N′-(Propan-2-yl­idene)nicotinohydrazide

Bao, F.-Y.; Zhang, Y.-X.; Zhou, Y.-X.; Zhang, H.-Y.

doi:10.1107/S1600536809034734

organic compounds

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Volume 65| Part 10| October 2009| Page o2335

doi:10.1107/S1600536809034734

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N′-(Propan-2-ylidene)nicotinohydrazide

Feng-Yu Bao,^a ^* Yu-Xia Zhang,^b Ying-Xia Zhou ^a and Hai-Yan Zhang ^a

^aDepartment of Applied Chemistry, College of Sciences, Henan Agricultural University, Zhengzhou 450002, People's Republic of China, and ^bSanonda Zhengzhou Pesticide Co Ltd, Zhengzhou 450009, People's Republic of China
^*Correspondence e-mail: bfyu2008@126.com

(Received 27 August 2009; accepted 29 August 2009; online 5 September 2009)

Crystals of the title compound, C₉H₁₁N₃O, were obtained from a condensation reaction of nicotinohydrazide and acetone. In the molecular structure, the pyridine ring is oriented at a dihedral angle of 36.28 (10)° with respect to the amide plane. In the crystal structure, molecules are linked via N—H⋯O hydrogen bonds, forming chains.

Related literature

For applications of Schiff base compounds, see: Kahwa et al. (1986 ); Santos et al. (2001 ).

Experimental

Crystal data

C₉H₁₁N₃O
M_r = 177.21
Monoclinic, P 2₁ /n
a = 7.5439 (4) Å
b = 18.0292 (9) Å
c = 7.6172 (4) Å
β = 115.937 (3)°
V = 931.67 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.42 × 0.21 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.978, T_max = 0.990
14297 measured reflections
2172 independent reflections
1301 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.161
S = 1.02
2172 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Oⁱ	0.86	2.08	2.9136 (18)	162
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034734/xu2604sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034734/xu2604Isup2.hkl

checkCIF report

Comment top

The chemistry of Schiff bases has attracted a great deal of interest in recent years. These compounds play an important role in the development of various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). As part of our interest in the coordination chemistry of Schiff bases, we have synthesized the title compound and report here its crystal structure.

IN the molecular structure (Fig. 1), the pyridine ring is oriented with respect to N2/C4/O plane with a dihedral angle of 36.28 (10)°. In the crystal structure intermolecular N—H···O hydrogen bonding links the molecules to form the one-dimensional chains (Table 1).

Related literature top

For applications of Schiff base compounds, see: Kahwa et al. (1986); Santos et al. (2001).

Experimental top

Nicotinohydrazide (1 mmol, 0.137 g) was dissolved in anhydrous ethanol (15 ml). The mixture was stirred for several min at 351 K, then the acetone (1 mmol, 0.058 g) in ethanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The solid product was isolated and recrystallized from methanol. Colourless single crystals were obtained after 3 d.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.

N'-(Propan-2-ylidene)nicotinohydrazide top

Crystal data top

C₉H₁₁N₃O	F(000) = 376
M_r = 177.21	D_x = 1.263 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3071 reflections
a = 7.5439 (4) Å	θ = 2.3–27.0°
b = 18.0292 (9) Å	µ = 0.09 mm⁻¹
c = 7.6172 (4) Å	T = 296 K
β = 115.937 (3)°	Block, colourless
V = 931.67 (8) Å³	0.42 × 0.21 × 0.12 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2172 independent reflections
Radiation source: fine-focus sealed tube	1301 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ω scans	θ_max = 27.7°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −9→9
T_min = 0.978, T_max = 0.990	k = −23→23
14297 measured reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.161	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0882P)² + 0.0683P] where P = (F_o² + 2F_c²)/3
2172 reflections	(Δ/σ)_max < 0.001
120 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₉H₁₁N₃O	V = 931.67 (8) Å³
M_r = 177.21	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5439 (4) Å	µ = 0.09 mm⁻¹
b = 18.0292 (9) Å	T = 296 K
c = 7.6172 (4) Å	0.42 × 0.21 × 0.12 mm
β = 115.937 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2172 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1301 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.990	R_int = 0.046
14297 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.161	H-atom parameters constrained
S = 1.02	Δρ_max = 0.21 e Å⁻³
2172 reflections	Δρ_min = −0.22 e Å⁻³
120 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.6021 (2)	0.20018 (9)	0.3243 (2)	0.0526 (4)
N2	0.5607 (2)	0.23097 (8)	0.1426 (2)	0.0498 (4)
H2A	0.4896	0.2078	0.0361	0.060*
N3	0.5259 (3)	0.44511 (10)	−0.2362 (3)	0.0683 (5)
O	0.74766 (19)	0.33093 (7)	0.29001 (19)	0.0640 (4)
C1	0.5162 (3)	0.07664 (11)	0.1687 (3)	0.0707 (6)
H1A	0.3751	0.0725	0.1065	0.106*
H1B	0.5731	0.0290	0.2184	0.106*
H1C	0.5612	0.0935	0.0755	0.106*
C2	0.5773 (2)	0.13080 (11)	0.3328 (3)	0.0522 (5)
C3	0.6197 (3)	0.10093 (13)	0.5301 (3)	0.0748 (6)
H3A	0.6712	0.1398	0.6252	0.112*
H3B	0.7147	0.0617	0.5627	0.112*
H3C	0.5003	0.0821	0.5293	0.112*
C4	0.6361 (2)	0.29792 (10)	0.1407 (3)	0.0470 (5)
C5	0.5842 (2)	0.33173 (9)	−0.0540 (2)	0.0448 (4)
C6	0.5646 (3)	0.29200 (11)	−0.2158 (3)	0.0553 (5)
H7A	0.5770	0.2406	−0.2101	0.066*
C7	0.5262 (3)	0.32960 (13)	−0.3867 (3)	0.0649 (6)
H8A	0.5129	0.3040	−0.4978	0.078*
C8	0.5083 (3)	0.40459 (13)	−0.3895 (3)	0.0678 (6)
H9A	0.4821	0.4292	−0.5055	0.081*
C9	0.5659 (3)	0.40808 (11)	−0.0721 (3)	0.0547 (5)
H10A	0.5827	0.4353	0.0377	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0529 (9)	0.0484 (9)	0.0449 (9)	0.0063 (7)	0.0108 (7)	0.0040 (7)
N2	0.0472 (8)	0.0448 (9)	0.0428 (8)	−0.0020 (7)	0.0062 (6)	−0.0001 (7)
N3	0.0776 (12)	0.0534 (11)	0.0617 (11)	−0.0046 (8)	0.0191 (9)	0.0067 (9)
O	0.0620 (8)	0.0498 (8)	0.0513 (8)	−0.0055 (6)	−0.0019 (6)	−0.0041 (6)
C1	0.0713 (13)	0.0476 (12)	0.0699 (14)	0.0045 (10)	0.0092 (11)	0.0022 (10)
C2	0.0411 (9)	0.0499 (11)	0.0542 (11)	0.0086 (8)	0.0103 (8)	0.0066 (9)
C3	0.0817 (14)	0.0678 (14)	0.0718 (15)	0.0150 (12)	0.0306 (12)	0.0183 (12)
C4	0.0382 (8)	0.0406 (10)	0.0480 (10)	0.0027 (7)	0.0056 (7)	−0.0036 (8)
C5	0.0341 (8)	0.0432 (10)	0.0481 (11)	−0.0022 (7)	0.0096 (7)	−0.0036 (8)
C6	0.0563 (11)	0.0473 (11)	0.0605 (13)	−0.0027 (8)	0.0239 (9)	−0.0063 (9)
C7	0.0699 (13)	0.0732 (15)	0.0559 (13)	−0.0130 (11)	0.0315 (10)	−0.0100 (11)
C8	0.0732 (13)	0.0705 (15)	0.0555 (13)	−0.0120 (11)	0.0244 (11)	0.0041 (11)
C9	0.0528 (10)	0.0466 (11)	0.0532 (11)	−0.0041 (8)	0.0127 (8)	−0.0030 (9)

