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Logo of actae2this articlesearchopen accesssubmitActa Crystallographica Section E: Crystallographic CommunicationsActa Crystallographica Section E: Crystallographic Communications
 
Acta Crystallogr E Crystallogr Commun. 2017 July 1; 73(Pt 7): 1029–1032.
Published online 2017 June 13. doi:  10.1107/S205698901700857X
PMCID: PMC5499283

Crystal structure and Hirshfeld surface analysis of (E)-4-amino-N′-[1-(4-methyl­phen­yl)ethyl­idene]benzohydrazide

Abstract

The structure of the title Schiff base, C16H17N3O, displays a trans configuration with respect to the C=N double bond, with a dihedral angle of 14.98 (9)° between the benzene rings. In the crystal, mol­ecules are linked by N—H(...)O and C—H(...)O hydrogen-bonding inter­actions, giving sheets extending across the (001) plane. Hirshfeld surface analysis gave fingerprint plots showing enrichment ratios for H(...)H, O(...)H, N(...)H and C(...)H contacts compared to C(...)C, N(...)N and C(...)N contacts, indicating a high propensity for H(...)H interactions to form in the crystal.

Keywords: crystal structure, Schiff base, substituted benzohydrazide, hydrogen bonding, Hirshfeld surface analysis

Chemical context  

Schiff bases are an important class of compounds in the medicinal and pharmaceutical fields and have played a role in the development of coordination chemistry as they readily form stable complexes with most transition metals. These complexes show inter­esting properties, e.g. their ability to reversibly bind oxygen, catalytic activity in the hydrogenation of olefins and transfer of an amino group, photochromic properties, and complexation ability towards toxic metals (Karthikeyan et al., 2006  ; Khattab et al., 2005  ; Küçükgüzel et al., 2006  ). Hydrazone Schiff base compounds (Cao et al., 2009  ; Zhou & Yang, 2010  ; Zhang et al., 2009  ), derived from the reaction of aldehydes with hydrazines have been shown to possess excellent biological activities, such as anti-bacterial, anti-convulsant and anti-tubercular (Bernhardt et al., 2005  ; Armstrong et al., 2003  ). As part of our studies in this area, the title Schiff base compound (E)-4-amino-N′-(1-(p-tol­yl)ethyl­idene)benzo­hydrazide, was prepared and the crystal structure is reported herein. Hirshfeld surface analysis was also performed for visualizing and qu­anti­fying inter­molecular inter­actions in the crystal packing of the compound.

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Structural commentary  

The asymmetric unit of the title compound contains one independent mol­ecule (Fig. 1  ), displaying a trans conformation with respect to its C=N double bond. The dihedral angle between the benzene rings is 14.98 (9)°. All the bond lengths are within normal ranges. The C8=N2 and C7=O1 bond lengths [1.281 (2) and 1.231 (2) Å, respectively] confirm their double-bond character, whereas the C3—N3, C7—N1 and N1—N2 values [1.365 (3), 1.357 (2) and 1.388 (2) Å, respectively]; these C—N bonds are much shorter than (nominal) isolated C—N bonds (1.46 Å) due to conjugation.

Figure 1
The mol­ecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

Supra­molecular features  

In the crystal, two types of inter­molecular hydrogen-bonding inter­actions are present (Table 1  ). The N3—H1N3(...)O1i hydrogen bond between the amino group and a symmetry-related carbonyl group generates zigzag chains extending along the b-axis direction, as shown in Fig. 2  . The secondary weak methyl C9—H9A(...)O1ii hydrogen-bonding inter­actions extend the structure across a (Fig. 3  ), generating a layer lying parallel to (001). No reasonable acceptors could be identified for either the second amine N3 H atom or the hydrazide N1 H atom.

Figure 2
Crystal packing of the title compound in the unit cell, showing mol­ecules linked across b via N—H(...)O hydrogen bonds (dashed lines).
Figure 3
The crystal packing in the title compound in which mol­ecules are linked across a via weak C—H(...)O hydrogen bonds (dashed lines). H atoms not involved in hydrogen-bonding inter­actions have been omitted.
Table 1
Hydrogen-bond geometry (Å, °)

Hirshfeld surface analysis  

Hirshfeld surfaces and their associated two-dimensional fingerprint plots (Soman et al., 2014  ) have been used to qu­antify the various inter­molecular inter­actions in the title compound. The Hirshfeld surface of a mol­ecule is mapped using the descriptor d norm which encompasses two factors: one is d e, representing the distance of any surface point nearest to the inter­nal atoms, and the other one is d i, representing the distance of the surface point nearest to the exterior atoms and also with the van der Waals radii of the atoms (Dalal et al., 2015  ). The Hirshfeld surfaces mapped over d norm (range of −0.502–1.427 Å) are displayed in Fig. 4  . The surfaces are shown as transparent to allow visualization of the mol­ecule. The dominant inter­action between oxygen (O) and hydrogen (H) atoms can be observed in the Hirshfeld surface as the red areas (Fig. 4  ). Other visible spots in the Hirshfeld surfaces correspond to C—H and H—H contacts.

