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

Chen, T.; Tan, X.

doi:10.1107/S160053681004050X

organic compounds

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Volume 66| Part 11| November 2010| Page o2829

https://doi.org/10.1107/S160053681004050X

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

Ting Chen ^a ^* and Xiaosong Tan ^b

^aFaculty of Material Science and Chemical Engineering, China University of Geosciences, Wuhan 430074, People's Republic of China, and ^bKey Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China
^*Correspondence e-mail: chen3510@163.com

(Received 21 September 2010; accepted 9 October 2010; online 20 October 2010)

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 ). For the synthesis and biological activity of diacylhydrazine derivatives, see: Jia (2008 ); Zhang et al. (2005 ); Zhao et al. (2008 ). For a related structure, see: Jiang et al. (2009 ).

Experimental

Crystal data

C₁₆H₁₄Cl₂N₂O₄·H₂O
M_r = 387.21
Monoclinic, P 2/n
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[F² > 2σ(F²)] = 0.056
wR(F²) = 0.169
S = 1.06
2013 reflections
121 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O2ⁱ	0.93	2.47	3.382 (3)	166
O3—H3A⋯O2ⁱ	0.82 (1)	1.96 (1)	2.765 (2)	169 (4)
N1—H1⋯O3	0.86 (1)	2.12 (2)	2.911 (3)	153 (3)
N1—H1⋯O1	0.86 (1)	2.26 (3)	2.633 (2)	107 (2)
C7—H7⋯Cg1ⁱⁱ	0.97	2.76	3.592 (1)	144
Symmetry codes: (i) x-1, y-1, z; (ii) x+1, y, z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681004050X/vm2047sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681004050X/vm2047Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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%).

Structure description top

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

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	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.

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

Crystal data top

C₁₆H₁₄Cl₂N₂O₄·H₂O	F(000) = 400
M_r = 387.21	D_x = 1.455 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 2333 reflections
a = 4.8462 (9) Å	θ = 3.7–26.5°
b = 5.4411 (10) Å	µ = 0.40 mm⁻¹
c = 33.521 (6) Å	T = 292 K
β = 90.840 (3)°	Block, colourless
V = 883.8 (3) Å³	0.10 × 0.04 × 0.02 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	1380 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.059
Graphite monochromator	θ_max = 27.5°, θ_min = 1.2°
phi and ω scans	h = −6→6
9670 measured reflections	k = −6→6
2013 independent reflections	l = −43→43

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0947P)²] where P = (F_o² + 2F_c²)/3
2013 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.34 e Å⁻³
2 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₆H₁₄Cl₂N₂O₄·H₂O	V = 883.8 (3) Å³
M_r = 387.21	Z = 2
Monoclinic, P2/n	Mo Kα radiation
a = 4.8462 (9) Å	µ = 0.40 mm⁻¹
b = 5.4411 (10) Å	T = 292 K
c = 33.521 (6) Å	0.10 × 0.04 × 0.02 mm
β = 90.840 (3)°

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.056	2 restraints
wR(F²) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.34 e Å⁻³
2013 reflections	Δρ_min = −0.27 e Å⁻³
121 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

