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

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.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.056
• wR factor = 0.169
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT919_ALERT_3_B Reflection(s) # Likely Affected by the Beamstop           1

Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.12
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........    <I>CG</
PLAT731_ALERT_1_C Bond    Calc     0.82(3), Rep   0.815(10) ......       3.00 su-Ra
              O3   -H3A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(3), Rep   0.815(10) ......       3.00 su-Ra
              O3   -H3A     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.96(3), Rep   1.961(13) ......       2.31 su-Ra
              H3A  -O2      1.555   1.445
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C16 H14 Cl2 N2 O4
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         17

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2
PLAT128_ALERT_4_G Alternate Setting of Space-group P2/c    .......      P2/n
PLAT804_ALERT_5_G ARU-Pack Problem in PLATON Analysis ............          1 Times

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. 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).

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).

S2. 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%).

S3. 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 U_iso(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.

Computing details

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

	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

Crystal data

C16H14Cl2N2O4·H2O	F(000) = 400
Mr = 387.21	Dx = 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) Å^3	0.10 × 0.04 × 0.02 mm
Z = 2

Data collection

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

Refinement

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

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—N1^i	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—N1^i	119.77 (17)
C3—C5—H5	120.1	C8—N1—H1	120 (2)
C6—C5—H5	120.1	N1^i—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—N1^i	−4.2 (4)
C2—C4—C6—C5	1.4 (4)	C7—C8—N1—N1^i	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)

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2^ii	0.93	2.47	3.382 (3)	166
O3—H3A···O2^ii	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···Cg1^iii	0.97	2.76	3.592 (1)	144

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