(2E)-2-Hydroxy­imino-N′-[(E)-2-pyridyl­methyl­ene]propanohydrazide

doi:10.1107/S1600536809034400

Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2413.

Published online 2009 September 9. doi: 10.1107/S1600536809034400

PMCID: PMC2970200

(2E)-2-Hydroxyimino-N′-[(E)-2-pyridylmethylene]propanohydrazide

Yurii S. Moroz,^a^* Valentina A. Kalibabchuk,^b Elżbieta Gumienna-Kontecka,^c Viktor V. Skopenko,^a and Svetlana V. Pavlova^a

^aDepartment of Chemistry, Kyiv National Taras Shevchenko University, Volodymyrska Str. 64, 01601 Kyiv, Ukraine

^bDepartment of General Chemistry, O.O. Bohomolets National Medical University, Shevchenko blvd. 13, 01601 Kiev, Ukraine

^cFaculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie str., 50-383 Wrocław, Poland

Correspondence e-mail: ysmoroz/at/yahoo.com

Received August 26, 2009; Accepted August 27, 2009.

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

This article has been cited by other articles in PMC.

Abstract

In the title compound, C₉H₁₀N₄O₂, the pyridine ring is twisted by 16.5 (1)° from the mean plane defined by the remaining non-H atoms. An intramolecular N—H (...)

N interaction is present. In the crystal, intermolecular O—H (...)

N and N—H

O hydrogen bonds link molecules into layers parallel to the bc plane. The crystal packing exhibits π–π interactions indicated by the short distance of 3.649 (1) Å between the centroids of the pyridine rings of neighbouring molecules.

Related literature

For the crystal structures of related oxime derivatives, see: Mokhir et al. (2002

); Moroz et al. (2009

). For 2-hydroxyiminopropanamide and amide derivatives of 2-hydroxyiminopropanoic acid, see: Onindo et al. (1995

); Duda et al. (1997

); Sliva et al. (1997a

). For the preparation and characterization of 3d-metal complexes with the structural analog of the title compound, see: Moroz et al. (2008a

). For the synthesis of 2-(hydroxyimino)propanehydrazide, see Fritsky et al. (1998

An external file that holds a picture, illustration, etc.
Object name is e-65-o2413-scheme1.jpg Object name is e-65-o2413-scheme1.jpg

Experimental

Crystal data

C₉H₁₀N₄O₂
M _r = 206.21
Monoclinic,
a = 10.274 (4) Å
b = 9.717 (4) Å
c = 10.136 (4) Å
β = 109.28 (4)°
V = 955.2 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.4 × 0.4 × 0.3 mm

Data collection

Kuma KM-4-CCD diffractometer
Absorption correction: none
10648 measured reflections
2680 independent reflections
2449 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.106
S = 1.08
2680 reflections
176 parameters
All H-atom parameters refined
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006

); cell refinement: CrysAlis RED (Oxford Diffraction, 2006

); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008

); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008

); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997

); software used to prepare material for publication: WinGX (Farrugia, 1999

Table 1

Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809034400/cv2608sup1.cif

Click here to view.^{(16K, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034400/cv2608Isup2.hkl

Click here to view.^{(132K, hkl)}

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

Acknowledgments

The authors thank the Ministry of Education and Science of Ukraine for financial support (grant No. F28/241–2009).

supplementary crystallographic information

Comment

As a part of our research study we present the structure of the title compound, 1 (Fig. 1), which comprises several donor groups: oxime, hydrazone, azomethine, and pyridine. It has been shown previously that structurally similiar strand ligand forms mono- and tetranuclear grid-like assemblies with 3d-metal ions (Moroz et al., 2008a,b).

The C—N and N—O bond lengths in the oxime group, i.e. 1.285 (1) and 1.387 (1) Å, respectively, adopt typical values (Mokhir et al., 2002; Moroz et al., 2009). The oxime group is in a trans position with respect to the amide group, in accordance with the structures of 2-hydroxyiminopropanamide and other amide derivatives of 2-hydroxyiminopropanoic acid (Onindo et al., 1995; Duda et al., 1997; Sliva et al., 1997a). This conformation is stabilized by an N3—H···N4 intramolecular interaction (Table 1). The CH₃C(=NOH)C(O)NH fragment deviates from planarity because of a twist between the oxime and amide groups about the C7—C8 bond; the O1—C7—C8—N4 torsion angle is 173.3 (1)°. The C—N bond length in the azomethine group is 1.283 (1) Å, and the N2—C6—C5 angle has almost ideal value 120.5 (1)°. The pyridine nitrogen atom is situated in an anti- position with respect to the azomethine group.

