4-[(2E)-2-(4-Chloro­benzyl­idene)hydrazinyl­idene]-1-methyl-1,4-dihydro­pyridine monohydrate

Abdullah Aydın; Mehmet Akkurt; Vildan Alptüzün; Orhan Büyükgüngör; Ulrike Holzgrabe; Krzysztof Radacki

doi:10.1107/S1600536810015709

. 2010 May 12;66(Pt 6):o1324–o1325. doi: 10.1107/S1600536810015709

4-[(2E)-2-(4-Chlorobenzylidene)hydrazinylidene]-1-methyl-1,4-dihydropyridine monohydrate

Abdullah Aydın ^a,^*, Mehmet Akkurt ^b, Vildan Alptüzün ^c, Orhan Büyükgüngör ^d, Ulrike Holzgrabe ^e, Krzysztof Radacki ^f

PMCID: PMC2979526 PMID: 21579416

Abstract

In the title compound, C₁₃H₁₂ClN₃·H₂O, the organic molecule is almost planar, with a dihedral angle of 3.22 (10)° between the benzene and pyridine rings. The crystal structure is stabilized by O—H⋯N and C—H⋯O hydrogen bonding and π–π stacking interactions [centroid–centroid distances = 3.630 (1) and 3.701 (1) Å].

Related literature

For the synthesis and pharmacological activity of (benzylidene-hydrazono)-1,4-dihydropyridine derivatives, see: Douglas et al. (1977 ▶); Alptüzün et al. (2010 ▶); Savini et al. (2002 ▶); Pandey et al. (2002 ▶); Salgın-Gökşen et al. (2007 ▶); Silva et al. (2004 ▶); Vicini et al. (2009 ▶). For bond-length data, see: Allen et al. (1987 ▶); Diao et al. (2008 ▶); Odabaşoğlu et al. (2003 ▶). For quantum-chemical calculations, see: Pople & Beveridge (1970 ▶).

Experimental

Crystal data

C₁₃H₁₂ClN₃·H₂O
M _r = 263.72
Monoclinic,
a = 5.8492 (4) Å
b = 20.3101 (10) Å
c = 12.2035 (7) Å
β = 113.855 (4)°
V = 1325.90 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 296 K
0.60 × 0.30 × 0.04 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.905, T _max = 0.989
14028 measured reflections
2759 independent reflections
1746 reflections with I > 2σ(I)
R _int = 0.064

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.095
S = 0.95
2759 reflections
170 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810015709/sj2782sup1.cif

e-66-o1324-sup1.cif^{(20KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015709/sj2782Isup2.hkl

e-66-o1324-Isup2.hkl^{(135.5KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1	0.84 (3)	2.26 (3)	3.089 (3)	173 (3)
O1—H1B⋯N2ⁱ	0.91 (4)	1.95 (4)	2.859 (3)	174 (2)
C3—H3⋯O1ⁱⁱ	0.93	2.58	3.421 (3)	150
C11—H11⋯O1ⁱⁱⁱ	0.93	2.49	3.378 (3)	159

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund).

supplementary crystallographic information

Comment

Hydrazones, a special group of compounds in the class of the schiff bases, are known to show significant biological activities including antimicrobial, antitubercular, anticancer, analgesic, anti-inflammatory, antiplatelet and antiviral activities (Savini et al., 2002; Pandey et al., 2002; Salgın-Gökşen et al., 2007; Silva et al., 2004; Vicini et al., 2009). In addition, (benzylidene-hydrazono)-1,4-dihydropyridine derivatives have anticoccidial activity (Douglas et al., 1977) and also display anti-Alzheimer's activity by inhibiting ABeta fibril formation and acetylcholinesterase (Alptüzün et al., 2010).

