N′-(2,4-Di­nitro­phen­yl)acetohydrazide monohydrate

Essid, M.; Marouani, H.; Al-Deyab, S.S.; Rzaigui, M.

doi:10.1107/S1600536813018916

organic compounds

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Volume 69| Part 8| August 2013| Page o1249

doi:10.1107/S1600536813018916

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N′-(2,4-Dinitrophenyl)acetohydrazide monohydrate

Manel Essid,^a Houda Marouani,^a ^* Salem S. Al-Deyab ^b and Mohamed Rzaigui ^a

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia, and ^bChemistry Department, Faculty of Science, King Saud University, PO Box 2455, Riyadh 11451, Saudi Arabia
^*Correspondence e-mail: houda_marouani@voila.fr

(Received 18 June 2013; accepted 8 July 2013; online 13 July 2013)

In the crystal structure of the title compound, C₈H₈N₄O₅·H₂O, the organic and lattice water molecules are linked together via N—H⋯O and O—H⋯O hydrogen bonds. A C—H⋯O interaction is also observed between the organic molecules. These hydrogen bonds and interactions lead to the formation of a three-dimensional network. An intramolecular N—H⋯O hydrogen bond also occurs. The dihedral angle between the acetyl group and the almost planar hydrazide moiety [maximum deviation from the least-squares plane is 0.209 (2) Å for one of the nitro O atoms] is 88.5 (3)°.

Related literature

For background to the biological activity of hydrazines and hydrazones, see: Zahid & Sherazi (1997 ); Monfared et al. (2007 ). For a related crystal structure, see: Okabe et al. (1993 ). For hydrogen-bond graph-set motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₈N₄O₅·H₂O
M_r = 258.20
Monoclinic, P 2₁ /c
a = 7.702 (2) Å
b = 7.057 (3) Å
c = 21.550 (4) Å
β = 109.044 (19)°
V = 1107.3 (6) Å³
Z = 4
Ag Kα radiation
λ = 0.56083 Å
μ = 0.08 mm⁻¹
T = 293 K
0.5 × 0.4 × 0.3 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
7469 measured reflections
5411 independent reflections
2771 reflections with I > 2σ(I)
R_int = 0.064
2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.195
S = 0.98
5411 reflections
181 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW—H1W⋯O5	0.86 (1)	1.91 (1)	2.759 (3)	175 (3)
OW—H2W⋯O4ⁱ	0.84 (1)	2.05 (1)	2.868 (3)	165 (3)
N1—H1N⋯OWⁱⁱ	0.88 (3)	2.04 (3)	2.883 (3)	160 (2)
N2—H2N⋯O1	0.90 (3)	1.96 (3)	2.607 (2)	128 (2)
N2—H2N⋯OWⁱⁱⁱ	0.90 (3)	2.15 (3)	2.910 (3)	142 (2)
C6—H6⋯O5^iv	0.93	2.40	3.310 (3)	165
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x, y-1, z; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813018916/pv2637sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813018916/pv2637Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813018916/pv2637Isup3.cml

checkCIF report

Comment top

Hydrazine and its derivatives have been intensively investigated due to their attractive pharmacological applications (Zahid & Sherazi, 1997). In addition, hydrazones exhibit physiological activities in the treatment of several diseases such as tuberculosis (Monfared et al., 2007). We report here the synthesis and the crystal structure of the title compound.

The bond distances and angles in the title compound (Fig. 1) agree very well with the corresponding bond distances and angles reported in a closely related compound (Okabe, et al., 1993). There is a strong intramolecular N—H···O hydrogen bond that stabilizes the molecular structure of the title compound. In the crystal structure, pairs of symmetry-related molecules are connected into centrosymmetric clusters via medium O—H···O and N—H···O hydrogen bonds forming twenty-six-membered rings with an R₆⁶ (26) motif (Bernstein, et al., 1995). The water molecule is surrounded by three organic groups through hydrogen bonds type O—H···O and N—H···O. The crystal packing (Fig. 2) is stabilized by these intermolecular hydrogen bonds and C—H···O interactions (Table 1) resulting in a three dimensional network.

