Ancillary Ligands Dependent Structural Diversity of A Series of Metal

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Ancillary Ligands Dependent Structural Diversity of A Series of MetalOrganic Frameworks Based on 3,5-Bis(3-carboxyphenyl)pyridine Liming Fan, Xiu-tang Zhang, Zhong Sun, Wei Zhang, Yuanshuai Ding, Weiliu Fan, Liming Sun, Xian Zhao, and Lei Han Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg400172w • Publication Date (Web): 23 Apr 2013 Downloaded from http://pubs.acs.org on April 23, 2013

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Crystal Growth & Design

Ancillary Ligands Dependent Structural Diversity of A Series of Metal-Organic Frameworks Based on 3,5-Bis(3-carboxyphenyl)pyridine Liming Fan,a Xiutang Zhang,*a,b Zhong Sun,a Wei Zhang,a Yuanshuai Ding,a Weiliu Fan,b Liming Sun,b Xian Zhao,*b Lei Han*c [a] Advanced Material Institute of Research, College of Chemistry and Chemical Engineering, Qilu Normal University, Jinan, 250013, China; [b] State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China; [c] State Key Laboratory Base of Novel Functional Materials & Preparation Science, Faculty of Materials Science & Chemical Engineering, Ningbo University, Ningbo, Zhejiang, 315211, China. ABSTRACT: A series of novel multi-dimensional transition metal-organic frameworks (MOFs), [Cu(Hbcpb)2]n (1), [Co(bcpb)]n (2), [Co(Hbcpb)2(1,4-bib)]n (3), {[M(bcpb)(1,4-bimb)]·xH2O}n (M = Co (4), Cu (5), Ni (6), x= 1 for 5, 2 for 4 and 6), [Co(bcpb)(4,4'-bibp)]n (7), {[Co(bcpb)(4,4'-bibp)]·2H2O}n (8), and [Ni2(bcpb)2(4,4'-bimbp)2]n (9), were synthesized under hydrothermal conditions in the presence of N-donor ancillary ligands (H2bcpb = 3,5-bis(3carboxyphenyl)pyridine,

1,4-bib

= 1,4-bis(1H-imidazol-4-yl)benzene,

1,4-bimb

= 1,4-

bis(imidazol-1-ylmethyl)benzene, 4,4'-bibp = 4,4'-bis(imidazol-1-yl)biphenyl, 4,4'-bimbp = 4,4'bis(imidazol-1-ylmethyl)biphenyl). Their structures have been determined by single-crystal Xray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-

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ray diffraction (PXRD), and thermogravimetric (TG) analyses. By adjusting the reaction pH, H2bcpb ligand is partially deprotonated to give Hbcpb- form in 1 and 3, and completely deprotonated to afford bcpb2- form in 2 and 4-9. Complex 1 exhibits a 2D (3,6)-connected kgd topology with the Schläfli symbol of (43)2(46·66·83). The 3D framework of 2 is defined as a (4,4)connected pts topology with the Schläfli symbol of (42·84). Complex 3 displays a (4,6)-connected pcu topology with the Schläfli symbol of (412·63) built from 44 2D nets with the help of 1,4-bib. Complexes 4-6 are isomorphism and show a 3D (3,5)-connected mbm framework with the Point Schläfli symbol of (4·62)(4·66·83). The supramolecular isomers of 7 and 8, resulted from the different pH in the reaction, exhibit (3,5)-connected (42·67·8)(42·6) 3,5-L2 and (4,6)-connected (44·610·8)(44·62) fsc topology, respectively. Complex 9 can be regard as an unprecedented (3,5)connected 3D 3,5-T1 frameworks with point schläfli symbol of (42·65·83)(42·6). The results revealed that the crystal architectures and the coordination modes of H2bcpb are attributed to the factors including metal cations, pH, and the N-donor ancillary ligands. Introduction The design and synthesis of metal-organic frameworks (MOFs) have attracted upsurging research interest not only because of their appealing structural and topological novelty but also owing to their tremendous potential applications in gas storage, microelectronics, ion exchange, chemical separations, nonlinear optics and heterogeneous catalysis.1-3 Generally, the structural diversity of such materials are always dependent on many factors, such as metal ion, template, metal-ligand ratio, pH value, counteranion, and number of coordination sites provided by organic ligands.4,5 Without a doubt, among these factors, the rational design and reasonable use of the characteristic ligand occupies the capital. The length, rigidly, coordination modes, functional groups or substituent of organic ligands have consequential effect on the final structures of


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MOFs.6 Especially, the aromatic polycarboxylate ligands can serve as excellent candidates for building highly connected, self-penetrating, or helical coordination frameworks due to their bent backbones and versatile bridging fashions.7,8 Apart from the carboxylate linkers, N-donor polyamine ligands are frequently used as ancillary ligand to give multipodal anions acting as bridging, chelating, and charge balance ligands for synthesizing polynuclear species.9 Moreover, the ancillary N-donor ligands also play important role on adjusting the coordination mode of polycarboxylate acid, rarely documented to date. The particular behaviors allow them to be promising candidates for designing beautiful frameworks with diverse topologies, such as pcu, dia, sxa, nbo, mon, scu, fsc, and so on.10 Thus, these considerations inspired us to explore new coordination frameworks with novel designed 3,5-bis(3-carboxyphenyl)pyridine (H2bcpb) and different N-donor ancillary ligands. However, to the best of our knowledge, MOFs based on 3,5-bis(3-carboxyphenyl)pyridine (H2bcpb) have never been documented to date. Compared with the rigid 3,5-pyridine dicarboxylic acid,11 H2bcpb is a more flexible and longer ligand, which possesses several interesting characters: (i) It has two carboxyl groups that may be completely or partially deprotonated, inducing rich coordination modes and allowing interesting structures with higher dimensionalities, (ii) It can act as hydrogen-bond acceptor as well as donor, depending upon the degree of deprotonation, (iii) Two carboxyl groups separated by two phenyl rings can form different dihedral angles through the rotation of C-C single bonds, thus it may ligate metal centers in different orientations. These characters may lead to cavities, interpenetration, helical structures, and other novel motifs with unique topologies. Taking account of these, recently we began to assemble 3,5-bis(3-carboxyphenyl)pyridine (H2bcpb) to react with different metal salts under solvothermal conditions in the presence of imidazole derivatives ligands. In this paper, we


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reported the syntheses and characterizations of nine novel coordination polymers, [Cu(Hbcpb)2]n (1), [Co(bcpb)]n (2), [Co(Hbcpb)2(1,4-bib)]n (3), {[M(bcpb)(1,4-bimb)]·xH2O}n (M = Co (4), Cu (5), Ni (6)), [Co(bcpb)(4,4'-bibp)]n (7), {[Co(bcpb)(4,4'-bibp)]·2H2O}n (8), and [Ni2(bcpb)2(4,4'bimbp)2]n (9), which exhibit a systematic variation of architectures from 2D layers to 3D frameworks by the employment of H2bcpb and five different N-donor ancillary ligands (1,4-bib, 1,4-bimb, 4,4'-bibp, 4,4'-bimbp, shown in Chart 1). These results reveal that the ancillary ligand backbones have great influence on the topology of coordination architectures and may be used as a tool to tune the degree of interpenetrations.

