Five Mn(II) Coordination Polymers Based on 2,3 ... - ACS Publications

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Five Mn(II) Coordination Polymers Based on 2,3′,5,5′-Biphenyl Tetracarboxylic Acid: Syntheses, Structures, and Magnetic Properties Ying Zhao,†,‡ Xin-Hong Chang,† Guang-Zhen Liu,† Lu-Fang Ma,*,† and Li-Ya Wang*,†,§ †

College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, P. R. China College of Chemistry and Molecular Engineering, Zhengzhou University, Henan 450052, P. R. China § College of Chemistry and Pharmaceutical Engineering, Nanyang Normal University, Nanyang 473061, P. R. China ‡

S Supporting Information *

ABSTRACT: Five manganese(II) coordination polymers with 2,3′,5,5′-biphenyl tetracarboxylic acid (H4bptc) and five N-donor ancillary ligands, {[Mn2(bptc)(2,2′bipy)2]·2H2O}n (1), {[Mn2(H2bptc)2(phen)4]·6H2O} (2), {[Mn3(Hbptc)2(4,4′bipy) 4 ( H 2 O) 4 ]·4H 2 O } n (3) , { [ Mn 2 ( bptc)(1,4-biyb) 2 ]} n (4), and {[Mn3(Hbptc)2(biip)2(H2O)2]}n (5) [2,2′-bipy = 2,2′-bipyridine, phen = 1,10phenanthroline, 4,4′-bipy = 4,4′-bipyridine, 1,4-biyb = 1,4-bis(imidazol-1ylmethyl)benzene, biip = 3,5-bis(1-imidazol)pyridine], have been synthesized under hydrothermal conditions. Complexes 1−5 were structurally characterized by elemental analysis, infrared (IR) spectra, X-ray single-crystal diffraction, and powder X-ray diffraction (PXRD). Complex 1 exhibits a 2D layered structure with a (3,6)-connected (43)2(46.66.83) topology. Complex 2 shows a 0D structure and further stacks via hydrogen-bonding interactions to give a 3D supramolecular architecture. Complex 3 possesses a 3D structure with a 4-connected (4.63.82)(44.62)(43.63) topology. Complex 4 displays a 3D structure with a (4,5)-connected (4.52.6.7.8)(5.64.74.8)(4.52.62.74.8) topology. Complex 5 features a 3D structure with a (4,5,6)-connected (42.64)(43.67)(42.68.73.82) topology. Magnetic susceptibility measurements indicate weak antiferromagnetic interactions between the Mn(II) ions in 1, 2, and 4.

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INTRODUCTION

because their two phenyl rings can be rotated around the C−C single bond. Mixed multicarboxylate and nitrogen donor linkers have been widely utilized to construct CPs. The mixed-ligands strategy incorporating N-donor colinkers with different lengths and rigidness/flexibility has proved successful to create various CPs.63−70 2,3′,5,5′-Biphenyl tetracarboxylic acid (H4bptc) with flexible backbones and rigid multicoordination sites has been studied by only our group,71,72 which shows excellent coordination abilities the same as the above biphenyl tetracarboxylate ligands. In order to further the study coordination chemistry of H4bptc and the effect of mixed ligands in the selfassembly process of CPs, we have herein taken H4bptc and five different N-donor ligands (Scheme 1) and yielded five new CPs under hydrothermal conditions, {[Mn2(bptc)(2,2′-bipy)2]· 2H2O}n (1), {[Mn2(H2bptc)2(phen)4]·6H2O} (2), {[Mn3(Hbptc)2(4,4′-bipy)4(H2O)4]·4H2O}n (3), {[Mn2(bptc)(1,4-biyb)2]}n (4), {[Mn3(Hbptc)2(biip)2(H2O)2] }n (5) [2,2′-bipy = 2,2′-dipyridyl, phen = 1,10-phenanthroline, 4,4′-bipy = 4,4′- dipyridyl, 1,4-biyb = 1,4bis(imidazol-1-ylmethyl)benzene, biip = 3,5-bis(1-imidazol)pyridine]. The structures and magnetic properties of these complexes have been studied in detail.

