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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2829.
Published online 2010 October 20. doi:  10.1107/S160053681004050X
PMCID: PMC3009049

2-(4-Chloro­phen­oxy)-N′-[2-(4-chloro­phen­oxy)acet­yl]acetohydrazide monohydrate

Abstract

In the title compound, C16H14Cl2N2O4·H2O, the hydrazine and water mol­ecules are both located on twofold axes. The C—N—N—C torsion angle is −72.66 (1)° and the dihedral angle between the two benzene rings is 67.33 (1)°. In the crystal, mol­ecules are linked into a layer structure by a combination of O—H(...)O, N—H(...)O and C—H(...)O hydrogen bonds. Adjacent layers are linked into a three-dimensional network by Cl(...)Cl inter­actions [3.400 (2) Å]. C—H(...)π inter­actions are also observed.

Related literature

For the synthesis and biological activity of title compound and its derivatives, see: Dovlatvan (1961 [triangle]). For the synthesis and biological activity of diacyl­hydrazine derivatives, see: Jia (2008 [triangle]); Zhang et al. (2005 [triangle]); Zhao et al. (2008 [triangle]). For a related structure, see: Jiang et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2829-scheme1.jpg

Experimental

Crystal data

  • C16H14Cl2N2O4·H2O
  • M r = 387.21
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2829-efi1.jpg
  • a = 4.8462 (9) Å
  • b = 5.4411 (10) Å
  • c = 33.521 (6) Å
  • β = 90.840 (3)°
  • V = 883.8 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.40 mm−1
  • T = 292 K
  • 0.10 × 0.04 × 0.02 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • 9670 measured reflections
  • 2013 independent reflections
  • 1380 reflections with I > 2σ(I)
  • R int = 0.059

Refinement

  • R[F 2 > 2σ(F 2)] = 0.056
  • wR(F 2) = 0.169
  • S = 1.06
  • 2013 reflections
  • 121 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [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 I, global. DOI: 10.1107/S160053681004050X/vm2047sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681004050X/vm2047Isup2.hkl

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

Acknowledgments

We gratefully acknowledge the financial support of this work by the Hubei Provincial Natural Science Foundation of China (No. 2009CDB175).

supplementary crystallographic information

Comment

Most diacylhydrazine derivatives have insecticide activity (Zhang et al., 2005; Jia, 2008; Zhao et al., 2008). While in our research of herbicidal compounds, we found some diacylhydrazine derivatives showing herbicidal activity. We have synthesized the title compound and report its crystal structure here.

In the title compound (Fig. 1), the hydrazine and water molecules are both located on twofold axes. The torsion angle C8—N1—N1(-x + 5/2, y, -z + 1/2)—C8(-x + 5/2, y, -z + 1/2) is -72.66 (1)° and the dihedral angle between the two benzene rings is 67.33 (1)°. Intermolecular N—H···O and intramolecular O—H···O, C—H···O hydrogen bonds are found in the crystal structure (Table 1), and one C—H···π interaction [C7···Cg1(x + 1, y, z) = 3.592 (1) Å, Cg1 is the centroid defined by benzene atoms C1—C6] is also observed.

In the crystal packing, the molecules are linked into a two-dimensional layer structure by a combination of O—H···O, N—H···O and C—H···O hydrogen bonds (Fig. 2). These adjacent layers are linked into a three-dimensional network by the Cl1···Cl1(-x, -y, 1 - z) interaction (3.400 (2) Å, Fig. 3).

Experimental

4-chlorophenoxyacetyl chloride (4.10 g, 20 mmol) was dissolved in toluene (20 ml), together with hydrazine hydrate (85%, 0.59 g, 10 mmol). The solution was stirred at room temperature and then pyridine (1.60 g, 20 mmol) was added dropwise. Then the solution was heated at 373 K for two hours. The product was isolated and recrystallized as a colorless solid from ethanol (yield 80.3%).

Refinement

H atoms on C atoms were positioned geometrically and refined using a riding model with C—H = 0.93Å (aromatic) and 0.97Å (methylene). The Uiso(H) values were set 1.2 times of their parent atoms. H atoms attached to N and O atoms were found from the difference maps and refined with restraints (N—H = 0.86 (1)Å and O—H = 0.82 (1) Å), and their thermal factors were set 1.2 times (for N) or 1.5 times (for O) of the parent atoms.

