4-Dimethyl­amino-N′-(3-pyridyl­methyl­idene)benzohydrazide

Ding, Y.-W.; Ni, L.-L.

doi:10.1107/S1600536810037670

organic compounds

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Volume 66| Part 10| October 2010| Page o2636

doi:10.1107/S1600536810037670

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4-Dimethylamino-N′-(3-pyridylmethylidene)benzohydrazide

Yan-Wei Ding ^a ^* and Li-Li Ni ^b

^aCollege of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, People's Republic of China, and ^bThe Miyun High School Attached to Capital Normal University, Beijing 101500, People's Republic of China
^*Correspondence e-mail: dingyanwei@sohu.com

(Received 14 September 2010; accepted 20 September 2010; online 25 September 2010)

The title compound, C₁₅H₁₆N₄O, was prepared by the reaction of pyridine-3-carbaldehyde with 4-dimethylaminobenzohydrazide in methanol. The dihedral angle between the pyridine and the benzene rings is 5.1 (3)°. In the crystal structure, the hydrazone molecules are linked through intermolecular N—H⋯O hydrogen bonds, forming chains along the b axis.

Related literature

For the synthesis and biological applications of hydrazone compounds, see: Alvarez et al. (2008 ); Angelusiu et al. (2010 ); Ajani et al. (2010 ); El-Dissouky et al. (2010 ); Avaji et al. (2009 ); Fouda et al. (2008 ). For the crystal structures of similar hydrazone compounds, see: Wen et al. (2009 ); Fun et al. (2008 ); Ji & Lu (2010 ); Ahmad et al. (2010 ); Cui et al. (2009 ).

Experimental

Crystal data

C₁₅H₁₆N₄O
M_r = 268.32
Orthorhombic, P b c a
a = 11.513 (2) Å
b = 7.898 (2) Å
c = 30.359 (3) Å
V = 2760.5 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.10 × 0.07 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.992, T_max = 0.996
20776 measured reflections
2991 independent reflections
1163 reflections with I > 2σ(I)
R_int = 0.190

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.151
S = 0.79
2991 reflections
186 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1ⁱ	0.89 (1)	2.16 (1)	3.035 (3)	166 (3)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810037670/rz2491sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037670/rz2491Isup2.hkl

checkCIF report

Comment top

In the last few years, considerable attention has focused on the preparation and biological application of hydrazone compounds (Alvarez et al., 2008; Angelusiu et al., 2010; Ajani et al., 2010; El-Dissouky et al., 2010; Avaji et al., 2009; Fouda et al., 2008). In this paper, the crystal structure of the title new hydrazone compound is reported.

The molecular structure of the title compound is shown in Fig. 1. The dihedral angle between the pyridine and the benzene rings is 5.1 (3)°. The torsion angles C1—C6—N2—N3, C6—N2—N3—C7, N2—N3—C7—C8, and N2—N3—C7—O1 are 2.4 (3), 2.4 (3), 3.4 (3), and 0.9 (3)°, respectively. All the bond lengths are within normal values and are comparable with the similar hydrazone compounds (Wen et al., 2009; Fun et al., 2008; Ji & Lu, 2010; Ahmad et al., 2010; Cui et al., 2009). In the crystal structure, the hydrazone molecules are linked through intermolecular hydrogen bonds of type N—H···O (Table 1), forming chains along the b axis, as shown in Fig. 2.

Related literature top

For the synthesis and biological applications of hydrazone compounds, see: Alvarez et al. (2008); Angelusiu et al. (2010); Ajani et al. (2010); El-Dissouky et al. (2010); Avaji et al. (2009); Fouda et al. (2008). For the crystal structures of similar hydrazone compounds, see: Wen et al. (2009); Fun et al. (2008); Ji & Lu (2010); Ahmad et al. (2010); Cui et al. (2009).