Metal−organic coordination polymers (CPs) have currently attracted considerable attention for their intriguing structural topologies1−10 and potential applications as functional materials in magnetism,11−16 catalysis,17−22 optics,23−26 sorption,27−30 separation,31−35 chemical sensors,36 and many more.37−45 CPs possess extended structures constructed with metal ions and organic linkers. However, it is difficult to predict the construction of CPs, because the process of aggregation is influenced by several key factors, such as temperature, solvent, reactant concentration, pH value, the selection of organic ligands, and coordination geometries of the central metals, etc. Of all these, the organic ligand plays an important role in extending and reconstructing the structure. As is well known, CPs on the basis of multicarboxylate linkers have been extensively focused. Among them, flexible biphenyl tetracarboxylate ligands, such as 2,2′,3,3′-biphenyl tetracarboxylate, 2,2′,4,4′-biphenyl tetracarboxylate, 2,2′,6,6′-biphenyl tetracarboxylate, 2,3′,3,4′biphenyl tetracarboxylate, 2,2′,5,5′- biphenyl tetracarboxylate, 3,3′,4,4′-biphenyl tetracarboxylate, 3,3′,5,5′-biphenyl tetracarboxylate,46−62 etc., have attracted much recent interest because these ligands may be completely or partially deprotonated, inducing versatile coordination modes and allowing interesting structures with higher dimensionalities. Meanwhile, it can act as hydrogen-bond acceptor as well as donor, depending upon the degree of deprotonation. More importantly, the flexible ligands can conform to the coordination geometries of the metal ions © XXXX American Chemical Society

Received: December 5, 2014 Revised: December 22, 2014

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DOI: 10.1021/cg501768f Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Crystal Growth & Design Scheme 1. Synthesis of Complexes 1−5

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RESULTS AND DISCUSSION Descriptions of Crystal Structures. {[Mn2(bptc)(2,2′-bipy)2]· 2H2O}n (1). Single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the orthorhombic space group Pbca, and its structure shows a 2D layer. The asymmetric unit of 1 consists of two crystallographically independent Mn(II) ions, one bptc4− anion and two 2,2′-bipy ligands (as shown in Figure 1a). Each

