4-Eth­oxy-N′-propanoylpyridine-2-carbohydrazide

Tang, S.-J.; Li, H.-P.; Lin, X.-Y.; Wu, W.-S.

doi:10.1107/S1600536810010135

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o920

doi:10.1107/S1600536810010135

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4-Ethoxy-N′-propanoylpyridine-2-carbohydrazide

Sheng-Jiao Tang,^a Hai-Ping Li,^a Xin-Yong Lin ^a and Wen-Shi Wu ^a ^*

^aCollege of Materials Science and Engineering, Huaqiao University, Xiamen, Fujian 361021, People's Republic of China
^*Correspondence e-mail: wws@hqu.edu.cn

(Received 6 March 2010; accepted 18 March 2010; online 27 March 2010)

In the crystal structure of the title compound, C₁₁H₁₅N₃O₃, molecules are linked into a chain by intermolecular N—H⋯O hydrogen bonds.

Related literature

For the structure of N-propionylpicoloylhydrazide, see: Wu & Liu (2001 ).

Experimental

Crystal data

C₁₁H₁₅N₃O₃
M_r = 237.26
Monoclinic, P 2₁ /c
a = 11.377 (5) Å
b = 4.745 (2) Å
c = 23.244 (10) Å
β = 99.534 (5)°
V = 1237.3 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
1.00 × 0.45 × 0.10 mm

Data collection

Bruker P4 diffractometer
9032 measured reflections
2803 independent reflections
2297 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.150
S = 0.96
2803 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱ	0.86	2.43	3.067 (2)	132
N3—H3A⋯O2ⁱⁱ	0.86	2.06	2.831 (2)	150
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y+1, z.

Data collection: XSCANS (Bruker, 1999 ); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 2008 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810010135/jh2133sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810010135/jh2133Isup2.hkl

checkCIF report

Comment top

It has been reported that the structure of N-propionylpicoloylhydrazide (II, Wu et al., 2001), based on which we reported the structure of 4-ethoxy-N-propionyl-2-pyridine formylhydrazine (I), C₁₁H₁₅N₃O₃. The structure of the title compound shown in Fig. 1 exhibits a stable one-dimension chain structure which is stabilized by inter-molecular hydrogen bonds of N2—H2A···O2ⁱ, N3—H3A···O2ⁱⁱ. All these bonds are detailed in Fig. 2 and Table 1.

In this title compound, the torsion angle of C6—N2—N3—C7 is -77.1 (2) ° which is slightly smaller than the torsion angle of the structure (II) (-73.5 (2) ° for C6—N2—N3—C7). The distances of C6—N2, N2—N3 and C7—N3 are 1.345 (2) Å, 1.335 (2) and 1.380 (2) Å respectively. They are similar to homologous bonds of structure (II) with distances 1.334 (2) Å for C6—N2, 1.383 (2) Å for N2—N3 and 1.337 (2) Å for C7—N3. And in structure (I), it's almost coplanar for C1, C2, C3, C4, C5, N1, C6, O1, N2, N3, O3, C10 and C11, and the maximum atomic deviation being 0.0920 Å. The dihedral angle between the mean planes of the C1, C2, C3, C4, C5, N1, C6, O1, N2, N3, O3, C10 and C11 and the mean planes of the N3, C7 and O2 is 72.44 (8) °.

Related literature top

For the structure of N-propionylpicoloylhydrazide, see: Wu et al. (2001).

Experimental top

4-ethoxyl-2-pyridine formylhydrazine (3.42 g, 14.41 mmol) was dissolved in a mixed solution of CHCl₃ (30 ml) and EtOH (20 ml), then filtered. Propionic anhydride (3.64 ml) was added and refluxed 2hrs with whisked. Colorless needle crystals of the title compound were obtained by slow evaporation of solvent at room temperature. Melting point: 407 - 407.5 K.

Computing details top

Data collection: XSCANS (Bruker, 1999); cell refinement: XSCANS (Bruker, 1999); data reduction: SHELXTL (Sheldrick, 2008); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. View of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by circles of arbitrary radius.
	Fig. 2. Hydrogen bonds diagram of the title compound, showing the H-bonded interactions (dashed lines). O2I, O2II represent O2ⁱ, O2ⁱⁱ, respectively.

