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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2338.
Published online 2008 November 13. doi:  10.1107/S1600536808037008
PMCID: PMC2960119

N′-[(Z)-4-Methyl­benzyl­idene]-4-nitro­benzohydrazide monohydrate

Abstract

In the title compound, C15H13N3O3·H2O, the two benzene rings form a dihedral angle of 2.03 (2)°. In the crystal structure, adjacent hydrazide mol­ecules are linked into dimers by water mol­ecules; these dimers are then stacked along the b axis. Inter­molecular O—H(...)O, O—H(...)N and C—H(...)O hydrogen bonds and a π–π stacking inter­action between the nitro­benzene and tolyl rings with a centroid–centroid distance of 3.8208 (3) Å are observed. There is also a short O(...)N contact [2.6824 (7) Å].

Related literature

For related literature on hydrazones, see: Sridhar & Perumal (2003 [triangle]). For the biological applications of hydrazides/hydrazones, see: Bedia et al. (2006 [triangle]). For a related structure, see: Fun et al. (2008 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-64-o2338-scheme1.jpg

Experimental

Crystal data

  • C15H13N3O3·H2O
  • M r = 301.30
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2338-efi1.jpg
  • a = 6.5387 (1) Å
  • b = 6.9730 (1) Å
  • c = 15.9064 (3) Å
  • α = 80.524 (1)°
  • β = 82.628 (1)°
  • γ = 85.036 (1)°
  • V = 707.85 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 100.0 (1) K
  • 0.68 × 0.44 × 0.23 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.932, T max = 0.976
  • 31311 measured reflections
  • 7380 independent reflections
  • 6571 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.118
  • S = 1.05
  • 7380 reflections
  • 211 parameters
  • 4 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.48 e Å−3
  • Δρmin = −0.59 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [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 and PLATON (Spek, 2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808037008/is2358sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037008/is2358Isup2.hkl

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

Acknowledgments

FHK and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post–doctoral research fellowship.

supplementary crystallographic information

Comment

Hydrazones are versatile intermediates and important building blocks. Aryl hydrazones are important building blocks for the synthesis of a variety of heterocyclic compounds such as pyrazolines and pyrazoles (Sridhar & Perumal, 2003). Hydrazones of aliphatic and aromatic methyl ketones yield pyrazole-4-carboxaldehyde on diformylation by the treatment with Vilsmeier reagent. A series of hydrazide-hydrazones were reported to possess good antituberculosis activity (Bedia et al., 2006). Prompted by these review and in continuation of our work (Fun et al., 2008), we here in report the crystal structure of the title compound, (I).

Bond lengths and angles in (I) (Fig. 1) are found to have normal values (Allen et al., 1987). The two benzene rings are essentially planar with the maximum deviation from planarity being -0.004 (1) Å for atom C6 and 0.002 (1) Å for atom C12, respectively. The dihedral angle formed by the benzene (C1—C6) and (C9—C14) rings is 2.03 (2)°.

The crystal packing is consolidated by O—H···O, O—H···N, C—H···O and N—H···O inter and intramolecular hydrogen bonding (Table 1). Furthermore, the packing is strengthened by π-π stacking interactions involving the benzene (C1—C6) (Cg1) and the symmetry related (C9—C14) ring (Cg2) [Cg1···Cg2i = 3.8208 (3) Å; symmetry code: (i) 2-x, 1-y, -z] together with O···N short contacts [2.6824 (7) Å]. In the crystal packing, adjacent molecules are linked into dimers by water molecules and the dimers were then stacked down the [010] direction (Fig. 2).

Experimental

The title compound, C15H15N3O4, was obtained by refluxing 4-nitrobenzhydrazide (0.01 mol) and 4-methylbenzaldehyde (0.01 mol) in ethanol (30 ml) by adding 3 drops of concentrated sulfuric acid for 3 h. Excess ethanol was removed from the reaction mixture under reduced pressure. The solid product obtained was filtered, washed with water and dried. Crystals suitable for X-ray analysis were obtained from ethanol by slow evaporation.

Refinement

The amino and water H atoms were located in a difference map and refined with restraints of N—H = 0.85 (1) Å and O—H = 0.84 (1) Å. The remaining H atoms were positioned geometrically [C—H = 0.93 Å (aromatic) or 0.96 Å (methyl)] and refined using a riding model, with Uiso(H) = 1.2Ueq(aromatic C) and 1.5Ueq(methyl C). A rotating group model was used for the methyl group.

