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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2636.
Published online 2010 September 25. doi:  10.1107/S1600536810037670
PMCID: PMC2983199

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

Abstract

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

An external file that holds a picture, illustration, etc.
Object name is e-66-o2636-scheme1.jpg

Experimental

Crystal data

  • C15H16N4O
  • M r = 268.32
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2636-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.151
  • S = 0.79
  • 2991 reflections
  • 186 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

Atom H3 attached to N3 was located in a difference Fourier map and refined with the N3—H3 distance restrained to 0.90 (1) Å and an isotropic displacement parameter fixed at 0.08 Å2. All other H atoms were positioned geometrically and refined using a riding-model approximation, with C—H = 0.93–0.96 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. Crystals were small and very weakly diffracting and this is reflected in the large value of Rint (0.19), and the low ratio of observed/unique reflections (39%).

Figures

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.

Crystal data

C15H16N4OF(000) = 1136
Mr = 268.32Dx = 1.291 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1003 reflections
a = 11.513 (2) Åθ = 2.3–24.0°
b = 7.898 (2) ŵ = 0.09 mm1
c = 30.359 (3) ÅT = 298 K
V = 2760.5 (9) Å3Block, colourless
Z = 80.10 × 0.07 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer2991 independent reflections
Radiation source: fine-focus sealed tube1163 reflections with I > 2σ(I)
graphiteRint = 0.190
ω scansθmax = 27.0°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −14→14
Tmin = 0.992, Tmax = 0.996k = −10→9
20776 measured reflectionsl = −38→37

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151H atoms treated by a mixture of independent and constrained refinement
S = 0.79w = 1/[σ2(Fo2) + (0.0518P)2] where P = (Fo2 + 2Fc2)/3
2991 reflections(Δ/σ)max < 0.001
186 parametersΔρmax = 0.20 e Å3
1 restraintΔρmin = −0.25 e Å3

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 (Å2)

xyzUiso*/Ueq
N10.7015 (2)0.4212 (3)0.79621 (8)0.0715 (8)
N20.74617 (19)0.2877 (3)0.66360 (7)0.0442 (6)
N30.7654 (2)0.2199 (3)0.62206 (7)0.0462 (6)
N40.8832 (2)0.0665 (3)0.41884 (7)0.0548 (7)
O10.89752 (16)0.4234 (2)0.60695 (5)0.0494 (5)
C10.6436 (2)0.2668 (4)0.73145 (8)0.0425 (7)
C20.5449 (3)0.2126 (4)0.75284 (10)0.0636 (9)
H20.49230.14160.73870.076*
C30.5253 (3)0.2652 (4)0.79551 (10)0.0677 (10)
H3A0.45950.22960.81070.081*
C40.6033 (3)0.3691 (4)0.81491 (10)0.0664 (10)
H40.58710.40690.84330.080*
C50.7181 (3)0.3692 (4)0.75487 (9)0.0581 (9)
H50.78540.40500.74070.070*
C60.6688 (2)0.2116 (4)0.68628 (9)0.0459 (8)
H60.62830.12100.67420.055*
C70.8431 (2)0.2965 (4)0.59507 (9)0.0405 (7)
C80.8553 (2)0.2255 (3)0.55060 (8)0.0374 (7)
C90.7769 (2)0.1128 (3)0.53203 (8)0.0416 (7)
H90.71570.07320.54910.050*
C100.7866 (2)0.0575 (3)0.48906 (8)0.0456 (7)
H100.7325−0.01850.47780.055*
C110.8776 (2)0.1154 (3)0.46229 (9)0.0423 (7)
C120.9577 (2)0.2268 (4)0.48112 (9)0.0506 (8)
H121.01980.26560.46430.061*
C130.9464 (2)0.2797 (3)0.52384 (9)0.0470 (8)
H131.00120.35400.53540.056*
C140.8071 (3)−0.0613 (4)0.40150 (9)0.0736 (10)
H14A0.8202−0.16600.41680.110*
H14B0.8225−0.07650.37070.110*
H14C0.7279−0.02660.40550.110*
C150.9728 (3)0.1326 (4)0.38994 (9)0.0780 (11)
H15A0.97550.25370.39240.117*
H15B0.95560.10180.36010.117*
H15C1.04670.08590.39820.117*
H30.728 (2)0.124 (2)0.6156 (9)0.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.084 (2)0.094 (2)0.0365 (16)−0.0072 (18)0.0065 (15)−0.0122 (15)
N20.0460 (15)0.0567 (17)0.0298 (13)0.0026 (13)0.0005 (11)−0.0049 (12)
N30.0557 (17)0.0556 (18)0.0274 (12)−0.0044 (13)0.0040 (11)−0.0085 (12)
N40.0619 (17)0.0693 (18)0.0331 (14)−0.0091 (15)0.0156 (13)−0.0065 (13)
O10.0555 (13)0.0565 (13)0.0363 (12)−0.0069 (11)−0.0072 (9)−0.0053 (10)
C10.0428 (17)0.0533 (19)0.0313 (16)0.0044 (15)0.0021 (13)0.0008 (14)
C20.050 (2)0.087 (3)0.054 (2)−0.0078 (18)0.0038 (16)−0.0122 (18)
C30.058 (2)0.103 (3)0.042 (2)0.004 (2)0.0161 (17)−0.0005 (19)
C40.078 (3)0.088 (3)0.0328 (18)0.018 (2)0.0087 (19)−0.0037 (18)
C50.062 (2)0.076 (2)0.0366 (18)−0.0078 (18)0.0079 (16)−0.0041 (16)
C60.0441 (18)0.055 (2)0.0382 (17)0.0024 (15)−0.0041 (14)−0.0068 (15)
C70.0432 (18)0.0435 (19)0.0348 (17)0.0083 (15)−0.0065 (14)0.0014 (15)
C80.0382 (16)0.0434 (18)0.0305 (16)0.0019 (14)−0.0009 (12)0.0024 (13)
C90.0453 (18)0.0491 (19)0.0304 (15)−0.0046 (15)0.0082 (13)0.0051 (13)
C100.0497 (18)0.053 (2)0.0340 (16)−0.0088 (15)0.0014 (14)−0.0004 (14)
C110.0454 (18)0.0516 (19)0.0301 (16)0.0027 (15)0.0065 (14)0.0013 (14)
C120.0433 (18)0.064 (2)0.0445 (18)−0.0057 (16)0.0133 (14)−0.0009 (16)
C130.0407 (18)0.057 (2)0.0431 (18)−0.0047 (15)−0.0024 (14)−0.0050 (15)
C140.102 (3)0.087 (3)0.0322 (18)−0.014 (2)0.0041 (18)−0.0140 (17)
C150.088 (3)0.098 (3)0.047 (2)−0.010 (2)0.0301 (19)−0.0022 (18)

