Crystal structure of 2-hy-droxy-imino-2-(pyridin-2-yl)-N'-[1-(pyridin-2-yl)ethyl-idene]acetohydrazide.

The mol-ecule of the title compound, C14H13N5O2, is approximately planar (r.m.s deviation for all non-H atoms = 0.093 Å), with the planes of the two pyridine rings inclined to one another by 5.51 (7)°. The oxime group is syn to the amide group, probably due to the formation of an intra-molecular N-H⋯N hydrogen bond that forms an S(6) ring motif. In the crystal, mol-ecules are linked by pairs of bifurcated O-H⋯(O,N) hydrogen bonds, forming inversion dimers. The latter are linked via C-H⋯O and C-H⋯N hydrogen bonds, forming sheets lying parallel to (502). The sheets are linked via π-π stacking inter-actions [inter-centroid distance = 3.7588 (9) Å], involving the pyridine rings of inversion-related mol-ecules, forming a three-dimensional structure.

Chemical context

Polynuclear oxime-containing ligands have attracted considerable inter­est because of their ability to act as efficient bridging ligands and for their tendency to form polynuclear metal complexes (Penkova et al., 2010 ▶; Pavlishchuk et al., 2010 ▶, 2011 ▶). The presence of additional non-oxime donor functions (e.g. hydrazide, azomethine, pyridine) in the ligand mol­ecule favours the formation of metal complexes with strong magnetic exchange inter­actions between the metal ions (Pavlishchuk et al., 2011 ▶), and complexes which efficiently stabilize unusual high oxidation states of 3d metal ions (Kanderal et al., 2005 ▶; Fritsky et al., 1998 ▶, 2006 ▶). As a part of our research study, we present the structure of the title compound, which contains several donor functions of a different nature; oxime, hydrazide, and two different pyridine groups.

Structural commentary

The mol­ecular structure of the title compound is illustrated in Fig. 1 ▶. The mol­ecule is approximately planar (r.m.s deviation for all non-H atoms = 0.093 Å) with the maximum deviations from the mean plane being 0.255 (1) Å for atom N1, and 0.198 (1) Å for atom O1. The two pyridine rings (N1/C1–C5) and N5/C10–C14) are inclined to one another by 5.51 (7)°. The N2—O1 [1.3691 (14) Å] and C6—N2 [1.2866 (17) Å] bond lengths of the oxime group have typical values (Fritsky et al., 1998 ▶). The pyridine N atom, N1, is situated in an anti position with respect to the azomethine group, in accordance with the structures of earlier synthesized ligands of this type (Plutenko et al., 2011 ▶, 2013 ▶).

Figure 1

A view of the mol­ecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The intra­molecular N—H⋯N hydrogen bond is shown as a dashed line (see Table 1 ▶ for details).

The N4—N3, N3—C7 and C7—O2 bond lengths of the hydrazide group are 1.3776 (16), 1.3471 (18) and 1.2269 (17) Å, respectively, typical for protonated moieties of this type (Plutenko et al., 2011 ▶, 2013 ▶). The oxime group is situated in a syn position with respect to the amide group, in contrast to earlier synthesized ligands of this type (Plutenko et al., 2012 ▶, 2013 ▶). Such a disposition of these moieties is atypical for amide derivatives of 2-hy­droxy­imino­propanoic acid (Onindo et al., 1995 ▶; Sliva et al., 1997 ▶; Duda et al., 1997 ▶). It can be explained by the presence of an intra­molecular N3—H3⋯N1 hydrogen bond in which the azomethine N atom, N3, acts as donor and the pyridine N atom, N1, acts as an acceptor (Fig. 1 ▶ and Table 1 ▶).

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N3H3N1	0.89(2)	1.84(2)	2.6126(17)	144(2)
O1H1O2i	0.93(2)	1.98(2)	2.8327(14)	151(2)
O1H1N2i	0.93(2)	2.13(2)	2.8489(16)	133(2)
C2H2O2ii	0.95	2.54	3.1985(15)	127
C3H3AO1iii	0.95	2.56	3.4755(15)	163
C13H13N5iv	0.95	2.46	3.3811(19)	163

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Supra­molecular features

In the crystal, mol­ecules are linked by pairs of bifurcated O—H⋯(O,N) hydrogen bonds forming inversion dimers (Fig. 2 ▶ and Table 1 ▶). The dimers are linked via C—H⋯O and C—H⋯N hydrogen bonds, forming sheets lying parallel to plane (502). The sheets are linked via π–π stacking inter­actions, forming a three-dimensional structure [Cg1⋯Cg2i = 3.7588 (9) Å; Cg1 and Cg2 are the centroids of pyridine rings N1/C1–C5 and N5/C10–C14, respectively; symmetry code: (i) −x + 1, −y + 2, −z + 1].

