A Novel Three-Dimensional Network Containing Mn(II) Ions and Tricyanomethanide with Rare 46.64 Topology Hao-Ling Sun,† Bao-Qing Ma,† Song Gao,*,† and Stuart R. Batten*,‡ College of Chemistry and Molecular Engineering, State Key Laboratory of Rare Earth Materials Chemistry and Applications, PKU-HKU Joint Laboratory on Rare Earth Materials and Bioinorganic Chemistry, Peking University, Beijing 100871, China and School of Chemistry, P.O. Box 23, Monash University, Clayton, Victoria 3800, Australia
CRYSTAL GROWTH & DESIGN 2005 VOL. 5, NO. 4 1331-1333
Received March 6, 2005
ABSTRACT: A novel three-dimensional network Mn(tcm)2(bpeado) (1) (tcm ) tricyanomethanide, bpeado ) 1,2-bis(4pyridyl)ethane-N,N′-dioxide) consisting of 5-connected Mn(II) ions with a rare 46.64 topology has been synthesized; two such nets interlock to generate a 2-fold interpenetrated structure. Variable temperature magnetic susceptibility studies have shown that this compound displays weak antiferromagnetic coupling because of the long bpeado and tcm pathways. Consequently, no magnetic ordering was found. Coordination networks are of great interest both for their potential applications in the field of materials1 and for their intriguing architectures and topologies.2 The most usual and efficient strategy for synthesizing coordination networks is based on a “building block” approach, and the topology of the final structure is greatly dependent on the geometry of the nodes (connection centers) and/or the flexibility of the “building blocks”. The tricyanomethanide [tcm, C(CN)3-] ligand is a versatile “building block” for constructing high-dimensional coordination polymers because it has three potentially coordinating nitrogen atoms and several coordination modes observed, including monodentate, bidentate (µ1,5), tridentate (µ1,5,7), and tetradentate (µ1,1,5,7). The binary systems display either 2-fold interpenetrated rutile networks for M(tcm)2 [M ) Cr(II), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Hg(II)]3 or doubly interpenetrated (6,3) sheets for Ag(tcm),4 in which tcm serves as a µ1,5,7 tridentate bridge. In addition to the binary systems, the introduction of co-ligands, such as coordination solvent and ditopic ones, leads to a dramatic modification in the structural motifs.5 Among such systems, particularly noteworthy are those containing Cu(I), Ag(I), or Cd(II) metal ions and bridging ligands, such as hexamethylenetetramine, 4,4′-bipyridine (4,4′-bpy), 1,2-bis(4pyridyl)ethane or pyrazine, which display interesting structures with a variety of topologies including doubly interpenetrated (4,4) sheets, 3D rutile networks, or 3D networks with mixed 3- and 5-connecting centers.6 By contrast, the combination of the M-tcm binary system [M ) Mn(II), Fe(II), Co(II), Ni(II), Cu(II)] with various coligands usually results in (4,4) sheets or one-dimensional (1D) chains bridged by µ1,5-tcm.7 Herein we reported a novel 3D framework with a rare 46.64 topology containing 5-connected Mn(II) ions, tcm and 1,2-bis(4-pyridyl)ethane-N,N′dioxide (bpeado) co-ligands, which was chosen based on the following considerations: (a) the flexible angular connection modes of bpeado compared with that of 1,2-bis(4-pyridyl)ethane;8 (b) the successful combination of heterocyclic N-oxide with dca reported in our previous work.9,10 Compound Mn(tcm)2(bpeado) (1) was prepared by mixing MnCl2‚6H2O, bpeado, and tcm in aqueous solution under stirring.11 X-ray diffraction analysis revealed that 1 consists of a 3D network containing both bpeado and tcm bridges.12 As shown in Figure 1, the structure of 1 contains octahedral * To whom correspondence should be addressed. E-mail: gaosong@ pku.edu.cn (S.G.) and
[email protected] (S.R.B.). † Peking University. ‡ Monash University.
Figure 1. Local coordination geometry and 1D ladder substructure in the structure of 1. Metal atoms are depicted in pink, while the ligand atoms are depicted in green (carbon), blue (nitrogen), and red (oxygen); a lighter shade is used for the bpeado ligands compared to the tcm anions.
Mn atoms which lie on general positions and are coordinated to four tcm anions [Mn-N ) 2.228(2), 2.232(2), 2.236(2), and 2.275(2) Å] and two cis disposed bpeado ligands [Mn-O ) 2.125(1) and 2.114(1) Å]. The tcm anions bridge in a bidentate (µ1,5) fashion, connecting the Mn atoms into ladder-like motifs in which single tcm bridges form the sides of the ladders, and double tcm bridges form the rungs (Figure 1), which is similar to that found in a 1D Cu-tcm complex.13 These ladders are then cross-linked by the bridging cis bpeado ligands to generate a threedimensional (3D) 5-connected network with 46.64 topology (Figure 2). Two such nets interpenetrate such that the ladders are not penetrated. Rather, the four-membered rings generated by the cross-linking of the ladders in the two nets are catenated (Figure 3). The Mn‚‚‚Mn separation is 7.435 Å across the single tcm bridges, 7.644 Å across the double tcm bridges, and 14.93 Å across the bpeado bridges. The Mn‚‚‚Mn separations through tcm are shorter
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Figure 2. Schematic representation of the 3D 5-connected 46.64 network structure of 1. Only metal atoms are shown, with the tcm links represented by the orange bonds, and the bpeado links, which bridge the Mn(tcm)2 ladders, represented by the green bonds.
