N′-[1-(2-Pyrid­yl)ethyl­idene]nicotino­hydrazide

Yi-Min, F.; Xi-Shi, T.

doi:10.1107/S1600536807056024

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o65

https://doi.org/10.1107/S1600536807056024

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N′-[1-(2-Pyridyl)ethylidene]nicotinohydrazide

Feng Yi-Min ^a and Tai Xi-Shi ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: taixishi@lzu.edu.cn

(Received 5 November 2007; accepted 5 November 2007; online 6 December 2007)

In the the title compound, C₁₃H₁₂N₄O, the dihedral angle between the aromatic ring planes is 21.7 (3)°. In the crystal structure, intermolecular N—H⋯O hydrogen bonds lead to C(4) chains.

Related literature

For related literature, see: Tai et al. (2003 ).

Experimental

Crystal data

C₁₃H₁₂N₄O
M_r = 240.27
Orthorhombic, P b c n
a = 18.264 (3) Å
b = 7.9300 (9) Å
c = 16.471 (2) Å
V = 2385.5 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 (2) K
0.46 × 0.43 × 0.40 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.960, T_max = 0.965
9146 measured reflections
2107 independent reflections
1568 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.106
S = 1.06
2107 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.27	3.125 (2)	171
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807056024/hb2634sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807056024/hb2634Isup2.hkl

checkCIF report

Comment top

As part of our ongoing studies of the coordination chemistry of aroylhydrazones ligands (Tai et al., 2003), we now report the synthesis and structure of the title compound, (I), (Fig. 1).

In the molecule of (I), both C8—N2 [1.284 (2) Å] and C1—O1 [1.220 (2) Å] are close to double-bond separations, indicating that the Lewis structure shown in the scheme is only an approximation to the electron distribution in the molecule. Otherwise, the geometrical parameters for (I) are normal. The dihedral angle between the pyridine ring mean planes is 21.7 (3)°, indicating that the molecule is significantly twisted, perhaps for steric reasons.

In the crystal, an N—H···O hydrogen bond (Table 1) leads to C(4) chains.

Related literature top

For related literature, see: Tai et al. (2003).

Experimental top

10 mmol of 2-acetylpyridine (10 mmol) was added to a solution of nicotinic acid hydrazine (10 mmol) in 10 ml of ethanol. The mixture was continuously stirred for 3 h at refluxing temperature, evaporating some ethanol, then, upon cooling, the solid product was collected by filtration and dried in vacuo (yield 68%). Colourless blocks of (I) were obtained by evaporation from a methanol solution after two weeks.

Structure description top

As part of our ongoing studies of the coordination chemistry of aroylhydrazones ligands (Tai et al., 2003), we now report the synthesis and structure of the title compound, (I), (Fig. 1).

In the crystal, an N—H···O hydrogen bond (Table 1) leads to C(4) chains.

For related literature, see: Tai et al. (2003).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top

Fig. 1. The molecular structure of (I) showing 30% displacement ellipsoids (arbitrary spheres for the H atoms).

N'-[1-(2-Pyridyl)ethylidene]nicotinohydrazide top

Crystal data top

C₁₃H₁₂N₄O	D_x = 1.338 Mg m⁻³
M_r = 240.27	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 2977 reflections
a = 18.264 (3) Å	θ = 2.2–27.1°
b = 7.9300 (9) Å	µ = 0.09 mm⁻¹
c = 16.471 (2) Å	T = 298 K
V = 2385.5 (5) Å³	Block, colourless
Z = 8	0.46 × 0.43 × 0.40 mm
F(000) = 1008

Data collection top

Bruker SMART CCD diffractometer	2107 independent reflections
Radiation source: fine-focus sealed tube	1568 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −17→21
T_min = 0.960, T_max = 0.965	k = −9→8
9146 measured reflections	l = −19→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0375P)² + 1.131P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2107 reflections	Δρ_max = 0.21 e Å⁻³
164 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0194 (13)

Crystal data top

C₁₃H₁₂N₄O	V = 2385.5 (5) Å³
M_r = 240.27	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 18.264 (3) Å	µ = 0.09 mm⁻¹
b = 7.9300 (9) Å	T = 298 K
c = 16.471 (2) Å	0.46 × 0.43 × 0.40 mm