molecule (Mn2−N1 = 2.256(5) Å, Mn2−N2 = 2.243(5) Å) to furnish a distorted octahedral geometry. The dihedral angle between the two phenyl rings of the bptc4− ligand is 35.3°. Four carboxylate groups (2-, 3′-, 5-, and 5′-COO−) have a dihedral angle of 63.2°, 7.75°, 16.6°, and 11.17° toward the plane of the corresponding linking phenyl rings, respectively. The fully deprotonated bptc4− ligand connects six Mn(II) atoms in monodentate, bidentate bridging, and chelating modes (Scheme 2a) to yield a 2D layer with a 2,2′-bipy ligand dangling on two sides of it (Figure 1b). From the topological view, both the Mn1 and the Mn2 can be considered as 3-connected nodes, and the bptc4− ligand can be a considered as a 6-connected node. Then the framework of 1 features a (3,6)-connected 2D net (Figure 1c) with a Schläfli symbol of (43)2(46.66.83). {[Mn2(H2bptc)2(phen)4]·6H2O} (2). Single-crystal X-ray diffraction analysis reveals that complex 2 crystallizes in the monoclinic space group P2(1)/c. The asymmetric unit of 2 consists of one Mn(II) ion, two H2bptc2− ligands, and two phen ligands (as shown in Figure 2a). Each Mn(II) ion is six coordinated with four nitrogen atoms from two chelate phen molecules (Mn1−N1 = 2.269(4) Å, Mn1−N2 = 2.265(4) Å, Mn1−N3 = 2.262(4) Å, Mn1−N4 = 2.299(4) Å) and two oxygen atoms from two different H2bptc2− ligands (Mn1−O1A = 2.119(3) Å, Mn1−O2 = 2.110(3) Å). The dihedral angle between the two phenyl rings of the H2bptc2− ligand is 29.6°. In 2, the 3′- and 5-carboxylic group of H2bptc2− is protonated and free of coordination. The partly deprotonated H2bptc2− ligand with one bidentate carboxylate group is coordinated to two Mn(II) atoms to form a 0D structure. The adjacent 0D structures are connected together through hydrogen-bonding interactions among C29−H29···O7A (3.271 Å) to form a 2D layer parallel to the bc plane in the lattice (Figure 2b). Then the 2D layers are further connected together through hydrogen-bonding interactions among C33−H33···O4B (3.236 Å) to produce a 3D supramolecular network (Figure 2c). The free water molecules lie in the 3D supramolecular network. The typical hydrogen bonds are O(9)−H(1W)···O(3) 2.810 Å, O(9)−H(2W)···O(7) 2.967 Å, O(10)−H(3W)···O(3) 2.635 Å, O(10)−H(4W)···O(4) 2.619 Å, O(11)−H(5W)···O(6) 2.566 Å, O(11)−H(6W)···O(10) 2.971 Å, O(4)−H(4)···O(11) 2.691 Å, and O(8)−H(8)···O(10) 2.554 Å. The hydrogen bondings enhance the stability of the complex. {[Mn3(Hbptc)2(4,4′-bipy)4(H2O)4]·4H2O}n (3). Single-crystal X-ray diffraction analysis reveals that complex 3 crystallizes in the monoclinic space group P2(1)/n. As shown in Figure 3a, Mn1 ion is coordinated by two 4,4′-bipy nitrogen atoms (Mn1−N3 = Mn1−N4B = 2.263(3) Å), two Hbptc3− oxygen atoms (Mn1−O1 = 2.154(3) Å, Mn(1)−O(3)#1= 2.111(3) Å), and two coordinated

Figure 1. (a) Coordination environments of the Mn(II) ion in 1. Hydrogen atoms are omitted for clarity. Symmetry codes: A = x + 1/2, y, −z + 1/2, B = −x + 1, y + 1/2, −z + 1/2, C = −x + 1, y − 1/2, −z + 1/2. (b) Polyhedral view of the 2D layer of 1. (c) Schematic view of the 2D (3,6)-connected (43)2(46.66.83) network of 1. Yellow and blue balls represent bptc4− ligands and Mn(II) ions, respectively.

Mn1 ion is five coordinated with two nitrogen atoms from one chelate 2,2′-bipy molecule (Mn1−N3 = 2.252(5) Å, Mn1−N4 = 2.271(4) Å) and three oxygen atoms from three different bptc4− ligands (Mn1−O4A = 2.065(4) Å, Mn1−O6B = 2.091(4) Å, Mn1−O10 = 2.114(4) Å). Mn2 ion is coordinated by four oxygen atoms from three different bptc4− ligands (Mn2−O3A = 2.108(4) Å, Mn2−O7C = 2.342(4) Å, Mn2−O8C = 2.201(4) Å, Mn2−O9 = 2.109(4) Å) and two nitrogen atoms from one chelate 2,2′-bipy B


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Crystal Growth & Design Scheme 2. Coordination Modes of 2,3′,5,5′-Biphenyl Tetracarboxylate Ligand in 1−5

Figure 2. (a) Coordination environments of the Mn(II) ion in 2. Hydrogen atoms are omitted for clarity. Symmetry codes: A = −x + 1, −y + 1, −z + 2. (b) View of the 2D supramolecular layer of 2. (c) View of the 3D supramolecular network of 2. C


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Crystal Growth & Design

Figure 3. (a) Coordination environments of the Mn(II) ion in 3. Hydrogen atoms are omitted for clarity. Symmetry codes: A = x + 1, y, z; B = x + 1, −y + 3/2, z + 1/2; C = −x, −y + 2, −z + 2; D = −x + 1, −y + 2, −z + 2. (b) View of the 1D chain of 3. (c) Polyhedral view of the 3D framework of 3. (d) Schematic view of the 3D 4-connected (4.63.82)(44.62)(43.63) network of 3.