Figure 4
Hirshfeld surfaces mapped over d norm for the title compound.

The inter­molecular inter­actions of the title compound are shown in the 2D fingerprint plots shown in Fig. 5  . H(...)H (46.1%) contacts make the largest contribution to the Hirshfeld surfaces. O(...)H/H(...)O (10.5%), inter­actions are represented by left-side blue spikes, top and bottom. The pale yellow N(...)H/H(...)N (8.8%) inter­actions are near the C(...)H regions while the green C(...)H/H(...)C inter­actions (34.2%) are between the N—H and O—H regions. The whole fingerprint region and all other inter­actions, which are a combination of d e and d i, are displayed in Fig. 6  .

Figure 5
Two-dimensional fingerprint plots of the title compound.
Figure 6
Two-dimensional fingerprint plots with a d norm view of the C(...)H/H(...)C (34.2%), H(...)H (46.1%), N(...)H/H(...)N (8.8%) and O(...)H/H(...)O (10.5%) contacts in the title compound.

Synthesis and crystallization  

The title compound was synthesized by the reaction of a 1:1 molar ratio mixture of a hot methano­lic solution (20 mL) of 4-amini­benzoic­hydrazide (0.151 mg, Aldrich) and a hot methano­lic solution of 4-methyl­aceto­phenone (0.134 mg, Aldrich), which was refluxed for 8 h. The solution was then cooled and kept at room temperature after which colourless block-shaped crystals suitable for the X-ray analysis were obtained in a few days.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 2  . Hydrogen atoms were positioned geometrically (N—H = 0.86 Å, and C—H = 0.93 or 0.96 Å) and were refined using a riding model, with U iso(H) = 1.2 U eq(N, C) or 1.5U eq(methyl C). One reflection (011) was considered to be affected by the beamstop.

Table 2
Experimental details

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901700857X/zs2381sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901700857X/zs2381Isup2.hkl

CCDC reference: 1554995

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

PS and KB thank the Department of Science and Technology (DST–SERB), grant No. SB/FT/CS-058/2013, New Delhi, India, for financial support.

supplementary crystallographic information

Crystal data

C16H17N3OF(000) = 568
Mr = 267.33Dx = 1.241 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 6816 reflections
a = 5.7011 (4) Åθ = 5.0–49.0°
b = 15.4836 (10) ŵ = 0.08 mm1
c = 16.2128 (10) ÅT = 296 K
V = 1431.16 (16) Å3Block, colorless
Z = 40.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer3501 independent reflections
Radiation source: fine-focus sealed tube2784 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω and [var phi] scanθmax = 28.3°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2004)h = −7→7
Tmin = 0.976, Tmax = 0.984k = −17→20
17427 measured reflectionsl = −21→21

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.141w = 1/[σ2(Fo2) + (0.0847P)2 + 0.1161P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
3501 reflectionsΔρmax = 0.17 e Å3
182 parametersΔρmin = −0.20 e Å3
0 restraintsAbsolute structure: Flack (1983), 1489 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.6 (19)

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 (Å2)

