Ethyl 5-{[(E)-2-(isonicotinoyl)hydrazinyl­idene]methyl}-3,4-dimethyl-1H-pyrrole-2-carboxyl­ate dihydrate

Zhao-Po Zhang; Yuan Wang; Ming-Jia Lu; Lei-Wei Jia; Hong-Chang Qiao

doi:10.1107/S1600536811017132

. 2011 May 14;67(Pt 6):o1413. doi: 10.1107/S1600536811017132

Ethyl 5-{[(E)-2-(isonicotinoyl)hydrazinylidene]methyl}-3,4-dimethyl-1H-pyrrole-2-carboxylate dihydrate

Zhao-Po Zhang ^a, Yuan Wang ^a,^*, Ming-Jia Lu ^a, Lei-Wei Jia ^a, Hong-Chang Qiao ^a

PMCID: PMC3120595 PMID: 21754795

Abstract

In the title compound, C₁₆H₁₈N₄O₃·2H₂O, the dihedral angle between the pyrrole and pyridine rings in the hydrazone molecule is 7.12 (3)°. In the crystal structure, intermolecular N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds link the hydrazone and water molecules into double layers parallel to (101). The crystal packing exhibits weak π–π interactions between the pyrrole and pyridine rings of neighbouring hydrazone molecules [centroid–centroid distance = 3.777 (3) Å]. The crystal studied was a non-merohedral twin, the refined ratio of twin domains being 0.73 (3):0.27 (3).

Related literature

For the antioxidant and DNA-binding properties of hydrazone complexes, see: Liu & Yang (2009 ▶). For the synthesis and structure of 5-formyl-3,4-dimethyl-1H-pyrrole-2-carboxylate, see: Wu et al. (2009 ▶). For the similar structure of ethyl 5-[(3,4-dimethyl-1H-pyrrole-2-carboxylimino)-methyl]-3,4-dimethyl-1H-pyrrole-2-carboxylate monohydrate, see: Wang et al. (2009 ▶).

Experimental

Crystal data

C₁₆H₁₈N₄O₃·2H₂O
M _r = 350.38
Monoclinic,
a = 8.297 (4) Å
b = 18.120 (6) Å
c = 11.834 (4) Å
β = 91.814 (4)°
V = 1778.3 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.23 × 0.21 × 0.16 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.977, T _max = 0.984
10998 measured reflections
3839 independent reflections
2671 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.074
wR(F ²) = 0.176
S = 1.02
3839 reflections
241 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811017132/cv5084sup1.cif

e-67-o1413-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017132/cv5084Isup2.hkl

e-67-o1413-Isup2.hkl^{(188.2KB, 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
N2—H2A⋯O1Wⁱ	0.86	2.08	2.919 (4)	164
N4—H4A⋯O2W	0.86	2.24	3.084 (4)	165
O1W—H1C⋯N1	0.69 (5)	2.18 (5)	2.854 (4)	164 (6)
O1W—H1D⋯O2Wⁱⁱ	0.91 (5)	1.88 (5)	2.790 (5)	174 (5)
O2W—H2C⋯O2ⁱⁱⁱ	0.92 (5)	2.06 (5)	2.941 (4)	160 (4)
O2W—H2D⋯O1	0.82 (5)	2.27 (5)	3.048 (4)	159 (5)
O2W—H2D⋯N3	0.82 (5)	2.43 (5)	3.014 (4)	129 (4)

Open in a new tab

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

Acknowledgments

The authors are grateful to the National Natural Science Foundation of China for financial support (grant No. 21001040).

supplementary crystallographic information

Comment

In recent years, hydrazone complexes have received extensive attention due to their biological and pharmaceutical activities (Liu et al., 2009). As a part of our studies of hydrazone ligands bearing pyrrole unit (Wang et al., 2009), we present here the crystal structure of the title compound.

In the title compound (Fig. 1), the imine C=N double bond has an E configuration. The dihedral angle between pyrrole (N4/C8–C11, r.m.s. deviation 0.0030 Å) and pyridine rings (N1/C1–C5, r.m.s. deviation 0.0038 Å) in the hydrazone molecule is 7.12 (3)°. In the crystal structure, intermolecular N—H···O, O—H···N and O—H···O hydrogen bonds link the hydrazone and water molecules into doubled layers parallel to (101) plane. The crystal packing exhibits weak π–π interactions between the pyrrole and pyridine rings from the neighbouring hydrazone molecules [centroid-to-centroid distance of 3.777 (3) Å].

Experimental

Isonicotinohydrazide (0.137 g, 1 mmol) and ethyl 5-formyl-3,4-dimethyl-1H-pyrrole-2-carboxylate (0.167 g, 1 mmol) (Wu et al., 2009) was dissolved in an ethanol solution. The mixture was stirred for 4 h at room temperture. The resulting solution was left in air for a few days, yielding yellow prism-shaped crystals.