(Mn2−O3D = 2.1064(15) Å, Mn2−O2 = 2.1368(13) Å) and three N atoms from three 1,4-biyb ligands (Mn2−N7 = 2.1556(19) Å, Mn2−N1E = 2.2345(19) Å, Mn2−N3 = 2.2455(19) Å). The dihedral angle between the two phenyl rings of the bptc4− ligand is 26.0°. Four carboxylate groups (2-, 3′-, 5-, and 5′-COO−) have a dihedral angle of 65.5°, 9.4°, 4.7°, and 18.8° toward the plane of the corresponding linking phenyl rings, respectively. Four deprotonated carboxylates of bptc4− ligand adopt the monodentate, chelating, and bimonodentate fashion (Scheme 2d), linking the Mn(II) centers together to form a 3D polymeric framework (Figure 4b). In addition, 1,4-biyb ligands link the adjacent Mn1···Mn2, Mn2 ···Mn2 within the above 3D network to build a complicated 3D framework (Figure 4c). From the topological view, Mn1 can be considered as a 4-connected node, the Mn2 and the ligand bptc4− can be seen as 5-connected node, and the 3D framework of 4 can be considered as a (4,5)-connected (4.52.6.7.8)(5.64.74.8)(4.52.62.74.8) topology (Figure 4d). {[Mn3(Hbptc)2(biip)2(H2O)2] }n (5). Complex 5 crystallizes in a triclinic system with space group P1̅ and displays a (4,5,6)connected 3D framework. As depicted in Figure 5a, Mn1 center adopts a distorted trigonal biyramid geometry and is coordinated with three carboxylate oxygen atoms from three Hbptc3− ligands (Mn1−O6A = 2.112(4) Å, Mn1−O8 = 2.237(4) Å, Mn1−O9B = 2.120(4) Å), one nitrogen atom from one biip (Mn1−N5C = 2.231(5) Å), and one water molecule (Mn1−O1 = 2.192(5) Å), while the Mn2 center is coordinated by two nitrogen atoms from two biip (Mn2−N1 = 2.175(4) Å, Mn2−N1D = 2.175(4) Å) and four carboxylic oxygen atoms from four different Hbptc3− ligands (Mn2−O3E = 2.288(4) Å, Mn2−O3F = 2.288(4) Å, Mn2−O4 = 2.221(4) Å, Mn2−O4D = 2.221(4) Å), showing a slightly distorted octahedral geometry. The dihedral angle between the two

water oxygen atoms (Mn1−O9 = 2.216(3) Å, Mn1−O10 = 2.248(3) Å) in a distorted octahedral geometry {MnN2O4}. The Mn2 ion also locates in a distorted octahedral geometry, with two nitrogen atoms from two 4,4′-bipy ligands (Mn2−N1 = Mn2−N1D = 2.306(3) Å) and four oxygen atoms from four different Hbptc3− ligands (Mn2−O2 = Mn2−O2D = 2.183(3) Å, Mn2−O4A= Mn2−O4C = 2.136(3) Å). The dihedral angle between the two phenyl rings of the Hbptc3− ligand is 45.1°. Four carboxylate groups (2-, 3′-, 5-, and 5′-COO−) have a dihedral angle of 50.6°, 10.5°, 20.8°, and 6.68° toward the plane of the corresponding linking phenyl rings, respectively. 2- and 5-COO− adopt bimonodentate-bridging modes to link four Mn(II) ions to form a 1D chain (Figure 3b). Furthermore, these 1D chains are combined together through additional Mn−N bonds by 4,4′-bipy to construct a 3D framework (Figure 3c). From the topological view, the Mn1, Mn2, and ligand Hbptc3− can all be considered as 4-connected nodes; the framework of 3 features a 4-connected 3D framework with a Schläfli symbol of (4.63.82)(44.62)(43.63) (Figure 3d). {[Mn2(bptc)(1,4-biyb)2]}n (4). Single-crystal X-ray diffraction measurement reveals that complex 4 crystallizes in the monoclinic system with P2(1)/n space group. The asymmetric unit possesses two crystallographically unique Mn(II) ions, two biyb ligands, and one bptc4− ligand. As shown in Figure 4a, Mn1 is six coordinated with a distorted octahedral environment by five carboxylic O atoms from three different bptc4− ligands (Mn1− O1 = 2.1404(14) Å, Mn1−O7B = 2.2022(14) Å, Mn1−O5C = 2.2419(15) Å, Mn1−O6C = 2.2518(14) Å, Mn1−O8B = 2.3541(14) Å) and one N atom from one 1,4-biyb ligand (Mn1− N5A = 2.1717(17) Å). Each Mn2 center is surrounded by two carboxylic oxygen atoms from two different bptc4− ligands D


