4-(All­yloxy)benzohydrazide

Khan, S.S.; Howlader, M.B.H.; Miyatake, R.; Sheikh, M.C.; Zangrando, E.

doi:10.1107/S2414314622011956

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 1| January 2023| x221195

https://doi.org/10.1107/S2414314622011956

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4-(Allyloxy)benzohydrazide

Sultana Shakila Khan,^a Md. Belayet Hossain Howlader,^a ^* Ryuta Miyatake,^b Md. Chanmiya Sheikh ^c and Ennio Zangrando ^d

^aDepartment of Chemistry, Rajshahi University, Rajshahi-6205, Bangladesh, ^bCenter for Environmental Conservation and Research Safety, University of Toyama, 3190 Gofuku, Toyama, 930-8555, Japan, ^cDepartment of Applied Science, Faculty of Science, Okayama University of Science, Japan, and ^dDepartment of Chemical and Pharmaceutical Science, University of Trieste, Italy
^*Correspondence e-mail: mbhhowlader@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 16 December 2022; accepted 17 December 2022; online 6 January 2023)

The non-H atoms of the title compound, C₁₀H₁₂N₂O₂, are approximately coplanar with the exception of those at the ends: the terminal allyl carbon atom and terminal hydrazide nitrogen atom are displaced from the mean plane by 0.67 (2) and 0.20 (2) Å, respectively. In the crystal, the molecules are linked by N—H⋯O and N—H⋯N hydrogen bonds, which give rise a two-dimensional network propagating in the (001) plane.

Keywords: crystal structure; allyl; benzohydrazide.

CCDC reference: 2210836

Structure description

Hydrazides containing an R—C(=O)—NH—NH₂ functional group may act as a pharmacophore and present biological activity (see, for example, Joshi et al. 2008 ). Hydrazide-containing molecules are effective ligands in coordination chemistry (see, for example, Saygıdeğer Demir et al., 2021 ). As part of our studies in this area, we now describe the synthesis and structure of the title compound (Fig. 1).

Figure 1
The molecular structure of the title compound showing 50% displacement ellipsoids.

The X-ray diffraction analysis revealed that the non-hydrogen atoms are approximately coplanar with the exception of the terminal atoms, which deviate by 0.67 (2) Å for C10 and 0.20 (2) Å for N2. In the crystal, the molecules are connected by N—H⋯O and N—H⋯N hydrogen bonds involving the carbohydrazide moieties of symmetry-related molecules (Fig. 2 and Table 1) that form a two-dimensional network propagating in the ab plane. This arrangement favours weak aromatic π–stacking interactions of the phenyl rings [centroid-to-centroid distance of 4.092 (3) Å, see Fig. 2].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	1.02 (7)	2.00 (7)	3.018 (6)	174 (6)
N1—H1B⋯O1ⁱⁱ	0.96 (7)	2.50 (6)	3.095 (6)	120 (4)
N2—H2⋯N1ⁱⁱⁱ	0.92 (6)	2.11 (6)	2.964 (6)	153 (4)
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Figure 2
Detail of the crystal packing showing hydrogen-bonding interactions as blue dashed lines.

Synthesis and crystallization

A mixture of ethyl-4-hydroxybenzoate (8.3 g, 50 mmol) and allyl bromide (6.0 g, 50 mmol) in acetone (100 ml) was refluxed for 20 h over anhydrous potassium carbonate (13.8 g, 100 mmol). The filtrate was collected and the solvent removed in vacuo. The resulting colourless oily mass was treated with hydrazine hydrate (5.0 g, 100 mmol) and refluxed for 10 h in ethanol (40 ml). The reaction mixture was left overnight and colourless crystals suitable for X-ray characterization were obtained, filtered off and washed with ethanol. Yield: 7.0 g, (73%), melting point: 355–356 K.

FT–IR (KBr), (cm⁻¹): 1650 ν (C=O_ester), 1621, 1575 ν (C=C), 3328, 3280, 3183 ν (NH—NH₂).

¹H NMR(CDCl₃, 400 MHz), δ: 7.72 (d, 2H, C-2,6, J = 8.8 Hz), 6.94 (d, 2H, C-3,5, J = 8.8 Hz), 7.65 (s, NH), 4.13 (s, 2H, NH₂), 5.42 (dq, H_a, J = 16 Hz, 1.6 Hz), 5.32 (dq, H_b, J = 10.4 Hz, 1.2 Hz), 6.05 (m, Hc), 4.58 (dt, 2H, CH₂O, J = 5.2 Hz, 1.2 Hz).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The absolute structure was indeterminate in the present refinement and the structure was refined as an inversion twin.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₂
M_r	192.22
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	263
a, b, c (Å)	5.967 (4), 4.092 (3), 20.358 (14)
β (°)	93.080 (18)
V (Å³)	496.3 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.47 × 0.21 × 0.06

Data collection
Diffractometer	Rigaku R-AXIS RAPID CCD
Absorption correction	Multi-scan (ABSCOR; Rigaku, 1995 )
T_min, T_max	0.299, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	4612, 2075, 1596
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.081, 0.228, 1.05
No. of reflections	2075
No. of parameters	139
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.30
Absolute structure	Refined as an inversion twin
Absolute structure parameter	0.5
Computer programs: RAPID-AUTO (Rigaku, 2010 ), SHELXT2014/5 (Sheldrick, 2015a ) and SHELXL2019/2 (Sheldrick, 2015b ) and DIAMOND (Brandenburg & Putz, 1999 ).

