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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2667.
Published online 2010 September 30. doi:  10.1107/S1600536810038328
PMCID: PMC2983383

N′-[(E)-1-(3,5-Dichloro-2-hy­droxy­phen­yl)ethyl­idene]-4-meth­oxy­benzo­hydrazide monohydrate

Abstract

The title compound, C16H14Cl2N2O3·H2O, displays a trans conformation with respect to the C=N double bond. The dihedral angle between the two benzene rings is 4.98 (12)°. Intra­molecular O—H(...)N and O—H(...)O hydrogen bonds occur. The crystal structure is stabilized by inter­molecular O—H(...)O and N—H(...)O hydrogen bonds. In addition, there are π–π inter­actions between the chemically distinct benzene rings of inversion-related mol­ecules [centroid–centroid separation = 3.715 (1) Å].

Related literature

For further details of the chemistry of the title compound, see: Carcelli et al. (1995 [triangle]); Salem (1998 [triangle]). For a related stucture, see: Chang et al. (2007 [triangle]).

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Object name is e-66-o2667-scheme1.jpg

Experimental

Crystal data

  • C16H14Cl2N2O3·H2O
  • M r = 371.21
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2667-efi1.jpg
  • a = 7.033 (5) Å
  • b = 7.516 (7) Å
  • c = 16.647 (10) Å
  • α = 85.105 (10)°
  • β = 81.386 (12)°
  • γ = 79.414 (10)°
  • V = 853.7 (11) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.40 mm−1
  • T = 298 K
  • 0.30 × 0.23 × 0.16 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.906, T max = 0.946
  • 4423 measured reflections
  • 2936 independent reflections
  • 1997 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.066
  • wR(F 2) = 0.170
  • S = 1.00
  • 2936 reflections
  • 220 parameters
  • H-atom parameters constrained
  • Δρmax = 0.56 e Å−3
  • Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); 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/S1600536810038328/pk2270sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038328/pk2270Isup2.hkl

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

Acknowledgments

This project was supported by the Postgraduate Foundation of Taishan University (No. Y05–2–09)

supplementary crystallographic information

Comment

The chemistry of aroylhydrazones continues to attract much attention due to their coordination ability to metal ions and their biological activity (Carcelli et al., 1995; Salem, 1998; Chang et al., 2007). As an extension of work on the structural characterization of aroylhydrazone derivatives, the title compound, was synthesized and its crystal structure is reported here.

The title molecule displays a trans conformation with respect to the C7=N1 double bond (Fig. 1). The dihedral angle between the two benzene rings is 4.98 (12) °. The crystal structure is stabilized by intramolecular O—H···N, O—H···O and intermolecular O—H···O, N—H···O hydrogen bonds. (Table. 1, Figs. 1 and 2). There are π - π interactions between the chemically distinct benzene rings on inversion related molecules [Cg···Cg = 3.715 (1) Å; Cg represents a ring centroid].

Experimental

4-methoxybenzohydrazide (0.01 mol,1.66 g) was dissolved in anhydrous ethanol (50 ml), and 1-(3,5-dichloro-2-hydroxyphenyl)ethanone (0.01 mol, 2.05 g) was added. The reaction mixture was refluxed for 5 h with stirring, then the resulting precipitate was collected by filtration, washed several times with ethanol and dried in vacuo (yield 78%). The compound (1.0 mmol,0.35 g) was dissolved in dimethylformamide (30 ml) and kept at room temperature for 20d to obtain yellow single crystals suitable for X-ray diffraction.

Refinement

All H atoms were positioned geometrically and treated as riding on their parent atoms, with C—H (methyl) = 0.96 Å, C—H (aromatic) = 0.93 Å, O—H = 0.82 Å, N—H = 0.86 Å and with Uiso(H) = 1.5Ueq(Cmethyl, O and 1.2Ueq(Caromatic, Cmethylene, N).

Figures

Fig. 1.
The molecular structure of compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30° probability level. Dashed lines show intramolecular O—H···N, O—H···O ...
Fig. 2.
Packing diagram of compound, Showing intermolecular O—H···O and N—H···O hydrogen bonds (dashed lines).