4-Ethoxy-N'-propanoylpyridine-2-carbohydrazide top

Crystal data top

C₁₁H₁₅N₃O₃	F(000) = 504
M_r = 237.26	D_x = 1.274 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 407–407.5 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.377 (5) Å	Cell parameters from 2827 reflections
b = 4.745 (2) Å	θ = 2.7–27.5°
c = 23.244 (10) Å	µ = 0.09 mm⁻¹
β = 99.534 (5)°	T = 293 K
V = 1237.3 (9) Å³	Prism, colourless
Z = 4	1.00 × 0.45 × 0.10 mm

Data collection top

Bruker P4 diffractometer	2297 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 27.5°, θ_min = 2.7°
Detector resolution: 0 pixels mm^-1	h = −14→11
ω scans	k = −6→6
9032 measured reflections	l = −24→30
2803 independent reflections

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) = 0.150	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.080P)² + 0.3962P] where P = (F_o² + 2F_c²)/3
2803 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₁H₁₅N₃O₃	V = 1237.3 (9) Å³
M_r = 237.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.377 (5) Å	µ = 0.09 mm⁻¹
b = 4.745 (2) Å	T = 293 K
c = 23.244 (10) Å	1.00 × 0.45 × 0.10 mm
β = 99.534 (5)°

Data collection top

Bruker P4 diffractometer	2297 reflections with I > 2σ(I)
9032 measured reflections	R_int = 0.022
2803 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 0.96	Δρ_max = 0.27 e Å⁻³
2803 reflections	Δρ_min = −0.28 e Å⁻³
154 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
C1	0.16780 (13)	0.4979 (3)	0.41169 (7)	0.0451 (4)
C2	0.18448 (13)	0.3174 (3)	0.45907 (7)	0.0476 (4)
H2	0.1211	0.2618	0.4771	0.057*
C3	0.29993 (13)	0.2221 (4)	0.47874 (6)	0.0467 (4)
C4	0.39038 (13)	0.3146 (4)	0.45039 (7)	0.0552 (4)
H4	0.4682	0.2531	0.4622	0.066*
C5	0.36375 (14)	0.4981 (4)	0.40462 (8)	0.0608 (5)
H5	0.4260	0.5619	0.3867	0.073*
C6	0.04284 (13)	0.5972 (4)	0.38881 (7)	0.0493 (4)
C7	−0.15075 (13)	0.6370 (3)	0.27838 (7)	0.0446 (4)
C8	−0.26718 (18)	0.7610 (4)	0.24930 (10)	0.0732 (6)
H8A	−0.2938	0.8948	0.2760	0.088*
H8B	−0.2530	0.8654	0.2152	0.088*
C9	−0.36264 (19)	0.5625 (6)	0.23120 (15)	0.1004 (9)
H9D	−0.4327	0.6624	0.2134	0.151*
H9A	−0.3795	0.4607	0.2646	0.151*
H9B	−0.3391	0.4325	0.2036	0.151*
C10	0.24191 (15)	−0.0530 (4)	0.55627 (8)	0.0557 (4)
H10A	0.1822	−0.1624	0.5311	0.067*
H10B	0.2029	0.1047	0.5718	0.067*
C11	0.30482 (18)	−0.2325 (5)	0.60472 (9)	0.0708 (6)
