Two-Dimensional Homometallic- to a Three Dimensional

Publication Date (Web): January 10, 2014. Copyright © 2014 American ... The reaction of in situ generated 1 with Me3SnCl afforded the heterometallic ...
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Two-Dimensional Homometallic- to a Three Dimensional Heterometallic Coordination Polymer: A Metalloligand Approach Chandrajeet Mohapatra† and Vadapalli Chandrasekhar*,†,‡,$ †

Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India Tata Institute of Fundamental Research, Centre for Interdisciplinary Sciences, 21, Brindavan Colony, Narsingi, Hyderabad 500075, India $ National Institute of Science Education and Research, Institute of Physics Campus, School of Chemical Sciences, Bhubaneshwar-751 005, Odisha, India ‡

S Supporting Information *

ABSTRACT: A metalloligand type of synthetic route has been followed to generate a novel heterometallic threedimensional (3D)-coordination polymer containing Cu(II) and trimethyltin as nodes. The first step of this synthetic path consisted of the preparation of a two-dimensional-coordination polymer of Cu(II), [Cu(μ-LH)2]n (1) (LH 2 = pyridine-2,5dicarboxylic acid). The reaction of in situ generated 1 with Me3SnCl afforded the heterometallic 3D-coordination polymer, [Cu(Me3Sn)2(μ-L)2]n (2). The latter is a 4,4-connected polymer with a sqc topology. This 3D-framework contains a paddle-wheel-shaped core comprised of two heterometallic (CuII/SnIV) macrocycles.

M

(2D)-coordinaton polymer (1). Compound 1 was isolated and characterized (see below). Reaction of the in situ generated 1 with Me3SnCl afforded the novel CuII/SnIV three-dimensional (3D)-heterometallic coordination polymer (2) (Scheme 1; see also the Supporting Information).

olecular heterometallic compounds have been of great interest from the point of view of catalysis1 as well as molecular materials.2 For example, 3d/4f complexes have been attracting considerable interest because many such compounds show single-molecule magnet behavior.3 In general, the preparation of heterometallic complexes is accomplished by utilizing compartmental ligands which have distinct binding sites for diverse metal ions (Supporting Information).3a On the other hand, another popular approach is the use of a metal complex itself as a ligand, the so-called metalloligand approach, which allows the preparation of heterometallic complexes of specific nuclearity and metal ions.4 In contrast to these molecular systems, coordination polymers containing heterometallic motifs are extremely sparse. Development of appropriate synthetic strategies for building such systems will kindle interest in these polymers for various applications. The known heterometallic coordination polymers have been prepared by using a molecular metal complex containing a functional periphery, which could be elaborated into a coordination polymer (Supporting Information).5 Another method is using a mixture of metal salts along with a polyfunctional ligand utilizing hydro/solvothermal methods (Supporting Information).6 To the best of our knowledge, there does not seem to be an available protocol that allows an existing homometallic coordination polymer to be elaborated into a heterometallic derivative. In the following, we report the conversion of the two-dimensional coordination polymer [Cu(μ-LH)2]n into the heterometallic derivative [Cu(Me3Sn)2(μ-L)2]n. Reaction of Cu(NO3)2·3H2O with pyridine-2,5-dicarboxylic acid in a 1:1 ratio at room temperature afforded the two-dimensional © 2014 American Chemical Society

Scheme 1

Received: November 14, 2013 Revised: December 31, 2013 Published: January 10, 2014 406

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Figure 1. ESI-MS of compound 1.

Figure 2. (a) 2D Polymeric structure of 1, (b) 24-membered macrocyclic repeating unit of 1, (c) 1D channels along the crystallographic a axis in the solid state of 1.

Figure 3. ESI-MS of compound 2.

as parallel sheets along crystallographic a and c axes (see the Supporting Information) but show one-dimensional (1D)-channels along the b axis (Figure 2c). In 1, only one oxygen of each carboxylate group of the ligand binds to a Cu(II) center, while the other oxygen atom is free. This provides an opportunity for further coordination with metal ions. The known oxophilicity of Sn(IV), along with our interest in organotin carboxylates, together with our recent work on organotin coordination polymers7 prompted us to look at the reactivity of 1 with Me3SnCl. The reaction proceeds smoothly, affording 2 in reasonable yield (see the Supporting Information).

Compound 1 is a 2D-coordination polymer containing Cu(II) as the node (Figure 2a). The ESI-MS of 1 shows a peak at 393.9496 m/z, which can be assigned to [Cu(LH)(L)]− (Figure 1). The asymmetric unit of 1 contains a mono deprotonated ligand (LH−) connected to a Cu(II) center (see the Supporting Information). The Cu(II) center in 1 is six-coordinated, having a distorted octahedral geometry [Cu1−O3, 2.472(4)Å; Cu1−O1, 1.96(4)Å; Cu1−N1, 1.982(4)Å; O3−Cu1−O3*, 180° (see the Supporting Information)]. 1 possesses a 24-membered macrocycle as a repeating building block (Figure 2b). The polymers of 1 remain 407

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Figure 4. (a) 3D Heterometallic framework of 2 showing 1D channels along the crystallographic b axis, (b) 1D channels along the crystallographic a axis in 2, (c) 1D channels along the crystallographic c axis in 2, and (d) representation of 4,4-connected net with sqc topology [Schläfli symbol {6̂4.8̂2}2{6̂6}] of 2 (methyl groups are deleted for clarity).