Related literature top

For background to the biological activity of hydrazines and hydrazones, see: Zahid & Sherazi (1997); Monfared et al. (2007). For a related crystal structure, see: Okabe et al. (1993). For hydrogen-bond graph-set motifs, see: Bernstein et al. (1995).

Experimental top

An aqueous solution (10 ml) containing of 2,4-dinitro-phenylhydrazine (2 mmol) was added to pure acetic acid (10 ml). The obtained solution was stirred at 333 K for 30 min and then left to stand at room temperature. Yellow single crystals of the title compound were obtained after some days.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. An ORTEP view of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are represented as dashed lines.
	Fig. 2. Unit cell packing of the title compound projected along the a axis. The H-atoms not involved in H-bonding are omitted.

N'-(2,4-Dinitrophenyl)acetohydrazide monohydrate top

Crystal data top

C₈H₈N₄O₅·H₂O	F(000) = 536
M_r = 258.20	D_x = 1.549 Mg m⁻³
Monoclinic, P2₁/c	Ag Kα radiation, λ = 0.56083 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 7.702 (2) Å	θ = 9–11°
b = 7.057 (3) Å	µ = 0.08 mm⁻¹
c = 21.550 (4) Å	T = 293 K
β = 109.044 (19)°	Prism, yellow
V = 1107.3 (6) Å³	0.5 × 0.4 × 0.3 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.064
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.2°
Graphite monochromator	h = −12→12
non–profiled ω scans	k = −11→2
7469 measured reflections	l = −36→14
5411 independent reflections	2 standard reflections every 120 min
2771 reflections with I > 2σ(I)	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.071	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.195	w = 1/[σ²(F_o²) + (0.0627P)² + 0.2081P] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max = 0.004
5411 reflections	Δρ_max = 0.25 e Å⁻³
181 parameters	Δρ_min = −0.23 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.027 (4)

