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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

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 [triangle]); Moroz et al. (2009 [triangle]). For 2-hydroxy­imino­propanamide and amide derivatives of 2-hydroxy­imino­propanoic acid, see: Onindo et al. (1995 [triangle]); Duda et al. (1997 [triangle]); Sliva et al. (1997a [triangle]). For the preparation and characterization of 3d-metal complexes with the structural analog of the title compound, see: Moroz et al. (2008a [triangle],b [triangle]). For the synthesis of 2-(hydroxy­imino)propane­hydrazide, see Fritsky et al. (1998 [triangle]).

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

Experimental

Crystal data

  • C9H10N4O2
  • M r = 206.21
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2413-efi1.jpg
  • 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
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034400/cv2608Isup2.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(COamid I), 1040, 895 ν(NOoxim), 3345 ν(NHas). Anal. calc. for C9H10N4O2 C, 52.42; H, 4.89; N, 27.17. Found: C, 52.30; H, 4.98; N, 26.98.

Refinement

All H atoms were located in a difference Fourier map and refined isotropically.

Figures

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

Crystal data

C9H10N4O2F(000) = 432
Mr = 206.21Dx = 1.434 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybcCell parameters from 11569 reflections
a = 10.274 (4) Åθ = 3–37°
b = 9.717 (4) ŵ = 0.11 mm1
c = 10.136 (4) ÅT = 100 K
β = 109.28 (4)°Block, white
V = 955.2 (7) Å30.4 × 0.4 × 0.3 mm
Z = 4

Data collection

Kuma KM-4-CCD diffractometer2449 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray SourceRint = 0.023
graphiteθmax = 30.0°, θmin = 3.2°
Detector resolution: 8.3359 pixels mm-1h = −14→13
ω scansk = −13→10
10648 measured reflectionsl = −14→14
2680 independent reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106All H-atom parameters refined
S = 1.08w = 1/[σ2(Fo2) + (0.0621P)2 + 0.2439P] where P = (Fo2 + 2Fc2)/3
2680 reflections(Δ/σ)max < 0.001
176 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = −0.18 e Å3

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)

xyzUiso*/Ueq
O10.59592 (7)0.23238 (7)0.23853 (7)0.01751 (17)
O20.24735 (8)0.10483 (8)−0.16272 (8)0.01954 (17)
H210.2245 (17)0.1328 (17)−0.2501 (18)0.032 (4)*
N10.85431 (9)0.66853 (8)−0.05564 (8)0.01561 (18)
N20.70574 (8)0.39826 (8)0.08234 (8)0.01477 (17)
N30.59208 (9)0.31588 (9)0.02612 (9)0.01608 (18)
H310.5529 (16)0.3104 (16)−0.0650 (17)0.030 (4)*
N40.36471 (8)0.18113 (8)−0.09566 (8)0.01500 (17)
C10.95964 (11)0.75821 (10)−0.01987 (11)0.0176 (2)
H10.9570 (16)0.8267 (16)−0.0903 (16)0.029 (4)*
C21.06781 (10)0.75321 (10)0.10549 (10)0.0168 (2)
H21.1433 (15)0.8188 (14)0.1263 (15)0.023 (3)*
C31.06686 (10)0.64989 (10)0.20031 (10)0.0167 (2)
H31.1409 (16)0.6414 (16)0.2873 (16)0.026 (4)*
C40.95703 (10)0.55828 (10)0.16717 (10)0.01493 (19)
H40.9544 (15)0.4838 (15)0.2317 (15)0.024 (3)*
C50.85205 (10)0.57099 (9)0.03849 (9)0.01315 (18)
C60.73225 (10)0.47858 (10)−0.00602 (10)0.01499 (19)
H60.6756 (15)0.4825 (15)−0.1032 (15)0.026 (3)*
C70.54344 (10)0.23721 (9)0.11115 (10)0.01334 (18)
C80.41629 (10)0.15545 (9)0.03573 (10)0.01366 (19)
C90.36358 (11)0.05663 (11)0.11943 (11)0.0188 (2)
H9A0.2794 (19)0.0181 (19)0.0675 (19)0.044 (5)*
H9B0.3462 (17)0.1013 (17)0.1967 (18)0.037 (4)*
H9C0.4325 (17)−0.0149 (17)0.1626 (17)0.035 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0173 (3)0.0225 (4)0.0118 (3)−0.0006 (3)0.0036 (3)0.0006 (2)
O20.0176 (4)0.0249 (4)0.0133 (3)−0.0076 (3)0.0014 (3)−0.0023 (3)
N10.0163 (4)0.0174 (4)0.0136 (4)0.0008 (3)0.0055 (3)0.0016 (3)
N20.0133 (4)0.0166 (4)0.0145 (4)−0.0022 (3)0.0046 (3)−0.0024 (3)
N30.0160 (4)0.0202 (4)0.0109 (4)−0.0054 (3)0.0029 (3)−0.0011 (3)
N40.0128 (4)0.0168 (4)0.0146 (4)−0.0022 (3)0.0036 (3)−0.0028 (3)
C10.0192 (5)0.0172 (4)0.0180 (5)−0.0002 (3)0.0084 (4)0.0029 (3)
C20.0155 (4)0.0163 (4)0.0198 (5)−0.0018 (3)0.0076 (4)−0.0022 (3)
C30.0147 (4)0.0188 (4)0.0153 (4)0.0002 (3)0.0034 (3)−0.0017 (3)
C40.0161 (4)0.0153 (4)0.0132 (4)0.0001 (3)0.0046 (3)0.0007 (3)
C50.0139 (4)0.0138 (4)0.0128 (4)0.0006 (3)0.0058 (3)−0.0011 (3)
C60.0147 (4)0.0171 (4)0.0126 (4)−0.0005 (3)0.0038 (3)−0.0014 (3)
C70.0133 (4)0.0139 (4)0.0133 (4)0.0011 (3)0.0050 (3)−0.0004 (3)
C80.0136 (4)0.0139 (4)0.0139 (4)0.0001 (3)0.0051 (3)−0.0010 (3)
C90.0201 (5)0.0190 (4)0.0170 (4)−0.0037 (4)0.0058 (4)0.0024 (3)

