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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

ZnII Complexes Based on Hybrid N-Pyrazole, N′-imine Ligands: Synthesis, X-Ray Crystal Structure, NMR Characterisation, and 3D Supramolecular Properties

Miguel Guerrero A , Lourdes Rivas A , Teresa Calvet B , Mercè Font-Bardia B C and Josefina Pons A D
+ Author Affiliations
- Author Affiliations

A Departament de Química, Universitat Autònoma de Barcelona, 08193-Bellaterra, Barcelona, Spain.

B Cristallografia, Mineralogia i Dipòsits Minerals, Universitat de Barcelona, Martí i Franquès s/n, 08028-Barcelona, Spain.

C Unitat de Difracció de Raig-X, Centres Científics i Tecnològics de la Universitat de Barcelona (CCiTUB), Universitat de Barcelona, Solé i Sabaris, 1-3, 08028-Barcelona, Spain.

D Corresponding author. Email: Josefina.Pons@uab.es

Australian Journal of Chemistry 68(5) 749-757 https://doi.org/10.1071/CH14344
Submitted: 29 May 2014  Accepted: 29 July 2014   Published: 14 October 2014

Abstract

The present report is on the synthesis of two new 3-imine-3,5-dimethylpyrazole ligands, N-[3-(3,5-dimethyl-1H-pyrazol-1-yl)propylidene]ethylamine (L1) and N-[3-(3,5-dimethyl-1H-pyrazol-1-yl)propylidene]propylamine (L2). These ligands form molecular complexes with the formula [ZnCl2(L)] (L = L1 (1) and L2 (2)) when the reacting with ZnCl2 in a metal (M)/ligand (L) ratio of 1 : 1. These new ZnII complexes have been characterised by elemental analyses, conductivity measurements, mass spectrometry, and infrared, 1H and 13C{1H} NMR spectroscopy techniques. The two crystalline structures of complexes 1 and 2 have been solved by X-ray diffraction methods. Finally, we have studied the self-assembly three-dimensional supramolecular structure through different intra- and intermolecular contacts. The application of these ZnII complexes in supramolecular crystal engineering is interesting due to (1) the easy preparation and the high efficiency of this system and (2) the different bonding properties of the heteroatoms (N-pyrazole vs N-imine) present in the structure of the ligands.


References

[1]  (a) L. E. Kreno, K. Leong, O. K. Farha, M. Allendorf, R. P. Van Duyne, J. T. Hupp, Chem. Rev. 2012, 112, 1105.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhsVCgtL%2FI&md5=e75459a9fbf8784addf4d6b6c9fd5fc9CAS | 22070233PubMed |
      (b) A. A. Talin, A. Centrone, A. C. Ford, M. E. Foster, V. Stavila, P. Haney, R. A. Kinney, V. Szalai, F. Gabaly, H. P. Yoon, F. Léonard, M. D. Allendorf, Science 2014, 343, 66.
         | Crossref | GoogleScholarGoogle Scholar |

[2]  (a) P. Cordier, F. Tournilhac, C. Soulie-Zikovic, L. Liebler, Nature 2008, 451, 977.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXit1yns70%3D&md5=0e54d126642a500759f2e361459025e9CAS | 18288191PubMed |
      (b) H. J. Schneider, R. M. Strongin, Accounts Chem. Res. 2009, 42, 1489.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) N. N. Adarsh, P. Dastidar, Chem. Soc. Rev. 2012, 41, 3039.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) N. Robertson, L. Cronin, Coord. Chem. Rev. 2002, 227, 93.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) E. Lindler, T. Schneller, F. Auer, H. A. Mayer, Angew. Chem., Int. Ed. 1999, 38, 2155.
      (f) V. V. Grushin, Chem. Rev. 2004, 104, 1629.
         | Crossref | GoogleScholarGoogle Scholar |
      (g) A. L. Gavrilova, B. Bosnich, Chem. Rev. 2004, 104, 349.
         | Crossref | GoogleScholarGoogle Scholar |