Structural data

CCDC reference: 2210836

Crystal structure: contains datablocks I, General. DOI: https://doi.org/10.1107/S2414314622011956/hb4420sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622011956/hb4420Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314622011956/hb4420Isup3.cml

checkCIF report

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2010); cell refinement: RAPID-AUTO (Rigaku, 2010); data reduction: RAPID-AUTO (Rigaku, 2010); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 1999).

4-(Prop-2-en-1-yloxy)benzohydrazide top

Crystal data top

C₁₀H₁₂N₂O₂	F(000) = 204
M_r = 192.22	D_x = 1.286 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71075 Å
a = 5.967 (4) Å	Cell parameters from 702 reflections
b = 4.092 (3) Å	θ = 3.9–27.4°
c = 20.358 (14) Å	µ = 0.09 mm⁻¹
β = 93.080 (18)°	T = 263 K
V = 496.3 (6) Å³	Plate, colorless
Z = 2	0.47 × 0.21 × 0.06 mm

Data collection top

Rigaku R-AXIS RAPID CCD diffractometer	1596 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.073
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	h = −7→7
T_min = 0.299, T_max = 0.995	k = −5→4
4612 measured reflections	l = −26→26
2075 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.081	w = 1/[σ²(F_o²) + (0.1107P)² + 0.1955P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.228	(Δ/σ)_max = 0.043
S = 1.05	Δρ_max = 0.30 e Å⁻³
2075 reflections	Δρ_min = −0.30 e Å⁻³
139 parameters	Absolute structure: Refined as an inversion twin
1 restraint	Absolute structure parameter: 0.5
Primary atom site location: dual

Special details top

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. Refined as a 2-component perfect inversion twin

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	1.0223 (5)	0.0117 (11)	0.59637 (15)	0.0501 (10)
O2	0.6099 (6)	0.6905 (12)	0.84332 (16)	0.0576 (11)
N1	0.7352 (6)	0.0258 (13)	0.48583 (18)	0.0420 (10)
H1A	0.810 (10)	0.20 (2)	0.459 (3)	0.070 (18)*
H1B	0.828 (9)	−0.162 (18)	0.495 (3)	0.053 (15)*
N2	0.6987 (6)	0.1941 (12)	0.54599 (17)	0.0422 (10)
H2	0.568 (9)	0.310 (17)	0.551 (2)	0.053 (15)*
C1	0.8432 (7)	0.1605 (13)	0.5991 (2)	0.0381 (10)
C2	0.7721 (7)	0.3101 (12)	0.6615 (2)	0.0368 (10)
C3	0.9130 (7)	0.2748 (14)	0.7179 (2)	0.0466 (13)
H3	1.048347	0.163742	0.715485	0.056*
C4	0.8538 (8)	0.4031 (15)	0.7774 (2)	0.0512 (14)
H4	0.948590	0.375286	0.814732	0.061*
C5	0.6535 (8)	0.5734 (13)	0.7817 (2)	0.0450 (12)
C6	0.5104 (9)	0.6088 (14)	0.7266 (2)	0.0499 (14)
H6	0.374650	0.718525	0.729247	0.060*
C7	0.5717 (8)	0.4782 (15)	0.6669 (2)	0.0476 (13)
H7	0.475950	0.504343	0.629677	0.057*
C8	0.4030 (9)	0.8680 (17)	0.8490 (2)	0.0558 (14)
H8A	0.275903	0.726145	0.838444	0.067*
H8B	0.396374	1.050785	0.818586	0.067*
C9	0.3954 (12)	0.9884 (19)	0.9178 (3)	0.0743 (19)
H9	0.525899	1.076453	0.937629	0.089*
C10	0.2180 (15)	0.978 (3)	0.9519 (3)	0.105 (3)
H10A	0.084985	0.891368	0.933402	0.126*
H10B	0.223805	1.057220	0.994739	0.126*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0359 (16)	0.058 (2)	0.0565 (18)	0.0103 (18)	0.0023 (12)	−0.0034 (17)
O2	0.064 (2)	0.064 (3)	0.0447 (18)	−0.003 (2)	0.0052 (14)	−0.0052 (17)
N1	0.033 (2)	0.045 (3)	0.048 (2)	0.0006 (19)	0.0049 (14)	−0.0047 (19)
N2	0.0352 (19)	0.048 (3)	0.0436 (19)	0.007 (2)	0.0032 (14)	−0.0050 (17)
C1	0.034 (2)	0.035 (2)	0.046 (2)	−0.004 (2)	0.0044 (16)	0.0039 (19)
C2	0.032 (2)	0.031 (3)	0.048 (2)	−0.0047 (19)	0.0051 (15)	0.0019 (18)
C3	0.041 (2)	0.047 (3)	0.052 (3)	0.001 (2)	−0.0016 (18)	0.002 (2)
C4	0.046 (3)	0.061 (4)	0.046 (2)	−0.005 (3)	−0.0056 (19)	0.000 (2)
C5	0.050 (3)	0.039 (3)	0.046 (2)	−0.010 (2)	0.0081 (18)	0.000 (2)
C6	0.047 (3)	0.055 (4)	0.048 (2)	0.008 (3)	0.006 (2)	0.001 (2)
C7	0.044 (3)	0.055 (4)	0.044 (2)	0.009 (3)	−0.0007 (17)	0.003 (2)
C8	0.061 (3)	0.050 (3)	0.058 (3)	−0.004 (3)	0.014 (2)	−0.007 (2)
C9	0.094 (4)	0.066 (5)	0.065 (3)	−0.006 (4)	0.020 (3)	−0.009 (3)
C10	0.131 (6)	0.117 (8)	0.072 (4)	0.017 (7)	0.046 (4)	−0.006 (5)

