(E)-N′-[1-(4-Amino­phen­yl)ethyl­­idene]benzohydrazide

Crystals of the title compound, C₁₅H₁₅N₃O, were obtained from a condensation reaction of benzohydrazide and 1-(4-amino­phen­yl)ethanone. The mol­ecule assumes an E configuration with the amino­phenyl and benzohydrazide units located on opposite sites of the C=N double bond. In the crystal structure, the benzene rings of the mol­ecule are slightly twisted with respect to the central hydrazide, the dihedral angles being 18.22 (12) and 27.62 (12)°. The crystal structure contains inter­molecular N—H⋯O and weak C—H⋯N hydrogen bonding.

Related literature

For general background, see: Okabe et al. (1993); Shan et al. (2003). For a related structure, see: Shan et al. (2008).

Experimental

Crystal data

• C₁₅H₁₅N₃O

• M_r = 253.30

• Monoclinic, P 2₁ /n

• a = 12.261 (9) Å

• b = 5.324 (4) Å

• c = 19.882 (15) Å

• β = 94.57 (2)°

• V = 1293.7 (17) ų

• Z = 4

• Mo Kα radiation

• μ = 0.08 mm⁻¹

• T = 295 (2) K

• 0.42 × 0.36 × 0.32 mm

Data collection

• Rigaku R-AXIS RAPID IP diffractometer

• Absorption correction: none

• 10914 measured reflections

• 2303 independent reflections

• 1594 reflections with I > 2σ(I)

• R_int = 0.042

Refinement

• R[F² > 2σ(F²)] = 0.048

• wR(F²) = 0.156

• S = 1.05

• 2303 reflections

• 174 parameters

• H-atom parameters constrained

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯O1^i	0.86	2.44	3.169 (3)	143
C15—H15C⋯N2^ii	0.96	2.62	3.468 (3)	147
Symmetry codes: (i) -x, -y+2, -z+1; (ii) x, y-1, z.

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Supporting information

S1. Comment

Since some hydrazone derivatives have shown to be potential DNA damaging and mutagenic agents (Okabe et al., 1993), a series of new hydrazone derivatives have been prepared in our laboratory (Shan et al., 2003). As part of the ongoing investigation, the title compound has recently been prepared and its crystal structure is reported here.

The molecular structure of the title compound is shown in Fig. 1. The N2—C8 bond distance of 1.292 (2) Å indicates a typical C═N double bond. The aminophenyl and benzohydrazide moieties located on the opposite sites of the C═N bond, the molecule assumes an E configuration, similat to that found in a related compound, (E)-acetylpyrazine 4-nitrophenylhydrazone (Shan et al., 2008). The terminal benzene rings are slightly twisted to the central hydrazide (O1/C7/N1/N2), with dihedral angles of 18.22 (12)° between C1-benzene and hydrazide planes and 27.62 (12)° between aminophenylethylidene and hydrazide planes, indicating the approximately co-planar molecular structure except for methyl H atoms.

The crystal structure contains molecular classic N—H···O hydrogen bonding and weak C—H···N hydrogen bonding (Table 1).

Related literature

For general background, see: Okabe et al. (1993); Shan et al. (2003). For a related structure, see: Shan et al. (2008).

S2. Experimental

Benzohydrazide (0.27 g, 2 mmol) was dissolved in ethanol (10 ml), then acetic acid (0.1 ml) was added to the ethanol solution with stirring. The solution was heated at 333 K for several minutes until the solution cleared. 1-(4-aminophenyl)ethanone (0.27 g, 2 mmol) was then added slowly into the solution, and the mixture was kept at 333 K with continuous stirring for 6 h. After the solution had cooled to room temperature yellow powder crystals appeared. The powder crystals were separated and washed with water three times. Recrystallization from an absolute ethanol yielded well shaped single crystals of the title compound.

S3. Refinement

Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and the torsion angle was refined to fit the electron density, U_iso(H) = 1.5U_eq(C). Other H atoms were placed in calculated positions with C—H = 0.93 and N—H = 0.86 Å, and refined in riding mode with U_iso(H) = 1.2U_eq(C,N).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The molecular structure of the title compound with 50% probability displacement ellipsoids for non-H atoms.