Figures

Fig. 1.
The molecular structure of the title compound, showing the atom-labeling scheme for the non-H atoms and 50% probability displacement ellipsoids.
Fig. 2.
Two-dimensional layer structure by hydrogen bonding indicated as dashed lines.
Fig. 3.
Three-dimensional network formed via Cl1···Cl1 (-x, -y, 1 - z) interactions.

Crystal data

C16H14Cl2N2O4·H2OF(000) = 400
Mr = 387.21Dx = 1.455 Mg m3
Monoclinic, P2/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yacCell parameters from 2333 reflections
a = 4.8462 (9) Åθ = 3.7–26.5°
b = 5.4411 (10) ŵ = 0.40 mm1
c = 33.521 (6) ÅT = 292 K
β = 90.840 (3)°Block, colourless
V = 883.8 (3) Å30.10 × 0.04 × 0.02 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer1380 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.059
graphiteθmax = 27.5°, θmin = 1.2°
phi and ω scansh = −6→6
9670 measured reflectionsk = −6→6
2013 independent reflectionsl = −43→43

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)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.169H atoms treated by a mixture of independent and constrained refinement
S = 1.06w = 1/[σ2(Fo2) + (0.0947P)2] where P = (Fo2 + 2Fc2)/3
2013 reflections(Δ/σ)max < 0.001
121 parametersΔρmax = 0.34 e Å3
2 restraintsΔρmin = −0.27 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
C10.3940 (6)0.2592 (5)0.43058 (8)0.0523 (7)
C20.5608 (6)0.4610 (6)0.43082 (7)0.0596 (8)
H20.56260.56640.45270.072*
C30.3829 (6)0.1066 (5)0.39794 (9)0.0585 (7)
H30.2647−0.02810.39770.070*
C40.7276 (5)0.5091 (5)0.39850 (7)0.0504 (7)
H40.84250.64600.39870.060*
C50.5469 (5)0.1529 (5)0.36551 (8)0.0499 (6)
H50.53940.04990.34340.060*
C60.7225 (5)0.3534 (4)0.36602 (6)0.0389 (5)
C71.0585 (5)0.5868 (4)0.33195 (7)0.0412 (6)
H7A1.17680.58500.35560.049*
H7B0.95020.73670.33240.049*
C81.2341 (5)0.5841 (4)0.29520 (6)0.0391 (5)
Cl10.1904 (2)0.1932 (2)0.47157 (2)0.0884 (4)
O10.8805 (3)0.3820 (3)0.33266 (4)0.0459 (5)
O21.4157 (4)0.7389 (3)0.29242 (6)0.0582 (5)
N11.1790 (4)0.4132 (4)0.26786 (5)0.0394 (5)
O30.75000.0536 (4)0.25000.0484 (6)
H11.042 (4)0.316 (5)0.2707 (9)0.066 (9)*
H3A0.636 (6)−0.036 (6)0.2602 (11)0.099*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0490 (15)0.0682 (17)0.0399 (14)−0.0006 (12)0.0127 (11)0.0082 (12)
C20.0648 (18)0.080 (2)0.0345 (13)−0.0098 (15)0.0128 (12)−0.0117 (13)
C30.0557 (16)0.0530 (16)0.0673 (18)−0.0132 (12)0.0187 (13)0.0008 (13)
C40.0531 (15)0.0583 (16)0.0400 (13)−0.0155 (12)0.0092 (11)−0.0082 (11)
C50.0516 (15)0.0500 (14)0.0485 (15)−0.0076 (12)0.0129 (11)−0.0088 (11)
C60.0358 (12)0.0482 (13)0.0330 (12)0.0004 (10)0.0064 (9)−0.0009 (9)
C70.0433 (13)0.0442 (13)0.0363 (12)−0.0054 (10)0.0079 (10)−0.0026 (10)
C80.0381 (12)0.0435 (13)0.0357 (12)−0.0001 (10)0.0051 (9)0.0044 (10)
Cl10.0842 (6)0.1257 (8)0.0562 (5)−0.0160 (5)0.0333 (4)0.0175 (4)
O10.0480 (10)0.0540 (10)0.0362 (9)−0.0121 (8)0.0154 (7)−0.0079 (7)
O20.0606 (12)0.0641 (12)0.0504 (11)−0.0269 (9)0.0149 (9)−0.0052 (8)
N10.0383 (11)0.0435 (11)0.0368 (10)−0.0052 (9)0.0135 (8)−0.0018 (8)
O30.0477 (15)0.0424 (14)0.0558 (15)0.0000.0216 (11)0.000