Experimental top

The title compound was prepared by the reaction of pyridine-3-carbaldehyde (0.107 g, 1 mmol) with 4-dimethylaminobenzohydrazide (0.179 g, 1 mmol) in methanol at ambient temperature. Colourless block-like single crytals were formed by slow evaporation of the solution in air.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

	Fig. 1. Molecular structure of the title compound with 30% probability displacement ellipsoids.
	Fig. 2. Molecular packing of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.

4-Dimethylamino-N'-(3-pyridylmethylidene)benzohydrazide top

Crystal data top

C₁₅H₁₆N₄O	F(000) = 1136
M_r = 268.32	D_x = 1.291 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1003 reflections
a = 11.513 (2) Å	θ = 2.3–24.0°
b = 7.898 (2) Å	µ = 0.09 mm⁻¹
c = 30.359 (3) Å	T = 298 K
V = 2760.5 (9) Å³	Block, colourless
Z = 8	0.10 × 0.07 × 0.05 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2991 independent reflections
Radiation source: fine-focus sealed tube	1163 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.190
ω scans	θ_max = 27.0°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −14→14
T_min = 0.992, T_max = 0.996	k = −10→9
20776 measured reflections	l = −38→37

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 0.79	w = 1/[σ²(F_o²) + (0.0518P)²] where P = (F_o² + 2F_c²)/3
2991 reflections	(Δ/σ)_max < 0.001
186 parameters	Δρ_max = 0.20 e Å⁻³
1 restraint	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₅H₁₆N₄O	V = 2760.5 (9) Å³
M_r = 268.32	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.513 (2) Å	µ = 0.09 mm⁻¹
b = 7.898 (2) Å	T = 298 K
c = 30.359 (3) Å	0.10 × 0.07 × 0.05 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2991 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1163 reflections with I > 2σ(I)
T_min = 0.992, T_max = 0.996	R_int = 0.190
20776 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	1 restraint
wR(F²) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 0.79	Δρ_max = 0.20 e Å⁻³
2991 reflections	Δρ_min = −0.25 e Å⁻³
186 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
N1	0.7015 (2)	0.4212 (3)	0.79621 (8)	0.0715 (8)
N2	0.74617 (19)	0.2877 (3)	0.66360 (7)	0.0442 (6)
N3	0.7654 (2)	0.2199 (3)	0.62206 (7)	0.0462 (6)
N4	0.8832 (2)	0.0665 (3)	0.41884 (7)	0.0548 (7)
O1	0.89752 (16)	0.4234 (2)	0.60695 (5)	0.0494 (5)
C1	0.6436 (2)	0.2668 (4)	0.73145 (8)	0.0425 (7)
C2	0.5449 (3)	0.2126 (4)	0.75284 (10)	0.0636 (9)
H2	0.4923	0.1416	0.7387	0.076*
C3	0.5253 (3)	0.2652 (4)	0.79551 (10)	0.0677 (10)
H3A	0.4595	0.2296	0.8107	0.081*