[3]  (a) J. Pons, J. Ros, M. Llagostera, J. A. Pérez, M. Ferrer, Spanish Patent 01494 2003,
      (b) R. W.-Y. Sun, D. L. Ma, E. L.-M. Wong, C. M. Che, Dalton Trans. 2007, 4884.
      (c) A. Satake, T. Nakata, J. Am. Chem. Soc. 1998, 120, 10391.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) C. Navarro-Ranninger, L. López-Solera, V. M. González, J. M. Pérez, A. Alvarez-Valdes, A. Martín, P. R. Raithby, J. R. Massager, C. Alonso, Inorg. Chem. 1996, 35, 5181.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) K. Sakai, Y. Tomita, T. Ue, K. Goshima, M. Ohminato, T. Tsubomura, K. Matsumoto, K. Ohmura, K. Kawakami, Inorg. Chim. Acta 2000, 297, 64.
         | Crossref | GoogleScholarGoogle Scholar |

[4]  (a) M. Guerrero, J. Pons, V. Branchadell, T. Parella, X. Solans, M. Font-Bardía, J. Ros, Inorg. Chem. 2008, 47, 11084.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXhtlSlsrbN&md5=f9dab0365ef3b2dbb47cc5a49fef6e7fCAS | 19228024PubMed |
      (b) A. de León, M. Guerrero, J. García-Antón, J. Ros, M. Font-Bardía, J. Pons, CrystEngComm 2013, 15, 1762.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) J. J. Neuman, M. Suri, G. Frank, Angew. Chem., Int. Ed. Engl. 2010, 49, 7790.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) M. Guerrero, J. A. Pérez, T. Calvet, M. Font-Bardía, J. Pons, Aust. J. Chem. 2013, 66, 685.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) J. M. Lehn, Science 1993, 260, 1762.
         | Crossref | GoogleScholarGoogle Scholar |
      (f) C. A. Mirkin, M. A. Ratner, Annu. Rev. Phys. Chem. 1992, 43, 719.
         | Crossref | GoogleScholarGoogle Scholar |

[5]  (a) J. Pérez, L. Riera, Eur. J. Inorg. Chem. 2009, 4913.
         | Crossref | GoogleScholarGoogle Scholar |
      (b) M. Guerrero, J. Pons, J. Ros, J. Organomet. Chem. 2010, 695, 1957.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) V. Montoya, J. Pons, V. Branchadell, J. García-Antón, X. Solans, M. Font-Bardía, J. Ros, Organometallics 2008, 27, 1084.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) J. Y. Lee, O. K. Farha, J. Roberts, K. Scheidt, S. T. Nguyen, J. T. Hupp, Chem. Soc. Rev. 2009, 38, 1450.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) D. Peral, F. Gómez-Villarraga, X. Sala, J. Pons, J. C. Bayón, J. Ros, M. Guerrero, L. Vendier, P. Lecante, J. García-Antón, K. Philippot, Catal. Sci. Technol. 2013, 3, 475.
         | Crossref | GoogleScholarGoogle Scholar |
      (f) S. Ojwach, J. Darkwa, Inorg. Chim. Acta 2010, 363, 1947.
         | Crossref | GoogleScholarGoogle Scholar |

[6]  (a) J. Yang, B. Wu, F. Y. Zhuge, J. J. Liang, C. D. Jia, Y. Y. Wang, N. Tang, X. J. Yang, Q. Z. Shi, Cryst. Growth Des. 2010, 10, 2331.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXkvV2kurs%3D&md5=11b99a1b6d30b8bb653091fe8593ef1cCAS |
      (b) H. Fleischer, Y. Dienes, B. Mathiasch, V. Schmitt, D. Schollmeyer, Inorg. Chem. 2005, 44, 8087.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) M. Guerrero, J. Pons, M. Font-Bardia, T. Calvet, J. Ros, Polyhedron 2010, 29, 1083.
         | Crossref | GoogleScholarGoogle Scholar |

[7]  (a) S. Muñoz, J. Pons, J. Ros, C. A. Kilner, M. A. Halcrow, J. Organomet. Chem. 2011, 696, 2736.
         | Crossref | GoogleScholarGoogle Scholar |
      (b) G. Esquius, J. Pons, R. Yáñez, J. Ros, R. Mathieu, N. Lugan, B. Donnadieu, J. Organomet. Chem. 2003, 667, 126.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) G. Esquius, J. Pons, R. Yáñez, J. Ros, R. Mathieu, B. Donnadieu, N. Lugan, Eur. J. Inorg. Chem. 2002, 2999.
         | Crossref | GoogleScholarGoogle Scholar |