(E)-N'-[1-(4-Aminophenyl)ethylidene]benzohydrazide

Crystal data

C15H15N3O	F(000) = 536
Mr = 253.30	Dx = 1.301 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3256 reflections
a = 12.261 (9) Å	θ = 2.0–25.0°
b = 5.324 (4) Å	µ = 0.08 mm^−1
c = 19.882 (15) Å	T = 295 K
β = 94.57 (2)°	Prism, yellow
V = 1293.7 (17) Å^3	0.42 × 0.36 × 0.32 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer	1594 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.042
Graphite monochromator	θmax = 25.2°, θmin = 1.9°
Detector resolution: 10.00 pixels mm^-1	h = −14→13
ω scans	k = −6→6
10914 measured reflections	l = −23→23
2303 independent reflections

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) = 0.156	w = 1/[σ^2(Fo^2) + (0.0957P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2303 reflections	Δρmax = 0.21 e Å^−3
174 parameters	Δρmin = −0.15 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.029 (5)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
N1	0.31065 (12)	0.5389 (3)	0.53755 (7)	0.0458 (4)
H1	0.3349	0.3881	0.5344	0.055*
N2	0.21647 (12)	0.6131 (3)	0.49876 (7)	0.0445 (4)
N3	−0.22800 (14)	0.7277 (3)	0.31088 (8)	0.0636 (5)
H3A	−0.2549	0.6375	0.2777	0.076*
H3B	−0.2616	0.8609	0.3223	0.076*
O1	0.33735 (12)	0.9288 (3)	0.58300 (7)	0.0629 (5)
C1	0.45840 (15)	0.6003 (3)	0.62353 (9)	0.0436 (5)
C2	0.51973 (16)	0.3936 (4)	0.60532 (10)	0.0542 (6)
H2	0.5019	0.3119	0.5646	0.065*
C3	0.60765 (18)	0.3099 (4)	0.64827 (12)	0.0653 (6)
H3	0.6489	0.1736	0.6357	0.078*
C4	0.63412 (18)	0.4268 (4)	0.70911 (11)	0.0646 (6)
H4	0.6927	0.3692	0.7375	0.078*
C5	0.57340 (18)	0.6300 (4)	0.72783 (10)	0.0620 (6)
H5	0.5904	0.7084	0.7691	0.074*
C6	0.48743 (16)	0.7162 (4)	0.68502 (9)	0.0545 (6)
H6	0.4479	0.8553	0.6976	0.065*
C7	0.36407 (15)	0.7045 (4)	0.58023 (8)	0.0449 (5)
C8	0.17939 (15)	0.4585 (3)	0.45231 (8)	0.0402 (5)
C9	0.07430 (14)	0.5262 (3)	0.41483 (8)	0.0397 (5)
C10	0.01535 (15)	0.7400 (3)	0.43293 (8)	0.0450 (5)
H10	0.0437	0.8397	0.4685	0.054*
C11	−0.08369 (16)	0.8054 (4)	0.39912 (9)	0.0480 (5)
H11	−0.1199	0.9492	0.4118	0.058*
C12	−0.12988 (15)	0.6578 (4)	0.34612 (9)	0.0477 (5)
C13	−0.07350 (17)	0.4434 (4)	0.32890 (9)	0.0536 (6)
H13	−0.1032	0.3403	0.2944	0.064*
C14	0.02614 (16)	0.3814 (3)	0.36233 (9)	0.0496 (5)
H14	0.0622	0.2378	0.3492	0.060*
C15	0.23698 (17)	0.2176 (3)	0.43604 (10)	0.0544 (6)
H15A	0.3141	0.2481	0.4361	0.082*
H15B	0.2093	0.1587	0.3923	0.082*
H15C	0.2241	0.0929	0.4694	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0451 (10)	0.0419 (9)	0.0490 (9)	0.0038 (7)	−0.0059 (7)	−0.0028 (7)
N2	0.0436 (10)	0.0446 (10)	0.0437 (8)	0.0004 (7)	−0.0059 (7)	0.0019 (7)
N3	0.0596 (12)	0.0707 (12)	0.0572 (10)	0.0061 (10)	−0.0166 (8)	0.0062 (9)
O1	0.0652 (10)	0.0461 (9)	0.0735 (10)	0.0083 (7)	−0.0176 (8)	−0.0082 (7)
C1	0.0390 (11)	0.0435 (11)	0.0478 (10)	−0.0025 (9)	0.0012 (8)	0.0016 (8)
C2	0.0469 (13)	0.0506 (12)	0.0643 (12)	0.0026 (9)	0.0000 (10)	−0.0059 (10)
C3	0.0582 (14)	0.0520 (13)	0.0851 (16)	0.0127 (11)	0.0029 (12)	0.0019 (11)
C4	0.0526 (14)	0.0656 (15)	0.0735 (15)	0.0092 (11)	−0.0078 (11)	0.0144 (12)
C5	0.0581 (14)	0.0714 (15)	0.0537 (12)	0.0061 (12)	−0.0128 (10)	−0.0033 (11)
C6	0.0530 (13)	0.0545 (13)	0.0545 (12)	0.0089 (10)	−0.0046 (9)	−0.0078 (10)
C7	0.0440 (12)	0.0439 (11)	0.0463 (10)	0.0004 (9)	0.0011 (8)	−0.0029 (8)
C8	0.0467 (11)	0.0343 (10)	0.0395 (9)	−0.0034 (8)	0.0020 (8)	0.0043 (7)
C9	0.0440 (11)	0.0346 (10)	0.0398 (9)	−0.0047 (8)	−0.0011 (8)	0.0047 (7)
C10	0.0487 (12)	0.0419 (11)	0.0433 (10)	−0.0021 (9)	−0.0031 (8)	−0.0043 (8)
C11	0.0474 (12)	0.0476 (12)	0.0487 (10)	0.0028 (9)	0.0030 (9)	0.0027 (9)
C12	0.0485 (12)	0.0492 (12)	0.0442 (10)	−0.0055 (9)	−0.0036 (9)	0.0126 (8)
C13	0.0646 (14)	0.0466 (12)	0.0462 (11)	−0.0057 (10)	−0.0160 (10)	0.0004 (9)
C14	0.0622 (14)	0.0380 (11)	0.0469 (10)	0.0019 (9)	−0.0071 (10)	−0.0020 (8)
C15	0.0584 (13)	0.0437 (12)	0.0588 (12)	0.0055 (10)	−0.0095 (10)	−0.0035 (9)