In the crystal packing, molecules are connected by O2—H···N1 and N3—H···O1 hydrogen bonds (Table 1), where the oximic oxygen and hydrazone nitrogen atoms act as donors and the hydrazone oxygen and pyridine nitrogen atoms act as acceptors. Due to the presence of the system of O2—H···N1 and N3—H···O1 hydrogen bonds, layers parallel to bc plane are formed. The layers are connected in three-dimensional structure by π-π contacts with centroid-to-centroid distance of 3.649 (2) Å, which arise between the pyridine rings of neighbour molecules.

Experimental

The compound 1 has beeen prepared accourding to following procedure: picolinaldehyde (1.1 ml, 0.012 mol) was added to 20 ml of a stirred warm ethanol/water solution of 2-(hydroxyimino)propanehydrazide (1.17 g, 0.01 mol) prepared according to early reported method (Fritsky et al., 1998). After 20 minutes of stirring at 60°C a yellowish precipitate was formed. It was filtered off, washed with water and acetone and recrystalized from methanol. Yield: 1.65 g, 80%. ¹H NMR, 400.13 MHz, (DMSO-d₆): 1.983 (s, 3H, CH₃), 7.393 (dd, 1H, py-5, J = 5.1 Hz, J = 7.2 Hz, py—H), 7.854 (t, 1H, py-4, J = 7.2 Hz, py—H), 7.932 (d, 1H, py-3, J = 7.2 Hz, py—H), 8.494 (s, 1H, CH), 8.594 (d, 1H, py-6, J = 5.1 Hz, py—H), 11.703 (s, 1H, NH), 11.932 (s, 1H, NOH); IR (KBr, cm^-1): 1670 ν(CO_{amid I}), 1040, 895 ν(NO_oxim), 3345 ν(NH_as). Anal. calc. for C₉H₁₀N₄O₂ C, 52.42; H, 4.89; N, 27.17. Found: C, 52.30; H, 4.98; N, 26.98.

Figures

Fig. 1.

A view of 1, with displacement ellipsoids shown at the 40% probability level and atom labelling.

Crystal data

C₉H₁₀N₄O₂	F(000) = 432
M_r = 206.21	D_x = 1.434 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybc	Cell parameters from 11569 reflections
a = 10.274 (4) Å	θ = 3–37°
b = 9.717 (4) Å	µ = 0.11 mm⁻¹
c = 10.136 (4) Å	T = 100 K
β = 109.28 (4)°	Block, white
V = 955.2 (7) Å³	0.4 × 0.4 × 0.3 mm
Z = 4

Data collection

Kuma KM-4-CCD diffractometer	2449 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.023
graphite	θ_max = 30.0°, θ_min = 3.2°
Detector resolution: 8.3359 pixels mm^-1	h = −14→13
ω scans	k = −13→10
10648 measured reflections	l = −14→14
2680 independent reflections

Refinement

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	All H-atom parameters refined
S = 1.08	w = 1/[σ²(F_o²) + (0.0621P)² + 0.2439P] where P = (F_o² + 2F_c²)/3
2680 reflections	(Δ/σ)_max < 0.001
176 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Special details

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)

	x	y	z	U_iso*/U_eq
O1	0.59592 (7)	0.23238 (7)	0.23853 (7)	0.01751 (17)
O2	0.24735 (8)	0.10483 (8)	−0.16272 (8)	0.01954 (17)
H21	0.2245 (17)	0.1328 (17)	−0.2501 (18)	0.032 (4)*
N1	0.85431 (9)	0.66853 (8)	−0.05564 (8)	0.01561 (18)
N2	0.70574 (8)	0.39826 (8)	0.08234 (8)	0.01477 (17)
N3	0.59208 (9)	0.31588 (9)	0.02612 (9)	0.01608 (18)
H31	0.5529 (16)	0.3104 (16)	−0.0650 (17)	0.030 (4)*
N4	0.36471 (8)	0.18113 (8)	−0.09566 (8)	0.01500 (17)
C1	0.95964 (11)	0.75821 (10)	−0.01987 (11)	0.0176 (2)
H1	0.9570 (16)	0.8267 (16)	−0.0903 (16)	0.029 (4)*
C2	1.06781 (10)	0.75321 (10)	0.10549 (10)	0.0168 (2)
H2	1.1433 (15)	0.8188 (14)	0.1263 (15)	0.023 (3)*
C3	1.06686 (10)	0.64989 (10)	0.20031 (10)	0.0167 (2)
H3	1.1409 (16)	0.6414 (16)	0.2873 (16)	0.026 (4)*
C4	0.95703 (10)	0.55828 (10)	0.16717 (10)	0.01493 (19)
H4	0.9544 (15)	0.4838 (15)	0.2317 (15)	0.024 (3)*
C5	0.85205 (10)	0.57099 (9)	0.03849 (9)	0.01315 (18)
C6	0.73225 (10)	0.47858 (10)	−0.00602 (10)	0.01499 (19)
H6	0.6756 (15)	0.4825 (15)	−0.1032 (15)	0.026 (3)*
C7	0.54344 (10)	0.23721 (9)	0.11115 (10)	0.01334 (18)
C8	0.41629 (10)	0.15545 (9)	0.03573 (10)	0.01366 (19)
C9	0.36358 (11)	0.05663 (11)	0.11943 (11)	0.0188 (2)
H9A	0.2794 (19)	0.0181 (19)	0.0675 (19)	0.044 (5)*
H9B	0.3462 (17)	0.1013 (17)	0.1967 (18)	0.037 (4)*
H9C	0.4325 (17)	−0.0149 (17)	0.1626 (17)	0.035 (4)*