xyzUiso*/Ueq
N10.2405 (3)0.16299 (10)0.88410 (10)0.0543 (4)
H1N0.38480.17890.88710.065*
N20.1715 (3)0.08479 (10)0.91817 (10)0.0519 (4)
C110.0364 (4)−0.07382 (12)0.98126 (12)0.0518 (5)
H11−0.0509−0.05040.93830.062*
O1−0.1236 (3)0.19158 (9)0.83572 (11)0.0718 (5)
C50.0187 (3)0.35074 (11)0.77149 (11)0.0477 (4)
H5−0.12500.32830.75480.057*
C80.3188 (3)0.04879 (11)0.96690 (11)0.0450 (4)
C100.2444 (3)−0.03365 (11)1.00549 (10)0.0434 (4)
C12−0.0420 (4)−0.14777 (12)1.02002 (12)0.0557 (5)
H12−0.1814−0.17301.00260.067*
N30.3577 (4)0.55025 (11)0.74979 (15)0.0824 (6)
H2N30.49050.57090.76540.099*
H1N30.26500.58110.72010.099*
C30.2940 (4)0.46854 (11)0.77215 (12)0.0514 (4)
C40.0803 (4)0.43309 (12)0.74768 (11)0.0518 (4)
H4−0.02150.46530.71510.062*
C60.1661 (3)0.30033 (10)0.81983 (10)0.0408 (4)
C70.0810 (3)0.21446 (11)0.84607 (11)0.0472 (4)
C130.0821 (4)−0.18536 (12)1.08434 (11)0.0509 (4)
C16−0.0112 (5)−0.26470 (15)1.12687 (15)0.0721 (7)
H16A0.0964−0.28231.16920.108*
H16B−0.0287−0.31051.08740.108*
H16C−0.1608−0.25191.15110.108*
C20.4428 (3)0.41823 (12)0.82025 (13)0.0527 (4)
H20.58680.44050.83680.063*
C10.3806 (3)0.33609 (11)0.84366 (12)0.0474 (4)
H10.48290.30380.87590.057*
C90.5540 (4)0.08701 (17)0.98774 (16)0.0755 (7)
H9A0.64270.09520.93800.113*
H9B0.63720.04861.02380.113*
H9C0.53220.14161.01470.113*
C150.3706 (4)−0.07226 (13)1.06905 (11)0.0529 (5)
H150.5109−0.04751.08630.063*
C140.2906 (4)−0.14736 (14)1.10736 (13)0.0574 (5)
H140.3796−0.17221.14920.069*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0503 (8)0.0419 (7)0.0706 (10)−0.0063 (7)−0.0069 (8)0.0095 (7)
N20.0532 (9)0.0386 (7)0.0638 (9)−0.0062 (7)−0.0056 (7)0.0055 (7)
C110.0551 (11)0.0474 (9)0.0529 (10)−0.0027 (9)−0.0118 (9)0.0072 (8)
O10.0552 (9)0.0525 (8)0.1078 (12)−0.0153 (7)−0.0246 (9)0.0154 (8)
C50.0450 (9)0.0491 (9)0.0489 (9)0.0012 (8)−0.0064 (8)−0.0028 (8)
C80.0472 (9)0.0423 (8)0.0455 (8)−0.0025 (7)0.0007 (8)−0.0019 (7)
C100.0446 (9)0.0428 (8)0.0429 (8)0.0027 (8)−0.0001 (7)−0.0014 (7)
C120.0513 (11)0.0527 (10)0.0632 (12)−0.0089 (9)−0.0074 (10)0.0053 (9)
N30.0756 (13)0.0518 (10)0.1198 (17)−0.0061 (10)−0.0042 (13)0.0306 (11)
C30.0549 (11)0.0407 (9)0.0585 (10)0.0024 (8)0.0096 (9)0.0037 (8)
C40.0553 (11)0.0483 (9)0.0518 (10)0.0099 (8)−0.0029 (9)0.0057 (8)
C60.0417 (8)0.0383 (7)0.0424 (8)−0.0001 (7)−0.0012 (7)−0.0031 (6)
C70.0500 (10)0.0391 (8)0.0527 (9)−0.0048 (8)−0.0078 (8)−0.0021 (7)
C130.0527 (11)0.0493 (9)0.0507 (10)0.0021 (9)0.0060 (8)0.0079 (8)
C160.0745 (15)0.0686 (13)0.0731 (14)−0.0103 (12)0.0057 (12)0.0248 (11)
C20.0418 (10)0.0453 (9)0.0709 (11)−0.0054 (8)−0.0022 (9)0.0010 (8)
C10.0417 (9)0.0418 (8)0.0586 (10)0.0006 (8)−0.0083 (8)0.0035 (7)
C90.0624 (14)0.0771 (14)0.0870 (15)−0.0209 (13)−0.0199 (12)0.0280 (12)
C150.0447 (10)0.0606 (11)0.0534 (10)−0.0010 (9)−0.0079 (8)0.0058 (9)
C140.0545 (12)0.0640 (12)0.0536 (10)0.0040 (10)−0.0068 (9)0.0161 (9)

Geometric parameters (Å, º)

