Nicotinohydrazide

Gustavo Portalone; Marcello Colapietro

doi:10.1107/S1600536807066561

. 2007 Dec 18;64(Pt 1):o304. doi: 10.1107/S1600536807066561

Nicotinohydrazide

Gustavo Portalone ^a,^*, Marcello Colapietro ^a

PMCID: PMC2915352 PMID: 21200868

Abstract

In the title compound (alternative name: pyridine-3-carbohydrazide, C₆H₇N₃O), the asymmetric unit contains a single molecule. In contrast with nicotinic acid and nicotinamide, the C=O bond is found to be oriented cis with respect to the C_ipso C N fragment in the pyridine ring. The pyridine ring and the hydrazide group make a dihedral angle of 34.0 (2)°. In the crystal structure, molecules are associated into a three-dimensional framework by a combination of N—H⋯N and three-centre N—H⋯O hydrogen bonds.

Related literature

The structure of the same compound has been determined independently and is reported in the preceding paper (Priebe et al., 2008 ▶). For related literature, see: Bhat et al. (1974 ▶); Kutoglu & Scheringer (1983 ▶); Miwa et al. (1999 ▶); Portalone (2007 ▶); Portalone & Colapietro (2007 ▶). For computation of ring patterns formed by hydrogen bonds in crystal structures, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶); Motherwell et al. (1999 ▶).

Experimental

Crystal data

C₆H₇N₃O
M _r = 137.15
Orthorhombic,
a = 3.8727 (10) Å
b = 10.481 (2) Å
c = 15.855 (2) Å
V = 643.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 (2) K
0.15 × 0.05 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur S CCD diffractometer
Absorption correction: none
3076 measured reflections
1139 independent reflections
695 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.131
S = 1.19
1139 reflections
93 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807066561/bh2149sup1.cif

e-64-0o304-sup1.cif^{(12.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066561/bh2149Isup2.hkl

e-64-0o304-Isup2.hkl^{(55.2KB, 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—H21⋯N1ⁱ	0.89 (4)	2.09 (4)	2.964 (4)	168 (4)
N3—H31⋯O1ⁱⁱ	0.84 (5)	2.57 (5)	3.146 (4)	127 (4)
N3—H32⋯O1ⁱⁱⁱ	1.00 (5)	2.08 (5)	3.027 (4)	157 (4)

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

Acknowledgments

We thank MIUR (Rome) for 2006 financial support of the project ‘X-ray diffractometry and spectrometry’.

supplementary crystallographic information

Comment

As a part of a more general study of multiple-hydrogen-bonding N -heterocyclic systems as potential supramolecular reagents (Portalone, 2007; Portalone & Colapietro, 2007), we report here the structure of the title compound (I, Fig. 1). The asymmetric unit of (I) comprises one independent molecule, and the angle between the mean planes of the acid hydrazine group and the pyridine ring is 34.0 (2)°. Noteworthy, in contrast to nicotinic acid (Kutoglu & Scheringer, 1983) and nicotinamide (Miwa et al., 1999), the C?O bond is oriented cis with respect to the C2—C3 bond.

Analysis of the crystal packing of (I) shows that, at variance with isonicotinohydrazide (Bhat et al., 1974), for which the crystal structure is stabilized by a network of N—H···N hydrogen bonds, in compound (I) two of the three independent N—H bonds act as donor in three-centre N—H···O systems (Table 1, entries 2 and 3), and the third is involved in a N—H···N interaction (Table 1, entry 1). These hydrogen bonds delineate patterns in which rings are the most prominent features (Fig. 2). Two small rings with descriptor R₂²(10) (Etter et al., 1990; Bernstein et al., 1995; Motherwell et al., 1999) are then formed by NH₂ functionalities and two symmetry-related carbonyl O atoms [O1ⁱⁱ and O1ⁱⁱⁱ, symmetry codes: (ii) x + 1/2, -y + 1/2, -z; (iii) x - 1/2, -y + 1/2, -z]. The formation of the N—H···N hydrogen bonds between the N—H groups and the pyridyl N atoms [N1ⁱ, symmetry code: (i) -x + 1, y + 1/2, -z + 1/2] leads to the formation of larger R₆⁶(30) rings.

Experimental

1 mmol of the title compound (purchased from Sigma-Aldrich at 97% purity) was dissolved in a mixture benzene/ethanol (8:1, 50 ml) and refluxed for 1 h. After cooling the solution to ambient temperature, a colorless precipitate was formed, which was collected by filtration and washed with benzene/ethanol (8:1). Crystals suitable for single-crystal X-ray diffraction were grown from a benzene solution, by slow evaporation of the solvent.