Abstract
Acyl-pyrazolones exist in four different tautomeric forms (two keto and two enol) in crystal structures. Routine crystal structure refinements using an independent atom model and routine isolated-molecule calculations fail in locating the mobile hydrogen atoms accurately in 22 investigated acyl-pyrazolone examples. However, a combination of both within the framework of quantum crystallography represented by the method of Hirshfeld atom refinement accurately locates the mobile hydrogen atom in a resonance-assisted hydrogen bond of title compound 3, a novel photolysis product. The impact of the hydrogen atom position on the resonance system of the non-hydrogen framework of the various tautomers is discussed, and the importance of intermolecular interactions for the positioning of the hydrogen atom is highlighted.
Similar content being viewed by others
Change history
22 August 2017
An erratum to this article has been published.
References
Antonov L (2013) Tautomerism: methods and theories. John Wiley & Sons,
Ädelroth P (2006) Special issue on proton transfer in biological systems Biochimica et Biophysica Acta (BBA)-Bioenergetics 1757(8):867–870
Geraldes C, Barros M, Maycock C, Silva M (1990) The preferential direction of enolization of some asymmetric 1, 3-dicarbonyl compounds in solution: a study by multinuclear NMR spectroscopy J Mol Struct 238:335–346
Allen G, Dwek RA (1966) An nmr study of keto–enol tautomerism in β-diketones. Journal of the Chemical Society B, Physical Organic, pp. 161–163
Zheglova D, Denkov N, Kol'tsov A (1984) Influence of intramolecular hydrogen bonds on the tautomeric equilibrium of 1,3-diketones J Mol Struct 115:371–374
Jones RD (1976) The crystal structure of the enol tautomer of 1,3-diphenyl-1,3-propanedione (dibenzoylmethane) by neutron diffraction Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry 32(6):1807–1811
Gilli G, Gilli P (2000) Towards an unified hydrogen-bond theory J Mol Struct 552(1):1–15
Cleland W (2000) Low-barrier hydrogen bonds and enzymatic catalysis Arch Biochem Biophys 382(1):1–5
Cleland WW, Kreevoy MM (1994) Low-barrier hydrogen bonds and enzymic catalysis Science 264(5167):1887–1887
Schiøtt B, Iversen BB, Madsen GKH, Larsen FK, Bruice TC (1998) On the electronic nature of low-barrier hydrogen bonds in enzymatic reactions Proc Natl Acad Sci 95(22):12799–12802
CCDC (2014) ConQuest version 1.17- CSD version 5.36 (May 2015)
Akama Y, Shiro M, Ueda T, Kajitani M (1995) Keto and enol tautomers of 4-benzoyl-3-methyl-1-phenyl-5 (2H)-pyrazolone Acta Crystallogr Sect C: Cryst Struct Commun 51(7):1310–1314 (CCDC: YUYDOL ( enol ), DEBFAR02 ( keto ))
Gloe K, Uzoukwu BA, Rademacher O (2000) 4-acetyl-5-methyl-2-phenyl-1, 2-dihydro-3H-pyrazol-3-one hydrate Acta Crystallogr Sect C: Cryst Struct Commun 56(12):e580–e581 (CCDC: XEGVEK)
Holzer W, Mereiter K, Plagens B (1999) 4-acyl-5-methyl-2-phenylpyrazolones: NMR and X-ray structure investigations Heterocycles 2(50):799–818 (CCDC: CIQFEN ( enol ), CIQDUB ( enol ), CIQFAJ ( keto ))
Guard JA, Steel PJ (1994) Heterocyclic tautomerism. VII. X-ray structures of two crystalline tautomers of 4-cinnamoyl-1, 3-dimethylpyrazol-5-one Aust J Chem 47(8):1453–1459 (CCDC: HESTUU ( enol ), HESTOO ( keto ))
Kataeva ON, Gubaidullin AT, Litvinov IA, Lodochnikova OA, Islamov LR, Movchan AI, Chmutova GA (2002) The structure of 1-phenyl-3-benzoylamino-4-benzoylpyrazol-2-in-5-one J Mol Struct 610(1):175–179 (CCDC: MUGQIO)
