N′-(2,4-Dinitro­phen­yl)acetohydrazide

In the title compound, C₈H₈N₄O₅, the nitro groups ortho and para to the hydrazone group are twisted by 10.0 (2) and 3.6 (2)°, respectively, relative to the aromatic ring. The structure exhibits an intra­molecular N—H...O hydrogen bond between the hydrazide and ortho-nitro groups. There is a strong inter­molecular C=O...H—N hydrogen bond, giving rise to chains, and weaker ONO...NO₂ [2.944 (2) Å] and C—H...O—N inter­actions linking the mol­ecules into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.079
• Data-to-parameter ratio = 11.1

checkCIF/PLATON results

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Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           30.57
           From the CIF: _reflns_number_total               1794
           Count of symmetry unique reflns         1797
           Completeness (_total/calc)             99.83%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
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S1. Comment

The chemistry of hydrazones has been intensely investigated in recent years due to their excellent coordinating capability (Domiano et al., 1984) and pharmacological activities (Li et al., 1988). These compounds are also being used as precursors for the efficient synthesis of various condensed heterocycles in organic chemistry (Rudnicka & Osmialowska, 1979) and as highly selective metal scavengers (Sakamoto et al., 1993) in analytical chemistry. In continuation of our ongoing work on the synthesis of various heterocyclic compounds (Zia-ur-Rehman et al., 2005, 2006; Siddiqui et al., 2007), the title compound, (I), was synthesized by reacting 2,4-dinitrophenylhydrazine with acetic anhydride.

Most of the bond lengths and angles in (I) are similar to those in related molecules (Guo, 2007). The nitro groups ortho and para to the hydrazone group are twisted out of this plane by 10.0 (2) and 3.6 (2)°, respectively. The larger twist of the ortho-nitro group arises due to the desire to form an intramolecular hydrogen bond which results in a six-membered ring (Fig. 1 and Table 1). Each molecule also forms an intermolecular N—H···O═C hydrogen bond giving rise to stacks of molecules parallel to a (Fig. 2). The hydrogen-bonded chains of (I) are further linked together into a three-dimensional network (Fig. 3) via weaker C—H···O—N interactions involving the nitro groups and methyl and aryl H atoms (range 2.4–2.6Å) along with some weak ONO···NO₂ interactions [O1···N1ⁱ = 2.944 (2)Å; symmetry code: (i) -0.5+x, 1.5-y, 2-z].

Related literature

For related literature, see: Domiano et al. (1984); Guo (2007); Li et al. (1988); Rudnicka & Osmialowska (1979); Sakamoto et al. (1993); Siddiqui et al. (2007); Zia-ur-Rehman, Choudary & Ahmad (2005); Zia-ur-Rehman, Choudary, Ahmad & Siddiqui (2006).

S2. Experimental

A mixture of 2,4-dinitrophenylhydrazine (1.981 g; 10.0 mmoles) and acetic anhydride (5.0 ml) was stirred for a period of six hours at room temperature. Then, this mixture was poured into ice cooled water and neutralized with 10% sodium bicarbonate solution. The precipitated solids were collected by filtration, washed and dried. Crystals suitable for X-ray crystallography were grown by slow evaporation of solution of the title compound in a mixture of ethanol and water (90:10); m.p. 471 K; yield: 82%.

S3. Refinement

1255 Friedel pairs were merged. H atoms bound to C were placed in geometric positions (C—H distance = 0.95 Å for aryl-H; 0.98 Å for methyl-H) using a riding model. H atoms on N had coordinates freely refined. U_iso values were set to 1.2U_eq of the carrier atom (1.5U_eq for methyl-H).

Computing details

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures

	Fig. 1. The asymmetric unit of the title compound showing the intramolecular hydrogen bond. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Perspective view of molecules linked via intermolecular N—H···O=C hydrogen bonds parallel to a.
	Fig. 3. Perspective view of the three-dimensional crystal packing showing hydrogen-bonds and other intermolecular interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.

N'-(2,4-Dinitrophenyl)acetohydrazide

Crystal data

C8H8N4O5	F(000) = 496
Mr = 240.18	Dx = 1.596 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3491 reflections
a = 4.8585 (4) Å	θ = 2.9–27.8°
b = 10.7703 (8) Å	µ = 0.14 mm^−1
c = 19.1059 (14) Å	T = 150 K
V = 999.76 (13) Å^3	Lath, orange
Z = 4	0.57 × 0.09 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer	1794 independent reflections
Radiation source: fine-focus sealed tube	1616 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ω rotation with narrow frames scans	θmax = 30.6°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −6→6
Tmin = 0.927, Tmax = 0.992	k = −15→15
11843 measured reflections	l = −27→27

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: all non-H atoms found by direct methods
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: geom except NH coords freely refined
wR(F^2) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0462P)^2 + 0.078P] where P = (Fo^2 + 2Fc^2)/3
1794 reflections	(Δ/σ)max < 0.001
161 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.17 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. 1255 Friedel pairs. Friedels merged.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3396 (3)	0.64098 (13)	0.89834 (7)	0.0206 (3)
N1	0.1186 (2)	0.67553 (11)	0.94555 (6)	0.0239 (2)
O1	0.0352 (2)	0.78314 (10)	0.94499 (6)	0.0298 (2)
O2	0.0219 (2)	0.59512 (11)	0.98457 (6)	0.0349 (3)
C2	0.4679 (3)	0.73783 (13)	0.86286 (7)	0.0234 (3)
H2	0.4153	0.8215	0.8710	0.028*
C3	0.6722 (3)	0.70968 (14)	0.81593 (7)	0.0245 (3)
N2	0.8161 (3)	0.81093 (13)	0.78132 (7)	0.0323 (3)
O3	0.7483 (3)	0.91873 (12)	0.79517 (7)	0.0428 (3)
O4	1.0012 (3)	0.78354 (13)	0.73998 (7)	0.0462 (3)
C4	0.7508 (3)	0.58725 (15)	0.80240 (7)	0.0253 (3)
H4A	0.8903	0.5700	0.7689	0.030*
C5	0.6255 (3)	0.49242 (13)	0.83774 (7)	0.0231 (3)
H5	0.6791	0.4093	0.8283	0.028*
C6	0.4174 (3)	0.51517 (13)	0.88817 (7)	0.0200 (3)
N3	0.3089 (3)	0.42103 (11)	0.92557 (7)	0.0243 (3)
H3	0.172 (4)	0.4329 (16)	0.9508 (10)	0.029*
N4	0.3548 (3)	0.29805 (11)	0.90659 (7)	0.0222 (2)
H4	0.518 (4)	0.2710 (16)	0.9126 (10)	0.027*
C7	0.1401 (3)	0.21961 (13)	0.91490 (7)	0.0222 (3)
O5	−0.0894 (2)	0.25786 (10)	0.93114 (6)	0.0291 (2)
C8	0.2055 (4)	0.08501 (14)	0.90370 (9)	0.0310 (3)
H8A	0.1747	0.0392	0.9473	0.047*
H8B	0.3984	0.0764	0.8895	0.047*
H8C	0.0861	0.0515	0.8669	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0161 (6)	0.0247 (6)	0.0211 (6)	−0.0007 (5)	−0.0003 (5)	−0.0036 (5)
N1	0.0187 (5)	0.0254 (5)	0.0276 (6)	−0.0018 (5)	0.0007 (5)	−0.0083 (5)
O1	0.0243 (5)	0.0272 (5)	0.0380 (6)	0.0046 (4)	−0.0021 (5)	−0.0092 (4)
O2	0.0334 (6)	0.0304 (6)	0.0408 (6)	−0.0044 (5)	0.0178 (5)	−0.0053 (5)
C2	0.0218 (6)	0.0241 (6)	0.0242 (6)	−0.0029 (5)	−0.0050 (5)	0.0001 (5)
C3	0.0229 (6)	0.0303 (7)	0.0203 (6)	−0.0070 (6)	−0.0027 (5)	0.0046 (5)
N2	0.0323 (7)	0.0384 (7)	0.0262 (6)	−0.0125 (6)	−0.0069 (6)	0.0095 (5)
O3	0.0475 (8)	0.0320 (6)	0.0489 (7)	−0.0124 (6)	−0.0052 (6)	0.0114 (5)
O4	0.0430 (7)	0.0581 (8)	0.0374 (6)	−0.0177 (7)	0.0111 (6)	0.0105 (6)
C4	0.0203 (7)	0.0352 (7)	0.0203 (6)	−0.0025 (6)	0.0020 (5)	0.0001 (6)
C5	0.0205 (6)	0.0267 (6)	0.0221 (6)	0.0012 (5)	0.0029 (5)	−0.0024 (5)
C6	0.0161 (6)	0.0238 (6)	0.0200 (6)	−0.0007 (5)	−0.0006 (5)	−0.0014 (5)
N3	0.0210 (6)	0.0217 (5)	0.0301 (6)	0.0006 (5)	0.0084 (5)	−0.0019 (5)
N4	0.0154 (5)	0.0200 (5)	0.0312 (6)	0.0011 (4)	0.0006 (5)	−0.0004 (5)
C7	0.0182 (6)	0.0256 (6)	0.0228 (6)	−0.0011 (5)	−0.0022 (5)	0.0029 (5)
O5	0.0159 (5)	0.0339 (6)	0.0375 (6)	−0.0002 (4)	0.0012 (4)	0.0046 (5)
C8	0.0308 (8)	0.0235 (6)	0.0389 (8)	−0.0011 (6)	−0.0008 (7)	0.0019 (6)

