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Molecular tectonics: generation and structural studies on 1- and 2D coordination networks based on a meta-cyclophane in 1,3-alternate conformation bearing four pyrazolyl units and cobalt, zinc and copper cations
J r me Ehrhart, Jean-Marc Planeix,* Nathalie Kyritsakas-Gruber and Mir Wais Hosseini* eo
Received 23rd February 2009, Accepted 19th May 2009 First published as an Advance Article on the web 29th June 2009 DOI: 10.1039/b903674a The combination of a [1111] metacyclophane blocked in 1,3-alternate conformation and bearing four pyrazolyl coordinating units with MX2 (M = Co, Zn and X = Cl or Br) leads to the formation of crystals formed by packing of 2D coordination networks. In the case of CuBr2 , the formation of a 1D network was observed. Structural studies by X-ray diffraction methods on single crystals were performed on all cases reported.

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Introduction
Since the pioneering work by Robson et al.,1 coordination polymers or MOFs, periodic architectures based on organic and metallic tectons,2,3 are attracting considerable interest. The interest in this class of solids results from its potential applications, in particular, in separation, storage and catalysis.4 Coordination networks are based on iterative formation of coordination bonds between organic units and metal centres. In other terms, both the organic construction units and the metallic centres upon mutual interactions generate structural nodes of the network. The formation of such assemblies results from the interconnection of organic tectons bearing at least two divergently oriented coordinating sites and metal centres or complexes offering at least two free coordination sites also divergently oriented. One of the characteristics associated with coordination networks is their dimensionality (1-, 2- or 3D). The latter, dened by the number of independent translations operating at the level of the structural nodes, in principle may be controlled by both characteristics of the organic and metallic tectons. Pursuing our investigation on the design and formation of new coordination networks,5 we describe in this contribution the design, synthesis and structural investigations of a series of 1- and 2D coordination networks based on the combination of a [1111] metacyclophane backbone bearing four pyrazolyl units 2 (Scheme 1) with metal cations (Zn(II), Co(II) and Cu(II)).

Results and discussion

As stated above, the generation of coordination networks is based on the formation of coordination bonds and its iteration generating the periodicity of the architecture. The latter process requires divergent orientation of coordination sites on the organic tecton. Another important factor associated with the design of
Laboratoire de Chimie de Coordination Organique (UMR CNRS 7140), Universit de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal, 67000, e Strasbourg, France. E-mail: hosseini@chimie.u-strasbg.fr; Fax: +33 390241325; Tel: +33 390241323 CCDC reference numbers 721426721431. For crystallographic data in CIF or other electronic format see DOI: 10.1039/b903674a

networks is the rigidity of the construction units employed which often determine the predictability of the construction process. Taking into account these two features, the [1111] metacyclophane backbone is of particular interest. Indeed, for this type of cyclic platform, among the four possible isomers, the 1,3-alternate conformation is the most stable one in solution over a wide range of temperature (-60 to 150 C) implying a high rigidity of the skeleton.6 Furthermore, in the solid state, its blocked 1,3-alternate conformation was established by X-ray diffraction on single crystals for a variety of derivatives such as tetrahydoxyl,6 tetracyano7 and tetramercapto,8 tetrapyridine,9,10 tetrakis bipyridine11 and tetrakis quinoline,12 tetraimidazolyl13 derivatives as well as for its disubstituted derivatives.14 Taking advantage of this rigid and blocked conformation, one may introduce up to four coordinating sites located two-by-two on both faces of the main plane of the backbone (Fig. 1a). In order to avoid the formation of discrete metallamacrotricycles (Fig. 1b), as we have previously demonstrated for the tetrakis imidazolyl derivative (compound 3, Scheme 1)13 and to promote the formation of innite networks (Fig. 1d and e), the pyrazolyl unit was chosen. The latter was connected to the cyclophane backbone by a CN bond using a methylene group as spacer between the aromatic moiety and the coordinating unit. This design principle is based on our previous investigations on the formation of innite 1D tubular coordination networks (Fig. 1d) generated upon combining the [1111] metacyclophane bearing pyridyl,9,10 or cyanophenyl7 groups with silver cation. We15 and others16 have previously used the pyrazolyl moiety as a coordinating site for the design of tectons and the formation of coordination networks. The use of cycltriveratrylene as preorganised macrocyclic backbone for the design of coordinating tectons and the generation of coordination networks has been also reported.17 Owing to the distance of ca. 7.0 A between the two CH2 groups located on the same face of the molecule and the bent angle imposed by the connection of the pyrazolyl unit through its N atom, the tecton 2 should generate periodic architectures when associated with appropriate metal centres. However, although the [1111] metacyclophane backbone is intrinsically rigid, the introduction of the methylene group between its phenyl group and the pyrazolyl unit and the rotational Dalton Trans., 2009, 63096314 | 6309