Crystal data top

C₈H₈N₄O₅·H₂O	V = 1107.3 (6) Å³
M_r = 258.20	Z = 4
Monoclinic, P2₁/c	Ag Kα radiation, λ = 0.56083 Å
a = 7.702 (2) Å	µ = 0.08 mm⁻¹
b = 7.057 (3) Å	T = 293 K
c = 21.550 (4) Å	0.5 × 0.4 × 0.3 mm
β = 109.044 (19)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.064
7469 measured reflections	2 standard reflections every 120 min
5411 independent reflections	intensity decay: 1%
2771 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.071	3 restraints
wR(F²) = 0.195	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.25 e Å⁻³
5411 reflections	Δρ_min = −0.23 e Å⁻³
181 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
OW	0.8341 (3)	0.6774 (3)	0.23696 (8)	0.0526 (5)
H1W	0.784 (4)	0.583 (3)	0.2497 (13)	0.088 (11)*
H2W	0.827 (4)	0.672 (5)	0.1972 (6)	0.091 (11)*
H2N	0.894 (4)	0.171 (4)	0.1927 (14)	0.073 (9)*
H1N	0.762 (3)	−0.050 (4)	0.2501 (11)	0.052 (7)*
C1	0.6447 (3)	0.1614 (3)	0.12985 (10)	0.0332 (4)
N2	0.7775 (3)	0.1390 (3)	0.18850 (8)	0.0416 (5)
C2	0.6778 (3)	0.2383 (3)	0.07398 (10)	0.0347 (5)
C4	0.3649 (3)	0.2020 (3)	0.00937 (10)	0.0387 (5)
N3	0.8583 (3)	0.2980 (3)	0.07563 (10)	0.0467 (5)
N4	0.2219 (3)	0.2185 (3)	−0.05403 (10)	0.0496 (5)
C3	0.5376 (3)	0.2593 (3)	0.01484 (10)	0.0383 (5)
H3	0.5615	0.3125	−0.0210	0.046*
N1	0.7353 (3)	0.0698 (3)	0.24205 (9)	0.0410 (5)
C6	0.4620 (3)	0.1034 (3)	0.12134 (10)	0.0385 (5)
H6	0.4349	0.0515	0.1568	0.046*
C5	0.3250 (3)	0.1218 (3)	0.06262 (11)	0.0422 (5)
H5	0.2065	0.0815	0.0580	0.051*
O5	0.6823 (3)	0.3600 (3)	0.27355 (9)	0.0607 (5)
C7	0.6972 (3)	0.1892 (3)	0.28405 (10)	0.0388 (5)
O4	0.2556 (3)	0.3098 (3)	−0.09698 (8)	0.0683 (6)
O2	0.8788 (3)	0.3578 (3)	0.02501 (9)	0.0723 (6)
O1	0.9859 (2)	0.2867 (3)	0.12714 (9)	0.0685 (6)
C8	0.6708 (3)	0.1000 (4)	0.34342 (10)	0.0492 (6)
H8A	0.7672	0.1403	0.3820	0.074*
H8B	0.6741	−0.0355	0.3397	0.074*
H8C	0.5542	0.1378	0.3465	0.074*
O3	0.0748 (3)	0.1398 (3)	−0.06187 (10)	0.0722 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
OW	0.0634 (11)	0.0483 (11)	0.0435 (10)	−0.0030 (9)	0.0139 (9)	0.0001 (8)
C1	0.0400 (11)	0.0272 (10)	0.0339 (10)	0.0000 (9)	0.0142 (9)	−0.0027 (9)
N2	0.0431 (10)	0.0511 (12)	0.0333 (9)	−0.0026 (10)	0.0161 (8)	0.0035 (9)
C2	0.0404 (11)	0.0309 (11)	0.0367 (10)	−0.0045 (9)	0.0179 (9)	−0.0028 (9)
C4	0.0432 (12)	0.0331 (11)	0.0358 (10)	0.0044 (10)	0.0074 (9)	−0.0024 (9)
N3	0.0510 (12)	0.0503 (12)	0.0443 (10)	−0.0083 (10)	0.0234 (10)	0.0013 (10)
N4	0.0566 (13)	0.0416 (11)	0.0436 (11)	0.0072 (10)	0.0068 (10)	−0.0066 (10)
C3	0.0543 (14)	0.0305 (11)	0.0339 (10)	−0.0001 (10)	0.0194 (10)	0.0016 (9)
N1	0.0534 (11)	0.0387 (11)	0.0342 (9)	0.0053 (9)	0.0188 (8)	0.0067 (9)
C6	0.0458 (12)	0.0372 (12)	0.0390 (11)	−0.0009 (10)	0.0226 (10)	0.0023 (10)
C5	0.0395 (12)	0.0386 (13)	0.0498 (13)	0.0002 (10)	0.0166 (10)	−0.0039 (10)
O5	0.0877 (13)	0.0382 (10)	0.0690 (12)	0.0093 (9)	0.0431 (11)	0.0063 (9)
C7	0.0399 (11)	0.0404 (13)	0.0378 (11)	0.0004 (10)	0.0152 (9)	0.0037 (10)
O4	0.0883 (14)	0.0697 (13)	0.0383 (9)	0.0014 (11)	0.0090 (9)	0.0087 (10)
O2	0.0695 (12)	0.1000 (16)	0.0573 (11)	−0.0166 (11)	0.0342 (10)	0.0137 (11)
O1	0.0465 (10)	0.1019 (16)	0.0551 (11)	−0.0231 (10)	0.0138 (9)	0.0105 (11)
C8	0.0548 (14)	0.0557 (16)	0.0397 (12)	0.0029 (12)	0.0188 (11)	0.0065 (11)
O3	0.0496 (10)	0.0774 (14)	0.0732 (13)	−0.0013 (11)	−0.0025 (9)	−0.0012 (11)

Geometric parameters (Å, º) top

OW—H1W	0.856 (10)	N4—O3	1.223 (3)
OW—H2W	0.841 (9)	N4—O4	1.224 (3)
C1—N2	1.351 (3)	C3—H3	0.9300
C1—C2	1.418 (3)	N1—C7	1.338 (3)
C1—C6	1.419 (3)	N1—H1N	0.88 (3)
N2—N1	1.386 (2)	C6—C5	1.364 (3)
N2—H2N	0.90 (3)	C6—H6	0.9300
C2—C3	1.384 (3)	C5—H5	0.9300
C2—N3	1.442 (3)	O5—C7	1.225 (3)
C4—C3	1.358 (3)	C7—C8	1.498 (3)
C4—C5	1.400 (3)	C8—H8A	0.9600
C4—N4	1.453 (3)	C8—H8B	0.9600
N3—O1	1.222 (2)	C8—H8C	0.9600
N3—O2	1.227 (2)