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Figure 4. (a) Coordination environments of the Mn(II) ion in 4. Hydrogen atoms are omitted for clarity. Symmetry codes: A = −x + 2, −y + 1, −z + 2; B = −x + 3/2, y + 1/2, −z + 3/2; C = −x + 1, −y + 1, −z + 1; D = x−1/2, −y + 1/2, z + 1/2. (b) View of the 3D framework of 4. The 1,4-biyb ligands are omitted for clarity. (c) View of the 3D framework of 4 (blue bonds represent 1,4-biyb ligands). (d) Schematic view of the 3D (4,5)-connected (4.52.6.7.8)(5.64.74.8)(4.52.62.74.8) network of 4. Yellow and blue balls represent bptc4− ligands and Mn(II) ions, respectively.

phenyl rings of the Hbptc4− ligand is 47.5°. Four carboxylate groups (2-, 3′-, 5-, and 5′-COO−) have a dihedral angle of 36.6°, 26.4°, 17.8°, and 12.3° toward the plane of the corresponding linking phenyl rings, respectively. Four carboxylates of Hbptc3− ligand adopt the monodentate and bimonodentate fashions (Scheme 2e), linking the Mn(II) ions together to form a 3D polymeric framework including 1D channels (Figure 5b). Furthermore, biip are fixed in the channels through additional Mn−N bonds (Figure 5c). From the topological point of view, each Mn1 ion can be considered as a four-connected node, each Mn2 ion can be considered as a sixconnected node, each Hbptc3− can be considered as a fiveconnected node, and biip ligands serve as linkers. The 3D framework of 5 can be abstracted into a (4,5,6)-connected (5.6.7)(4.52.6.7.8)(4.52.62.73.82) network topology (Figure 5d). Influence of N-Donor Ancillary Ligands on the Structures of the Complexes. Complexes 1−5 are prepared as single crystals by the hydrothermal reaction of manganese acetate, H4bptc, and five N-containing ligands (Scheme 1). In 1 and 2, two chelate N-donor ancillary ligands, 2,2′-bipy and phen, are used to give two low-dimensional structures, a 2D layered structure for 1 and a 0D structure for 2. While in 3, 4, and 5, three bridging N-donor ligands replace auxiliary chelating ligands, three different 3D frameworks are formed, a 3D structure with a 4-connected (4.63.82)(44.62)(43.63) topology for 3, a 3D structure with a (4,5)-connected (4.52.6.7.8)(5.64.74.8)(4.52.62.74.8) topology for 4, and a 3D structure with a (4,5,6)-connected

