2-(4-Methyl­phen­oxy)acetohydrazide

Abstract

In the title compound, C₉H₁₂N₂O₂, the acetohydrazide group is approximately planar [maximum deviation = 0.034 (2) Å]. In the crystal, mol­ecules are linked via inter­molecular N—H⋯O, N—H⋯N and C—H⋯O hydrogen bonds into infinite two-dimensional networks parallel to (001).

Related literature

For general background to and the biological activity of hydrazide derivatives, see: Isloor et al. (2009 ▶); Holla & Udupa (1992 ▶); Ozdemir et al. (2009 ▶); Khattab (2005 ▶); Yale et al. (1953 ▶). For the preparation of title compound, see: Conti (1964 ▶). For bond-length data, see: Allen et al. (1987 ▶). For related structures, see: Fun et al. (2009 ▶, 2010a ▶,b ▶).

Experimental

Crystal data

• C₉H₁₂N₂O₂

• M _r = 180.21

• Monoclinic,

• a = 6.3833 (2) Å

• b = 4.0755 (1) Å

• c = 35.9741 (12) Å

• β = 90.018 (2)°

• V = 935.87 (5) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 296 K

• 0.46 × 0.33 × 0.10 mm

Data collection

• Bruker SMART APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.959, T _max = 0.991

• 15060 measured reflections

• 2150 independent reflections

• 1747 reflections with I > 2σ(I)

• R _int = 0.042

Refinement

• R[F ² > 2σ(F ²)] = 0.067

• wR(F ²) = 0.149

• S = 1.14

• 2150 reflections

• 131 parameters

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

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

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—H1N1⋯N2i	0.92 (3)	2.17 (3)	2.982 (3)	147 (2)
N2—H2N2⋯O2ii	0.90 (3)	2.14 (3)	3.022 (3)	168 (3)
N2—H1N2⋯O2iii	0.98 (3)	2.47 (3)	3.166 (3)	128 (2)
C1—H1A⋯O2iv	0.93	2.53	3.410 (3)	157

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

supplementary crystallographic information

Comment

The full therapeutic possibilities of hydrazides were realized after the discovery of isonicotinic acid hydrazide (INH). Hydrazides and their derivatives have been described as useful synthons of various heterocyclic rings (Isloor et al., 2009; Holla & Udupa, 1992). A large number of hydrazides and their derivatives are reported to possess a broad spectrum of biological activities (Ozdemir et al., 2009; Khattab, 2005). The most widely used method to prepare hydrazides is hydrazinolysis of the corresponding esters with hydrazine hydrate (Yale et al., 1953). Prompted by the diverse activities of hydrazides and its derivatives, we have synthesized the title compound to study its crystal structure.

The molecular structure is shown in Fig. 1. The acetohydrazide group (C7/C8/N1/N2/O2) is approximately planar, with the maximum deviation of 0.034 (2) Å at atom C7. Bond lengths and angles are within normal ranges, and comparable to closely related structures (Fun et al., 2009, 2010a,b). In the solid state (Fig. 2), the molecules are linked via intermolecular N2–H1N2···O2, N2–H2N2···O2 and C1–H1A···O2 trifurcated acceptor bonds, together with N1–H1N1···N2 hydrogen bonds, into infinite two-dimensional networks parallel to plane (001).

Experimental

Ethyl(4-methylphenoxy)acetate (1.94 g, 0.01 mol) and hydrazine hydrate (99%, 0.02 mol) in ethanol (15 ml) was heated on a water-bath for 6 h. Excess ethanol was removed by distillation. On cooling, colourless needle-shaped crystals of 2-(4-methylphenoxy)acetohydrazide begin to separate. It was collected by filtration and recrystallized from ethanol. Yield: 1.2 g, 67.0 %, M.p.: 411-413K. (Conti, 1964).

Refinement

H1N1, H1N2 and H2N2 were located in a difference Fourier map and allowed to refined freely. The remaining H atoms were positioned geometrically and refined using a riding model with C–H = 0.93 –0.97 Å and U_iso(H) = 1.2 or 1.5 U_eq(C). The highest residual electron density peak is located at 0.94 Å from H9C and the deepest hole is located at 0.94 Å from C8.

Figures

Fig. 1.

The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme.

Fig. 2.

