research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 7| July 2015| Pages 795-798
doi:10.1107/S2056989015011147

Crystal structure of (E)-N-{2-[2-(2-chloro­benzyl­­idene)hydrazin-1-yl]-2-oxoeth­yl}-4-methyl­benzamide monohydrate

CROSSMARK_Color_square_no_text.svg
H. Purandara,a Sabine Forob and B. Thimme Gowdaa,c*

aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, bInstitute of Materials Science, Darmstadt University of Technology, Alarich Weiss Strasse 2, D-64287 Darmstadt, Germany, and cBangalore University, Jnanabharati, Bangalore 560 056, India
*Correspondence e-mail: gowdabt@yahoo.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 28 May 2015; accepted 8 June 2015; online 17 June 2015)

The title compound, C17H16ClN3O2·H2O, an acyl­hydrazone derivative, contains a glycine moiety and two substituted benzene rings on either end of the chain. It crystallized as a monohydrate. The mol­ecules adopt an E conformation with respect to the C=N double bond, as indicated by the N—N=C—C torsion angle of 179.38 (14)°. The mol­ecule is twisted in such a way that the almost planar Car—C(=O)—N(H)—C(H2) and C(H2)—C(=O)N(H)—N=C—Car [r.m.s deviations = 0.009 and 0.025 Å, respectively] segments are inclined to on another by 77.36 (8)°, while the benzene rings are normal to one another, making a dihedral angle of 89.69 (9)°. In the crystal, the water mol­ecule links three mol­ecules through two O—H⋯O and one N—H⋯O hydrogen bonds. The mol­ecules are linked via pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R22(14) ring motif. The dimers are linked by O—H⋯O hydrogen bonds, involving two mol­ecules of water, forming chains along [100], enclosing R22(14) and R22(18) ring motifs. The chains are linked through C—H⋯O inter­actions, forming sheets parallel to (010). Within the sheets, there are C—H⋯π and parallel slipped π–π stacking inter­actions present [inter-centroid distance = 3.6458 (12) Å].

CCDC reference: 1405614

1. Chemical context

N-Acyl­hydrazones have been reported to be promising in terms of their future potential as anti­bacterial drugs (Osorio et al., 2012[Osorio, T. M., Monache, F. D., Chiaradia, L. D., Mascarello, A., Stumpf, T. R., Zanetti, C. R., Silveira, D. B., Barardi, C. R. M., Smania, E. de F. A., Viancelli, A., Garcia, L. A. T., Yunes, R. A., Nunes, R. J. & Smânia, A. Jr (2012). Bioorg. Med. Chem. Lett. 22, 225-230.]). These predictions have provided a therapeutic pathway to develop new effective biologically active Schiff-base derivatives. N-Acyl­hydrazones may exist as Z/E geom­etrical isomers about the C=N double bond and as syn/anti amide conformers (Palla et al., 1986[Palla, G., Predieri, G., Domiano, P., Vignali, C. & Turner, W. (1986). Tetrahedron, 42, 3649-3654.]). The carbonyl group in the acyl­hydrazone provides the possibility for electron delocal­ization within the hydrazone moiety. The anti-TNF-α activity of glycinyl-hydrazone derivatives indicate that differences in the hydro­phobicity of the imine-attached framework plays an important role. The study of conformational isomers of the amide unit of an N-methyl N-acyl­hydrazone derivative suggested that the amino spacer does not participate as a hydrogen-bond donor in the stabilization of the conformational isomers in solution (Lacerda et al., 2012[Lacerda, R. B., da Silva, L. L., de Lima, C. K. F., Miguez, E., Miranda, A. L. P., Laufer, S. A., Barreiro, E. J. & Fraga, C. A. M. (2012). PLoS One, 7, e46925.]).

[Scheme 1]

Prompted by the biological and structural importance of Schiff bases, as part of our structural studies (Gowda et al., 2000[Gowda, B. T., Kumar, B. H. A. & Fuess, H. (2000). Z. Naturforsch. Teil A Phys. Sci. 55, 721-728.]; Rodrigues et al., 2011[Rodrigues, V. Z., Foro, S. & Gowda, B. T. (2011). Acta Cryst. E67, o2179.]; Jyothi & Gowda, 2004[Jyothi, K. & Gowda, B. T. (2004). Z. Naturforsch. Teil A Phys. Sci. 59, 64-68.]; Usha & Gowda, 2006[Usha, K. M. & Gowda, B. T. (2006). J. Chem. Sci. 118, 351-359.]; Purandara et al., 2015[Purandara, H., Foro, S. & Gowda, B. T. (2015). Acta Cryst. E71, 602-605.]), we report herein on the synthesis, characterization and crystal structure of the title compound, (I)[link], a new N-acyl­hydrazone derivative.