(42.64)(43.67)(42.68.73.82) topology for 5. From the structural descriptions above it can be seen that the neutral N-containing ligands have an important influence on the frameworks of these complexes. PXRD. In order to check the phase purity of 1, 2, and 4, the X-ray powder diffraction (XRPD) pattern was checked at room temperature. The simulated and experimental PXRD patterns of 1, 2, and 4 are in good agreement with each other (Figure S1, Supporting Information), indicating the phase purity of the products. The differences in intensity may be due to the preferred orientation of the powder samples. Magnetic Properties. The magnetic susceptibilities, χM, of 1, 2, and 4 were measured in the 2−300 K range at 2000 Oe and shown as χMT and χM versus T plots in Figure 6. As the temperature lowers to 2 K, the χMT values of 1, 2, and 4 continuously decrease, which suggests that the effect of spin− orbit coupling known for MnII ions and antiferromagnetic interactions are operative in 1, 2, and 4. The experimental χMT values of 1, 2, and 4 at room temperature are 8.48, 9.16, and 8.54 cm3·K·mol−1, which are close to that of two isolated spinonly Mn2+ ions (8.75 cm3·K·mol−1). According to the crystal structures, complexes 1, 2, and 4 can be considered as dinuclear units from the viewpoint of magnetism. In 1 two MnII centers are linked by two carboxylate bridges since the coupling through bptc4− ligands can almost be negligible, and in 2 two MnII centers are also connected by two carboxylate bridges. In 4, two MnII centers E


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Figure 5. (a) Coordination environments of the Mn(II) ion in 5. Hydrogen atoms are omitted for clarity. Symmetry codes: A = x, y + 1, z; B = −x + 2, −y + 2, −z + 1; C = x + 1, y + 1, z − 1; D = −x + 2, −y + 2, −z + 2; E = x − 1, y, z; F = −x + 3, −y + 2, −z + 2. (b) View of the 3D framework of 5. The biip ligands are omitted for clarity. (c) View of the 3D framework of 5. (d) Schematic view of the 3D (4,5,6)-connected (5.6.7)(4.52.6.7.8)(4.52.62.73.82) network of 5.

are linked by one carboxylate bridge since the coupling through bptc4− ligands and 1,4-biyb can almost be negligible. Two coupling parameters J and zJ′ must be considered to interpret the two possible magnetic interactions. Here, J is the exchange coupling parameter between Mn1−Mn3, Mn1− Mn1A, and Mn1−Mn2, zJ′ accounts for the rest of interactions for 1, 2, and 4. Taking into account the dinuclear MnII model, the magnetic susceptibility data are analyzed using the familiar Bleaney−Bowers expression based on a Heisenberg Hamiltonian Ĥ = −J S1̂ S2̂ ,73,74 where N, g, β, and k have their usual meanings. χM = 2

Ng 2β 2 A KT B

B = 1 + 3 exp[2J /KT ] + 5 exp[6J /KT ] + 7 exp[12J /KT ] + 9 exp[20J /KT ] + 11 exp[30J /KT ]

Least-squares analysis of magnetic susceptibility data led to J = −0.15 cm−1, g = 2.00, and R = 1.41 × 10−5 for 1, J = −1.55 cm−1, g = 2.09, and R = 8.79 × 10−5 for 2, and J = −0.21 cm−1, g = 1.98, and R = 8.65 × 10−5 for 4.

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CONCLUSIONS

In summary, five new CPs based on 2,3′,5,5′-biphenyl tetracarboxylate ligand have been prepared and characterized, which show diverse architectures such as a 2D layered structure (1), a 0D structure and further stacks via hydrogen-bonding interactions to give a 3D supramolecular architecture (2), a 3D structure with a 4-connected (4.63.82)(44.62)(43.63) topology (3), a 3D structure with a (4,5)-connected (4.52.6.7.8)(5.64.74.8)(4.52.62.74.8) topology (4), and a 3D structure with a (4,5,6)-connected

(1)

A = exp[2J /KT ] + 5 exp[6J /KT ] + 14 exp[12J /KT ] + 30 exp[20J /KT ] + 55 exp[30J /KT ] F