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(i) or periphery (o)), several extreme rotamers may coexist. Fig. 2 shows a demonstrative example of one of the rotamers (Ci Ni ,Co No ,Ci No ,Co Ni ).

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Fig. 2 Owing to the rotational freedom of the CCH2 and CH2 N bonds, compound 2 blocked in 1,3-alternate conformation may adopt several rotamers. Here, the Ci Ni ,Co No ,Ci No ,Co Ni rotamer is schematically represented (i = in; o = out with respect to the centroid of the backbone). The red plane represents the main plane of the cyclophane.

Fig. 1 Schematic representation of a discrete metallamacrocycle (b) formed by the (i,i,i,i) rotamer (a) of 3 and of 1D (d) and 2D (e) innite coordination networks generated by combining the (o,o,o,o) rotamer (c) of 2 with tetra coordinated metal centres bearing two free coordination sites.

The synthesis of 2 (Scheme 1) was achieved in 73% yield upon condensation of the chlorinated precursor 117 with sodium pyrazolate, generated in situ by treatment of pyrazol with sodium hydride, in DMF at 95 C and in the presence of catalytic amounts of NaI (see experimental section). The 1,3-alternate conformation of compound 1 has been established by X-ray diffraction on single crystals.18 As expected, the synthetic step performed did not alter the 1,3-alternate conformation of the free tecton 2 as veried in the solid state by X-ray diffraction on single crystal (See Experimental, and Fig. 3).

Fig. 3 The solid state structure of free 2 showing the blocked 1,3-alternate conformation of the cyclophane backbone. Compound 2 is present as its Co Ni ,Ci No ,Co Ni ,Co Ni rotamer (see Fig. 2 for notation). For sake of clarity, H atoms and solvent molecules are omitted. For bond distances and angles see text.

Scheme 1

freedom resulting from the single CN bond render the tecton 2 rather exible. Indeed, depending on the orientation of the pyrazolyl and methylene groups (each may adopt two extreme orientations with respect to the backbone: towards the centre
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The compound 2 is a neutral ligand. In order to generate neutral coordination networks, the ligand 2 was combined with neutral metal complexes offering two free coordination sites. Thus, metal halide MX2 type complexes were used. Whereas the combination of 2 with MX2 (M = Co2+ , Zn2+ X = Cl- , Br- ) afforded four isostructural 2D coordination networks, in the case of CuBr2 a 1D metallaorganic architecture was obtained (see Experimental). This journal is The Royal Society of Chemistry 2009

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Structural investigations The solid state structure of the free tecton 2 was investigated by X-ray diffraction on single crystal. The crystal (triclinic, space group P1), in addition to the ligand 2 contains 0.5 CHCl3 solvent molecules. The structural determination (see Experimental) conrmed the 1,3-alternate conformation of the tecton 2 (Fig. 3). For the four pyrazolyl units connected to the cyclophane backbone through methylene junctions, the following metrics (d CC in the range of 1.511.52 A, d CN in the range of 1.451.46 A, CNC angle in the range of 124.5126.3 ) were observed. Among the four pyra zolyl units (d CN in the range of 1.451.46 A d NN in the range of 1.34 1.35 A and NCN angle in the range of 129.0130.0 ), three are oriented outwardly and one inwardly (Ni Ni Ni No isomer) with respect to the interior of the backbone. When taking into account both the orientation of the pyrazolyl and methylene groups, the Co Ni ,Ci No , Co Ni ,Co Ni rotamer is observed (see Fig. 2 for notation). The nitrogen atoms (secondary) of two pyrazolyl moieties located on the same face of the molecule are distant by 8.49 and 10.94 A. The ability of tecton 2 to generate innite coordination networks was investigated by combining 2 with metal halides (MX2 , M = Co2+ and Zn2+ X = Cl- and Br- and CuBr2 ). In all cases, the crystal structures of the coordination networks has been studied by X-ray diffraction on single crystals (see Experimental, and Fig. 4, Fig. 5 and 7).