2. Structural commentary

The title compound crystallizes as a monohydrate (Fig. 1[link]). The conformation of the N—H bond in the amide part is anti with respect to both the C=O bonds in the mol­ecule, while the N—H bond in the hydrazone part is syn to both the C=O(hydrazone) and the C—H(imine) bonds. The C9—O2 bond length of 1.2251 (19) Å indicates that the mol­ecule exists in the keto form in the solid state, and the C10—N3 bond length of 1.271 (2) Å confirms its significant double-bond character. The C9—N2 and N2—N3 bond distances of 1.351 (2) and 1.3771 (18) Å, respectively, indicate a significant delocalization of the π-electron density over the hydrazone portion of the mol­ecule. Variations in the C—N bond lengths of 1.330 (2), 1.442 (2) and 1.351 (2) Å for C7—N1, C8—N1 and C9—N2, respectively, characterize mobility of the bridge and the integral flexibility of the –C(=O)–NH–CH2C(=O)–NH–N=CH– group connecting the two benzene rings. The mol­ecule is twisted at atom C8, the C7—N1—C8—C9 torsion angle being 79.8 (2)°. The hydrazone part of the mol­ecule is almost planar, with C9—N2—N3—C10 and N2—N3—C10—C11 torsion angles of −177.07 (15) and 179.38 (14)°, respectively. Further, the dihedral angle between the almost planar hydrazone segment (O2/N2/N3/C8–C11; maximum deviation of 0.029 (1) Å for atom N2) and the attached benzene ring (C11–C16) is 8.17 (6)°. The two benzene rings (C1–C6 and C11–C16) are orthogonal to each other, making a dihedral angle of 89.69 (9)°. The planar amide segment (O1/N1/C1/C7/C8; r.m.s. deviation = 0.009 Å) is inclined to the attached toluene ring (C1–C6) by 8.06 (9) Å.

[Figure 1]
Figure 1
The mol­ecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

3. Supra­molecular features

In the crystal of (I)[link], the amide carbonyl O-atom, O1, shows bifurcated hydrogen bonding (Table 1[link] and Fig. 2[link]); one with the hydrazide hydrogen atom and the other with one of the hydrogen atoms of the water mol­ecule (O3). The two hydrogen atoms of the water mol­ecule are involved in hydrogen bonding with the O atoms of the amide carbonyl (O3—H31⋯O1) and glycine carbonyl (O3—H32⋯O2) groups of two different mol­ecules of the title compound. The O atom is also involved in hydrogen bonding with the H atom of the carbonyl­amide group of a third symmetry-related mol­ecule (N1—H1N⋯O3). A pair of N2—H2N⋯O1 inter­molecular hydrogen bonds link the mol­ecules, forming inversion dimers, with an R22(14) ring motif. The dimers are further linked via hydrogen bonds involving the water mol­ecule generating R44(14) and R44(18) ring motifs. Further, the N2—H2N⋯O1 and N1—H1N⋯O3 hydrogen bonds between the mol­ecules of the main compound and water mol­ecules translate into C22(6) chains along the a-axis direction (Table 1[link] and Fig. 2[link]) The chains are linked by a C—H⋯O inter­action, forming sheets parallel to (010). Within the sheets there are C—H⋯π, and parallel slipped π–π stacking inter­actions [Cg2⋯Cg2i = 3.6458 (12) Å; inter-planar distance = 3.4135 (8) Å, slippage = 1.281 Å; Cg2 is the centroid of ring C11–C16; symmetry code: (i) −x + 1, −y + 1, −z + 1] involving inversion-related chloro­benzene rings; see Fig. 3[link].

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the toluene ring C1–C6.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
O3—H31⋯O1 0.84 (2) 2.13 (2) 2.897 (2) 152 (3)
O3—H32⋯O2i 0.86 (2) 1.92 (2) 2.772 (2) 174 (3)
N1—H1N⋯O3ii 0.84 (2) 2.15 (2) 2.941 (2) 158 (2)
N2—H2N⋯O1i 0.87 (2) 2.09 (2) 2.944 (2) 165 (2)
C14—H14⋯O2iii 0.93 2.57 3.404 (2) 150
C15—H15⋯Cg1iii 0.93 2.89 3.793 (2) 165
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x+1, y, z; (iii) x, y, z+1.
[Figure 2]
Figure 2
Hydrogen-bonding pattern in the title compound (see Table 1[link] for details). [Symmetry codes: (a) −x + 1, −y + 1, −z; (d) x + 1, y, z; (e) x, y, z + 1.]
[Figure 3]
Figure 3
A view along the a axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines and C—H⋯π inter­actions are represented as red arrows (see Table 1[link] for further details).