Cingolani A, Marchetti F, Pettinari C, Pettinari R, Skelton BW, White AH (2004) A 4-acyl-5-pyrazolone ligand (HQ) in N-unidentate coordination mode in a Rh(CO)2Cl (HQ)-type complex Inorg Chem Commun 7(2):235–237 (CCDC: ASELEP)
Pettinari R, Pettinari C, Marchetti F, Skelton BW, White AH, Bonfili L, Cuccioloni M, Mozzicafreddo M, Cecarini V, Angeletti M (2014) Arene–ruthenium (II) acylpyrazolonato complexes: apoptosis-promoting effects on human cancer cells J Med Chem 57(11):4532–4542 (CCDC: ZOJZAB)
Pettinari C, Marchetti F, Pettinari R, Natanti P, Drozdov A, Semenov S, Troyanov SI, Zolin V (2006) Syntheses, spectroscopic characterization and X-ray structural studies of lanthanide complexes with adamantyl substituted 4-acylpyrazol-5-one Inorg Chim Acta 359(12):4063–4070 (CCDC: MELNEX)
Remya P, Suresh C, Reddy M (2007) Rapid reduction and complexation of vanadium by 1-phenyl-3-methyl-4-toluoyl-5-pyrazolone: spectroscopic characterization and structure modelling Polyhedron 26(17):5016–5022 (CCDC: VIMPAJ)
Cingolani A, Effendy, Marchetti F, Pettinari C, Pettinari R, Skelton BW, White AH (2002) First structurally characterized silver (I) derivatives with nonfluorinated β-Diketones Inorg Chem 41(5):1151–1161 (C2/c phase; CCDC: ADURIA)
Sheikh TU, Khan MA, Arshad MN, Khan IU, Stoeckli-Evans H (2009) 1-(5-Hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl) ethanone: a new monoclinic polymorph Acta Crystallogr Sect E: Struct Rep Online 65(2):o330–o330 (P21/n phase; CCDC: ADURIA01)
Shi M, Li F, Yi T, Zhang D, Hu H, Huang C (2005) Tuning the triplet energy levels of pyrazolone ligands to match the 5D0 level of europium (III) Inorg Chem 44(24):8929–8936 (CCDC: RAXXUK)
Begantsova YE, Bochkarev LN, Malysheva IP, Stolyarova NE, Kurskii YA, Lopatin MA, Baranov EV, Ilichev VA, Abakumov GA, Bochkarev MN (2011) Synthesis, photo-and electroluminescent properties of norbornene based platinum-containing copolymers Synth Met 161(11):1043–1050 (CCDC: ASUPUA)
Uzoukwu AB, Al-Juaid SS, Hitchcock PB, Smith JD (1993) The synthesis and crystal structures of 1-phenyl-3-methyl-4-butanolypyrazol-5-one and of two pyrazolonato complexes of iron Polyhedron 12(22):2719–2724 (CCDC: LELDIP)
O'Connell M, Ramsay C, Steel P (1985) Heterocyclic Tautomerism. II. 4-Acylpyrazolones. X-ray crystal structures of 4-benzoyl-5-methyl-2-phenylpyrazol-3 (2H)-one and 4-Acetoacetyl-3-methyl-1-phenylpyrazol-5-ol Aust J Chem 38(3):401–409 (CCDC: DEBFAR, DEBFEV)
Marchetti F, Marinelli A, Pettinari C, Skelton BW, White AH (2011) Binuclear diorganotin (IV) complexes with bis (O, O′-4-acyl-5-pyrazolonato) bis (bidentate) ligands Inorg Chim Acta 366(1):388–393 (CCDC: ULUFOX)
Deng G-M, Zhang H-M, Ou-Yang L-Q, Tong Q-Z, Li S (2012) [1-(4-Chlorophenyl)-5-hydroxy-3-phenyl-1H-pyrazol-4-yl](thiophen-2-yl) methanone Acta Crystallogr Sect E: Struct Rep Online 68(6):o1639–o1639 (CCDC: PAXWUI)
Li J-Z, Zhang H-Q, Li H-X, Che P-Z, Wang T-C (2007) 1-(4-Chlorophenyl)-4-(2-furoyl)-3-(2-furyl)-1H-pyrazol-5-ol Acta Crystallogr Sect E: Struct Rep Online 63(3):o1289–o1290 (CCDC: DEYSIK)
Elguero J (2011) Polymorphism and desmotropy in heterocyclic crystal structures Cryst Growth Des 11(11):4731–4738
Desiraju GR (2008) Polymorphism: the same and not quite the same Crystal Growth Des 8(1):3–5
