Supramolecular Dimers and Chains Resulting from Second

CRYSTAL GROWTH & DESIGN

Supramolecular Dimers and Chains Resulting from Second Coordination Sphere Interactions Nastase,†

Tuna,‡

Maxim,†

Silviu Floriana Catalin Christopher A. Richard E. P. Winpenny,‡ and Marius Andruh*,†

Muryn,‡

Narcis

2007 VOL. 7, NO. 9 1825-1831

Avarvari,§

Inorganic Chemistry Laboratory, Faculty of Chemistry, UniVersity of Bucharest, Strasse DumbraVa Rosie nr. 23, 020464-Bucharest, Romania, School of Chemistry, UniVersity of Manchester, Oxford Road, Manchester M13 9PL, U.K., and Laboratoire Chimie, Inge´ nierie Mole´ culaire et Mate´ riaux d’Angers (CIMMA) UMR 6200 CNRS-UniVersite´ d’Angers, UFR Sciences, Baˆ t. K, 2 bd. LaVoisier, 49045 Angers, France ReceiVed April 5, 2007; ReVised Manuscript ReceiVed June 29, 2007

ABSTRACT: Three new complexes of manganese(III) have been synthesized and crystallographically characterized: [Mn(valen)(H2O)(NCS)]‚2CH3CN 1, {0.63[(H2O)(valen)Mn-µ1,3-N3-Mn(valen)(H2O)]}{0.37 {[Mn(valen)(H2O)2][Mn(valen)(H2O)(N3)]}(ClO4)(CH3 OH) 2 (0.63 and 0.37 are the occupation factors for the disordered azido group), and [(H2O)(valen)Mn-NCAgCN]‚H2O 3. H2valen is a bicompartimental Schiff base proligand, resulting from the 2:1 condensation of 3-methoxysalicyladehyde with ethylenediamine. The packing of these complexes in the crystals is governed by second coordination sphere interactions. The complex species are self-complementary: one aqua ligand from one complex can be hosted into the free compartment (O2O′2) of a similar complex. Supramolecular dimers result in the case of complex 1. The packing of the azido-bridged dimers in 2 affords supramolecular chains. In the case of compound 3, the hydrogen-bonded dimers are further connected through Ag‚‚‚Ag interactions, resulting in supramolecular chains. The crystallization water molecules in crystal 3 are grouped in almost planar hexamers. The magnetic properties of complexes 1 and 2 are discussed. Introduction The deliberate construction of molecular crystals with new structures, properties, and functions is the ultimate goal of crystal engineering.1 Appropriate synthetic routes and new connectivity rules are needed, in order to control the dimensionality and the network topology, which are crucial factors in determining the physical and chemical properties of the resulting materials. Most of the employed strategies in designing hybrid inorganicorganic networks rely upon the strong directionality of coordination bonds and of hydrogen bond interactions.2 Other noncovalent forces, such as π-π,3 and metallophilic interactions,4 play an important role in sustaining supramolecular solidstate architectures. Recent papers show that such interactions can also be manipulated in order to obtain the desired network topologies.3,4 The concept of the second coordination sphere is not new in coordination chemistry: it originates from Werner’s classical works on coordination chemistry, and it is nowadays largely employed in supramolecular chemistry.5 In a recent paper, we have shown that interesting supercomplexes can be constructed by using mononuclear complexes with bicompartmental ligands, whose free compartment acts as a receptor for the aqua ligand belonging to a second complex.6 Such compartmental ligands result from the 2:1 condensation of 3-methoxysalicyladehyde with a diamine (Scheme 1). The metal ion is hosted into the N2O2 compartment, while the second compartment acts as a receptor for the aqua ligand belonging to another complex. The stability of the resulting supercomplexes is reinforced by π-π stacking interactions established between the aromatic moieties of the ligands (Scheme 2). Similar systems have been described * Author to whom correspondence should be addressed. Tel: +40.744.870.656. Fax: +40.21.315.9249. E-mail: [email protected]. † University of Bucharest. ‡ University of Manchester. § Universite ´ d’Angers.

Scheme 1

Scheme 2

by others.7 In this paper we report on new supramolecular solidstate architectures resulting from second coordination sphere interactions. Experimental Section Syntheses of [Mn(valen)(H2O)(NCS)]‚2CH3CN (1), {0.63[(H2O)(valen)Mn-µ1,3-N3Mn(valen)(H2O)]}{0.37{[Mn(valen)(H2O)2][Mn (valen)(H2O)(N3)]}(ClO4)(CH3OH) (2), and [(H2O)(valen)Mn-

10.1021/cg070332g CCC: $37.00 © 2007 American Chemical Society Published on Web 08/21/2007

1826 Crystal Growth & Design, Vol. 7, No. 9, 2007

Nastase et al.

