2-(3,5-Dimethyl-1H-pyrazol-1-yl)-2-hy­droxy­imino-N′-[1-(pyridin-2-yl)ethyl­idene]acetohydrazide

Abstract

In the title compound, C₁₄H₁₆N₆O₂, the dihedral angles formed by the mean plane of the acetohydrazide group [maximum deviation 0.0629 (12) Å] with the pyrazole and pyridine rings are 81.62 (6) and 38.38 (4)° respectively. In the crystal, mol­ecules are connected by N—H⋯O and O—H⋯N hydrogen bonds into supra­molecular chains extending parallel to the c-axis direction.

Related literature  

For uses of polynuclear complexes, see: Świątek-Kozłowska et al. (2000 ▶); Wörl et al. (2005 ▶). For the use of oximes having additional donor functions as versatile ligands, see: Krämer & Fritsky (2000 ▶); Sachse et al. (2008 ▶); Kanderal et al. (2005 ▶). For related structures, see: Moroz et al. (2012 ▶); Mokhir et al. (2002 ▶); Sliva et al. (1997 ▶). For the synthesis, see: Kozikowski & Adamczyk (1983 ▶).

Experimental  

Crystal data  

• C₁₄H₁₆N₆O₂

• M _r = 300.33

• Monoclinic,

• a = 24.5792 (6) Å

• b = 7.5795 (2) Å

• c = 8.3072 (2) Å

• β = 107.335 (1)°

• V = 1477.32 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 100 K

• 0.36 × 0.28 × 0.21 mm

Data collection  

• Bruker Kappa APEXII DUO CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T _min = 0.966, T _max = 0.980

• 8846 measured reflections

• 4395 independent reflections

• 4096 reflections with I > 2σ(I)

• R _int = 0.016

Refinement  

• R[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 0.081

• S = 1.03

• 4395 reflections

• 204 parameters

• 3 restraints

• H-atom parameters constrained

• Δρ_max = 0.36 e Å⁻³

• Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯N6i	0.88	1.79	2.6686 (13)	175
N3—H3N⋯O1i	0.86	2.17	3.0196 (13)	174

Symmetry code: (i) .

supplementary crystallographic information

Comment

Polynuclear complexes and supramolecular assemblies based on the bridging ligands are widely used in molecular magnetism, crystal engineering, bioinorganic modeling and catalysis (Świątek-Kozłowska et al., 2000; Wörl et al., 2005). One of the most efficient bridging ligands are oximes. Polydentate ligands containing both oxime and other donor functions (e.g., carboxylic, amide, hydroxamic) are of special interest due to their potential for the bridging mode of coordination and mediation of strong magnetic exchange interactions between metal ions (Sachse et al., 2008) and for the preparation of metal complexes with efficient stabilization of unusually high oxidation states of 3d-metal ions (e.g., copper(III) and nickel(III)) (Kanderal et al., 2005). As a part of our research study we present the structure of the title compound, which comprises several donor groups: oxime, hydrazone, azomethine, and pyridine. It has been shown previously that structurally similiar strand ligands form mono- and tetranuclear grid-like assemblies with 3d-metal ions (Moroz et al., 2012).

In the title compound (Fig. 1), the N—N, N—C and C—O bond lengths of the acetohydrazide group (1.3814 (14), 1.3607 (14) and 1.2204 (14) Å respectively) are typical for the protonated amide group (Kanderal et al., 2005; Sachse et al., 2008; Moroz et al., 2012). The NC(=NOH)C(O)NH fragment deviates from the planarity because of a twist between the oxime and the amide groups about the C(8)—C9 bond; the O(1)—C(8)—C(9)—N(4) torsion angle is 168.65 (11)°. The N—O and C—N bond lengths of the oxime group are 1.370 (1) and 1.281 (0) Å, respectively, that is typical for the amide derivatives of 2-hydroxypropanoic acid (Sliva et al., 1997; Mokhir et al., 2002). The pyridine nitrogen atom is situated in an anti-position with respect to the azomethine group. The C—C, C—N and N—N' (1.3314 (15)–1.4098 (12) Å) bond lengths in the pyrazole ring have typical values. The N4—C9—N5—N6 torsion angle is 63.95 (15)°. The C—N and C—C bond lengths in the pyridine ring are normal for 2-substituted pyridine derivatives (Krämer & Fritsky, 2000; Sachse et al., 2008).

In the crystal packing (Fig. 2), the molecules are connected by N—H···O and O—H···N hydrogen bonds (Table 1) to form chains parallel to the c axis, where the amide nitrogen and the oxime oxygen atoms act as donors and the amide oxygen and the pyrazole nitrogen atoms act as acceptors.