Geometric parameters (Å, °)

C1—C21.363 (4)C6—O11.373 (2)
C1—C31.374 (4)C7—O11.410 (3)
C1—Cl11.741 (2)C7—C81.507 (3)
C2—C41.386 (3)C7—H7A0.9700
C2—H20.9300C7—H7B0.9700
C3—C51.379 (3)C8—O21.223 (3)
C3—H30.9300C8—N11.330 (3)
C4—C61.380 (3)N1—N1i1.390 (3)
C4—H40.9300N1—H10.856 (10)
C5—C61.383 (3)O3—H3A0.815 (10)
C5—H50.9300
C2—C1—C3120.5 (2)O1—C6—C5115.4 (2)
C2—C1—Cl1120.3 (2)C4—C6—C5119.9 (2)
C3—C1—Cl1119.2 (2)O1—C7—C8111.02 (18)
C1—C2—C4120.0 (2)O1—C7—H7A109.4
C1—C2—H2120.0C8—C7—H7A109.4
C4—C2—H2120.0O1—C7—H7B109.4
C1—C3—C5120.1 (2)C8—C7—H7B109.4
C1—C3—H3120.0H7A—C7—H7B108.0
C5—C3—H3120.0O2—C8—N1124.5 (2)
C6—C4—C2119.8 (2)O2—C8—C7118.1 (2)
C6—C4—H4120.1N1—C8—C7117.39 (19)
C2—C4—H4120.1C6—O1—C7116.86 (17)
C3—C5—C6119.7 (2)C8—N1—N1i119.77 (17)
C3—C5—H5120.1C8—N1—H1120 (2)
C6—C5—H5120.1N1i—N1—H1119 (2)
O1—C6—C4124.7 (2)
C3—C1—C2—C4−2.1 (4)C3—C5—C6—C4−1.7 (4)
Cl1—C1—C2—C4178.4 (2)O1—C7—C8—O2−173.5 (2)
C2—C1—C3—C51.8 (4)O1—C7—C8—N16.8 (3)
Cl1—C1—C3—C5−178.6 (2)C4—C6—O1—C7−0.3 (3)
C1—C2—C4—C60.5 (4)C5—C6—O1—C7179.0 (2)
C1—C3—C5—C60.1 (4)C8—C7—O1—C6175.62 (18)
C2—C4—C6—O1−179.4 (2)O2—C8—N1—N1i−4.2 (4)
C2—C4—C6—C51.4 (4)C7—C8—N1—N1i175.4 (2)
C3—C5—C6—O1179.0 (2)

Symmetry codes: (i) −x+5/2, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
C5—H5···O2ii0.932.473.382 (3)166
O3—H3A···O2ii0.82 (1)1.96 (1)2.765 (2)169 (4)
N1—H1···O30.86 (1)2.12 (2)2.911 (3)153 (3)
N1—H1···O10.86 (1)2.26 (3)2.633 (2)107 (2)
C7—H7···Cg1iii0.972.763.592 (1)144

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: VM2047).

References

  • Bruker (2001). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Dovlatvan, V. V. (1961). Khim. Nauki, 14, 347–352.
  • Jia, B.-T. (2008). J. Chin. Mod. Agro.7, 9–13.
  • Jiang, X.-Y., Feng, X.-J., Yang, S., Xu, H.-J. & Hao, L.-Y. (2009). Acta Cryst. E65, o2189. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhang, X.-N., Ni, Y.-P., Li, Y.-F. & Jiang, M. G. (2005). J. Nanjing Agric. Univ.28, 135–139.
  • Zhao, Q.-Q., Qu, X.-M., Huang, Z.-Q., Bi, F.-Ch., Huang, R.-Q. & Wang Q.-M. (2008). J. Agric. Food Chem.56, 10799–10804. [PubMed]

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