Data collection top

Bruker SMART CCD diffractometer	2107 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1568 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.965	R_int = 0.041
9146 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.06	Δρ_max = 0.21 e Å⁻³
2107 reflections	Δρ_min = −0.17 e Å⁻³
164 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	0.74333 (8)	0.92565 (18)	0.94870 (8)	0.0347 (4)
H1	0.7208	0.8309	0.9442	0.042*
N2	0.71633 (8)	1.05276 (17)	0.99711 (9)	0.0342 (4)
N3	0.81694 (9)	0.5927 (2)	0.76098 (10)	0.0499 (5)
N4	0.55759 (8)	1.1916 (2)	1.09086 (10)	0.0472 (5)
O1	0.83904 (7)	1.08958 (17)	0.91028 (9)	0.0518 (4)
C1	0.80666 (10)	0.9551 (2)	0.90842 (11)	0.0346 (4)
C2	0.83536 (9)	0.8086 (2)	0.86108 (10)	0.0329 (4)
C3	0.79344 (10)	0.7247 (2)	0.80384 (11)	0.0399 (5)
H3	0.7460	0.7627	0.7947	0.048*
C4	0.88433 (12)	0.5398 (3)	0.77688 (13)	0.0540 (6)
H4	0.9013	0.4453	0.7493	0.065*
C5	0.93084 (11)	0.6157 (3)	0.83154 (13)	0.0553 (6)
H5	0.9778	0.5740	0.8400	0.066*
C6	0.90614 (10)	0.7548 (3)	0.87343 (12)	0.0451 (5)
H6	0.9367	0.8113	0.9094	0.054*
C7	0.60952 (12)	0.8730 (3)	1.03313 (15)	0.0600 (6)
H7A	0.5709	0.8875	0.9942	0.090*
H7B	0.5888	0.8539	1.0859	0.090*
H7C	0.6391	0.7779	1.0180	0.090*
C8	0.65592 (10)	1.0280 (2)	1.03520 (10)	0.0352 (4)
C9	0.63030 (9)	1.1754 (2)	1.08347 (10)	0.0339 (4)
C10	0.67883 (10)	1.2881 (2)	1.11839 (11)	0.0390 (5)
H10	0.7291	1.2719	1.1133	0.047*
C11	0.65202 (12)	1.4242 (3)	1.16058 (13)	0.0503 (5)
H11	0.6837	1.5011	1.1847	0.060*
C12	0.57744 (12)	1.4446 (3)	1.16657 (14)	0.0561 (6)
H12	0.5576	1.5366	1.1938	0.067*
C13	0.53299 (12)	1.3260 (3)	1.13141 (14)	0.0560 (6)
H13	0.4826	1.3399	1.1361	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0408 (9)	0.0252 (8)	0.0381 (8)	−0.0008 (7)	0.0054 (7)	−0.0048 (7)
N2	0.0403 (9)	0.0279 (8)	0.0344 (8)	0.0058 (7)	0.0007 (6)	−0.0029 (7)
N3	0.0511 (11)	0.0497 (10)	0.0490 (10)	0.0043 (9)	−0.0005 (8)	−0.0147 (9)
N4	0.0367 (9)	0.0506 (11)	0.0542 (10)	0.0046 (8)	0.0029 (7)	−0.0111 (9)
O1	0.0480 (8)	0.0377 (8)	0.0698 (10)	−0.0094 (7)	0.0109 (7)	−0.0114 (7)
C1	0.0365 (10)	0.0304 (10)	0.0370 (10)	0.0005 (8)	−0.0021 (8)	−0.0010 (8)
C2	0.0357 (10)	0.0316 (10)	0.0313 (9)	−0.0005 (8)	0.0058 (7)	0.0018 (8)
C3	0.0381 (10)	0.0393 (11)	0.0422 (11)	0.0032 (9)	0.0008 (8)	−0.0026 (9)
C4	0.0550 (13)	0.0546 (14)	0.0523 (13)	0.0154 (11)	0.0061 (10)	−0.0168 (11)
C5	0.0416 (12)	0.0690 (15)	0.0552 (13)	0.0182 (11)	−0.0003 (10)	−0.0128 (12)
C6	0.0389 (11)	0.0552 (13)	0.0413 (11)	0.0016 (9)	−0.0003 (8)	−0.0074 (10)
C7	0.0580 (14)	0.0460 (13)	0.0760 (16)	−0.0101 (11)	0.0213 (12)	−0.0188 (12)
C8	0.0368 (10)	0.0335 (10)	0.0352 (10)	0.0011 (8)	0.0012 (8)	−0.0009 (8)
C9	0.0376 (10)	0.0338 (10)	0.0304 (9)	0.0013 (8)	0.0019 (7)	0.0003 (8)
C10	0.0389 (10)	0.0403 (11)	0.0378 (10)	−0.0005 (9)	0.0025 (8)	−0.0033 (9)
C11	0.0559 (13)	0.0454 (12)	0.0495 (12)	−0.0060 (10)	0.0033 (10)	−0.0136 (10)
C12	0.0605 (14)	0.0483 (13)	0.0594 (13)	0.0099 (11)	0.0116 (11)	−0.0154 (11)
C13	0.0425 (12)	0.0581 (14)	0.0672 (15)	0.0111 (11)	0.0059 (11)	−0.0127 (12)