Experimental

Synthesis of ethyl 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyiminoacetate: a mixture of ethyl 2-chloro-2-hydroxyiminoacetate synthesized according to Kozikowski et al. (1983) (0.906 g, 6 mmol) and 3,5-dimethylpyrazole (1.152 g, 12 mmol) in 10 ml of chloroform was left for evaporation in the air overnight. The resulting precipitate was recrystallized from water. Yield: 1.12 g (88%).

Synthesis of 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyiminoacetohydrazide: a solution of hydrazine hydrate (0.57 ml, 60%, 10.6 mmol) in water was added to a solution of ethyl 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyiminoacetate (1.12 g, 5.3 mmol) in methanol (30 ml). The resulting mixture was heating under reflux for 1.5 h. After that the solvent was evaporated and the product was recrystallized from methanol. Yield 0.5 g (48%).

Synthesis of 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyimino-N'-[1-(2-pyridyl)ethylidene]acetohydrazide (1): a solution of 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyiminoacetohydrazide (0.5 g, 2.54 mmol) in methanol (30 ml) was treated with 2-acetylpyridine (0.307 g, 2.54 mmol) and the mixture was heated under reflux for 3 h. After that the solvent was evaporated in vacuum and the product was recrystallized from methanol. Yield 0.65 g (85%).

Refinement

The crystal was refined as a racemic twin, with the BASF value refined to 0.4 (8) for 1715 Friedel pairs. The oxime H atom was located in a difference Fourier map and refined as riding with U_iso = 1.5 U_eq(O). The hydrazide H atom was also located in a difference Fourier map but not refined; the N—H distance was constrained to be 0.86 (1) Å and the isotropic displacement parameter was set to 1.5 times that of the N parent atom. All other hydrogen atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.95–0.98 Å, and U_iso = 1.2–1.5 U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.

Fig. 2.

Crystal packing of the title compound. Hydrogen bonds are indicated by dashed lines. H atoms not involved in H-bonds are omitted for clarity.

Crystal data

C14H16N6O2	F(000) = 632
Mr = 300.33	Dx = 1.350 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 5439 reflections
a = 24.5792 (6) Å	θ = 3.5–32.2°
b = 7.5795 (2) Å	µ = 0.10 mm−1
c = 8.3072 (2) Å	T = 100 K
β = 107.335 (1)°	Block, colourless
V = 1477.32 (6) Å3	0.36 × 0.28 × 0.21 mm
Z = 4