Table 1. Crystallographic Data, Details of Data Collection and Structure Refinement Parameters for Compounds 1-3

chemical formula M (g mol-1) temperature (K) wavelength (Å) crystal system space group a (Å) b (Å) c (Å) R (deg) β (deg) γ (deg) V(Å3) Z Dc (g cm-3) µ (mm-1) F(000) goodness-of-fit on F2 final R1, wR2 [I > 2σ(I)] R1, wR2 (all data) largest diff peak and hole (e Å-3)

1

2

3

C23H26 MnN5O5S 539.49 100(2) 0.71073 monoclinic P21/c 11.3758(16) 13.230(2) 18.426(3) 90 117.185(10) 90 2466.8(6) 4 1.453 0.664 1120 0.782 0.0337, 0.0618 0.0751, 0.0651 0.529, -0.259

C37H46ClMn2N7O15. 5 982.14 100(2) 0.71073 triclinic P1h 12.2204(15) 13.387(3) 14.260(3) 14.260(3) 95.156(12) 91.053(13) 2095.0(6) 2 1.557 0.746 1016 1.033 0.0385, 0.0867 0.0770, 0.1068 0.872, -0.579

C20H20AgMnN4O6 575.21 293(2) 0.71073 trigonal R3h 27.3405(18) 27.3204(16) 16.0942(7) 90 90 119.998(7) 10411.2(10) 9 0.826 0.717 2592 0.998 0.0414, 0.0836 0.0974, 0.0997 0.770, -0.476

NCAgCN]‚H2O (3). All the chemicals used for the present study were purchased from commercial sources and used without any further purification. The tetradentate Schiff base H2valen was prepared by reacting 3-methoxysalicylaldehyde and ethylenediamine (2:1 molar ratio) in ethanol. [Mn(valen)(H2O)(CH3CN)](ClO4)‚CH3CN, used as a starting material for the synthesis of compounds 1 and 3, was obtained from the reaction of Mn(ClO4)2‚6H2O with H2valen (1:1 molar ratio) in acetonitrile (blackreddish crystals). IR data (KBr, cm-1): 3374, 1623, 1551, 1468, 1442, 1400, 1301, 1257, 1220, 1083, 984, 966, 862, 733. Compound 1. To an acetonitrile solution (20 mL) containing 0.135 mmol of (Et4N)2[Co(NCS)4] was added, under stirring, 0.27 mmol of [Mn(valen)(H2O)(CH3CN)](ClO4)‚CH3CN dissolved in 20 mL of acetonitrile. Black crystals of 1 formed within several days, and they have been isolated by filtration. Single crystals suitable for X-ray diffraction were obtained directly from the reaction mixture, by slow evaporation of the solvent at room temperature. IR (KBr, cm-1): 3429, 2923, 2066, 1622, 1550, 1468, 1439, 1401, 1302, 1252, 1218, 1084, 1045, 986, 964, 860, 779, 732 cm-1. The direct reaction between [Mn(valen)(H2O)(CH3CN)](ClO4)‚CH3CN and KSCN, in order to obtain the compound 1, was not successful, resulting in an amorphous brown precipitate. The role of the [Co(NCS)4]2- ion is to release slowly the NCS- ions, that will act as ligands toward manganese. Compound 2. To a methanolic solution (10 mL) containing 0.113 mmol of Mn(ClO4)2‚6H2O was added 0.113 mmol of H2valen dissolved in 15 mL of methanol. The resulting brown solution was stirred for about 3 h, after which 0.115 mmol of sodium azide dissolved in 5 mL of methanol was added. The slow evaporation of this solution yielded black crystals of compound 2. IR (KBr, cm-1): 3417, 2929, 2053, 1602, 1551, 1470, 1444, 1397, 1330, 1296, 1252, 1221, 1083, 1043, 984, 860, 730, 622, 573, 465. Compound 3. To a solution of [Mn(valen)(H2O)(CH3CN)](ClO4)‚CH3CN (0.045 mmol) in 20 mL of 1:1 CH3CN/H2O mixture was added a 10 mL solution of potassium dicyanoargentate(I) (0.045 mmol in a 1:1 CH3CH/H2O mixture). The slow evaporation of the resulting solution yielded black crystals. IR data (KBr, cm-1): 3452, 3406, 2964, 2895, 2833, 2144, 1623, 1600, 1550, 1468, 1440, 1296, 1253, 1219, 1085, 738. Physical Measurements. IR spectra were recorded on a Bio-Rad FTS 135 in the 4000-400 cm-1 range. Samples were run as KBr pellets. Magnetic data were obtained with a Quantum Design MPMS XL SQUID magnetometer. Magnetic susceptibility measurements were performed in the 1.8-300 K temperature range in a 1000 G applied magnetic field, and diamagnetic corrections were applied by using Pascal’s constants. Isothermal magnetization measurements as a function of the external magnetic field were performed up to 7 T at 2 K. X-ray Structure Determination. X-ray diffraction measurements were performed on a Bruker AXS SMART1 CCD diffractometer for compounds 1 and 2, and on a Nonius Kappa CCD diffractometer for compound 3, using graphite-monochromated Mo KR radiation (λ )

