Generation of Three-Dimensional Networks through Aliphatic Chain

Nov 24, 2008 - Lyman Briggs College and Department of Chemistry, Michigan State University, E-30 Holmes Hall, East Lansing, Michigan 48825, and Depart...
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CRYSTAL GROWTH & DESIGN

Generation of Three-Dimensional Networks through Aliphatic Chain Disorder in a Divalent Metal Dicarboxylate/Organodiimine Coordination Polymer System

2009 VOL. 9, NO. 1 358–363

Subhashree Mallika Krishnan,† Ronald M. Supkowski,‡ and Robert L. LaDuca*,† Lyman Briggs College and Department of Chemistry, Michigan State UniVersity, E-30 Holmes Hall, East Lansing, Michigan 48825, and Department of Chemistry and Physics, King’s College, Wilkes-Barre, PennsylVania 18711 ReceiVed May 21, 2008; ReVised Manuscript ReceiVed September 8, 2008

ABSTRACT: Hydrothermal synthesis has afforded coordination polymers incorporating the kinked dipodal organodiimine 4,4′dipyridylamine (dpa) and the flexible aliphatic dicarboxylate suberate dianion, with a general formulation of [M(sub)(dpa)(H2O)]n (sub ) suberate, M ) Co, 1; M ) Ni, 2). Both 1 and 2 exhibit crystallographically disordered suberate ligands, producing a threedimensional “ligand vacancy” R-Po coordination polymer network composed of two different types of [M(sub)(dpa)(H2O)]n idealized layers. Table 1. Crystal and Structure Refinement Dataa,b

Introduction Ongoing research effort toward the synthesis and characterization of metal polycarboxylate coordination polymers has been inspired by these materials’ applicability in diverse applications such as gas storage,1 small molecule absorption and separation,2 ion exchange,3 catalysis,4 and luminescence.5 The anionic polycarboxylate ligands act as both the structural scaffolding and the requisite charge-balancing components for the construction of neutral coordination polymer frameworks. Cooperative effects among the donor orientation and binding modes within the dicarboxylate groups, along with coordination geometry preferences and significant supramolecular interactions, impart the final coordination polymer structure assumed during selfassembly. The ligands of choice among investigators in the field to date have been primarily aromatic dicarboxylates because of their propensity to produce robust porous networks.6 Nevertheless, aliphatic R,ω-dicarboxylate tethering ligands have allowed generation of coordination polymers with intriguing structural topologies,7 in part because of their ability to respond to structure-directing forces such as geometric preferences and supramolecular interactions through energetically facile conformational alterations. Coordination polymers based on malonate,8 succinate,9 and adipate10 ligands have been prepared, either with or without an organodiimine coligand such as 4,4′bipyridine (4,4′-bpy). Reports of pimelate-,11 suberate-,12 or azelate-based13 phases are rarer; the coordination polymer chemistry of these longer, extremely flexible potential tethering ligands remains underexplored. Recently, we have been investigating the synthesis and characterization of coordination solids containing the organodiimine 4,4′-dipyridylamine (dpa).14-19 Unlike the ubiquitous rigid-rod tether 4,4′-bpy, dpa presents a kinked disposition of its terminal nitrogen donor atoms, in addition to a potentially structure-directing hydrogen-bonding point of contact at its central secondary amine. Hydrothermal reactions of divalent metal precursors with succinic acid and dpa afforded five new coordination polymers, including {[Ni(dpa)2(succinate)0.5]Cl}n, which adopted an unprecedented self-penetrated five-connected 610 topology, and [Co(succinate)(dpa)2]n, which possessed * To whom correspondence should be addressed. E-mail: [email protected]. † Michigan State University. ‡ King’s College.

data empirical formula formula weight collection T (K) color and habit crystal size (mm3) λ (Å) crystal system space group a (Å) b (Å) c (Å) β (°) V (Å3) Z Dcalcd (g cm-3) µ (mm-1) min/max trans. hkl ranges total reflections unique reflections R(int) parameters/restraints R1 (all data) R1 [I > 2σ(I)] wR2 (all data) wR2 [I > 2σ(I)] max/min residual (e-/Å3) G.O.F. a

1

2

C18H23CoN3O5 420.32 173(2) pink block 0.20 × 0.10 × 0.08 0.71073 monoclinic P21/c 8.670(2) 15.806(4) 14.265(3) 106.628(4) 1873.1(7) 4 1.490 0.951 0.828 -11 e h e 11, -20 e k e 20, -18 e l e 19 22685 4570 0.1560 254/4 0.1676 0.0880 0.1846 0.1577 0.733/-0.819 1.074