H11A	0.2481	−0.3041	0.6274	0.106*
H11B	0.3636	−0.1216	0.6292	0.106*
H11C	0.3431	−0.3871	0.5886	0.106*
N1	0.25346 (11)	0.5917 (3)	0.38402 (6)	0.0540 (4)
N2	0.03317 (11)	0.7407 (3)	0.33833 (6)	0.0506 (3)
H2A	0.0960	0.7822	0.3240	0.061*
N3	−0.07761 (11)	0.8213 (3)	0.30948 (6)	0.0490 (3)
H3A	−0.0999	0.9937	0.3116	0.059*
O1	−0.04003 (11)	0.5488 (4)	0.41406 (6)	0.0787 (5)
O2	−0.12542 (11)	0.3873 (2)	0.27472 (6)	0.0604 (4)
O3	0.33191 (10)	0.0459 (3)	0.52425 (5)	0.0598 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0370 (7)	0.0495 (8)	0.0482 (8)	0.0069 (6)	0.0051 (6)	−0.0025 (6)
C2	0.0360 (7)	0.0558 (9)	0.0511 (8)	0.0084 (6)	0.0075 (6)	0.0029 (7)
C3	0.0396 (7)	0.0533 (9)	0.0463 (8)	0.0093 (6)	0.0044 (6)	0.0002 (7)
C4	0.0325 (7)	0.0737 (11)	0.0576 (9)	0.0083 (7)	0.0025 (6)	0.0038 (8)
C5	0.0358 (8)	0.0857 (13)	0.0609 (10)	0.0011 (8)	0.0083 (7)	0.0104 (9)
C6	0.0391 (8)	0.0530 (9)	0.0554 (9)	0.0111 (7)	0.0062 (6)	0.0044 (7)
C7	0.0503 (8)	0.0319 (7)	0.0501 (8)	0.0043 (6)	0.0037 (6)	0.0105 (6)
C8	0.0658 (11)	0.0457 (9)	0.0953 (15)	0.0063 (8)	−0.0247 (10)	0.0110 (9)
C9	0.0567 (12)	0.0702 (14)	0.162 (3)	0.0015 (10)	−0.0182 (14)	0.0214 (15)
C10	0.0455 (8)	0.0638 (10)	0.0591 (10)	0.0094 (7)	0.0124 (7)	0.0056 (8)
C11	0.0607 (11)	0.0857 (14)	0.0659 (11)	0.0081 (10)	0.0104 (9)	0.0210 (10)
N1	0.0393 (7)	0.0669 (9)	0.0549 (8)	0.0039 (6)	0.0054 (6)	0.0076 (7)
N2	0.0378 (6)	0.0494 (7)	0.0627 (8)	0.0066 (5)	0.0027 (6)	0.0113 (6)
N3	0.0445 (7)	0.0314 (6)	0.0666 (8)	0.0084 (5)	−0.0034 (6)	0.0054 (6)
O1	0.0440 (7)	0.1159 (12)	0.0797 (9)	0.0281 (7)	0.0204 (6)	0.0354 (8)
O2	0.0739 (8)	0.0305 (6)	0.0743 (8)	0.0092 (5)	0.0053 (6)	0.0045 (5)
O3	0.0407 (6)	0.0781 (8)	0.0612 (7)	0.0186 (5)	0.0099 (5)	0.0205 (6)

Geometric parameters (Å, º) top

C1—N1	1.330 (2)	C8—C9	1.446 (3)
C1—C2	1.383 (2)	C8—H8A	0.9700
C1—C6	1.508 (2)	C8—H8B	0.9700
C2—C3	1.393 (2)	C9—H9D	0.9600
C2—H2	0.9300	C9—H9A	0.9600
C3—O3	1.3502 (19)	C9—H9B	0.9600
C3—C4	1.382 (2)	C10—O3	1.440 (2)
C4—C5	1.369 (3)	C10—C11	1.496 (3)
C4—H4	0.9300	C10—H10A	0.9700
C5—N1	1.342 (2)	C10—H10B	0.9700
C5—H5	0.9300	C11—H11A	0.9600
C6—O1	1.212 (2)	C11—H11B	0.9600
C6—N2	1.345 (2)	C11—H11C	0.9600
C7—O2	1.2256 (19)	N2—N3	1.3800 (17)
C7—N3	1.335 (2)	N2—H2A	0.8600
C7—C8	1.504 (2)	N3—H3A	0.8600

