Supporting Information Double Interpenetration in a Chiral Three-Dimensional Magnet with a (10,3)-a Structure

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1 Supporting Information Double Interpenetration in a Chiral Three-Dimensional Magnet with a (10,3)-a Structure Thais Grancha, Marta Mon, Francesc Lloret, Jesús Ferrando-Soria,* Yves Journaux, Jorge Pasán, and Emilio Pardo* S1

2 Experimental Section Materials. All chemicals were of reagent grade quality, and they were purchased from commercial sources and used as received. The ligand, the chiral cation and the tetrabutylamonium salt of the mononuclear copper(ii) complex were prepared as previously reported. 1 Preparation of [(S)-(1-PhEt)Me 3 N] 2 [Cu(Et 2 pma) 2 ] 4H 2 O: The precursor complex was obtained from a metathesis from the previously reported (n-bu 4 N) 2 [Cu(Et 2 pma) 2 ] 2H 2 O 1a (5.39 g, 5 mmol), with AgNO 3 (1.70 g, 10 mmol) and [(S)-(1-PhEt)Me 3 N]Cl (2.00 g, 10 mmol) in 25 ml of water and 25 ml of methanol. The solution was evaporated to dryness. The solid was washed with acetone and diethyl ether and dried under vacuum (3.52 g, 78 %). Analysis calculated for C 46 H 70 CuN 4 O 10 (902.6) C, 61.21; H, 7.81; N, Found: C, 61.12; H, 7.77; N, 6.23; IR (KBr) 1667 (CO) cm -1. Preparation of [(S)-(1-PhEt)Me 3 N] 4 [Mn 4 Cu 6 (Et 2 pma) 12 ](DMSO) 3 ] 3DMSO 5H 2 O (1): Wellformed pale green tiny prisms of 1, which were suitable for synchrotron diffraction, were obtained by following a synthetic procedure already reported. 9 In a typical experiment, Mn(NO 3 ). 2 4H 2 O (0.025 g, 0.1 mmol) was dissolved in hot DMSO (25 ml) and added dropwise to a hot DMSO solution (25 ml, 80 ºC) of [(S)-(1-PhEt)Me 3 N] 2 [Cu(Et 2 pma) 2 ] 4H 2 O (0.451 g, 0.5 mmol). The resulting dark-green solution was filtered while hot and the filtrate was allowed to stand at RT. After several days, green crystals of 1 appeared, and they were filtered off and air-dried. (0.04 g, 37 %). Elemental analysis calcd. (%) for C 200 H 274 Cu 6 Mn 4 N 16 O 47 S 6 ( ): C 54.01, H 6.21, N 5.04, S 4.32; found: C 54.19, H 6.13, N 5.07, S 4.33; IR (KBr): ν = 1604, 1584 cm 1 (C=O). Physical Techniques. Elemental (C, H, S, N) and Inductively coupled plasma atomic emission spectroscopy (ICP-AES) analyses were performed at the Microanalytical Service of the Universitat de València. The thermogravimetric analyses were performed on crystalline samples under a dry N 2 atmosphere with a Mettler Toledo TGA/STDA 851 e thermobalance operating at a heating rate of 10 ºC min 1.IR spectra were recorded on a Perkin-Elmer 882 spectrophotometer as KBr pellets. Variabletemperature direct current (dc) magnetic susceptibility measurements were carried out on a powdered sample of 1 with a Quantum Design SQUID magnetometer. The susceptibility data were corrected for the diamagnetism of the constituent atoms and the sample holder. Crystal Structure Data Collection and Refinement. Crystal data for 1: C 200 H 274 N 16 O 47 S 6 Cu 6 Mn 4 M r = , orthorhombic, space group P , a = (6), b = (6), c = (6) Å, V = 23724(8) Å 3, T = 100(2) K, λ = Å, Z = 4, ρ calc = g cm -3, µ = mm -1, Measured reflections = , Unique reflections = 26156, Reflections with I > 2σ(I) = [R(int) = ]. The data collection was carried out in the BM16 beamline at the ESRF (Grenoble, France) and the data S2