Chart 1. The structurally related ancillary ligands. Experimental Section Materials and General Methods. The syntheses of 1–9 were performed in Teflon-lined stainless steel autoclaves under autogenous pressure. The chemicals of 3-bromobenzoic acid, bis(pinacolato)diborane, Pd(dppf)2Cl2, Pd(PPh3)4, 2,6-dibromopyridine, 1,4-bis(imidazol-1ylmethyl)benzene, 4,4′-bis(1-imidazolyl)biphenyl, 1,4-bis(1H-imidazol-4-yl)benzene, and 4,4'bis(imidazol-1-ylmethyl)biphenyl were purchased from Jinan Henghua Sci. & Tec. Co. Ltd. without further purification. IR spectra were measured on a Nicolet 740 FTIR Spectrometer at the range of 400-4000 cm-1. Elemental analyses were carried out on a CE instruments EA 1110 elemental analyzer. TGA was measured from 25 to 800 oC on a SDT Q600 instrument at a


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heating rate 5 oC/min under the N2 atmosphere (100 mL/min). X-ray powder diffractions were measured on a Panalytical X-Pert pro diffractometer with Cu-Kα radiation. Synthesis of 3,5-bis(3-carboxyphenyl)pyridine (H2bcpb). Synthesis of ethyl 3-bromobenzoate (II). The mixture of 3-bromobenzoic acid (0.1 mol, 20.0 g), 500 mL ethanol, and 10 mL concentrated H2SO4 was refluxed for 12 hours, and then poured into 500 mL H2O. The solution was extracted with ethyl acetate (200 mL × 3), dried with anhydrous magnesium sulfate, and then concentrated on rotary evaporator to give a white powder (95 %). Anal. (%) calcd. for C9H9BrO2: C, 47.19; H, 3.96. Found: C, 47.02; H, 3.78. Synthesis of 4,4,5,5-tetramethyl-2-(ethyl 3-carboxylphenyl)-1,3-dioxolane (III). The synthetic method was modified from the published 4,4,5,5-tetramethyl-2-(dimethyl 3,5dicarboxylatephenyl)-1,3-dioxolan.7e,12

The

mixture

of

II

(0.10

mol,

22.8

g),

bis(pinacolato)diborane (0.12 mmol, 30.5 g), potassium acetate (0.12 mmol, 16.6 g), Pd(dppf)2Cl2 (1.00 mmol, 0.8 g), and dried 1,4-dioxane (500 mL) was refluxed at 120 ˚C overnight and afterward extracted with ethyl acetate (200 mL × 3). The organic layer was decolored with activated carbon, and dried by anhydrous Na2SO4. The crude product was obtained from concentration under a vacuum and purified by column chromatography (silica gel, ethylacetate/petroleum ether, 6 v %). Yield 78 %. Anal. (%) calcd. for C15H21BO4: C, 65.24; H, 7.67. Found: C, 65.10; H, 7.56. Synthesis of diethyl pyridine-3,5-bis(phenyl-3-carboxylate) (IV). The mixture of III (0.21 mol, 60.0 g), 3,5-dibromopyridine (0.10 mol, 23.7 g), and K3PO4 (0.20 mol, 42.4 g) were mixed in 1,4-dioxane (500 mL), and the mixture was deaerated using N2 for 10 min. Pd(PPh3)4 (1.00 mmol, 1.2 g) was added to the stirred reaction mixture and the mixture was heated to reflux for ca. one week under N2. The crude product of IV was obtained after 1,4-dioxane was removed


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under a vacuum. Recrystallization from methanol offered the pure diethyl pyridine-3,5bis(phenyl-3-carboxylate). Anal. (%) calcd. for C23H21NO4: C, 73.58; H, 5.64; N, 3.73. Found: C, 73.39; H, 5.55; N, 3.67. Synthesis of 3,5-bis(3-carboxyphenyl)pyridine (H2bcpb, V). The mixture of IV (0.10 mol, 37.5 g) and 20 g NaOH in 500 mL H2O was refluxed for 2 hours, and then cooled to room temperature. The solution was neutralized with concentrated HCl. White powder was obtained with the yield of 95 %. EI-MS: m/z [M-H]–, 328.1 (calcd for C19H13NO4, 329.1). Anal. (%) calcd. for C19H13NO4: C, 71.47; H, 4.10; N, 4.39. Found: C, 71.35; H, 4.02; N, 4.26.

Scheme 1. The scheme for the synthesis of H2bcpb. General Synthesis Procedure for Complexes 1–9. The synthesis for the target nine complexes were performed in 25 mL Teflon-lined stainless steel vessels by utilizing the hydrothermal method with the same stoichiometric ratio for the starting materials in the presence of NaOH. The one-pot mixture was heated to an appropriate temperature and held for 72 h, then cooled at a descent rate of 10 oC/h. Finally, the crystals suitable for the single-crystal X-ray diffraction analysis were obtained after cooling to room temperature. Synthesis of [Cu(Hbcpb)2]n (1). A mixture of H2bcpb (0.20 mmol, 0.064 g), 1,4-bis(1Himidazol-4-yl)benzene (0.20 mmol, 0.048 g), copper(II) sulfate pentahydrate (0.20 mmol, 0.050 g), NaOH (0.20 mmol, 0.008 g) and 14 mL H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 oC/h) to room


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temperature. Blue block crystals of 1 were obtained. Yield of 69% (based on Cu). Anal. (%) calcd. for C38H24CuN2O8: C, 65.19; H, 3.46; N, 4.00. Found: C, 64.37; H, 3.51; N, 3.89. IR (KBr pellet, cm-1): 3438 (s), 3079 (m), 2361 (m), 1689 (vs), 1567 (vs), 1393 (vs), 1229 (s), 887 (m), 742 (s), 522 (w). Synthesis of [Co(bcpb)]n (2). A mixture of H2bcpb (0.20 mmol, 0.064 g), 1,3,5tris(imidazol-1-ylmethyl)benzene (0.10 mmol, 0.032 g), cobalt(II) dichloride hexahydrate (0.20 mmol, 0.048 g), NaOH (0.30 mmol, 0.012 g) and 14 mL H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 o

C/h) to room temperature. Purple block crystals of 2 were obtained. Yield of 57% (based on

Co). Anal. (%) calcd. for C19H11CoNO4: C, 60.66; H, 2.95; N, 3.72. Found: C, 59.73; H, 2.92; N, 3.67. IR (KBr pellet, cm-1): 3434 (m), 3078 (m), 2366(m), 1641 (vs), 1580 (vs), 1396 (vs), 1227 (m), 897 (m), 778 (s), 526 (w). Synthesis of [Co(Hbcpb)2(1,4-bib)]n (3). A mixture of H2bcpb (0.20 mmol, 0.064 g), 1,4bib (0.40 mmol, 0.084 g), cobalt(II) nitrate hexahydrate (0.40 mmol, 0.116 g), NaOH (0.20 mmol, 0.008 g) and 12 mL H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 oC/h) to room temperature. Pink block crystals of 3 were obtained. Yield of 44% (based on Co). Anal. (%) calcd. for C50H32CoN6O8: C, 66.45; H, 3.57; N, 9.30. Found: C, 65.78; H, 3.42; N, 9.16. IR (KBr pellet, cm-1): 3440 (s),3123 (m), 3067 (m), 2365(m), 1537 (vs), 1310 (s), 1247 (m), 1143 (s), 842 (m), 739 (m), 531 (w). Synthesis of {[Co(bcpb)(1,4-bimb)]·2H2O}n (4). A mixture of H2bcpb (0.20 mmol, 0.064 g), 1,4-bimb (0.20 mmol, 0.048 g), cobalt(II) nitrate hexahydrate (0.20 mmol, 0.058 g), NaOH (0.30 mmol, 0.012 g) and 14 mL H2O was placed in a Teflon-lined stainless steel vessel, heated


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to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 oC/h) to room temperature. Pink block crystals of 4 were obtained. Yield of 49% (based on Co). Anal. (%) calcd. for C33H29CoN5O6: C, 61.21; H, 4.05; N, 10.82. Found: C, 60.87; H, 3.91; N, 10.27. IR (KBr pellet, cm-1): 3419 (s),3104 (m), 3045 (m), 2367(m), 1683 (vs), 1556 (vs), 1394 (vs), 1247 (m), 1143 (s), 816 (m), 742 (m), 517 (w). Synthesis of {[Cu(bcpb)(1,4-bimb)]·H2O}n (5). A mixture of H2bcpb (0.20 mmol, 0.064 g), 1,4-bimb (0.20 mmol, 0.048 g), copper(II) sulfate pentahydrate (0.20 mmol, 0.050 g), NaOH (0.30 mmol, 0.012 g) and 14 mL H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 oC/h) to room temperature. Blue block crystals of 5 were obtained. Yield of 63% (based on Cu). Anal. (%) calcd. for C33H27CuN5O5: C, 62.21; H, 4.27; N, 10.99. Found: C, 62.03; H, 4.31; N, 10.76. IR (KBr pellet, cm-1): 3441 (s), 3082 (m), 2363 (s), 1693 (vs), 1565 (s), 1391 (vs), 1239 (s), 886 (m), 788 (m), 529 (w). Synthesis of {[Ni(bcpb)(1,4-bimb)]·2H2O}n (6). A mixture of H2bcpb (0.20 mmol, 0.064 g), 1,4-bimb (0.40 mmol, 0.096 g), nickel(II) dichloride pexahydrate (0.40 mmol, 0.095 g), NaOH (0.30 mmol, 0.012 g) and 14 mL H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 oC/h) to room temperature. Green block crystals of 6 were obtained. Yield of 58% (based on Ni). Anal. (%) calcd. for C33H29NiN5O6: C, 60.95; H, 4.49; N, 10.77. Found: C, 60.37; H, 4.29; N, 10.31. IR (KBr pellet, cm-1): 3443 (s), 3106 (m), 2363 (m), 1608 (vs), 1546 (vs), 1412 (vs), 1386 (vs), 1225 (m), 1089 (s), 834 (m), 771 (vs), 537 (w). Synthesis of [Co(bcpb)(4,4′-bibp)]n (7). A mixture of H2bcpb (0.20 mmol, 0.064 g), 4,4′bibp (0.20 mmol, 0.057 g), cobalt(II) nitrate hexahydrate (0.30 mmol, 0.087 g), NaOH (0.30


