2-(2-Methyl­anilino)-N′-(propan-2-yl­idene)acetohydrazide

Abstract

The conformation of the title compound, C₁₂H₁₇N₃O, is consolidated by an intra­molecular N—H⋯O hydrogen bond, generating an S(5) ring. In the crystal, inversion dimers linked by pairs of N—H⋯O inter­actions occur, resulting in R ₂ ²(8) ring motifs.

Related literature

For related structures, see: Salim et al. (2009 ▶); Shi et al. (2007 ▶). For graph-set theory, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

• C₁₂H₁₇N₃O

• M _r = 219.29

• Monoclinic,

• a = 13.2194 (9) Å

• b = 4.3865 (3) Å

• c = 21.7413 (13) Å

• β = 103.433 (3)°

• V = 1226.22 (14) ų

• Z = 4

• Mo Kα radiation

• μ = 0.08 mm⁻¹

• T = 296 K

• 0.28 × 0.25 × 0.22 mm

Data collection

• Bruker Kappa APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.979, T _max = 0.984

• 13485 measured reflections

• 2998 independent reflections

• 1608 reflections with I > 2σ(I)

• R _int = 0.040

Refinement

• R[F ² > 2σ(F ²)] = 0.048

• wR(F ²) = 0.166

• S = 1.00

• 2998 reflections

• 148 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

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
N1—H1⋯O1	0.81 (3)	2.21 (3)	2.604 (2)	110 (2)
N2—H2⋯O1i	0.88 (2)	2.06 (2)	2.920 (2)	166 (2)

Symmetry code: (i) .

supplementary crystallographic information

Comment

Literature has shown that hydrazides as well as their derivatives are characterized by low toxicity and possess a broad spectrum of pharmaceutical activities. The title compound (I, Fig. 1) is one of the several hydrazide derivatives prepared with substitution and alteration of the basic moiety as a key to obtain good potency. In this context we have already reported the crystal structure of 2-(3,4-Dimethylanilino)acetohydrazide (Salim et al., 2009).

The crystal structure of (II) 2-(1H-Benzotriazol-1-yl)-N'-(propan-2-ylidene)acetohydrazide (Shi et al., 2007) has been published which contains the side chain of (I).

In (I) the 2-methylanilinic group A (C1—C6/N1/C12) and the side chain group B (C7/C8/N2/N3/C9—C11/O1) are planar with maximum r. m. s. deviations of 0.0064 and 0.0146 Å respectively, from the respective mean square planes. The dihedral angle between A/B is 4.70 (10)°. In (I), there exists intramolecular H-bonding of N—H···O type (Table 1, Fig. 1) completing S(5) ring motif (Bernstein et al., 1995). The molecules are dimerized due to intermolecular H-bonding of N—H···O type (Table 1, Fig. 2) completing R₂²(8) ring motif. There does not exist any C–H···π or π···π interactions.

Experimental

2-[(2-Methylphenyl)amino]acetohydrazide (0.9 g, 5 mmol) and acetone (0.29 g, 5 mmol) were refluxed along with stirring in 100 ml of ethylalcohol for 30 minutes and after evaporation of the solvent, the crude product obtained was recrystallized in methylalcohol to obtain colorless prisms of (I).

Refinement

The coordinates of H1, H2, H7A and H7B were refined. The other H-atoms were positioned geometrically (C–H = 0.93–0.96 Å) and refined as riding with U_iso(H) = 1.2U_eq(carrier) or 1.5U_eq(methyl C).

Figures

Fig. 1.

View of (I) with displacement ellipsoids drawn at the 50% probability level. The dotted line represent the intramolecular H-bond.

Fig. 2.

The partial packing of (I), which shows that molecules form inversion dimers due to H-bondings.