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Fig. 5 A portion of the 2D coordination network (view along the c axis) generated upon combining the tecton 2 with ZnCl2 . H atoms and solvent molecules are omitted for clarity. For bond distances and angles see text.

Fig. 4 A portion of the 2D coordination network (view along the c axis) generated upon combining the tecton 2 with CoCl2 . H atoms and solvent molecules are omitted for clarity. For bond distances and angles see text.

Fig. 6 Representation (CPK model) of a portion of the structure of the crystal obtained upon combining 2 with CoCl2 showing the packing along the c axis of two consecutive 2D networks. For sake of clarity, the two networks are differentiated by the colour of C atoms. H atoms and solvent molecules are omitted for clarity.

For [2-(MX2 )]n (M = Co2+ and Zn2+ X = Cl or Br) (Fig. 46), the X-ray studies revealed the formation of isostructural 2D networks. Although all four structures are discussed below, we shall only present graphically the 2D networks obtained with CoCl2 (Fig. 4) and ZnCl2 (Fig. 5). For all four cases, the crystal system is orthorhombic with Pbcn as the space group. In all cases, the crystal contains disordered solvent molecules (see Experimental). Whereas in the case of the Co based network the solvent mixture was dichloroethaneethanol, for the Zn based coordination polymer, a mixture of dichloroethanemethanol was found. Owing to the disorder and rapid loss of solvent molecules, their proportion could not be precisely determined and the SQUEEZE command19 was used for the structural resolution. Thus, although the metric precision is low, the connectivity pattern however remains reliable. This journal is The Royal Society of Chemistry 2009

Although the same type of architecture (Fig. 1e) is obtained in all 4 cases, as expected, the bond distances and angles are different for each network (Tab. 1). The tecton 2 adopts the Co Ni ,Co Ni ,Co Ni ,Co Ni conformation (all four pyrazolyl units are outwardly oriented and for each pyrazolyl unit, the coordinating N atom is inwardly positioned). In other terms, the only difference between the free tecton 2 (Fig. 3) and engaged ones in 2D networks, is based on the rotation of one of the four pyrazolyl groups. Both Co(II) and Zn(II) cations adopt distorted tetrahedral coordination geometry (for angles see Table 1). Their coordination sphere is composed of two halides (Cl or Br) and two N atoms belonging to pyrazolyl moieties of consecutive tectons 2 (for d MN and d MX see Tab. 1) leading thus to neutral nodes. The 2D networks thus formed are neutral. For the 2D networks formed with (CoCl2 ) (Fig. 4) and (CoBr2 ), as expected, both d NCo and d XCo distances are increased upon Dalton Trans., 2009, 63096314 | 6311

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Table 1 Average bond distances (A) and angles ( ) M X d NM /A) d XM /A) NMN/ XMX/ Co Cl 1.95 2.00 102.0 114.0 Co Br 2.00 2.37 103.5 113.2 Zn Cl 2.00 2.24 101.2 115.0 Zn Br 2.00 2.39 101.6 115.2

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Fig. 7 TGA analysis of solvated crystals of [2-(CoCl2 )]n (red) and of [2-(ZnCl2 )]n (blue) between 30 and 400 C (under N2 , rate scan 2 min-1 ). Whereas in the case of the Co based network the solvent mixture was dichloroethaneethanol, for the Zn based coordination polymer, a mixture of dichloroethanemethanol was used.

substitution of chloride by bromide anion. For both cases, the two cobalt centres located on the same face of the cyclophane are distant by ca. 11.13 A. For the 2D networks formed with (ZnCl2 ) (Fig. 5) and (ZnBr2 ), whereas in average the same d NZn distance (2.00 A) is observed for both cases, the d XZn distance is increased when chloride is replaced by bromide anion (Table 1). Compared to the network based on Co cation, the increase in distance between two zinc cations located on the side of the macrocycle is substantially higher (d ZnZn = 10.33 A for bromide). for chloride and d ZnZn = 11.13 A The consecutive 2D networks are packed along the c axis. However, the packing mode is of the type ABA with staggered arrangement of consecutive sheets (Fig. 6). This mode of packing generates pores which are occupied by solvent molecules. The porosity of all four crystals was analysed using the PLATON software (see Table 2). A free volume per unit cell of ca. 50% was calculated for all four crystals studied.
Table 2 Porosity characteristic of the four crystalline materials obtained upon combining the tecton 2 with (MX2 ) (M = Co2+ and Zn2+ X = Cl or Br) M X Unit cell volume/A3 Total potential solvent area volume/A3 a Free volume per unit cell (%)
a

