The new salt bis(4,5-dihydro-1H-benzo[g]indazole)silver(I) hexafluorophosphate, [Ag(N2H10C11)2]PF6, has been synthesized in methanol at ambient temperature and characterized by elemental and thermal analyses, FTIR and 1HNMR spectroscopies, Rietveld refinement from powder diffraction data and DFT studies. The salt crystallizes in the triclinic space group P-1 with the parameters: a = 7.776 ?, b = 8.676 ?, c = 9.226 ?, α = 69.27° β = 89.86°, γ = 74.50°, V = 558.02 ?3, Z = 1. In the structure, the silver center is coordinated to two nitrogen atoms from two 4,5-dihydro-1H-benzo[g]indazole ligands, forming a centrosymmetric complex cation, [Ag(N2H10C11)2]+, with a linear coordination geometry around the silver center. The hexafluorophosphate ion, , acts as counter anion. The crystal packing is governed by N-H···F and C-H···F hydrogen bonds that interconnect the ionic constituents and Ag···F and Ag···π interactions help for the stabilization of the packing. The optimized structure was obtained at B3LYP/LanL2DZ level in the gas phase. The stability and reactivity of the structure were studied using respectively HOMO-LUMO gap and electronic global quantities (ionization potential (I) and electron affinity (A)) as descriptors.
References
[1]
Menozzi, G., Mosti, L., Schenone, P., D’Amico, M., Falciani, M. and Filippelli, W. (1994) 1-Aryl-1H-Pyrazole-5-Acetic Acids with Anti-Inflammatory, Analgesic and Other Activities. Farmaco, 49, 115-119.
[2]
Soliman, R., Habib, N.S., Ashour, F.A. and El-Taiebi, M. (2001) Synthesis and Antimicrobial Activity of Novel Pyrazole, Pyrazoline, Pyrazolinone and Pyrazolidinedione Derivatives of Benzimidazole. Bollettino Chimico Farmaceutico, 140, 140-148.
Trofimenko, S. (1972) The Coordination Chemistry of Pyrazole-Derived Ligands Chemical Reviews, 72, 497-509.
[5]
Ten-Hoedt, R.W., Driessen, W.L. and Verschoor, G. (1983) Structure of Hexakis(pyrazole) nickel(II) Bis(tetrafluoroborate), [Ni(C3H4N2)6](BF4)2. Acta Crystallographica, C39, 71-72.
[6]
Reimann, C.W., Santoro, A. and Mighell, A.D. (1970) The Crystal and Molecular Structure of Hexapyrazolenickel(II) Nitrate, Ni(C3H4N2)6(NO3)2. Acta Crystallographica, B26, 521-526. https://doi.org/10.1107/S0567740870002741
[7]
Lumme, P.O., Lindell, E. and Mutikainen, I. (1988) Trans-Hexakis(pyrazole)manganese(II) Bisperchlorate (1) and Trans-Dichlorotetrakis(pyrazole)manganese(II) (2). Acta Crystallographica, C44, 967-970. https://doi.org/10.1107/S0108270188001131
[8]
Pettinari, C., Marinelli, A., Marchetti, F., Ngoune, J., Gallindo, A., Alvarez, E. and Gomez, M. (2010) Sythesis and Coordination Chemistry of Two N2-Donor Chelating Di(indazolyl)methane Ligands: Structural Characterization and Comparison of their Metal Chelating Aptitudes. Inorganic Chemistry, 49, 10543-10556.
https://doi.org/10.1021/ic101577k
[9]
Ding, L., Grehn, L., De Clercq, E., Andrei, G., Snoeck, R., Balzarini, J., Fransson, B. and Ragnarsson, U. (1994) Synthesis and Antiviral Activity of Three Pyrazole Analogues of Distamycin A. Acta Chemica Scandinavica, 48, 498-505.
https://doi.org/10.3891/acta.chem.scand.48-0498
[10]
Goslar, J., Sczaniecki, P.B., Strawiak, M.M. and Mrozinski, J. (1988) Chemical-Properties, Magnetic and Epr Studies of Pyrazole Copper(II) Complexes. Transition Metal Chemistry, 13, 81-86. https://doi.org/10.1007/BF01087793
[11]
Ovejero, P., Mayoral, M.J., Cano, M. and Lagunas, M.C. (2007) Luminescence of Neutral and Ionic Gold(I) Complexes Containing Pyrazole or Pyrazolate-Type Ligands. Journal of Organometallic Chemistry, 692, 1690-1697.