	x	y	z	U_iso*/U_eq
C1	0.3940 (6)	0.2592 (5)	0.43058 (8)	0.0523 (7)
C2	0.5608 (6)	0.4610 (6)	0.43082 (7)	0.0596 (8)
H2	0.5626	0.5664	0.4527	0.072*
C3	0.3829 (6)	0.1066 (5)	0.39794 (9)	0.0585 (7)
H3	0.2647	−0.0281	0.3977	0.070*
C4	0.7276 (5)	0.5091 (5)	0.39850 (7)	0.0504 (7)
H4	0.8425	0.6460	0.3987	0.060*
C5	0.5469 (5)	0.1529 (5)	0.36551 (8)	0.0499 (6)
H5	0.5394	0.0499	0.3434	0.060*
C6	0.7225 (5)	0.3534 (4)	0.36602 (6)	0.0389 (5)
C7	1.0585 (5)	0.5868 (4)	0.33195 (7)	0.0412 (6)
H7A	1.1768	0.5850	0.3556	0.049*
H7B	0.9502	0.7367	0.3324	0.049*
C8	1.2341 (5)	0.5841 (4)	0.29520 (6)	0.0391 (5)
Cl1	0.1904 (2)	0.1932 (2)	0.47157 (2)	0.0884 (4)
O1	0.8805 (3)	0.3820 (3)	0.33266 (4)	0.0459 (5)
O2	1.4157 (4)	0.7389 (3)	0.29242 (6)	0.0582 (5)
N1	1.1790 (4)	0.4132 (4)	0.26786 (5)	0.0394 (5)
O3	0.7500	0.0536 (4)	0.2500	0.0484 (6)
H1	1.042 (4)	0.316 (5)	0.2707 (9)	0.066 (9)*
H3A	0.636 (6)	−0.036 (6)	0.2602 (11)	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0490 (15)	0.0682 (17)	0.0399 (14)	−0.0006 (12)	0.0127 (11)	0.0082 (12)
C2	0.0648 (18)	0.080 (2)	0.0345 (13)	−0.0098 (15)	0.0128 (12)	−0.0117 (13)
C3	0.0557 (16)	0.0530 (16)	0.0673 (18)	−0.0132 (12)	0.0187 (13)	0.0008 (13)
C4	0.0531 (15)	0.0583 (16)	0.0400 (13)	−0.0155 (12)	0.0092 (11)	−0.0082 (11)
C5	0.0516 (15)	0.0500 (14)	0.0485 (15)	−0.0076 (12)	0.0129 (11)	−0.0088 (11)
C6	0.0358 (12)	0.0482 (13)	0.0330 (12)	0.0004 (10)	0.0064 (9)	−0.0009 (9)
C7	0.0433 (13)	0.0442 (13)	0.0363 (12)	−0.0054 (10)	0.0079 (10)	−0.0026 (10)
C8	0.0381 (12)	0.0435 (13)	0.0357 (12)	−0.0001 (10)	0.0051 (9)	0.0044 (10)
Cl1	0.0842 (6)	0.1257 (8)	0.0562 (5)	−0.0160 (5)	0.0333 (4)	0.0175 (4)
O1	0.0480 (10)	0.0540 (10)	0.0362 (9)	−0.0121 (8)	0.0154 (7)	−0.0079 (7)
O2	0.0606 (12)	0.0641 (12)	0.0504 (11)	−0.0269 (9)	0.0149 (9)	−0.0052 (8)
N1	0.0383 (11)	0.0435 (11)	0.0368 (10)	−0.0052 (9)	0.0135 (8)	−0.0018 (8)
O3	0.0477 (15)	0.0424 (14)	0.0558 (15)	0.000	0.0216 (11)	0.000

Geometric parameters (Å, º) top

C1—C2	1.363 (4)	C6—O1	1.373 (2)
C1—C3	1.374 (4)	C7—O1	1.410 (3)
C1—Cl1	1.741 (2)	C7—C8	1.507 (3)
C2—C4	1.386 (3)	C7—H7A	0.9700
C2—H2	0.9300	C7—H7B	0.9700
C3—C5	1.379 (3)	C8—O2	1.223 (3)
C3—H3	0.9300	C8—N1	1.330 (3)
C4—C6	1.380 (3)	N1—N1ⁱ	1.390 (3)
C4—H4	0.9300	N1—H1	0.856 (10)
C5—C6	1.383 (3)	O3—H3A	0.815 (10)
C5—H5	0.9300