4. Database survey

A search of the Cambridge Structural Database (Version 5.36, May 2015; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) for the fragment –NH–CH2–C(=O)–NH–N=CH–, yielded only one hit, namely N-(2-hy­droxy-1-naphthyl­methyl­ene)-N′-(N-phenyl­glyc­yl)hydrazine (MEMTOO; Gudasi et al., 2006[Gudasi, K. B., Patil, M. S., Vadavi, R. S., Shenoy, R. V., Patil, S. A. & Nethaji, M. (2006). Transition Met. Chem. 31, 580-585.]). A comparison of the structural details of the title compound, (I)[link], with those of the recently published sulfonyl derivative, (E)-N-{2-[2-(3-chlorobenzyl­idene)hydrazin­yl]-2-oxoeth­yl}-4-methyl­benzene­sulf­onamide monohydrate (II) (Purandara et al., 2015[Purandara, H., Foro, S. & Gowda, B. T. (2015). Acta Cryst. E71, 602-605.]), reveals the trans orientation of the amide group (C1–C7(=O1)N1) and hydrazone segment (N2–N3=C10–C11) with respect to the glycinyl C8—C9 bond in (I)[link], as is evident from the N1—C8—C9—N2 torsion angle of 173.58 (15)°, in contrast to the cis orientation of the sulfonamide and hydrazone segments, with respect to the glycinyl C—C bond, observed in compound (II). In the structure of (I)[link], the benzene ring (C1–C6) is almost coplanar with the amide group [dihedral angle = 8.21 (13)°]. This is in contrast to the L-shaped conformation (bent at the S atom) of the sulfonamide group with respect to the benzene ring in compound (II). The amide carbonyl O atom forms stronger O—H⋯O hydrogen bonds with the water H atoms than the sulfonyl O atom as observed in compound (II), indicating the stronger electron-withdrawing character of the amide group compared to the sulfonamide group.

5. Synthesis and crystallization

Tri­ethyl­amine (0.03 mol) and 4-methyl­benzoyl chloride (0.01 mol) were added to a stirred suspension of glycine ethyl­ester hydro­chloride (0.01 mol) in di­chloro­methane (50 ml) in an ice bath. The reaction mixture was stirred at room temperature for 20 h. After completion of the reaction, 2N hydro­chloric acid (80 ml) was added slowly. The organic phase was separated and washed with water (30 ml), dried with anhydrous Na2SO4 and evaporated to yield the corresponding ester, N-(4-methyl­benzo­yl)glycine ethyl ester (L1). L1 (0.01 mol) was added in small portions to a stirred solution of 99% hydrazine hydrate (10 ml) in 30 ml ethanol. The mixture was refluxed for 6 h. After cooling to room temperature, the resulting precipitate was filtered, washed with cold water and dried to give N-(4-methyl­benzo­yl)-glycinyl hydrazide (L2). 2-Chloro­benzaldehyde (0.01 mol) and two drops of glacial acetic acid were added to L2 (0.01 mol) in anhydrous methanol (30 ml). The reaction mixture was refluxed for 8 h. After cooling, the precipitate was collected by vacuum filtration, washed with cold methanol and dried. It was recrystallized to constant melting point from methanol (479–480 K). Prism-like colourless single crystals of the title compound were grown from a solution in DMF by slow evaporation of the solvent.

The purity of the compound was checked by TLC and characterized by its IR spectrum. The characteristic absorptions observed are 3323.3, 3203.8, 1685.8, 1620.2 and 1566.2 cm−1 for the stretching bands of N—H (amide I), N—H (amide II), C=O(hydrazone), C=O(amide) and C=N, respectively. The characteristic 1H and 13C NMR spectra of the title compound are as follows: 1H NMR (400 MHz, DMSO-d6, δ p.p.m.): 2.36 (s, 3H), 4.01, 4.45 (2d, 2H, J = 5.8 Hz), 7.25 (d, 2H, Ar-H, J = 8.0 Hz), 7.33–7.40 (m, 2H, Ar-H), 7.42–7.45 (m, 1H, Ar-H), 7.81 (d, 2H, Ar-H), 7.97–7.99 (m, 1H, Ar-H), 8.39, 8.63 (2s, 1H), 8.54, 8.76 (2t, 1H, J = 5.7 Hz), 11.65, 11.73 (2s, 1H). 13C NMR (400 MHz, DMSO-d6, δ p.p.m.): 20.97, 40.74, 42.04, 126.60, 126.83, 127.28, 128.64, 129.66, 130.85, 131.35, 133.10, 139.45, 141.06, 142.70, 165.98, 166.54, 170.48.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. The water H atoms and the NH H atoms were located in a difference Fourier map and refined with distances restraints: O—H = 0.85 (2), N—H = 0.86 (2) Å with Uiso(H) = 1.5Ueq(O) and 1.2Ueq(N). The C-bound H atoms were positioned with idealized geometry and refined as riding atoms: C—H = 0.93–0.97 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula C17H16ClN3O2·H2O
Mr 347.79
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 293
a, b, c (Å) 6.9729 (7), 10.642 (1), 11.879 (1)
α, β, γ (°) 95.049 (8), 100.324 (9), 102.870 (9)
V (Å3) 837.88 (14)
Z 2
Radiation type Mo Kα
μ (mm−1) 0.25
Crystal size (mm) 0.50 × 0.40 × 0.32
 
Data collection
Diffractometer Oxford Diffraction Xcalibur with Sapphire CCD detector
Absorption correction Multi-scan (CrysAlis RED; Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.])
Tmin, Tmax 0.886, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections 5538, 3393, 2829
Rint 0.009
(sin θ/λ)max (Å−1) 0.625
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.103, 1.04
No. of reflections 3393
No. of parameters 230
No. of restraints 4
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.24, −0.33
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]), SHELXS97 and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information

