Four Three-Dimensional Coordination Polymers Constructed by 2

Article pubs.acs.org/crystal

Four Three-Dimensional Coordination Polymers Constructed by 2-((1H-1,2,4-Triazol-1-yl)methyl)-1H-Imidazole-4,5-Dicarboxylate: Syntheses, Topological Structures, and Magnetic Properties Li-Xia Xie,*,† Xiao-Wei Hou,‡ Yao-Ting Fan,*,‡ and Hong-Wei Hou‡ †

College of Sciences, Henan Agricultural University, Zhengzhou 450002, People’s Republic of China Department of Chemistry, Zhengzhou University, Zhengzhou 450052, People’s Republic of China

‡

S Supporting Information *

ABSTRACT: Hydrothermal reactions of Mn(II), Co(II), Cu(II), and Cd(II) salts with 2-((1H-1,2,4-triazol-1-yl)methyl)-1H-imidazole-4,5-dicarboxylic acid (H3tmidc) lead to four novel coordination polymers, namely, [Mn3(tmidc)2(H2O)4]·(H2O)6 (1), [Co3(tmidc)2(H2O)4]·(H2O)4 (2), [Cu3(tmidc)2(H2O)]·(H2O) (3), and [Cd(Htmidc)] (4). Compound 1 has a three-dimensional (3D) architecture, and the topological study shows that its framework features a 3D (3,4)-connected fsc-3,4-Pbca network with the Schläfli topological symbol of (63)(63.83). Compound 2 exhibits a 3D pillared framework constructed by 4-fold one-dimensional (1D) helical chains and possesses open helical channels in the framework. Topological analysis reveals that it is a unique (3,4)connected net with the Schläfli symbol of (4.52)(4.5.114) which is not enumerated in RCSR andTOPOS, and has not been reported in the literature. Compound 3 features a 3D intricate framework displaying a new (3,4)-connected 4-nodal net with the Schläfli symbol of (5.72)(4.5.7)(52.72.8.10)(4.5.73.8) which has not been observed in any other coordination polymers. Topological analysis of the 3D network found in compound 4 reveals that the whole structure can be rationalized as a (4.65)(4.65) crb topological net.

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groups.5−10 Recently, particular attention has been paid to the functionalized H3IDC ligands, at the 2-position of the imidazole ring, with diverse substituent groups such as methyl, ethyl, or pyridyl, for these analogues present distinct coordination fashions relative to the parent H3IDC ligand. Accordingly, many research groups have effectively employed H3IDC derivatives, such as 2-methyl-1H-imidazole-4,5-dicarboxylic acid, 2ethyl-1H-imidazole-4,5-dicarboxylic acid, 2-propyl-1H-imidazole-4,5-dicarboxylic acid, 2-phenyl-1H-imidazole-4,5-dicarboxylic acid, 2-hydroxymethyl-1H-imidazole-4,5-dicarboxylic acid, and 2-(pyridine-4-yl)-1H-imidazole-4,5-dicarboxylic acid to build up novel MOFs.11 Taking the factors mentioned above into account, we endowed the backbone of H3IDC with the triazole group and synthesized 2-((1H-1,2,4-triazol-1-yl)methyl)-1H-imidazole4,5-dicarboxylic acid (H3tmidc) (Scheme 1). It is important to mention that the modification employed on the H3IDC with the triazole group can increase the resultant ligand’s flexibility and coordination diversity and is expected to produce novel topologies of resulting transition metal H3tmidc-based compounds. In this paper, we report the construction and properties of four novel MOFs based on the newly synthesized 2((1H-1,2,4-triazol-1-yl)methyl)-1H-imidazole-4,5-dicarboxylic

INTRODUCTION During the past decades, the rational design and construction of novel metal−organic frameworks (MOFs) have attracted significant interest owing to their enormous structural diversity and intriguing molecular topologies as well as promising applications as functional materials in the areas of catalysis, sorption, ion exchange, sensors, nonlinear optics, magnetism, and so on.1−3 It is well-known that one of the most effective approaches to synthesizing novel MOFs is the judicious selection of multifunctional organic ligands, especially the N-heterocyclic carboxylates, because these building blocks contain multioxygen and nitrogen atoms and can coordinate with metal ions in versatile ways, resulting in the formations of various MOFs with specific topologies and useful properties.4−10 For example, 4,5-imidazoledicarboxylic acid (H 3IDC), a planar rigid N-heterocyclic carboxylic acid containing two nitrogen and four oxygen atoms, has attracted much interest in coordination chemistry, showing more interesting traits in the construction of MOFs. H3IDC can be partially or fully deprotonated to generate various species with different proton numbers (H2IDC−, HIDC2−, and IDC3−) at different pH values. Therefore, H3IDC can potentially afford various coordination modes in multicoordinated ways with metal ions to form a large diversity of MOFs with different structures and useful properties. Up to now, some 4,5-imidazoledicarboxylate coordination polymers that exhibit useful properties, such as porosity, magnetism, and catalysis, have been reported by multitudinous research © 2012 American Chemical Society

