1-(4-Amino­phen­yl)ethanone isonicotinoylhydrazone

Chen, S.-S.; Zhang, S.-P.; Huang, C.-B.; Shao, S.-C.

doi:10.1107/S1600536805039516

1-(4-Aminophenyl)ethanone isonicotinoylhydrazone

S.-S. Chen, S.-P. Zhang, C.-B. Huang and S.-C. Shao

The title molecule, C₁₄H₁₄N₄O, adopts a trans configuration with respect to the C=N double bond. The dihedral angle between the two rings is 73.1 (4)°. The crystal structure is stabilized by intermolecular N—H

N and N—H

O hydrogen bonds which link the molecules into a chain along the c axis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039516/sj6169sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039516/sj6169Isup2.hkl Contains datablock I

CCDC reference: 296658

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.006 Å
R factor = 0.100
wR factor = 0.183
Data-to-parameter ratio = 9.6

checkCIF/PLATON results

No syntax errors found



Alert level C
RFACG01_ALERT_3_C  The value of the R factor is > 0.10
            R factor given   0.100
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT088_ALERT_3_C Poor Data / Parameter Ratio ....................       9.62
PLAT147_ALERT_1_C su on Symmetry Constrained Cell Angle(s) .......          ?
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.48 Ratio
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          6
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1B    ...          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Schiff base compounds have been of great interest for many years. These compounds play an important role in the development of coordination chemistry related to catalysis and enzymatic reactions (Brunner et al., 1983), magnetism and molecular architectures (Miller et al., 2000). As an extension of work on the structural characterization of hydrazone Schiff base compounds (Shao et al., 2004), we report here the crystal structure of (I), a new isonicotinohydrazone with 1-(4-aminophenyl)ethanone.

In the title compound, (I) (Fig. 1), the C7═N2 bond, 1.277 (5) Å, and the C9—N3 bond, 1.340 (5) Å, are both shorter than normal because of conjugation effects. All other bond lengths are within normal ranges (Allen et al., 1987). The dihedral angle between the benzene and pyridine rings [73.1 (4)°] is significantly larger than normal (Shao et al., 2004) due to the steric effect of the C8 methyl substituent. The structure of (I) is stabilized by intermolecular N—H···N and N—H···O hydrogen bonds, forming chains along the c axis (Table 1 and Fig. 2).

Experimental top

1-(4-aminophenyl)ethanone (0.2 mmol, 27 mg) and isonicotinohydrazide (0.2 mmol, 27.4 mg) were dissolved in methanol (10 ml). The mixture was stirred at room temperature for 10 min. to give a clear yellow solution. The solution was set aside for 8 d to allow slow evaporation of the solvent. Large colourless block-shaped crystals separated; these were collected and washed three times with water.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal packing of (I), viewed along the a axis. Dashed lines indicate intermolecular hydrogen bonds.

1-(4-Aminophenyl)ethanone isonicotinoylhydrazone top

Crystal data top

C₁₄H₁₄N₄O	F(000) = 536
M_r = 254.29	D_x = 1.352 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1324 reflections
a = 7.9137 (15) Å	θ = 5.2–53.9°
b = 5.3466 (10) Å	µ = 0.09 mm⁻¹
c = 29.650 (6) Å	T = 298 K
β = 95.415 (3)°	Block, colourless
V = 1248.9 (4) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX area-detector diffractometer	2193 independent reflections
Radiation source: fine-focus sealed tube	1936 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −9→9
T_min = 0.974, T_max = 0.982	k = −6→6
5756 measured reflections	l = −29→35

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)] = 0.100	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.183	All H-atom parameters refined
S = 1.33	w = 1/[σ²(F_o²) + (0.034P)² + 1.5639P] where P = (F_o² + 2F_c²)/3
2193 reflections	(Δ/σ)_max < 0.001
228 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₄H₁₄N₄O	V = 1248.9 (4) Å³
M_r = 254.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.9137 (15) Å	µ = 0.09 mm⁻¹
b = 5.3466 (10) Å	T = 298 K
c = 29.650 (6) Å	0.30 × 0.20 × 0.20 mm
β = 95.415 (3)°

