3-Penta­none 2,4-dinitro­phenyl­hydrazone

Crystals of the title compound, C₁₁H₁₄N₄O₄, were obtained from a condensation reaction of 2,4-dinitro­phenyl­hydrazine and 3-penta­none. In the crystal structure, the mol­ecule, except one methyl group, displays a nearly planar structure. The imino group links to the adjacent nitro group via intra­molecular hydrogen bonding. The partially overlapped arrangement and face-to-face separation of 3.410 (9) Å between parallel benzene rings indicate the existence of π–π stacking between adjacent mol­ecules. The crystal structure also contains weak inter­molecular C—H...O hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.044
• wR factor = 0.137
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

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Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C7     --  C10     ..       9.72 su

Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         44 Perc.

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
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S1. Comment

As some phenylhydrazone derivatives have shown to be potentially DNA damaging and mutagenic agents (Okabe et al., 1993), a series of new phenylhydrazone derivatives have been synthesized in our laboratory (Shan et al., 2003; Shan et al., 2006). As part of the ongoing investigation, the title compound has recently been prepared and its crystal structure is reported here.

The molecular structure of the title compound is shown in Fig. 1. The molecule, except the C11-methyl group, displays a nearly co-planar structure, the angle between the C11—C10 bond and C1/N3/N4/C7/C8/C9 mean plane being 61.4 (2)°. The N4—C7 bond distance is significantly shorter than N3—N4 and N3—C1 bond distances (Table 1), and indicates the typical C═N double bond. The imino group links with adjacent nitro group via intra-molecular hydrogen bonding (Fig. 1 and Table 2), which agrees with that found in related structures, e.g. furyl methyl ketone 2,4-dinitrophenylhydrazone (Shan et al., 2008a) and 2-thiazolyl methyl ketone 2,4-dinitrophenylhydrazone (Shan et al., 2008b).

A partially overlapped arrangement between parallel benzene rings of the adjacent molecules is illustrated in Fig. 2. The face-to-face separation of 3.410 (9) Å between C1-benzene and C1ⁱ-benzene rings [symmetry code: (i) 1 - x,1 - y,-z] is significantly shorter than van der Waals thickness of the aromatic ring (3.70 Å, Cotton & Wilkinson, 1972) and indicates the existence of π-π stacking in the crystal structure. The crystal structure also contains intermolecular weak C—H···O hydrogen bonding (Table 2).

Related literature

For general background, see: Okabe et al. (1993); Shan et al. (2003); Shan et al. (2006). For related structures, see: Shan et al. (2008a,b); Cotton & Wilkinson (1972).

S2. Experimental

2,4-Dinitrophenylhydrazine (0.4 g, 2 mmol) was dissolved in ethanol (10 ml), and H₂SO₄ solution (98%, 0.5 ml) was slowly added to the ethanol solution with stirring. The solution was heated at about 333 K for several min until the solution cleared. 3-Pentanone (0.17 g, 2 mmol) was then added to the above solution with continuous stirring. The mixture was refluxed for 30 min. When the solution had cooled to room temperature red powder crystals appeared. The powder crystals were separated and washed with water three times. Recrystallization from absolute ethanol solution yielded well shaped single crystals of the title compound.

S3. Refinement

Imino H atom was located in a difference Fourier map and refined isotropically. Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and torsion angles were refined to fit the electron density, U_iso(H) = 1.5U_eq(C). Other H atoms were placed in calculated positions with C—H = 0.93 (aromatic) and 0.97 Å (methylene), and refined in riding mode with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of the title compound with 30% probability displacement ellipsoids for non-H atoms, dashed line indicates hydrogen bonding.
	Fig. 2. A diagram showing the partially overlapped arrangement of benzene rings [symmetry code: (i) 1 - x,1 - y,-z].

3-Pentanone 2,4-dinitrophenylhydrazone

Crystal data

C11H14N4O4	F(000) = 560
Mr = 266.26	Dx = 1.356 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 2556 reflections
a = 12.5298 (15) Å	θ = 3.5–25.0°
b = 14.089 (2) Å	µ = 0.11 mm^−1
c = 7.3983 (8) Å	T = 294 K
β = 93.235 (12)°	Prism, red
V = 1303.9 (3) Å^3	0.31 × 0.29 × 0.22 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer	1130 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 26.0°, θmin = 3.1°
Detector resolution: 10.00 pixels mm^-1	h = −15→15
ω scans	k = −17→17
10943 measured reflections	l = −9→8
2543 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.136	w = 1/[σ^2(Fo^2) + (0.0627P)^2 + 0.0303P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
2543 reflections	Δρmax = 0.15 e Å^−3
179 parameters	Δρmin = −0.12 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (2)

