A New Quartz-like Metal–Organic Framework Constructed from a

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A new quartz-like metal-organic framework constructed from a versatile pyrazole-based spacer Guilherme P Guedes, Igor F. Santos, Luiza A Mercante, Nivaldo Lucio Speziali, Jackson A. L. C. Resende, Alice M. R. Bernardino, Marius Andruh, and Maria G. F. Vaz Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg5018328 • Publication Date (Web): 13 Feb 2015 Downloaded from http://pubs.acs.org on February 16, 2015

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Crystal Growth & Design

A new quartz-like metal-organic framework constructed from a versatile pyrazole-based spacer

Guilherme P. Guedes,†,‡ Igor F. Santos,† Luiza A. Mercante,† Nivaldo L. Speziali,# Jackson A. L. C. Resende,† Alice M. R. Bernardino,† Marius Andruh,*,§ and Maria G. F. Vaz*,†

†

Universidade Federal Fluminense, Instituto de Química, Niterói, Rio de Janeiro,

Brazil. ‡

Universidade Federal Rural do Rio de Janeiro, Instituto de Ciências Exatas,

Departamento de Química, Seropédica, Rio de Janeiro, Brazil. #

Universidade Federal de Minas Gerais, Departamento de Física, Belo Horizonte,

Minas Gerais, Brazil. §

Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest, Str.

Dumbrava Rosie nr. 23, 020464-Bucharest, Romania.

ACS Paragon Plus Environment

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ABSTRACT. Two new coordination polymers, 1∞[Cu2(L)4(MeOH)]⋅MeOH 1 and 3

∞[Cu(L)2]•5H2O 2, have been obtained exploring the potential of 5-amino-1-phenyl-

1H-pyrazole-4-carboxylate (L−) to act as a spacer. The different architectures of these compounds arise from the versatility of this organic ligand. In compound 1, the carboxylato groups (syn-syn bridging mode) and the copper ions generate the binuclear paddle-wheel motif. Each binuclear entity coordinates to another one, through one out of the four pyrazole rings, resulting in double chains. In crystal 2, the organic ligand is coordinated to a copper ion through the carboxylato group (asymmetric chelating) and to another copper ion through the pyrazole nitrogen atom. Compound 2 crystallizes in the hexagonal system with the chiral space group P6122, featuring a quartz-like topology. The magnetic properties of both compounds have been investigated.


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The explosive development of crystal engineering has stimulated the search for new molecules that can act as linkers (spacers) in constructing coordination polymers (CPs). The essential property of a linker arises from the number and the relative positions of the donor atoms, which are crucial factors influencing the solid-state architecture of the resulting CPs.1-3 The classical spacers in crystal engineering are exo-dentate (divergent) ligands, neutral or anionic, such as 4,4’-bipyridyl and the terephthalato anion, which can be considered as archetypes.4-7 When a molecule contains two or more functional groups, with different donor atoms, the coordination modes cannot be easily predicted. Very often, such molecules act as versatile ligands generating various topologies of the coordination polymers even for the same assembling cation. For example, the presence of one carboxylato group within a molecule that also contains other functional groups increases the number of coordination modes, simply because the carboxylato group itself is extremely versatile.8,9 The rich chemistry of 5- and 6-membered N-heterocyclic compounds is an important source of ligands. Focusing now only to the pyrazole ring, its functionalization with additional coordinating groups leads to a quite large library of chelating ligands.10-12 The main interest in such molecules arises from their relevance in medicinal and bioinorganic chemistry and in designing spin crossover materials.1013

More recently, several substituted pyrazoles have been employed as tectons in

constructing CPs.14 Herein we report on the first examples of extended structures assembled from copper(II) ions and 5-amino-1-phenyl-1H-pyrazole-4-carboxylate (L−) - Chart 1. The HL acid was synthesized following the synthetic procedure described by Zia-ur-Rehman and co-workers.15 The potassium salt was obtained by neutralization with KOH. The reaction between Cu(OAc)2.H2O (1.1 mmol) and the potassium salt of HL (2.1 mmol) in methanol leads to two compounds, 1∞[Cu2(L)4(MeOH)]⋅MeOH 1 and 3

∞[Cu(L)2]•5H2O 2. Experimental details are presented in the Supporting Information.

