R1 = 0.1311
wR2 = 0.2921
1.254
Formula weight
Crystal system
Space group
˚
a/A
˚
b/A
˚
c/A
a/◦
b/◦
a/◦
3
˚
V/A
Z
s calcd/g cm-3
0.985
0.405
45 269
16 440
m/mm-1
No. of reflections
No. of data I > 2s(I)
R(int)
0.0439
Final R indices [I > 2s(I)]
R1 = 0.1026
wR2 = 0.3039
R1 = 0.1480
wR2 = 0.340
1.263
R indices (all data)
GoF
(10-[ZnCl2]2)n: in a crystallisation tube (15 cm height, 0.4 cm
diameter), single-crystals were obtained at room temperature
after ca. 3 days upon slow diffusion of 1.5 ml of a MeOH
solution containing 3 mg of the metallic salt into 1 ml of a 1,2-
dichloroethane solution containing 1 mg of the compound 10.
(12-CoX2)n (X = Cl, Br): in a crystallisation tube (15 cm
height, 0.4 cm diameter), single-crystals were obtained at room
temperature after ca. 3 days upon slow diffusion of 1.5 ml of a
MeOH solution containing 3 mg of the metallic salt into 1 ml
of a 1,2-dichloroethane solution containing 1 mg of the com-
pound 12.
are acknowledged for financial support and for a scholarship
to J. E.
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Crystallography†
Data were collected at 173(2) K on a Bruker APEX8 CCD
Diffractometer equipped with an Oxford Cryosystem liquid N2
device, using graphite-monochromated Mo Ka (l = 0.71073)
radiation. The structures were solved using SHELXS-97 and
refined by full matrix least-squares on F2 using SHELXL-97.21
The hydrogen atoms were introduced at calculated positions
and not refined (riding model). All hydrogen atoms have been
calculated except those connected to disordered atoms. In some
cases, because of the disorder of the solvent molecules, the squeeze
command20 was used. In several cases, the diffraction power of
crystals generated was also rather low. Consequently, in some
cases, the R factors obtained are rather high. However, this should
not affect significantly the structural descriptions of the networks
reported.
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Universite´ de Strasbourg, the International Centre for Frontier
Research in Chemistry (FRC), Strasbourg, Institut Universitaire
de France, the CNRS and the Ministry of Education and Research
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2146 | Dalton Trans., 2010, 39, 2137–2146
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