N1—C71.357 (2)C3—C21.391 (3)
N1—N21.388 (2)C3—C41.394 (3)
N1—H1N0.8600C4—H40.9300
N2—C81.281 (2)C6—C11.397 (2)
C11—C121.380 (3)C6—C71.478 (2)
C11—C101.395 (3)C13—C141.378 (3)
C11—H110.9300C13—C161.506 (3)
O1—C71.231 (2)C16—H16A0.9600
C5—C41.378 (2)C16—H16B0.9600
C5—C61.389 (2)C16—H16C0.9600
C5—H50.9300C2—C11.374 (3)
C8—C101.483 (2)C2—H20.9300
C8—C91.504 (3)C1—H10.9300
C10—C151.392 (3)C9—H9A0.9600
C12—C131.388 (3)C9—H9B0.9600
C12—H120.9300C9—H9C0.9600
N3—C31.365 (2)C15—C141.395 (3)
N3—H2N30.8600C15—H150.9300
N3—H1N30.8600C14—H140.9300
C7—N1—N2120.20 (17)O1—C7—N1121.87 (17)
C7—N1—H1N119.9O1—C7—C6122.06 (17)
N2—N1—H1N119.9N1—C7—C6116.05 (16)
C8—N2—N1116.05 (16)C14—C13—C12117.64 (17)
C12—C11—C10121.11 (18)C14—C13—C16121.95 (18)
C12—C11—H11119.4C12—C13—C16120.41 (19)
C10—C11—H11119.4C13—C16—H16A109.5
C4—C5—C6121.61 (18)C13—C16—H16B109.5
C4—C5—H5119.2H16A—C16—H16B109.5
C6—C5—H5119.2C13—C16—H16C109.5
N2—C8—C10116.57 (16)H16A—C16—H16C109.5
N2—C8—C9123.50 (17)H16B—C16—H16C109.5
C10—C8—C9119.90 (17)C1—C2—C3121.04 (17)
C15—C10—C11117.15 (17)C1—C2—H2119.5
C15—C10—C8122.29 (17)C3—C2—H2119.5
C11—C10—C8120.51 (16)C2—C1—C6121.12 (17)
C11—C12—C13121.66 (19)C2—C1—H1119.4
C11—C12—H12119.2C6—C1—H1119.4
C13—C12—H12119.2C8—C9—H9A109.5
C3—N3—H2N3120.0C8—C9—H9B109.5
C3—N3—H1N3120.0H9A—C9—H9B109.5
H2N3—N3—H1N3120.0C8—C9—H9C109.5
N3—C3—C2120.36 (19)H9A—C9—H9C109.5
N3—C3—C4121.45 (19)H9B—C9—H9C109.5
C2—C3—C4118.18 (16)C10—C15—C14121.25 (19)
C5—C4—C3120.48 (18)C10—C15—H15119.4
C5—C4—H4119.8C14—C15—H15119.4
C3—C4—H4119.8C13—C14—C15121.16 (18)
C5—C6—C1117.57 (15)C13—C14—H14119.4
C5—C6—C7118.01 (16)C15—C14—H14119.4
C1—C6—C7124.35 (15)
C7—N1—N2—C8−166.25 (17)C5—C6—C7—O1−9.6 (3)
N2—N1—C7—O1−4.9 (3)C5—C6—C7—N1171.91 (16)
N2—N1—C7—C6173.63 (15)N2—C8—C10—C117.5 (3)
N1—N2—C8—C90.2 (3)N2—C8—C10—C15−169.65 (18)
N1—N2—C8—C10178.39 (15)C9—C8—C10—C11−174.22 (18)
C6—C1—C2—C30.1 (3)C9—C8—C10—C158.6 (3)
C2—C1—C6—C50.2 (3)C8—C10—C11—C12−176.11 (18)
C2—C1—C6—C7−176.59 (17)C15—C10—C11—C121.2 (3)
C1—C2—C3—N3179.6 (2)C8—C10—C15—C14176.54 (18)
C1—C2—C3—C4−0.5 (3)C11—C10—C15—C14−0.7 (3)
N3—C3—C4—C5−179.5 (2)C10—C11—C12—C13−0.1 (3)
C2—C3—C4—C50.6 (3)C11—C12—C13—C14−1.4 (3)
C3—C4—C5—C6−0.4 (3)C11—C12—C13—C16178.4 (2)
C4—C5—C6—C1−0.1 (3)C12—C13—C14—C151.9 (3)
C4—C5—C6—C7176.93 (17)C16—C13—C14—C15−177.9 (2)
C1—C6—C7—O1167.14 (18)C13—C14—C15—C10−0.9 (3)
C1—C6—C7—N1−11.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
N3—H1N3···O1i0.862.102.914 (2)159
C9—H9A···O1ii0.962.603.475 (3)152

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) x+1, y, z.

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