CCDC reference: 1405614

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989015011147/su5148sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015011147/su5148Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015011147/su5148Isup3.cml

checkCIF report


Chemical context top

N-Acyl­hydrazones have been reported to be promising in terms of their future potential as anti­bacterial drugs (Osorio et al., 2012). These predictions have provided a therapeutic pathway to develop new effective biologically active Schiff-base derivatives. N-Acyl­hydrazones may exist as Z/E geometrical isomers about the C═N double bond and as syn/anti amide conformers (Palla et al., 1986). The carbonyl group in the acyl­hydrazone provides the possibility for electron delocalization within the hydrazone moiety. The anti-TNF-α activity of glycinyl-hydrazone derivatives indicate that differences in the hydro­phobicity of the imine-attached framework plays an important role. The study of conformational isomers of the amide unit of an N-methyl N-acyl­hydrazone derivative suggested that the amino spacer does not participate as a hydrogen-bond donor in the stabilization of the conformational isomers in solution (Lacerda et al., 2012). Prompted by the biological and structural importance of Schiff bases, as part of our structural studies (Gowda et al., 2000; Rodrigues et al., 2011; Jyothi & Gowda, 2004; Usha & Gowda, 2006; Purandara et al., 2015), we report herein on the synthesis, characterization and crystal structure of the title compound, (I), a new N-acyl­hydrazone derivative.

Structural commentary top

The title compound crystallizes as a monohydrate (Fig. 1). The conformation of the N—H bond in the amide part is anti with respect to both the C═ O bonds in the molecule, while the N—H bond in the hydrazone part is syn to both the C═O(hydrazone) and the C—H (imine) bonds. The C9—O2 bond length of 1.2251 (19) Å indicates that the molecule exists in the keto form in the solid state, and the C10—N3 bond length of 1.271 (2) Å confirms its significant double-bond character. The C9—N2 and N2—N3 bond distances of 1.351 (2) and 1.3771 (18) Å, respectively, indicate a significant delocalization of the π-electron density over the hydrazone portion of the molecule. Variations in the C—N bond lengths of 1.330 (2), 1.442 (2) and 1.351 (2) Å for C7—N1, C8—N1 and C9—N2, respectively, characterize mobility of the bridge and the integral flexibility of the –C(═O)–NH–CH2C(═O)–NH—N=CH– group connecting the two benzene rings. The molecule is twisted at atom C8, the C7—N1—C8—C9 torsion angle being 79.8 (2)°. The hydrazone part of the molecule is almost planar, with C9—N2—N3—C10 and N2—N3—C10—C11 torsion angles of -177.07 (15) and 179.38 (14)°, respectively. Further, the dihedral angle between the almost planar hydrazone segment (O2/N2/N3/C8–C11; maximum deviation of 0.029 (1) Å for atom N2) and the attached benzene ring (C11–C16) is 8.17 (6)°. The two benzene rings (C1–C6 and C11–C16) are orthogonal to each other, making a dihedral angle of 89.69 (9)°. The planar amide segment (O1/N1/C1/C7/C8; r.m.s. deviation = 0.009 Å) is inclined to the attached toluene ring (C1–C6) by 8.06 (9) Å.

Supra­molecular features top

In the crystal of (I), the amide carbonyl O-atom, O1, shows bifurcated hydrogen bonding (Table 1 and Fig. 2); one with the hydrazide hydrogen atom and the other with one of the hydrogen atoms of the water molecule (O3). The two hydrogen atoms of the water molecule are involved in hydrogen bonding with the O atoms of the amide carbonyl (O3—H31···O1) and glycine carbonyl (O3—H32···O2) groups of two different molecules of the title compound. The O atom is also involved in hydrogen bonding with the H atom of the carbonyl­amide group of a third symmetry-related molecule (N1—H1N···O3). A pair of N2—H2N···O1 inter­molecular hydrogen bonds link the molecules, forming inversion dimers, with an R22(14) ring motif. The dimers are further linked via hydrogen bonds involving the water molecule generating R44(14) and R44(18) ring motifs. Further, the N2—H2N···O1 and N1—H1N···O3 hydrogen bonds between the molecules of the main compound and water molecules translate into C22(6) chains along the a-axis direction (Table 1 and Fig. 2) The chains are linked by a C—H···O inter­action, forming sheets parallel to (010). Within the sheets there are C—H···π, and parallel slipped π–π stacking inter­actions [Cg2···Cg2i = 3.6458 (12) Å; inter-planar distance = 3.4135 (8) Å, slippage = 1.281 Å; Cg2 is the centroid of ring C11–C16; symmetry code: (i) -x + 1, -y + 1, -z + 1] involving inversion-related chloro­benzene rings; see Fig. 3.