The crystal structure of the title compound, viewed along the b axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

Crystal data

C9H12N2O2	F(000) = 384
Mr = 180.21	Dx = 1.279 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4756 reflections
a = 6.3833 (2) Å	θ = 3.2–25.4°
b = 4.0755 (1) Å	µ = 0.09 mm−1
c = 35.9741 (12) Å	T = 296 K
β = 90.018 (2)°	Block, colourless
V = 935.87 (5) Å3	0.46 × 0.33 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	2150 independent reflections
Radiation source: fine-focus sealed tube	1747 reflections with I > 2σ(I)
graphite	Rint = 0.042
φ and ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
Tmin = 0.959, Tmax = 0.991	k = −5→5
15060 measured reflections	l = −46→45

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ2(Fo2) + (0.0368P)2 + 0.8025P] where P = (Fo2 + 2Fc2)/3
2150 reflections	(Δ/σ)max = 0.001
131 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.16 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.8895 (2)	0.9310 (5)	0.16293 (4)	0.0486 (5)
O2	0.5021 (2)	0.4131 (5)	0.20181 (5)	0.0518 (5)
N1	0.8051 (3)	0.6119 (5)	0.22475 (5)	0.0386 (5)
N2	0.7875 (3)	0.4400 (6)	0.25893 (6)	0.0424 (5)
C1	1.1646 (4)	1.1960 (7)	0.13257 (7)	0.0492 (6)
H1A	1.2259	1.2295	0.1557	0.059*
C2	1.2626 (4)	1.3059 (7)	0.10089 (8)	0.0568 (7)
H2A	1.3912	1.4113	0.1030	0.068*
C3	1.1765 (5)	1.2649 (7)	0.06605 (8)	0.0581 (7)
C4	0.9852 (5)	1.1122 (8)	0.06415 (7)	0.0614 (8)
H4A	0.9226	1.0843	0.0410	0.074*
C5	0.8816 (4)	0.9975 (7)	0.09561 (7)	0.0529 (7)
H5A	0.7514	0.8967	0.0935	0.063*
C6	0.9740 (3)	1.0352 (6)	0.12983 (6)	0.0407 (5)
C7	0.7042 (3)	0.7393 (6)	0.16147 (6)	0.0405 (5)
H7A	0.7183	0.5731	0.1423	0.049*
H7B	0.5864	0.8784	0.1550	0.049*
C8	0.6637 (3)	0.5776 (6)	0.19811 (6)	0.0374 (5)
C9	1.2895 (6)	1.3842 (10)	0.03148 (9)	0.0890 (11)
H9A	1.3602	1.2033	0.0199	0.133*
H9B	1.3900	1.5489	0.0383	0.133*
H9C	1.1897	1.4761	0.0144	0.133*
H1N1	0.919 (4)	0.745 (7)	0.2202 (7)	0.058 (8)*
H2N2	0.712 (5)	0.572 (8)	0.2738 (8)	0.066 (9)*
H1N2	0.705 (5)	0.243 (9)	0.2537 (8)	0.070 (9)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0452 (9)	0.0592 (11)	0.0415 (9)	−0.0185 (8)	0.0003 (7)	0.0002 (8)
O2	0.0347 (8)	0.0604 (11)	0.0604 (11)	−0.0179 (8)	−0.0005 (7)	0.0015 (9)
N1	0.0297 (9)	0.0437 (11)	0.0424 (10)	−0.0053 (8)	0.0015 (7)	0.0008 (9)
N2	0.0350 (10)	0.0473 (12)	0.0448 (11)	0.0032 (9)	0.0032 (8)	0.0029 (10)
C1	0.0411 (12)	0.0547 (15)	0.0519 (14)	−0.0064 (11)	−0.0038 (10)	0.0032 (12)
C2	0.0443 (13)	0.0590 (17)	0.0671 (18)	−0.0089 (12)	0.0074 (12)	0.0027 (14)
C3	0.0676 (17)	0.0532 (16)	0.0534 (16)	−0.0053 (14)	0.0135 (13)	0.0042 (13)
C4	0.0749 (19)	0.0663 (19)	0.0431 (14)	−0.0118 (16)	−0.0020 (13)	0.0015 (13)
C5	0.0507 (14)	0.0592 (17)	0.0487 (14)	−0.0118 (13)	−0.0026 (11)	−0.0002 (12)
C6	0.0405 (11)	0.0396 (12)	0.0418 (12)	−0.0001 (10)	0.0020 (9)	−0.0010 (10)
C7	0.0329 (11)	0.0430 (13)	0.0455 (13)	−0.0068 (10)	−0.0008 (9)	−0.0037 (10)
C8	0.0283 (10)	0.0385 (11)	0.0453 (12)	0.0015 (9)	0.0027 (8)	−0.0053 (10)
C9	0.107 (3)	0.091 (3)	0.070 (2)	−0.022 (2)	0.0300 (19)	0.010 (2)