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mmol, 0.012 g) and 12 mL H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 oC/h) to room temperature. Red block crystals of 7 were obtained. Yield of 71% (based on Co). Anal. (%) calcd. for C37H25CoN5O4: C, 67.07; H, 3.80; N, 10.57. Found: C, 66.86; H, 3.69; N, 10.24. IR (KBr pellet, cm-1): 3437 (s), 3067 (m), 2376 (m), 1705 (vs), 1517 (vs), 1412 (vs), 1232 (s), 1136 (s), 820 (m), 758 (s), 541 (w). Synthesis of {[Co(bcpb)(4,4′-bibp)]·2H2O}n (8). A mixture of H2bcpb (0.20 mmol, 0.064 g), 4,4′-bibp (0.40 mmol, 0.114 g), cobalt(II) nitrate hexahydrate (0.40 mmol, 0.116 g), NaOH (0.40 mmol, 0.016 g) and 14 mL H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 oC/h) to room temperature. Yellow block crystals of 8 were obtained. Yield of 43% (based on Co). Anal. (%) calcd. for C37H30CoN5O6: C, 63.52; H, 4.32; N, 10.01. Found: C, 63.27; H, 4.12; N, 9.73. IR (KBr pellet, cm-1): 3413 (s), 3084 (m), 2372 (m), 1605 (m), 1563 (vs), 1498 (vs), 1386 (vs), 1247 (s), 1056 (s), 826 (s), 767 (s), 535 (w). Synthesis of [Ni2(bcpb)2(4,4′-bimbp)2]n (9). A mixture of H2bcpb (0.20 mmol, 0.064 g), 4,4′-bimbp (0.20 mmol, 0.053 g), nickel(II) sulfate hexahydrate (0.30 mmol, 0.085 g), NaOH (0.30 mmol, 0.012 g) and 12 mL H2O was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 3 days, followed by slow cooling (a descent rate of 10 oC/h) to room temperature. Green block crystals of 9 were obtained. Yield of 59 % (based on Ni). Anal. (%) calcd. for C79H58Ni2N9O8: C, 68.82; H, 4.24; N, 9.14. Found: C, 68.30; H, 4.13; N, 9.02. IR (KBr pellet, cm-1): 3429 (s), 3067 (m), 2367 (m), 1618 (vs), 1547 (vs), 1438 (vs), 1389 (vs), 1241 (m), 1074 (s), 834 (s), 773 (s), 543 (w).


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X-ray crystallography. Intensity data collection was carried out on a Siemens SMART diffractometer equipped with a CCD detector using Mo-Kα monochromatized radiation (λ = 0.71073 Å) at 293(2) K. The absorption correction was based on multiple and symmetryequivalent reflections in the data set using the SADABS program based on the method of Blessing. The structures were solved by direct methods and refined by full-matrix least-squares using the SHELXTL package.13 Crystallographic data for complexes 1–9 are given in Table 1. Selected bond lengths and angles for 1–9 are listed in Table 2. For complexes of 1–9, further details on the crystal structure investigations may be obtained from the Cambridge Crystallographic Data Centre, CCDC, 12 Union Road, CAMBRIDGE CB2 1EZ, UK, [Telephone: +44-(0)1223-762-910, Fax: +44-(0)1223-336-033; Email: [email protected], http://www.ccdc.cam.ac.uk/deposit], on quoting the depository number CCDC-921761 for 1, 921762 for 2, 921763 for 3, 921764 for 4, 921765 for 5, 921766 for 6, 921767 for 7, 921768 for 8, and 921769 for 9. Result and discussion Synthesis and Characterization. The synthesis of 3,5-bis(3-carboxyphenyl)pyridine (H2bcpb) is shown in Scheme 1. In order to obtain the pure product and the high yield, the used organic solvents should be dried completely during the synthesis of chemicals (II) and (III). The synthesis of (IV) was performed under the N2 atmosphere. The final product of H2bcpb is white if the obtained crude product of (IV) was decolored by refluxing in EtOH with activated carbon. In the present study, complexes 1-9 were prepared from the solvothermal reaction of the related first transitional metal salts and the ligand of H2bcpb in the presence of N-donor ancillary ligands. Although there are no N-donor ancillary ligands in compounds 1 and 2, the reactions without N-donor chemicals as secondary ligands usually gave only some unknown precipitates.


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However, when the auxiliary N-donor ligands were introduced, satisfactory single crystals of nine complexes were obtained. The Diverse Coordination Modes of H2bcpb and the Structural Comparison. As shown in the Table 3 and Scheme 2, H2bcpb exhibits versatile coordination modes in complexes 1-9 and the two carboxyl groups of H2bcpb are completely deprotonated except for 1 and 3. The pyridyl N atoms coordinated with center metal ions in all the complexes. It is also worth noting that H2bcpb exhibits completely different coordination mode in the presence of each employed Ndonor ligands. In complex 1 and 3, the H2bcpb ligands are partially deprotonated. Whereas, both of two carboxyl groups in 1 adopt µ1-η1:η0 coordination modes (named as Mode I), and only the deprotonated carboxyl group coordinates with MII ions with µ1-η1:η0 coordination mode in 3 (Mode III). In complexes 2 and 4-9, H2bcpb are completely deprotonated and exhibits different coordination modes. The H2bcpb ligand in complex 2 acts as a “W” bridge to link three Co ions with µ1-η1:η1 and µ2-η2:η1 coordination modes to connect four MII ions (Mode II). In complexes 4-6, the two carboxyl groups of H2bcpb adopt µ1-η1:η1 and µ1-η1:η0 coordination modes (Mode IV). Whereas, just as shown in Scheme 2, the two benzoate groups in 8 exhibits more close distance compared to Mode II and adopt syn-anti µ2-η1:η1 and µ1-η1:η0 modes (Mode VI) to connect four MII ions. In complex 7, the two carboxyl groups of H2bcpb adopt µ1-η1:η1 mode (Mode V). For complex 9, the two unique H2bcpb exhibit different coordination modes, one: Mode V, another: Mode VII. On the other hand, the title nine complexes exhibit completely different connection and topology, mainly due to the pH value, metal ions, and ancillary ligands. The decisive effect of ancillary N-donor ligands on the coordination mode of polycarboxylate acid and the structural diversity is rarely documented to date. The synthetic conditions are similar for 4(5,6) and 9


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except for the distance of flexible ancillary ligands (1,4-bis(imidazol-1-ylmethyl)benzene in 4(5,6), 4,4'-bis(imidazol-1-ylmethyl)biphenyl in 9). This difference results in that 4(5,6) and 9 own the (3,5)-connected mbm net and three-fold (3,5)-connected 3D 3,5-T1 net, respectively. The utilized rigid ligand (4,4'-bis(imidazol-1-yl)biphenyl) in 7 leads to a (3,5)-connected 3,5L2 framework, different from 9. In a word, the ancillary ligands have a great effect on the coordination modes of the host polycarboxylate aromatic acid and the final packing structures. With the length of the ancillary ligands increasing, the longer separation of neighboring central ions makes the host aromatic polycarboxylate ligand adopt more “open” coordination modes, and the overall structure a higher degree of interpenetration. The more flexibility of ancillary ligands could make the aromatic polycarboxylate more twisted and the final structure more complicated.