Database survey top

A search of the Cambridge Structural Database (Version 5.36, May 2015; Groom & Allen, 2014) for the fragment –NH–CH2–C(═O)–NH–N═CH–, yielded only one hit, namely N-(2-hy­droxy-1-naphthyl­methyl­ene)-N'-(N-phenyl­glycyl)hydrazine (MEMTOO; Gudasi et al., 2006). A comparison of the structural details of the title compound, (I), with those of the recently published sulfonyl derivative, (E)-N-{2-[2-(3-chloro­benzyl­idene)hydrazinyl]-2-oxo­ethyl}-4-methyl­benzene­sulfonamide monohydrate (II) (Purandara et al., 2015), reveals the trans orientation of the amide group (C1–C7(═O1)N1) and hydrazone segment (N2–N3═C10–C11) with respect to the glycinyl C8—C9 bond in (I), as is evident from the N1—C8—C9—N2 torsion angle of 173.58 (15)°, in contrast to the cis orientation of the sulfonamide and hydrazone segments, with respect to the glycinyl C—C bond, observed in compound (II). In the structure of (I), the benzene ring (C1–C6) is almost coplanar with the amide group [dihedral angle = 8.21 (13)°]. This is in contrast to the L-shaped conformation (bent at the S atom) of the sulfonamide group with respect to the benzene ring in compound (II). The amide carbonyl O atom forms stronger O—H···O hydrogen bonds with the water H atoms than the sulfonyl O atom as observed in compound (II), indicating the stronger electron-withdrawing character of the amide group compared to the sulfonamide group.

Synthesis and crystallization top

Tri­ethyl­amine (0.03 mol) and 4-methyl­benzoyl chloride (0.01 mol) were added to a stirred suspension of glycine ethyl­ester hydro­chloride (0.01 mol) in di­chloro­methane (50 ml) in an ice bath. The reaction mixture was stirred at room temperature for 20 h. After completion of the reaction, 2N hydro­chloric acid (80 ml) was added slowly. The organic phase was separated and washed with water (30 ml), dried with anhydrous Na2SO4 and evaporated to yield the corresponding ester, N-(4-methyl­benzoyl)­glycine ethyl ester (L1). L1 (0.01 mol) was added in small portions to a stirred solution of 99% hydrazine hydrate (10 ml) in 30 ml ethanol. The mixture was refluxed for 6 h. After cooling to room temperature, the resulting precipitate was filtered, washed with cold water and dried to give N-(4-methyl­benzoyl)-glycinyl hydrazide (L2). 2-Chloro­benzaldehyde (0.01 mol) and two drops of glacial acetic acid were added to L2 (0.01 mol) in anhydrous methanol (30 ml). The reaction mixture was refluxed for 8 h. After cooling, the precipitate was collected by vacuum filtration, washed with cold methanol and dried. It was recrystallized to constant melting point from methanol (479–480 K). Prism-like colourless single crystals of the title compound were grown from a solution in DMF by slow evaporation of the solvent.

The purity of the compound was checked by TLC and characterized by its IR spectrum. The characteristic absorptions observed are 3323.3, 3203.8, 1685.8, 1620.2 and 1566.2 cm-1 for the stretching bands of N—H (amide I), N—H (amide II), C═O(hydrazone), C═O(amide) and C═N, respectively. The characteristic 1H and 13C NMR spectra of the title compound are as follows: 1H NMR (400 MHz, DMSO-d6, δ p.p.m.): 2.36 (s, 3H), 4.01, 4.45 (2d, 2H, J = 5.8 Hz), 7.25 (d, 2H, Ar—H, J = 8.0 Hz), 7.33–7.40 (m, 2H, Ar—H), 7.42–7.45 (m, 1H, Ar—H), 7.81 (d, 2H, Ar—H), 7.97–7.99 (m, 1H, Ar—H), 8.39, 8.63 (2s, 1H), 8.54, 8.76 (2t, 1H, J = 5.7 Hz), 11.65, 11.73 (2s, 1H). 13C NMR (400 MHz, DMSO-d6, δ p.p.m.): 20.97, 40.74, 42.04, 126.60, 126.83, 127.28, 128.64, 129.66, 130.85, 131.35, 133.10, 139.45, 141.06, 142.70, 165.98, 166.54, 170.48.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The water H atoms and the NH H atoms were located in a difference Fourier map and refined with distances restraints: O—H = 0.85 (2), N—H = 0.86 (2) Å with Uiso(H) = 1.5Ueq(O) and 1.2Ueq(N). The C-bound H atoms were positioned with idealized geometry and refined as riding atoms: C—H = 0.93–0.97 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.