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom numbering scheme.
Fig. 2.
The crystal packing of the title compound, viewed down the a axis, showing stacking of the dimers along the b axis.

Crystal data

C15H13N3O3·H2OZ = 2
Mr = 301.30F000 = 316
Triclinic, P1Dx = 1.414 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 6.5387 (1) ÅCell parameters from 9969 reflections
b = 6.9730 (1) Åθ = 2.6–26.3º
c = 15.9064 (3) ŵ = 0.11 mm1
α = 80.524 (1)ºT = 100.0 (1) K
β = 82.628 (1)ºBlock, colourless
γ = 85.036 (1)º0.68 × 0.44 × 0.23 mm
V = 707.85 (2) Å3

Data collection

Bruker SMART APEXII CCD area-detector diffractometer7380 independent reflections
Radiation source: fine-focus sealed tube6571 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.020
T = 100.0(1) Kθmax = 37.5º
[var phi] and ω scansθmin = 2.6º
Absorption correction: multi-scan(SADABS; Bruker, 2005)h = −11→11
Tmin = 0.932, Tmax = 0.976k = −11→10
31311 measured reflectionsl = −27→27

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.119  w = 1/[σ2(Fo2) + (0.0681P)2 + 0.1283P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
7380 reflectionsΔρmax = 0.48 e Å3
211 parametersΔρmin = −0.59 e Å3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

Experimental. The data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.
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
O11.27580 (6)0.77076 (7)−0.04714 (3)0.01642 (8)
O20.75581 (8)1.18850 (8)−0.38841 (3)0.02159 (10)
O30.46360 (8)1.16591 (9)−0.30724 (3)0.02477 (11)
N11.08155 (7)0.62939 (7)0.10666 (3)0.01228 (8)
N20.97488 (7)0.71707 (7)0.03900 (3)0.01180 (8)
N30.65301 (8)1.14188 (7)−0.31919 (3)0.01517 (9)
C11.25937 (9)0.43357 (8)0.25978 (3)0.01394 (9)
H1A1.35280.45560.21050.017*
C21.32689 (9)0.33958 (9)0.33630 (4)0.01558 (9)
H2A1.46600.29920.33750.019*
C31.19044 (10)0.30421 (9)0.41173 (4)0.01618 (10)
C40.98236 (10)0.36711 (9)0.40850 (4)0.01732 (10)
H4A0.88910.34550.45790.021*
C50.91322 (9)0.46166 (9)0.33225 (4)0.01511 (9)
H5A0.77440.50320.33130.018*
C61.05015 (8)0.49509 (8)0.25695 (3)0.01205 (8)
C70.96681 (8)0.59124 (8)0.17866 (3)0.01265 (9)
H7A0.82590.62610.18090.015*
C81.08418 (8)0.78209 (7)−0.03665 (3)0.01124 (8)
C90.96283 (8)0.87393 (7)−0.10826 (3)0.01078 (8)
C100.74981 (8)0.92155 (8)−0.09685 (3)0.01259 (9)
H10A0.67600.8932−0.04280.015*
