Propanone 2-chloro-4,6-di­nitro­phenyl­hydrazone

The molecule of the title compound, C₉H₉ClN₄O₄, is nearly planer except for the ortho-nitro group, with the non-H atoms exhibiting an average deviation of 0.099 Å from the mean plane. The ortho-nitro group is nearly perpendicular to the phenyl group, with a dihedral angle of 88.46 (3)°. The N-N and N=C bond lengths of the iso­propyl­idene-hydrazine moiety are 1.3928 (14) and 1.2865 (15) Å, respectively.

Key indicators

• Single-crystal X-ray study
• T = 93 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.030
• wR factor = 0.103
• Data-to-parameter ratio = 12.8

checkCIF results

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ADDSYM reports no extra symmetry

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S1. Comment

The structures of a wide range of 2,4-dinitrophenylhydrazones have been studied extensively, particularly with respect to the hydrogen bonding (Fronczek, 1994; Kaberia et al., 1980; Vickery et al., 1981). In most of these compounds, the ortho-nitro group forms a strong intramolecular hydrogen bond to the imino-group and nearly all the atoms are coplanar (Fronczek, 1994; Vickery et al., 1981).

However, the introduction of a chlorine atom to the other ortho-position drastically changes the molecular structure. When an ortho-chlorine atom is present, there are no intra- and inter-molecular hydrogen bonds. The ortho-nitro group of the title compound, (I), is nearly perpendicular to the phenyl group, with an O1—N3—C5—C6 torsion angle of 88.7 (2)°.

S2. Experimental

The title compound was synthesized according to the method of Kawai et al. (2002). Spectroscopic analysis for (I), ¹H NMR (CDCL₃, 300 MHz, δ, p.p.m.): 2.02(s, 3H), 2.06(s, 3H), 8.36(d, 1H, J=2.54 Hz), 8.46(s, 1H), 8.50(d, 1H, J=2.54 Hz). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of a methylene chloride solution at room temperature.

S3. Refinement

H atoms were found in the difference Fourier maps and refined isotropically, with C—H distances in the range 0.87 (1)–0.88 (2) Å for aromatic-H and 0.96 (2)–1.01 (2) Å for alkyl-H, and an N—H distance of 0.85 (2) Å.

Computing details

Data collection: CrystalClear (Rigaku/MSC and Rigaku Corporation, 2001); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC and Rigaku Corporation, 2001); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Watkin et al., 1999); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: please supply.

Figures

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

propane-2-one 6-chloro-2,4-dinitrophenylhydrazone

Crystal data

C9H9ClN4O4	F(000) = 560.00
Mr = 272.65	Dx = 1.609 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2yab	Cell parameters from 3753 reflections
a = 8.6057 (11) Å	θ = 1.5–13.7°
b = 16.110 (1) Å	µ = 0.35 mm^−1
c = 8.9967 (11) Å	T = 93 K
β = 115.557 (5)°	Prism, yellow
V = 1125.3 (2) Å^3	0.47 × 0.38 × 0.22 mm
Z = 4

Data collection

Rigaku Mercury diffractometer	Rint = 0.020
Detector resolution: 14.62 pixels mm^-1	θmax = 27.5°
ω scans	h = −11→9
8602 measured reflections	k = −20→20
2545 independent reflections	l = −11→11
2376 reflections with F^2 > 2σ(F^2)

Refinement

Refinement on F^2	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.030	w = 1/[0.0012Fo^2 + 1.0000σ^2(Fo)]/(4Fo^2)
wR(F^2) = 0.103	(Δ/σ)max = 0.004
S = 1.03	Δρmax = 0.38 e Å^−3
2545 reflections	Δρmin = −0.32 e Å^−3
199 parameters