The TGA analysis on crystals containing 2 and CoCl2 or ZnCl2 revealed two intermediate regimes, the rst one between 30 and 100 C and the second one between 100 and 200 C, prior to decomposition of the samples, which appeared at ca. 350 C (Fig. 7). The rst loss of mass corresponds to the release of the alcohol (EtOH in the case of cobalt and MeOH in the case of zinc) solvent molecules and the second one to the release of dichloroethane. In the case of [2-(ZnCl2 )]n , owing to the lower boiling point of MeOH with respect to EtOH present in crystals based on [2-(ZnCl2 )]n networks, the slope of the solvent release in the 30100 C range was steeper as expected. In both cases, the uptake of solvent molecules was also studied by TGA measurements. In order to evacuate the solvent molecules and to avoid decomposition, the sample was rst heated to 220 C under nitrogen ow and then allowed to cool to room temperature. The desolvated samples were exposed to different solvents (CH2 Cl2 , CHCl3 , ClCH2 C-CH2 Cl, MeOH and EtOH) either in the liquid or vapour phase for 24 h. TGA analysis showed in both cases the absence of solvent uptake. A possible reason for this observation could be the loss of structural integrity. Indeed, it was observed that after the complete removal of solvent molecules, although the material appeared as crystalline however crystals were strongly striated. In order to investigate the crystallinity of samples, they were studied by both X-ray diffraction on single crystal and on powder. Both techniques revealed the complete loss of order and crystallinity. Surprisingly, the combination of 2 with CuBr2 leads to a different architecture. Indeed, the X-ray diffraction on single crystal revealed the formation of 1D network (Fig. 8). The network

Co Cl 8797.1 4481.0 50.9

18

Co Br 8945.9 4573.2 51.1

Zn Cl 8769.9 4401.4 50.2

Zn Br 8947.1 4525.9 50.6

Calculated by PLATON software.

Fig. 8 A portion of the 1D coordination network generated upon combining the tecton 2 with CuBr2 . To emphasis the coordination around the two non-equivalent Cu centres, two different views are presented. H atoms and solvent molecules are omitted for clarity. For bond distances and angles see text.

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belongs to the category of a 1D tubular architectures (Fig. 1d). We have previously observed the formation of such networks using either calixarene derivatives20 or cyclophane type tectons bearing 4 nitrile or pyridine groups.7,10 The brownish crystal (monoclinic, P2/c) is composed of tecton 2, CuBr2 and EtOH and dichloroethane solvent molecules. The latter are disordered and the diffraction power of the crystal appeared to be rather low. For the structural resolution again the SQUEEZE command was used.18 Consequently, the quality of the resolution was rather low. The tecton 2 adopts the Co Ni ,Co No ,Co Ni ,Co Ni conformation (one of the four pyrazolyl units is outwardly oriented). Two types of Cu atoms are present (see Fig. 8a and b). Although both Cu centres are tetra-coordinated with their coordination sphere composed of two Br- anions and two N atoms of two pyrazolyl units belonging to two consecutive tectons 2, they differ considerably by their coordination geometry. Indeed, whereas as one of the Cu atom adopts an almost tetrahedral coordination geometry (d CuN of 1.97 and 1.96 A, d CuBr of 2.37 A, NCuN angle of 130.0 and BrCuBr angle of 135.5 ), the coordination geometry of the other is almost square planar (d CuN of 1.80 and 1.98 A, d CuBr of 2.33 A, NCuN angle of 166.6 and BrCuBr angle of 169.0 ). Consequently, two different distances between Cu atoms within the 1D network are observed (8.03 A and 9.96 A). In conclusion, the neutral tecton 2, based on [1111] metacyclophane as a backbone adopting the blocked 1,3-alternate conformation equipped with four pyrazolyl coordinating groups leads to the formation of 4 analogous neutral 2D networks. The latter are packed along the c-axis in a staggered fashion leading to 4 isostructural crystals. Although formally these crystals may be considered as porous (packing of 2D networks generating voids occupied by molecules not belonging to the networks), the crystalline materials are not robust and upon removal of solvent molecules, they lose their structural integrity. Unexpectedly, the same tecton leads to the formation of 1D networks in the presence of CuBr2 complex. In order to increase the robustness of the crystalline material, we currently pursue our effort by combining the tecton 2 with other metal centres.