[8]  (a) S. Muñoz, M. Guerrero, J. Ros, T. Parella, M. Font-Bardía, J. Pons, Cryst. Growth Des. 2012, 12, 6234.
         | Crossref | GoogleScholarGoogle Scholar |
      (b) S. Muñoz, J. Pons, J. García-Antón, X. Solans, M. Font-Bardía, J. Ros, J. Coord. Chem. 2009, 62, 3940.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) S. Muñoz, J. Pons, X. Solans, M. Font-Bardía, J. Ros, J. Organomet. Chem. 2008, 693, 2132.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) R. Tribó, S. Muñoz, J. Pons, R. Yáñez, A. Alvarez-Larena, J. F. Piniella, J. Ros, J. Organomet. Chem. 2005, 690, 4072.
         | Crossref | GoogleScholarGoogle Scholar |

[9]  (a) M. Guerrero, J. A. Pérez, M. Font-Bardía, J. Pons, J. Coord. Chem. 2013, 66, 3314.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXhtlGlu77N&md5=521ff5407e09805cfbaad8691846fc0dCAS |
      (b) J. A. Pérez, V. Montoya, J. A. Ayllón, M. Font-Bardía, T. Calvet, J. Pons, Inorg. Chim. Acta 2013, 394, 21.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) M. Guerrero, J. Pons, J. Ros, M. Font-Bardía, O. Vallcorba, J. Rius, V. Branchadell, A. Merkoçi, CrystEngComm 2011, 13, 6457.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) S. Muñoz, J. Pons, J. Ros, M. Font-Bardía, C. A. Kilner, M. A. Halcrow, Inorg. Chim. Acta 2011, 373, 211.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) C. Luque, J. Pons, T. Calvet, M. Font-Bardía, J. García-Antón, J. Ros, Inorg. Chim. Acta 2011, 367, 35.
         | Crossref | GoogleScholarGoogle Scholar |
      (f) V. Montoya, J. Pons, X. Solans, M. Font-Bardía, J. Ros, Inorg. Chim. Acta 2007, 360, 625.
         | Crossref | GoogleScholarGoogle Scholar |
      (g) A. Boixassa, J. Pons, X. Solans, M. Font-Bardía, J. Ros, Inorg. Chim. Acta 2004, 357, 733.
         | Crossref | GoogleScholarGoogle Scholar |
      (h) A. Boixassa, J. Pons, X. Solans, M. Font-Bardía, J. Ros, Inorg. Chim. Acta 2003, 355, 254.
         | Crossref | GoogleScholarGoogle Scholar |
      (i) A. Boixassa, J. Pons, X. Solans, M. Font-Bardía, J. Ros, Inorg. Chim. Acta 2002, 340, 49.
         | Crossref | GoogleScholarGoogle Scholar |

[10]  (a) J. García-Antón, J. Pons, X. Solans, M. Font-Bardía, J. Ros, Inorg. Chim. Acta 2004, 357, 571.
         | Crossref | GoogleScholarGoogle Scholar |
      (b) J. García-Antón, J. Pons, X. Solans, M. Font-Bardía, J. Ros, Inorg. Chim. Acta 2003, 355, 87.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) J. García-Antón, J. Pons, X. Solans, M. Font-Bardía, J. Ros, Eur. J. Inorg. Chem. 2003, 2992.
         | Crossref | GoogleScholarGoogle Scholar |

[11]  (a) M. C. Castellano, J. Pons, J. García-Antón, X. Solans, M. Font-Bardía, J. Ros, Inorg. Chim. Acta 2008, 361, 2923.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXntlams7s%3D&md5=df4d961b35cb4aab5c65d31c42f2a467CAS |
      (b) J. Pons, J. García-Antón, M. Font-Bardía, T. Calvet, J. Ros, Inorg. Chim. Acta 2009, 362, 2698.
         | Crossref | GoogleScholarGoogle Scholar |