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0173 (3)	0.0225 (4)	0.0118 (3)	−0.0006 (3)	0.0036 (3)	0.0006 (2)
O2	0.0176 (4)	0.0249 (4)	0.0133 (3)	−0.0076 (3)	0.0014 (3)	−0.0023 (3)
N1	0.0163 (4)	0.0174 (4)	0.0136 (4)	0.0008 (3)	0.0055 (3)	0.0016 (3)
N2	0.0133 (4)	0.0166 (4)	0.0145 (4)	−0.0022 (3)	0.0046 (3)	−0.0024 (3)
N3	0.0160 (4)	0.0202 (4)	0.0109 (4)	−0.0054 (3)	0.0029 (3)	−0.0011 (3)
N4	0.0128 (4)	0.0168 (4)	0.0146 (4)	−0.0022 (3)	0.0036 (3)	−0.0028 (3)
C1	0.0192 (5)	0.0172 (4)	0.0180 (5)	−0.0002 (3)	0.0084 (4)	0.0029 (3)
C2	0.0155 (4)	0.0163 (4)	0.0198 (5)	−0.0018 (3)	0.0076 (4)	−0.0022 (3)
C3	0.0147 (4)	0.0188 (4)	0.0153 (4)	0.0002 (3)	0.0034 (3)	−0.0017 (3)
C4	0.0161 (4)	0.0153 (4)	0.0132 (4)	0.0001 (3)	0.0046 (3)	0.0007 (3)
C5	0.0139 (4)	0.0138 (4)	0.0128 (4)	0.0006 (3)	0.0058 (3)	−0.0011 (3)
C6	0.0147 (4)	0.0171 (4)	0.0126 (4)	−0.0005 (3)	0.0038 (3)	−0.0014 (3)
C7	0.0133 (4)	0.0139 (4)	0.0133 (4)	0.0011 (3)	0.0050 (3)	−0.0004 (3)
C8	0.0136 (4)	0.0139 (4)	0.0139 (4)	0.0001 (3)	0.0051 (3)	−0.0010 (3)
C9	0.0201 (5)	0.0190 (4)	0.0170 (4)	−0.0037 (4)	0.0058 (4)	0.0024 (3)

Geometric parameters (Å, °)

O1—C7	1.2249 (13)	C2—H2	0.972 (14)
O2—N4	1.3872 (12)	C3—C4	1.3886 (14)
O2—H21	0.881 (17)	C3—H3	0.959 (15)
N1—C1	1.3427 (13)	C4—C5	1.3967 (15)
N1—C5	1.3505 (12)	C4—H4	0.982 (14)
N2—C6	1.2832 (13)	C5—C6	1.4691 (14)
N2—N3	1.3746 (12)	C6—H6	0.965 (14)
N3—C7	1.3643 (12)	C7—C8	1.5042 (14)
N3—H31	0.879 (16)	C8—C9	1.4962 (13)
N4—C8	1.2848 (14)	C9—H9A	0.930 (19)
C1—C2	1.3854 (16)	C9—H9B	0.962 (17)
C1—H1	0.970 (15)	C9—H9C	0.985 (17)
C2—C3	1.3921 (14)