H1W—OW—H2W	114 (2)	C4—C3—H3	120.1
N2—C1—C2	123.22 (18)	C2—C3—H3	120.1
N2—C1—C6	120.24 (18)	C7—N1—N2	120.3 (2)
C2—C1—C6	116.53 (18)	C7—N1—H1N	124.5 (16)
C1—N2—N1	120.55 (18)	N2—N1—H1N	113.5 (16)
C1—N2—H2N	119.4 (18)	C5—C6—C1	121.78 (19)
N1—N2—H2N	120.0 (18)	C5—C6—H6	119.1
C3—C2—C1	121.36 (18)	C1—C6—H6	119.1
C3—C2—N3	116.61 (18)	C6—C5—C4	119.25 (19)
C1—C2—N3	122.03 (18)	C6—C5—H5	120.4
C3—C4—C5	121.3 (2)	C4—C5—H5	120.4
C3—C4—N4	118.6 (2)	O5—C7—N1	121.5 (2)
C5—C4—N4	120.1 (2)	O5—C7—C8	122.7 (2)
O1—N3—O2	122.08 (19)	N1—C7—C8	115.7 (2)
O1—N3—C2	119.13 (17)	C7—C8—H8A	109.5
O2—N3—C2	118.79 (19)	C7—C8—H8B	109.5
O3—N4—O4	123.4 (2)	H8A—C8—H8B	109.5
O3—N4—C4	118.5 (2)	C7—C8—H8C	109.5
O4—N4—C4	118.1 (2)	H8A—C8—H8C	109.5
C4—C3—C2	119.74 (19)	H8B—C8—H8C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
OW—H1W···O5	0.86 (1)	1.91 (1)	2.759 (3)	175 (3)
OW—H2W···O4ⁱ	0.84 (1)	2.05 (1)	2.868 (3)	165 (3)
N1—H1N···OWⁱⁱ	0.88 (3)	2.04 (3)	2.883 (3)	160 (2)
N2—H2N···O1	0.90 (3)	1.96 (3)	2.607 (2)	128 (2)
N2—H2N···OWⁱⁱⁱ	0.90 (3)	2.15 (3)	2.910 (3)	142 (2)
C6—H6···O5^iv	0.93	2.40	3.310 (3)	165

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

Experimental details

Crystal data
Chemical formula	C₈H₈N₄O₅·H₂O
M_r	258.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.702 (2), 7.057 (3), 21.550 (4)
β (°)	109.044 (19)
V (Å³)	1107.3 (6)
Z	4
Radiation type	Ag Kα, λ = 0.56083 Å
µ (mm⁻¹)	0.08
Crystal size (mm)	0.5 × 0.4 × 0.3

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7469, 5411, 2771
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.836

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.195, 0.98
No. of reflections	5411
No. of parameters	181
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.23

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
OW—H1W···O5	0.856 (10)	1.905 (11)	2.759 (3)	175 (3)
OW—H2W···O4ⁱ	0.841 (9)	2.047 (13)	2.868 (3)	165 (3)
N1—H1N···OWⁱⁱ	0.88 (3)	2.04 (3)	2.883 (3)	160 (2)
N2—H2N···O1	0.90 (3)	1.96 (3)	2.607 (2)	128 (2)
N2—H2N···OWⁱⁱⁱ	0.90 (3)	2.15 (3)	2.910 (3)	142 (2)
C6—H6···O5^iv	0.93	2.40	3.310 (3)	164.8

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

Acknowledgements

This work was supported by the Tunisian Ministry of HEScR, and the Deanship of Scientific Research at King Saud University is also thanked for funding the paper through the Research Group Project No. RGP-VPP-089.

References

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