0.71073 Å). The structures were solved by direct methods and refined by full-matrix least-squares techniques based on F2. The non-H atoms were refined with anisotropic displacement parameters. Calculations were performed using SHELX-97 crystallographic software package. A summary of the crystallographic data and the structure refinement for crystals 1-3 is given in Table 1. CCDC reference numbers: 643165-643167.

Results and Discussion The compartmental ligand used in this work is the Schiff base derived from 3-methoxysalicyladehyde and ethylenediamine, H2valen. Its complexes with metal ions, preferring a square planar geometry (NiII, PdII), act as hydrogen bond acceptors (receptor) toward water molecules from complementary complex species (substrate), as illustrated in Scheme 2. If the metal ion coordinates one or two aqua ligands into its apical positions, then the resulting complex species are self-complementary: one aqua ligand from one complex can be hosted into the free compartment (O2O′2) of a similar complex (Scheme 3). In order to illustrate this concept we have chosen manganese(III) complexes. Three such complexes have been synthesized and crystallographically characterized. One of them is mononuclear, [Mn(valen)(H2O)(NCS)]‚2CH3CN, the second one contains an azido-bridged dimer, [(H2O)(valen)Mn-µ1,3-N3-Mn(valen)(H2O)]+, while the third compound is a cyano-bridged heterobinuclear compound, [(H2O)(valen)Mn-NCAgCN]‚H2O. Supramolecular Dimers. Compound 1 is a mononuclear MnIII complex with the organic ligand forming the equatorial plane and the apical positions occupied by the aqua ligand and the NCS- ion coordinated through nitrogen (Figure 1a). The manganese ion displays an elongated octahedral stereochemistry, as expected for a Jahn-Teller ion. The bond distances in the equatorial plan are as follows: Mn1-N1 ) 1.976(2); Mn1N2 ) 1.969(2), Mn1-O2 ) 1.8837(17); Mn1-O3 ) 1.8809(17) Å, while the axial distances are: Mn1-O1 ) 2.263(2) and Mn1-N3 ) 2.214(2) Å. These distances are close to those Scheme 3

Supramolecular Dimers and Chains

Crystal Growth & Design, Vol. 7, No. 9, 2007 1827

Figure 1. (a) Perspective view of compound 1 along with the atom numbering scheme. (b) Formation of the supramolecular dimer. (c) π-π stacking interactions within the supramolecular dimer.

already observed with similar complexes.8 The analysis of the packing diagram reveals, as expected, the formation of the dimeric supercomplexes (Figure 1b): the aqua ligand from a mononuclear complex is hydrogen bonded to the oxygen atoms from the free compartment of the other one [O‚‚‚O distances vary between 2.839 and 2.997 Å]. Moreover, the stability of the resulting complex of complexes is reinforced by π-π stacking interactions established between the aromatic rings of the Schiff base (3.4-3.8 Å), Figure 1c. The intradimer Mn‚‚‚ Mn distance is 4.891 Å. It is interesting to note that only supramolecular dimers are assembled even if the manganese(III) ion contains two aqua ligands into the apical positions.8 Supramolecular Chains of Dimers. The reaction between manganese(II) perchlorate and H2valen followed by the addition of NaN3 leads to the system 2, that contains 0.63[(H2O)(valen)Mn-µ1,3-N3-Mn(valen)(H2O)](ClO4)(CH3OH) and 0.37{[Mn(valen)(H2O)2][Mn(valen)(H2O)(N3)](ClO4)‚CH3OH} (0.63 and 0.37 are the occupation factors for the disordered azido group). Within the major component, the metal atoms are connected by a µ1,3-azido bridge (Figure 2a). Each manganese(III) ion is hexaoordinated, with an elongated octahedral geometry. The basal plane is formed by two oxygen (Mn-O distances vary between 1.882(2) and 1.890(2) Å) and two nitrogen atoms