Received: September 29, 2011 Revised: January 14, 2012 Published: January 27, 2012 1282

dx.doi.org/10.1021/cg201287t | Cryst. Growth Des. 2012, 12, 1282−1291

Crystal Growth & Design

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compound 1 is formed. Yield: 16.2 mg (35% based on Cu). Anal. Found (Calcd) for C16H12N10O10Cu3: C, 27.51 (27.63); H, 1.84 (1.73); N, 20.35 (20.14). IR (KBr, cm−1): 3431(m), 1572(s), 1547(s), 1457(s), 1384(s), 1345(w), 1288(w), 1265(w), 1129(m), 1022(w), 998(w), 881(w), 833(m), 788(w), 761(w), 671(m), 652(w), 544(w). Preparation of [Cd(Htmidc)] (4). A mixture of H3tmidc (0.10 mmol, 0.0240 g), Cd(NO3)2·3H2O (0.10 mmol, 0.0305 g), NaOH (0.30 mmol, 0.0120 g), and H2O (10 mL) was kept in a Teflon-lined autoclave at 185 °C for 48 h. After slowly cooling to room temperature, colorless crystals were collected as a monophasic product. Xray powder diffraction was used to check the purity. As shown in Figure S2, Supporting Information, the pattern calculated from the single-crystal X-ray data was in good agreement with the observed one indicating a single phase is formed. Yield: 20.1 mg (58% based on Cd). Anal. Found (Calcd) for C8H5N5O4Cd: C, 27.54 (27.67); H, 1.55 (1.44); N, 20.31 (20.12). IR (KBr, cm−1): 3430(w), 1574(s), 1524(s), 1487(s), 1470(s), 1383(m), 1281(m), 1137(s), 1004(s), 958(m), 860(m), 813(m), 775(m), 689(m), 669(s), 646(m), 491(m). X-ray Crystallographic Studies. Crystallographic data were collected on a Rigaku AFC10Saturn72 CCD diffractometer using graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å) at room temperature. A hemisphere of data was collected using a narrow-frame method with scan width of 0.50° in ω. The data were integrated using the CrystalClear-SM 1.3.6 SP3r6 program, with the intensities corrected for Lorentz factor, polarization, air absorption, and absorption due to variation in the path length through the detector faceplate. Multiscan absorption corrections were applied. The structures were solved by direct methods and refined on F2 by full matrix least-squares using SHELXTL.14 All the non-hydrogen atoms were located from the Fourier maps and were refined anisotropically. All H atoms were refined isotropically, with the isotropic vibration parameters related to the non-H atom to which they are bonded. The crystallographic data for the four compounds are listed in Table 1, and the selected bond lengths are given in Table 2. CCDC publication nos. 808357, 770104, 808358, 808359 for compounds 1−4 contain the supplementary crystallographic data for this paper.

Scheme 1. H3tmidc

acid formulated as [Mn3(tmidc)2(H2O)4]·(H2O)6 (1), [Co3(tmidc)2(H2O)4]·(H2O)4 (2), [Cu3(tmidc)2(H2O)]·(H2O) (3), and [Cd(Htmidc)] (4). To the best of our knowledge, no metal-tmidc compounds have been reported in the literature so far. Compounds 2 and 3 exhibit new types of topologic structures not found in the known MOFs.