Communications
Figure 4. Temperature dependence of χMT and 1/χM for 1. The red line shows the best-fit curve according to the Curie-Weiss fit law.
temperature, 4.26 cm3 mol-1 K, is in good agreement with the spin-only value (4.38 cm3 mol-1 K) expected for an uncoupled Mn(II) system. The χMT value remains nearly constant to about 30 K then decreases rapidly to 1.38 cm3 mol-1 K at 1.9 K, which is similar to that found in Mn(tcm)2.14 The magnetic susceptibilities of 1 can be fitted well by the Curie-Weiss law χ ) C/(T - θ), with θ ) - 2.7 K, C ) 4.31 cm3 mol-1 K for 1. The small negative θ value suggests a very weak antiferromagnetic interaction mediated by Mn-NtC-C-CtN-Mn pathways. In conclusion, a novel three-dimensional network consisting of 5-connected Mn(II) ions with a rare 46.64 topology has been synthesized. Magnetic studies reveal that this compound is paramagnetic with weak antiferromagnetic coupling between the metal centers. Acknowledgment. Financially supported by the National Natural Science Foundation of China (No. 20125104, 20221101, 20490210), the National Key Project for Fundamental Research (2003CCA00800), and the Australian Research Council.
Figure 3. The two interpenetrating 3D nets in the structure of 1; again only the Mn atoms are shown, and the tcm and bpeado links in each net are represented by different colored bonds.
than those found in Mn(tcm)2,14 and the Mn‚‚‚Mn separations through bpeado are longer than that found in the M(dca)2(bpeado) (dca ) dicyanamide) complexes.10 Structures containing 5-connected metal centers are very rare,15 and the coordination polymer Cu(4,4′-bpy)1.5Cr2O7‚ H2O is the only one reported example containing 5-connected metal centers with 46.64 topology.16 However, there is also some difference between these two structures. In 1, there are six bridges around the metal centers; however, only five bridges were found in the previously reported compound. The difference comes from the different nature of the bridging ligands around the metal centers. The steric hindrance of three 4,4′-bipyridine bridges around the Cu(II) ions means only two other Cr2O7 bridges are possible. Compared with 4,4′-bipyridine, however, the extended oxygen atoms and the unique angular coordination mode of bpeado decreases the steric hindrance efficiently and makes it possible for the Mn(II) to adopt another four tcm bridges. The variable-temperature magnetic susceptibility χM for a collection of crystals of 1 in the temperature range of 1.9-300 K was measured in a field of 1000 Oe, and the results are shown in Figure 4. The value of χMT at room
Supporting Information Available: CIF files for the compound 1. This material is available free of charge via the Internet at http://pubs.acs.org.
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C20H12MnN8O2: C, 53.23; H, 2.68; N, 24.83%. Found: C, 53.13; H, 2.90; N, 25.09%. IR (cm-1): 2239 w, 2191 s, 2180 s, 2168 s. Crystal data: compound 1: C20H12MnN8O2, M ) 451.32, monoclinic, space group P21/c, a ) 11.5319(3), b ) 24.2933(5), c ) 7.4351(1) Å, β ) 95.1658(8)°, U ) 2074.47(7) Å3, Z ) 4, Dc ) 1.445 Mg/m3, µ(Mo KR) ) 0.671 mm-1, F(000) ) 916, GOF ) 0.923. A total of 38 271 reflections were collected and 4727 are unique (Rint ) 0.0840). R1 and wR2 are 0.0335 and 0.0656, respectively, for 280 parameters and 2859 reflections [I > 2σ(I)]. The data were collected on a Nonius Kappa CCD with Mo KR radiation (λ ) 0.71073 Å) at 293 K. The structures were solved by direct methods and refined by a full matrix least squares technique based on F2 using the SHELXL 97 program. Thetiot, F.; Triki, S.; Pala, J. S.; Golhen, S. Inorg. Chim. Acta 2003, 350, 314. Manson, J. L.; Campana, C.; Miller, J. S. Chem. Commun. 1998, 251. (a) Yeung, W. F.; Gao, S.; Wong, W. T.; Lau, T. C. New J. Chem. 2002, 26, 523. (b) Long, D. L.; Blake, A. J.; Champness, N. R.; Wilson, C.; Schroder, M. J. Am. Chem. Soc. 2001, 123, 3401. Pan, L.; Ching, N.; Huang, X. Y.; Li, J. Chem. Commun. 2001, 1064.
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