C18H23N3NiO5 420.10 173(2) green block 0.20 × 0.16 × 0.10 0.71073 monoclinic P21/c 8.646(2) 15.702(4) 14.241(4) 106.772(3) 1851.2(8) 4 1.507 1.083 0.704 -11 e h e 11, -20 e k e 20, -18 e l e 18 23131 4142 0.0972 254/6 0.1128 0.0598 0.1505 0.1292 0.906/-1.205 1.060

R1 ) ∑|Fo| - |Fc|/∑|Fo|. b wR2 ) {∑[w(Fo2 - Fc2)2]/∑[wFo2]2}1/2.

homochiral one-dimensional (1D) helices locked into a threedimensional (3D) supramolecular network through dpa-mediated hydrogen bonding.14 Employment of the longer adipate ligand permitted generation of the first-ever triply interpenetrated PtS lattice, within the structure of [Ni(adipate)(dpa)]n.15 We were thus moved to investigate the synthesis of dpa-based coordination polymers with longer R,ω-dicarboxylate tethers. Herein, we report the synthesis, structural characterization, and thermal properties of the coordination polymers [M(sub)(dpa)(H2O)]n (sub ) suberate, M ) Co, 1; M ) Ni, 2), wherein the length and crystallographic disorder within the aliphatic dicarboxylate tethers play a crucial role in the overall network dimensionality.

10.1021/cg800539j CCC: $40.75  2009 American Chemical Society Published on Web 11/24/2008

Generation of 3D Networks through Aliphatic Chain Disorder

Crystal Growth & Design, Vol. 9, No. 1, 2009 359

Table 2. Selected Bond Distance (Å) and Angle (°) Data for 1 and 2a 1 Co1-O5 Co1-N1 Co1-O4#1 Co1-O1 Co1-N3#2 Co1-O2 O5-Co1-N1 O5-Co1-O4#1 N1-Co1-O4#1 O5-Co1-O1 N1Co1-O1 O4#1-Co1-O1 O5-Co1-N3#2 N1-Co1-N3#2 O4#1-Co1-N3#2 O1-Co1-N3#2 O5Co1O2 N1-Co1-O2 O4#1-Co1-O2 O1-Co1-O2 N3#2-Co1-O2

2 2.089(4) 2.097(4) 2.113(4) 2.141(4) 2.180(5) 2.192(4) 91.47(17) 91.94(16) 89.67(17) 106.94(16) 161.18(16) 85.90(15) 94.27(17) 95.46(17) 171.83(16) 87.21(16) 167.23(15) 100.89(16) 84.99(15) 60.53(15) 87.80(16)

Ni1-N3#3 Ni1-O5 Ni1-O3#4 Ni1-O2 Ni1-N1 Ni1-O1 N3#3-Ni1-O5 N3#3-Ni1-O3#4 O5-Ni1-O3#4 N3#3-Ni1-O2 O5Ni1-O2 O3#4-Ni1-O2 N3#3-Ni1-N1 O5-Ni1-N1 O3#4-Ni1N1 O2-Ni1-N1 N3#3-Ni1-O1 O5-Ni1-O1 O3#4-Ni1-O1 O2-Ni1-O1 N1-Ni1-O1

2.050(4) 2.058(3) 2.088(3) 2.112(3) 2.128(4) 2.158(3) 92.01(13) 89.45(13) 93.05(12) 162.12(13) 105.32(12) 85.33(12) 94.98(14) 93.80(13) 171.71(12) 88.36(13) 100.90(13) 166.96(12) 85.32(12) 61.67(12) 86.96(13)

Symmetry transformations to generate equivalent atoms: (#>1) -x, y + 1/2, -z + 3/2; (#2) -x + 1, y - 1/2, -z + 3/2; (#3) -x + 1, y + 1/2, -z + 3/2; (#4) -x, y + 1/2, -z + 3/2. a