Figure 2

Crystal packing of the title compound viewed along the b axis. Hydrogen bonds are indicated by dashed lines (see Table 1 ▶ for details). H atoms not involved in hydrogen bonds have been omitted for clarity.

Database survey

The crystal structures of two very similar compounds have been reported, viz. 2-hy­droxy­imino-N′-(1-(pyridin-2-yl)ethyl­idene)propano­hydrazide (Moroz et al., 2009 ▶) and two polymorphs of 2-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(hy­droxyimino)-N′-(1-(pyridin-2-yl) ethyl­idene)acetohydrazide (Plutenko et al., 2012 ▶, 2013 ▶).

Synthesis and crystallization

A solution of 2-hy­droxy­imino-2-(pyridin-2-yl)acetohydrazide (0.36 g, 2 mmol), prepared according to a published procedure (Zyl et al., 1961 ▶; Kolar et al., 1991 ▶), in methanol (20 ml) was treated with 2-acetyl­pyridine (0.242 g, 2 mmol) and the mixture was heated under reflux for 3 h. After cooling, the solvent was evaporated under vacuum and the resulting product was recrystallized from methanol, giving colourless block-like crystals of the title compound (yield 0.52 g; 92%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▶. The N—H and O—H hydrogen atoms were located in difference Fourier maps and freely refined. The C-bound H atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.95–0.98 Å, and with U iso = 1.5U eq(C) for methyl H atoms and = 1.2U eq(C) for other H atoms.

Table 2

Experimental details

Crystal data
Chemical formula	C14H13N5O2
M r	283.29
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	123
a, b, c ()	11.4319(9), 9.3598(4), 12.4297(9)
()	105.016(3)
V (3)	1284.57(15)
Z	4
Radiation type	Mo K
(mm1)	0.10
Crystal size (mm)	0.27 0.15 0.14
Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 ▶)
T min, T max	0.973, 0.986
No. of measured, independent and observed [I > 2(I)] reflections	7900, 2850, 2226
R int	0.032
(sin /)max (1)	0.651
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.044, 0.115, 1.05
No. of reflections	2850
No. of parameters	196
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
max, min (e 3)	0.33, 0.22

Computer programs: APEX2 and SAINT (Bruker, 2010 ▶), SHELXS97 and SHELXL97 (Sheldrick, 2008 ▶), DIAMOND (Brandenburg, 2008 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814025793/su5024sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814025793/su5024Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814025793/su5024Isup3.mol

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814025793/su5024Isup4.cml

CCDC reference: 1035993

Additional supporting information: crystallographic information; 3D view; checkCIF report

C14H13N5O2	F(000) = 592
Mr = 283.29	Dx = 1.465 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 12859 reflections
a = 11.4319 (9) Å	θ = 1.0–27.5°
b = 9.3598 (4) Å	µ = 0.10 mm−1
c = 12.4297 (9) Å	T = 123 K
β = 105.016 (3)°	Block, colourless
V = 1284.57 (15) Å3	0.27 × 0.15 × 0.14 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	2850 independent reflections
Radiation source: fine-focus sealed tube	2226 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.032
Detector resolution: 16 pixels mm-1	θmax = 27.6°, θmin = 3.6°
φ scans and ω scans with κ offset	h = −14→7
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→12
Tmin = 0.973, Tmax = 0.986	l = −13→16
7900 measured reflections