Crystal data

C16H14Cl2N2O3·H2OZ = 2
Mr = 371.21F(000) = 384
Triclinic, P1Dx = 1.444 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.033 (5) ÅCell parameters from 1429 reflections
b = 7.516 (7) Åθ = 3.0–25.5°
c = 16.647 (10) ŵ = 0.40 mm1
α = 85.105 (10)°T = 298 K
β = 81.386 (12)°Plate, yellow
γ = 79.414 (10)°0.30 × 0.23 × 0.16 mm
V = 853.7 (11) Å3

Data collection

Bruker APEXII CCD area-detector diffractometer2936 independent reflections
Radiation source: fine-focus sealed tube1997 reflections with I > 2σ(I)
graphiteRint = 0.025
[var phi] and ω scansθmax = 25.1°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)h = −8→8
Tmin = 0.906, Tmax = 0.946k = −6→8
4423 measured reflectionsl = −19→19

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)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.170H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.0727P)2 + 0.8688P] where P = (Fo2 + 2Fc2)/3
2936 reflections(Δ/σ)max < 0.001
220 parametersΔρmax = 0.56 e Å3
0 restraintsΔρmin = −0.32 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
Cl11.0655 (2)−0.37144 (18)0.19059 (9)0.0675 (5)
Cl20.8926 (3)0.3075 (2)0.05875 (8)0.0774 (6)
O10.9149 (5)−0.2090 (4)0.34325 (19)0.0462 (8)
H10.8675−0.15990.38560.069*
O20.7613 (6)−0.2102 (4)0.5397 (2)0.0611 (10)
O30.5111 (6)0.0452 (6)0.8985 (2)0.0714 (12)
O40.7853 (6)0.4252 (4)0.5716 (3)0.0710 (12)
N10.7805 (5)0.0497 (5)0.4303 (2)0.0367 (9)
N20.7259 (5)0.0879 (5)0.5112 (2)0.0392 (9)
H20.69830.19730.52640.047*
C10.8427 (6)0.1022 (6)0.2902 (3)0.0360 (9)
C20.9122 (6)−0.0844 (6)0.2809 (3)0.0374 (10)
C30.9789 (7)−0.1428 (6)0.2023 (3)0.0442 (11)
C40.9757 (7)−0.0251 (7)0.1341 (3)0.0488 (11)
H41.0221−0.06680.08260.059*
C50.9020 (7)0.1566 (7)0.1441 (3)0.0448 (11)
C60.8384 (7)0.2200 (6)0.2203 (3)0.0419 (10)
H60.79180.34320.22550.050*
C70.7781 (6)0.1720 (6)0.3720 (3)0.0357 (9)
C80.7186 (6)−0.0562 (6)0.5645 (3)0.0387 (10)
C90.6577 (6)−0.0211 (6)0.6511 (3)0.0387 (10)
C100.5662 (7)0.1480 (7)0.6775 (3)0.0452 (11)
H100.53930.24420.63960.054*
C110.5141 (7)0.1750 (7)0.7606 (3)0.0508 (12)
H110.45420.28870.77800.061*