Experimental Section General Considerations. CoCl2 · 6H2O, NiCl2 · 6H2O (Fisher), and suberic acid (Aldrich) were obtained commercially. The organodiimine 4,4′-dipyridylamine (dpa) was prepared via a published procedure.20 Water was deionized above 3 MΩ in-house. Thermogravimetric analysis was performed on a TA Instruments TGA 2050 Thermogravimetric Analyzer with a heating rate of 10 °C/min up to 900 °C. Elemental analysis was carried out using a Perkin-Elmer 2400 Series II CHNS/O Analyzer. IR spectra were recorded on powdered samples on a PerkinElmer Spectrum One instrument. Preparation of [Co(suberate)(dpa)(H2O)] (1). CoCl2 · 6H2O (88 mg, 0.37 mmol), dpa (63 mg, 0.37 mmol), and suberic acid (64 mg, 0.37 mmol) were added to 10 mL of distilled H2O in a 23 mL Teflon-lined Parr acid digestion bomb. The bomb was sealed, heated to 120 °C for 51 h, and then gradually cooled to ambient temperature. Magenta blocks of 1 (60 mg, 38% yield based on Co) were obtained after filtration, washing with distilled water and acetone, and drying in air. Crystals of 1 were stable indefinitely in air. Anal. calcd for C18H23CoN3O5 1: C, 51.44; H, 5.12; N, 9.99%. Found: C, 51.71; H, 5.51; N, 10.23%. IR (cm-1): 2932 w br, 1609 w, 1590 s, 1543 m, 1514 s, 1482 m, 1436 m, 1420 m, 1396 m, 1337 s, 1306 m, 1202 m, 1131 w, 1096 w, 1058 w, 1020 s, 1012 s, 944 w, 932 w, 904 w, 862 w, 844 w, 815 s, 731 m, 718 m, 673 w. Preparation of [Ni(suberate)(dpa)(H2O)] (2). The procedure for the synthesis of 1 was followed but with NiCl2 · 6H2O (88 mg, 0.37 mmol) as the metal source. Green blocks of 2 (49 mg, 31% yield based on Ni) were obtained after filtration, washing with distilled water and acetone, and drying in air. Crystals of 2 were stable indefinitely in air. Anal. calcd for C18H23NiN3O5 2: C, 51.47; H, 5.52; N, 10.00%. Found: C, 51.72; H, 5.63; N, 10.20%. IR (cm-1): 2931 w br, 1607 w, 1590 s, 1543 m, 1514 s, 1482 m, 1436 m, 1420 m, 1395 m, 1336 s, 1306 m, 1203 m, 1131 w, 1096 w, 1059 m, 1024 m, 944 w, 932 w, 904 w, 862 w, 844 w, 823 s, 730 m, 718 m, 672 w.

X-ray Crystallography Single crystals of 1 and 2 were subjected to X-ray diffraction using a Bruker-AXS SMART 1k CCD instrument at 173(2) K. Reflection data were acquired using graphite-monochromated Mo KR radiation (λ ) 0.71073 Å). The data were integrated via SAINT.21 Lorentz and polarization effect and empirical absorption corrections were applied with SADABS.22 The structures were solved using direct methods and refined on F2 using SHELXTL.23 All nonhydrogen atoms were refined aniso-

Figure 1. Coordination environment of 2 with thermal ellipsoids shown at 50% probability and partial numbering scheme. Both disordered suberate orientations are shown; most hydrogen atoms have been omitted. The coordination environment of 1 is essentially identical.

tropically. Hydrogen atoms bound to carbon atoms were placed in calculated positions and refined isotropically with a riding model. The hydrogen atoms bound to the central nitrogen of the dpa moieties and all aqua ligands were found via Fourier difference maps, restrained at fixed positions, and then refined isotropically with thermal parameters 1.2 times the average Uij values of the atoms to which they are bound. Disordered carbon atoms in 1 and 2 were modeled with partial occupancies and anisotropic thermal parameters; their occupancies were allowed to refine freely in early stages of the refinement and then were fixed. Pertinent crystallographic data are listed in Table 1. Results and Discussion Synthesis and Spectral Characterization. The coordination polymers 1 and 2 were prepared cleanly under hydrothermal conditions via combination of a hydrated cobalt or nickel chloride, dpa, and suberic acid. Their infrared spectra were consistent with their crystal structures. Sharp, medium intensity bands in the range of ∼1600 to ∼1200 cm-1 were ascribed to stretching modes of the pyridyl rings of the dpa moieties.24 Features corresponding to pyridyl ring puckering mechanisms were evident in the region between 820 and 600 cm-1. Asymmetric and symmetric C-O stretching modes of the carboxylate moieties were evidenced by very strong, slightly broadened bands at ∼1590 and ∼1340 cm-1. Broad bands in the region of ∼3400 to ∼3200 cm-1 in all cases represent N-H stretching modes within the dpa ligands and O-H stretching modes within the bound water molecules. The broadness of these latter spectral features is caused by significant hydrogen-bonding pathways within these materials. Structural Description of [M(suberate)(dpa)(H2O)] (M ) Co, 1; M ) Ni, 2). Compounds 1 and 2 are isomorphous, both crystallizing in the monoclinic space group P21/c and possessing an asymmetric unit consisting of a metal atom, one doubly deprotonated suberate moiety, one dpa ligand, and one bound water molecule. While there were two fully occupied carbon positions at each end of the aliphatic chain, the central four atoms of the suberate ligands were split over two sets of positions. Thus, the suberate ligands in these materials can adopt two different sets of positions (orientation A, C11-C12-