Crystal data

C12H17N3O	F(000) = 472
Mr = 219.29	Dx = 1.188 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2998 reflections
a = 13.2194 (9) Å	θ = 3.0–28.2°
b = 4.3865 (3) Å	µ = 0.08 mm−1
c = 21.7413 (13) Å	T = 296 K
β = 103.433 (3)°	Prism, colourless
V = 1226.22 (14) Å3	0.28 × 0.25 × 0.22 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer	2998 independent reflections
Radiation source: fine-focus sealed tube	1608 reflections with I > 2σ(I)
graphite	Rint = 0.040
Detector resolution: 7.40 pixels mm-1	θmax = 28.2°, θmin = 3.0°
ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −5→5
Tmin = 0.979, Tmax = 0.984	l = −28→28
13485 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.166	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.067P)2 + 0.3661P] where P = (Fo2 + 2Fc2)/3
2998 reflections	(Δ/σ)max < 0.001
148 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.16 e Å−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.47742 (12)	0.3771 (4)	0.42354 (7)	0.0780 (6)
N1	0.53042 (16)	0.2794 (5)	0.31712 (8)	0.0739 (7)
N2	0.61215 (13)	0.6771 (4)	0.46619 (8)	0.0572 (6)
N3	0.70384 (12)	0.8122 (4)	0.46023 (7)	0.0550 (5)
C1	0.54130 (15)	0.2216 (5)	0.25657 (8)	0.0537 (6)
C2	0.46554 (16)	0.0463 (5)	0.21591 (9)	0.0597 (7)
C3	0.47980 (19)	−0.0121 (6)	0.15595 (10)	0.0751 (9)
C4	0.5629 (2)	0.0969 (6)	0.13542 (10)	0.0768 (9)
C5	0.63565 (18)	0.2686 (6)	0.17511 (10)	0.0704 (8)
C6	0.62626 (15)	0.3307 (5)	0.23575 (9)	0.0622 (7)
C7	0.59948 (16)	0.4699 (5)	0.36058 (9)	0.0551 (7)
C8	0.55802 (15)	0.5040 (5)	0.41921 (8)	0.0536 (6)
C9	0.75244 (15)	0.9750 (4)	0.50608 (9)	0.0524 (6)
C10	0.71970 (17)	1.0357 (6)	0.56608 (9)	0.0674 (8)
C11	0.85192 (17)	1.1136 (6)	0.49869 (11)	0.0728 (8)
C12	0.3731 (2)	−0.0733 (7)	0.23729 (13)	0.0865 (10)
H1	0.478 (2)	0.222 (6)	0.3270 (12)	0.0887*
H2	0.5864 (16)	0.694 (5)	0.4998 (11)	0.0686*
H3	0.43077	−0.13040	0.12853	0.0902*
H4	0.56980	0.05417	0.09469	0.0922*
H5	0.69216	0.34476	0.16126	0.0845*
H6	0.67688	0.44581	0.26275	0.0747*
H7A	0.6053 (16)	0.673 (5)	0.3444 (10)	0.0661*
H7B	0.6679 (17)	0.383 (5)	0.3735 (10)	0.0661*
H10A	0.65304	1.13419	0.55670	0.1011*
H10B	0.76993	1.16536	0.59273	0.1011*
H10C	0.71507	0.84643	0.58744	0.1011*
H11A	0.86472	1.05450	0.45867	0.1092*
H11B	0.90797	1.04383	0.53216	0.1092*
H11C	0.84711	1.33164	0.50050	0.1092*
H12A	0.39624	−0.20103	0.27369	0.1299*
H12B	0.33007	−0.18975	0.20383	0.1299*
H12C	0.33383	0.09441	0.24803	0.1299*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0743 (10)	0.1126 (13)	0.0574 (9)	−0.0338 (9)	0.0366 (7)	−0.0246 (8)
N1	0.0746 (12)	0.1060 (16)	0.0500 (10)	−0.0339 (11)	0.0325 (9)	−0.0234 (10)
N2	0.0590 (10)	0.0746 (12)	0.0433 (9)	−0.0111 (8)	0.0229 (7)	−0.0086 (8)
N3	0.0568 (9)	0.0646 (10)	0.0474 (9)	−0.0067 (8)	0.0196 (7)	−0.0032 (8)
C1	0.0570 (11)	0.0650 (12)	0.0420 (10)	0.0042 (9)	0.0173 (8)	−0.0040 (9)
C2	0.0613 (12)	0.0670 (13)	0.0512 (11)	0.0067 (10)	0.0141 (9)	−0.0076 (10)
C3	0.0838 (16)	0.0852 (17)	0.0534 (12)	0.0070 (13)	0.0099 (11)	−0.0179 (12)
C4	0.0926 (17)	0.0973 (18)	0.0456 (11)	0.0234 (15)	0.0262 (12)	−0.0069 (12)
C5	0.0678 (13)	0.0986 (18)	0.0523 (12)	0.0206 (13)	0.0291 (11)	0.0085 (12)
C6	0.0561 (11)	0.0851 (15)	0.0489 (11)	0.0012 (10)	0.0192 (9)	−0.0021 (10)
C7	0.0580 (11)	0.0679 (14)	0.0431 (10)	−0.0073 (10)	0.0195 (9)	−0.0039 (10)
C8	0.0571 (11)	0.0649 (12)	0.0426 (10)	−0.0054 (10)	0.0192 (8)	−0.0049 (9)
C9	0.0565 (10)	0.0556 (11)	0.0467 (10)	−0.0007 (9)	0.0152 (8)	0.0010 (9)
C10	0.0738 (14)	0.0787 (15)	0.0522 (12)	−0.0106 (12)	0.0198 (10)	−0.0122 (11)
C11	0.0697 (13)	0.0839 (16)	0.0685 (14)	−0.0171 (12)	0.0234 (11)	−0.0067 (12)
C12	0.0758 (15)	0.102 (2)	0.0831 (17)	−0.0268 (14)	0.0212 (13)	−0.0220 (15)