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EXPERIMENTAL SECTION

Materials and Methods. 2-((1H-1,2,4-Triazol-1-yl)methyl)-1Himidazole-4,5-dicarboxylic acid (H3tmidc) was prepared according to the literature.12 All other starting materials were purchased as reagentgrade chemicals and used without further purification. Elemental analyses were performed on a Carlo-Erba 1160 elemental analyzer. The IR spectra were obtained as KBr disks on a Shimadzu IR 435 spectrometer. Thermogravimetric analyses were carried out on a NETZSCH STA409PC unit at a heating rate of 10 °C/min under an oxygen atmosphere. Powder X-ray diffraction patterns were recorded on a Bruker D8 X-ray diffractometer with Cu Kα radiation (λ = 1.5406 Å). The fluorescence spectra for the solid state were recorded at room temperature on a Hitachi F-2500 spectrophotometer. Magnetic susceptibility data were obtained on microcrystalline samples (25.18 mg for 1, 42.28 mg for 2, and 48.65 mg for 3), using a Quantum Design MPMS-XL7 SQUID magnetometer. Diamagnetic corrections were made for both the sample holder and the compound estimated from Pascal’s constants.13 Preparation of [Mn3(tmidc)2(H2O)4]·(H2O)6 (1). A mixture of H3tmidc (0.10 mmol, 0.0240 g), MnCl2·4H2O (0.10 mmol, 0.0205 g), and H2O (10 mL) was kept in a Teflon-lined autoclave at 150 °C for 48 h. After slowly cooling to room temperature, pink blocky crystals were obtained together with a small amount of unidentified white flocculent material. The crystals were manually selected and used for structural measurement and physical measurements. Yield: 13.6 mg (50% based on Mn). Anal. Found (Calcd) for C16H28N10O18Mn3: C, 23.31 (23.62); H, 3.54 (3.44); N, 17.56 (17.22). IR (KBr, cm−1): 3422(m), 1570(s), 1457(s), 1362(s), 1285(m), 1251(m), 1205(w), 1119(s), 1030(m), 987(w), 878(m), 817(m), 796(w), 688(m), 670(m), 635(w), 522(m). Preparation of [Co3(tmidc)2(H2O)4]·(H2O)4 (2). A mixture of H3tmidc (0.10 mmol, 0.0240 g), Co(NO3)2·6H2O (0.10 mmol, 0.0290 g), NaOH (0.30 mmol, 0.0120 g), and H2O (10 mL) was sealed in a Teflon-lined autoclave at 180 °C for 72 h. After slowly cooling to room temperature, pink octahedron-shaped crystals were obtained together with a small quantity of pink powders. The crystals were manually selected and used for structural measurement and physical measurements. Yield: 20.3 mg (78% based on Co). Anal. Found (Calcd) for C16H24N10O16Co3: C, 24.82 (24.35); H, 3.23 (3.07); N, 17.76 (17.75). IR (KBr, cm−1): 3419(m), 1565(m), 1457(s), 1379(s), 1290(m), 1263(s), 1208(w), 1127(s), 1024(m), 992(w), 884(m), 832(m), 816(s), 792(s), 686(m), 670(m), 638(w), 527(m). Preparation of [Cu3(tmidc)2(H2O)]·(H2O) (3). A mixture of H3tmidc (0.10 mmol, 0.0240 g), Cu(NO3)2·3H2O (0.20 mmol, 0.0486 g), and H2O (10 mL) was kept in a Teflon-lined autoclave at 185 °C for 48 h. After slowly cooling to room temperature, blue blocky crystals were collected as a monophasic material. X-ray powder diffraction was used to check the purity. As shown in Figure S1, Supporting Information, all the peaks displayed in the measured pattern at room temperature closely match those in the simulated pattern generated from single-crystal diffraction data, which indicates single phase of

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RESULTS AND DISCUSSION Description of Structure [Mn3(tmidc)2(H2O)4]·(H2O)6 (1). Compound 1 is a three-dimensional (3D) open framework consisting of concertina sheets linked by triazole rings and crystallizes in the space group Pbca. The asymmetric unit consists of one and half crystallographically distinguishing Mn(II) ions, one tmidc3− anion, two coordinated water molecules, and three dissociative water molecules. Figure 1a shows the coordination environments of Mn(II) ions in compound 1. The Mn1 ion is six-coordinated with distorted octahedral geometry surrounded by two nitrogen and one oxygen atoms (N3, N4B, and O4A) from three crystallographic independent μ4-tmidc3− ligands and one water molecule (O5) in the equatorial plane, and two oxygen atoms (O2A and O1B) in axial positions (symmetry code: $A −x + 2, y − 1/2, −z − 1/2; $B −x + 3/2, y − 1/2, z). The Mn1−N distances range between 2.199 and 2.274 Å, and the Mn1−O bond lengths range from 2.139 to 2.253 Å. The Mn2 ion resides on an inversion center and is octahedrally coordinated by two nitrogen and two oxygen atoms (N5, N5C, O3, and O3C) from two individual μ4tmidc3− ligands and two aqua oxygen atoms (O6 and O6C) (symmetry code: $C −x + 2, −y, −z − 1). The Mn2−N bond length is 2.152 Å and the Mn2−O bond lengths range between 2.226 and 2.287 Å. These Mn−N and Mn−O bond lengths are comparable to those reported for other imidazole-based dicarboxylate Mn(II) complexes.5d,7b,8b,11c,g In each μ4tmidc3− ligand, the imidazole ring and triazole ring are almost vertical with a dihedral angle of 85.9°. Each tmidc3− anion 1283



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Table 1. Crystallographic Data for 1−4a compound formula fw crystal system 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) observed reflections unique reflections Rint GOF on F2 R indices [I > 2σ(I)] R indices (all data) (Δρ)max, (Δρ)min, e Å−3 a