Geometric parameters (Å, º) top

O1—C1	1.234 (6)	C4—C5	1.390 (7)
O2—C5	1.380 (6)	C4—H4	0.9300
O2—C8	1.442 (7)	C5—C6	1.381 (7)
N1—N2	1.432 (5)	C6—C7	1.395 (7)
N1—H1A	1.02 (7)	C6—H6	0.9300
N1—H1B	0.96 (7)	C7—H7	0.9300
N2—C1	1.352 (6)	C8—C9	1.488 (8)
N2—H2	0.92 (6)	C8—H8A	0.9700
C1—C2	1.493 (6)	C8—H8B	0.9700
C2—C3	1.393 (6)	C9—C10	1.297 (9)
C2—C7	1.389 (6)	C9—H9	0.9300
C3—C4	1.383 (7)	C10—H10A	0.9300
C3—H3	0.9300	C10—H10B	0.9300

C5—O2—C8	116.8 (4)	C6—C5—C4	119.8 (4)
N2—N1—H1A	102 (4)	O2—C5—C4	115.8 (4)
N2—N1—H1B	109 (3)	C5—C6—C7	119.2 (5)
H1A—N1—H1B	114 (5)	C5—C6—H6	120.4
C1—N2—N1	121.0 (4)	C7—C6—H6	120.4
C1—N2—H2	118 (3)	C2—C7—C6	121.7 (4)
N1—N2—H2	121 (3)	C2—C7—H7	119.1
O1—C1—N2	122.1 (4)	C6—C7—H7	119.1
O1—C1—C2	121.8 (4)	O2—C8—C9	108.1 (5)
N2—C1—C2	116.1 (4)	O2—C8—H8A	110.1
C3—C2—C7	118.1 (4)	C9—C8—H8A	110.1
C3—C2—C1	118.2 (4)	O2—C8—H8B	110.1
C7—C2—C1	123.7 (4)	C9—C8—H8B	110.1
C4—C3—C2	120.7 (5)	H8A—C8—H8B	108.4
C4—C3—H3	119.7	C10—C9—C8	124.0 (8)
C2—C3—H3	119.7	C10—C9—H9	118.0
C3—C4—C5	120.4 (4)	C8—C9—H9	118.0
C3—C4—H4	119.8	C9—C10—H10A	120.0
C5—C4—H4	119.8	C9—C10—H10B	120.0
C6—C5—O2	124.3 (5)	H10A—C10—H10B	120.0

N1—N2—C1—O1	7.3 (8)	C8—O2—C5—C4	180.0 (5)
N1—N2—C1—C2	−171.9 (4)	C3—C4—C5—C6	1.4 (8)
O1—C1—C2—C3	−0.8 (7)	C3—C4—C5—O2	179.8 (5)
N2—C1—C2—C3	178.5 (5)	O2—C5—C6—C7	−179.6 (5)
O1—C1—C2—C7	−179.7 (5)	C4—C5—C6—C7	−1.3 (8)
N2—C1—C2—C7	−0.5 (7)	C3—C2—C7—C6	−0.1 (8)
C7—C2—C3—C4	0.2 (7)	C1—C2—C7—C6	178.8 (5)
C1—C2—C3—C4	−178.8 (5)	C5—C6—C7—C2	0.7 (8)
C2—C3—C4—C5	−0.8 (8)	C5—O2—C8—C9	−176.7 (5)
C8—O2—C5—C6	−1.7 (8)	O2—C8—C9—C10	−137.3 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	1.02 (7)	2.00 (7)	3.018 (6)	174 (6)
N1—H1B···O1ⁱⁱ	0.96 (7)	2.50 (6)	3.095 (6)	120 (4)
N2—H2···N1ⁱⁱⁱ	0.92 (6)	2.11 (6)	2.964 (6)	153 (4)

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

Acknowledgements

MBHH and SSK are grateful to the Department of Chemistry, Rajshahi University for the provision of laboratory facilities. MBHH is indebted to Rajshahi University for financial support. MCS and RM acknowledge the Center for Environmental Conservation and Research Safety, University of Toyama, for providing facilities for single-crystal X-ray analyses.

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