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0444P)2 + 0.5602P] where P = (Fo2 + 2Fc2)/3
2850 reflections	(Δ/σ)max < 0.001
196 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.53771 (10)	0.81661 (11)	0.01882 (9)	0.0275 (3)
H1	0.547 (2)	0.873 (3)	−0.0406 (19)	0.061 (7)*
O2	0.41325 (12)	1.10609 (11)	0.18548 (9)	0.0365 (3)
N1	0.42020 (13)	0.68309 (13)	0.29508 (10)	0.0269 (3)
N2	0.49655 (12)	0.91005 (12)	0.08547 (10)	0.0227 (3)
N3	0.39671 (12)	0.95674 (13)	0.32531 (10)	0.0217 (3)
H3	0.3983 (18)	0.865 (2)	0.3433 (16)	0.045 (6)*
N4	0.36523 (11)	1.06522 (12)	0.38730 (9)	0.0211 (3)
N5	0.27415 (12)	1.10442 (13)	0.63724 (10)	0.0249 (3)
C1	0.40835 (17)	0.54907 (16)	0.32784 (14)	0.0332 (4)
H1A	0.3841	0.5347	0.3946	0.040*
C2	0.42966 (11)	0.43023 (11)	0.26956 (9)	0.0279 (3)
H2	0.4195	0.3363	0.2946	0.033*
C3	0.46609 (11)	0.45322 (11)	0.17415 (9)	0.0261 (3)
H3A	0.4818	0.3742	0.1320	0.031*
C4	0.48006 (15)	0.59117 (15)	0.13888 (12)	0.0258 (3)
H4	0.5061	0.6074	0.0732	0.031*
C5	0.45529 (13)	0.70606 (14)	0.20141 (11)	0.0196 (3)
C6	0.46209 (13)	0.85875 (14)	0.16827 (11)	0.0198 (3)
C7	0.42130 (14)	0.98666 (14)	0.22744 (12)	0.0225 (3)
C8	0.33284 (13)	1.02516 (14)	0.47426 (11)	0.0206 (3)
C9	0.32455 (16)	0.87266 (15)	0.50997 (13)	0.0282 (4)
H9A	0.2782	0.8166	0.4466	0.042*
H9B	0.2838	0.8694	0.5702	0.042*
H9C	0.4062	0.8327	0.5363	0.042*
C10	0.30190 (13)	1.14279 (14)	0.54298 (11)	0.0200 (3)
C11	0.30120 (14)	1.28513 (15)	0.50943 (12)	0.0253 (3)
H11	0.3217	1.3094	0.4424	0.030*
C12	0.27019 (15)	1.39034 (16)	0.57523 (13)	0.0281 (3)
H12	0.2690	1.4879	0.5539	0.034*
C13	0.24098 (14)	1.35182 (16)	0.67237 (12)	0.0257 (3)
H13	0.2188	1.4216	0.7190	0.031*
C14	0.24502 (15)	1.20881 (16)	0.69948 (12)	0.0275 (3)
H14	0.2259	1.1824	0.7667	0.033*

	U11	U22	U33	U12	U13	U23
O1	0.0449 (7)	0.0188 (5)	0.0253 (6)	0.0028 (4)	0.0206 (5)	−0.0006 (4)
O2	0.0691 (9)	0.0166 (5)	0.0338 (6)	0.0044 (5)	0.0315 (6)	0.0034 (4)
N1	0.0415 (8)	0.0172 (6)	0.0263 (6)	0.0000 (5)	0.0165 (6)	−0.0005 (5)
N2	0.0321 (7)	0.0180 (6)	0.0197 (6)	0.0003 (5)	0.0100 (5)	−0.0028 (4)
N3	0.0323 (7)	0.0147 (6)	0.0213 (6)	0.0013 (5)	0.0128 (5)	−0.0003 (4)
N4	0.0278 (7)	0.0173 (6)	0.0203 (6)	0.0010 (5)	0.0102 (5)	−0.0027 (4)
N5	0.0344 (7)	0.0215 (6)	0.0219 (6)	−0.0003 (5)	0.0126 (6)	−0.0005 (5)
C1	0.0550 (11)	0.0207 (7)	0.0314 (8)	−0.0003 (7)	0.0247 (8)	0.0026 (6)
C2	0.0387 (9)	0.0165 (7)	0.0310 (8)	−0.0002 (6)	0.0136 (7)	0.0024 (6)
C3	0.0354 (9)	0.0177 (7)	0.0276 (8)	0.0000 (6)	0.0124 (7)	−0.0035 (5)
C4	0.0372 (9)	0.0196 (7)	0.0242 (7)	−0.0003 (6)	0.0143 (7)	−0.0020 (5)
C5	0.0218 (7)	0.0174 (7)	0.0199 (6)	−0.0007 (5)	0.0062 (5)	−0.0001 (5)
C6	0.0251 (7)	0.0165 (7)	0.0192 (7)	−0.0003 (5)	0.0080 (6)	−0.0008 (5)
C7	0.0315 (8)	0.0164 (7)	0.0218 (7)	−0.0015 (5)	0.0107 (6)	−0.0018 (5)
C8	0.0241 (7)	0.0177 (7)	0.0211 (7)	0.0001 (5)	0.0079 (6)	0.0000 (5)
C9	0.0432 (10)	0.0188 (7)	0.0275 (8)	−0.0003 (6)	0.0177 (7)	0.0015 (5)
C10	0.0229 (7)	0.0188 (7)	0.0190 (7)	−0.0008 (5)	0.0066 (6)	−0.0008 (5)
C11	0.0357 (9)	0.0201 (7)	0.0236 (7)	0.0008 (6)	0.0138 (7)	0.0002 (5)
C12	0.0365 (9)	0.0197 (7)	0.0297 (8)	0.0017 (6)	0.0117 (7)	−0.0011 (6)
C13	0.0289 (8)	0.0237 (7)	0.0257 (7)	0.0024 (6)	0.0090 (6)	−0.0063 (6)
C14	0.0360 (9)	0.0277 (8)	0.0223 (7)	0.0000 (6)	0.0141 (7)	−0.0028 (6)