C120.5526 (7)0.0310 (7)0.8165 (3)0.0483 (11)
C130.6383 (7)−0.1378 (7)0.7914 (3)0.0517 (12)
H130.6614−0.23460.82940.062*
C140.6904 (7)−0.1634 (7)0.7088 (3)0.0457 (11)
H140.7484−0.27800.69190.055*
C150.4310 (10)0.2206 (10)0.9292 (4)0.0819 (19)
H15A0.52020.30290.91090.123*
H15B0.41070.21030.98760.123*
H15C0.30860.26570.90950.123*
C160.7148 (6)0.3729 (4)0.3805 (3)0.0605 (15)
H16A0.68500.39690.43710.091*
H16B0.60080.41480.35420.091*
H16C0.81830.43510.35550.091*
H150.78390.53820.56110.14 (3)*
H160.89050.38840.59190.09 (2)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0958 (12)0.0380 (7)0.0647 (9)−0.0048 (7)−0.0002 (8)−0.0142 (6)
Cl20.1369 (15)0.0568 (9)0.0331 (7)−0.0125 (9)−0.0067 (8)0.0091 (6)
O10.067 (2)0.0312 (17)0.0383 (18)−0.0054 (15)−0.0049 (16)0.0012 (14)
O20.104 (3)0.0296 (18)0.046 (2)−0.0090 (18)−0.0052 (19)0.0065 (15)
O30.089 (3)0.084 (3)0.034 (2)−0.001 (2)−0.0038 (19)0.0013 (19)
O40.090 (3)0.037 (2)0.096 (3)−0.0169 (19)−0.044 (3)0.007 (2)
N10.050 (2)0.031 (2)0.0279 (19)−0.0080 (16)−0.0040 (16)0.0009 (15)
N20.053 (2)0.0283 (19)0.035 (2)−0.0060 (16)−0.0037 (17)−0.0006 (16)
C10.038 (2)0.039 (2)0.032 (2)−0.0095 (18)−0.0057 (17)−0.0004 (17)
C20.041 (2)0.033 (2)0.038 (2)−0.0108 (18)−0.0052 (18)0.0006 (18)
C30.048 (2)0.041 (2)0.045 (2)−0.0085 (19)−0.005 (2)−0.007 (2)
C40.057 (3)0.049 (3)0.040 (2)−0.013 (2)−0.003 (2)−0.006 (2)
C50.058 (3)0.043 (2)0.034 (2)−0.013 (2)−0.007 (2)0.0028 (19)
C60.048 (2)0.038 (2)0.038 (2)−0.0076 (19)−0.0049 (19)0.0003 (19)
C70.043 (2)0.031 (2)0.033 (2)−0.0059 (17)−0.0058 (18)0.0025 (17)
C80.047 (2)0.029 (2)0.039 (2)−0.0067 (18)−0.0073 (19)0.0035 (18)
C90.040 (2)0.040 (2)0.037 (2)−0.0101 (18)−0.0062 (18)0.0037 (18)
C100.051 (3)0.043 (2)0.039 (2)−0.005 (2)−0.005 (2)0.002 (2)
C110.057 (3)0.047 (3)0.046 (3)−0.006 (2)−0.002 (2)−0.002 (2)
C120.048 (3)0.059 (3)0.037 (2)−0.008 (2)−0.005 (2)0.001 (2)
C130.051 (3)0.058 (3)0.043 (2)−0.006 (2)−0.008 (2)0.011 (2)
C140.050 (3)0.044 (2)0.041 (2)−0.006 (2)−0.005 (2)0.006 (2)
C150.100 (5)0.092 (5)0.048 (3)−0.004 (4)0.003 (3)−0.018 (3)
C160.098 (4)0.035 (3)0.041 (3)−0.001 (3)−0.001 (3)−0.001 (2)