C4	0.6033 (3)	0.3691 (4)	0.81491 (10)	0.0664 (10)
H4	0.5871	0.4069	0.8433	0.080*
C5	0.7181 (3)	0.3692 (4)	0.75487 (9)	0.0581 (9)
H5	0.7854	0.4050	0.7407	0.070*
C6	0.6688 (2)	0.2116 (4)	0.68628 (9)	0.0459 (8)
H6	0.6283	0.1210	0.6742	0.055*
C7	0.8431 (2)	0.2965 (4)	0.59507 (9)	0.0405 (7)
C8	0.8553 (2)	0.2255 (3)	0.55060 (8)	0.0374 (7)
C9	0.7769 (2)	0.1128 (3)	0.53203 (8)	0.0416 (7)
H9	0.7157	0.0732	0.5491	0.050*
C10	0.7866 (2)	0.0575 (3)	0.48906 (8)	0.0456 (7)
H10	0.7325	−0.0185	0.4778	0.055*
C11	0.8776 (2)	0.1154 (3)	0.46229 (9)	0.0423 (7)
C12	0.9577 (2)	0.2268 (4)	0.48112 (9)	0.0506 (8)
H12	1.0198	0.2656	0.4643	0.061*
C13	0.9464 (2)	0.2797 (3)	0.52384 (9)	0.0470 (8)
H13	1.0012	0.3540	0.5354	0.056*
C14	0.8071 (3)	−0.0613 (4)	0.40150 (9)	0.0736 (10)
H14A	0.8202	−0.1660	0.4168	0.110*
H14B	0.8225	−0.0765	0.3707	0.110*
H14C	0.7279	−0.0266	0.4055	0.110*
C15	0.9728 (3)	0.1326 (4)	0.38994 (9)	0.0780 (11)
H15A	0.9755	0.2537	0.3924	0.117*
H15B	0.9556	0.1018	0.3601	0.117*
H15C	1.0467	0.0859	0.3982	0.117*
H3	0.728 (2)	0.124 (2)	0.6156 (9)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.084 (2)	0.094 (2)	0.0365 (16)	−0.0072 (18)	0.0065 (15)	−0.0122 (15)
N2	0.0460 (15)	0.0567 (17)	0.0298 (13)	0.0026 (13)	0.0005 (11)	−0.0049 (12)
N3	0.0557 (17)	0.0556 (18)	0.0274 (12)	−0.0044 (13)	0.0040 (11)	−0.0085 (12)
N4	0.0619 (17)	0.0693 (18)	0.0331 (14)	−0.0091 (15)	0.0156 (13)	−0.0065 (13)
O1	0.0555 (13)	0.0565 (13)	0.0363 (12)	−0.0069 (11)	−0.0072 (9)	−0.0053 (10)
C1	0.0428 (17)	0.0533 (19)	0.0313 (16)	0.0044 (15)	0.0021 (13)	0.0008 (14)
C2	0.050 (2)	0.087 (3)	0.054 (2)	−0.0078 (18)	0.0038 (16)	−0.0122 (18)
C3	0.058 (2)	0.103 (3)	0.042 (2)	0.004 (2)	0.0161 (17)	−0.0005 (19)
C4	0.078 (3)	0.088 (3)	0.0328 (18)	0.018 (2)	0.0087 (19)	−0.0037 (18)
C5	0.062 (2)	0.076 (2)	0.0366 (18)	−0.0078 (18)	0.0079 (16)	−0.0041 (16)
C6	0.0441 (18)	0.055 (2)	0.0382 (17)	0.0024 (15)	−0.0041 (14)	−0.0068 (15)
C7	0.0432 (18)	0.0435 (19)	0.0348 (17)	0.0083 (15)	−0.0065 (14)	0.0014 (15)
C8	0.0382 (16)	0.0434 (18)	0.0305 (16)	0.0019 (14)	−0.0009 (12)	0.0024 (13)
C9	0.0453 (18)	0.0491 (19)	0.0304 (15)	−0.0046 (15)	0.0082 (13)	0.0051 (13)
C10	0.0497 (18)	0.053 (2)	0.0340 (16)	−0.0088 (15)	0.0014 (14)	−0.0004 (14)
C11	0.0454 (18)	0.0516 (19)	0.0301 (16)	0.0027 (15)	0.0065 (14)	0.0013 (14)
C12	0.0433 (18)	0.064 (2)	0.0445 (18)	−0.0057 (16)	0.0133 (14)	−0.0009 (16)
C13	0.0407 (18)	0.057 (2)	0.0431 (18)	−0.0047 (15)	−0.0024 (14)	−0.0050 (15)
C14	0.102 (3)	0.087 (3)	0.0322 (18)	−0.014 (2)	0.0041 (18)	−0.0140 (17)
C15	0.088 (3)	0.098 (3)	0.047 (2)	−0.010 (2)	0.0301 (19)	−0.0022 (18)