1

2

3

4

C16H28N10O18Mn3 813.30 orthorhombic Pbca 12.170(2) 13.601(3) 17.400(4) 90 90 90 2880.1(10) 4 1.876 1.395 1652 19381 2829 0.0466 1.093 R1 = 0.0514 wR2 = 0.1390 R1 = 0.0531 wR2 = 0.1407 0.354, −0.417

C16H24N10O16Co3 789.18 tetragonal P43212 12.5879(18) 12.5879(18) 25.090(5) 90 90 90 3975.6(11) 8 1.305 1.302 1564 43631 3898 0.0444 1.195 R1 = 0.0658 wR2 = 0.2021 R1 = 0.0662 wR2 = 0.2025 1.077, −0.655

C16H12N10O10Cu3 694.98 monoclinic P21/c 11.271(2) 15.663(3) 12.609(3) 90 104.43(3) 90 2155.8(7) 4 2.141 3.016 1380 21510 3795 0.1042 1.053 R1 = 0.0851 wR2 = 0.2104 R1 = 0.1152 wR2 = 0.2353 0.841, −0.740

C16H10N10O8Cd2 695.14 monoclinic P21/c 7.9459(16) 10.560(2) 11.698(2) 90 105.25(3) 90 947.0(3) 4 2.438 2.324 672 8595 1849 0.0232 1.071 R1 = 0.0234 wR2 = 0.0604 R1 = 0.0253 wR2 = 0.0621 0.456, −0.725

R1 = ∑ || F0 | − | Fc ||/∑ | F0 |; wR2 = [∑w(F02 − Fc2)2/∑ w(F02)2]1/2.

Table 2. Selected Bond Lengths (Å) for Compounds 1−4a

adopts a μ4-kN,O:kN′,O′:kO,O′:kN″ mode connecting four Mn centers. As shown in Figure 1b, all the Mn(II) ions are interlinked by tmidc3− ligands to generate a two-dimensional (2D) concertina sheet in the ac plane, which is composed of hexagonal 24-membered rings. Each 24-membered ring shows a chain-conformation and is formed by six tmidc3− ligands, four Mn1 ions, and two Mn2 ions. The triazole rings act as linear connectors through the coordination interactions of N3 atoms in the original formed sheet to the Mn1 ions from adjacent layer. As a result, the neighboring sheets are further pillared together by bridging triazole rings to result in a 3D architecture with channels running parallel to the [1 0 0] and [0 1 0] directions (Figure 1c). The lattice water molecules reside in these channels and form hydrogen bonds with coordinated water molecules and the carboxylate groups, as well as with the nitrogen atoms (N2) from triazole rings (O7···N2#8, 2.929 Å; O7···O4#9, 2.932 Å; O8···O6, 2.922 Å; O9···O6, 2.884 Å; O9···O7, 2.901 Å; symmetry codes: #8 x + 1/2, −y + 1/2, −z − 1; #9 x − 1/2, −y + 1/2, −z − 1). When these extraframework species are not considered, the total accessible volume within the crystal is estimated as 18.7% as calculated by the program PLATON. Topologically, each μ4-tmidc3− ligand is connected to three Mn1 centers and one Mn2 center through Mn−O and Mn−N bonds. Contrarily each Mn1 center links with three μ4tmidc3− ligands and each Mn2 ion links with two μ4-tmidc3− ligands. Therefore, each Mn1 center is considered as a threeconnecting node, each Mn2 center is regarded as a connection, and each μ4-tmidc3− ligand can be defined as a four-connecting node. On the basis of this simplification, the 3D architecture can be described as a binodal (3,4)-connected fsc-3,4-Pbca network with the Schläfli topological symbol of (63)(63.83), as illustrated in Figure 1d. The topological analysis of compound 1 has been performed on the TOPOS40 program giving

1 Mn1−O2A Mn1−N4B Mn1−O1B Mn2−N5C Mn2−O3C Mn2−O6C

2.139(3) 2.199(3) 2.253(3) 2.153(3) 2.226(3) 2.287(3)

Co1−N4A Co1−O4 Co1−O2A Co2−O1 Co2−O3C Co2−O6

2.053(5) 2.135(5) 2.138(5) 2.034(5) 2.074(5) 2.134(7)

Cu1−O7 Cu1−N4 Cu1−O5 Cu2−O2 Cu2−O9 Cu3−N9C Cu3−O3 Cu3−N8D

1.960(7) 1.986(8) 2.199(7) 1.963(7) 1.976(7) 1.960(8) 1.971(7) 2.322(12)

Cd1−N5A Cd1−O1B Cd1−N2A

2.189(2) 2.340(2) 2.581(2)

Mn1−O4A Mn1−O5 Mn1−N3 Mn2−N5 Mn2−O3 Mn2−O6

2.156(3) 2.209(3) 2.275(3) 2.153(3) 2.226(3) 2.287(3)