Scheme 2. Diverse coordination types of H2bcpb in complex 1-9. Structural Description of [Cu(Hbcpb)2]n (1). Single-crystal X-ray diffraction analysis reveals that complex 1 crystallize in the orthorhombic system, space group Pbca. The asymmetric unit of 1 consists of one half of CuII atom, and one Hbcpb-. Each CuII center is hexacoordinated by two N atoms from two Hbcpb- ligands [Cu(1)–N(1) = 2.002(6) Å] and four O atoms from another four Hbcpb- ligands [Cu(1)–O(1) = 1.936(4), Cu(1)–O(3)A = 2.670(2) Å],


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showing a distorted octahedral coordination geometry (Figure 1a). The ligand of H2bcpb in 1 is partially deprotonated and act as one µ3 node to coordinate with three CuII ions via three dentate atoms including one N and two O atoms, in which both of two carboxyl groups adopt similar µ1η1:η0 coordination mode (named as Mode I). The dihedral angles between two phenyl rings and the central pyridine ring in one Hbcpb- are 28.16(1) and 52.27(1)°, respectively. And the angle between two phenyl rings in one Hbcpb- is 32.37(1)°. These dihedral data indicates that Hbcpbwas extremely unsymmetrical and not as flat as the disassociated molecule. The divalent Cu ions are linked by Hbcpb- ligands to form a 2D polymeric [Cu(Hbcpb)2]n double-layer with the alternately arranged left- and right-handed helical chains (Figure 1b). Moreover, adjacent nets are further connected through C-H···O interactions (C(1)-H(1)···O(1) = 2.875(1) Å, C(5)H(5)···O(1) = 3.000(4) Å) to form a 3D packing diagram. The topology analysis method was accessed to simplify the structure.14 The overall framework can be defined as a (3,6)-connected kgd topology with the Schläfli symbol of (43)2(46·66·83) by denoting the CuII atoms as sixconnected nodes and Hbcpb- as three-connected nodes, respectively (Figure 1c).


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Figure 1. (a) Coordination environment of CuII ion in 1 (Symmetry codes: A: 1–x, 1-y, 1-z; B: 0.5-x, 0.5+y, z; C: 0.5+x, 0.5-y, 1-z). (b) The 2D double-layer nets with left- and right-handed helix axis. (c) Schematic view of a (3,6)-connected kgd topology with the Schläfli symbol of (43)2(46·66·83) of 1 (green spheres: CuII atoms; violet spheres: Hbcpb- ligands). Structural Description of [Co(bcpb)]n (2). Single-crystal X-ray diffraction analysis reveals that complex 2 crystallizes in the monoclinic system, space group P21/c. As shown in Figure 2a, there are one crystallographically independent CoII atom and one bcpb2- ligand in the asymmetric unit. Similar to compound 1, the Co(1)-O(3A) bond length is much longer (2.690(9) Å, symmetry code, (A): −x, 1−y, 2−z). The CoII center can be regarded as hexa-coordinated by two N atoms from two bcpb2- ligands [Co(1)–N(1) = 2.082(4) Å, Co(1)–O(1) = 2.271(4), Co(1)– O(2) = 2.046(4), Co(1)–O(3B) = 2.021(4), Co(1)–O(4C) = 2.043(4), symmetry codes: (B): x+1,y+1/2,-z+3/2; (C): x+1,-y+3/2,z-1/2], showing a distorted octahedral coordination geometry.


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The ligand of H2bcpb, different from the one in 1, is completely deprotonated and act as one µ4 node to coordinate with four CoII ions, in which two carboxyl groups adopt µ2-η2:η1 and µ1η1:η1 coordination modes (named as Mode II). Similar to 1, bcpb2- was extremely unsymmetrical and not as flat as the disassociated molecule. The dihedral angle between two phenyl rings and the central pyridine ring in bcpb2- are 28.24(1) and 29.78(1)°, respectively. And the one between two phenyl rings is in bcpb2- is 20.84(1)°. The bow-kont dinuclear CoII subunits are generated by sharing the µ2-η2:η1 carboxyl groups with the Co···Co distance is 3.811(3) Å, based on which one unprecedented 3D framework was constructed via the linkage of four-connected bcpb2- ligands (Figure 2b). At the sight of topology, the final framework can be defined as a (4,4)-connected pts topology with the Schläfli symbol of (42·84) by denoting the CoII atoms to four-connected nodes and bcpb2- ligands to four-connected nodes, respectively (Figure 2c).

Figure 2. (a) Coordination environment of CoII ion in 2 (Symmetry codes: A: 1–x, 0.5+y, 1.5-z; B: 1+x, 1.5-y, -0.5+z; C: 1-x, 2-y, 1-z). (b) The 3D framework viewed along c axis. (c)


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Schematic view of the (4,4)-connected pts network of 2 (cyan-bluespheres: CoII atoms; yellow spheres: bcpb2- ligands). Structural Description of [Co(Hbcpb)2(1,4-bib)]n (3). Single-crystal X-ray diffraction analysis reveals that complex 3 crystallizes in the monoclinic system, space group P21/c. As shown in Figure 3a, there are one half of crystallographically independent CoII atom, one Hbcpbligand, and one half of 1,4-bib ligand in the asymmetric unit. Each CoII center is hexacoordinated by four N atoms from two 1,4-bip ligands and two Hbcpb- ligands [Co(1)–N(1) = 2.146(5) and Co(1)–N(3) = 2.204(7) Å] and two O atoms from two different Hbcpb- ligands [Co(1)–O(2) = 2.059(7) Å], showing a distorted octahedral coordination geometry. Although the ligand of H2bcpb is partially deprotonated, the coordination mode is different from 1. Hbcpb- act as one µ2 node to coordinate with two CoII ions via the deprotonated carboxylate oxygen atom and the Npyridine atom (named as Mode III). The dihedral angle between two phenyl rings and central pyridine ring in Hbcpb- are 19.74(1) and 36.01(1)°, respectively. And the one between two phenyl rings in one Hbcpb- is 28.84(1)°. The bridging Hpdpc- ligands connected two neighboring CoII ions along bc plane giving a 44 2D net with right- and left-helix chains alternately arranged (Figure 3b). Furthermore, the 1,4-bib ligands act as pillars and further link the neutral layers into a 3D framework (Figure 3c). The Co···Co distance separated by the 1,4-bib ligand is 12.510(8) Å. From the viewpoint of structural topology, the whole structure of complex 3 can be defined as a (4,6)-connected pcu topology with the Schläfli symbol of (412·63) by denoting the CoII atoms to six-connected nodes and Hbcpb- and 1,4-bib ligands to linkers, respectively (Figure 3d).


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Figure 3. (a) Coordination environment of CoII ion in 3(Symmetry codes: A: 1–x, -y, -z; B: x, 0.5-y, 0.5+z; C: 1-x, -0.5+y, -0.5-z). (b) The 2D 44 net bridged by the Hbcpb- ligands. (c) View of the 3D framework with triangle opening channels. (d) Schematic view of the 6-connected pcu network of 3 (green spheres: CoII atoms). Structural Description of {[M(bcpb)(1,4-bimb)]·xH2O}n (M=Co, x=2 for 4; M=Cu, x=1 for 5; M=Ni, x=2 for 6). The single-crystal X-ray diffraction analyses reveal that complexes 4-6 are isomorphism and crystallize in the monoclinic system, space group P2/n, herein only the structure of 4 will be discussed as a representation. As shown in Figure 4a, there are one crystallographically independent CoII atom, one bcpb2- ligand, one 1,4-bimb ligand, and two free water molecules in the asymmetric unit. Each CoII center is hexa-coordinated by three N atoms from two 1,4-bimb ligands and one bcpb2- ligand [Co(1)–N(1) = 2.179(2), Co(1)–N(2) =


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2.118(2), Co(1)–N(5) = 2.131(2) Å], and three O atoms from three two bcpb2- ligands [Co(1)– O(1) = 2.171(5), Co(1)–O(2) = 2.194(8), Co(1)–O(4) = 2.032(7) Å], showing a distorted octahedral coordination geometry. The ligand of H2bcpb is completely deprotonated and act as one µ3 node to coordinate with three CoII ions, in which two carboxyl groups adopt µ1-η1:η1 and µ1-η1:η0 coordination modes (named as Mode IV). The dihedral angles between two phenyl rings and central pyridine ring in bcpb2- are 19.98(1) and 25.46(1)°, respectively. And the one between two phenyl rings is in bcpb2- is 26.43(1)°. It is worth noting that the dihedral angles are much bigger for compounds 5 and 6: 43.10(1), 28.80(1), and 61.16(1) for 5; 44.13(1), 27.17(1), and 61.28(1) for 6 (Table 3). The 3-connecetd bcpb2- ligands linked the CoII ions together to form a polymeric (4·82) [Co(bcpb)]n net along ac plane (Figure 4b). Two adjacent 2D sheets are linked in a trans fashion by the 1,4'-bimb ligands to generate a 3D framework. And the Co···Co distance separated by the 1,4-bimb ligand is 13.664(5) Å (Figure 4c). From a topology view, the network of 6 can be rationalized to a (3,5)-connected 3D mbm network with the Point Schläfli symbol of (4·62)(4·66·83), in which CoII and bcpb2- act as five-connected and three-connected node (Figure 4d).


