(E)-2-(4-Methylbenzylidene)hydrazinecarboxamide

Kia, Y.; Osman, H.; Murugaiyah, V. al; Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536810052797

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o242

doi:10.1107/S1600536810052797

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(E)-2-(4-Methylbenzylidene)hydrazinecarboxamide

Yalda Kia,^a Hasnah Osman,^a Vikneswaran al Murugaiyah,^b Madhukar Hemamalini ^c and Hoong-Kun Fun ^c ^*‡

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bSchool of Pharmaceutical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 15 December 2010; accepted 16 December 2010; online 8 January 2011)

The title compound, C₉H₁₁N₃O, was synthesized by the reaction of 4-methylbenzaldehyde with semicarbazide. The molecule adopts an E configuration about the central C=N double bond and the dihedral angle between the mean planes of the benzene ring and the carboxamide groups is 17.05 (9)°. The hydrazine N atoms are twisted slightly out of the plane of the carboxamide group [C—C—N—N torsion angle = 178.39 (14)°] and an intramolecular N—H⋯N bond generates an S(5) ring. In the crystal, adjacent molecules are connected via a pair of N—H⋯O hydrogen bonds, generating R₂²(8) loops, resulting in supramolecular [001] ribbons.

Related literature

For applications of Schiff bases, see: Dhar et al. (1982 ); Przybylski et al. (2009 ); Bringmann et al. (2004 ); De Souza et al. (2007 ); Guo et al. (2007 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₁₁N₃O
M_r = 177.21
Monoclinic, P 2₁ /c
a = 17.2186 (13) Å
b = 4.5304 (3) Å
c = 11.9846 (9) Å
β = 93.348 (3)°
V = 933.29 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.76 × 0.23 × 0.05 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.937, T_max = 0.996
6322 measured reflections
1833 independent reflections
1285 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.149
S = 1.09
1833 reflections
131 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1ⁱ	0.928 (18)	1.998 (18)	2.9260 (19)	177.7 (17)
N3—H2N3⋯N1	0.93 (2)	2.22 (2)	2.667 (2)	108.6 (16)
N3—H1N3⋯O1ⁱⁱ	0.97 (2)	1.97 (2)	2.9106 (19)	163.5 (17)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810052797/hb5772sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810052797/hb5772Isup2.hkl

checkCIF report

Comment top

Schiff bases are formed from the reaction of a primary amine with aldehydes or ketones. They exhibit interesting biological activities, such as antifungal, antibacterial, antimalarial, antiproliferative, anti-inflammatory, antiviral and antipyretic properties (Dhar et al., 1982; Przybylski et al., 2009). The Imine functional group present in these compounds is responsible for their vast biological activities. In addition, Schiff bases are also employed as intermediates in the total synthesis of bioactive natural products (Bringmann et al., 2004; De Souza et al., 2007; Guo et al., 2007).

The asymmetric unit of the title compound is shown in Fig. 1. The molecule adopts an E configuration about the central C═N double bond. The dihedral angle between the mean planes of the benzene (C1–C6) ring and carboxamide (N1–N3/O1/C8) group is 17.05 (9)°. The hydrazine N atoms are twisted slightly out of the plane of the carboxamide group [C6-C7-N1-N2 torsion angle = 178.39 (14)°].

In the crystal packing (Fig. 2), the adjacent molecules are connected via pair of N—H···O hydrogen bonds, generating an R₂²(8) ring motifs, resulting in supramolecular ribbons along the c-axis.

Related literature top

For applications of Schiff bases, see: Dhar et al. (1982); Przybylski et al. (2009); Bringmann et al. (2004); De Souza et al. (2007); Guo et al. (2007). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A mixture of 4-methylbenzaldehyde (0.1 g, 0.83 mmol) and semicarbazide (0.062 g, 0.83 mmol) was dissolved in ethanol (5.0 ml) and water (1.0 ml) which was then refluxed in the presence of sodium hydroxide (0.25M) for 3-4 hours. After completion of the reaction (through TLC monitoring), the mixture was poured into ice. The precipitate which was formed was filtered and washed with water. The pure solid was then recrystallised from ethanol to afford the title compound as colourless plates.

Computing details top

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

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids.
	Fig. 2. A supramolecular ribbon generated by N—H···O hydrogen bonds.