Co1−N5 Co1−N3B Co1−O5 Co2−O1C Co2−O3 Co2−O6C

2.060(4) 2.137(5) 2.211(5) 2.034(5) 2.074(5) 2.134(7)

Cu1−O1 Cu1−N3A Cu2−N10B Cu2−O8B Cu2−O4 Cu3−N5 Cu3−O6C

1.966(7) 1.986(8) 1.945(8) 1.970(7) 2.176(7) 1.961(8) 2.001(7)

Cd1−N3 Cd1−N4B Cd1−O2C

2.250(2) 2.354(2) 2.863(2)

2

3

4

Symmetry code. For 1: $A −x + 2, y − 1/2, −z − 1/2; $B −x + 3/2, y − 1/2, z; $C −x + 2, −y, −z − 1. For 2: $A x − 1/2, −y + 3/2, −z + 1/4; $B y − 1/2, −x + 3/2, z + 1/4; $C −y + 1, −x + 1, −z + 1/2. For 3: $A x, −y + 1/2, z − 1/2; $B x + 1, y, z; $C −x + 2, y + 1/2, −z + 3/ 2; $D x + 1, −y + 1/2, z + 1/2. For 4: $A −x, y + 1/2, −z + 1/2; $B x − 1, y, z; $C x − 1, −y + 3/2, z − 1/2. a

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Figure 1. (a) The coordination environments of Mn(II) ions in compound 1. Hydrogen atoms are omitted for clarity. (b) The 2D concertina sheet with chair-conformational 24-membered rings viewed along the b axis for compound 1. Triazole rings of the ligand are omitted for clarity. (c) The 3D pillar-layer MOF with the 1D channels along the a axis for compound 1. The coordinated and lattice water molecules are omitted for clarity. (d) Schematic illustrating the (63)(63.83) topology of the fsc-3,4-Pbca net for compound 1. μ4-tmidc3− ligands are represented by blue spheres, Mn1 ions by red.

dimer unit of [Co(1)2(tmidc3−)4(H2O)2] (Figure 2b). These dimer units of [Co(1)2(tmidc3−)4(H2O)2] are alternately connected along the direction of c axis through the imidazoledicarboxylic groups chelating two Co1 ions in a bis-bidentate fashion via the oxygen atoms of the carboxylic group (O2 and O4) and nitrogen atoms of the imidazole ring (N4 and N5) to form a left-handed helical infinite chain (Figure 2c). The helix is generated around the crystallographic 41 screw axis by which four complex units, namely, four dimer units of [Co(1)2(tmidc3−)4(H2O)2]4 are interrelated to complete one helical turn with a pitch of 25.09 Å, which marks the c lattice parameter. A notable structural feature of compound 2 is that it comprises channels formed by the intertwist of the helical chains. The channels have a 6.294 × 6.294 Å2 square section and its total solvent-accessible volume in the unit is 1936 Å3, which account for 48.7% of the total cell volume as calculated by PLATON. These helical chains are further assembled by Co2 ions into a 3D open framework. The interchain coordination interactions of O1 and O3 atoms from μ4-tmidc3− ligands in original formed helical chains to Co2 ions can allow the left-handed chirality to transfer uniformly, leading to the formation of a homochiral 3D frameworks (Figure 2d), in which all the helical chains are left-handed chirality. It is regrettable that right-handed enantiomers crystallize synchronously in compound 2 together; thus, the chiral structure of compound 2 cannot be obtained by spontaneous resolution.

the long vertex symbols of the two nodes as 6·6·6 and 6·82·6·83·6·83, respectively. Description of Structure [Co3(tmidc)2(H2O)4]·(H2O)4 (2). Compound 2 exhibits a 3D pillared framework constructed by 4-fold one-dimensional (1D) helical chains and crystallizes in a tetragonal chiral space group P43212, with an absolute structure parameter being 0.51(4) indicating that it is twinned. The asymmetric unit contains one and half crystallographically independent Co(II) ions, one tmidc3− anion, two coordinated water molecules, and two lattice water molecules. As shown in Figure 2a, each Co1 ion is surrounded by three nitrogen (N5, N4A, and N3B) and two oxygen atoms (O4 and O2A) from three individual μ4-tmidc3− ligands, and one water molecule, forming a slightly distorted octahedral geometry (symmetry code: $A x − 1/2, −y + 3/2, −z + 1/4; $B y − 1/2, −x + 3/2, z + 1/4). Co2 ion, however, resides on an inversion center and is octahedrally coordinated by four oxygen atoms (O1, O3, O1C, and O3C) from two individual μ4-tmidc3− ligands and two oxygen atoms (O6 and O6C) from two aqua molecules (symmetry code: $C −y + 1, −x + 1, −z + 1/2). The Co− O(N) distances are in the range of 2.034−2.211 Å, and they are comparable to the previously reported values.5e,7b,d,9a,11f The tmidc3− anion utilizes three nitrogen and two carboxylate oxygen atoms adopting a μ2-kN,O:kN″ coordination mode to link Co1 ions. Accordingly, two Co1 ions are held together with four tmidc3− anions and two water molecules to build a 1285