Marchetti F, Pettinari C, Pettinari R (2005) Acylpyrazolone ligands: synthesis, structures, metal coordination chemistry and applications Coord Chem Rev 249(24):2909–2945
Malaspina LA, Edwards AJ, Woinska M, Jayatilaka D, Turner MJ, Price JR, Herbst-Irmer R, Sugimoto K, Nishibori E, Grabowsky S (2017) Predicting the position of the hydrogen atom in the short intramolecular hydrogen bond of the hydrogen maleate anion from geometric correlations Cryst Growth Des 17:3812–3825
Hoser AA, Dominiak PM, Woźniak K (2009) Towards the best model for H atoms in experimental charge-density refinement Acta Crystallogr A: Found Crystallogr 65(4):300–311
Allen FH, Bruno IJ (2010) Bond lengths in organic and metal-organic compounds revisited: X—H bond lengths from neutron diffraction data Acta Crystallogr Sect B: Struct Sci 66(3):380–386
Lusi M, Barbour LJ (2011) Determining hydrogen atom positions for hydrogen bonded interactions: a distance-dependent neutron-normalized method Crystal Growth Des 11(12):5515–5521
Deringer VL, Hoepfner V, Dronskowski R (2012) Accurate hydrogen positions in organic crystals: assessing a quantum-chemical aide Cryst Growth Des 12(2):1014–1021
Dittrich B, Lübben J, Mebs S, Wagner A, Luger P, Flaig R (2017) Accurate bond lengths to hydrogen atoms from single-crystal X-ray diffraction by including estimated hydrogen ADPs and comparison to neutron and QM/MM benchmarks Chem Eur J 23:4605–4614
Dittrich B, Hübschle C, Pröpper K, Dietrich F, Stolper T, Holstein J (2013) The generalized invariom database (GID) Acta Crystallogr Sect B: Struct Sci Cryst Eng Mater 69(2):91–104
Jarzembska KN, Dominiak PM (2012) New version of the theoretical databank of transferable aspherical pseudoatoms, UBDB2011—towards nucleic acid modelling Acta Crystallogr A: Found Crystallogr 68(1):139–147
Domagała S, Fournier B, Liebschner D, Guillot B, Jelsch C (2012) An improved experimental databank of transferable multipolar atom models–ELMAM2. Construction details and applications Acta Crystallogr A: Found Crystallogr 68(3):337–351
Jayatilaka D, Dittrich B (2008) X-ray structure refinement using aspherical atomic density functions obtained from quantum-mechanical calculations Acta Crystallogr A: Found Crystallogr 64(3):383–393
Capelli SC, Bürgi HB, Dittrich B, Grabowsky S, Jayatilaka D (2014) Hirshfeld atom refinement IUCrJ 1(5):361–379
Woińska M, Grabowsky S, Dominiak PM, Woźniak K, Jayatilaka D (2016) Hydrogen atoms can be located accurately and precisely by x-ray crystallography Sci Adv 2(5):e1600192
Woińska M, Jayatilaka D, Spackman MA, Edwards AJ, Dominiak PM, Wozniak K, Nishibori E, Sugimoto K, Grabowsky S (2014) Hirshfeld atom refinement for modelling strong hydrogen bonds Acta Crystallogr Section A: Found Adv 70(5):483–498
Grabowsky S, Genoni A, Bürgi HB (2017) Quantum crystallography Chem Sci 8:4159–4176
Massa L, Huang L, Karle J (1995) Quantum crystallography and the use of kernel projector matrices Int J Quantum Chem 56(S29):371–384
Huang L, Massa L, Karle J (1999) Quantum crystallography applied to crystalline maleic anhydride Int J Quantum Chem 73(5):439–450
Sheldrick GM (2008) A short history of SHELX Acta Crystallogr Section A 64(1):112–122
Wege D (1998) In: Thummel RP (ed) Advances in theoretically interesting molecules, vol 4. JAI Press Inc., Stamford, Connecticut, and London, U.K.