O1—N2	1.3691 (14)	C4—C5	1.3981 (19)
O1—H1	0.93 (2)	C4—H4	0.9500
O2—C7	1.2269 (17)	C5—C6	1.4950 (18)
N1—C1	1.3365 (19)	C6—C7	1.5392 (18)
N1—C5	1.3435 (18)	C8—C10	1.4911 (18)
N2—C6	1.2866 (17)	C8—C9	1.5051 (19)
N3—C7	1.3471 (18)	C9—H9A	0.9800
N3—N4	1.3776 (16)	C9—H9B	0.9800
N3—H3	0.89 (2)	C9—H9C	0.9800
N4—C8	1.2858 (18)	C10—C11	1.3954 (19)
N5—C10	1.3398 (18)	C11—C12	1.3837 (19)
N5—C14	1.3407 (18)	C11—H11	0.9500
C1—C2	1.3831 (18)	C12—C13	1.382 (2)
C1—H1A	0.9500	C12—H12	0.9500
C2—C3	1.3719	C13—C14	1.378 (2)
C2—H2	0.9500	C13—H13	0.9500
C3—C4	1.3861 (17)	C14—H14	0.9500
C3—H3A	0.9500
N2—O1—H1	104.1 (14)	O2—C7—C6	120.28 (12)
C1—N1—C5	119.39 (12)	N3—C7—C6	115.45 (11)
C6—N2—O1	118.04 (11)	N4—C8—C10	115.40 (12)
C7—N3—N4	119.85 (12)	N4—C8—C9	125.33 (12)
C7—N3—H3	115.7 (13)	C10—C8—C9	119.27 (12)
N4—N3—H3	124.4 (13)	C8—C9—H9A	109.5
C8—N4—N3	115.41 (12)	C8—C9—H9B	109.5
C10—N5—C14	117.37 (12)	H9A—C9—H9B	109.5
N1—C1—C2	123.35 (13)	C8—C9—H9C	109.5
N1—C1—H1A	118.3	H9A—C9—H9C	109.5
C2—C1—H1A	118.3	H9B—C9—H9C	109.5
C3—C2—C1	117.44 (8)	N5—C10—C11	122.20 (12)
C3—C2—H2	121.3	N5—C10—C8	116.62 (12)
C1—C2—H2	121.3	C11—C10—C8	121.17 (12)
C2—C3—C4	120.34 (7)	C12—C11—C10	119.04 (13)
C2—C3—H3A	119.8	C12—C11—H11	120.5
C4—C3—H3A	119.8	C10—C11—H11	120.5
C3—C4—C5	118.95 (12)	C13—C12—C11	119.20 (14)
C3—C4—H4	120.5	C13—C12—H12	120.4
C5—C4—H4	120.5	C11—C12—H12	120.4
N1—C5—C4	120.51 (12)	C14—C13—C12	117.83 (13)
N1—C5—C6	116.12 (12)	C14—C13—H13	121.1
C4—C5—C6	123.34 (12)	C12—C13—H13	121.1
N2—C6—C5	128.74 (12)	N5—C14—C13	124.36 (14)
N2—C6—C7	106.58 (11)	N5—C14—H14	117.8
C5—C6—C7	124.62 (11)	C13—C14—H14	117.8
O2—C7—N3	124.27 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N1	0.89 (2)	1.84 (2)	2.6126 (17)	144 (2)
O1—H1···O2i	0.93 (2)	1.98 (2)	2.8327 (14)	151 (2)
O1—H1···N2i	0.93 (2)	2.13 (2)	2.8489 (16)	133 (2)
C2—H2···O2ii	0.95	2.54	3.1985 (15)	127
C3—H3A···O1iii	0.95	2.56	3.4755 (15)	163
C13—H13···N5iv	0.95	2.46	3.3811 (19)	163