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Figure 2. Single [Ni(H2O)(dpa)]n2n+ chain in 2.

Figure 3. Idealized layer A motif in 2. Hydrogen-bonding interactions are shown as dashed lines. Top, face-on view; bottom, edge-on view.

C13-C14-C15-C16-C17-C18; orientation B, C11-C12C13A-C14A-C15A-C16A-C17-C18). In the case of 1, the suberate ligands in orientations A and B refined to a 60:40 ratio; that for 2 is 70:30. The coordination environment of 2 is displayed in Figure 1, showing both suberate orientations A and B; that of 1 is essentially identical. The coordination spheres about the divalent metal ions in these materials are slightly distorted [MO4N2] octahedra, with the two nitrogen donors from two different dpa molecules oriented in a cis fashion with respect to each other. Two of the oxygen donors belong to the chelating terminus of a suberate ligand. The aqua ligand is disposed in a cis manner with respect to the remaining oxygen donor, part of another suberate ligand. Bond lengths and angles (Table 1) about

the metal ions are standard for distorted octahedral coordination complexes with one chelating ligand. The bond lengths for 2 are slightly shorter than those for 1, consistent with ionic radius trends.25 Extension of the structures of 1 and 2 through their dpa ligands generates 1D [M(H2O)(dpa)]n2n+ chains that course along the b crystal direction (Figure 2), with Co · · · Co and Ni · · · Ni through imine distances of 11.586 and 11.505 Å, respectively. The slight difference in these contact distances is reflective of the shorter bond lengths to Ni, accompanied by subtly varying inter-ring torsions within the dpa ligands (43.8° in 1 and 43.6° in 2). These cationic chains are subsequently linked into covalent coordination polymer layers of formulation

Generation of 3D Networks through Aliphatic Chain Disorder

Crystal Growth & Design, Vol. 9, No. 1, 2009 361

Figure 4. Idealized layer B motif in 2. Hydrogen-bonding interactions are shown as dashed lines. Top, face-on view; bottom, edge-on view.

[M(sub)(dpa)(H2O)]n by crystallographically disordered subligands in both A and B orientations. For ease of discussion, the idealized structural motifs generated by the suberate ligands in A and B orientations will be treated separately. The suberate ligands in orientation A adopt a gauche-anti-anti-gauche-gauche conformation (four Catom torsion angles ) 65.3, 170.6, 177.8, 96.6, and 73.2° for 1 and 65.7, 169.1, 177.4, 93.9, and 72.2° for 2). These bridge metal atoms in adjacent [M(H2O)(dpa)]n2n+ chains in an exobidentate chelating/monodentate fashion; if all of the suberate ligands were to adopt orientation A, a ruffled [M(suberate)(dpa)(H2O)]n two-dimensional (2D) layer motif parallel to the (001) crystal plane would be generated (layer A, shown in Figure 3 as face-on and edge-on perspectives). In idealized layer A motifs, each metal ion is covalently connected to four others, with two connections each via suberate and dpa ligands, constructing a pinched (4,4) rhomboid grid motif. The metal-metal contact distances through the suberate ligands in idealized layer A patterns measure 9.020 and 8.965 Å for 1 and 2, respectively. The incipient void spaces within the resulting puckered rhomboid circuits in 1 are 8.670 and 15.806 Å, as