3 were indexed, integrated, and scaled using the HKL2000 program. 2 The crystals of 1 diffract poorly, and therefore the completeness is limited at high angles. All the measured independent reflections were used in the analysis. The structure was solved by direct methods and refined with full-matrix least-squares technique on F 2 using the SHELXS-97 and SHELXL-97 programs. 3 The hydrogen atoms from the organic ligands were set on calculated positions, whereas those of the water molecules were neither found nor set. Refinement of 2235 parameters with anisotropic thermal parameters for all non-hydrogen atoms gave R1 (all) = , R1 (obs) = , wr2 (all) = and wr2 (obs) = , with S = Since the ratio reflections/parameters is not good, we have fixed some parameters during the refinement, in particular, the x, y, z coordinates of 15 atoms were fixed after a initial refinement. These parameters exhibit the highest variation during the final cycles of refinement. Also, restraints and constraints were applied to all the atoms in the structure, in order to diminish the effect of the overparametrization. The final Fourier-difference map showed maximum and minimum height peaks of and e Å -3. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: (+44) ; deposit@ccdc.cam.ac.uk). X-ray Powder Diffraction Measurements. A polycrystalline sample of 1 were introduced into 0.5 mm borosilicate capillaries prior to being mounted and aligned on a Empyrean PANalytical powder diffractometer, using Cu Kα radiation (λ = Å). For each sample, five repeated measurements were collected at room temperature (2θ = 2 40 ) and merged in a single diffractogram. Magnetic Measurements. Variable-temperature direct current (dc) and alternating current (ac) magnetic susceptibility measurements were carried out on a crystalline sample of 1 with a Quantum Design SQUID magnetometer. The susceptibility data were corrected for the diamagnetism of both the constituent atoms and the sample holder. S3

4 Table 1. Summary of Crystallographic Data for 1 Compound 1 Formula C 200 H 274 N 16 O 47 S 6 Cu 6 Mn 4 M (g mol 1 ) Crystal system orthorhombic Space group P a (Å) (6) b (Å) (6) c (Å) (6) V (Å 3 ) 23724(8) Z 4 ρ calc (g cm 3 ) µ (mm 1 ) T (K) 100(2) Measured reflections Unique reflections (Rint) (0.0398) Observed reflections [I > 2σ(I)] Flack parameter 0.07(3) Goof R a [I > 2σ(I)] (all data) (0.1562) wr b [I > 2σ(I)] (all data) (0.4130) a R = ( F o F c )/ F o. b wr = [ w( F o F c ) 2 / w F o 2 ] 1/2. S4

5 Figure 1. Perspective view of the doubly interpenetrated 3D framework of 1 along the [100] direction. All atoms are represented as space filling spheres (Van der Waals radii). The two mutually interpenetrated nets are shown in different dark and light green colors. The aromatic rings of the oxamate ligand and the cations have been omitted for clarity. S5

6 Figure S2. Perspective view of the doubly interpenetrated 3D framework of 1 along the [100] direction showing the (S)-(1PhEt)Me3N cations. S6

7 Figure S3. Experimental X-ray powder diffraction pattern for 1 (red), compared to the pattern calculated from crystal data (blue). S7

8 Figure S4. Field dependence of the magnetization (M) of 1 at T = 2.0 K emphasizing the hysteresis loop. S8

9 References 1 (a) Ferrando-Soria, J.; Grancha, T.; Julve, M.; Cano, J.; Lloret, F.; Journaux, Y.; Pasán, J.; Ruiz-Pérez, C.; Pardo, E. Chem. Commun. 2012, 48, (b) Clemente-León, M.; Coronado, E.; Dias, J. C.; Soriano-Portillo, A.; Willett, R. D.; Inorg. Chem., 2008, 47, Otwinowski, Z.; Minor, W.; Processing of X-ray Diffraction Data Collected in Oscillation Mode, Methods in Enzymology 276, Macromolecular Crystallography, part A, 1997, , C. W. Carter, Jr., R. M. Sweet, Eds., Academic Pres (New York). 3 Sheldrick, G. M.; Acta Crystallogr. Sect. A, Found. Crystallogr. 2008, 64, 112. S9