Geometric parameters (Å, °)

O1—C6	1.375 (3)	C3—C4	1.372 (4)
O1—C7	1.418 (3)	C3—C9	1.518 (4)
O2—C8	1.238 (3)	C4—C5	1.392 (4)
N1—C8	1.323 (3)	C4—H4A	0.9300
N1—N2	1.420 (3)	C5—C6	1.374 (3)
N1—H1N1	0.92 (3)	C5—H5A	0.9300
N2—H2N2	0.90 (3)	C7—C8	1.496 (3)
N2—H1N2	0.98 (3)	C7—H7A	0.9700
C1—C2	1.375 (4)	C7—H7B	0.9700
C1—C6	1.385 (3)	C9—H9A	0.9600
C1—H1A	0.9300	C9—H9B	0.9600
C2—C3	1.378 (4)	C9—H9C	0.9600
C2—H2A	0.9300
C6—O1—C7	117.73 (17)	C6—C5—H5A	120.4
C8—N1—N2	121.39 (19)	C4—C5—H5A	120.4
C8—N1—H1N1	118.1 (16)	C5—C6—O1	125.0 (2)
N2—N1—H1N1	120.5 (16)	C5—C6—C1	119.6 (2)
N1—N2—H2N2	105.3 (19)	O1—C6—C1	115.4 (2)
N1—N2—H1N2	106.3 (17)	O1—C7—C8	110.74 (17)
H2N2—N2—H1N2	108 (2)	O1—C7—H7A	109.5
C2—C1—C6	119.7 (2)	C8—C7—H7A	109.5
C2—C1—H1A	120.2	O1—C7—H7B	109.5
C6—C1—H1A	120.2	C8—C7—H7B	109.5
C1—C2—C3	122.2 (2)	H7A—C7—H7B	108.1
C1—C2—H2A	118.9	O2—C8—N1	123.2 (2)
C3—C2—H2A	118.9	O2—C8—C7	118.52 (19)
C4—C3—C2	117.1 (2)	N1—C8—C7	118.25 (19)
C4—C3—C9	121.8 (3)	C3—C9—H9A	109.5
C2—C3—C9	121.1 (3)	C3—C9—H9B	109.5
C3—C4—C5	122.3 (3)	H9A—C9—H9B	109.5
C3—C4—H4A	118.8	C3—C9—H9C	109.5
C5—C4—H4A	118.8	H9A—C9—H9C	109.5
C6—C5—C4	119.2 (2)	H9B—C9—H9C	109.5
C6—C1—C2—C3	0.7 (4)	C7—O1—C6—C1	−174.4 (2)
C1—C2—C3—C4	0.9 (5)	C2—C1—C6—C5	−2.3 (4)
C1—C2—C3—C9	−179.1 (3)	C2—C1—C6—O1	179.2 (2)
C2—C3—C4—C5	−0.9 (5)	C6—O1—C7—C8	165.76 (19)
C9—C3—C4—C5	179.1 (3)	N2—N1—C8—O2	4.7 (3)
C3—C4—C5—C6	−0.6 (5)	N2—N1—C8—C7	−173.8 (2)
C4—C5—C6—O1	−179.4 (2)	O1—C7—C8—O2	176.8 (2)
C4—C5—C6—C1	2.2 (4)	O1—C7—C8—N1	−4.6 (3)
C7—O1—C6—C5	7.2 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2i	0.92 (3)	2.17 (3)	2.982 (3)	147 (2)
N2—H2N2···O2ii	0.90 (3)	2.14 (3)	3.022 (3)	168 (3)
N2—H1N2···O2iii	0.98 (3)	2.47 (3)	3.166 (3)	128 (2)
C1—H1A···O2iv	0.93	2.53	3.410 (3)	157.

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