measured by the through-space Co-Co distances; these are markedly pinched, with Co-Co-Co angles subtending 86.0, 47.8, 122.4, and 47.8° The comparable through-space distances in layer A patterns in 2 are slightly shorter, at 8.646 and 15.702 Å, with very similar angles around the grid perimeter. In contrast to those in the A orientation, the suberate ligands in the B orientation rest in an anti-anti-anti-gauche-gauche conformation (four C-atom torsion angles ) 169.0, 176.7, 175.8, 66.4, and 62.4° for 1 and 168.9, 176.1, 173.7, 66.9, and 59.6° for 2). As before, these dicarboxylate ligands bridge metal atoms in neighboring [M(H2O)(dpa)]n2n+ chains in an exobidentate chelating/monodentate manner. If all of the suberate ligands were to lie in orientation B, an idealized [M(suberate)(dpa)(H2O)]n 2D (4,4)-grid layer motif parallel to the (1j02) crystal plane would be constructed (layer B, shown in Figure 4 as faceon and edge-on perspectives). The geometrical requirements of the anti-anti-anti-gauche-gauche conformation of the bridging suberate ligands in the layer B enforces longer M-M through-ligand contact distances than those in layer A: 10.762 Å in 1 and 10.705 Å in 2. The through-space distances within the putative layer B motifs in 1 are 14.556 and 16.976 Å.

362 Crystal Growth & Design, Vol. 9, No. 1, 2009 Table 3. Hydrogen-Bonding Distance (Å) and Angle (°) Data D-H

symmetry transformation d(H · · · A) ∠DHA d(D · · · A) for A

1 O5-H5A · · · O1 O5--H5B · · · O3 N2-H2N · · · O4

1.79(2) 1.74(2) 1.95(6)

172(6) 167(6) 174(6)

2.672(6) -x, -y, -z + 2 2.623(6) -x, y + 1/2, -z + 3/2 2.829(6) -x + 1, y + 1/2, -z + 1/2

2 O5-H5A · · · O2 O5-H5B · · · O4 N2-H2N · · · O3

1.84(2) 1.78(2) 1.95(2)

172(4) 161(5) 170(4)

2.694(4) -x, -y, -z + 2 2.611(5) -x, y + 1/2, -z + 3/2 2.833(5)

Corresponding distances for 2 are slightly shorter at 14.471 and 16.868 Å. The M-M-M angles around the grid spaces in layer B are 81.2 and 98.8° in both 1 and 2. Thus, the grid spaces within the idealized layer B are much more open than the corresponding voids in layer A. The covalent connectivity within the idealized layers A and B is supplemented by supramolecular hydrogen-bonding donation from the amine functional groups of the dpa tethers to an oxygen atom within the chelating carboxylate termini of the suberate ligands. In addition, the aqua ligand provides a hydrogen-bonding point of contact to the unligated oxygen atom within the monodentate carboxylate termini, possibly preventing a bis-bridging bis-chelating binding mode for the suberate ligand. Information regarding these interactions is given in Table 3. Because of the disorder in the suberate ligands, sited in orientations A and B, the actual coordination polymer connectivity in 1 and 2 is a 3D network that is essentially a hybrid of idealized layers A and B. If the network were treated as an

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intersection of the idealized layers, a six-connected R-Po framework would result. However, regardless of the specific suberate orientations (A/A, A/B, B/B) present at each individual metal center, each metal atom must only be linked covalently to four others. Therefore, the underlying covalent framework of each of these coordination polymers can be viewed as a modified 3D R-Po primitive cubic lattice with randomly distributed “ligand vacancies” (Figure 5). Thermogravimetric Analysis. Thermogravimetric analysis was performed to evaluate the thermal stability of the coordination polymers in this study. Compound 1 underwent dehydration between 165 and 225 °C marked by a mass loss of 4.5% (4.3% calcd for 1 equiv of bound water). Ejection of the organic components began at ∼250 °C and was complete by ∼550 °C; the mass remnant of 28.0% at this temperature is consistent with CoCO3 (28.3% calcd). The dehydration of 2 commenced at a slightly higher temperature (∼190 °C), perhaps attributable to the shorter Ni-O bond length. Water elimination was complete by ∼235 °C, as indicated by the 4.7% mass loss (4.3% calcd). Combustion of the organic ligands ensued at ∼265 °C. The mass remnant of 14.7% at 750 °C is roughly consistent with Ni metal (14.0% calcd). TGA traces for 1 and 2 are depicted in Figures S1 and S2 of the Supporting Information, respectively. Conclusions Employment of a long-spanning tethering aliphatic R,ωdicarboxylate ligand in conjunction with a kinked and hydrogenbonding capable organodiimine has resulted in a pair of divalent

Figure 5. Network perspective of the 3D connectivity of 1 and 2, based on a primitive cubic lattice with random “ligand vacancies”. Metal atoms are shown as spheres. Linkages through suberate dianions in orientations A and B are represented in green and red, respectively. Linkages through dpa are represented in blue.