Related literature top

For related literature, see: Groom & Allen (2014); Gudasi et al. (2006); Jyothi & Gowda (2004); Lacerda et al. (2012); Osorio et al. (2012); Palla et al. (1986); Rodrigues et al. (2011); Usha & Gowda (2006).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis CCD (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Hydrogen-bonding pattern in the title compound (see Table 1 for details). [Symmetry codes: (a) -x + 1, -y + 1, -z; (d) x + 1, y, z; (e) x, y, z + 1.]
[Figure 3] Fig. 3. A view along the a axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines and C—H···π interactions are represented as red arrows (see Table 1 for further details).
(E)-N-{2-[2-(2-Chlorobenzylidene)hydrazin-1-yl]-2-oxoethyl}-4-methylbenzamide monohydrate top
Crystal data top
C17H16ClN3O2·H2OZ = 2
Mr = 347.79F(000) = 364
Triclinic, P1Dx = 1.379 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.9729 (7) ÅCell parameters from 3287 reflections
b = 10.642 (1) Åθ = 3.1–27.7°
c = 11.879 (1) ŵ = 0.25 mm−1
α = 95.049 (8)°T = 293 K
β = 100.324 (9)°Prism, colourless
γ = 102.870 (9)°0.50 × 0.40 × 0.32 mm
V = 837.88 (14) Å3
Data collection top
Oxford Diffraction Xcalibur single crystal X-ray
diffractometer with a Sapphire CCD detector		3393 independent reflections
Radiation source: fine-focus sealed tube2829 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.009
Rotation method data acquisition using ω scansθmax = 26.4°, θmin = 3.1°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)		h = −7→8
Tmin = 0.886, Tmax = 0.925k = −12→13
5538 measured reflectionsl = −14→11
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0396P)2 + 0.4048P]
where P = (Fo2 + 2Fc2)/3
3393 reflections(Δ/σ)max < 0.001
230 parametersΔρmax = 0.24 e Å−3
4 restraintsΔρmin = −0.33 e Å−3
Crystal data top
C17H16ClN3O2·H2Oγ = 102.870 (9)°
Mr = 347.79V = 837.88 (14) Å3
Triclinic, P1Z = 2
a = 6.9729 (7) ÅMo Kα radiation
b = 10.642 (1) ŵ = 0.25 mm−1
c = 11.879 (1) ÅT = 293 K
α = 95.049 (8)°0.50 × 0.40 × 0.32 mm
β = 100.324 (9)°
Data collection top
Oxford Diffraction Xcalibur single crystal X-ray
diffractometer with a Sapphire CCD detector		3393 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)		2829 reflections with I > 2σ(I)
Tmin = 0.886, Tmax = 0.925Rint = 0.009
5538 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0394 restraints
wR(F2) = 0.103H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.24 e Å−3
3393 reflectionsΔρmin = −0.33 e Å−3
230 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
xyzUiso*/Ueq
Cl10.60321 (11)0.19118 (5)0.47068 (5)0.0724 (2)
O10.62994 (17)0.78208 (12)−0.04768 (11)0.0451 (3)
O20.7257 (2)0.49520 (12)−0.03656 (10)0.0499 (3)
N10.9290 (2)0.75016 (14)0.03466 (12)0.0417 (3)
H1N1.054 (2)0.766 (2)0.0404 (17)0.050*
N20.6958 (2)0.45136 (14)0.14178 (11)0.0395 (3)
H2N0.617 (3)0.3748 (16)0.1142 (16)0.047*
N30.7330 (2)0.49621 (14)0.25783 (11)0.0365 (3)
C10.9132 (2)0.87432 (15)−0.12558 (13)0.0340 (3)
C20.8034 (3)0.93929 (18)−0.19759 (16)0.0470 (4)
H20.67030.9352−0.19340.056*
C30.8883 (3)1.0105 (2)−0.27602 (17)0.0543 (5)
H30.81121.0537−0.32350.065*
C41.0838 (3)1.01864 (17)−0.28502 (15)0.0471 (4)
C51.1929 (3)0.9537 (2)−0.21334 (17)0.0551 (5)
H51.32590.9581−0.21790.066*
C61.1104 (3)0.8822 (2)−0.13474 (17)0.0503 (5)
H61.18790.8390−0.08760.060*
C70.8130 (2)0.79820 (15)−0.04311 (13)0.0349 (3)
C80.8517 (3)0.67330 (17)0.11810 (14)0.0418 (4)
H8A0.75360.71130.14790.050*
H8B0.96080.67550.18220.050*
C90.7542 (2)0.53317 (16)0.06684 (13)0.0365 (4)
C100.6807 (2)0.41135 (17)0.32262 (14)0.0383 (4)
H100.62050.32560.29060.046*
C110.7154 (2)0.44844 (17)0.44785 (13)0.0365 (4)