[12]  A. Simion, C. Simion, T. Kanda, S. Nagashima, Y. Mitoma, T. Yamada, K. Mimura, M. Tashiro, J. Chem. Soc., Perkin Trans 1 2001, 2001, 2071.
         | Crossref | GoogleScholarGoogle Scholar |

[13]  O. S. Attaryan, S. K. Antanosyan, F. S. Kinoyan, R. A. Tamazyan, G. A. Panosyan, S. G. Matsoyan, Russ. J. Org. Chem. 2006, 42, 1868.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXlt1OktA%3D%3D&md5=08230f5c3fd5d254d62f867a56fbfb69CAS |

[14]     (a) E. Pretsh, T. Clerc, J. Seibl, W. Simon, Tables of Determination of Organic Compounds. 13C NMR, 1H NMR, IR, MS, UV/Vis, Chemical Laboratory Practice 1989 (Springer-Verlag: Berlin, Germany).
         (b) D. H. Williams, I. Fleming, Spectroscopic Methods in Organic Chemistry 1995 (McGraw-Hill: London, UK).

[15]  (a) L. K. Thompson, F. I. Lee, E. J. Gabe, Inorg. Chem. 1988, 27, 39.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1cXkslOqsw%3D%3D&md5=bd33af8040e7ed5e72e8e5f3318dae51CAS |
      (b) W. J. Geary, Coord. Chem. Rev. 1971, 7, 81.
         | Crossref | GoogleScholarGoogle Scholar |

[16]  P. H. M. Butzelaar, g NMR ver. 4.0. IvorySoft 1997 (Cherwell Scientific: Oxford, UK).

[17]  (a) C. Y. Wang, Acta Crystallogr., Sect.E: Struct. Rep. Online 2011, 67, m1085.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXpslahsr4%3D&md5=818b509c10b5fb65df6c7927b1de2ad7CAS |
      (b) U. Köhn, M. Klopfleisch, H. Görls, E. Anders, Tetrahedron: Asymmetry 2006, 17, 811.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) U. Köhn, M. Schulz, H. Görls, E. Anders, Tetrahedron: Asymmetry 2005, 16, 2125.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) M. Amirnasr, A. H. Mahmoudkani, A. Gorji, S. Dehghanpour, H. R. Bijanzadeh, Polyhedron 2002, 21, 2733.
         | Crossref | GoogleScholarGoogle Scholar |

[18]  (a) S. Bieller, A. Haghiri, M. Bolte, J. W. Bats, M. Wagner, H. W. Lerner, Inorg. Chim. Acta 2006, 359, 1559.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XhvF2qtr4%3D&md5=8597a6c0307d779f626b5fba6adf4247CAS |
      (b) A. M. Schuitema, M. Engelen, I. A. Koval, S. Gorter, W. L. Driessen, J. Reedijk, Inorg. Chim. Acta 2001, 324, 57.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) C. J. Tokar, P. B. Kettler, W. B. Tolman, Organometallics 1992, 11, 2737.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) M. Guerrero, J. Pons, T. Parella, M. Font-Bardía, T. Calvet, J. Ros, Inorg. Chem. 2009, 48, 8736.
         | Crossref | GoogleScholarGoogle Scholar |

[19]  (a) U. Köhn, M. Schulz, H. Görls, E. Anders, Tetrahedron: Asymmetry 2005, 16, 2125.
         | Crossref | GoogleScholarGoogle Scholar |
      (b) U. Köhn, M. Schulz, H. Görls, E. Anders, Tetrahedron: Asymmetry 2006, 17, 811.
         | Crossref | GoogleScholarGoogle Scholar |

[20]  (a) A. Ustinov, H. Weissman, E. Shirman, I. Pinkas, X. B. Zuo, B. Rybtchinski, J. Am. Chem. Soc. 2011, 133, 16201.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXht1SrsrnP&md5=de8469b9b3770b49b306504f12ffdeb8CAS | 21882828PubMed |
      (b) B. Bhayana, C. S. Wilcox, Angew. Chem., Int. Ed. 2007, 46, 6833.
         | Crossref | GoogleScholarGoogle Scholar |

[21]  G. M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr. 2008, 64, 112.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXhsVGhurzO&md5=e60798290754f1a9dfe9beb4e8e0b93dCAS |