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Figure 2. (a) View of the coordination environments of Co(II) ions in compound 2. Hydrogen atoms are omitted for clarity. (b) View of an individual dimer unit [Co(1)2(tmidc3−)4(H2O)2]. (c) Schematic representation of 4-fold helical chain for compound 2. (d) 3D pillared layered framework with the 1D square channels in compound 2 viewed down the c axis. Lattice water molecules are omitted for clarity.

A better insight into the nature of compound 2 can be achieved by the application of topological analysis using the program TOPOS. As discussed above, each Co2 center is regarded as a linker, each μ4-tmidc3− ligand is simplified to a 4-connected node, and each Co1 center can be viewed as a 3-connected node. Topological analysis reveals that it is a unique binodal (3,4)-connected net with the Schläfli symbol of (4.52)(4.5.114) and the long vertex symbol is 4·5·5 and 4·52·11·113·113·115, respectively (Figure 3). It is noted that such a (3,4)-connected net is a new topology which is not enumerated in RCSR and TOPOS, and has not been reported in the literature. Description of Structure [Cu3(tmidc)2(H2O)]·(H2O) (3). Compound 3 crystallizes in the space group P21/c. The asymmetric unit comprises three crystallographically independent Cu(II) ions, two tmidc3− anions with uniform coordination mode, one coordinated water molecule, and one lattice water molecule in which the Cu1, Cu2, and Cu3 ions all adopt distorted square pyramidal geometries. As depicted in Figure 4a, the Cu1 ion is five-coordinated with three oxygen (O1, O5, and O7) and two nitrogen atoms (N4 and N3A) from three individual μ4-tmidc3− ligands (symmetry code: $A x, −y + 1/2, z − 1/2). Each Cu2 ion is surrounded by one nitrogen (N10B) and three carboxylate oxygen atoms (O2, O4, and O8B) from

Figure 3. Schematic illustrating the (4.52)(4.5.114) topology of the 3D framework of compound 2. μ4-tmidc3− ligands are represented by blue spheres, Co1 ions by red.

two independent μ4-tmidc3− ligands, and one aqua oxygen atom (O9) (symmetry code: $B x + 1, y, z). Each Cu3 ion is 1286



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Figure 4. (a) View of the coordination environments of Cu(II) ions in compound 3. Hydrogen atoms are omitted for clarity. (b) View of an individual dimer unit [Cu(2)Cu(3)(tmidc3−)4(H2O)]. (c) Perspective view of the helical chain along the b direction in compound 3. (d) View of 2D coordination layer in compound 3 along the crystallographic a-axis.

in a left-handed helix to meet the request of the coordination of triazole rings in the original right-handed chain to the Cu3 ions in neighboring helical chain. Thus the adjacent helical chains are fused together through the coordination of triazole rings, leading to the formation of an achiral 2D sheet in the bc plane (Figure 4d). The adjacent achiral sheets are further linked by Cu1 ions (through the coordination connection of Cu1 ion to O1, N4, O5, O7, and N3 atoms) to generate a 3D framework (Figure 5a). The most remarkably structural feature of compound 3 is that it possesses the 3D intricate framework displaying new (3,4)-connected topology. In compound 3, the network topology can be acquired by defining each μ4-tmidc3− ligand as a 4-connected node and Cu1 (Cu3) ion as a 3-connected node. The resulting (3,4)-connected 4-nodal net has a (5.72)(4.5.7)(52.72.8.10)(4.5.73.8) topology with an extended vertex symbol of (5·7·7)(4·5·7)(5·5·7·7·8·104)(4·7·5·8·7·7) (Figure 5b). Although many (3,4)-connected networks in coordination polymers have been reported, to our best knowledge, this type of topology defined by compound 3 has not been observed in any other coordination polymers.