Their crystal structures have been solved by X-ray diffraction and a summary of crystal structure, data collection and refinement is given in reference 16. Let us start with the discussion of structural results of compound 1, which is a 1-D coordination polymer assembled in a quite interesting way. First of all, we notice that four carboxylato groups arising from four L ligands generate, together with two copper(II) ions the classical paddle-wheel motif, with Cu1···Cu2 = 2.625(1) Å


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(Figure 1a). The axial positions of the copper ions are occupied by a methanol molecule (Cu2 – O9 = 2.132(6) Å) and by a pyrazole nitrogen atom arising from another paddle-wheel binuclear entity (Cu1 – N10 = 2.241(8) Å). Each dinuclear entity coordinates to another one, through one out of the four pyrazole rings, resulting in double chains running along the crystallographic b axis (Figure 1b). Similar 1D structures formed by paddle-wheel motifs were also reported in literature.17-18 Compounds 1 and 2 have the same Cu : L = 1 : 2 composition, but the coordinating mode of the carboxylato ligand is different in 2, namely asymmetric chelating, one oxygen atom from each carboxylato group being semicoordinated to the metal ion (Cu1 – O1i = 1.939(2), Cu1 – O1ii = 1.941(2), Cu1 – O2i = 2.775(2) and Cu1 – O2ii = 2.776(2) Å, where the symmetry operations are: (i) x−y, x, z+1/6; (ii) −x+1, −x+y+1, −z+5/3). Besides, the coordination environment is filled by two nitrogen atoms arising from pyrazole rings of different ligands (Cu1 – N1 = 1.978(2) and Cu – N1iii = 1.976(2) Å, (iii) −y+1, −x+1, −z+11/6) Figure 2a. Every L ligand connects two copper ions, interacting though the carboxylato group with one metal center, and through the pyrazole nitrogen with another one, the distance between the metal ions being 8.101(1) Å. Each copper ion is thus connected to four others, building up a distorted tetrahedron (Figure 2a). Compound 2 crystallizes in the hexagonal system with the chiral space group P6122. The packing of the distorted tetrahedra shown in Figure 2a leads to a 3-D network, with the characteristic features of a quartz topology, in which the silicon atoms are replaced by copper ions and the oxygen atoms by the organic ligand (Figure 2b): (i) a 3-fold screw axis parallel to the crystallographic c axis; the linking of copper tetrahedra along this axis generate left (M) handed helices (Figure 2c left); (ii) six M helices are interconnected by sharing copper(II) ions, resulting in right (P) double stranded helices running along the c axis as well (Figure 2c bottom). The hexagonal chiral channels have dimensions of 11.3 × 11.3 Å, based on diagonal Cu···Cu distances, and host the crystallization water molecules (Figure S1). Selected bond distances and angles are collected in Table S1. The thermal analysis of 2 shows that the water molecules are completely removed between 40 and 100 ºC (Figure S2). After the elimination of the water molecules, the observed change in the X-Ray powder diffraction pattern indicates that the architecture of the crystal is not preserved. The magnetic properties of compound 2 were investigated in detail.