Geometric parameters (Å, º)

N1—C7	1.355 (2)	C5—H5	0.9300
N1—N2	1.394 (2)	C6—H6	0.9300
N1—H1	0.8600	C8—C9	1.481 (3)
N2—C8	1.292 (2)	C8—C15	1.512 (3)
N3—C12	1.394 (2)	C9—C14	1.391 (2)
N3—H3A	0.8600	C9—C10	1.410 (3)
N3—H3B	0.8600	C10—C11	1.385 (3)
O1—C7	1.241 (2)	C10—H10	0.9300
C1—C6	1.390 (3)	C11—C12	1.398 (3)
C1—C2	1.396 (3)	C11—H11	0.9300
C1—C7	1.493 (3)	C12—C13	1.391 (3)
C2—C3	1.394 (3)	C13—C14	1.384 (3)
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.376 (3)	C14—H14	0.9300
C3—H3	0.9300	C15—H15A	0.9600
C4—C5	1.381 (3)	C15—H15B	0.9600
C4—H4	0.9300	C15—H15C	0.9600
C5—C6	1.380 (3)
C7—N1—N2	120.00 (16)	N2—C8—C9	116.56 (16)
C7—N1—H1	120.0	N2—C8—C15	123.33 (17)
N2—N1—H1	120.0	C9—C8—C15	120.10 (16)
C8—N2—N1	116.36 (16)	C14—C9—C10	116.33 (17)
C12—N3—H3A	120.0	C14—C9—C8	122.89 (17)
C12—N3—H3B	120.0	C10—C9—C8	120.74 (16)
H3A—N3—H3B	120.0	C11—C10—C9	121.78 (17)
C6—C1—C2	118.19 (18)	C11—C10—H10	119.1
C6—C1—C7	118.33 (17)	C9—C10—H10	119.1
C2—C1—C7	123.48 (17)	C10—C11—C12	120.77 (18)
C3—C2—C1	119.9 (2)	C10—C11—H11	119.6
C3—C2—H2	120.0	C12—C11—H11	119.6
C1—C2—H2	120.0	C13—C12—N3	121.40 (18)
C4—C3—C2	120.7 (2)	C13—C12—C11	117.86 (18)
C4—C3—H3	119.6	N3—C12—C11	120.73 (19)
C2—C3—H3	119.6	C14—C13—C12	120.99 (17)
C3—C4—C5	119.8 (2)	C14—C13—H13	119.5
C3—C4—H4	120.1	C12—C13—H13	119.5
C5—C4—H4	120.1	C13—C14—C9	122.26 (18)
C6—C5—C4	119.8 (2)	C13—C14—H14	118.9
C6—C5—H5	120.1	C9—C14—H14	118.9
C4—C5—H5	120.1	C8—C15—H15A	109.5
C5—C6—C1	121.62 (19)	C8—C15—H15B	109.5
C5—C6—H6	119.2	H15A—C15—H15B	109.5
C1—C6—H6	119.2	C8—C15—H15C	109.5
O1—C7—N1	122.51 (17)	H15A—C15—H15C	109.5
O1—C7—C1	121.83 (16)	H15B—C15—H15C	109.5
N1—C7—C1	115.66 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O1^i	0.86	2.44	3.169 (3)	143
C15—H15C···N2^ii	0.96	2.62	3.468 (3)	147

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