Geometric parameters (Å, º) top

N1—C1	1.354 (2)	C5—H5	0.9300
N1—N2	1.3765 (19)	C6—H6	0.9300
N1—H1	0.8600	C7—C8	1.494 (3)
N2—C8	1.284 (2)	C7—H7A	0.9600
N3—C4	1.326 (3)	C7—H7B	0.9600
N3—C3	1.333 (2)	C7—H7C	0.9600
N4—C13	1.336 (3)	C8—C9	1.489 (2)
N4—C9	1.340 (2)	C9—C10	1.384 (3)
O1—C1	1.220 (2)	C10—C11	1.374 (3)
C1—C2	1.494 (2)	C10—H10	0.9300
C2—C6	1.377 (3)	C11—C12	1.375 (3)
C2—C3	1.385 (2)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.371 (3)
C4—C5	1.376 (3)	C12—H12	0.9300
C4—H4	0.9300	C13—H13	0.9300
C5—C6	1.377 (3)

C1—N1—N2	117.63 (14)	C8—C7—H7A	109.5
C1—N1—H1	121.2	C8—C7—H7B	109.5
N2—N1—H1	121.2	H7A—C7—H7B	109.5
C8—N2—N1	118.61 (15)	C8—C7—H7C	109.5
C4—N3—C3	116.25 (17)	H7A—C7—H7C	109.5
C13—N4—C9	117.09 (17)	H7B—C7—H7C	109.5
O1—C1—N1	123.55 (17)	N2—C8—C9	114.28 (16)
O1—C1—C2	121.51 (16)	N2—C8—C7	127.01 (17)
N1—C1—C2	114.94 (15)	C9—C8—C7	118.68 (16)
C6—C2—C3	118.06 (17)	N4—C9—C10	122.35 (17)
C6—C2—C1	119.59 (16)	N4—C9—C8	115.81 (16)
C3—C2—C1	122.34 (16)	C10—C9—C8	121.85 (16)
N3—C3—C2	124.04 (17)	C11—C10—C9	119.30 (18)
N3—C3—H3	118.0	C11—C10—H10	120.3
C2—C3—H3	118.0	C9—C10—H10	120.3
N3—C4—C5	124.33 (19)	C10—C11—C12	118.80 (19)
N3—C4—H4	117.8	C10—C11—H11	120.6
C5—C4—H4	117.8	C12—C11—H11	120.6
C4—C5—C6	118.39 (19)	C13—C12—C11	118.39 (19)
C4—C5—H5	120.8	C13—C12—H12	120.8
C6—C5—H5	120.8	C11—C12—H12	120.8
C2—C6—C5	118.84 (19)	N4—C13—C12	124.0 (2)
C2—C6—H6	120.6	N4—C13—H13	118.0
C5—C6—H6	120.6	C12—C13—H13	118.0

C1—N1—N2—C8	179.30 (16)	N1—N2—C8—C9	−177.98 (14)
N2—N1—C1—O1	−3.1 (3)	N1—N2—C8—C7	−0.3 (3)
N2—N1—C1—C2	176.40 (14)	C13—N4—C9—C10	2.3 (3)
O1—C1—C2—C6	53.1 (3)	C13—N4—C9—C8	−177.68 (17)
N1—C1—C2—C6	−126.43 (18)	N2—C8—C9—N4	148.85 (17)
O1—C1—C2—C3	−126.2 (2)	C7—C8—C9—N4	−29.1 (3)
N1—C1—C2—C3	54.3 (2)	N2—C8—C9—C10	−31.1 (2)
C4—N3—C3—C2	1.4 (3)	C7—C8—C9—C10	150.92 (19)
C6—C2—C3—N3	1.3 (3)	N4—C9—C10—C11	−1.6 (3)
C1—C2—C3—N3	−179.39 (17)	C8—C9—C10—C11	178.37 (18)
C3—N3—C4—C5	−2.5 (3)	C9—C10—C11—C12	−0.2 (3)
N3—C4—C5—C6	0.7 (4)	C10—C11—C12—C13	1.3 (3)
C3—C2—C6—C5	−3.1 (3)	C9—N4—C13—C12	−1.2 (3)
C1—C2—C6—C5	177.58 (18)	C11—C12—C13—N4	−0.6 (4)
C4—C5—C6—C2	2.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.27	3.125 (2)	171

Symmetry code: (i) −x+3/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂N₄O
M_r	240.27
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	298
a, b, c (Å)	18.264 (3), 7.9300 (9), 16.471 (2)
V (Å³)	2385.5 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.46 × 0.43 × 0.40

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.960, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	9146, 2107, 1568
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.106, 1.06
No. of reflections	2107
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.17

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.27	3.125 (2)	171

Symmetry code: (i) −x+3/2, y−1/2, z.

Acknowledgements

The authors thank the National Natural Science Foundation of China (20671073), NingXia Natural Gas Transfer Key Laboratory (2004007), the Science and Technology Foundation of Weifang and Weifang University for a research grant.

References

Bruker (2000). SMART, SAINT, SADABS and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Tai, X.-S., Yin, X.-H., Tan, M.-Y. & Li, Y.-Z. (2003). Acta Cryst. E59, o681–o682. Web of Science CSD CrossRef IUCr Journals Google Scholar