C120.6834 (3)0.35608 (18)0.52341 (15)0.0426 (4)
C130.7134 (3)0.3916 (2)0.64139 (15)0.0517 (5)
H130.68940.32840.68990.062*
C140.7787 (3)0.5207 (2)0.68642 (16)0.0558 (5)
H140.79840.54510.76560.067*
C150.8151 (3)0.6143 (2)0.61429 (16)0.0539 (5)
H150.86130.70160.64480.065*
C160.7828 (3)0.57766 (19)0.49659 (15)0.0453 (4)
H160.80690.64150.44870.054*
C171.1791 (4)1.0976 (2)−0.36898 (19)0.0688 (6)
H17A1.08581.1420−0.40730.103*
H17B1.21401.0409−0.42520.103*
H17C1.29811.1602−0.32790.103*
O30.3605 (2)0.76894 (15)0.11275 (13)0.0555 (4)
H310.452 (3)0.799 (3)0.078 (2)0.083*
H320.340 (4)0.6869 (17)0.094 (2)0.083*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.1083 (5)0.0530 (3)0.0572 (3)0.0101 (3)0.0233 (3)0.0258 (2)
O10.0388 (6)0.0496 (7)0.0445 (7)0.0007 (5)0.0129 (5)0.0100 (5)
O20.0698 (9)0.0503 (7)0.0277 (6)0.0064 (6)0.0134 (6)0.0093 (5)
N10.0383 (7)0.0470 (8)0.0364 (7)−0.0009 (6)0.0082 (6)0.0159 (6)
N20.0474 (8)0.0396 (8)0.0278 (7)0.0010 (6)0.0081 (6)0.0094 (6)
N30.0372 (7)0.0458 (8)0.0270 (6)0.0077 (6)0.0077 (5)0.0115 (6)
C10.0395 (8)0.0314 (8)0.0285 (7)0.0016 (6)0.0088 (6)0.0038 (6)
C20.0442 (10)0.0510 (10)0.0485 (10)0.0116 (8)0.0115 (8)0.0165 (8)
C30.0641 (12)0.0526 (11)0.0495 (11)0.0152 (9)0.0112 (9)0.0241 (9)
C40.0656 (12)0.0367 (9)0.0349 (9)−0.0020 (8)0.0169 (8)0.0061 (7)
C50.0463 (10)0.0709 (13)0.0527 (11)0.0093 (9)0.0227 (9)0.0204 (10)
C60.0454 (10)0.0651 (12)0.0476 (10)0.0167 (9)0.0155 (8)0.0250 (9)
C70.0384 (8)0.0322 (8)0.0303 (8)−0.0005 (6)0.0090 (6)0.0028 (6)
C80.0467 (9)0.0454 (9)0.0290 (8)0.0003 (7)0.0072 (7)0.0117 (7)
C90.0379 (8)0.0433 (9)0.0288 (8)0.0075 (7)0.0077 (6)0.0115 (7)
C100.0424 (9)0.0427 (9)0.0322 (8)0.0093 (7)0.0112 (7)0.0126 (7)
C110.0328 (8)0.0508 (10)0.0308 (8)0.0137 (7)0.0102 (6)0.0153 (7)
C120.0396 (9)0.0558 (10)0.0377 (9)0.0141 (8)0.0123 (7)0.0196 (8)
C130.0470 (10)0.0817 (15)0.0340 (9)0.0208 (10)0.0120 (8)0.0276 (9)
C140.0490 (11)0.0920 (16)0.0288 (9)0.0226 (10)0.0071 (8)0.0091 (9)
C150.0540 (11)0.0652 (13)0.0408 (10)0.0157 (9)0.0067 (8)0.0015 (9)
C160.0478 (10)0.0527 (11)0.0382 (9)0.0135 (8)0.0112 (7)0.0140 (8)
C170.0966 (17)0.0565 (12)0.0513 (12)−0.0029 (12)0.0318 (12)0.0176 (10)
O30.0576 (8)0.0586 (8)0.0554 (8)0.0145 (7)0.0223 (7)0.0109 (7)
Geometric parameters (Å, º) top
Cl1—C121.740 (2)C6—H60.9300
O1—C71.240 (2)C8—C91.516 (2)
O2—C91.2251 (19)C8—H8A0.9700
N1—C71.330 (2)C8—H8B0.9700
N1—C81.442 (2)C10—C111.467 (2)
N1—H1N0.842 (15)C10—H100.9300
N2—C91.351 (2)C11—C161.386 (3)
N2—N31.3771 (18)C11—C121.397 (2)
N2—H2N0.873 (15)C12—C131.385 (3)
N3—C101.271 (2)C13—C141.373 (3)
C1—C21.379 (2)C13—H130.9300
C1—C61.383 (2)C14—C151.381 (3)
C1—C71.496 (2)C14—H140.9300
C2—C31.384 (3)C15—C161.382 (3)
C2—H20.9300C15—H150.9300
C3—C41.371 (3)C16—H160.9300
C3—H30.9300C17—H17A0.9600
C4—C51.373 (3)C17—H17B0.9600
C4—C171.510 (2)C17—H17C0.9600
C5—C61.380 (2)O3—H310.840 (17)
C5—H50.9300O3—H320.856 (17)
C7—N1—C8122.85 (15)H8A—C8—H8B107.9
C7—N1—H1N121.7 (14)O2—C9—N2121.16 (16)
C8—N1—H1N115.4 (14)O2—C9—C8122.74 (14)
C9—N2—N3119.90 (14)N2—C9—C8116.08 (14)
C9—N2—H2N118.6 (13)N3—C10—C11120.13 (16)
N3—N2—H2N120.7 (13)N3—C10—H10119.9
C10—N3—N2115.65 (14)C11—C10—H10119.9
C2—C1—C6117.83 (15)C16—C11—C12116.92 (16)
C2—C1—C7118.58 (15)C16—C11—C10121.14 (15)
C6—C1—C7123.59 (15)C12—C11—C10121.94 (16)
C1—C2—C3121.00 (17)C13—C12—C11121.76 (18)
C1—C2—H2119.5C13—C12—Cl1117.92 (14)
C3—C2—H2119.5C11—C12—Cl1120.32 (14)
C4—C3—C2121.22 (18)C14—C13—C12119.63 (17)
C4—C3—H3119.4C14—C13—H13120.2
C2—C3—H3119.4C12—C13—H13120.2
C3—C4—C5117.71 (16)C13—C14—C15120.05 (17)
C3—C4—C17121.75 (19)C13—C14—H14120.0
C5—C4—C17120.53 (19)C15—C14—H14120.0