Data collection

Bruker Kappa APEXII DUO CCD diffractometer	4395 independent reflections
Radiation source: fine-focus sealed tube	4096 reflections with I > 2σ(I)
Curved graphite crystal monochromator	Rint = 0.016
Detector resolution: 16 pixels mm-1	θmax = 32.2°, θmin = 1.7°
φ scans and ω scans with κ offset	h = −28→36
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	k = −11→11
Tmin = 0.966, Tmax = 0.980	l = −12→12
8846 measured 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0459P)2 + 0.467P] where P = (Fo2 + 2Fc2)/3
4395 reflections	(Δ/σ)max = 0.001
204 parameters	Δρmax = 0.36 e Å−3
3 restraints	Δρmin = −0.24 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.36481 (4)	0.69023 (11)	0.54259 (10)	0.01537 (16)
O2	0.22703 (4)	0.54704 (12)	0.05549 (11)	0.01825 (18)
H2O	0.2225	0.4597	−0.0165	0.027*
N1	0.56071 (4)	0.19215 (14)	0.65828 (13)	0.01662 (19)
N2	0.42935 (4)	0.41283 (13)	0.53143 (12)	0.01403 (18)
N3	0.38561 (4)	0.46283 (14)	0.39135 (11)	0.01331 (17)
H3N	0.3778	0.4153	0.2937	0.019 (4)*
N4	0.27952 (4)	0.51059 (13)	0.16581 (12)	0.01522 (18)
N5	0.26314 (4)	0.76793 (12)	0.30874 (11)	0.01181 (17)
N6	0.21438 (4)	0.73146 (13)	0.35109 (11)	0.01289 (18)
C1	0.51137 (5)	0.25530 (15)	0.67204 (14)	0.01364 (19)
C2	0.50044 (5)	0.27091 (17)	0.82763 (15)	0.0172 (2)
H2	0.4648	0.3142	0.8333	0.021*
C3	0.54243 (6)	0.22232 (18)	0.97295 (16)	0.0202 (2)
H3	0.5360	0.2318	1.0799	0.024*
C4	0.59418 (5)	0.15935 (17)	0.96004 (15)	0.0185 (2)
H4	0.6240	0.1262	1.0575	0.022*
C5	0.60086 (5)	0.14650 (17)	0.80058 (15)	0.0179 (2)
H5	0.6360	0.1026	0.7916	0.021*
C6	0.46826 (5)	0.30868 (16)	0.51196 (14)	0.01365 (19)
C7	0.47343 (6)	0.24075 (18)	0.34765 (15)	0.0189 (2)
H7A	0.4467	0.1428	0.3084	0.028*
H7B	0.5124	0.1994	0.3634	0.028*
H7C	0.4645	0.3357	0.2638	0.028*
C8	0.35246 (5)	0.59735 (15)	0.41689 (13)	0.01189 (19)
C9	0.29671 (5)	0.62508 (16)	0.28350 (13)	0.01239 (19)
C10	0.19299 (5)	0.88846 (16)	0.37111 (14)	0.0156 (2)
C11	0.13847 (6)	0.89937 (19)	0.41554 (17)	0.0226 (3)
H11A	0.1083	0.9459	0.3192	0.034*
H11B	0.1435	0.9780	0.5126	0.034*
H11C	0.1278	0.7815	0.4440	0.034*
C12	0.22777 (6)	1.02525 (16)	0.34214 (16)	0.0191 (2)
H12	0.2216	1.1485	0.3478	0.023*
C13	0.27257 (5)	0.94425 (15)	0.30399 (15)	0.0156 (2)
C14	0.32359 (6)	1.01682 (18)	0.26595 (17)	0.0227 (3)
H0AA	0.3555	1.0228	0.3700	0.034*
H0AB	0.3151	1.1355	0.2182	0.034*
H0AC	0.3338	0.9401	0.1846	0.034*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0150 (4)	0.0166 (4)	0.0135 (4)	0.0014 (3)	0.0026 (3)	−0.0019 (3)
O2	0.0122 (4)	0.0191 (4)	0.0188 (4)	0.0038 (3)	−0.0025 (3)	−0.0061 (3)
N1	0.0132 (4)	0.0191 (5)	0.0162 (4)	0.0036 (4)	0.0025 (4)	0.0002 (4)
N2	0.0111 (4)	0.0165 (4)	0.0129 (4)	0.0010 (3)	0.0012 (3)	0.0014 (3)
N3	0.0116 (4)	0.0160 (4)	0.0110 (4)	0.0033 (3)	0.0013 (3)	−0.0007 (3)
N4	0.0110 (4)	0.0163 (4)	0.0161 (4)	0.0018 (4)	0.0007 (3)	−0.0024 (4)
N5	0.0111 (4)	0.0104 (4)	0.0139 (4)	0.0001 (3)	0.0036 (3)	−0.0001 (3)
N6	0.0108 (4)	0.0134 (4)	0.0147 (4)	0.0011 (3)	0.0040 (3)	0.0013 (3)
C1	0.0126 (5)	0.0130 (5)	0.0145 (5)	0.0012 (4)	0.0028 (4)	0.0005 (4)
C2	0.0148 (5)	0.0221 (6)	0.0151 (5)	0.0044 (4)	0.0052 (4)	0.0023 (4)
C3	0.0199 (6)	0.0250 (6)	0.0153 (5)	0.0036 (5)	0.0048 (5)	0.0035 (4)
C4	0.0166 (5)	0.0189 (5)	0.0168 (5)	0.0021 (4)	0.0001 (4)	0.0041 (4)
C5	0.0119 (5)	0.0203 (5)	0.0197 (5)	0.0045 (4)	0.0018 (4)	0.0005 (4)
C6	0.0113 (5)	0.0155 (5)	0.0133 (5)	0.0008 (4)	0.0024 (4)	0.0002 (4)
C7	0.0161 (5)	0.0242 (6)	0.0151 (5)	0.0072 (5)	0.0027 (4)	−0.0004 (4)
C8	0.0101 (5)	0.0129 (5)	0.0128 (4)	0.0001 (4)	0.0034 (4)	0.0013 (4)
C9	0.0111 (4)	0.0125 (5)	0.0135 (5)	0.0016 (4)	0.0035 (4)	0.0003 (4)
C10	0.0155 (5)	0.0154 (5)	0.0156 (5)	0.0037 (4)	0.0039 (4)	−0.0009 (4)
C11	0.0183 (6)	0.0264 (6)	0.0249 (6)	0.0057 (5)	0.0094 (5)	−0.0016 (5)
C12	0.0215 (6)	0.0115 (5)	0.0237 (6)	0.0026 (4)	0.0056 (5)	−0.0001 (4)
C13	0.0165 (5)	0.0126 (5)	0.0170 (5)	−0.0014 (4)	0.0039 (4)	0.0018 (4)
C14	0.0208 (6)	0.0207 (6)	0.0277 (6)	−0.0052 (5)	0.0087 (5)	0.0048 (5)