Geometric parameters (Å, º) top

N1—C2	1.271 (2)	C3—H3A	0.9600
N1—N2	1.394 (2)	C3—H3B	0.9600
N2—C4	1.337 (2)	C3—H3C	0.9600
N2—H2A	0.8600	C4—C5	1.489 (2)
N3—C9	1.330 (2)	C5—C6	1.376 (2)
N3—C8	1.334 (3)	C5—C9	1.384 (2)
O—C4	1.232 (2)	C6—C7	1.382 (3)
C1—C2	1.492 (3)	C6—H7A	0.9300
C1—H1A	0.9600	C7—C8	1.358 (3)
C1—H1B	0.9600	C7—H8A	0.9300
C1—H1C	0.9600	C8—H9A	0.9300
C2—C3	1.493 (3)	C9—H10A	0.9300

C2—N1—N2	117.96 (15)	H3B—C3—H3C	109.5
C4—N2—N1	117.32 (14)	O—C4—N2	123.21 (17)
C4—N2—H2A	121.3	O—C4—C5	119.84 (16)
N1—N2—H2A	121.3	N2—C4—C5	116.93 (14)
C9—N3—C8	116.26 (18)	C6—C5—C9	117.46 (17)
C2—C1—H1A	109.5	C6—C5—C4	123.87 (16)
C2—C1—H1B	109.5	C9—C5—C4	118.56 (16)
H1A—C1—H1B	109.5	C5—C6—C7	118.99 (18)
C2—C1—H1C	109.5	C5—C6—H7A	120.5
H1A—C1—H1C	109.5	C7—C6—H7A	120.5
H1B—C1—H1C	109.5	C8—C7—C6	118.78 (19)
N1—C2—C1	126.87 (17)	C8—C7—H8A	120.6
N1—C2—C3	115.77 (18)	C6—C7—H8A	120.6
C1—C2—C3	117.34 (18)	N3—C8—C7	124.1 (2)
C2—C3—H3A	109.5	N3—C8—H9A	117.9
C2—C3—H3B	109.5	C7—C8—H9A	117.9
H3A—C3—H3B	109.5	N3—C9—C5	124.38 (18)
C2—C3—H3C	109.5	N3—C9—H10A	117.8
H3A—C3—H3C	109.5	C5—C9—H10A	117.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Oⁱ	0.86	2.08	2.9136 (18)	162

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O
M_r	177.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.5439 (4), 18.0292 (9), 7.6172 (4)
β (°)	115.937 (3)
V (Å³)	931.67 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.42 × 0.21 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.978, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	14297, 2172, 1301
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.655

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.161, 1.02
No. of reflections	2172
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.22

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Oⁱ	0.86	2.08	2.9136 (18)	162.0

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

References

Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kahwa, I. A., Selbin, I., Hsieh, T. C. Y. & Laine, R. A. (1986). Inorg. Chim. Acta, 118, 179–185. CrossRef CAS Web of Science Google Scholar
Santos, M. L. P., Bagatin, I. A., Pereira, E. M. & Ferreira, A. M. D. C. (2001). J. Chem. Soc. Dalton Trans. pp. 838–844. Web of Science CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2335

doi:10.1107/S1600536809034734

Open

access