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Figure 4. (a) Coordination environment of CoII ion in 4 (Symmetry codes: A: 1.5–x, -0.5+y, 1.5z; B: 0.5+x, 1.5-y, -0.5+z; C: x, y, 1+z). (b) The 2D 3-connected net constructed by the bcpb2ligands. (c) View of the 3D framework with the 1,4-bimb bridged 2D nets. (d) Schematic view of the (3,5)-connected mbm net of 4 (green spheres: CoII atoms; violet spheres: bcpb2- ligands). Structural Description of [Co(bcpb)(4,4'-bibp)]n (7). The supramolecular isomers of 7 and 8, resulted from the different pH in the reaction, exhibit (3,5)-connected (42·67·8)(42·6) 3,5L2 and (4,6)-connected (44·610·8)(44·62) fsc topology, respectively. Single-crystal X-ray diffraction analysis reveals that complex 7 crystallizes in the monoclinic system, space group P2/c. As shown in Figure 5a, there are one crystallographically independent CoII atom, one bcpb2ligand, and one 4,4'-bibp ligand in the asymmetric unit. Each CoII center is hepta-coordinated by


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three N atoms from two 4,4'-bibp ligands and one bcpb2- ligand [Co(1)–N(1) = 2.211(3), Co(1)– N(3) = 2.177(2) Å], and four O atoms from three bcpb2- ligands [Co(1)–O(1) = 2.194(2), Co(1)– O(2) = 2.344(3) Å], showing a distorted heptahedral coordination geometry. The ligand of H2bcpb is completely deprotonated and acts as one µ3 node to coordinate with three CoII ions, in which two carboxyl groups adopt µ1-η1:η1 chelating coordination mode (named as Mode V). The dihedral angles between two phenyl rings and central pyridine ring in bcpb2- is 33.23(1)°. And the one between two phenyl rings is in Hbcpb- is 63.70(1)°. The Co(II) atoms are bridged by bcpb2- ligands to result in a 1D ladder-like structure, which can be defined as a single left- or right-handed helix (Figure 5b). The [Co(bcpb)]n ladders are extended via the bridge of 4,4'-bibp to form a corrugated 2D network parallel to the ab crystal plane (Figure 5c). Moreover, adjacent nets are further connected through C-H···O interactions (C(5)-H(5)···O(2) = 3.444(4) Å), forming a 3D packing diagram with the solvent-accessible void space 9.6% (146.7 Å3 of the whole volume 1528.7 Å3). The topology analysis shows the overall framework of complex 7 can be rationalized to a (3,5)-connected 3,5-L2 topology with the Schläfli symbol of (42·67·8)(42·6) by denoting the CoII atoms to five-connected nodes and bcpb2- ligands to threeconnected nodes, respectively (Figure 5d).


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Figure 5. (a) Coordination environment of CoII ion in 7 (Symmetry codes: A: 1–x, y, 1.5-z, 1.5z; B: x, 1-y, 0.5+z; C: 1-x, 1-y, 1-z). (b) 1D ladder chain formed by the bcpb2- ligands connected the CoII ions. (c) The double-layer 2D net with the 4,4′-bibp linked the 1D ladder chains. (d) Schematic view of the (3,5)-connected (42·67·8)(42·6) network of 7 (green spheres: CoII atoms; light purple spheres: bcpb2- ligands; pink bonds: 4,4′-bibp ligands). Structural Description of {[Co(bcpb)(4,4'-bibp)]·2H2O}n (8). Single-crystal X-ray diffraction analysis reveals that complex 8 crystallizes in the triclinic system, space group Pī. As shown in Figure 6a, there are one crystallographically independent CoII atom, one bcpb2- ligand, one 4,4'-bibp ligand, and two free water molecules in the asymmetric unit. Each CoII center is hexa-coordinated by two N atoms from two 4,4'-bibp ligands and one N atom from one bcpb2ligand [Co(1)–N(1) = 2.227(5), Co(1)–N(5) = 2.381(5) and Co(1)–N(4)D = 2.244(5) Å], and three O atoms from three bcpb2- ligands [Co(1)–O(1)B = 2.186(5), Co(1)–O(2)C= 2.196(5) and


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Co(1)–O(3)A = 2.138(5) Å], showing a distorted octahedral coordination geometry, respectively. The ligand of H2bcpb is completely deprotonated and act as one µ4 node to coordinate with four CoII ions, in which two carboxyl groups adopt trans µ2-η1:η1 and µ1-η1:η0 coordination modes (named as Mode VI). The dihedral angles between two phenyl rings and central pyridine ring in bcpb2- are 34.88(1) and 33.35(1)°, respectively. And the one between two phenyl rings is in bcpb2- is 57.58(1) °. The V-shaped bcpb2- ligands conjoin the {Co2} dinuclear units into a polymeric [Co2(bcpb)2]n layer motif that lies parallel to the ab crystal plane (Figure 2). The closest throughligand Co···Co distances within the layer measure 9.164, 9.370, and 10.227 Å. It is interesting to note that the bcpb2- ligands linked the Co ions to left- and right-handed helix chains along a crystallographic a axis. The resulting left- or right-handed helices with a pitch of 9.633(8) Å and alternately arrange in a left- and right-handed sequence, so that the whole sheet does not show chirality. The pyridine N atoms link other dinuclear CoII subunits, giving a (3,6)-connected 2D 63 net (Figure 6b). Furthermore, the 4,4'-bibp ligands act as pillars and further link the neutral layers into a 3D framework (Figure 6c). The Co···Co distance separated by the 4,4'-bibp lignd is 17.901 Å. From the viewpoint of structural topology, the overall framework can be defined as a (4,6)-connected fsc topology with the Schläfli symbol of (44·610·8)(44·62) by denoting CoII and bcpb2- as six-connected nodes and four-connected nodes, respectively (Figure 6d).


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Figure 6. (a) Coordination environment of CoII ion in 8 (Symmetry codes: A: 1–x, 1-y, 1-z; B: x, 1-y, 1-z; C: x, -1+y, z; D: -1+x, y, -1+z). (b) The 2D [Co(bcpb)]n net with left- and righthanded helix axis alternately. (c) The 3D framework with rectangular holes. (d) Schematic view of the (4,6)-connected fsc network with the Point Schläfli symbol of (44·610·8)(44·62) (green spheres: CoII atoms; light purple spheres: bcpb2- ligands; pink bonds: 4,4′-bibp ligands). Structural Description of [Ni2(bcpb)2(4,4'-bimbp)2]n (9). Single-crystal X-ray diffraction analysis reveals that complex 9 crystallizes in the triclinic system, space group Pī, showing an unprecedented (3,5)-connected 3D network with the Schläfli symbol of (42·65·83)(42·6). As shown in Figure 7a, there are two crystallographically independent NiII atoms, two bcpb2ligands, and two 4,4'-bimbp ligands in the asymmetric unit. Both Ni(1) and Ni(2) are coordinated by three N atoms from two 4,4'-bimbp ligands and one bcpb2- ligand, and three O atoms from


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two bcpb2- ligands. The Ni-O/N bond lengths and the bond angles around each NiII center are 2.039(3)-2.176(4)/2.108(5)-2.101(4) Å and 83.54(16)-175.39(14)°, respectively. In 9, two bcpb2- ligands exhibit different coordination modes; two carboxyl groups in one adopt µ1-η1:η1 (Mode V), another shows similar µ1-η1:η0 coordination mode (Mode VII). The NiII ions are bridged alternately by the above two kinds of bcpb2- ligands to form ladder chains along b axis, Figure 7b, which are further linked along a and c axis by the trans 4,4'-bimbp ligands to generate a 3D framework consisting of rhombic cavities with effective sizes of 15.39 × 17.40 Å2 (Figure 7c). From a topology view, the final structure of 9 can be regard as a novel (3,5)-connected 3D 3,5-T1 frameworks with point schläfli symbol of (42·65·83)(42·6) by denoting the CoII ions to five-connected nodes and bcpb2- ligands simplified as three-connected nodes (Figure 7d).