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Compound 1 shows a low paramagnetic signal at room temperature. This could be interpreted as the combined effects of the strong antiferromagnetic interaction between the two copper ions within the paddle-wheel moiety and the high molecular mass that leads to the partial compensation of the paramagnetic contribution by the diamagnetic components. The temperature dependences of the χMT and of χM-1 for 2 are shown in Figure 3 (χM is the paramagnetic susceptibility). The magnetic behavior of compound 2 is in line with its structure. The large distance between the copper ions suggests the occurrence of weak magnetic interactions. Indeed, by lowering the temperature, χMT remains constant down to 60 K then decreases abruptly showing the onset of antiferromagnetic interactions. The magnetic data were fitted to a CurieWeiss law, leading to the following values: C = 0.42 cm3 mol-1 K and θ = −2.8 K (solid line, Figure 3). In conclusion, we have illustrated for the first time that the substituted pyrazole L− is a versatile ligand, able to generate interesting coordination polymers. Its potential in crystal engineering is not yet explored and deserves further work. Although quartz was one of the first prototypes illustrated by Robson in his seminal papers on coordination polymers mimicking mineral structures,19,20 the number of coordination polymers featuring this topology is still small.21-37 Compound 2 represents a new interesting example. ACKNOWLEDGEMENTS The authors are thankful for financial support provided by FAPERJ, CAPES and CNPq. We also acknowledge LabCri (Universidade Federal de Minas Gerais, Brazil) for crystal data collection and Prof. Dr. Miguel A. Novak for the magnetic measurements. M.A. thanks CNPq for financial support. SUPPORTING INFORMATION Crystallographic data for compounds 1 and 2 in CIF format are available as CCDC-No. 1036567 and 1036568, which can be obtained from The Cambridge Crystallographic

Data

Centre

via

www.ccdc.cam.ac.uk/data_request/cif.

Selected bond distances and angles for 1 and 2 are listed in Table S1. Fig. S1 displays a view of a channel of 2 along the c axis, showing the hosted water


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molecules. The TGA curve of compound 2 is depicted in Fig. S2. This material is

available

free

of

charge

via

the

Internet

at http://pubs.acs.org.


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REFERENCES (1) Cassaro, R. A. A.; Ciattini, S.; Soriano, S.; Amorim, H. S.; Speziali, N. L.; Andruh, M.; Vaz, M. G. F. Cryst. Growth Des. 2013, 13, 2711-2715. (2) Cassaro, R. A. A.; Resende, J. A. L. C.; Santos Jr, S.; Sorace, L.; Andruh, M.; Vaz, M. G. F. CrystEngComm, 2013, 15, 8422-8425. (3) Cai Y.; Kulkarni, A. R.; Huang, Y.-G.; Sholl, D. S.; Walton, K. S. Cryst. Growth Des., 2014, 14, 6122-6128. (4) Eddaoudi, M.; Moler, D. B.; Li, H.; Chen, B.; Reineke, T. M.; O’Keeffe, M.; Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319-330. (5) Zaworotko, M. J. Chem. Commun. 2001, 1-9. (6) Roesky, H. W.; Andruh, M. Coord. Chem. Rev. 2003, 236, 91-119. (7) Kitagawa, S.; Kitaura, R.; Noro, S. Angew. Chem., Int. Ed. 2004, 43, 2334-2375. (8) Oldham, C. In Comprehensive Coordination Chemistry I; Wilkinson, G.; Gillard, R. D.; McCleverty, J. A., Eds.; Pergamon: Oxford, 1987; Vol. 2, p. 435. (9) Zheng, Y.-Z.; Zheng, Z.; Chen, X.-M. Coord. Chem. Rev. 2014, 258-259, 1-15. (10) Zhang, J.-P.; Zhang, Y.-B.; Lin, J.-B.; Chen, X.-M. Chem. Rev. 2012, 112, 10011033. (11) Mukherjee, R. Coord. Chem. Rev. 2000, 203, 151-170. (12) Santos, I. F.; Guedes, G. P.; Mercante, L. A.; Bernardino, A. M. R.; Vaz, M. G. F. J. Mol. Struct. 2012, 1011, 99-104. (13) Olguín, J.; Brooker, S. Coord. Chem. Rev. 2011, 255, 203-240. (14) Hawes, C. S.; Moubaraki, B.; Murray, K. S.; Kruger, P. E.; Turner, D. R.; Batten, S. R. Cryst. Growth Des. 2014, 14, 5749-5760. (15) Zia-ur-Rehman, M.; Elsegood, M. R. J.; Akbar, N.; Saleem, R. S. Z. Acta Crystallogr., Sect. E: Struct. Rep. Online, 2008, 64, o1312-o1312. (16) X-ray crystal data for 1: CCDC 1036567; Formula: C42H40Cu2N12O10; Formula weight: 999.96 g.mol-1; Crystal System: Monoclinic; Space Group: P21; Unit cell dimensions: a = 12.4202(6), b = 13.8430(6), c = 13.9603(8) Å, β=115.446(6)º, Volume = 2167.39(19) Å3; Z=2; D = 1.532