Geometric parameters (Å, °)

O1—C8	1.225 (3)	C9—C10	1.491 (3)
N1—C1	1.381 (2)	C3—H3	0.9300
N1—C7	1.423 (3)	C4—H4	0.9300
N2—N3	1.382 (2)	C5—H5	0.9300
N2—C8	1.339 (3)	C6—H6	0.9300
N3—C9	1.272 (2)	C7—H7A	0.97 (2)
N1—H1	0.81 (3)	C7—H7B	0.96 (2)
N2—H2	0.88 (2)	C10—H10A	0.9600
C1—C2	1.402 (3)	C10—H10B	0.9600
C1—C6	1.390 (3)	C10—H10C	0.9600
C2—C3	1.384 (3)	C11—H11A	0.9600
C2—C12	1.500 (4)	C11—H11B	0.9600
C3—C4	1.365 (4)	C11—H11C	0.9600
C4—C5	1.361 (3)	C12—H12A	0.9600
C5—C6	1.380 (3)	C12—H12B	0.9600
C7—C8	1.507 (3)	C12—H12C	0.9600
C9—C11	1.491 (3)
C1—N1—C7	123.25 (19)	C4—C5—H5	120.00
N3—N2—C8	119.78 (16)	C6—C5—H5	120.00
N2—N3—C9	117.48 (16)	C1—C6—H6	120.00
C7—N1—H1	117.5 (18)	C5—C6—H6	120.00
C1—N1—H1	118.7 (18)	N1—C7—H7A	113.1 (13)
N3—N2—H2	124.1 (15)	N1—C7—H7B	112.1 (13)
C8—N2—H2	116.2 (15)	C8—C7—H7A	106.9 (13)
N1—C1—C2	118.99 (19)	C8—C7—H7B	107.1 (13)
N1—C1—C6	121.23 (19)	H7A—C7—H7B	108.8 (19)
C2—C1—C6	119.78 (17)	C9—C10—H10A	109.00
C3—C2—C12	121.8 (2)	C9—C10—H10B	109.00
C1—C2—C3	117.5 (2)	C9—C10—H10C	109.00
C1—C2—C12	120.72 (19)	H10A—C10—H10B	109.00
C2—C3—C4	122.7 (2)	H10A—C10—H10C	109.00
C3—C4—C5	119.4 (2)	H10B—C10—H10C	109.00
C4—C5—C6	120.5 (2)	C9—C11—H11A	109.00
C1—C6—C5	120.14 (19)	C9—C11—H11B	109.00
N1—C7—C8	108.46 (18)	C9—C11—H11C	109.00
O1—C8—N2	121.29 (17)	H11A—C11—H11B	109.00
O1—C8—C7	120.90 (18)	H11A—C11—H11C	109.00
N2—C8—C7	117.81 (18)	H11B—C11—H11C	109.00
N3—C9—C11	116.23 (18)	C2—C12—H12A	109.00
C10—C9—C11	117.65 (18)	C2—C12—H12B	109.00
N3—C9—C10	126.12 (19)	C2—C12—H12C	109.00
C2—C3—H3	119.00	H12A—C12—H12B	109.00
C4—C3—H3	119.00	H12A—C12—H12C	109.00
C3—C4—H4	120.00	H12B—C12—H12C	109.00
C5—C4—H4	120.00
C7—N1—C1—C2	−176.0 (2)	C6—C1—C2—C12	−179.9 (2)
C7—N1—C1—C6	4.8 (3)	N1—C1—C6—C5	179.7 (2)
C1—N1—C7—C8	174.7 (2)	C2—C1—C6—C5	0.5 (3)
C8—N2—N3—C9	179.89 (19)	C1—C2—C3—C4	−0.9 (4)
N3—N2—C8—O1	178.75 (19)	C12—C2—C3—C4	179.4 (2)
N3—N2—C8—C7	−1.3 (3)	C2—C3—C4—C5	0.4 (4)
N2—N3—C9—C10	−0.2 (3)	C3—C4—C5—C6	0.5 (4)
N2—N3—C9—C11	179.05 (18)	C4—C5—C6—C1	−0.9 (4)
N1—C1—C2—C3	−178.8 (2)	N1—C7—C8—O1	0.2 (3)
N1—C1—C2—C12	0.9 (3)	N1—C7—C8—N2	−179.80 (19)
C6—C1—C2—C3	0.4 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.81 (3)	2.21 (3)	2.604 (2)	110 (2)
N2—H2···O1i	0.88 (2)	2.06 (2)	2.920 (2)	166 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1.