The title molecule (I), Fig. 1, crystallized as a monohydrate in the monoclinic space group P2₁/c. All bond lengths are as expected (Allen et al., 1987). The Cl1—C4, and N1—N2 bond lengths are 1.742 (2) Å, and 1.388 (2) Å, respectively. The Cl1—C4—C5 and N2—N1—C7 bond angles are 119.88 (18) ° and 113.95 (19) °, respectively. The bond lengths and the bond angles of (I) are comparable to those observed in related structures (Diao et al., 2008; Odabaşoğlu et al., 2003).

The main molecule is almost planar, except the methyl H atoms, forming a dihedral angle of 3.22 (10)° between the benzene (C1–C6) and dihydropyridine (N3/C8–C12) rings.

The crystal structure is stabilized by O—H···N and C—H···O hydrogen bonding (Table 1, Fig. 2) and π-π stacking interactions [Cg1···Cg1(-x, 1-y, -z) = 3.630 (1) Å and Cg1···Cg2(1-x, 1-y, 1-z) = 3.701 (1) Å, Cg1 and Cg2 are the centroids of the pyridine and benzene rings, respectively].

We have also carried out the quantum mechanical calculations using the CNDO (Pople et al., 1970) approximation. The spatial view of the single molecule considered in a vacuum, is shown in Fig.3. According to the theoretical CNDO and experimental X-rays results, the values of the geometric parameters of (I) are closely comparable within the observed experimental errors. The calculated dipole moment of (I) is about 11.481 Debye. The HOMO and LUMO energy levels are -8.3484 and 1.3565 eV, respectively.

Experimental

4-Hydrazinylpyridine (1.09 g, 0.01 mol) and 4-chlorobenzaldehyde (1.41 g, 0.01 mol) were stirred in ethanol (30 ml) at room temperature for 5-10 h. The precipitate was filtered and washed with cool ethanol and crystallized from ethanol. A mixture of 4-[(4-Chlorobenzylidene)hydrazinyl] pyridine (0.232 g, 0.001 mol) and methyl iodide (0.141 g, 0.002 mol) was refluxed in ethanol (20 ml) for 20 h. The mixture was cooled to room temperature and the resulting precipitate was filtered and washed with cool ethanol. The crude products were crystallized from ethanol to give the compound 4-(2-(4-Chlorobenzylidenehydrazinyl)-1-methylpyridinium iodide. This product (0.374 g, 0.001 mol) was partitioned between CH₂Cl₂ (50 ml) and 2 M NaOH (50 ml). The organic layer was evaporated to dryness and the residue recrystallized from ethanol-water.

Yield 88%, yellow needles, mp 407-409 K (lit. (Douglas et al. , 1977) 403-405 K). IR (KBr) v_max 1654, 1517, 1492, 1203, 824 cm^-1. ¹H-NMR (DMSO-d₆): δ ppm 3.29 (3H, s, N—CH₃), 6.12 (1H, dd, J=2.4/8.0 Hz, H-3 or H-5), 6.98 (1H, dd, J=2.0/7.8 Hz, H-3 or H-5), 7.23 (2H, td, J=7.2/2.0 Hz, H-2, H-6 ), 7.39 (2H, d, J=8.4 Hz, H-2', H-6'), 7.69 (2H, d, J=8.4 Hz, H-3', H-5'), 8.16 (1H, s, N=CH). 13 C NMR (CH₃OH- d4): δ ppm 43.18 (q), 107.78 (d), 112.11 (d), 129.35 (d), 129.79 (d), 135.59 (s), 136.58 (s), 140.15 (d), 140.75 (d), 148.84 (d), 162.25 (s). EI—MS m/z (% relative intensity): 247 (M+2, 14), 246 (M+1, 28), 245 (M+, 43), 181 (25), 93 (100), 92 (24), 66 (30), 42 (18). C₁₃H₁₂N₃Cl.H₂O. C, H, N combustion analysis: Calc. (%) C 59.21, H 5.36, N 15.93; found (%) C 59.45, H 5.33, N 15.72.