Data collection top

Bruker SMART APEX area-detector diffractometer	2193 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1936 reflections with I > 2σ(I)
T_min = 0.974, T_max = 0.982	R_int = 0.043
5756 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.100	0 restraints
wR(F²) = 0.183	All H-atom parameters refined
S = 1.33	Δρ_max = 0.31 e Å⁻³
2193 reflections	Δρ_min = −0.23 e Å⁻³
228 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.7070 (5)	0.6729 (6)	−0.00750 (10)	0.0637 (10)
N1	0.9652 (7)	0.6134 (9)	0.26696 (13)	0.0618 (13)
H1A	1.021 (6)	0.529 (9)	0.2871 (16)	0.058 (15)*
H1B	0.896 (6)	0.729 (9)	0.2747 (15)	0.055 (15)*
N2	0.7709 (4)	0.3526 (6)	0.06240 (10)	0.0423 (9)
N3	0.7454 (5)	0.2766 (7)	0.01766 (11)	0.0419 (9)
H3A	0.749 (4)	0.124 (7)	0.0101 (12)	0.025 (10)*
N4	0.6067 (5)	0.1699 (7)	−0.14986 (11)	0.0475 (9)
C1	0.8754 (5)	0.2929 (7)	0.13793 (12)	0.0360 (9)
C2	0.7838 (6)	0.4994 (8)	0.15080 (14)	0.0448 (11)
H2	0.705 (4)	0.572 (6)	0.1293 (12)	0.029 (10)*
C3	0.8106 (6)	0.6030 (8)	0.19332 (14)	0.0473 (11)
H3	0.742 (5)	0.748 (8)	0.1996 (13)	0.044 (11)*
C4	0.9308 (6)	0.5017 (8)	0.22575 (13)	0.0431 (11)
C5	1.0166 (6)	0.2902 (9)	0.21401 (14)	0.0492 (12)
H5	1.089 (5)	0.217 (7)	0.2360 (14)	0.043 (11)*
C6	0.9887 (6)	0.1890 (8)	0.17131 (14)	0.0432 (11)
H6	1.059 (5)	0.058 (8)	0.1648 (13)	0.045 (12)*
C7	0.8539 (5)	0.2061 (7)	0.09040 (12)	0.0331 (9)
C8	0.9342 (8)	−0.0317 (11)	0.07727 (19)	0.0563 (14)
H8A	0.856 (6)	−0.137 (9)	0.0653 (17)	0.070 (17)*
H8B	1.010 (6)	0.002 (9)	0.0545 (17)	0.072 (16)*
H8C	1.004 (7)	−0.101 (10)	0.1000 (18)	0.087 (19)*
C9	0.7076 (5)	0.4484 (8)	−0.01463 (13)	0.0388 (10)
C10	0.6681 (5)	0.3456 (7)	−0.06160 (12)	0.0354 (9)
C11	0.7245 (6)	0.4743 (8)	−0.09750 (14)	0.0446 (11)
