Pyridine-4-carbaldehyde 4-phenylsemicarbazone

Rafael Mendoza-Meroño; Laura Menéndez-Taboada; Eva Fernández-Zapico; Santiago García-Granda

doi:10.1107/S1600536811013134

. 2011 Apr 16;67(Pt 5):o1135. doi: 10.1107/S1600536811013134

Pyridine-4-carbaldehyde 4-phenylsemicarbazone

Rafael Mendoza-Meroño ^a, Laura Menéndez-Taboada ^a, Eva Fernández-Zapico ^a, Santiago García-Granda ^a,^*

PMCID: PMC3089140 PMID: 21754444

Abstract

In the title compound, C₁₃H₁₂N₄O, the semicarbazone fragment links a benzene and a pyridine ring in the structure. The crystal packing is stabilized by strong intermolecular N—H⋯O hydrogen bonds, which connect two molecules to form a synthon unit, and by N—H⋯N hydrogen bonds and weak C—H⋯π interactions. The molecular conformation is stabilized by intramolecular N—H⋯N and C—H⋯O interactions.

Related literature

For related compounds and their biological activity, see: Pavan et al. (2010 ▶); Yogeeswari et al. (2005 ▶).

Experimental

Crystal data

C₁₃H₁₂N₄O
M _r = 240.27
Monoclinic,
a = 9.2794 (6) Å
b = 10.3384 (8) Å
c = 12.8244 (8) Å
β = 100.744 (6)°
V = 1208.73 (15) Å³
Z = 4
Cu Kα radiation
μ = 0.72 mm⁻¹
T = 295 K
0.30 × 0.11 × 0.06 mm

Data collection

Oxford Diffraction Xcalibur Gemini R diffractometer
Absorption correction: multi-scan (ABSPACK in CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.888, T _max = 1.000
7257 measured reflections
2310 independent reflections
1702 reflections with I > 2σ(I)
R _int = 0.066

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.143
S = 1.06
2310 reflections
176 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2010 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ▶), PLATON (Spek, 2009) ▶ and PARST95 (Nardelli, 1995 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811013134/fy2007sup1.cif

e-67-o1135-sup1.cif^{(17KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013134/fy2007Isup2.hkl

e-67-o1135-Isup2.hkl^{(113.6KB, hkl)}

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

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

Cg2 is the centroid of the C8–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O1ⁱ	0.93 (2)	1.91 (2)	2.833 (2)	172 (2)
N4—H4N⋯N1ⁱⁱ	0.91 (2)	2.24 (2)	3.122 (3)	161.8 (19)
N4—H4N⋯N2	0.91 (2)	2.29 (2)	2.685 (2)	105.4 (16)
C13—H13⋯O1	0.93	2.31	2.854 (2)	117
C1—H1⋯Cg2ⁱⁱⁱ	0.93	2.88	3.644 (2)	140

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

Acknowledgments

Financial support by the Agencia Española de Cooperación Internacional y Desarrollo (AECID), FEDER funding, the Spanish MICINN (MAT2006–01997, MAT2010-15094 and the Factoría de Cristalización Consolider Ingenio 2010), the Gobierno del Principado de Asturias (PCTI), the University of Oviedo and Banco Santander is acknowledged.

supplementary crystallographic information

Comment

Semicarbazones and their metal complexes are important classes of compounds which have long attracted attention owing to their remarkable biological and pharmacological properties, such as antibacterial, antiviral, antineoplastic and anti Mycobacterium tuberculosis activity (Pavan et al., 2010). Using the semicarbazone template (Yogeeswari et al., 2005), significant anticonvulsant potential was demonstrated in epilepsy models for aryl semicarbazones. In view of the importance of these compounds, a new semicarbazone (I) has been synthesized, and its crystal structure is reported here (Fig. 1).

The configuration of (I) is E with respect to the C6═N2 bond. The pyridine and benzene rings are conected by a semicarbazone fragment (C6/N2/N3/C7/O1/N4). The values of the dihedral angles between the aromatic rings and the semicarbazone fragnent are 23.99 (7)° and 42.15 (7)° for the benzene and pyridine rings, respectively. This indicates the lack of planarity.

The crystal packing is stabilized by a pair of strong intermolecular N—H···O hydrogen bonds conecting two molecules to form a centrosymmtric unit (synthon), and by an N—H···N hydrogen bond (Fig. 2), which extends the packing along the c axis (Fig 3). The crystal is also stabilized by intermolecular C—H···π interactions (Fig. 4). This type of interaction affects the conformation of the molecule, specifically the torsion angle between the benzene ring and the semicarbazone moeity. The molecular conformation is stabilized by intramolecular N4—H4N···N2 and C13—H13···O1 interactions (Table 1).

From the centroid–centroid distance between two pyridine rings [4.0085 (2)Å] and the angle between the normal of the aromatic plane and the centroid–centroid vector [35.13 (5)°], we conclude that there is no significant π-π stacking interaction between the pyridine rings.

Experimental

A solution of 4-pyridine carboxaldehyde (1.0711 g, 0.01 mol) and 4-phenylsemicarbazide (1.5117 g, 0.01 mol) in absolute methanol (50 ml) was refluxed for 4 h in the presence of p-toluenesulfonic acid as catalyst, with continuous stirring. On cooling to room temperature the precipitate was filtered off, washed with copious cold methanol and dried in air (m.p. 493.15 K). White single crystals of compound (I) were obtained after recrystallization from a solution in methanol.