Geometric parameters (Å, º) top

N1—C4	1.331 (4)	C6—H6	0.9300
N1—C5	1.334 (3)	C7—C8	1.469 (3)
N2—C6	1.276 (3)	C8—C9	1.388 (3)
N2—N3	1.388 (3)	C8—C13	1.394 (3)
N3—C7	1.356 (3)	C9—C10	1.380 (3)
N3—H3	0.894 (10)	C9—H9	0.9300
N4—C11	1.376 (3)	C10—C11	1.402 (3)
N4—C14	1.436 (3)	C10—H10	0.9300
N4—C15	1.451 (3)	C11—C12	1.397 (3)
O1—C7	1.236 (3)	C12—C13	1.369 (3)
C1—C2	1.377 (4)	C12—H12	0.9300
C1—C5	1.377 (4)	C13—H13	0.9300
C1—C6	1.468 (3)	C14—H14A	0.9600
C2—C3	1.379 (4)	C14—H14B	0.9600
C2—H2	0.9300	C14—H14C	0.9600
C3—C4	1.352 (4)	C15—H15A	0.9600
C3—H3A	0.9300	C15—H15B	0.9600
C4—H4	0.9300	C15—H15C	0.9600
C5—H5	0.9300

C4—N1—C5	115.3 (3)	C9—C8—C7	123.8 (2)
C6—N2—N3	114.8 (2)	C13—C8—C7	119.4 (3)
C7—N3—N2	118.8 (2)	C10—C9—C8	122.3 (2)
C7—N3—H3	124.4 (19)	C10—C9—H9	118.8
N2—N3—H3	116.7 (19)	C8—C9—H9	118.8
C11—N4—C14	121.3 (2)	C9—C10—C11	120.3 (3)
C11—N4—C15	120.8 (3)	C9—C10—H10	119.8
C14—N4—C15	117.7 (2)	C11—C10—H10	119.8
C2—C1—C5	116.9 (3)	N4—C11—C12	122.5 (2)
C2—C1—C6	120.8 (3)	N4—C11—C10	119.9 (3)
C5—C1—C6	122.3 (3)	C12—C11—C10	117.5 (2)
C1—C2—C3	119.0 (3)	C13—C12—C11	121.2 (2)
C1—C2—H2	120.5	C13—C12—H12	119.4
C3—C2—H2	120.5	C11—C12—H12	119.4
C4—C3—C2	118.9 (3)	C12—C13—C8	122.0 (3)
C4—C3—H3A	120.6	C12—C13—H13	119.0
C2—C3—H3A	120.6	C8—C13—H13	119.0
N1—C4—C3	124.5 (3)	N4—C14—H14A	109.5
N1—C4—H4	117.8	N4—C14—H14B	109.5
C3—C4—H4	117.8	H14A—C14—H14B	109.5
N1—C5—C1	125.3 (3)	N4—C14—H14C	109.5
N1—C5—H5	117.4	H14A—C14—H14C	109.5
C1—C5—H5	117.4	H14B—C14—H14C	109.5
N2—C6—C1	120.1 (3)	N4—C15—H15A	109.5
N2—C6—H6	119.9	N4—C15—H15B	109.5
C1—C6—H6	119.9	H15A—C15—H15B	109.5
O1—C7—N3	121.4 (3)	N4—C15—H15C	109.5
O1—C7—C8	122.0 (3)	H15A—C15—H15C	109.5
N3—C7—C8	116.6 (3)	H15B—C15—H15C	109.5
C9—C8—C13	116.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.89 (1)	2.16 (1)	3.035 (3)	166 (3)

Symmetry code: (i) −x+3/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₆N₄O
M_r	268.32
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	11.513 (2), 7.898 (2), 30.359 (3)
V (Å³)	2760.5 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.10 × 0.07 × 0.05

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.992, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	20776, 2991, 1163
R_int	0.190
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.151, 0.79
No. of reflections	2991
No. of parameters	186
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.25

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.894 (10)	2.159 (12)	3.035 (3)	166 (3)

Symmetry code: (i) −x+3/2, y−1/2, z.

References

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doi:10.1107/S1600536810037670

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