[12]
Sakai, K., Tomista, Y., Ue, T., Goshima, K., Ohminato, M., Tsubomura, T., Matsumoto, K., Ohmura, K. and Kawakami, K. (2000) Syntheses, Antitumor Activity, and Molecular Mechanics Studies of Cis-PtCl2(pzH)2 (pzH = pyrazole) and Related Complexes. Crystal Structure of a Novel Magnus-Type Double-Salt [Pt(pzH)4][PtCl4][cis-PtCl2(pzH)2]2 Involving Two Perpendicularly Aligned 1D Chains. Inorganica Chimica Acta, 297, 64-71.
[13]
Kratz, F., Nuber, B., Weiss, J. and Keppler, B.K. (1992) Synthesis and Characterization of Potential Antitumour and Antiviral Gallium(III) Complexes of N-Heterocycles. Polyhedron, 11, 487-498.
[14]
Schore, N.E. (2007) Study Guide and Solutions Manual for Organic Chemistry: Structure and Function. 5th Edition, W.H. Freeman and Company, New York.
Fomuta, T.R., Djimassingar, G., Ngoune, J., Ngnabeuye, N.O., Anguile, J.J. and Nenwa, J. (2017) Synthesis, Structural Characterization and DFT Studies of Silver(I) Complex Salt of Bis(4,5-dihydro-1H-benzo[g]indazole). Crystal Structure Theory and Applications, 6, 11-24. https://doi.org/10.4236/csta.2017.62002
[17]
TOPAS-R (2005) V.3.0, Bruker AXS, Karlsruhe, Germany.
[18]
March, A.Z. (1932) Mathematische Theorie der Regelung nach der Korngestah bei Affiner Deformation. Kristallographie, 81, 285-297.
https://doi.org/10.1524/zkri.1932.81.1.285
[19]
Dollase, W.A. (1986) Correction of Intensities for Preferred Orientation in Powder Diffractometry: Application of the March Model. Journal of Applied Crystallography, 19, 267-272. https://doi.org/10.1107/S0021889886089458
[20]
Amsterdam Density Functional (ADF) Version 2007.01. http://www.scm.com
[21]
Umadevi, P. and Lalitha, P. (2012) Synthesis and Antimicrobial Evaluation of Imino Substituted 1, 3, 4 Oxa and Thiadiazoles. International Journal of Pharmacy and Pharmaceutical Sciences, 4, 523-527.
[22]
Mebi, A.C. (2011) DFT Study on Structure, Electronic Properties, and Reactivity of Cis-Isomers of [(NC5H4-S)2Fe(CO)2]. Journal of Chemical Sciences, 123, 727-731.
https://doi.org/10.1007/s12039-011-0131-2
[23]
Nazmul, I. and Dulal, C.G. (2012) On the Electrophilic Character of Molecules through Its Relation with Electronegativity and Chemical Hardness. International Journal of Molecular Sciences, 13, 2160-2175. https://doi.org/10.3390/ijms13022160
[24]
Sayed, I., Kosy, S.M., Abdel, M.F., Hamed, M.A., Gokha, A.A. and Sattar, M.M.A. (2011) One-Pot Synthesis of Novel α-Aminophosphonate Derivatives Containing a Pyrazole Moiety. Journal of American Science, 7, 604-608.
[25]
Swarnkar, D., Ameta, R. and Vyas, R. (2014) Microwave Assisted Synthesis of Some Pyrazole Derivatives and Their Antibacterial and Antifungal Activity. The Pharma Innovation Journal, 3, 5-9.
[26]
Calhorda, M., Costa, P.J., Crespo, M.O., Gimeno, C., Jones, P.G., Laguna, A., Naranjo, M., Quintal, S., Shia, Y. and Villacampa, M.D. (2006) Group 11 Complexes with the Bis(3,5-dimethylpyrazol-1-yl)methane Ligand. How Secondary Bonds can Influence the Coordination Environment of Ag(I): The Role of Coordinated Water in [Ag2(μ-L)2(OH2)2](OTf)2. Dalton Transactions, 34, 4104-4113.
https://doi.org/10.1039/B605034D
[27]
Beheshti, A., Zafarian, H.R., Khorramdin, R., Monavvar, M.F. and Carmel, T.A. (2012) Novel Silver(I) Pyrazole-Based Coordination Polymers: Synthetic and Structural Studies. Polyhedron, 48, 245-252.
[28]
Ramasamy, R. (2015) Vibrational Spectroscopic Studies of Imidazole. Armenian Journal of Physics, 8, 51-55.
[29]
Yongxiu, L. and Zhaoai, N. (1993) The Coordination between Silver Nitrate and Open Chain Polyether. Transactions of Nonferrous Metals Society of China, 3, 38-41.