Generation of 3D Networks through Aliphatic Chain Disorder

network coordination polymers with a curious 3D “ligand vacancy” primitive cubic type covalent network. The ability of the suberate ligand to adopt two energetically similar conformations that can span two distinct metal-metal distances during hydrothermal self-assembly of the complexes plays a predominant role in the formation of the intriguing 3D connectivity. The hydrogen-bonding facility of the central amine functional group of the dpa ligand plays a supplemental role in enforcing the bis-bridging chelating/monodentate binding mode of the suberate ligand, in the process likely altering the conformational preferences of the suberate ligand. Continued efforts exploring dual-ligand coordination polymer synthesis using underutilized long, flexible R,ω-dicarboxylate are underway in our laboratory. Acknowledgment. We gratefully acknowledge Michigan State University for financial support of this work. We thank Dr. Rui Huang for elemental analysis and Ms. Lindsey Johnston for the acquisition of the infrared spectra. Supporting Information Available: Crystallographic data (excluding structure factors) for the structures in this paper deposited with the Cambridge Crystallographic Data Centre with nos. 682875 and 682876. Copies obtained free of charge via the Internet at http://www.ccdc.cam.ac.uk/conts/retrieving.html or by post at CCDC, 12 Union Road, Cambridge CB2 1EZ, United Kingdom (Fax: 44-1223336033. E-mail: [email protected]). CIF files and TGA traces for 1 and 2. This material is available free of charge via the Internet at http://pubs.acs.org.

References (1) (a) Li, H.; Eddaoudi, M.; O’Keeffe, M.; Yaghi, O. M. Nature 2005, 402, 276–279. (b) Matsuda, R.; Kitaura, R.; Kitagawa, S.; Kubota, Y.; Belosludov, R. U.; Kobayashi, T. C.; Sakamoto, H.; Chiba, T.; Takata, M.; Kawazoe, Y.; Mita, Y. Nature 2005, 436, 238–241. (c) Pan, L.; Holson, D.; Ciemnolonski, L. R.; Heddy, R.; Li, J. Angew. Chem., Int. Ed. 2006, 46, 616–619. (d) Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak, D. J.; Kim, J.; O’Keeffe, M.; Yaghi, O. M. Science 2003, 300, 1127–1129. (e) Dinca, M.; Yu, A. F.; Long, J. R. J. Am. Chem. Soc. 2006, 128, 8904–8913. (f) Ferey, G.; Latroche, M.; Serre, C.; Millange, F.; Loiseau, T.; Percheron-Guegan, A. Chem. Commun. 2003, 2976–2977. (g) Zhao, X.; Xiao, B.; Fletcher, A. J.; Thomas, K. M.; Bradshaw, D.; Rosseinsky, M. J. Science 2004, 306, 1012–1015. (h) Roswell, J. L. C.; Yaghi, O. M. Agnew. Chem. Int. Ed. Engl. 2005, 44, 4670–4679. (i) Kondo, M.; Okubo, T.; Asami, A.; Noro, S.-I.; Yoshitomi, T.; Kitagawa, S.; Ishii, T.; Matsuzaka, H. Agnew. Chem. Int. Ed. Engl. 1999, 38, 140–143. (j) Sudik, A. C.; Millward, A. R.; Ockwig, N. W.; Cote, A. P.; Kim, J.; Yaghi, O. M. J. Am. Chem. Soc. 2005, 127, 7110–7118. (2) (a) Seo, J. S.; Whang, D.; Lee, H.; Jun, S. I.; Oh, J.; Jeon, Y. J.; Kim, K. Nature 2000, 404, 982–986. (b) Cingolani, A.; Galli, S.; Masciocchi, N.; Pandolfo, L.; Pettinari, C.; Sironi, A. J. Am. Chem. Soc. 2005, 127, 6144–6145. (3) (a) Fang, Q.-R.; Zhu, G.-S.; Xue, M.; Sun, J.-Y.; Qiu, S.-L. Dalton Trans. 2006, 2399–2402. (b) Zhang, X.-M.; Tong, M.-L.; Lee, H. K.; Chen, X.-M. J. Solid State Chem. 2001, 160, 118–122. (c) Yaghi, O. M.; Li, H.; Groy, T. L. Inorg. Chem. 1997, 36, 4292–4293. (4) (a) Guillou, N.; Forster, P. M.; Gao, Q.; Chang, J. S.; Nogues, M.; Park, S.-E.; Cheetham, A. K.; Ferey, G. Angew. Chem., Int. Ed. 2001, 40, 2831–2834. (b) Wu, C.-D.; Hu, A.; Zhang, L.; Lin, W. J. Am. Chem. Soc. 2005, 127, 8940–8941. (c) Han, H.; Zhang, S.; Hou, H.; Fan, Y.; Zhu, Y. Eur. J. Inorg. Chem. 2006, 8, 1594–1600. (d) Mori, W.; Takamizawa, S.; Kato, C. N.; Ohmura, T.; Sato, T. Microporous Mesoporous Mater. 2004, 73, 15–30. (e) Baca, S. G.; Reetz, M. T.; Goddard, R.; Filippova, I. G.; Simonov, Y. A.; Gdaniec, M.; Gerbeleu, N. Polyhedron 2006, 25, 1215–1222. (5) (a) Tao, J.; Shi, J. X.; Tong, M. L.; Zhang, X. X.; Chen, X. M. Inorg. Chem. 2001, 40, 6328–6330. (b) Tao, J.; Tong, M. L.; Shi, J. X.; Chen, X. M.; Ng, S. W. Chem. Commun. 2000, 2043–2044. (c) Dai, J. C.; Wu, X. T.; Fu, Z. Y.; Cui, C. P.; Hu, S. M.; Du, W. X.; Wu, L. M.; Zhang, H. H.; Sun, R. Q. Inorg. Chem. 2002, 41, 1391–1396. (d) Chen, W.; Wang, J. Y.; Chen, C.; Yue, Q.; Yuan, H. M.; Chen, J. S.; Wang, S. N. Inorg. Chem. 2003, 42, 944–946. (e) Hao, N.; Shen, E.; Li,