Geometric parameters (Å, °)

O1—C71.2249 (13)C2—H20.972 (14)
O2—N41.3872 (12)C3—C41.3886 (14)
O2—H210.881 (17)C3—H30.959 (15)
N1—C11.3427 (13)C4—C51.3967 (15)
N1—C51.3505 (12)C4—H40.982 (14)
N2—C61.2832 (13)C5—C61.4691 (14)
N2—N31.3746 (12)C6—H60.965 (14)
N3—C71.3643 (12)C7—C81.5042 (14)
N3—H310.879 (16)C8—C91.4962 (13)
N4—C81.2848 (14)C9—H9A0.930 (19)
C1—C21.3854 (16)C9—H9B0.962 (17)
C1—H10.970 (15)C9—H9C0.985 (17)
C2—C31.3921 (14)
N4—O2—H21103.1 (11)N1—C5—C4122.25 (9)
C1—N1—C5117.71 (9)N1—C5—C6114.84 (9)
C6—N2—N3114.32 (9)C4—C5—C6122.90 (9)
C7—N3—N2120.18 (8)N2—C6—C5120.45 (9)
C7—N3—H31119.6 (10)N2—C6—H6122.7 (9)
N2—N3—H31120.2 (10)C5—C6—H6116.8 (9)
C8—N4—O2113.47 (8)O1—C7—N3124.18 (9)
N1—C1—C2123.77 (9)O1—C7—C8121.44 (9)
N1—C1—H1115.0 (9)N3—C7—C8114.38 (8)
C2—C1—H1121.2 (9)N4—C8—C9127.58 (9)
C1—C2—C3118.17 (9)N4—C8—C7114.58 (9)
C1—C2—H2121.1 (9)C9—C8—C7117.84 (9)
C3—C2—H2120.7 (9)C8—C9—H9A112.3 (11)
C4—C3—C2119.06 (10)C8—C9—H9B111.8 (10)
C4—C3—H3120.1 (9)H9A—C9—H9B104.7 (15)
C2—C3—H3120.8 (9)C8—C9—H9C111.3 (9)
C3—C4—C5118.98 (9)H9A—C9—H9C111.4 (15)
C3—C4—H4120.7 (8)H9B—C9—H9C104.8 (13)
C5—C4—H4120.3 (8)
C6—N2—N3—C7−172.56 (9)N1—C5—C6—N2−167.65 (9)
C5—N1—C1—C22.31 (14)C4—C5—C6—N213.31 (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—C8178.35 (8)
C2—C3—C4—C51.19 (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—C6178.54 (8)O1—C7—C8—N4173.25 (9)
C3—C4—C5—N10.71 (14)N3—C7—C8—N4−6.14 (12)
C3—C4—C5—C6179.68 (8)O1—C7—C8—C9−6.08 (13)
N3—N2—C6—C5−178.98 (8)N3—C7—C8—C9174.52 (8)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H21···N1i0.881 (17)1.897 (18)2.7667 (17)168.6 (15)
N3—H31···O1ii0.879 (16)2.217 (16)2.9656 (15)142.9 (14)
N3—H31···N40.879 (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

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