C2—C1—C3	120.5 (2)	O1—C6—C5	115.4 (2)
C2—C1—Cl1	120.3 (2)	C4—C6—C5	119.9 (2)
C3—C1—Cl1	119.2 (2)	O1—C7—C8	111.02 (18)
C1—C2—C4	120.0 (2)	O1—C7—H7A	109.4
C1—C2—H2	120.0	C8—C7—H7A	109.4
C4—C2—H2	120.0	O1—C7—H7B	109.4
C1—C3—C5	120.1 (2)	C8—C7—H7B	109.4
C1—C3—H3	120.0	H7A—C7—H7B	108.0
C5—C3—H3	120.0	O2—C8—N1	124.5 (2)
C6—C4—C2	119.8 (2)	O2—C8—C7	118.1 (2)
C6—C4—H4	120.1	N1—C8—C7	117.39 (19)
C2—C4—H4	120.1	C6—O1—C7	116.86 (17)
C3—C5—C6	119.7 (2)	C8—N1—N1ⁱ	119.77 (17)
C3—C5—H5	120.1	C8—N1—H1	120 (2)
C6—C5—H5	120.1	N1ⁱ—N1—H1	119 (2)
O1—C6—C4	124.7 (2)

C3—C1—C2—C4	−2.1 (4)	C3—C5—C6—C4	−1.7 (4)
Cl1—C1—C2—C4	178.4 (2)	O1—C7—C8—O2	−173.5 (2)
C2—C1—C3—C5	1.8 (4)	O1—C7—C8—N1	6.8 (3)
Cl1—C1—C3—C5	−178.6 (2)	C4—C6—O1—C7	−0.3 (3)
C1—C2—C4—C6	0.5 (4)	C5—C6—O1—C7	179.0 (2)
C1—C3—C5—C6	0.1 (4)	C8—C7—O1—C6	175.62 (18)
C2—C4—C6—O1	−179.4 (2)	O2—C8—N1—N1ⁱ	−4.2 (4)
C2—C4—C6—C5	1.4 (4)	C7—C8—N1—N1ⁱ	175.4 (2)
C3—C5—C6—O1	179.0 (2)

Symmetry code: (i) −x+5/2, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2ⁱⁱ	0.93	2.47	3.382 (3)	166
O3—H3A···O2ⁱⁱ	0.82 (1)	1.96 (1)	2.765 (2)	169 (4)
N1—H1···O3	0.86 (1)	2.12 (2)	2.911 (3)	153 (3)
N1—H1···O1	0.86 (1)	2.26 (3)	2.633 (2)	107 (2)
C7—H7···Cg1ⁱⁱⁱ	0.97	2.76	3.592 (1)	144

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄Cl₂N₂O₄·H₂O
M_r	387.21
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	292
a, b, c (Å)	4.8462 (9), 5.4411 (10), 33.521 (6)
β (°)	90.840 (3)
V (Å³)	883.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.10 × 0.04 × 0.02

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9670, 2013, 1380
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.169, 1.06
No. of reflections	2013
No. of parameters	121
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.27

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2ⁱ	0.93	2.47	3.382 (3)	165.9
O3—H3A···O2ⁱ	0.815 (10)	1.961 (13)	2.765 (2)	169 (4)
N1—H1···O3	0.856 (10)	2.119 (16)	2.911 (3)	153 (3)
N1—H1···O1	0.856 (10)	2.26 (3)	2.633 (2)	107 (2)
C7—H7···Cg1ⁱⁱ	0.97	2.76	3.592 (1)	144

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

Acknowledgements

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

References

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dovlatvan, V. V. (1961). Khim. Nauki, 14, 347–352. CAS Google Scholar
Jia, B.-T. (2008). J. Chin. Mod. Agro. 7, 9–13. CAS Google Scholar
Jiang, X.-Y., Feng, X.-J., Yang, S., Xu, H.-J. & Hao, L.-Y. (2009). Acta Cryst. E65, o2189. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, X.-N., Ni, Y.-P., Li, Y.-F. & Jiang, M. G. (2005). J. Nanjing Agric. Univ. 28, 135–139. CAS Google Scholar
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. Web of Science CrossRef PubMed CAS Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2829

https://doi.org/10.1107/S160053681004050X

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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