N4—O2—H21	103.1 (11)	N1—C5—C4	122.25 (9)
C1—N1—C5	117.71 (9)	N1—C5—C6	114.84 (9)
C6—N2—N3	114.32 (9)	C4—C5—C6	122.90 (9)
C7—N3—N2	120.18 (8)	N2—C6—C5	120.45 (9)
C7—N3—H31	119.6 (10)	N2—C6—H6	122.7 (9)
N2—N3—H31	120.2 (10)	C5—C6—H6	116.8 (9)
C8—N4—O2	113.47 (8)	O1—C7—N3	124.18 (9)
N1—C1—C2	123.77 (9)	O1—C7—C8	121.44 (9)
N1—C1—H1	115.0 (9)	N3—C7—C8	114.38 (8)
C2—C1—H1	121.2 (9)	N4—C8—C9	127.58 (9)
C1—C2—C3	118.17 (9)	N4—C8—C7	114.58 (9)
C1—C2—H2	121.1 (9)	C9—C8—C7	117.84 (9)
C3—C2—H2	120.7 (9)	C8—C9—H9A	112.3 (11)
C4—C3—C2	119.06 (10)	C8—C9—H9B	111.8 (10)
C4—C3—H3	120.1 (9)	H9A—C9—H9B	104.7 (15)
C2—C3—H3	120.8 (9)	C8—C9—H9C	111.3 (9)
C3—C4—C5	118.98 (9)	H9A—C9—H9C	111.4 (15)
C3—C4—H4	120.7 (8)	H9B—C9—H9C	104.8 (13)
C5—C4—H4	120.3 (8)

C6—N2—N3—C7	−172.56 (9)	N1—C5—C6—N2	−167.65 (9)
C5—N1—C1—C2	2.31 (14)	C4—C5—C6—N2	13.31 (14)
N1—C1—C2—C3	−0.46 (15)	N2—N3—C7—O1	−1.03 (15)
C1—C2—C3—C4	−1.31 (14)	N2—N3—C7—C8	178.35 (8)
C2—C3—C4—C5	1.19 (14)	O2—N4—C8—C9	−0.54 (14)
C1—N1—C5—C4	−2.42 (14)	O2—N4—C8—C7	−179.80 (7)
C1—N1—C5—C6	178.54 (8)	O1—C7—C8—N4	173.25 (9)
C3—C4—C5—N1	0.71 (14)	N3—C7—C8—N4	−6.14 (12)
C3—C4—C5—C6	179.68 (8)	O1—C7—C8—C9	−6.08 (13)
N3—N2—C6—C5	−178.98 (8)	N3—C7—C8—C9	174.52 (8)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H21···N1ⁱ	0.881 (17)	1.897 (18)	2.7667 (17)	168.6 (15)
N3—H31···O1ⁱⁱ	0.879 (16)	2.217 (16)	2.9656 (15)	142.9 (14)
N3—H31···N4	0.879 (16)	2.240 (16)	2.6059 (15)	104.7 (12)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2608).

References

Duda, A. M., Karaczyn, A., Kozłowski, H., Fritsky, I. O., Głowiak, T., Prisyazhnaya, E. V., Sliva, T. Yu. & Świątek-Kozłowska, J. (1997). J. Chem. Soc. Dalton Trans. pp. 3853–3859.
Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
Fritsky, I. O., Kozłowski, H., Sadler, P. J., Yefetova, O. P., Świątek-Kozłowska, J., Kalibabchuk, V. A. & Glowiak, T. (1998). J. Chem. Soc. Dalton Trans. pp. 3269–3274.
Mokhir, A. A., Gumienna-Kontecka, E., Świątek-Kozłowska, J., Petkova, E. G., Fritsky, I. O., Jerzykiewicz, L., Kapshuk, A. A. & Sliva, T. Yu. (2002). Inorg. Chim. Acta, 329, 113–121.
Moroz, Y. S., Konovalova, I. S., Iskenderov, T. S., Pavlova, S. V. & Shishkin, O. V. (2009). Acta Cryst. E65, o2242. [PMC free article] [PubMed]
Moroz, Yu. S., Kulon, K., Haukka, M., Gumienna-Kontecka, E., Kozłowski, H., Meyer, F. & Fritsky, I. O. (2008a). Inorg. Chem.47, 5656–5665. [PubMed]
Moroz, Y. S., Sliva, T. Yu., Kulon, K., Kozłowski, H. & Fritsky, I. O. (2008b). Acta Cryst. E64, m353–m354.
Onindo, C. O., Sliva, T. Yu., Kowalik-Jankowska, T., Fritsky, I. O., Buglyo, P., Pettit, L. D., Kozłowski, H. & Kiss, T. (1995). J. Chem. Soc. Dalton Trans. pp. 3911–3915.
Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED Oxford Diffraction Ltd, Abingdon,England.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
Sliva, T. Yu., Duda, A. M., Glowiak, T., Fritsky, I. O., Amirkhanov, V. M., Mokhir, A. A. & Kozłowski, H. (1997a). J. Chem. Soc. Dalton Trans. pp. 273–276.

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