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Figure 6. Temperature dependence of χMT and χM for 1 (a), 2 (b), and 4 (c). Open points are the experimental data, and solid line represents the best fit obtained from the Hamiltonian given in the text. Synthesis of {[Mn2(H2bptc)2(phen)4]·6H2O} (2). Synthesis of 2 was similar to that of 1 except that 2,2′-bipy was replaced by phen (18.0 mg, 0.1 mmol). Colorless block crystals of 2 were obtained (yield 47% based on manganese). Anal. Calcd for C80H60Mn2N8O22: C, 60.23; H, 3.79; N, 7.02. Found: C, 60.29; H, 3.11; N, 6.92. IR (cm−1): 3094 m, 1723 w, 1639 s, 1604 m, 1499 s, 1450 w, 1314 w, 1294 m, 1259 m, 1239 m 1194 m, 1116 m, 1065 s, 1009 m, 955 m, 929 m, 871 s, 825 m, 772 m. Synthesis of {[Mn3(Hbptc)2(4,4′-bipy)4(H2O)4]·4H2O}n (3). Synthesis of 3 was similar to that of 1 except that 2,2′-bipy was replaced by 4,4′-bipy (18.0 mg, 0.1 mmol). Traces of colorless crystals of 3 were obtained. Anal. Calcd for C72H60Mn3N8O24: C, 54.52; H, 3.81; N, 7.06. Found: C, 54.59; H, 3.76; N, 7.16. Synthesis of {[Mn2(bptc)(1,4-biyb)2]}n (4). Synthesis of 4 was similar to that of 1 except that 2,2′-bipy was replaced by 1,4-biyb (23.8 mg, 0.1 mmol). Colorless block crystals of 4 were obtained (yield 53% based on manganese). Anal. Calcd for C44H34Mn2N8O8: C, 57.90; H, 3.75; N, 12.28. Found: C, 57.81; H, 3.77; N, 12.19. IR (cm−1): 3120 m, 1599 w, 1567 s, 1520 m, 1397 s, 1356 s, 1310 m, 1232 s, 1107 s, 1079 s, 1022 m, 933 s, 910 m, 850 m, 832 m, 771 s, 716 s. Synthesis of {[Mn3(Hbptc)2(biip)2(H2O)2] }n (5). Synthesis of 5 was similar to that of 1 except that 2,2′-bipy was replaced by biip (21.1 mg, 0.1 mmol). Traces of colorless crystals of 5 were obtained. Anal. Calcd for C18H12MnN3.33O6: C, 50.76; H, 2.84 N, 3.29. Found: C, 50.67; H, 2.79; N, 3.23. X-ray Crystallographic Data Collection and Structural Determination. Crystallographic diffraction data for complexes 1−5 were collected on a Bruker SMART APEX II CCD diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at 296(2) K using the φ/ω scanning technique. All structures were solved using direct methods and successive Fourier difference synthesis and refined using the full-matrix least-squares method on F2 with anisotropic thermal parameters for all non-hydrogen atoms by SHELXS-97. An empirical absorption correction was applied using the SADABS program. Basic information pertaining to crystal parameters and structure

(42.64)(43.67)(42.68.73.82) topology (5). According to the above structural description, the 2,3′,5,5′-biphenyl tetracarboxylate ligand exhibits five distinct kinds of bridging modes as shown in Scheme 2. The structural differences of these compounds may be attributed to the different bridging fashions of 2,3′,5,5′biphenyl tetracarboxylate ligand and various N-donor ligands. Further investigations on this domain are underway in our laboratory.