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Figure 7. (a) Coordination environment of NiII ions in 9. Symmetry transformations used to generate equivalent atoms: (A) 1–x ,-y , -z; (B) 2-x, 1-y , -z; (C) –x, 2-y, -z. (b) A drawing showing the 1D snaked [Co(4,4′-bimbp)] chain and 1D ladder [Co2(bcpb)2] chain. (c) View of the 3D porous frameworks. (d) Schematic view of the three-fold (3,5)-connected (42·67·8)(42·6) network of 9 (green spheres: NiII atoms; pink spheres: bcpb2- ligands). IR spectra. The IR spectras of complexes 1–9 and H2bcpb ligand are shown in Figure 8 and Figure S1. For complexes 1 and 3, 2 and 4, the similar peaks in the range 1200-1700 cm-1 indicated the aucillary ligands have little effect on the IR characteristic spectra of carboxylate groups. The peaks of in the range of 1485–1682 cm-1 are corresponded with the symmetric stretching the carboxylic groups. The (νas-νs) values (173/194 cm-1 for 1, 146/192 cm-1 for 2, 160/185 cm-1 for 3, 141/194 cm-1 for 4, 147/171 cm-1 for 5, 135/170 cm-1 for 6, 137/140 cm-1 for 7, 155/183 cm-1 for 8, and 158/172 cm-1 for 9) are attributed to the diverse carboxylate coordination modes, which are in accordance with the spectroscopic criteria on determining the modes of the carboxylate binding ( △ (chelating) < △ (bridging) < △ (ionic) < △ (monodentate)).15


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Figure 8. Infrared spectras of compounds 1-9 and the H2bcpb ligand: displaying the positions of the peaks which allow one to characterize the coordination modes in the frameworks. X-ray Power Diffraction Analyses and Thermal Analyses. Powder X-ray diffraction (XRD) has been used to check the phase purity of the bulky samples in the solid state. For complex 1–9, the measured XRD patterns closely match the simulated patterns generated from the results of single-crystal diffraction data, indicative of pure products (Figure S2, Supporting Information). The thermogravimetric (TG) analysis was performed in N2 atmosphere on polycrystalline samples of complex 1–9 and the TG curves are shown in Figure 9. For compounds 1 and 2, the whole structure began to collapse around 139 and 165 °C with the residual weight is ca. 10.9% (calc. for CuO 11.4%) for 1, 21.1% (calc. for Co2O3 21.9%) for 2, respectively. For 3, the loss of 1,4-bib (obsd: 22.79%; calcd: 23.26%) and bcpb2- (obsd: 68.7%; calcd: 70.22%) took place aroud 78 and 196 °C, respectively. For isomorphism of 4-6, an initial weight loss of 5.3% in 4, 2.7% in 5, and 5.1% in 6 corresponds to the loss of lattice water (calcd: 5.5% in 4, 2.6% in 5, and 5.6% in 6). The second weight loss corresponds to the loss of


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4,4′-bimb and bcpb2- with the residual weight is ca. 12.3% (calc. for Co2O3 12.7%) for 4, 11.9% (calc. for CuO 12.5%) for 5, and 11.9% (calc. for NiO 11.5%) for 6, respectively. For 7, two stages of weight occurred at 152 and 243°C, and corresponded to 4,4'-bibp and bcpb2-, respectively. For 8, the first weight loss at 57 °C is attributed to the release of lattice water molecules (obsd: 4.9%; calcd: 5.1%). The second weight loss of 36.1% (calcd: 36.6 %) from147 °C corresponds to the loss of the 4,4′-bimp. The third weight loss is related with bcpb2- with the residual weight is ca. 11.1% (calc. for Co2O3 11.8%). For 9, two weight loss steps observed at 310 and 370 °C are attributed to 4,4'-bimbp and bcpb2-, with the residual weight is ca. 10.2% (calc. for NiO 10.8%).

Figure 9. TG curves for complexes 1-9. Magnetic Properties. The variable-temperature magnetic susceptibility measurements of dinuclear complexes 2 and 8 were performed on the Quantum Design SQUID MPMS XL-7 instruments in the temperature range of 2-300 K under a field of 1000 Oe. Temperature dependence of χMT and 1/χM for complexes complexes 2 and 8 are displayed in Figure 10. The χMT values for 2 and 8 at room temperature are 5.25 and 5.31 cm3 K mol-1, respectively, larger than that for two isolated CoII ions (3.75 cm3 K mol-1), which can be attributed to the


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contribution to the susceptibility from orbital angular momentum at higher temperatures. The fitting result is comparable with those reported for other coupled Co(II) dimmers.16

Figure 10. Temperature dependence of 1/χM and χMT in dinuclear complex 2 (a) and 8 (b). Solid lines represent the best theoretical fits. Conclusion

In summary, we have successfully designed and synthesized one novel polycarboxylates ligand of H2bcpb, based on which nine novel coordination polymers were obtained under the hydrothermal conditions in the presence of five imidazole ligands. Compounds 1–9 displayed appealing structural features from 2D layers to 3D frameworks, such as rarely reported (3,5)connected (42·67·8)(42·6) 3,5-L2 of 7, (4,6)-connected (44·610·8)(44·62) fsc of 8, and(3,5)connected 3D 3,5-T1 framework of 9. Detailed comparison of these networks reveals that the ancillary N-donor ligands play important role on adjusting the coordination modes of polycarboxylate acid and and structural topology. With the length of the ancillary ligands increasing, the longer separation of neighboring central ions makes the host aromatic polycarboxylate ligand adopt more “open” coordination modes, and the overall structure a higher degree of interpenetration. The more flexibility of ancillary ligands could make the aromatic polycarboxylate more twisted and the final structure more complicated.


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ASSOCIATED CONTENT Supporting Information Crystallographic data in CIF format, powder X-ray diffraction (PXRD) patterns and IR spectras for 1 – 9. This information is available free of charge via the Internet at http://pubs.acs.org/. AUTHOR INFORMATION Corresponding Author *E-mails:

[email protected]

(X.Z.),

[email protected]

(X.

Zhao),

[email protected] (H.L.). ACKNOWLEDGMENT The work was supported by financial support from the Natural Science Foundation of China (Grant Nos. 21101097), Natural Science Foundation of Shandong Province (ZR2010BQ023), and Qilu Normal University is acknowledged. REFERENCES (1) (a) O’Keeffe, M.; Yaghi, O. M. Chem. Rev. 2012, 112, 675. (b) Chen, B. L.; Ockwig, N. W.; Millward, A. R.; Contreras, D. S.; Yaghi, O. M. Angew. Chem. Int. Ed. 2005, 44, 4745. (c) Cui, Y.; Yue, Y.; Qian, G.; Chen, B. L. Chem. Rev. 2012, 112, 1126. (d) Férey, G.; Serre, C. Chem. Soc. Rev. 2009, 38, 1380. (e) Li, L. N.; Zhang S. Q.; Han, L.; Sun, Z. H.; Luo, J. H.; Hong, M. C. Cryst. Growth Des. 2013, 13, 106. (f) Liao, P. Q.; Zhou, D. D.; Zhu, A. X.; Jiang, L.; Lin, R. B.; Zhang, J. P.; Chen, X. M. J. Am. Chem. Soc. 2012, 134, 17380. (2) (a) Zhao, X. L.; Sun, D.; Yuan, S.; Feng, S. Y.; Cao, R.; Yuan, D. Q.; Wang, S. N.; Dou, J. M.; Sun, D. F. Inorg. Chem. 2012, 51, 10350. (b) Zhang, X. T.; Sun, D.; Li, B.; Fan, L. M.; Li, B.; Wei, P. H. Cryst. Growth Des. 2012, 12, 3845. (c) Liu, Q. K.; Ma, J. P.; Dong, Y. B. Chem.