Hixson SS, Mariano PS, Zimmerman HE (1973) Di-. pi.-methane and oxa-di-. pi.-methane rearrangements Chem Rev 73(5):531–551
Karichiappan K, Wege D (2000) Naphtho[2,3-c]furan-4,9-dione and a further exploratory approach to the ring system of Ventilone A Aust J Chem 53(9):743–747
Hirshfeld FL (1977) Bonded-atom fragments for describing molecular charge densities Theor Chim Acta 44(2):129–138
Hirshfeld FL (1977) XVII. Spatial partitioning of charge density Israel J Chem 16(2–3):198–201
Frisch M, Trucks G, Schlegel H, Scuseria G, Robb M, Cheeseman J, Scalmani G, Barone V, Mennucci B, Petersson G, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery Jr JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Keith T, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, revision D. 01. Gaussian, Inc., Wallingford CT,
Glendening ED, Landis CR, Weinhold F (2013) NBO 6.0: natural bond orbital analysis program J Comput Chem 34(16):1429–1437
Koritsanszky T, Howard S, Macchi P, Gatti C, Farrugia L, Mallinson P, Volkov A, Su Z, Richter T, Hansen N (2003) XD (version 4.10, July), a computer program package for multipole refinement and analysis of electron densities from diffraction data. Free University of Berlin, Germany,
Wolff SK, Grimwood DJ, McKinnon JJ, Turner MJ, Jayatilaka D, Spackman MA (2012) CrystalExplorer (Version 3.1)
Miao Fangming LX, Yongqiang L (1991) Wuji Huaxue Xuebao Chinese J Inorg Chem 7(6):129–132 (CCDC: DEBFAR01)
Steiner T (2002) The hydrogen bond in the solid state Angew Chem Int Ed 41(1):48–76
Goerigk L, Grimme S (2011) A thorough benchmark of density functional methods for general main group thermochemistry, kinetics, and noncovalent interactions Phys Chem Chem Phys 13(14):6670–6688
Spackman MA, Byrom PG (1997) A novel definition of a molecule in a crystal Chem Phys Lett 267(3–4):215–220
Spackman MA, Jayatilaka D (2009) Hirshfeld surface analysis Cryst Eng Comm 11(1):19–32
McKinnon JJ, Jayatilaka D, Spackman MA (2007) Towards quantitative analysis of intermolecular interactions with Hirshfeld surfaces Chem Commun 37:3814–3816
Spackman MA, McKinnon JJ (2002) Fingerprinting intermolecular interactions in molecular crystals Cryst Eng Comm 4(66):378–392
Matta CF, Hernández-Trujillo J, Tang TH, Bader RFW (2003) Hydrogen–hydrogen bonding: a stabilizing interaction in molecules and crystals Chem Eur J 9:1940–1951
Weinhold F, Landis CR (2001) Natural bond orbitals and extensions of localized bonding concepts Chem Educ Res Pract 2(2):91–104
Acknowledgements
We gratefully acknowledge useful consultations with Prof. C. Pettinari of the University of Camerino in respect of accessing/acquiring data on relevant compounds. S. Grabowsky thanks the German Research Foundation (Deutsche Forschungsgemeinschaft DFG) for funding within the Emmy Noether scheme GR 4451/1-1.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
This paper is dedicated to Professor Louis J. Massa on the occasion of his Festschrift.
The original version of this article was revised: a modification has been made to the layout of Table 2.
Allan H. White is deceased.
An erratum to this article is available at https://doi.org/10.1007/s11224-017-1023-y.
Rights and permissions
About this article
Cite this article
Malaspina, L.A., White, A.H., Wege, D. et al. Tautomerism in acyl-pyrazolones and in a novel photolysis product—importance and impact of the accurate localization of hydrogen atoms in crystal structures. Struct Chem 28, 1343–1357 (2017). https://doi.org/10.1007/s11224-017-1005-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11224-017-1005-0