C110.64812 (8)1.01101 (8)−0.16601 (3)0.01320 (9)
H11A0.50671.0435−0.15890.016*
C120.76204 (8)1.05088 (8)−0.24589 (3)0.01220 (8)
C130.97361 (9)1.00639 (8)−0.25947 (3)0.01340 (9)
H13A1.04651.0355−0.31370.016*
C141.07314 (8)0.91711 (8)−0.18969 (3)0.01269 (9)
H14A1.21480.8857−0.19720.015*
C151.26554 (12)0.20102 (11)0.49388 (4)0.02473 (13)
H15A1.15170.18990.53860.037*
H15B1.36870.27400.50960.037*
H15C1.32420.07330.48590.037*
O1W0.56488 (7)0.60570 (7)0.07749 (3)0.01669 (8)
H1N20.8430 (12)0.7058 (17)0.0471 (8)0.027 (3)*
H2W10.5907 (17)0.4907 (12)0.0684 (8)0.031 (3)*
H1W10.4410 (13)0.6364 (17)0.0668 (8)0.035 (3)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.00972 (15)0.0221 (2)0.01583 (17)0.00035 (13)−0.00227 (13)0.00155 (14)
O20.0250 (2)0.0269 (2)0.01076 (17)−0.00148 (17)−0.00275 (15)0.00358 (15)
O30.01615 (19)0.0361 (3)0.0199 (2)0.00133 (18)−0.00737 (16)0.00461 (19)
N10.01330 (18)0.01250 (17)0.01075 (17)−0.00018 (13)−0.00421 (13)0.00081 (13)
N20.01085 (17)0.01426 (18)0.00977 (16)−0.00046 (13)−0.00339 (13)0.00113 (13)
N30.0174 (2)0.01585 (19)0.01215 (18)−0.00094 (15)−0.00535 (15)0.00083 (14)
C10.0137 (2)0.0152 (2)0.01227 (19)−0.00081 (16)−0.00285 (15)0.00066 (15)
C20.0155 (2)0.0166 (2)0.0143 (2)0.00085 (17)−0.00481 (16)−0.00018 (16)
C30.0208 (2)0.0158 (2)0.01158 (19)0.00194 (17)−0.00496 (17)−0.00040 (16)
C40.0199 (2)0.0196 (2)0.01066 (19)0.00142 (18)−0.00093 (17)0.00081 (16)
C50.0148 (2)0.0174 (2)0.01210 (19)0.00041 (16)−0.00163 (16)−0.00002 (16)
C60.01369 (19)0.01192 (19)0.01037 (18)−0.00115 (15)−0.00323 (14)0.00030 (14)
C70.01325 (19)0.0133 (2)0.01122 (18)−0.00088 (15)−0.00333 (15)0.00004 (15)
C80.01101 (18)0.01159 (18)0.01084 (18)0.00006 (14)−0.00243 (14)−0.00044 (14)
C90.01090 (18)0.01125 (18)0.00998 (17)−0.00020 (14)−0.00238 (14)−0.00045 (14)
C100.01106 (18)0.0154 (2)0.01048 (18)0.00026 (15)−0.00182 (14)0.00036 (15)
C110.01170 (19)0.0154 (2)0.01187 (19)0.00029 (15)−0.00297 (15)0.00029 (15)
C120.01382 (19)0.01256 (19)0.01019 (18)−0.00090 (15)−0.00400 (15)0.00040 (14)
C130.0141 (2)0.0151 (2)0.01041 (18)−0.00143 (16)−0.00148 (15)−0.00005 (15)
C140.01159 (19)0.0146 (2)0.01130 (18)−0.00053 (15)−0.00128 (14)−0.00060 (15)
C150.0321 (3)0.0271 (3)0.0134 (2)0.0068 (2)−0.0081 (2)0.0011 (2)
O1W0.01130 (16)0.0212 (2)0.01725 (18)−0.00029 (13)−0.00349 (13)−0.00109 (14)