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
N1	0.49005 (19)	0.29067 (16)	0.0607 (3)	0.0817 (6)
N2	0.79233 (17)	0.4911 (2)	0.2228 (3)	0.0928 (7)
N3	0.35067 (15)	0.43228 (17)	0.2123 (3)	0.0742 (6)
N4	0.28589 (14)	0.50533 (14)	0.2635 (2)	0.0758 (6)
O1	0.39384 (16)	0.27125 (13)	0.0591 (3)	0.1056 (6)
O2	0.55348 (16)	0.23773 (14)	−0.0069 (3)	0.1145 (7)
O3	0.84951 (15)	0.42733 (18)	0.1731 (3)	0.1230 (8)
O4	0.82618 (14)	0.56837 (18)	0.2750 (3)	0.1248 (8)
C1	0.45801 (16)	0.44522 (16)	0.2116 (2)	0.0610 (6)
C2	0.52770 (16)	0.37825 (16)	0.1427 (2)	0.0636 (6)
C3	0.63704 (17)	0.39319 (17)	0.1474 (3)	0.0707 (6)
H3	0.6823	0.3478	0.1019	0.085*
C4	0.67726 (16)	0.47555 (18)	0.2196 (3)	0.0687 (6)
C5	0.61123 (17)	0.54410 (17)	0.2870 (3)	0.0696 (6)
H5	0.6402	0.6000	0.3352	0.083*
C6	0.50387 (17)	0.52968 (16)	0.2827 (3)	0.0665 (6)
H6	0.4599	0.5763	0.3275	0.080*
C7	0.18529 (19)	0.4892 (2)	0.2520 (3)	0.0854 (7)
C8	0.11384 (19)	0.5688 (2)	0.3035 (4)	0.1065 (9)
H8A	0.0615	0.5796	0.2040	0.128*
H8B	0.0752	0.5485	0.4068	0.128*
C9	0.1670 (2)	0.6608 (2)	0.3497 (4)	0.1228 (11)
H9A	0.2204	0.6513	0.4462	0.184*
H9B	0.1148	0.7054	0.3874	0.184*
H9C	0.2001	0.6851	0.2453	0.184*
C10	0.1317 (2)	0.3981 (2)	0.1833 (4)	0.1104 (10)
H10A	0.0593	0.4123	0.1380	0.132*
H10B	0.1703	0.3733	0.0836	0.132*
C11	0.1285 (3)	0.3250 (3)	0.3265 (4)	0.1350 (11)
H11A	0.2002	0.3082	0.3670	0.202*
H11B	0.0920	0.2697	0.2788	0.202*
H11C	0.0914	0.3496	0.4264	0.202*
H3N	0.3286 (18)	0.3785 (18)	0.167 (3)	0.092 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0977 (15)	0.0693 (15)	0.0780 (13)	0.0007 (13)	0.0042 (12)	−0.0036 (11)
N2	0.0699 (15)	0.116 (2)	0.0930 (15)	−0.0022 (14)	0.0047 (11)	0.0069 (14)
N3	0.0693 (13)	0.0696 (15)	0.0838 (13)	−0.0045 (12)	0.0044 (10)	0.0017 (11)
N4	0.0664 (12)	0.0779 (15)	0.0833 (12)	0.0052 (10)	0.0063 (9)	0.0082 (10)
O1	0.1008 (13)	0.0832 (14)	0.1323 (15)	−0.0184 (11)	0.0006 (11)	−0.0159 (11)
O2	0.1273 (15)	0.0911 (15)	0.1265 (16)	0.0073 (12)	0.0198 (12)	−0.0373 (12)
O3	0.0742 (11)	0.143 (2)	0.1533 (19)	0.0159 (12)	0.0156 (11)	−0.0054 (14)
O4	0.0865 (13)	0.138 (2)	0.1503 (18)	−0.0311 (13)	0.0091 (11)	−0.0206 (15)
C1	0.0659 (13)	0.0637 (16)	0.0532 (11)	−0.0012 (11)	0.0020 (10)	0.0093 (10)
C2	0.0733 (14)	0.0604 (15)	0.0570 (12)	0.0004 (12)	0.0022 (10)	0.0053 (11)
C3	0.0761 (15)	0.0749 (17)	0.0613 (13)	0.0131 (12)	0.0072 (11)	0.0077 (11)
C4	0.0618 (13)	0.0807 (17)	0.0637 (13)	−0.0006 (13)	0.0040 (10)	0.0075 (12)
C5	0.0746 (15)	0.0700 (16)	0.0637 (12)	−0.0068 (12)	0.0010 (11)	0.0018 (11)
C6	0.0700 (14)	0.0647 (15)	0.0647 (13)	0.0042 (11)	0.0043 (10)	0.0014 (11)
C7	0.0660 (15)	0.099 (2)	0.0907 (17)	−0.0043 (14)	0.0038 (12)	0.0060 (14)
C8	0.0719 (16)	0.124 (3)	0.124 (2)	0.0170 (17)	0.0121 (15)	0.0007 (19)
C9	0.104 (2)	0.103 (3)	0.163 (3)	0.0176 (18)	0.0196 (19)	−0.003 (2)
C10	0.0770 (17)	0.136 (3)	0.118 (2)	−0.0064 (17)	0.0036 (16)	0.002 (2)
C11	0.147 (3)	0.123 (3)	0.135 (3)	−0.027 (2)	0.015 (2)	−0.001 (2)