ligated by three nitrogen (N5, N9C, and N8D) and two oxygen atoms (O3 and O6C) from three crystallographically different μ4-tmidc3− ligands (symmetry code: $C −x + 2, y + 1/2, −z + 3/2; $D x + 1, −y + 1/2, z + 1/2). The Cu−O(N) distances are in the range of 1.945−2.322 Å, and they are comparable to the previously reported values.11b,h Each tmidc3− anion adopts identical μ4-kN,O:kN′,O′:kO,O′:kN″ coordination mode connecting four Cu centers. The tmidc3− anion utilizes three oxygen (O2, O3, and O4) and one nitrogen atoms (N5) in bidentate-bridging and bidentate-chelating fashions to link Cu2 and Cu3 ions. Thereby, Cu2 and Cu3 ions are bound together to construct a dimer unit of [Cu(2)Cu(3)(tmidc3−)4(H2O)] (Figure 4b). These dimer units of [Cu(2)Cu(3)(tmidc3−)4(H2O)] are alternately linked along the direction of the b axis through the oxygen atoms of the carboxylic group (O6 and O8) and nitrogen atoms of the imidazole ring (N9 and N10) to form a 1D right-handed helical infinite chain around the crystallographic 21 axis, with the pitch of 15.663 Å (Figure 4c). The N8 atoms coordinate to the remaining coordination sites of Cu3 ions within the chain in a parallel way. Therefore, the neighboring chains must be formed 1287



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Figure 5. (a) Packing diagram of compound 3 viewed along the c axis. (b) Schematic description of the 4-nodal (3,4)-connected net for compound 3 constructed from the 4-connected μ4-tmidc3− ligands and 3-connected Cu center nodes (blue or purple: μ4-tmidc3− ligand; red: Cu1 ions; yellow: Cu3 ions).

Description of Structure [Cd(Htmidc)] (4). Compound 4 crystallizes in the space group P21/c. The asymmetric unit consists of one Cd(II) ion and one Htmidc2− ligand in which each Cd(II) ion is seven-coordinated with a distorted [CdN4O3] pentagonal bipyramidal geometry. As shown in Figure 6a, the coordination sphere around Cd(II) ion is composed of three oxygen atoms (O3A, O1B, and O2C) and four nitrogen atoms (N3, N2A, N5A, and N4B) atoms from four individual μ4-Htmidc2− ligands (symmetry code: $A −x, y + 1/2, −z + 1/2; $B x − 1, y, z; $C x − 1, −y + 3/2, z − 1/2). The equatorial plane is completed by O1B, N2A, O2C, O3A, and N4B atoms, and the axial sites are occupied by two nitrogen atoms N3 and N5A. The Cd−O bond lengths vary from 2.340 to 2.863 Å, while the Cd−N bond lengths are in the range of 2.189−2.581 Å. All lengths are consistent with those reported in other imidazolebased dicarboxylate Cd(II) complexes.5j,6b,7a,b,e,f,9b,11b−d,g Each Htmidc2− anion adopts a μ4-kN,O:kN′,O′,N″:kO:kN‴ mode connecting four Cd(II) centers. First, in the [0 1 0] direction adjacent Cd(II) ions are linked together by imidazole dicarboxylate groups (N4, O1, N5, and O3) to generate a single-chain helicate motif with a pitch of 10.560 Å. Then the adjacent helical chains are fused through the coordination of the triazole rings (N2 and N3) to the Cd atom, hence generating a 2D layer in the ab plane (Figure 6b). Eventually, the neighboring layers are pillared through the O2 atoms from carboxyl group along the c-axis, leading to the formation of a 3D framework (Figure 6c). The topological representation of the 3D network found in compound 4 is shown in Figure S3, Supporting Information. A binodal (4,4) net is constructed by considering each μ4-Htmidc2− ligand and each Cd(II) center as a node. Topological analysis of this net reveals that the

Figure 6. (a) The coordination environments of Cd(II) ions in compound 4. Hydrogen atoms are omitted for clarity. (b) View of 2D coordination layer in compound 4 along the crystallographic c-axis. (c) View of crystal packing of compound 4 along the a-axis. All the H atoms are omitted for clarity.

whole structure can be rationalized as a (4.65)(4.65) crb topological net. TGA Studies. The TGA curves of compounds 1−4 were measured from 30 to 700 °C (see Figure S4, Supporting Information). Compound 1 exhibits three main steps of weight losses. The first and second steps are overlapping and complete at 330 °C. The weight loss of 22.52% from 30 to 330 °C corresponds to removal of six lattice water molecules and four coordinated water molecules, which is in good agreement with the calculated value (22.14%). The third step started at 330 °C and was completed at 495 °C, which correspond to the decomposition of the tmidc3− ligands and the collapse of the lattice structure. The total observed weight loss at 650 °C is 69.97%. The final residual product is MnO2. The TGA curve of compound 1288