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EXPERIMENTAL SECTION

Materials and General Methods. All chemicals purchased commercially were used as received without further purification. All products were highly stable in air at ambient conditions. The infrared spectra (4000−600 cm−1) were recorded on a NICOLET 6700 FT-IR spectrometer. Elemental analyses for carbon, hydrogen, and nitrogen atoms were performed on a Vario EL III elemental analyzer. Powder X-ray diffraction (PXRD) measurements were performed on a Bruker D8-ADVANCE X-ray diffractometer with Cu Kα radiation (λ = 1.5418 Å) and 2θ ranging from 5° to 50°. Variable-temperature magnetic susceptibilities for 1, 2, and 4 were measured using a MPMS-7 SQUID magnetometer. Synthesis of {[Mn2(bptc)(2,2′-bipy)2]·2H2O}n (1). A mixture of H4bptc (33.0 mg, 0.1 mmol), 2,2′-bipy (15.6 mg, 0.1 mmol), Mn(OAc)2 ·4H2O (24.2 mg, 0.1 mmol), and KOH (5.6 mg, 0.1 mmol) was added to water (12 mL) in a 25 mL Teflon-lined stainless steel vessel. The mixture was heated at 413 K for 3 days and then slowly cooled down to room temperature. Yellow block crystals of 1 were obtained (yield 44% based on manganese). Anal. Calcd for C36H26Mn2N4O10: C, 55.11; H, 3.34; N, 7.14. Found: C, 54.92; H, 3.23; N, 7.26. IR (cm−1): 3056 m, 1617 m, 1596 s, 1563 m, 1500 m, 1472 m, 1427 s, 1398 m, 1359 m, 1314 m, 1272 w, 1247 m, 1175 w, 1156 s, 1102 s, 1057 s, 1041 w, 1017 s, 917 m, 851 s, 832 s, 806 w, 755 s. G


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Crystal Growth & Design Table 1. Crystallographic Data and Structure Refinement Details for 1−5 formula fw temp. cryst syst space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z Dc(g cm−3) μ (mm−1) F (000) Rint GOOF R1,a wR2b [I > 2σ (I)] R1, wR2 (all data) Δρmax and Δρmin (e Å−3) a

1

2

3

4

5

C36H26Mn2N4O10 784.49 296(2) orthorhombic Pbca 16.038(4) 14.499(3) 29.508(7) 90 90 90 6862(3) 8 1.519 0.801 3200 0.1086 1.031 0.0696, 0.1196 0.1377, 0.1500 0.550, −0.638

C80H60Mn2N8O22 1595.24 296(2) monoclinic P2(1)/c 13.1418(5) 20.3611(7) 14.6089(7) 90 110.305(6) 90 3666.1(3) 2 1.445 0.429 1644 0.0690 1.007 0.0675, 0.1438 0.1409, 0.1844 0.991, − 0.350

C72H62Mn3N8O24 1588.12 296(2) monoclinic P2(1)/n 9.5561(9) 17.3966(14) 22.1223(16) 90 112.042(3) 90 3408.9(5) 2 1.547 0.637 1634 0.0927 1.000 0.0539, 0.0983 0.1291, 0.1261 0.370, −0.307

C44H34Mn2N8O8 912.67 296(2) monoclinic P2(1)/n 14.9620(12) 15.0110(12) 17.5963(15) 90 98.0920(10) 90 3912.7(6) 4 1.549 0.714 1872 0.0274 1.026 0.0314, 0.0780 0.0410, 0.0841 0.365, − 0.293

C18H12MnN3.33O6 425.92 296(2) triclinic Pi ̅ 7.570(7) 10.630(10) 16.062(15) 97.955(10) 94.363(11) 103.286(10) 1238(2) 3 1.714 0.847 649 0.0000 1.060 0.0615, 0.1627 0.0693, 0.1690 1.217, − 0.758

R1 = Σ(|Fo| − |Fc|)/Σ|Fo|. bwR2 = {Σ[w(|Fo|2 − |Fc|2)2]/ Σ[w(|Fo|2)2]}1/2.

refinements are summarized in Table 1. Selected bond lengths and angles for 1−5 are listed in Table S1, Supporting Information. Hydrogen-bonding distance and angle data are listed in Table S2, Supporting Information. Crystallographic data for structural analysis have been deposited with the Cambridge Crystallographic Data Center. CCDC reference numbers: 1037620 for 1, 1037621 for 2, 1037622 for 3, 1037623 for 4, and 1037624 for 5.

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ASSOCIATED CONTENT

S Supporting Information *

Additional tables and PXRD. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (21073082, 21071074), Program for New Century Excellent Talents in University (NCET-11-0947), Program for Science & Technology Innovation Talents in Universities of Henan Province (2011HASTIT027), and Program for Innovative Research Team (in Science and Technology) in University of Henan Province (14IRTSTHN008).

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