Special details

Refinement. Refinement using reflections with F² > 0.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
Cl1	0.33699 (3)	0.43411 (2)	0.45674 (4)	0.02049 (10)
O1	−0.31962 (12)	0.60709 (6)	0.13845 (12)	0.0231 (3)
O2	−0.35061 (11)	0.51900 (6)	−0.05483 (11)	0.0198 (2)
O3	−0.36916 (11)	0.32077 (6)	0.42289 (11)	0.0197 (2)
O4	−0.11639 (12)	0.27118 (6)	0.58146 (11)	0.0205 (2)
N1	0.00184 (13)	0.60166 (6)	0.08574 (12)	0.0143 (2)
N2	0.09849 (13)	0.54896 (6)	0.21565 (13)	0.0146 (2)
N3	−0.28442 (12)	0.54264 (6)	0.08914 (13)	0.0142 (2)
N4	−0.21164 (13)	0.31848 (6)	0.47281 (12)	0.0137 (2)
C1	−0.0154 (2)	0.71643 (8)	−0.0845 (2)	0.0197 (3)
C2	0.0865 (2)	0.66020 (7)	0.0565 (1)	0.0144 (3)
C3	0.2764 (2)	0.67653 (8)	0.1505 (2)	0.0182 (3)
C4	0.0170 (1)	0.49174 (7)	0.2672 (1)	0.0120 (3)
C5	−0.1624 (1)	0.48569 (7)	0.21387 (13)	0.0115 (3)
C6	−0.2386 (2)	0.42925 (7)	0.2776 (1)	0.0122 (3)
C7	−0.1329 (1)	0.37593 (7)	0.40036 (13)	0.0119 (3)
C8	0.0451 (2)	0.37700 (7)	0.4577 (1)	0.0127 (3)
C9	0.1160 (1)	0.43322 (7)	0.3906 (1)	0.0126 (3)
H1	−0.007 (2)	0.7729 (11)	−0.048 (2)	0.028 (4)*
H2	0.040 (2)	0.7162 (10)	−0.158 (2)	0.024 (4)*
H3	−0.137 (2)	0.6948 (10)	−0.146 (2)	0.027 (4)*
H4	0.299 (2)	0.7333 (11)	0.134 (2)	0.029 (4)*
H5	0.320 (2)	0.6666 (11)	0.268 (2)	0.039 (5)*
H6	0.349 (2)	0.6370 (12)	0.123 (2)	0.035 (5)*
H7	0.206 (3)	0.5449 (11)	0.243 (2)	0.035 (5)*
H8	−0.351 (2)	0.4269 (9)	0.245 (2)	0.020 (4)*
H9	0.115 (2)	0.3454 (10)	0.537 (2)	0.024 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0086 (2)	0.0238 (2)	0.0277 (2)	0.00171 (10)	0.0065 (1)	0.00650 (11)
O1	0.0282 (5)	0.0163 (5)	0.0270 (5)	0.0088 (4)	0.0140 (4)	0.0032 (4)
O2	0.0156 (4)	0.0250 (5)	0.0140 (4)	−0.0017 (4)	0.0018 (3)	0.0006 (3)
O3	0.0138 (4)	0.0234 (5)	0.0234 (5)	−0.0036 (3)	0.0093 (4)	0.0023 (4)
O4	0.0219 (5)	0.0174 (5)	0.0236 (5)	0.0046 (3)	0.0111 (4)	0.0084 (3)
N1	0.0158 (5)	0.0139 (5)	0.0134 (5)	−0.0009 (4)	0.0064 (4)	−0.0001 (4)
N2	0.0109 (5)	0.0149 (5)	0.0176 (5)	−0.0008 (4)	0.0058 (4)	0.0026 (4)
N3	0.0109 (5)	0.0157 (5)	0.0163 (5)	−0.0010 (4)	0.0062 (4)	0.0024 (4)
N4	0.0170 (5)	0.0110 (5)	0.0144 (5)	−0.0010 (4)	0.0081 (4)	−0.0003 (4)
C1	0.0277 (7)	0.0160 (6)	0.0156 (6)	−0.0017 (5)	0.0097 (5)	0.0011 (5)
C2	0.0182 (6)	0.0138 (5)	0.0136 (5)	−0.0017 (4)	0.0091 (5)	−0.0036 (4)
C3	0.0185 (6)	0.0170 (6)	0.0214 (6)	−0.0045 (5)	0.0107 (5)	−0.0005 (5)
C4	0.0128 (6)	0.0106 (5)	0.0138 (5)	−0.0007 (4)	0.0068 (4)	−0.0025 (4)
C5	0.0108 (5)	0.0118 (5)	0.0109 (5)	0.0006 (4)	0.0038 (4)	−0.0004 (4)
C6	0.0105 (6)	0.0124 (5)	0.0136 (5)	−0.0011 (4)	0.0049 (4)	−0.0015 (4)
C7	0.0134 (5)	0.0110 (5)	0.0129 (5)	−0.0024 (4)	0.0072 (4)	−0.0021 (4)
C8	0.0133 (5)	0.0113 (5)	0.0121 (5)	0.0023 (4)	0.0039 (4)	−0.0006 (4)
C9	0.0079 (5)	0.0136 (6)	0.0149 (5)	0.0001 (4)	0.0036 (4)	−0.0021 (4)

