ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2013, Vol. 39, No. 12, pp. 849–856. © Pleiades Publishing, Ltd., 2013. Original Russian Text © L.D. Popov, S.I. Levchenkov, I.N. Shcherbakov, V.V. Minin, G.G. Aleksandrov, E.A. Ugolkova, V.V. Lukov, V.A. Kogan, 2013, published in Koordinatsion- naya Khimiya, 2013, Vol. 39, No. 12, pp. 743–750. 849 INTRODUCTION Development of the coordination chemistry of acylpyrazolones and their derivatives is due to their high ligating ability and biological activity [1–5]. From the theoretical viewpoint, compounds of this class are also interesting because of their plentiful tau- tomerism [1, 2, 6, 7]. Although complexes of acylhy- drazones and thiosemicarbazones of 4-formylpyrazo- lones have been extensively examined [6, 8–12], the ligating ability of 4-formylpyrazolone hetarylhydra- zones remains poorly studied. We obtained new ligand systems, namely, 4-formyl-3-methyl-1-phenylpyrazol-5-one quino- lin-2-ylhydrazone (H 2 L 1 ) and 4-formyl-3-methyl- 1-phenylpyrazol-5-one benzothiazol-2-ylhydrazone (H 2 L 2 ), and their copper(II) complexes [Cu(HL 1 )(EtOH)]NO 3 (I), [Cu(HL 1 )(EtOH)]ClO 4 (II), [Cu(HL 2 )(MeOH)]NO 3 (III), and [Cu(HL 2 )(MeOH)]ClO 4 (IV). EXPERIMENTAL Synthesis of hydrazones H 2 L 1 and H 2 L 2 . A hot solu- tion of 2-hydrazinoquinoline or 2-hydrazinoben- zothiazole (5 mmol) in ethanol (10 mL) was added to a hot solution of 4-formyl-3-methyl-1-phenylpyra- zol-5-one (5 mmol) in ethanol (10 mL). The reaction mixture was refluxed for 4 h and left overnight. The precipitate that formed was filtered off and recrystal- lized from butanol–DMF (4 : 1). The yield of H 2 L 1 was 1.17 g (68%), Т m = 176°C. 1 H NMR (DMSO-d 6 ), δ (ppm): 2.18 s (3H, Me), 6.99 d (1H, H(3), quinoline, J = 9.4 Hz), 7.10 t (1H, p-Ph, J = 7.3 Hz), 7.203 s (1H, CH, azomethine), 7.34–7.40 m (3H, m-Ph, H(8), quinoline), 7.66 t (1H, H(7), quinoline, J = 7.7 Hz), 7.81–7.86 m (2H, H(5), H(6), quinoline), 7.99 d (2H, o-Ph, J = 7.8 Hz), 8.15 d (1H, H(4), quinoline, J = 9.4 Hz), 12.83 s (1H, NH), 17.67 s (1H, NH). IR (ν, cm –1 ): 3390, 3188 ν(NH), 1640 ν(C=O), 1589 ν(C=N). The yield of H 2 L 2 was 0.96 g (55%), Т m = 198°C. 1 H NMR (DMSO-d 6 ), δ (ppm): 2.49 s (3H, Me), 7.09 t (1H, p-Ph, J = 7.8 Hz), 7.28–7.40 m (2H, CH arom , J = 8.1 Hz), 7.50–7.65 m (5H, CH arom ), 7.77 d (1H, CH arom , J = 7.5 Hz), 8.084 s (1H, CH azomet ), 12.20 s (1H, NH), 17.09 s (1H, NH). IR (ν, cm –1 ): 3408, 3185 ν(NH), 1632 ν(C=O), 1580 ν(C=N). For C 20 H 17 N 5 O anal. calcd., %: C, 69.96; H, 4.99; N, 20.39. Found, %: C, 70.11; H, 4.84; N, 20.52. For C 18 H 15 N 5 OS anal. calcd., %: C, 61.88; H, 4.33; N, 20.04. Found, %: C, 62.05; H, 4.46; N, 19.90. Polymeric Copper(II) Complexes with 4-Formyl-3-Methyl-1- Phenylpyrazol-5-one Hetarylhydrazones: Synthesis and Crystal Structures L. D. Popov a , S. I. Levchenkov b, *, I. N. Shcherbakov a , V. V. Minin c , G. G. Aleksandrov c , E. A. Ugolkova c , V. V. Lukov a , and V. A. Kogan a a Southern Federal University, Rostov-on-Don, Russia b Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don, Russia c Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 119991 Russia *e-mail: s.levchenkov@gmail.com Received March 20, 2013 Abstract—4-Formyl-3-methyl-1-phenylpyrazol-5-one quinolin-2-yl- (H 2 L 1 ) and benzothiazol-2-ylhydra- zones (H 2 L 2 ) were synthesized and studied. Quantum-chemical modeling of possible tautomers of the hydra- zones was performed. Copper(II) complexes of the general formula [Cu(HL)(ROH)]Y (R = CH 3 , C 2 H 5 ; Y = NO 3 , ClO 4 ) were obtained and examined by IR and EPR spectroscopy, magnetochemistry, and X-ray diffraction. Additional coordination through the N atom of the pyrazole ring enables the complex molecules to form zigzag polymer chains linked by intermolecular hydrogen bonds. DOI: 10.1134/S1070328413110079