N-Phenyl-2-(propan-2-yl­­idene)­hydrazine­carboxamide

In the title compound, C₁₀H₁₃N₃O, the hydrazinecarboxamide N—N—C(=O)—N unit is nearly planar [maximum deviation = 0.018 (2) Å] and is inclined at a dihedral angle of 8.45 (10)° with respect to the plane of the phenyl ring. The mol­ecular structure is stabilized by an intra­molecular C—H⋯O hydrogen bond which generates an S(6) ring motif. In the crystal, mol­ecules are linked into an inversion dimer by pairs of N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For general background to and the pharmacological activities of the title compound, see: Sander & Shorvon (1987); Dimmock et al. (1993). For the preparation of the starting material of the title compound, see: Aboul-Enein et al. (2012). For standard bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For a related compound, see: Thirumurugan et al. (2006).

Experimental

Crystal data

• C₁₀H₁₃N₃O

• M_r = 191.23

• Monoclinic, P 2₁ /c

• a = 6.2225 (3) Å

• b = 15.3429 (7) Å

• c = 11.8897 (5) Å

• β = 112.283 (4)°

• V = 1050.35 (8) ų

• Z = 4

• Cu Kα radiation

• μ = 0.66 mm⁻¹

• T = 296 K

• 0.50 × 0.11 × 0.08 mm

Data collection

• Bruker SMART APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009) T_min = 0.438, T_max = 0.949

• 7990 measured reflections

• 1657 independent reflections

• 938 reflections with I > 2σ(I)

• R_int = 0.135

Refinement

• R[F² > 2σ(F²)] = 0.048

• wR(F²) = 0.142

• S = 0.95

• 1657 reflections

• 130 parameters

• H-atom parameters constrained

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1^i	0.87	2.04	2.892 (3)	168
C1—H1A⋯O1	0.93	2.29	2.879 (3)	120
C9—H9A⋯O1^i	0.96	2.50	3.366 (3)	149
Symmetry code: (i) -x+2, -y, -z+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

S1. Comment

Epilepsy is one of the most widespread pathologies of the human brain, affecting approximately 1% of world population. Nevertheless, in the case of single drug treatment, the number of non-responding patients is as high as 30% and in chronic medication with currently available antiepileptic drugs (AEDs) may result in severe side-effects and undesired drug interactions (Sander & Shorvon, 1987). That is why, in recent years, intensive research has been carried out aiming at the development of new therapeutic strategies for epilepsy. Arylsemicarbazones have been documented to display significant anticonvulsant activity through the work of Dimmock and his colleagues (Dimmock et al., 1993). Arylsemicarbazones are structurally dissimilar from many common monocyclic anticonvulsants which incorporate the dicarboxamide functionality, such as hydantoins and succinimides, which may contribute to toxic side effects. In general, semicarbazones have rapid onsets of action and one of the ways in which these compounds exerted their anticonvulsant activity is likely to be their interaction with the chloride channels.

In the title molecule, Fig. 1, the hydrazinecarboxamide moiety (N1–N3/O1/C7) is nearly planar with a maximum deviation of 0.018 (2) Å at atom N1, and is inclined at an angle of 8.45 (10)° with the phenyl ring (C1–C6). Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to a related structure (Thirumurugan et al., 2006). The molecular structure is stabilized by an intramolecular C1—H1A···O1 hydrogen bond (Table 1), which generates an S(6) ring motifs (Bernstein et al., 1995). In the crystal (Fig. 2), molecules are linked into an inversion dimer by pairs of intermolecular N2—H2···O1 and C9—H9A···O1 hydrogen bonds (Table 1).

Related literature

For general background to and the pharmacological activities of the title compound, see: Sander & Shorvon (1987); Dimmock et al. (1993). For the preparation of the title compound, see: Aboul-Enein et al. (2012). For standard bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For a related compound, see: Thirumurugan et al. (2006).

S2. Experimental

A solution of N-phenylhydrazinecarboxamide (0.1 g, 0.66 mmol) (Aboul-Enein et al., 2012) and two drops of acetic acid in acetone (5 ml) was stirred at room temperature for 18 h. The solvent was evaporated under reduced pressure and the residue was recrystallized from ethanol to give the title compound. M.p. : 429-430 K.

S3. Refinement

N-bound H atoms were located in a difference Fourier map [N—H = 0.8488 and 0.8694 Å] and refined using a riding model, with U_iso(H) = 1.2 U_eq(N). The remaining hydrogen atoms were positioned geometrically [C—H = 0.93 or 0.96 Å] and were refined using a riding model, with U_iso(H) = 1.2 or 1.5 U_eq(C). A rotating group model was applied to the methyl groups.