g.cm-3; µ(MoKα) = 1.06 mm-1;

Temperature: 140(2) K; F(000) = 1028; Reflections collected = 14139; R(int) = 5.9 %; No. independent reflections: 8869; No. reflections observed: 7859 ; No. parameters: 38; R1 obs = 6.0%; wR2 obs = 12.3%; R1 all = 9.1%; wR2 all = 11.0%; S = 1.01; ∆ρmax = 0.81 e.Å−3; ∆ρmin = −0.66 e.Å−3. X-ray crystal data for 2: X-ray


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crystal data for 1: CCDC 1036568; Formula: C20H26CuN6O9; Formula weight: 558.01 g.mol-1; Crystal System: Hexagonal; Space Group: P6122; Unit cell dimensions: a = b = 11.3128(16), c = 34.111(7) Å, α=γ= 90º, β=120º, Volume = 3780.6(15) Å3; Z=6; D = 1.471 g.cm-3; µ(CuKα) = 1.76 mm-1; Temperature: 298(2) K; F(000) = 1734; Reflections collected = 45693; R(int) = 3.4 %; No. independent reflections: 2003; No. reflections observed: 2003; No. parameters: 168; R1 obs = 2.5%; wR2 obs = 6.8%; R1 all = 2.6%; wR2 all = 6.7%; S = 1.08; ∆ρmax = 0.14 e.Å−3; ∆ρmin = −0.18 e.Å−3. (17) Uvarova, M. A.; Sinelshchikova, A. A.; Golubnichaya, M. A.; Nefedov, S. E.; Enakieva, Y. Y.; Gorbunova, Y. G.; Tsivadze, A. Y.; Stern, C.; BessmertnykhLemeune, A.; Guilard, R. Cryst. Growth Des. 2014, 14, 5976−5984. (18) Burrows, A. D.; Frost, C. G.; Mahon, M. F.; Winsper, M.; Richardson, C.; Attfield, J. P.; Rodgers, J. A. Dalton Trans. 2008, 6788–6795. (19) Hoskins, B. F.; Robson, R.; Scarlett, N. V. Y. Angew. Chem., Int. Ed. 1995, 34, 1203-1204. (20) Robson, R. Dalton Trans. 2008, 5113-5131. (21) Sun, J.; Weng, L.; Zhou, Y.; Chen, J.; Chen, Z.; Liu, Z.; Zhao, D. Angew. Chem., Int. Ed. 2002, 41, 4471-4473. (22) Luo, T.-T.; Liu, Y.-H.; Chan, C.-C.; Huang, S.-M.; Chang, B.-C.; Lu, Y.-L.; Lee, G.-H.; Peng, S.-M.; Wang, J.-C.; Lu, K.-L. Inorg. Chem. 2007, 46, 10044-10046. (23) Tynan, E.; Jensen, P.; Kelly, N. R.; Kruger, P. E.; Lees, A. C.; Moubaraki, B.; Murray, K. S. Dalton Trans. 2004, 3440-3447. (24) Hu, S.; Tong, M.-L. Dalton Trans. 2005, 1165-1167. (25) Feller, R. K.; Cheetman, A. K. Dalton Trans. 2008, 2034-2042. (26) Guo, Y.; Liu, Z.-Q.; Zhao, B.; Feng, Y.-H.; Xu, G.-F.; Yan, S.-P.; Cheng, P.; Wang, Q.-L.; Liao, D.-Z. CrystEngComm 2009, 11, 61-66. (27) Banerjee, S.; Adrash, N. N.; Dastidar, P. CrystEngComm 2013, 15, 245-248. (28) Zheng, W.; Wei, Y.; Xiao, X.; Wu, K. Dalton Trans. 2012, 41, 3138-3140. (29) Wang, X.-F.; Zhang, Y.-B.; Lin, Y.-Y. CrystEngComm 2013, 15, 3470-3477. (30) Keene, T. D.; Rankine, D.; Evans, J. D.; Southon, P. D.; Kepert, C. J.; Aitken, J. B.; Sumby, C. J.; Doonan, C. J. Dalton Trans. 2013, 42, 7871-7879. (31) Mukerjee, G.; Biradha, K. CrystEngComm 2014, 16, 4701-4705. (32) Yuan, W.-G.; Xiong F.; Zhang, H.-L.; Tang, W.; Zhang, S.-F.; He, Z.; Jing, L.H.; Qin, D.-B. CrystEngComm 2014, 16, 7701-7710.