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The organic layer was washed with saturated aqueous NaHCO3 solution (50 mL) and twice with 50 mL of water before it was dried over MgSO4 . The mixture was evaporated to dryness. The slightly yellow solid thus obtained was dissolved in a mixture of CH2 Cl2 (10 mL) and MeOH (2 mL). 50 mL Et2 O was added and the solution was cooled in an ice bath for 2 h. The pure compound 2 (428 mg) was obtained in 73% yield after ltration of the precipitate. 1 H-NMR (CDCl3 , 300 MHz, 25 C, d/ppm): 7.56 (d, 4 H, Pyr-H, J = 1.8 Hz), 6.87 (d, 4 H, Pyr-H, J = 2.4 Hz), 6.15 (t, 4 H, Pyr-H, J 1 = 1.8 Hz, J 2 = 2.4 Hz), 5.44 (s, 8 H, Ph-CH2 Pyr), 4.06 (s, 8 H, Ph-CH2 -Ph), 2.36 (s, 24 H, o-CH3 ), 1.21 (s, 12 H, m-CH3 ). 13 C-RMN (CDCl3 , 300 MHz, 25 C, d/ppm): 139.2, 138.2, 136.2, 133.8, 129.4, 127.5, 104.9, 51.6, 33.1, 18.14, 17.1. Calcd for C56 H64 N8 0.5H2 O (MW = 867.16): C 78.47, H 7.53, N 13.07% found: C 78.27, H 7.65, N 12.98. Crystallisation. Crystals of 2 in a crystallisation tube (15 cm height, 0.4 cm diameter), upon slow diffusion at room temperature of Et2 O (5 mL) into a CHCl3 solution (1 mL) of 2 (4 mg), colourless crystals were obtained after ca. 3 d. Dark blue crystals of 2-CoX2 (X = Cl or Br) were obtained at room temperature in a crystallisation tube (15 cm height, 0.4 cm diameter) upon slow diffusion of 1.5 mL of an EtOH solution containing 1 mg of the metallic salt into 1 mL of a CH2 Cl2 solution containing 2 mg of the compound 2 after ca. 3 d. Colourless crystals of 2-MX2 (M = Zn, X = Cl or Br) and brownish crystals of 2-CuBr2 were obtained at room temperature in a crystallisation tube (15 cm height, 0.4 cm diameter) upon slow diffusion of 1.5 mL of a mixture of MeOHEtOH (1 : 1) containing 1 mg of the metallic salt into 1 mL of a 1,2-dichloroethane solution containing 2 mg of 2. 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 A) radiation. The structures were solved using SHELXS-97 and rened by full matrix least-squares on F 2 using SHELXL-97.21 The hydrogen atoms were introduced at calculated positions and not rened (riding model). All hydrogen atoms have been calculated except those connected to disordered atoms. Because of the disorder of the solvent molecules, the SQUEEZE command18 was used. In several cases, the diffraction power of crystals generated was rather low. Consequently, the R factors obtained are rather high. However, this does not affect signicantly the structural descriptions of the networks reported. Crystallographic data for 2. C112.50 H128.50 Cl1.50 N16 , M = 1757.99, triclinic, a = 10.6861(10), b = 12.9999(11), c = 17.5540(15) A, a = 88.348(2), b = 88.849(1), g = 78.015(2) , U = 2384.2(4) A3 , space group P1, Z = 1, m = 0.113 mm-1 , reections measured: 17 623, independent reections: 9998 [Rint = 0.0286], nal R indices [I > 2s(I)]: R1 = 0.0920, wR2 = 0.2594, GOF = 1.106, R indices (all data): R1 = 0.1473, wR2 = 0.3126. (SQUEEZE). Crystallographic data for [2-(CoCl2 )] C28 H32 Cl2 CoN4 (EtOH1,2-dichloroethane solvate), M = 554.41, orthorhombic, a = 26.3351(17), b = 20.7619(17), c = 16.0893(13) A, U = 8797.1(12) A3 , space group Pbcn, Z = 8, m = 0.526 mm-1 , reections measured: 45 247, independent reections: 8420 [Rint = 0.0844], R1 = 0.0638, wR2 = 0.1247, GOF = 1.055, R indices (all data) R1 = 0.1489, wR2 = 0.1323. Dalton Trans., 2009, 63096314 | 6313