ESI-MS of 2 was carried out in solution, which shows peaks at 557.9125 m/z that could be assigned to [(Cu)(Me3Sn)(L)2]− (Figure 3). The X-ray structure of 2 shows that it is a 3Dcoordination polymer containing both Cu(II) and Me3Sn motifs as nodes (Figure 4a). Here, the asymmetric unit contains one completely deprotonated ligand (L2−) connected to a Cu(II) as well as a Me3Sn center (see the Supporting Information). The geometry and bond parameters around Cu(II) are similar to that found in 1 [Cu1−O3, 2.537(3)Å; Cu1−O1, 1.939(3)Å; Cu1−N1, 1.981(3)Å; and O3−Cu1−O3*, 180° (see the Supporting Information)]. The tin atom shows a distorted trigonal bipyramidal (tbp) geometry having the oxygen atoms at the apical positions [Sn1−O4, 2.458(4)Å; Sn1−O2, 2.178(4)Å; and O4−Sn1−O2, 179.36(12)°] (see the Supporting Information). The X-ray structure of 2 clearly demonstrates that the free carboxylate oxygen atoms present in 1 are coordinating to tin atoms and the latter effectively glue the two 2D sheets of 1 to generate the 3D-coordination polymer 2 (Chart S2 and Figure S4 of the Supporting Information). In the solid state, 2 contains 1D channels along all its crystallographic axes (Figure 4, panels a and b), but it retains the similar type of 1D channels along the c axis as present along the a axis of 1 (Figure 4c). This 3D framework also shows a 4,4-connected net with sqc topology (Figure 4d).8 In this topological net, the copper center and the ligand are playing the role of 4-connected nodes (see the Supporting Information). This heterometallic coordination polymer possesses a paddle-wheel type of building unit which involves two heterometallic macrocycles, one 20-membered [Cu2Sn2O6N2C8] and another 26-membered [Cu2Sn2O8C14] (Figure 5). It may be noted that we recently reported a paddlewheel type of architecture in transition metal complexes, with phosphorus-supported ligands.9 In general, several coordination polymers and MOFs containing transition metal ions such as Zn2+ and Cu2+ possess [M2(OCO)4] (M = transition metal) type

Figure 5. Paddle-wheel type core containing 20-membered (green) and 26-membered (pink) rings with a dihedral angle of 85.4° between them.

of paddle-wheel building blocks.10 Unlike regular paddle-wheel [M2(OCO)4] cores, the current heterometallic 3D-coordination polymer 2 owns an unprecedented type of paddle-wheel core containing two different and large macrocycles with a Cu−Cu distance of 11.834 Å. These planar macrocycles bisect each other with a dihedral angle of 85.4°, having two Cu atoms as intersecting points between them. The thermogravimetric analysis of compound 1 shows a two-step weight loss at ∼140 °C and ∼280 °C, while 2 is stable up to ∼290 °C. In conclusion, we have successfully synthesized a heterometallic 3D-coordination polymer (2), containing both copper and triorganotin motifs with a sqc topology. The synthetic methodology adopted is akin to the metalloligand approach used in the preparation of heterometallic complexes and involves the conversion of a homometallic 2D-coordination polymer to a heterometallic 3D-coordination polymer. We believe that such 408

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Banerjee, R.; Mallick, A. Inorg. Chem. 2013, 52, 3579. (d) Chandrasekhar, V.; Mohapatra, C.; Metre, R. K. Cryst. Growth Des. 2013, 13, 4607. (e) Chandrasekhar, V.; Mohapatra, C. Cryst. Growth Des. 2013, 13, 4655. (8) (a) The network topology was evaluated by the program TOPOS4.0; see http://www.topos.ssu.samara.ru. Blatov, V. A. IUCr CompComm Newsletter 2006, 7, 4. (b) Blatov, V. A.; Shevchenko, A. P.; Serezhkin, V. N. J. Appl. Crystallogr. 2000, 33, 1193. (c) Blatov, V. A.; O’Keeffe, M.; Proserpio, D. M. CrystEngComm 2010, 12, 44. (9) (a) Chandrasekhar, V.; Azhakar, R.; Andavan, G. T. S.; Krishnan, V.; Zacchini, S.; Bickley, J. F.; Steiner, A.; Butcher, R. J.; Ko1gerler, P. Inorg. Chem. 2003, 42, 5989. (b) Chandrasekhar, V.; Azhakar, R.; Murugesapandian, B.; Senapati, T.; Bag, P.; Pandey, M. D.; Maurya, S. K.; Goswami, D. Inorg. Chem. 2010, 49, 4008. (10) (a) Sahu, J.; Ahmad, M.; Bharadwaj, P. K. Cryst. Growth Des. 2013, 13, 2618. (b) Medishetty, R.; Jung, D.; Song, X.; Kim, D.; Lee, S. S.; Lah, M. S.; Vittal, J. J. Inorg. Chem. 2013, 52, 2951. (c) Fernandez, C. A.; Liu, J.; Thallapally, P. K.; Strachan, D. M. J. Am. Chem. Soc. 2012, 134, 9046.

approaches will unravel new families of heterometallic coordination polymers.

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ASSOCIATED CONTENT

S Supporting Information *

Crystallographic information files (CIF) for 1 and 2, some additional diamond figures, additional experimental data, and a thermogravimetric curve for 1 and 2. This material 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] and [email protected]. Tel: (+91) 512-2597259. Fax: (+91) 521-259-0007/7436. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We thank the Department of Science and Technology, India, and the Council of Scientific and Industrial Research, India, for financial support. V.C. is thankful to the Department of Science and Technology for a J. C. Bose fellowship. C.M. thanks the UGC, India, for a Senior Research Fellowship.

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REFERENCES

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