H11	0.791 (5)	0.622 (8)	−0.0937 (13)	0.045 (12)*
C12	0.6912 (6)	0.3807 (9)	−0.14050 (14)	0.0513 (12)
H12	0.735 (5)	0.468 (7)	−0.1673 (13)	0.043 (11)*
C13	0.5499 (6)	0.0522 (9)	−0.11515 (15)	0.0451 (11)
H13	0.484 (5)	−0.089 (7)	−0.1217 (12)	0.031 (10)*
C14	0.5767 (6)	0.1298 (8)	−0.07084 (14)	0.0410 (10)
H14	0.537 (5)	0.047 (7)	−0.0481 (13)	0.042 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.109 (3)	0.0379 (18)	0.0410 (18)	0.0120 (18)	−0.0096 (17)	−0.0044 (14)
N1	0.094 (4)	0.057 (3)	0.033 (2)	0.013 (3)	−0.003 (2)	−0.004 (2)
N2	0.062 (2)	0.0406 (19)	0.0235 (17)	0.0065 (18)	0.0006 (15)	0.0001 (15)
N3	0.059 (2)	0.035 (2)	0.0315 (19)	0.0073 (18)	0.0002 (16)	−0.0042 (16)
N4	0.055 (2)	0.057 (2)	0.0306 (19)	0.008 (2)	0.0054 (16)	−0.0012 (18)
C1	0.040 (2)	0.033 (2)	0.036 (2)	−0.0015 (19)	0.0057 (17)	0.0018 (17)
C2	0.048 (3)	0.054 (3)	0.032 (2)	0.010 (2)	−0.0001 (19)	0.008 (2)
C3	0.063 (3)	0.043 (3)	0.036 (2)	0.013 (2)	0.008 (2)	0.003 (2)
C4	0.057 (3)	0.047 (3)	0.026 (2)	−0.002 (2)	0.0060 (19)	0.0016 (18)
C5	0.059 (3)	0.055 (3)	0.032 (2)	0.007 (2)	−0.004 (2)	0.007 (2)
C6	0.048 (3)	0.042 (2)	0.039 (2)	0.008 (2)	0.001 (2)	0.004 (2)
C7	0.038 (2)	0.032 (2)	0.030 (2)	−0.0043 (18)	0.0090 (16)	−0.0046 (17)
C8	0.067 (4)	0.056 (3)	0.043 (3)	0.015 (3)	−0.006 (3)	−0.005 (3)
C9	0.050 (3)	0.034 (2)	0.032 (2)	0.0101 (19)	0.0008 (18)	−0.0031 (18)
C10	0.040 (2)	0.034 (2)	0.031 (2)	0.0021 (19)	0.0029 (16)	0.0033 (17)
C11	0.050 (3)	0.042 (2)	0.042 (3)	−0.005 (2)	0.003 (2)	0.001 (2)
C12	0.067 (3)	0.054 (3)	0.034 (2)	−0.002 (3)	0.007 (2)	0.009 (2)
C13	0.047 (3)	0.043 (3)	0.045 (3)	0.001 (2)	−0.002 (2)	−0.002 (2)
C14	0.051 (3)	0.038 (2)	0.034 (2)	0.003 (2)	0.0053 (19)	0.0025 (19)