arising from the organic ligands [1.972(3) and 1.987(3) Å]. One aqua ligand [Mn1-O5 ) 2.260(3); Mn2-O12 ) 2.280(2) Å] and one nitrogen from the bridge [Mn1-N10 ) 2.255(18); Mn2-N12 ) 2.32(3) Å] are coordinated into the apical positions. The distance between the manganese ions within the binuclear entity is 5.76 Å. The minor component consists of two mononuclear complexes, with the manganese ions and the organic ligands located on the same positions as in the major one (Figure 2b). One manganese ion contains two aqua ligands coordinated into the apical positions, while in the second one the apical positions are occupied by one aqua and one azido ligand. Since the {(H2O)Mn(valen)} moieties reside on the same crystallographic positions in both major and minor components, the packing diagram is the same for the two systems. Consequently, it will be discussed only for the azidobridged dimer. Each aqua ligand from a dimer interacts with the O2O′2 compartment from neighboring dimers, resulting in supramolecular infinite zigzag chains (Figure 2c). The intermolecular O‚‚‚O distances associated to these hydrogen bonds vary between: 2.814 and 2.971 Å. Again, π-π graphite-like stacking interactions (3.5-3.8 Å) reinforce the stability of the supramolecular chains (Figure 2d).


Nastase et al.

Figure 2. (a) View of the major component in crystal 2. (b) View of the minor component in crystal 2. (c) Formation of the supramolecular chains through hydrogen bonds established between the azido-bridged dimers. (d) π-π stacking interactions within the supramolecular chains.

In a recent paper, it has been shown that the reaction of [Mn(valpn)(H2O)2]+ with sodium azide affords a mononuclear complex, [Mn(valpn)(N3)(H2O)] (H2valpn is the Schiff base obtained from 3-methoxysalicyladehyde and 1,3-diaminopropane).9 Supramolecular dimers, similar to those described for complex 1, are formed. Simultaneous Presence of Hydrogen Bond and Metallophilic Interactions. The third compound, [(H2O)(valen)MnNCAgCN]‚H2O 3, has been synthesized in order to emphasize how two types of intermolecular forces, hydrogen bonds and metallophilic interactions, influence the crystal packing. Compound 3 has been obtained by reacting [Mn(valen)(H2O)(CH3CN)](ClO4)(CH3CN) with K[Ag(CN)2]. Its structure consists of neutral binuclear entities, [(H2O)(valen)Mn-NCAgCN] (Figure 3a), and crystallization water molecules. Similarly to compounds 1 and 2, the manganese(III) ion exhibits the characteristic elongated octahedral symmetry, with one aqua

ligand [Mn1-O5 ) 2.294(3) Å] and one nitrogen from the cyano bridge [Mn1-N1A ) 2.277(4) Å] coordinated into the apical positions. The silver ion is bicoordinate, but the geometry is not strictly linear (the value of the C1A-Ag1-C2A angle is 165.33(19)°. The lengths of the Ag-C bonds are the same within experimental error: Ag1-C1A ) 2.056(5); Ag1-C2A ) 2.043(5) Å. The analysis of the packing diagram reveals interesting features. Two types of interactions govern the packing of the heterobinuclear species in crystal 3. As observed with compounds 1 and 2, the aqua ligand from one binuclear entity interacts with the [O2O′2] compartment from another entity resulting in supramolecular dimers similar to those observed with compound 1 (Figure 3b). These dimers are further interconnected through Ag‚‚‚Ag contacts (Ag‚‚‚Ag ) 3.092 Å) and generate infinite supramolecular chains running in three different directions. The typical silver-silver distance in cy-



Figure 3. (a) Perspective view of the heterobinuclear complex 3; (b) Formation of the supramolecular chains through hydrogen bonds and Ag‚‚‚Ag interactions;

Figure 4. (a) View of the water cluster. (b) Packing diagram for crystal 3 showing the channels filed with the water hexamers (the chains running in the same direction are drown with the same color). (c) View of the water clusters hosted into a channel.