Geometric parameters (Å, º)

N1—O2	1.218 (2)	C5—H5	0.9300
N1—O1	1.235 (2)	C6—H6	0.9300
N1—C2	1.442 (3)	C7—C8	1.497 (4)
N2—O3	1.219 (3)	C7—C10	1.523 (4)
N2—O4	1.222 (3)	C8—C9	1.489 (4)
N2—C4	1.457 (3)	C8—H8A	0.9700
N3—C1	1.358 (3)	C8—H8B	0.9700
N3—N4	1.377 (3)	C9—H9A	0.9600
N3—H3N	0.87 (2)	C9—H9B	0.9600
N4—C7	1.279 (3)	C9—H9C	0.9600
C1—C2	1.401 (3)	C10—C11	1.479 (4)
C1—C6	1.410 (3)	C10—H10A	0.9700
C2—C3	1.385 (3)	C10—H10B	0.9700
C3—C4	1.362 (3)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—C5	1.383 (3)	C11—H11C	0.9600
C5—C6	1.359 (3)
O2—N1—O1	121.3 (2)	N4—C7—C8	116.9 (2)
O2—N1—C2	119.4 (2)	N4—C7—C10	125.9 (2)
O1—N1—C2	119.3 (2)	C8—C7—C10	117.2 (2)
O3—N2—O4	123.5 (2)	C9—C8—C7	116.4 (2)
O3—N2—C4	118.8 (3)	C9—C8—H8A	108.2
O4—N2—C4	117.7 (3)	C7—C8—H8A	108.2
C1—N3—N4	120.0 (2)	C9—C8—H8B	108.2
C1—N3—H3N	114.2 (16)	C7—C8—H8B	108.2
N4—N3—H3N	125.4 (16)	H8A—C8—H8B	107.4
C7—N4—N3	116.3 (2)	C8—C9—H9A	109.5
N3—C1—C2	123.3 (2)	C8—C9—H9B	109.5
N3—C1—C6	119.7 (2)	H9A—C9—H9B	109.5
C2—C1—C6	117.06 (19)	C8—C9—H9C	109.5
C3—C2—C1	121.6 (2)	H9A—C9—H9C	109.5
C3—C2—N1	116.1 (2)	H9B—C9—H9C	109.5
C1—C2—N1	122.2 (2)	C11—C10—C7	112.2 (2)
C4—C3—C2	118.9 (2)	C11—C10—H10A	109.2
C4—C3—H3	120.6	C7—C10—H10A	109.2
C2—C3—H3	120.6	C11—C10—H10B	109.2
C3—C4—C5	121.4 (2)	C7—C10—H10B	109.2
C3—C4—N2	118.6 (2)	H10A—C10—H10B	107.9
C5—C4—N2	120.0 (2)	C10—C11—H11A	109.5
C6—C5—C4	119.9 (2)	C10—C11—H11B	109.5
C6—C5—H5	120.0	H11A—C11—H11B	109.5
C4—C5—H5	120.0	C10—C11—H11C	109.5
C5—C6—C1	121.1 (2)	H11A—C11—H11C	109.5
C5—C6—H6	119.4	H11B—C11—H11C	109.5
C1—C6—H6	119.4

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O1	0.87 (2)	1.91 (2)	2.606 (3)	136 (2)
C5—H5···O1^i	0.93	2.58	3.399 (3)	147

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