Geometric parameters (Å, º)

O1—C8	1.2204 (14)	C4—C5	1.3859 (17)
O2—N4	1.3697 (13)	C4—H4	0.9500
O2—H2O	0.8763	C5—H5	0.9500
N1—C1	1.3400 (15)	C6—C7	1.4991 (16)
N1—C5	1.3401 (15)	C7—H7A	0.9800
N2—C6	1.2870 (15)	C7—H7B	0.9800
N2—N3	1.3814 (13)	C7—H7C	0.9800
N3—C8	1.3607 (14)	C8—C9	1.4982 (15)
N3—H3N	0.8555	C10—C12	1.4094 (18)
N4—C9	1.2811 (15)	C10—C11	1.4943 (17)
N5—C13	1.3589 (14)	C11—H11A	0.9800
N5—N6	1.3738 (13)	C11—H11B	0.9800
N5—C9	1.4144 (14)	C11—H11C	0.9800
N6—C10	1.3314 (15)	C12—C13	1.3775 (18)
C1—C2	1.4013 (16)	C12—H12	0.9500
C1—C6	1.4884 (15)	C13—C14	1.4870 (18)
C2—C3	1.3841 (17)	C14—H0AA	0.9800
C2—H2	0.9500	C14—H0AB	0.9800
C3—C4	1.3922 (18)	C14—H0AC	0.9800
C3—H3	0.9500
N4—O2—H2O	102.0	H7A—C7—H7B	109.5
C1—N1—C5	117.66 (10)	C6—C7—H7C	109.5
C6—N2—N3	118.91 (9)	H7A—C7—H7C	109.5
C8—N3—N2	115.22 (9)	H7B—C7—H7C	109.5
C8—N3—H3N	119.2	O1—C8—N3	123.90 (10)
N2—N3—H3N	125.6	O1—C8—C9	119.44 (10)
C9—N4—O2	113.87 (9)	N3—C8—C9	116.61 (9)
C13—N5—N6	112.00 (9)	N4—C9—N5	123.87 (10)
C13—N5—C9	129.53 (10)	N4—C9—C8	119.37 (10)
N6—N5—C9	118.41 (9)	N5—C9—C8	116.30 (9)
C10—N6—N5	105.03 (9)	N6—C10—C12	110.72 (10)
N1—C1—C2	122.41 (11)	N6—C10—C11	119.80 (11)
N1—C1—C6	116.25 (10)	C12—C10—C11	129.47 (11)
C2—C1—C6	121.34 (10)	C10—C11—H11A	109.5
C3—C2—C1	118.94 (11)	C10—C11—H11B	109.5
C3—C2—H2	120.5	H11A—C11—H11B	109.5
C1—C2—H2	120.5	C10—C11—H11C	109.5
C2—C3—C4	119.01 (11)	H11A—C11—H11C	109.5
C2—C3—H3	120.5	H11B—C11—H11C	109.5
C4—C3—H3	120.5	C13—C12—C10	106.18 (10)
C5—C4—C3	117.96 (11)	C13—C12—H12	126.9
C5—C4—H4	121.0	C10—C12—H12	126.9
C3—C4—H4	121.0	N5—C13—C12	106.06 (10)
N1—C5—C4	124.00 (11)	N5—C13—C14	122.13 (11)
N1—C5—H5	118.0	C12—C13—C14	131.80 (11)
C4—C5—H5	118.0	C13—C14—H0AA	109.5
N2—C6—C1	114.35 (9)	C13—C14—H0AB	109.5
N2—C6—C7	126.36 (10)	H0AA—C14—H0AB	109.5
C1—C6—C7	119.29 (10)	C13—C14—H0AC	109.5
C6—C7—H7A	109.5	H0AA—C14—H0AC	109.5
C6—C7—H7B	109.5	H0AB—C14—H0AC	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···N6i	0.88	1.79	2.6686 (13)	175
N3—H3N···O1i	0.86	2.17	3.0196 (13)	174

Symmetry code: (i) x, −y+1, z−1/2.