Geometric parameters (Å, °)

N1—C41.331 (4)C6—H60.9300
N1—C51.334 (3)C7—C81.469 (3)
N2—C61.276 (3)C8—C91.388 (3)
N2—N31.388 (3)C8—C131.394 (3)
N3—C71.356 (3)C9—C101.380 (3)
N3—H30.894 (10)C9—H90.9300
N4—C111.376 (3)C10—C111.402 (3)
N4—C141.436 (3)C10—H100.9300
N4—C151.451 (3)C11—C121.397 (3)
O1—C71.236 (3)C12—C131.369 (3)
C1—C21.377 (4)C12—H120.9300
C1—C51.377 (4)C13—H130.9300
C1—C61.468 (3)C14—H14A0.9600
C2—C31.379 (4)C14—H14B0.9600
C2—H20.9300C14—H14C0.9600
C3—C41.352 (4)C15—H15A0.9600
C3—H3A0.9300C15—H15B0.9600
C4—H40.9300C15—H15C0.9600
C5—H50.9300
C4—N1—C5115.3 (3)C9—C8—C7123.8 (2)
C6—N2—N3114.8 (2)C13—C8—C7119.4 (3)
C7—N3—N2118.8 (2)C10—C9—C8122.3 (2)
C7—N3—H3124.4 (19)C10—C9—H9118.8
N2—N3—H3116.7 (19)C8—C9—H9118.8
C11—N4—C14121.3 (2)C9—C10—C11120.3 (3)
C11—N4—C15120.8 (3)C9—C10—H10119.8
C14—N4—C15117.7 (2)C11—C10—H10119.8
C2—C1—C5116.9 (3)N4—C11—C12122.5 (2)
C2—C1—C6120.8 (3)N4—C11—C10119.9 (3)
C5—C1—C6122.3 (3)C12—C11—C10117.5 (2)
C1—C2—C3119.0 (3)C13—C12—C11121.2 (2)
C1—C2—H2120.5C13—C12—H12119.4
C3—C2—H2120.5C11—C12—H12119.4
C4—C3—C2118.9 (3)C12—C13—C8122.0 (3)
C4—C3—H3A120.6C12—C13—H13119.0
C2—C3—H3A120.6C8—C13—H13119.0
N1—C4—C3124.5 (3)N4—C14—H14A109.5
N1—C4—H4117.8N4—C14—H14B109.5
C3—C4—H4117.8H14A—C14—H14B109.5
N1—C5—C1125.3 (3)N4—C14—H14C109.5
N1—C5—H5117.4H14A—C14—H14C109.5
C1—C5—H5117.4H14B—C14—H14C109.5
N2—C6—C1120.1 (3)N4—C15—H15A109.5
N2—C6—H6119.9N4—C15—H15B109.5
C1—C6—H6119.9H15A—C15—H15B109.5
O1—C7—N3121.4 (3)N4—C15—H15C109.5
O1—C7—C8122.0 (3)H15A—C15—H15C109.5
N3—C7—C8116.6 (3)H15B—C15—H15C109.5
C9—C8—C13116.7 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3···O1i0.89 (1)2.16 (1)3.035 (3)166 (3)

Symmetry codes: (i) −x+3/2, y−1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2491).

References

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