Experimental
General All reagents were purchased from commercial sources and used without further purication. 1 H NMR spectra were recorded at room temperature on a Bruker (300 MHz) NMR spectrometer. Microanalyses were performed by the Service de Microanalyses de la F d ration de Recherche de Chimie, Universit de Strasbourg, e e e Strasbourg. Synthesis Synthesis of 2. Under inert atmosphere and at room temperature, to a solution of sodium hydride (60% in oil) (335 mg, 8.3 mmol) in 50 mL of anhydrous DMF, pyrazole (570 mg, 8.37 mmol) was added and the mixture was stirred for 90 min before compound 118 (500 mg, 0.69 mmol) and a spatula of sodium iodide were slowly added. The solution was heated for 24 h at 95 C and after cooling to room temperature, DMF was removed under vacuum and the crude product dissolved in 50 mL of CH2 Cl2 . This journal is The Royal Society of Chemistry 2009

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Crystallographic data for [2-(CoBr2 )] (SQUEEZE). C28 H32 Br2 CoN4 (EtOH1,2-dichloroethane solvate), M = 643.33, orthorhombic, a = 26.3921(8), b = 20.8329(7), c = 16.2704(5) A, U = 8945.9(5) A3 , space group Pbcn, Z = 8, m = 2.185 mm-1 , reections measured: 65 983, independent reections: 10 294 [Rint = 0.0400], R1 = 0.0645, wR2 = 0.1439, GOF = 1.034, R indices (all data) R1 = 0.1618, wR2 = 0.1558. Crystallographic data for [2-(ZnCl2 )] (SQUEEZE). C28 H32 Cl2 ZnN4 (MeOH1,2-dichloroethane solvate), M = 560.85, orthorhombic, a = 26.4215(19), b = 20.6802(16), c = 16.0503(12) A, U = 8769.9(11) A3 , space group Pbcn, Z = -1 8, m = 0.697 mm , reections measured: 54 882, independent reections: 10 108 [Rint = 0.0946], R1 = 0.0647, wR2 = 0.1690, GOF = 1.010, R indices (all data) R1 = 0.1205, wR2 = 0.1813. (SQUEEZE). Crystallographic data for [2-(ZnBr2 )] C28 H32 Cl2 ZnN4 (MeOH1,2-dichloroethane solvate), M = 649.77, orthorhombic, a = 26.3680(10), b = 20.8457(8), c = 16.2776(7) A, U = 8947.1(6) A3 , space group Pbcn, Z = 8, m = 2.350 mm-1 , reections measured: 66 838, independent reections: 10 294 [Rint = 0.0971], R1 = 0.0642, wR2 = 0.1429, GOF = 1.018, R indices (all data) R1 = 0.1441, wR2 = 0.1554. (SQUEEZE). Crystallographic data for [2-(CuBr2 )] C56 H64 Br4 Cu2 N8 (EtOH1,2-dichloroethane solvate), M = 1295.87, monoclinic, a = 21.815(2), b = 14.8140(17), c = 22.496(3) A, b = 97.717(7) , U = 7204.1(14) A3 , space group P2/c, Z = 4, m = 2.843 mm-1 , reections measured: 51 944, independent reections: 15 895 [Rint = 0.0900], R1 = 0.1509, wR2 = 0.3734, GOF = 1.057, R indices (all data) R1 = 0.2414, wR2 = 0.4162.

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Acknowledgements
Universit de Strasbourg, the International Centre for Frontier e Research in Chemistry (FRC), Strasbourg, Institut Universitaire de France, the CNRS and the Ministry of Education and Research are acknowledged for nancial support and for a scholarship to J. E.
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