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Table 1. The crystal data for compound 1 - 9. Compound Empirical formula Formula weight Crystal system Space group a (Å) b (Å) c (Å) α (°) β (°) γ (°) V(Å3) Z Dcalcd (Mg/m3) µ(mm−1) T(K) Rint Final R indices[I > 2σ( I )] R indices (all data)

1 2 C38H24CuN2O8 C19H11CoNO4 700.16 376.22 Orthorhombic Monoclinic Pbca P2/c 15.433(1) 12.426(8) 12.904(8) 12.012(8) 15.776(2) 10.386(7) 90.00 90.00 90.00 107.14(1) 90.00 90.00 3142(1) 1481(4) 4 4 1.480 1.687 0.755 1.184 293(2) 296(2) 0.0600 0.0693 R1 = 0.0556, R1 = 0.0349, wR2 = 0.0693 wR2 = 0.1376 R1 = 0.0927, R1 = 0.0532, wR2 = 0.0751 wR2 = 0.1678 Gof 1.004 0.999 Compound 6 7 Empirical formula C33H29NiN5O6 C37H25CoN5O4 Formula weight 650.32 662.55 Crystal system Monoclinic Monoclinic Space group P2/c P2/c a (Å) 10.741(2) 9.530(5) b (Å) 15.253(3) 9.893(6) c (Å) 19.025(4) 16.379(2) α (°) 90.00 90.00 β (°) 98.161(4) 98.188(2) γ (°) 90.00 90.00 V(Å3) 3085(5) 1528(7) Z 4 2 Dcalcd (Mg/m3) 1.400 1.439 0.682 0.612 µ(mm−1) T(K) 296(2) 273(2) Rint 0.0695 0.0376 Final R indices[I > R1 = 0.0508, R1 = 0.0432, 2σ( I )] wR2 = 0.1271 wR2 = 0.1093 R indices (all data) R1 = 0.0816, R1 = 0.0581, wR2 = 0.1473 wR2 = 0.1208 Gof 0.997 1.003 R1 = Σ| |Fo|−|Fc| |/ Σ|Fo|, wR2 = [Σw(Fo2−Fc2)2]/ Σw(Fo2)2]1/2

3 C50H32CoN6O8 903.75 Monoclinic P2/c 12.510(9) 19.102(7) 8.649(5) 90.00 100.95(2) 90.00 2029(5) 2 1.479 0.491 296(2) 0.0191 R1 = 0.0287, wR2 = 0.0763 R1 = 0.0331, wR2 = 0.0797 1.040 8 C37H30CoN5O6 699.59 Triclinic Pī 9.370(4) 12.462(6) 16.242(7) 102.593(9) 95.875(8) 105.085(8) 1761(5) 2 1.319 0.539 293(2) 0.0489 R1 = 0.1052, wR2 = 0.2792 R1 = 0.1566, wR2 = 0.3269 1.071


4 C33H29CoN5O6 650.54 Monoclinic P2/n 13.437(5) 16.627(8) 13.664(6) 90.00 95.37(9) 90.00 3039(7) 4 1.422 0.619 296(2) 0.0361 R1 = 0.0392, wR2 = 0.1041 R1 = 0.0610, wR2 = 0.1175 1.001 9 C79H58Ni2N9O8 1378.76 Triclinic Pī 10.496(3) 16.263(4) 19.895(5) 70.954(4) 81.123(5) 87.101(4) 3171(7) 2 1.444 0.663 298(2) 0.0440 R1 = 0.0684, wR2 = 0.1743 R1 = 0.1149, wR2 = 0.2029 1.001

5 C33H27CuN5O5 637.14 Monoclinic P2/c 10.990(3) 16.233(4) 18.276(4) 90.00 96.61(7) 90.00 3238(7) 4 1.307 0.721 296(2) 0.0624 R1 = 0.0783, wR2 = 0.2563 R1 = 0.1124, wR2 = 0.3027 1.000