Geometric parameters (Å, °)

O1—C81.2400 (6)C6—C71.4605 (7)
O2—N31.2246 (7)C7—H7A0.9300
O3—N31.2298 (7)C8—C91.4970 (7)
N1—C71.2881 (7)C9—C141.3994 (7)
N1—N21.3859 (6)C9—C101.3994 (7)
N2—C81.3491 (7)C10—C111.3898 (7)
N2—H1N20.864 (8)C10—H10A0.9300
N3—C121.4703 (7)C11—C121.3867 (7)
C1—C21.3896 (8)C11—H11A0.9300
C1—C61.4019 (8)C12—C131.3884 (8)
C1—H1A0.9300C13—C141.3895 (7)
C2—C31.4008 (8)C13—H13A0.9300
C2—H2A0.9300C14—H14A0.9300
C3—C41.3977 (9)C15—H15A0.9600
C3—C151.5035 (8)C15—H15B0.9600
C4—C51.3913 (8)C15—H15C0.9600
C4—H4A0.9300O1W—H2W10.837 (8)
C5—C61.3999 (8)O1W—H1W10.851 (8)
C5—H5A0.9300
C7—N1—N2114.21 (4)O1—C8—N2122.52 (5)
C8—N2—N1118.48 (4)O1—C8—C9120.74 (5)
C8—N2—H1N2125.4 (8)N2—C8—C9116.74 (4)
N1—N2—H1N2115.2 (8)C14—C9—C10119.65 (5)
O2—N3—O3123.96 (5)C14—C9—C8116.93 (4)
O2—N3—C12118.18 (5)C10—C9—C8123.40 (5)
O3—N3—C12117.85 (5)C11—C10—C9120.23 (5)
C2—C1—C6119.91 (5)C11—C10—H10A119.9
C2—C1—H1A120.0C9—C10—H10A119.9
C6—C1—H1A120.0C12—C11—C10118.60 (5)
C1—C2—C3121.56 (5)C12—C11—H11A120.7
C1—C2—H2A119.2C10—C11—H11A120.7
C3—C2—H2A119.2C11—C12—C13122.73 (5)
C4—C3—C2118.18 (5)C11—C12—N3118.38 (5)
C4—C3—C15120.88 (6)C13—C12—N3118.89 (5)
C2—C3—C15120.95 (6)C12—C13—C14118.01 (5)
C5—C4—C3120.72 (5)C12—C13—H13A121.0
C5—C4—H4A119.6C14—C13—H13A121.0
C3—C4—H4A119.6C13—C14—C9120.79 (5)
C4—C5—C6120.80 (5)C13—C14—H14A119.6
C4—C5—H5A119.6C9—C14—H14A119.6
C6—C5—H5A119.6C3—C15—H15A109.5
C5—C6—C1118.83 (5)C3—C15—H15B109.5
C5—C6—C7118.05 (5)H15A—C15—H15B109.5
C1—C6—C7123.11 (5)C3—C15—H15C109.5
N1—C7—C6122.33 (5)H15A—C15—H15C109.5
N1—C7—H7A118.8H15B—C15—H15C109.5
C6—C7—H7A118.8H2W1—O1W—H1W1106.0 (10)
C7—N1—N2—C8172.77 (5)N2—C8—C9—C14−171.45 (5)
C6—C1—C2—C3−0.09 (9)O1—C8—C9—C10−168.59 (5)
C1—C2—C3—C4−0.32 (9)N2—C8—C9—C1010.18 (8)
C1—C2—C3—C15179.55 (6)C14—C9—C10—C110.09 (8)
C2—C3—C4—C50.20 (9)C8—C9—C10—C11178.42 (5)
C15—C3—C4—C5−179.67 (6)C9—C10—C11—C120.20 (8)
C3—C4—C5—C60.33 (9)C10—C11—C12—C13−0.47 (8)
C4—C5—C6—C1−0.73 (9)C10—C11—C12—N3178.76 (5)
C4—C5—C6—C7178.66 (5)O2—N3—C12—C11175.31 (5)
C2—C1—C6—C50.61 (8)O3—N3—C12—C11−4.94 (8)
C2—C1—C6—C7−178.75 (5)O2—N3—C12—C13−5.43 (8)
N2—N1—C7—C6178.63 (5)O3—N3—C12—C13174.32 (6)
C5—C6—C7—N1179.37 (5)C11—C12—C13—C140.42 (8)
C1—C6—C7—N1−1.26 (9)N3—C12—C13—C14−178.81 (5)
N1—N2—C8—O1−1.88 (8)C12—C13—C14—C9−0.10 (8)
N1—N2—C8—C9179.38 (4)C10—C9—C14—C13−0.14 (8)
O1—C8—C9—C149.78 (8)C8—C9—C14—C13−178.58 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H1N2···O1W0.864 (8)1.978 (9)2.8191 (7)164.4 (11)
O1W—H2W1···O1i0.837 (9)2.013 (9)2.8327 (7)166.1 (11)
O1W—H1W1···O1ii0.851 (9)2.258 (11)2.9430 (6)137.7 (10)
O1W—H1W1···N1ii0.851 (9)2.357 (9)3.1287 (7)151.0 (11)
C1—H1A···O1Wiii0.932.503.4090 (7)165
C4—H4A···O2iv0.932.583.4565 (8)157
C7—H7A···O1W0.932.553.2393 (7)132

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2358).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bedia, K.-K., Elçin, O., Seda, U., Fatma, K., Nathaly, S., Sevim, R. & Dimoglo, A. (2006). Eur. J. Med. Chem.41, 1253–1261. [PubMed]
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Fun, H.-K., Patil, P. S., Jebas, S. R., Sujith, K. V. & Kalluraya, B. (2008). Acta Cryst. E64, o1594–o1595. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Sridhar, R. & Perumal, P. T. (2003). Synth. Commun.33, 1483–1488.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography