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

The title compound, C(9)H(11)N(3)O, was synthesized by the reaction of 4-methyl-benzaldehyde with semicarbazide. The mol-ecule 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 intra-molecular N-H⋯N bond generates an S(5) ring. In the crystal, adjacent mol-ecules are connected via a pair of N-H⋯O hydrogen bonds, generating R(2) (2)(8) loops, resulting in supra-molecular [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 = 177.21

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.149

S = 1.09

1833 reflections

131 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.18 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 ▶).

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

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

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

C9H11N3O	F(000) = 376
Mr = 177.21	Dx = 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

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

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(Fo2) + (0.0825P)2 + 0.0212P] where P = (Fo2 + 2Fc2)/3
1833 reflections	(Δ/σ)max < 0.001
131 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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)

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) ; (ii) .