(E)-2-(4-Methylbenzylidene)hydrazinecarboxamide top

Crystal data top

C₉H₁₁N₃O	F(000) = 376
M_r = 177.21	D_x = 1.261 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1533 reflections
a = 17.2186 (13) Å	θ = 3.4–22.6°
b = 4.5304 (3) Å	µ = 0.09 mm⁻¹
c = 11.9846 (9) Å	T = 296 K
β = 93.348 (3)°	Plate, colourless
V = 933.29 (12) Å³	0.76 × 0.23 × 0.05 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	1833 independent reflections
Radiation source: fine-focus sealed tube	1285 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −21→20
T_min = 0.937, T_max = 0.996	k = −5→5
6322 measured reflections	l = −14→12

Refinement top

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) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0825P)² + 0.0212P] where P = (F_o² + 2F_c²)/3
1833 reflections	(Δ/σ)_max < 0.001
131 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₉H₁₁N₃O	V = 933.29 (12) Å³
M_r = 177.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.2186 (13) Å	µ = 0.09 mm⁻¹
b = 4.5304 (3) Å	T = 296 K
c = 11.9846 (9) Å	0.76 × 0.23 × 0.05 mm
β = 93.348 (3)°

Data collection top

Bruker SMART APEXII CCD diffractometer	1833 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1285 reflections with I > 2σ(I)
T_min = 0.937, T_max = 0.996	R_int = 0.025
6322 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.18 e Å⁻³
1833 reflections	Δρ_min = −0.18 e Å⁻³
131 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.50913 (6)	0.2012 (3)	0.63337 (10)	0.0540 (4)
N1	0.34815 (7)	0.3857 (3)	0.45522 (11)	0.0487 (4)
N2	0.41216 (8)	0.2357 (3)	0.49998 (12)	0.0505 (4)
H1N2	0.4366 (10)	0.093 (4)	0.4589 (16)	0.067 (6)*
N3	0.42019 (9)	0.5689 (3)	0.64575 (12)	0.0530 (4)
H2N3	0.3792 (10)	0.660 (5)	0.6044 (18)	0.076 (6)*
H1N3	0.4490 (10)	0.643 (4)	0.7121 (19)	0.072 (6)*
C1	0.20643 (10)	0.6318 (5)	0.35353 (17)	0.0676 (6)
H1A	0.2179	0.6835	0.4278	0.081*
C2	0.14128 (11)	0.7477 (5)	0.2966 (2)	0.0769 (7)
H2A	0.1093	0.8755	0.3337	0.092*
C3	0.12229 (11)	0.6785 (5)	0.18552 (18)	0.0663 (6)
C4	0.17074 (11)	0.4889 (5)	0.13342 (15)	0.0671 (6)
H4A	0.1595	0.4394	0.0589	0.081*
C5	0.23599 (10)	0.3697 (5)	0.18930 (15)	0.0647 (6)
H5A	0.2677	0.2417	0.1519	0.078*
C6	0.25475 (9)	0.4387 (4)	0.30032 (13)	0.0520 (5)
C7	0.32332 (10)	0.3054 (4)	0.35755 (14)	0.0531 (5)
H7A	0.3497	0.1574	0.3216	0.064*
C8	0.44997 (9)	0.3340 (4)	0.59601 (13)	0.0443 (4)
C9	0.05146 (12)	0.8111 (6)	0.1244 (2)	0.0941 (8)
H9A	0.0215	0.6574	0.0873	0.141*
H9B	0.0676	0.9508	0.0702	0.141*
H9C	0.0202	0.9092	0.1769	0.141*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0579 (7)	0.0596 (8)	0.0426 (7)	0.0045 (6)	−0.0143 (6)	0.0028 (5)
N1	0.0481 (8)	0.0571 (9)	0.0396 (8)	0.0016 (6)	−0.0072 (6)	0.0002 (6)
N2	0.0525 (8)	0.0584 (9)	0.0388 (8)	0.0084 (7)	−0.0125 (6)	−0.0024 (7)
N3	0.0623 (9)	0.0541 (9)	0.0410 (8)	0.0013 (7)	−0.0105 (7)	−0.0040 (7)
C1	0.0656 (11)	0.0847 (14)	0.0503 (11)	0.0149 (10)	−0.0135 (9)	−0.0105 (10)
C2	0.0643 (12)	0.0895 (15)	0.0749 (15)	0.0209 (11)	−0.0122 (11)	−0.0104 (12)
C3	0.0569 (11)	0.0752 (13)	0.0642 (12)	−0.0046 (10)	−0.0192 (10)	0.0128 (10)
C4	0.0674 (11)	0.0875 (14)	0.0443 (10)	−0.0055 (11)	−0.0160 (9)	0.0042 (10)
C5	0.0612 (11)	0.0872 (14)	0.0445 (10)	0.0076 (10)	−0.0080 (8)	−0.0041 (10)
C6	0.0497 (9)	0.0642 (11)	0.0412 (9)	−0.0002 (8)	−0.0056 (7)	0.0008 (8)
C7	0.0523 (9)	0.0656 (11)	0.0405 (9)	0.0088 (8)	−0.0050 (8)	−0.0040 (8)
C8	0.0491 (9)	0.0485 (10)	0.0343 (8)	−0.0080 (7)	−0.0058 (7)	0.0078 (7)
C9	0.0724 (14)	0.1056 (18)	0.100 (2)	0.0093 (13)	−0.0354 (13)	0.0148 (15)