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(9)

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(14) (15) (16)

(17) (18) (19) (20) (21) (22) (23) (24) (25)

Y. B.; Wang, E. B.; Hu, C. W.; Xu, L. Eur. J. Inorg. Chem. 2004, 4102–4107. (a) Lu, W.-G.; Su, C.-Y.; Lu, T.-B.; Jiang, L.; Chen, J.-M. J. Am. Chem. Soc. 2006, 128, 34–35. (b) Horike, S.; Matsuda, R.; Kitagawa, S. Stud. Surf. Sci. Catal. 2005, 156, 725–732. (c) Qin, C.; Wang, X.L.; Li, Y.-G.; Wang, E.-B.; Su, Z.-M.; Xu, L.; Clerac, R. Dalton Trans. 2005, 2609–2614. (d) Zheng, Y.-Q.; Ying, E.-R. Polyhedron 2005, 24, 397–406. (e) Ghosh, S. K.; Ribas, J.; Bharadwaj, P. K. Cryst. Growth Des. 2005, 5, 623–629. (f) Sun, X.-Z.; Sun, Y.-F.; Ye, B.-H.; Chen, X.-M. Inorg. Chem. Commun. 2003, 6, 1412–1414. (g) Dai, Y.-M.; Ma, E.; Tang, E.; Zhang, J.; Li, J.-Z.; Huang, X.-D.; Yao, Y.G. Cryst. Growth Des. 2005, 5, 1313–1315. (h) Chen, B.; Liang, C.; Yang, J.; Contreras, D. S.; Clancy, Y. L.; Lobkovsky, E. B.; Yaghi, O. M.; Dai, S. Angew. Chem., Int. Ed. 2006, 45, 1390–1393. (a) Borkowski, L. A.; Cahill, C. L. Cryst. Growth Des. 2006, 6, 2248– 2259. (b) Baier, J.; Thewalt, U. Z. Anorg. Allgem. Chem. 2002, 628, 315–321. (a) Rodriguez-Martin, Y.; Hernandez-Molina, M.; Delgado, F. S.; Pasan, J.; Ruiz-Perez, C.; Sanchiz, J.; Lloret, F.; Julve, M. CrystEngComm 2002, 4, 440–446. (b) Sain, S.; Maji, T. K.; Mostafa, G.; Lu, T.-H.; Chaudhuri, N. R New J. Chem. 2003, 27, 185–187. (c) Liu, T.-F.; Sun, H.-L.; Gao, S.; Zhang, S.-W.; Lau, T.-C. Inorg. Chem. 2003, 42, 4792–4794. (a) Vaidhyanathan, R.; Natarajan, S.; Rao, C. N. R. Inorg. Chem. 2002, 41, 5226–5234. (b) Livage, C.; Egger, C.; Fe´rey, G. Chem. Mater. 2001, 13, 410–414. (c) Livage, C.; Egger, C.; Nogues, M.; Fe´rey, G. Chem. Mater. 1999, 11, 1546–1550. (d) Livage, C.; Egger, C.; Nogues, M.; Fe´rey, G. J. Mater. Chem 1998, 8, 2743–2747. (e) Forster, P. M.; Cheetham, A. K Angew. Chem., Int. Ed., 2002, 41, 457–459. (f) Ying, S.-M.; Mao, J.-G.; Sun, Y.-Q.; Zen, H.-Y.; Dong, Z.-C. Polyhedron 2003, 22, 3097–3103. (g) Zheng, Y. Q.; Kong, Z. P. Z. Anorg. Allgem. Chem. 2003, 629, 1469–1471. (a) Long, L.-S.; Wu, Y.-R.; Huang, R.-B.; Zheng, L.-S. Inorg. Chem. 2004, 43, 3798–3800. (b) Hu, R.