anoargentate complexes vary between 3.05 and 3.26 Å.10 The packing of the chains in the crystal generates channels oriented along the c crystallographic axis. Another MnIII-AgI complex,11 that was obtained by reacting [Mn(salen)(OOCCH3]‚H2O with K[Ag(CN)2], crystallized as a 1-D coordination polymer with {Mn(salen)}+ connected through {Ag(CN)2}- spacers (H2salen is a Schiff base ligand with only one compartment, obtained by reacting salicylic aldehyde with ethylenediamine). No silversilver contacts were established. The cocrystallized water molecules are grouped in almost planar hexamers (Figure 4a) and hosted in the channels resulting from the packing of the chains (Figure 4b). The distances between the oxygen atoms vary between 2.713 and 2.715 Å. The O‚‚‚O‚‚‚O angles are close to 120°. Each water molecule

is also hydrogen bonded to the terminal cyano group (O‚‚‚N ) 2.851 Å). The distance between the water cluster within a channel is 16.09 Å (Figure 4c). Several other water hexamers have been described in the recent years.12 Most of them exhibit the chair conformation, but boat and planar conformations are also known. The planar conformation is the basic structural motif found in structure of ice II at high pressure.13 Selected bond distances and angles for compounds 1-3 are collected in Table 2. The geometrical parameters associated to the hydrogen bonds sustaining the supramolecular dimeric moieties in compounds 1-3 are gathered in Table 3. Magnetic Properties. The magnetic properties of compounds 1 and 2 have been investigated. The χMT vs T and magnetization vs field curves for compound 1 are presented in Figures 5 and


Nastase et al.

Table 2. Selected Bond Distances and Angles for Compounds 1-3 1 Mn1-N1 Mn1-N2 Mn1-O2 Mn1-O3 Mn1-O1 Mn1-N3 O3-Mn1-O1 O3-Mn1-N2 N2-Mn1-N3 N1-Mn1-N3 O2-Mn1-N1 O2-Mn1 O1 N3 Mn1-O1 O3-Mn1-N1 O2-Mn1-N2

2 1.976(2) 1.969(2) 1.8837(17) 1.8809(17) 2.263(2) 2.214(2) 88.42(7) 91.54(8) 91.50(8) 92.91(8) 91.97(8) 90.40(7) 175.28(8) 173.47(8) 172.42(9)

Mn1-O1 Mn1-O2 Mn1-N1 Mn1-N2 Mn1-N10 Mn1-O5 Mn2-O7 Mn2-O8 Mn2-N4 Mn2-N3 Mn2-N12 Mn2-O12 O2-Mn1-O5 O2-Mn1-N2 N2-Mn1-N10 N1-Mn1-N10 O1-Mn1-N1 O8-Mn2-N12 O8-Mn 2-N4 N4-Mn2-O12 O7-Mn2-O12 O7-Mn2-N12 N10-N11-N12

Table 3. The Geometrical Parameters Associated to the Hydrogen Bonds Sustaining the Supramolecular Dimeric Moieties in Compounds 1-3a D-H‚‚‚A

D‚‚‚A (Å)

D-H‚‚‚A (deg)

O1-H146‚‚‚O2i O1-H146‚‚‚O4i O1-H147‚‚‚O3i O1-H147‚‚‚O5i

Compound 1 2.949 2.997 2.839 2.967

138.92 147.17 141.56 146.69

O12-H50‚‚‚O9i O12-H50‚‚‚O7i O12-H51‚‚‚O8i O12-H51‚‚‚O10i O5-H200‚‚‚O1ii O5-H200‚‚‚O3ii O5-H201‚‚‚O2ii O5-H201‚‚‚O4ii

Compound 2 2.971 2.814 2.905 2.916 2.864 2.934 2.922 2.959

140.67 147.03 141.72 148.71 135.37 155.16 148.11 142.43

O5-H2‚‚‚O3ii O5-H2‚‚‚O2ii O5-H1‚‚‚O4ii O5-H1‚‚‚O1ii

Compound 3 2.995 2.950 3.055 2.866

141.74 137.94 154.22 139.93

a Symmetry codes for complex 1: (i) 1 - x, -y, 1 - z. Symmetry codes for complex 2: (i) -x, 2 - y, 2 - z; 1 - x, 1 - y, 2 - z. Symmetry codes for complex 3: (ii) 1.66667 - x, 0.33333 - y, 1.33333 - z.