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Table 2. Selected bond lengths (Å) and angles (º) for 1 – 9. Complex 1 Cu(1)-O(1)#1 1.939(7) Cu(1)-O(1) 1.939(7) Cu(1)-N(1)#2 2.005(9) Cu(1)-N(1)#3 2.005(9) Cu(1)- O(3) 2.670(2) O(1)-Cu(1)-N(1)#3 88.8(3) O(1)-Cu(1)-N(1)#2 91.2(3) N(1)#2-Cu(1)-N(1)#3 180.00 Symmetry codes: #1 -x+1, -y+1, -z+1. #2 x+1/2, -y+1/2, -z+1. #3 -x+1/2, y+1/2, z. #4 x-1/2, -y+1/2, -z+1. Complex 2 Co(1)-O(3)#1 2.021(4) Co(1)-O(4)#2 2.043(4) Co(1)-O(2) 2.046(4) Co(1)-N(1)#3 2.082(4) Co(1)-O(1) 2.271(4) Co(1)-O(3) #2 2.690(9) O(2)-Co(1)-O(1) 60.28(15) O(4)#2-Co(1)-N(1)#3 97.07(15) #3 #1 #2 #1 #3 N(1) -Co(1)-O(1) 88.81(16) O(3) -Co(1)-O(2) 128.40(15) O(4) -Co(1)-O(2) 100.11(15) O(3) -Co(1)-N(1) 101.19(16) #2 #3 #1 #1 #2 159.38(2) O(2)-Co(1)-N(1) 120.44(16) O(3) -Co(1)-O(1) 94.41(16) O(3) -Co(1)-O(4) 103.73(16) O(4) -Co(1)-O(1) Symmetry codes: #1 –x+1, y+1/2, -z+3/2. #2 x+1, -y+3/2, z-1/2. #3 –x+1, -y+2, -z+1. #4 –x+1, y-1/2, -z+3/2. #5 x-1, -y+3/2, z+1/2. Complex 3 Co(1)-O(2)#2 2.059 (7) Co(1)-N(1) 2.146(5) Co(1)-N(3) 2.204(7) N(1)-Co(1)-N(3) 89.92(5) O(2)#2-Co(1)-N(3) 88.56(5) N(1)#4-Co(1)-N(3) 90.08(5) N(3)#4-Co(1)-N(3) 180.00 O(2)#2-Co(1)-N(1) 88.32(5) #3 #4 #4 #3 O(2) -Co(1)-N(1) 91.68(5) N(1) -Co(1)-N(1) 180.00 N(1)-Co(1)-N(3) 90.08(5) O(2) -Co(1)-N(3) 91.44(5) Symmetry codes: #1 –x+2, -y, -z+1. #2 x, -y+1/2, z+1/2. #3 –x+1, y-1/2, -z-1/2. #4 –x+1, -y, -z. #5 –x+1, y+1/2, -z-1/2. Complex 4 2.032(7) Co(1)-N(2) 2.118(2) Co(1)-N(5)#3 2.131(2) Co(1)-O(1)#4 2.171(5) Co(1)-O(4)#2 Co(1)-N(1) 2.179(2) Co(1)-O(2)#4 2.194(8) O(4)#2-Co(1)-N(2) 87.98(9) N(2)-Co(1)-N(5)#3 178.82(8) N(2)-Co(1)-O(1)#4 88.81(8) O(4)#2-Co(1)-N(1) 100.90(8) N(2)-Co(1)-N(1) 92.69(8) N(5)#3-Co(1)-N(1) 86.14(8) O(1)#4-Co(1)-N(1) 97.96(7) N(2)-Co(1)-O(2)#4 89.34(8) N(1)-Co(1)-O(2)#4 157.95(7) Symmetry code: #1 –x+3/2, y-1/2, -z+3/2. #2 x+1/2, -y+3/2, z-1/2. #3 x, y, z+1. #4 –x+3/2, y+1/2, -z+3/2. #5 x, y, z-1. #6 x-1/2, -y+3/2, z+1/2. Complex 5 Cu(1)-N(5)#1 1.975(5) Cu(1)-N(2) 1.983(5) Cu(1)-O(4)#2 2.060(4) Cu(1)-N(1) 2.156(4) Cu(1)-O(2)#3 2.312(7) Cu(1)-O(1)#3 2.413(6) N(5)#1-Cu(1)-N(2) 176.4(2) N(2)-Cu(1)-O(4)#2 89.1(2) N(5)#1-Cu(1)-N(1) 91.3(2) N(2)-Cu(1)-N(1) 91.72(19) O(4)#2-Cu(1)-N(1) 130.65(18) N(2)-Cu(1)-O(2)#3 89.3(2) N(1)-Cu(1)-O(2)#3 141.8(2) N(2)-Cu(1)-O(1)#3 90.4(2) N(1)-Cu(1)-O(1)#3 88.6(2) Symmetry code: #1 x+1,–y+3/2, z+1/2. #2 -x+1, y-1/2, -z+1/2. #3 –x+2, -y+2, -z. #4 x-1, -y+3/2, z-1/2. #5 –x+1, y+1/2, -z+1/2. Complex 6 N(1)-Ni(1) 2.099(3) N(2)-Ni(1) 2.066(3) Ni(1)-O(4)#3 2.014(3) Ni(1)-N(5)#4 2.069(3) Ni(1)-O(2)#1 2.108(2) Ni(1)-O(1)#1 2.235(3) O(4)#3-Ni(1)-N(2) 87.90(12) N(2)-Ni(1)-N(5)#4 174.63(12) O(4)#3-Ni(1)-N(1) 110.31(1) N(2)-Ni(1)-N(1) 93.53(11) N(5)#4-Ni(1)-N(1) 91.81(12) O(4)#3-Ni(1)-O(2)#1 155.39(11) N(2)-Ni(1)-O(2)#1 89.25(11) N(1)-Ni(1)-O(2)#1 94.26(10) N(2)-Ni(1)-O(1)#1 87.85(11) N(1)-Ni(1)-O(1)#1 154.73(11) Symmetry code: #1 -x+2,–y+1, -z. #2 x-1, -y+1/2, z-1/2. #3 –x+1, y-1/2, -z+1/2. #4 x+1, -y+1/2, z+1/2. #5 –x+1, y+1/2, -z+1/2. Complex 7 Co(1)-N(3) 2.177(2) Co(1)-O(1)#3 2.194(2) Co(1)-N(1) 2.211(3) Co(1)-O(2)#3 2.344(3) N(3)-Co(1)-N(3)#1 180.00 N(3)-Co(1)-O(1)#3 83.69(8) N(3)-Co(1)-O(1)#4 96.34(8) N(3)-Co(1)-N(1) 90.22(6) N(3)#1-Co(1)-N(1) 90.22(6) O(1)#3-Co(1)-N(1) 86.35(7) O(1)#4-Co(1)-N(1) 86.35(7) N(3)-Co(1)-O(2)#4 81.84(9) N(1)-Co(1)-O(2)#4 140.93(6) N(3)-Co(1)-O(2)#3 97.82(9) N(1)-Co(1)-O(2)#3 140.93(6) Symmetry code: #1 -x+1, y, -z+3/2.#2 -x, y, -z+1/2.#3 -x+1, -y+1, -z+1. #4 x, -y+1, z+1/2. Complex 8 Co(1)-O(3)#1 2.138(5) Co(1)-O(1)#2 2.186(5) Co(1)-O(2)#3 2.196(5) Co(1)-N(1) 2.227(5) Co(1)-N(4)#4 2.244(5) Co(1)-N(5) 2.381(5) O(3)#1-Co(1)-N(1) 88.0(2) O(1)#2-Co(1)-N(1) 91.2(2) #3 #4 #1 #2 O(2) -Co(1)-N(1) 90.92(19) N(1)-Co(1)-N(4) 177.1(2) O(3) -Co(1)-N(5) 82.6(2) O(1) -Co(1)-N(5) 82.81(19) O(2)#3-Co(1)-N(5) 178.73(2) N(1)-Co(1)-N(5) 89.4(2) N(4)#4-Co(1)-N(5) 88.5(2) Symmetry code: #1 -x+1, -y+1, -z+1. #2 -x, -y+1, -z+1. #3 x, y-1, z. #4 x-1, y, z-1. #5 x+1, y, z+1. #6 x, y+1, z. Complex 9 N(4)-Ni(2) 2.098(4) N(8)-Ni(1) 2.090(4) N(10)-Ni(1) 2.090(4) Ni(2)-O(4)#3 2.039(3) Ni(2)-N(6)#2 2.108(5) Ni(2)-N(9)#3 2.118(4) Ni(2)-O(8) 2.123(3) Ni(2)-O(7) 2.297(4) #4 #1 Ni(1)-O(1) 2.050(3) Ni(1)-N(1) 2.101(4) Ni(1)-O(5) 2.176(4) Ni(1)-O(6) 2.198(4) O(4)#3-Ni(2)-N(4) 83.54(16) N(4)-Ni(2)-N(6)#2 172.03(17) N(4)-Ni(2)-N(9)#3 90.79(17) O(4)#3-Ni(2)-O(8) 158.83(15) N(4)-Ni(2)-O(8) 90.01(15) N(6)#2-Ni(2)-O(8) 91.93(16) N(9)#3-Ni(2)-O(8) 91.91(14) O(4)#3-Ni(2)-O(7) 100.16(14) N(4)-Ni(2)-O(7) 88.73(15) N(6)#2-Ni(2)-O(7) 85.62(15) N(9)#3-Ni(2)-O(7) 151.32(14) O(8)-Ni(2)-O(7) 59.42(13) #4 #4 #1 O(1) -Ni(1)-N(10) 94.21(15) O(1) -Ni(1)-N(8) 92.48(15) N(10)-Ni(1)-N(8) 94.76(17) N(10)-Ni(1)-N(1) 91.96(17) N(8)-Ni(1)-N(1)#1 172.96(2) O(1)#4-Ni(1)-O(5) 115.02(14) N(10)-Ni(1)-O(5) 149.98(15) N(8)-Ni(1)-O(5) 90.85(16) #1 #4 N(1) -Ni(1)-O(5) 82.27(15) O(1) -Ni(1)-O(6) 175.39(14) N(10)-Ni(1)-O(6) 90.40(15) N(8)-Ni(1)-O(6) 87.25(15) N(1)#1-Ni(1)-O(6) 90.63(15) O(5)-Ni(1)-O(6) 60.39(14) Symmetry codes: #1 -x+1, -y, -z. #2 -x+2, -y+1, -z. #3 -x+1, -y, -z+1. #4 -x, -y+2, -z.


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Talbe 3. The coordination types of H2bcpb ligand and the roles of ancillary ligands in complexes 1-9. Compound H4bpt Coordination Mode Ancillary Ligands/Role Dimension/Topology Dihedral angles in H2pbpc N/A 2D/(43)2(46·66·83) 28.16(1), 52.27(1),32.37(1)° µ3/Mode I 1 µ4/Mode II N/A 3D/(42·84) 28.24(1), 29.78(1), 20.84(1)° 2 1,4-bib/µ2-bridging 3D/(412·63) 19.74(1), 36.01(1), 28.84(1)° µ2/Mode III 3 2 6 3 µ3/Mode IV 1,4'-bimb/µ2-bridging 3D/(4·6 )(4·6 ·8 ) 19.98(1), 25.46(1), 26.43(1)° 4 µ3/Mode IV 1,4'-bimb/µ2-bridging 3D/(4·62)(4·66·83) 43.10(1), 28.80(1), 61.16(1)° 5 µ3/Mode IV 1,4'-bimb/µ2-bridging 3D/(4·62)(4·66·83) 27.17(1), 44.13(1), 61.28(1)° 6 µ3/Mode V 4,4'-bibp/µ2-bridging 2D/(42·67·8)(42·6) 33.23(1), 33.23(1),63.70(1) ° 7 4 10 4 2 µ4/Mode VI 4,4'-bibp/µ2-bridging 3D/(4 ·6 ·8)(4 ·6 ) 34.88(1), 33.35(1), 57.58(1)° 8 µ3/Mode V 4,4'-bimbp/µ2-bridging 3D/(42·65·83)(42·6) 29.38(1), 32.22(1), 52.52(1) ° 9 Note: 1,4-bib = 1,4-bis(1H-imidazol-4-yl)benzene, 1,4'-bimb = 1,4-bis(imidazol-1-ylmethyl)benzene, 4,4'-bibp = 4,4'-bis(imidazol-1-yl)biphenyl, 4,4'-bimbp = 4,4'-bis(imidazol-1-ylmethyl)biphenyl.


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For Table of Contents Use Only Table of Contents Graphic and Synopsis Ancillary Ligands Dependent Structural Diversity of A Series of Metal-Organic Frameworks Based on 3,5-Bis(3-carboxyphenyl)pyridine Liming Fan, Xiutang Zhang, Zhong Sun, Wei Zhang, Yuanshuai Ding, Weiliu Fan, Liming Sun, Xian Zhao, Lei Han Hydrothermal reactions of designed aromatic 3,5-bis(3-carboxyphenyl)pyridine (H2bcpb) and transitional metal cations in the presence of rigid or flexible N-donor ancillary ligands afford nine novel coordination polymers. Compounds 1-9 displayed appealing structural features from 2D layers to 3D frameworks, such as rarely reported (3,5)-connected (42·67·8)(42·6) 3,5-L2 of 7, (4,6)-connected (44·610·8)(44·62) fsc of 8, and(3,5)-connected 3D 3,5-T1 framework of 9.


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Ancillary Ligands Dependent Structural Diversity of A Series of Metal

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