Geometric parameters (Å, º) top

O1—C9	1.219 (5)	C4—C5	1.381 (6)
N1—C4	1.364 (5)	C5—C6	1.375 (6)
N1—H1A	0.84 (5)	C5—H5	0.91 (4)
N1—H1B	0.87 (5)	C6—H6	0.92 (4)
N2—C7	1.277 (5)	C7—C8	1.489 (6)
N2—N3	1.384 (4)	C8—H8A	0.89 (5)
N3—C9	1.340 (5)	C8—H8B	0.96 (5)
N3—H3A	0.85 (4)	C8—H8C	0.91 (6)
N4—C13	1.321 (5)	C9—C10	1.503 (5)
N4—C12	1.326 (6)	C10—C14	1.375 (5)
C1—C6	1.387 (5)	C10—C11	1.377 (5)
C1—C2	1.393 (6)	C11—C12	1.372 (6)
C1—C7	1.478 (5)	C11—H11	0.95 (4)
C2—C3	1.375 (6)	C12—H12	1.01 (4)
C2—H2	0.93 (4)	C13—C14	1.375 (6)
C3—C4	1.397 (6)	C13—H13	0.93 (4)
C3—H3	0.97 (4)	C14—H14	0.89 (4)

C4—N1—H1A	117 (3)	N2—C7—C8	124.0 (4)
C4—N1—H1B	118 (3)	C1—C7—C8	120.2 (4)
H1A—N1—H1B	120 (4)	C7—C8—H8A	110 (3)
C7—N2—N3	117.5 (3)	C7—C8—H8B	110 (3)
C9—N3—N2	119.1 (3)	H8A—C8—H8B	107 (4)
C9—N3—H3A	119 (2)	C7—C8—H8C	113 (3)
N2—N3—H3A	122 (2)	H8A—C8—H8C	113 (5)
C13—N4—C12	116.3 (4)	H8B—C8—H8C	103 (4)
C6—C1—C2	116.1 (4)	O1—C9—N3	123.8 (4)
C6—C1—C7	124.2 (4)	O1—C9—C10	121.1 (4)
C2—C1—C7	119.6 (4)	N3—C9—C10	115.1 (3)
C3—C2—C1	122.1 (4)	C14—C10—C11	117.9 (4)
C3—C2—H2	120 (2)	C14—C10—C9	123.4 (4)
C1—C2—H2	118 (2)	C11—C10—C9	118.6 (4)
C2—C3—C4	120.7 (4)	C12—C11—C10	119.2 (4)
C2—C3—H3	117 (2)	C12—C11—H11	118 (2)
C4—C3—H3	122 (2)	C10—C11—H11	123 (2)
N1—C4—C5	121.5 (4)	N4—C12—C11	123.6 (4)
N1—C4—C3	120.8 (4)	N4—C12—H12	115 (2)
C5—C4—C3	117.6 (4)	C11—C12—H12	121 (2)
C6—C5—C4	120.9 (4)	N4—C13—C14	124.6 (4)
C6—C5—H5	122 (3)	N4—C13—H13	117 (2)
C4—C5—H5	117 (3)	C14—C13—H13	118 (2)
C5—C6—C1	122.4 (4)	C13—C14—C10	118.3 (4)
C5—C6—H6	116 (3)	C13—C14—H14	123 (3)
C1—C6—H6	121 (2)	C10—C14—H14	119 (3)
N2—C7—C1	115.6 (3)

C7—N2—N3—C9	−159.7 (4)	C2—C1—C7—C8	−172.5 (4)
C6—C1—C2—C3	3.5 (6)	N2—N3—C9—O1	6.0 (7)
C7—C1—C2—C3	−173.6 (4)	N2—N3—C9—C10	−175.2 (3)
C1—C2—C3—C4	−0.8 (7)	O1—C9—C10—C14	−142.3 (4)
C2—C3—C4—N1	175.8 (4)	N3—C9—C10—C14	38.8 (6)
C2—C3—C4—C5	−2.2 (7)	O1—C9—C10—C11	37.0 (6)
N1—C4—C5—C6	−175.7 (4)	N3—C9—C10—C11	−141.8 (4)
C3—C4—C5—C6	2.3 (7)	C14—C10—C11—C12	−1.5 (6)
C4—C5—C6—C1	0.5 (7)	C9—C10—C11—C12	179.1 (4)
C2—C1—C6—C5	−3.4 (6)	C13—N4—C12—C11	1.7 (7)
C7—C1—C6—C5	173.6 (4)	C10—C11—C12—N4	−0.1 (7)
N3—N2—C7—C1	−179.0 (3)	C12—N4—C13—C14	−1.9 (6)
N3—N2—C7—C8	4.3 (6)	N4—C13—C14—C10	0.4 (7)
C6—C1—C7—N2	−166.3 (4)	C11—C10—C14—C13	1.3 (6)
C2—C1—C7—N2	10.6 (5)	C9—C10—C14—C13	−179.3 (4)
C6—C1—C7—C8	10.6 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N4ⁱ	0.84 (5)	2.20 (5)	3.018 (6)	164 (4)
N3—H3A···O1ⁱⁱ	0.85 (4)	2.48 (4)	3.320 (5)	169 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄N₄O
M_r	254.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	7.9137 (15), 5.3466 (10), 29.650 (6)
β (°)	95.415 (3)
V (Å³)	1248.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.974, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	5756, 2193, 1936
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.100, 0.183, 1.33
No. of reflections	2193
No. of parameters	228
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.23

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXL97.