Computing details

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

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The crystal structure of the title compound, viewed along the a axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

N-Phenyl-2-(propan-2-ylidene)hydrazinecarboxamide

Crystal data

C10H13N3O	F(000) = 408
Mr = 191.23	Dx = 1.209 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 751 reflections
a = 6.2225 (3) Å	θ = 5.0–67.2°
b = 15.3429 (7) Å	µ = 0.66 mm^−1
c = 11.8897 (5) Å	T = 296 K
β = 112.283 (4)°	Needel, colourless
V = 1050.35 (8) Å^3	0.50 × 0.11 × 0.08 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	1657 independent reflections
Radiation source: fine-focus sealed tube	938 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.135
ϕ and ω scans	θmax = 63.0°, θmin = 5.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→6
Tmin = 0.438, Tmax = 0.949	k = −17→17
7990 measured reflections	l = −13→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.142	w = 1/[σ^2(Fo^2) + (0.0676P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.95	(Δ/σ)max = 0.002
1657 reflections	Δρmax = 0.18 e Å^−3
130 parameters	Δρmin = −0.13 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0093 (12)

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	0.8269 (3)	0.06411 (10)	0.88218 (14)	0.0795 (5)
N1	0.5175 (3)	0.12926 (11)	0.90676 (16)	0.0686 (6)
H1	0.4585	0.1299	0.9605	0.082*
N2	0.7965 (3)	0.05943 (12)	1.06500 (16)	0.0691 (6)
H2	0.9184	0.0260	1.0912	0.083*
N3	0.6658 (3)	0.08137 (11)	1.13237 (17)	0.0671 (5)
C1	0.4742 (4)	0.16254 (14)	0.6968 (2)	0.0740 (7)
H1A	0.6202	0.1402	0.7087	0.089*
C2	0.3356 (5)	0.19777 (16)	0.5857 (2)	0.0844 (7)
H2A	0.3905	0.1989	0.5230	0.101*
C3	0.1202 (4)	0.23094 (16)	0.5654 (2)	0.0855 (8)
H3A	0.0301	0.2543	0.4900	0.103*
C4	0.0386 (4)	0.22947 (15)	0.6575 (2)	0.0800 (7)
H4A	−0.1074	0.2521	0.6450	0.096*
C5	0.1727 (4)	0.19460 (13)	0.7679 (2)	0.0715 (7)
H5A	0.1154	0.1933	0.8296	0.086*
C6	0.3922 (4)	0.16118 (12)	0.78967 (19)	0.0602 (6)
C7	0.7190 (4)	0.08280 (14)	0.9466 (2)	0.0640 (6)
C8	0.7504 (4)	0.06860 (13)	1.2464 (2)	0.0669 (6)
C9	0.9849 (4)	0.03171 (16)	1.3183 (2)	0.0873 (8)
H9A	1.0181	−0.0148	1.2733	0.131*
H9B	0.9871	0.0097	1.3943	0.131*
H9C	1.1001	0.0765	1.3333	0.131*
C10	0.6029 (4)	0.09321 (16)	1.3149 (2)	0.0883 (8)
H10A	0.4583	0.1166	1.2596	0.132*
H10B	0.6818	0.1364	1.3748	0.132*
H10C	0.5735	0.0426	1.3543	0.132*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0855 (11)	0.0935 (11)	0.0727 (11)	0.0206 (8)	0.0449 (9)	0.0105 (9)
N1	0.0766 (12)	0.0733 (11)	0.0652 (11)	0.0133 (10)	0.0374 (9)	0.0071 (10)
N2	0.0719 (12)	0.0784 (12)	0.0636 (12)	0.0100 (9)	0.0331 (9)	0.0026 (10)
N3	0.0725 (13)	0.0741 (11)	0.0650 (12)	0.0015 (9)	0.0375 (9)	−0.0009 (10)
C1	0.0778 (16)	0.0797 (14)	0.0764 (16)	0.0085 (11)	0.0427 (12)	0.0103 (13)
C2	0.0960 (19)	0.0941 (16)	0.0774 (18)	0.0090 (15)	0.0490 (13)	0.0165 (14)
C3	0.0818 (18)	0.0957 (17)	0.0816 (18)	0.0115 (14)	0.0338 (13)	0.0227 (15)
C4	0.0774 (17)	0.0878 (16)	0.0817 (18)	0.0106 (12)	0.0379 (13)	0.0125 (15)
C5	0.0796 (16)	0.0728 (13)	0.0733 (16)	0.0049 (12)	0.0415 (12)	0.0028 (12)
C6	0.0688 (15)	0.0544 (11)	0.0658 (14)	0.0002 (10)	0.0351 (10)	−0.0015 (11)
C7	0.0725 (16)	0.0627 (12)	0.0636 (16)	0.0014 (11)	0.0333 (11)	−0.0006 (12)
C8	0.0744 (16)	0.0662 (11)	0.0662 (16)	−0.0066 (11)	0.0335 (12)	−0.0052 (12)
C9	0.0894 (17)	0.0979 (16)	0.0719 (15)	0.0069 (13)	0.0275 (13)	−0.0016 (14)
C10	0.0961 (19)	0.1029 (17)	0.0802 (17)	0.0004 (15)	0.0496 (14)	−0.0007 (15)