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(33) Liang, L.-L.; Ren, S.-B.; Zhang, J.; Li, Y.-Z.; Du, H.-B.; You, X.-Z. Cryst. Growth Des. 2010, 10, 1307-1311. (34) Zhang, Q.; Lin, Z.; Bu, X.; Wu, T.; Feng, P. Chem. Mater. 2008, 20, 3239-3241. (35) Su, C.-Y.; Smith, M. D.; Goforth, A. M.; zur Loye, H.-H. Inorg. Chem. 2004, 43, 6881-6883. (36) Wu, J.-C.; Zhao, L.; Wang, D.-X.; Wang, M.-X. Inorg. Chem. 2012, 51, 38603867. (37) Chen, Z.-F.; Zhang, S.-F.; Luo, H.-S.; Abrahams, B. F.; Liang, H. CrystEngComm 2007, 9, 27-29.


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CAPTION TO THE FIGURES Figure 1. (a) The paddle-wheel motif in crystal 1 and its connection to another similar motif (i= −x, 1/2+y, −z); (b) Perspective view of the 1-D coordination polymer 1. Figure 2. (a) Coordination sphere of the copper(II) ions in 2 and the tetrahedral synthon (phenyl groups are removed for clarity); (b) View of the quartz-like network in 2 along the crystallographic c axis; (c) Single and double stranded helical chains in crystal 2. Figure 3. (a) Temperature dependence of χMT for compound 1; (b) Temperature dependences of χMT and χM-1 for compound 2.


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Chart 1


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(a)

(b)

Figure 1


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Figure 2a

Figure 2b


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Figure 2c


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Figure 3


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For Table of Contents Use Only A new quartz-like metal-organic framework constructed from a versatile pyrazole-based spacer Guilherme P. Guedes, Luiza A. Mercante, Igor F. Santos, Nivaldo L. Speziali, Jackson A. L. C. Resende, Alice M. R. Bernardino, Marius Andruh, and Maria G. F. Vaz

Two new coordination polymers, 1∞[Cu2(L)4(MeOH)]⋅MeOH 1 and 3∞[Cu(L)2]•5H2O 2 were obtained using the 5-amino-1-phenyl-1H-pyrazole-4-carboxylate (L−) as spacer. Compound 1 is a 1D system formed by paddle-wheel units connected to each other through the pyrazole rings, while 2 crystallizes in the chiral space group P6122 and features a quartz-like topology.


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A New Quartz-like Metal–Organic Framework Constructed from a

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