Geometric parameters (Å, º) top

O1—C8	1.2436 (18)	C2—H2A	0.9300
N1—C7	1.275 (2)	C3—C4	1.373 (3)
N1—N2	1.3766 (18)	C3—C9	1.510 (2)
N2—C8	1.363 (2)	C4—C5	1.384 (2)
N2—H1N2	0.93 (2)	C4—H4A	0.9300
N3—C8	1.337 (2)	C5—C6	1.386 (2)
N3—H2N3	0.935 (19)	C5—H5A	0.9300
N3—H1N3	0.97 (2)	C6—C7	1.461 (2)
C1—C2	1.382 (2)	C7—H7A	0.9300
C1—C6	1.388 (3)	C9—H9A	0.9600
C1—H1A	0.9300	C9—H9B	0.9600
C2—C3	1.388 (3)	C9—H9C	0.9600

C7—N1—N2	115.78 (15)	C4—C5—C6	120.91 (19)
C8—N2—N1	119.98 (15)	C4—C5—H5A	119.5
C8—N2—H1N2	117.8 (11)	C6—C5—H5A	119.5
N1—N2—H1N2	120.9 (11)	C5—C6—C1	118.08 (16)
C8—N3—H2N3	114.4 (13)	C5—C6—C7	119.61 (17)
C8—N3—H1N3	116.6 (11)	C1—C6—C7	122.30 (15)
H2N3—N3—H1N3	127.9 (19)	N1—C7—C6	122.12 (16)
C2—C1—C6	120.24 (18)	N1—C7—H7A	118.9
C2—C1—H1A	119.9	C6—C7—H7A	118.9
C6—C1—H1A	119.9	O1—C8—N3	123.50 (15)
C1—C2—C3	121.8 (2)	O1—C8—N2	119.12 (16)
C1—C2—H2A	119.1	N3—C8—N2	117.37 (15)
C3—C2—H2A	119.1	C3—C9—H9A	109.5
C4—C3—C2	117.53 (17)	C3—C9—H9B	109.5
C4—C3—C9	121.5 (2)	H9A—C9—H9B	109.5
C2—C3—C9	120.9 (2)	C3—C9—H9C	109.5
C3—C4—C5	121.45 (18)	H9A—C9—H9C	109.5
C3—C4—H4A	119.3	H9B—C9—H9C	109.5
C5—C4—H4A	119.3

C7—N1—N2—C8	170.10 (15)	C4—C5—C6—C7	178.99 (16)
C6—C1—C2—C3	−0.6 (3)	C2—C1—C6—C5	0.7 (3)
C1—C2—C3—C4	0.1 (3)	C2—C1—C6—C7	−178.66 (19)
C1—C2—C3—C9	−179.11 (19)	N2—N1—C7—C6	178.39 (14)
C2—C3—C4—C5	0.2 (3)	C5—C6—C7—N1	171.99 (17)
C9—C3—C4—C5	179.42 (19)	C1—C6—C7—N1	−8.7 (3)
C3—C4—C5—C6	−0.1 (3)	N1—N2—C8—O1	−177.76 (13)
C4—C5—C6—C1	−0.4 (3)	N1—N2—C8—N3	3.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1ⁱ	0.928 (18)	1.998 (18)	2.9260 (19)	177.7 (17)
N3—H2N3···N1	0.93 (2)	2.22 (2)	2.667 (2)	108.6 (16)
N3—H1N3···O1ⁱⁱ	0.97 (2)	1.97 (2)	2.9106 (19)	163.5 (17)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O
M_r	177.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	17.2186 (13), 4.5304 (3), 11.9846 (9)
β (°)	93.348 (3)
V (Å³)	933.29 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.76 × 0.23 × 0.05

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.937, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	6322, 1833, 1285
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.149, 1.09
No. of reflections	1833
No. of parameters	131
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.18

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1ⁱ	0.928 (18)	1.998 (18)	2.9260 (19)	177.7 (17)
N3—H2N3···N1	0.93 (2)	2.22 (2)	2.667 (2)	108.6 (16)
N3—H1N3···O1ⁱⁱ	0.97 (2)	1.97 (2)	2.9106 (19)	163.5 (17)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y+1/2, −z+3/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

YK, HO and VM thank the Malaysian Government and Universiti Sains Malaysia for the research University grant No. 1001/PKIMIA/811133. HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

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