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2 exhibits two well-separated weight loss stages. The first stage of 18.65% from 30 to 230 °C corresponds to the loss of the four lattice water molecules and four coordinated water molecules. The observed weight loss is in agreement with the calculated value (18.44%). The second stage, occurring between 230 and 500 °C, is equivalent to the decomposition of the tmidc3− ligands and the collapse of the lattice structure. The total observed weight loss at 500 °C is 77.04%. The TGA curve of compound 3 shows two main steps of weight losses. A mass loss of 5.31% of compound 3 occurred between 30 and 190 °C, attributed to the loss of the coordinated water molecules and lattice water molecules (calcd. 5.18%). Then it begins to decompose up to 650 °C, during which several processes occur: the decomposition of the tmidc3− ligands, as well as the collapse of the lattice structure. The total weight loss at 650 °C is 58.05%. Compound 4 is stable up to 370 °C, after which it begins to decompose up to 700 °C. The first step started at 370 °C and was completed at 450 °C. The second step and the first step are overlapping; the weight loss of 62.75% from 370 to 700 °C corresponds to the decomposition of the tmidc3− ligands and the collapse of the lattice structure, which is in good agreement with the calculated value (63.11%). The final residual product is CdO. Magnetic Properties, and Fluorescence Properties. The temperature-dependent magnetic susceptibility data of compounds 1−3 have been collected for polycrystalline samples in the temperature range 1.8−300 K. Figure 7a shows the χmT and χm−1 versus T plots for compound 1. At 300 K, the observed effective magnetic moment (μeff) is 6.04 μB per Mn, close to the expected spin-only value (5.92 μB) for isolated spin S = 5/2 with g = 2. On cooling from room temperature, the χm T value decreases smoothly, indicating a dominant antiferromagnetic interaction between the magnetic centers. In the temperature range 8−300 K, the magnetic behavior obeys the Curie−Weiss law with a Weiss constant of −18.1 K. The negative Weiss constant also confirms antiferromagnetic exchange between the Mn(II). Figure 7b shows the χmT and χm−1 versus T plots for compound 2. At 300 K, the effective magnetic moment per Co atom (5.22 μB) is much higher than the expected spin-only value for S = 3/2 (3.87 μB), attributed to the orbital contribution of Co(II) ion. The susceptibility data between 10 and 300 K follow the Curie−Weiss law with a Weiss constant θ = −51.0 K. Upon cooling from room temperature, χmT decreases continuously until it reaches a minimum of 1.42 cm3 mol−1 K at 4 K. Below 4 K, χmT increases abruptly to a maximum of 2.34 cm3 mol−1 K at 2 K. The upturn of χmT below 4 K suggests uncompensated magnetic moments of the system arising from spin canting of the antiferromagnetically coupled Co(II) ions. Figure 7c shows the χmT and χm−1 versus T plots for compound 3. The roomtemperature effective magnetic moment (μeff) per copper(II) atom, determined from the equation μeff = 2.828(χmT)1/2, is 1.96 μB, which is close to the value expected for an isolated system of S = 1/2 (μeff = 1.9 μB for g = 2.2). Upon cooling, the χmT decreases gradually, indicating that antiferromagnetic couplings are mediated between the Cu(II) ions. This is confirmed by a negative Weiss constant of −9.8 K determined by the Curie−Weiss law in the temperature range 10−300 K. The photoluminescent properties of compound 4 have been investigated in the solid state at room temperature. The emission spectra are illustrated in Figure S5. Compound 4 exhibits a broad emission at 667 nm. The emission can be assigned to the ligand-to-metal charge transfer (LMCT).

Figure 7. Plots of the temperature dependence of χmT and 1/χm for compounds 1 (a), 2 (b), 3 (c).

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CONCLUSIONS Through hydrothermal reactions of Mn(II), Co(II), Cu(II), and Cd(II) salts with 2-((1H-1,2,4-triazol-1-yl)methyl)-1Himidazole-4,5-dicarboxylic acid, four compounds, namely, [Mn3(tmidc)2(H2O)4]·(H2O)6 (1), [Co3(tmidc)2(H2O)4]· (H2O)4 (2), [Cu3(tmidc)2(H2O)]·(H2O) (3), and [Cd(Htmidc)] (4) have been obtained. The structure of 1 can be described as a binodal (63)(63.83) fsc-3,4-Pbca topological network. Topological analysis of compound 2 reveals that it is a unique (3,4)-connected net with (4.52)(4.5.114) topology. Compound 3 features a 3D 4-nodal net with the Schläfli symbol of (5.72)(4.5.7)(52.72.8.10)(4.5.73.8). The structure of compound 4 1289



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can be rationalized as a binodal (4.65)(4.65) crb topological network.

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ASSOCIATED CONTENT

S Supporting Information *

Crystallographic data in CIF format and Figures S1−S5 in pdf format. This information is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] (Y.-T.F.), [email protected] (L.-X.X.). Tel/Fax: +86-(0)371-67766017. 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 (Nos. 21171147 and 20871106), the China National Key Basic Research Special Funds (No. 2009CB220005).

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Four Three-Dimensional Coordination Polymers Constructed by 2

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