N1—C1—C2	125.26 (14)	C8—C9—H9D	109.5
N1—C1—C6	116.63 (14)	C8—C9—H9A	109.5
C2—C1—C6	118.10 (14)	H9D—C9—H9A	109.5
C1—C2—C3	117.38 (14)	C8—C9—H9B	109.5
C1—C2—H2	121.3	H9D—C9—H9B	109.5
C3—C2—H2	121.3	H9A—C9—H9B	109.5
O3—C3—C4	116.42 (13)	O3—C10—C11	106.39 (14)
O3—C3—C2	125.11 (14)	O3—C10—H10A	110.5
C4—C3—C2	118.46 (15)	C11—C10—H10A	110.5
C5—C4—C3	119.08 (14)	O3—C10—H10B	110.5
C5—C4—H4	120.5	C11—C10—H10B	110.5
C3—C4—H4	120.5	H10A—C10—H10B	108.6
N1—C5—C4	124.12 (16)	C10—C11—H11A	109.5
N1—C5—H5	117.9	C10—C11—H11B	109.5
C4—C5—H5	117.9	H11A—C11—H11B	109.5
O1—C6—N2	124.08 (14)	C10—C11—H11C	109.5
O1—C6—C1	122.24 (15)	H11A—C11—H11C	109.5
N2—C6—C1	113.69 (14)	H11B—C11—H11C	109.5
O2—C7—N3	122.59 (14)	C1—N1—C5	115.67 (15)
O2—C7—C8	123.14 (15)	C6—N2—N3	120.02 (13)
N3—C7—C8	114.25 (13)	C6—N2—H2A	120.0
C9—C8—C7	116.04 (16)	N3—N2—H2A	120.0
C9—C8—H8A	108.3	C7—N3—N2	121.25 (12)
C7—C8—H8A	108.3	C7—N3—H3A	119.4
C9—C8—H8B	108.3	N2—N3—H3A	119.4
C7—C8—H8B	108.3	C3—O3—C10	118.97 (12)
H8A—C8—H8B	107.4

N1—C1—C2—C3	−1.2 (3)	N3—C7—C8—C9	−161.1 (2)
C6—C1—C2—C3	178.43 (14)	C2—C1—N1—C5	0.4 (3)
C1—C2—C3—O3	179.96 (15)	C6—C1—N1—C5	−179.20 (15)
C1—C2—C3—C4	0.6 (2)	C4—C5—N1—C1	1.0 (3)
O3—C3—C4—C5	−178.73 (17)	O1—C6—N2—N3	−5.8 (3)
C2—C3—C4—C5	0.7 (3)	C1—C6—N2—N3	173.92 (13)
C3—C4—C5—N1	−1.6 (3)	O2—C7—N3—N2	1.7 (2)
N1—C1—C6—O1	−172.29 (17)	C8—C7—N3—N2	−179.35 (16)
C2—C1—C6—O1	8.0 (3)	C6—N2—N3—C7	−77.1 (2)
N1—C1—C6—N2	8.0 (2)	C4—C3—O3—C10	178.74 (16)
C2—C1—C6—N2	−171.66 (14)	C2—C3—O3—C10	−0.7 (3)
O2—C7—C8—C9	17.9 (3)	C11—C10—O3—C3	−177.84 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.86	2.43	3.067 (2)	132
N3—H3A···O2ⁱⁱ	0.86	2.06	2.831 (2)	150

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₅N₃O₃
M_r	237.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.377 (5), 4.745 (2), 23.244 (10)
β (°)	99.534 (5)
V (Å³)	1237.3 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	1.00 × 0.45 × 0.10

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9032, 2803, 2297
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.150, 0.96
No. of reflections	2803
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.28

Computer programs: XSCANS (Bruker, 1999), SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.86	2.43	3.067 (2)	131.8
N3—H3A···O2ⁱⁱ	0.86	2.06	2.831 (2)	149.6

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, y+1, z.

Acknowledgements

We are grateful for financial support from the National Science Foundation of Fujian Province of China (No. E0610017, 2003 F006).

References

Bruker (1999). XSCANS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, W. S. & Liu, S. X. (2001). Chin. J. Struct. Chem. 20, 226–228. CAS Google Scholar