Geometric parameters (Å, °)

Cl1—C31.731 (5)C5—C61.376 (7)
Cl2—C51.742 (5)C6—H60.9300
O1—C21.338 (5)C7—C161.506 (5)
O1—H10.8200C8—C91.474 (6)
O2—C81.231 (5)C9—C141.385 (6)
O3—C121.362 (6)C9—C101.391 (6)
O3—C151.440 (7)C10—C111.399 (7)
O4—H150.8511C10—H100.9300
O4—H160.8496C11—C121.381 (7)
N1—C71.279 (5)C11—H110.9300
N1—N21.383 (5)C12—C131.372 (7)
N2—C81.344 (5)C13—C141.389 (7)
N2—H20.8600C13—H130.9300
C1—C61.401 (6)C14—H140.9300
C1—C21.412 (6)C15—H15A0.9600
C1—C71.477 (6)C15—H15B0.9600
C2—C31.401 (6)C15—H15C0.9600
C3—C41.378 (7)C16—H16A0.9600
C4—C51.383 (7)C16—H16B0.9600
C4—H40.9300C16—H16C0.9600
C2—O1—H1109.5C14—C9—C10118.5 (4)
C12—O3—C15118.7 (5)C14—C9—C8118.6 (4)
H15—O4—H16104.1C10—C9—C8122.9 (4)
C7—N1—N2123.2 (4)C9—C10—C11120.7 (5)
C8—N2—N1115.9 (4)C9—C10—H10119.7
C8—N2—H2122.0C11—C10—H10119.7
N1—N2—H2122.0C12—C11—C10119.3 (5)
C6—C1—C2118.5 (4)C12—C11—H11120.4
C6—C1—C7120.8 (4)C10—C11—H11120.4
C2—C1—C7120.7 (4)O3—C12—C13115.8 (5)
O1—C2—C3118.2 (4)O3—C12—C11123.4 (5)
O1—C2—C1123.3 (4)C13—C12—C11120.8 (5)
C3—C2—C1118.5 (4)C12—C13—C14119.6 (5)
C4—C3—C2122.3 (4)C12—C13—H13120.2
C4—C3—Cl1119.1 (4)C14—C13—H13120.2
C2—C3—Cl1118.6 (4)C9—C14—C13121.2 (5)
C3—C4—C5118.5 (4)C9—C14—H14119.4
C3—C4—H4120.8C13—C14—H14119.4
C5—C4—H4120.8O3—C15—H15A109.5
C6—C5—C4121.1 (4)O3—C15—H15B109.5
C6—C5—Cl2119.6 (4)H15A—C15—H15B109.5
C4—C5—Cl2119.3 (4)O3—C15—H15C109.5
C5—C6—C1121.1 (4)H15A—C15—H15C109.5
C5—C6—H6119.5H15B—C15—H15C109.5
C1—C6—H6119.5C7—C16—H16A109.5
N1—C7—C1114.5 (4)C7—C16—H16B109.5
N1—C7—C16125.9 (4)H16A—C16—H16B109.5
C1—C7—C16119.6 (4)C7—C16—H16C109.5
O2—C8—N2119.6 (4)H16A—C16—H16C109.5
O2—C8—C9122.8 (4)H16B—C16—H16C109.5
N2—C8—C9117.6 (4)
C7—N1—N2—C8173.8 (4)C6—C1—C7—C16−2.6 (6)
C6—C1—C2—O1−177.2 (4)C2—C1—C7—C16176.7 (4)
C7—C1—C2—O13.5 (6)N1—N2—C8—O20.7 (6)
C6—C1—C2—C31.7 (6)N1—N2—C8—C9−179.0 (4)
C7—C1—C2—C3−177.5 (4)O2—C8—C9—C1414.7 (7)
O1—C2—C3—C4177.9 (4)N2—C8—C9—C14−165.6 (4)
C1—C2—C3—C4−1.1 (7)O2—C8—C9—C10−164.4 (5)
O1—C2—C3—Cl1−1.4 (6)N2—C8—C9—C1015.3 (6)
C1—C2—C3—Cl1179.7 (3)C14—C9—C10—C112.0 (7)
C2—C3—C4—C5−0.7 (7)C8—C9—C10—C11−178.9 (4)
Cl1—C3—C4—C5178.5 (4)C9—C10—C11—C12−0.7 (7)
C3—C4—C5—C61.9 (7)C15—O3—C12—C13176.6 (5)
C3—C4—C5—Cl2−178.9 (4)C15—O3—C12—C11−2.9 (8)
C4—C5—C6—C1−1.3 (7)C10—C11—C12—O3178.5 (5)
Cl2—C5—C6—C1179.6 (4)C10—C11—C12—C13−1.0 (8)
C2—C1—C6—C5−0.6 (7)O3—C12—C13—C14−178.2 (4)
C7—C1—C6—C5178.7 (4)C11—C12—C13—C141.3 (8)
N2—N1—C7—C1179.8 (4)C10—C9—C14—C13−1.7 (7)
N2—N1—C7—C16−0.8 (7)C8—C9—C14—C13179.2 (4)
C6—C1—C7—N1176.9 (4)C12—C13—C14—C90.1 (7)
C2—C1—C7—N1−3.9 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O40.862.152.926 (5)150
O1—H1···O20.822.583.287 (5)146
O1—H1···N10.821.772.484 (5)145
O4—H16···O1i0.852.092.887 (5)156
O4—H15···O2ii0.851.882.726 (5)176

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2270).

References

  • Bruker (2005). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Carcelli, M., Mazza, P., Pelizzi, G. & Zani, F. (1995). J. Inorg. Biochem.57, 43–62. [PubMed]
  • Chang, J.-G. & Ji, C.-Y. (2007). Acta Cryst. E63, o3212.
  • Salem, A. A. (1998). Microchem. J.60, 51–66.
  • Sheldrick, G. M. (2003). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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