Geometric parameters (Å, º)

O1—C7	1.229 (3)	C3—H3A	0.9300
N1—C7	1.362 (3)	C4—C5	1.369 (3)
N1—C6	1.401 (2)	C4—H4A	0.9300
N1—H1	0.8488	C5—C6	1.388 (3)
N2—C7	1.352 (3)	C5—H5A	0.9300
N2—N3	1.382 (2)	C8—C10	1.487 (3)
N2—H2	0.8694	C8—C9	1.495 (3)
N3—C8	1.270 (2)	C9—H9A	0.9600
C1—C6	1.381 (3)	C9—H9B	0.9600
C1—C2	1.385 (3)	C9—H9C	0.9600
C1—H1A	0.9300	C10—H10A	0.9600
C2—C3	1.367 (3)	C10—H10B	0.9600
C2—H2A	0.9300	C10—H10C	0.9600
C3—C4	1.371 (3)
C7—N1—C6	128.38 (18)	C1—C6—C5	118.7 (2)
C7—N1—H1	110.4	C1—C6—N1	124.4 (2)
C6—N1—H1	120.5	C5—C6—N1	116.88 (18)
C7—N2—N3	118.88 (18)	O1—C7—N2	121.6 (2)
C7—N2—H2	116.6	O1—C7—N1	123.6 (2)
N3—N2—H2	124.1	N2—C7—N1	114.8 (2)
C8—N3—N2	118.99 (18)	N3—C8—C10	117.0 (2)
C6—C1—C2	118.9 (2)	N3—C8—C9	126.0 (2)
C6—C1—H1A	120.6	C10—C8—C9	117.0 (2)
C2—C1—H1A	120.6	C8—C9—H9A	109.5
C3—C2—C1	121.9 (2)	C8—C9—H9B	109.5
C3—C2—H2A	119.1	H9A—C9—H9B	109.5
C1—C2—H2A	119.1	C8—C9—H9C	109.5
C2—C3—C4	119.3 (2)	H9A—C9—H9C	109.5
C2—C3—H3A	120.4	H9B—C9—H9C	109.5
C4—C3—H3A	120.4	C8—C10—H10A	109.5
C5—C4—C3	119.7 (2)	C8—C10—H10B	109.5
C5—C4—H4A	120.1	H10A—C10—H10B	109.5
C3—C4—H4A	120.1	C8—C10—H10C	109.5
C4—C5—C6	121.5 (2)	H10A—C10—H10C	109.5
C4—C5—H5A	119.3	H10B—C10—H10C	109.5
C6—C5—H5A	119.3
C7—N2—N3—C8	−171.93 (18)	C7—N1—C6—C1	−11.0 (3)
C6—C1—C2—C3	−0.1 (4)	C7—N1—C6—C5	169.99 (19)
C1—C2—C3—C4	0.0 (4)	N3—N2—C7—O1	−179.16 (18)
C2—C3—C4—C5	−0.3 (4)	N3—N2—C7—N1	2.0 (3)
C3—C4—C5—C6	0.7 (3)	C6—N1—C7—O1	2.5 (3)
C2—C1—C6—C5	0.5 (3)	C6—N1—C7—N2	−178.70 (18)
C2—C1—C6—N1	−178.47 (19)	N2—N3—C8—C10	−179.96 (18)
C4—C5—C6—C1	−0.8 (3)	N2—N3—C8—C9	0.5 (3)
C4—C5—C6—N1	178.26 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.87	2.04	2.892 (3)	168
C1—H1A···O1	0.93	2.29	2.879 (3)	120
C9—H9A···O1^i	0.96	2.50	3.366 (3)	149

Symmetry code: (i) −x+2, −y, −z+2.

 

Footnotes

‡Thomson Reuters ResearcherID: A-5525-2009.

§Thomson Reuters ResearcherID: A-3561-2009.