C4—C5—C6121.76 (18)C14—C15—C16119.8 (2)
C4—C5—H5119.1C14—C15—H15120.1
C6—C5—H5119.1C16—C15—H15120.1
C5—C6—C1120.49 (17)C15—C16—C11121.87 (17)
C5—C6—H6119.8C15—C16—H16119.1
C1—C6—H6119.8C11—C16—H16119.1
O1—C7—N1122.19 (14)C4—C17—H17A109.5
O1—C7—C1120.78 (15)C4—C17—H17B109.5
N1—C7—C1117.03 (14)H17A—C17—H17B109.5
N1—C8—C9112.26 (14)C4—C17—H17C109.5
N1—C8—H8A109.2H17A—C17—H17C109.5
C9—C8—H8A109.2H17B—C17—H17C109.5
N1—C8—H8B109.2H31—O3—H32102 (3)
C9—C8—H8B109.2
C9—N2—N3—C10−177.07 (15)N3—N2—C9—O2178.83 (15)
C6—C1—C2—C3−0.3 (3)N3—N2—C9—C8−2.4 (2)
C7—C1—C2—C3−179.62 (17)N1—C8—C9—O2−7.6 (2)
C1—C2—C3—C40.2 (3)N1—C8—C9—N2173.58 (15)
C2—C3—C4—C5−0.1 (3)N2—N3—C10—C11179.38 (14)
C2—C3—C4—C17−179.09 (19)N3—C10—C11—C167.7 (2)
C3—C4—C5—C60.1 (3)N3—C10—C11—C12−171.98 (16)
C17—C4—C5—C6179.14 (19)C16—C11—C12—C131.3 (2)
C4—C5—C6—C1−0.3 (3)C10—C11—C12—C13−179.00 (16)
C2—C1—C6—C50.3 (3)C16—C11—C12—Cl1−178.83 (13)
C7—C1—C6—C5179.62 (17)C10—C11—C12—Cl10.9 (2)
C8—N1—C7—O11.4 (3)C11—C12—C13—C14−0.8 (3)
C8—N1—C7—C1−179.01 (15)Cl1—C12—C13—C14179.30 (15)
C2—C1—C7—O17.7 (2)C12—C13—C14—C15−0.3 (3)
C6—C1—C7—O1−171.59 (17)C13—C14—C15—C160.9 (3)
C2—C1—C7—N1−171.90 (16)C14—C15—C16—C11−0.4 (3)
C6—C1—C7—N18.8 (2)C12—C11—C16—C15−0.7 (3)
C7—N1—C8—C979.8 (2)C10—C11—C16—C15179.63 (17)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the toluene ring C1–C6.
D—H···AD—HH···AD···AD—H···A
O3—H31···O10.84 (2)2.13 (2)2.897 (2)152 (3)
O3—H32···O2i0.86 (2)1.92 (2)2.772 (2)174 (3)
N1—H1N···O3ii0.84 (2)2.15 (2)2.941 (2)158 (2)
N2—H2N···O1i0.87 (2)2.09 (2)2.944 (2)165 (2)
C14—H14···O2iii0.932.573.404 (2)150
C15—H15···Cg1iii0.932.893.793 (2)165
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1, y, z; (iii) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the toluene ring C1–C6.
D—H···AD—HH···AD···AD—H···A
O3—H31···O10.84 (2)2.13 (2)2.897 (2)152 (3)
O3—H32···O2i0.86 (2)1.92 (2)2.772 (2)174 (3)
N1—H1N···O3ii0.84 (2)2.15 (2)2.941 (2)158 (2)
N2—H2N···O1i0.87 (2)2.09 (2)2.944 (2)165 (2)
C14—H14···O2iii0.932.573.404 (2)150
C15—H15···Cg1iii0.932.893.793 (2)165
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1, y, z; (iii) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC17H16ClN3O2·H2O
Mr347.79
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)6.9729 (7), 10.642 (1), 11.879 (1)
α, β, γ (°)95.049 (8), 100.324 (9), 102.870 (9)
V (Å3)837.88 (14)
Z2
Radiation typeMo Kα
µ (mm−1)0.25
Crystal size (mm)0.50 × 0.40 × 0.32
Data collection
DiffractometerOxford Diffraction Xcalibur single crystal X-ray
diffractometer with a Sapphire CCD detector
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2009)
Tmin, Tmax0.886, 0.925
No. of measured, independent and
observed [I > 2σ(I)] reflections		5538, 3393, 2829
Rint0.009
(sin θ/λ)max (Å−1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.103, 1.04
No. of reflections3393
No. of parameters230
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.24, −0.33

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

 

Acknowledgements

HP thanks the Department of Science and Technology, Government of India, New Delhi, for a research fellowship under its INSPIRE Program and BTG thanks the University Grants Commission, Government of India, New Delhi, for a special grant under the UGC–BSR one-time grant to faculty. The authors also thank SAIF Panjab University for providing an NMR facility.

References

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Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 71| Part 7| July 2015| Pages 795-798
doi:10.1107/S2056989015011147
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