Figure 5. χM vs T and χMT vs T curves for compound 1. The red lines represent to the best fit curves.

6. At room temperature the value of the χMT product is 6.83 cm3 mol-1 K, that corresponds for two high spin manganese(III) ions with S ) 2. Upon cooling, χMT remains constant down

3 1.885(2) 1.890(2) 1.982(3) 1.973(3) 2.255(18) 2.260(3) 1.883(2) 1.882(2) 1.972(3) 1.987(3) 2.32(3) 2.280(2) 92.01(9) 92.09(11) 88.3(4) 86.0(5) 91.01(11) 96.2(6) 91.73(12) 86.59(11) 92.59(9) 93.0(9) 174.6(16)

Mn1-N1M Mn1-N2M Mn1-O1 Mn1-O2 Mn1-O5 Mn1-N1A Ag1-Ag1 O2-Mn1-O5 O2-Mn1-N1A N2M-Mn1-N1A N1M-Mn1-N2M O1-Mn1-N1M N1M-Mn1-O5 N2A-C2A-Ag1 N1A-C1A-Ag1 C2A-Ag1-C1A

1.974(4) 1.987(3) 1.878(3) 1.877(3) 2.294(3) 2.277(4) 3.0922(8) 92.46(14) 92.50(13) 85.42(14) 83.07(16) 91.45(13) 84.78(14) 170.9(5) 175.5(4) 165.33(19)

to 120 K, and then decreases more and more, reaching 0.66 cm3 mol-1 K at 2 K. The susceptibility vs temperature curve shows a maximum at ∼6 K). The magnetic behavior of 1 might be due to one of the following causes, or to a combination of them: (i) zero field splitting (D) of the ground state of MnIII; (ii) antiferromagnetic interaction between the manganese(III) ions within the supramolecular dimer, mediated by hydrogen bonds. Both magnetization and susceptibility data were simultaneously fitted by full-matrix diagonalization of the following spin Hamiltonian:14

H ) -JS1S2 + D1[S1z2 - 1/3S1(S1 + 1)] + D2[S1z2 - 1/3S2(S2 + 1)] (1) The first term refers to the exchange interaction between the manganese(III) ions within the supramolecular dimer. The second and third terms take into account the zero field splitting (ZFS) effects for the two manganese ions (D1 ) D2). In view of the axially elongated structure around Mn(III), a negative sign is expected for D;15 thus, D was constrained to negative values in our calculations. The best set of parameters which match the experimental data were found to be J ) -0.42 cm-1, D ) -3.1 cm-1, and g ) 2.14. The solid lines in Figures 5 and 6 correspond to the calculated curves. The case of compound 2 is more complicated. According to the crystallographic investigation, it consists of 63% azidobridged dimer and 37% 1:1 mixture of mononuclear complexes. The χM vs T and χMT vs T curves are shown in Figure 7. The room-temperature value of the χMT product is 5.62 cm3 mol-1 K, slightly lower than the one expected for two high-spin MnIII ions (assuming g ) 2). By decreasing the temperature, χMT remains almost constant down to 150 K, and then it continuously decreases to reach 0.73 cm3 mol-1 K at 2 K. The magnetic susceptibility curve shows a maximum at 4.6 K. This behavior is due to the same causes as for compound 1: exchange interaction between the manganese ions bridged by the azido ligand; exchange interaction mediated by the hydrogen bonds; zero field splitting effects. The equation describing the temperature dependence of the magnetic susceptibility must contain the following parameters: g, J1 (exchange interaction mediated by the azido bridge); J2 (exchange interaction mediated by



(2)

(3)

(4)

Figure 6. M vs H curve for compound 1. The red line represents the calculated curve.

(5)

Figure 7. χM vs T and cMT vs T curves for crystal 2

hydrogen bonds); D1 (ZFS parameter for the manganese ions in the azido-bridged dimer); D2, D3 (ZFS splitting parameters for the manganese ions in the minor component). The modeling of the magnetic based data upon such an equation is not reliable because overparametrization. The examples presented herein illustrate that second coordination sphere interactions play an important role in the crystal packing. We have also shown that the manipulation of such interactions can become a paradigm in designing new supramolecular solid-state architectures.

(6) (7) (8)

(9) (10)

Acknowledgment. Financial support from the CEEX Program (Project D11-17) and EC “MAGMANet” NMP3-CT2005-515767 is gratefully acknowledged.

(11) (12)

Supporting Information Available: Crystallographic information in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.

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