Geometric parameters (Å, º)

Cl1—C9	1.7303 (12)	C1—H3	1.01 (2)
O1—N3	1.2177 (14)	C2—C3	1.5039 (16)
O2—N3	1.2291 (14)	C3—H4	0.96 (2)
O3—N4	1.2310 (13)	C3—H5	0.97 (2)
O4—N4	1.2316 (13)	C3—H6	0.99 (2)
N1—N2	1.3928 (14)	C4—C5	1.4088 (15)
N1—C2	1.2865 (15)	C4—C9	1.4249 (15)
N2—C4	1.3552 (15)	C5—C6	1.3820 (15)
N2—H7	0.85 (2)	C6—C7	1.3848 (16)
N3—C5	1.4787 (14)	C6—H8	0.88 (2)
N4—C7	1.4568 (14)	C7—C8	1.3896 (15)
C1—C2	1.4961 (16)	C8—C9	1.3697 (16)
C1—H1	0.96 (2)	C8—H9	0.871 (13)
C1—H2	0.97 (2)
N2—N1—C2	115.6 (1)	C2—C3—H6	113.2 (11)
N1—N2—C4	119.5 (1)	H4—C3—H6	112.6 (15)
N1—N2—H7	117.9 (12)	H5—C3—H6	100.0 (16)
C4—N2—H7	120.6 (12)	N2—C4—C5	125.7 (1)
O1—N3—O2	125.0 (1)	N2—C4—C9	119.5 (1)
O1—N3—C5	117.3 (1)	C5—C4—C9	114.8 (1)
O2—N3—C5	117.5 (1)	N3—C5—C4	122.1 (1)
O3—N4—O4	124.0 (1)	N3—C5—C6	114.5 (1)
O3—N4—C7	118.00 (9)	C4—C5—C6	123.4 (1)
O4—N4—C7	118.0 (1)	C5—C6—C7	118.24 (11)
C2—C1—H1	110.7 (11)	C5—C6—H8	122.7 (10)
C2—C1—H2	107.2 (10)	C7—C6—H8	119.0 (10)
H1—C1—H2	104.3 (15)	N4—C7—C6	118.6 (1)
C2—C1—H3	110.1 (11)	N4—C7—C8	119.5 (1)
H1—C1—H3	115.1 (15)	C6—C7—C8	121.9 (1)
H2—C1—H3	108.9 (15)	C7—C8—C9	118.3 (1)
N1—C2—C1	116.15 (11)	C7—C8—H9	124.2 (10)
N1—C2—C3	125.95 (11)	C9—C8—H9	117.5 (10)
C1—C2—C3	117.9 (1)	Cl1—C9—C4	117.49 (9)
C2—C3—H4	108.8 (11)	Cl1—C9—C8	119.09 (9)
C2—C3—H5	113.4 (12)	C4—C9—C8	123.4 (1)
H4—C3—H5	108.6 (16)
C2—N1—N2—C4	172.4 (2)	C9—C4—C5—N3	178.7 (1)
N2—N1—C2—C1	179.1 (1)	C9—C4—C5—C6	1.5 (2)
N2—N1—C2—C3	−0.8 (2)	N2—C4—C9—Cl1	−4.8 (2)
N1—N2—C4—C5	−7.9 (2)	N2—C4—C9—C8	175.4 (2)
N1—N2—C4—C9	174.8 (1)	C5—C4—C9—Cl1	177.59 (12)
O1—N3—C5—C4	−88.6 (2)	C5—C4—C9—C8	−2.2 (2)
O1—N3—C5—C6	88.7 (2)	N3—C5—C6—C7	−177.3 (1)
O2—N3—C5—C4	95.8 (2)	C4—C5—C6—C7	0.0 (3)
O2—N3—C5—C6	−86.8 (2)	C5—C6—C7—N4	177.6 (1)
O3—N4—C7—C6	−1.0 (2)	C5—C6—C7—C8	−1.1 (2)
O3—N4—C7—C8	177.8 (1)	N4—C7—C8—C9	−178.2 (1)
O4—N4—C7—C6	179.8 (1)	C6—C7—C8—C9	0.5 (3)
O4—N4—C7—C8	−1.5 (2)	C7—C8—C9—Cl1	−178.54 (12)
N2—C4—C5—N3	1.2 (3)	C7—C8—C9—C4	1.3 (2)
N2—C4—C5—C6	−176.0 (2)