-F.; Kang, Y.; Zhang, J.; Li, Z.-J.; Qin, Y.-Y.; Yao, Y.-G. Z. Anorg. Allgem. Chem. 2005, 631, 3053– 3057. (c) Zheng, Y.-Q.; Lin, J.-L.; Kong, Z.-P. Inorg. Chem. 2004, 43, 2590–2596. (a) Lin, J. L.; Wang, Y. Y. Acta Crystallogr. 2008, E64, m527–m528. (b) Mallika Krishnan, S.; Montney, M. R.; LaDuca, R. L. Polyhedron 2008, 27, 821–834. (c) Guillou, N.; Livage, C.; Ferey, G. Eur. J. Inorg. Chem. 2006, 4963–4978. (d) Flemig, H.; Pantenburg, I.; Meyer, G. Z. Anorg. Allgem. Chem. 2006, 632, 2205–2208. (a) Zheng, Y.-Q.; Sun, J.; Wang, Y.-F. J. Coord. Chem. 2005, 58, 1551–1559. (b) Benmerad, B.; Guehria-Laidoudi, A.; Dahaoui, S.; Lecomte, C. Acta Crystallogr. 2004, C60, m407–m409. (c) Sun, J.; Zheng, Y.-Q. Z. Anorg. Allgem. Chem. 2003, 629, 1001–1006. (a) Borkowski, L. A.; Cahill, C. L. Cryst. Growth Des. 2006, 6, 2241– 2247. (b) Kim, Y. J.; Lee, E. W.; Jung, D.-Y. Chem. Mater. 2001, 13, 2684–2690. Montney, M. R.; Mallika Krishnan, S.; Patel, N. M.; Supkowski, R. M.; LaDuca, R. L. Cryst. Growth Des. 2007, 7, 1145–1153. Montney, M. R.; Mallika Krishnan, S.; Patel, N. M.; Supkowski, R. M.; LaDuca, R. L. Inorg. Chem. 2007, 46, 7362–7370. Hagrman, D.; Warren, C. J.; Haushalter, R. C.; Seip, C.; O’Connor, C. J.; Rarig, R. S.; Johnson, K. M.; LaDuca, R. L.; Zubieta, J. Chem. Mater. 1998, 10, 3294–3297. Mallika Krishnan, S.; Patel, N. M.; Knapp, W. R.; Supkowski, R. M.; LaDuca, R. L. CrystEngComm 2007, 9, 503–514. Braverman, M. A.; Supkowski, R. M.; LaDuca, R. L. J. Solid State Chem. 2007, 180, 1852–1862. Martin, D. P.; Supkowski, R. M.; LaDuca, R. L. Inorg. Chem. 2007, 46, 7917–7922. Zapf, P. J.; LaDuca, R. L., Jr.; Rarig, R. S., Jr.; Johnson, K. M., Jr.; Zubieta, J. Inorg. Chem. 1998, 37, 3411–3414. SAINT, Software for Data Extraction and Reduction, Version 6.02; Bruker AXS, Inc.: Madison, WI, 2002. SADABS, Software for Empirical Absorption Correction, Version 2.03; Bruker AXS, Inc.: Madison, WI, 2002. Sheldrick, G. M. SHELXTL, Program for Crystal Structure Refinemen; University of Gottingen: Gottingen, Germany, 1997. Kurmoo, M.; Estournes, C.; Oka, Y.; Kumagai, H.; Inoue, K. Inorg. Chem. 2005, 44, 217–224. Shannon, R. D. Acta Crystallogr. 1976, A32, 751–767.

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