Geometric parameters (Å, º)

C1—C2	1.3915 (19)	C5—C6	1.4178 (18)
C1—C6	1.4202 (19)	C5—H5	0.9500
C1—N1	1.4508 (18)	C6—N3	1.3477 (18)
N1—O1	1.2278 (16)	N3—N4	1.3913 (17)
N1—O2	1.2354 (16)	N3—H3	0.83 (2)
C2—C3	1.371 (2)	N4—C7	1.3519 (18)
C2—H2	0.9500	N4—H4	0.85 (2)
C3—C4	1.397 (2)	C7—O5	1.2282 (17)
C3—N2	1.4543 (19)	C7—C8	1.500 (2)
N2—O4	1.233 (2)	C8—H8A	0.9800
N2—O3	1.2355 (19)	C8—H8B	0.9800
C4—C5	1.367 (2)	C8—H8C	0.9800
C4—H4A	0.9500
C2—C1—C6	121.96 (13)	C6—C5—H5	119.2
C2—C1—N1	116.25 (12)	N3—C6—C5	120.61 (13)
C6—C1—N1	121.79 (12)	N3—C6—C1	122.76 (12)
O1—N1—O2	122.79 (12)	C5—C6—C1	116.59 (12)
O1—N1—C1	118.74 (12)	C6—N3—N4	121.01 (12)
O2—N1—C1	118.47 (12)	C6—N3—H3	120.3 (12)
C3—C2—C1	118.50 (13)	N4—N3—H3	115.2 (12)
C3—C2—H2	120.8	C7—N4—N3	116.14 (12)
C1—C2—H2	120.8	C7—N4—H4	119.2 (12)
C2—C3—C4	121.83 (13)	N3—N4—H4	116.0 (13)
C2—C3—N2	118.65 (14)	O5—C7—N4	121.37 (13)
C4—C3—N2	119.49 (13)	O5—C7—C8	123.55 (14)
O4—N2—O3	123.81 (14)	N4—C7—C8	115.07 (13)
O4—N2—C3	117.56 (14)	C7—C8—H8A	109.5
O3—N2—C3	118.63 (15)	C7—C8—H8B	109.5
C5—C4—C3	119.47 (13)	H8A—C8—H8B	109.5
C5—C4—H4A	120.3	C7—C8—H8C	109.5
C3—C4—H4A	120.3	H8A—C8—H8C	109.5
C4—C5—C6	121.60 (13)	H8B—C8—H8C	109.5
C4—C5—H5	119.2
C2—C1—N1—O1	9.02 (18)	N2—C3—C4—C5	176.53 (13)
C6—C1—N1—O1	−170.04 (13)	C3—C4—C5—C6	−0.2 (2)
C2—C1—N1—O2	−171.10 (12)	C4—C5—C6—N3	−175.76 (14)
C6—C1—N1—O2	9.84 (19)	C4—C5—C6—C1	2.1 (2)
C6—C1—C2—C3	1.1 (2)	C2—C1—C6—N3	175.25 (13)
N1—C1—C2—C3	−177.94 (12)	N1—C1—C6—N3	−5.7 (2)
C1—C2—C3—C4	0.9 (2)	C2—C1—C6—C5	−2.53 (19)
C1—C2—C3—N2	−177.00 (13)	N1—C1—C6—C5	176.47 (12)
C2—C3—N2—O4	179.13 (13)	C5—C6—N3—N4	−13.1 (2)
C4—C3—N2—O4	1.2 (2)	C1—C6—N3—N4	169.18 (13)
C2—C3—N2—O3	−0.3 (2)	C6—N3—N4—C7	−142.12 (14)
C4—C3—N2—O3	−178.27 (14)	N3—N4—C7—O5	7.5 (2)
C2—C3—C4—C5	−1.3 (2)	N3—N4—C7—C8	−171.84 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2	0.83 (2)	2.001 (18)	2.5942 (16)	127.9 (16)
N4—H4···O5^i	0.85 (2)	1.95 (2)	2.7748 (16)	164.0 (17)
C5—H5···O4^ii	0.95	2.44	3.249 (2)	143
C8—H8A···O2^iii	0.98	2.58	3.269 (2)	128
C8—H8C···O3^iv	0.98	2.57	3.527 (2)	165

Symmetry codes: (i) x+1, y, z; (ii) −x+2, y−1/2, −z+3/2; (iii) x+1/2, −y+1/2, −z+2; (iv) x−1, y−1, z.