1-Chloro-1-[(4-nitro­phen­yl)hydrazinyl­idene]propan-2-one

Abstract

The non-H atoms of the title compound, C₉H₈ClN₃O₃, lie approximately on a plane (r.m.s. deviation = 0.111 Å), and the C=N double bond has a Z configuration. In the crystal, adjacent mol­ecules are linked by an N—H⋯O_carbon­yl hydrogen bond, forming a chain running along [101].

Related literature

For the synthesis, see: Benincori et al. (1990 ▶); Sayed et al. (2002 ▶). For background to the title compound, see: Asiri et al. (2010 ▶).

Experimental

Crystal data

• C₉H₈ClN₃O₃

• M _r = 241.63

• Monoclinic,

• a = 7.0628 (3) Å

• b = 13.4182 (5) Å

• c = 11.2884 (5) Å

• β = 95.589 (4)°

• V = 1064.72 (8) ų

• Z = 4

• Cu Kα radiation

• μ = 3.19 mm⁻¹

• T = 100 K

• 0.20 × 0.10 × 0.05 mm

Data collection

• Agilent SuperNova Dual diffractometer with an Atlas detector

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.568, T _max = 0.857

• 4113 measured reflections

• 2105 independent reflections

• 1839 reflections with I > 2σ(I)

• R _int = 0.020

Refinement

• R[F ² > 2σ(F ²)] = 0.054

• wR(F ²) = 0.152

• S = 1.09

• 2105 reflections

• 150 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 1.21 e Å⁻³

• Δρ_min = −0.48 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811026407/xu5261Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1i	0.85 (4)	2.26 (4)	3.000 (3)	145 (3)

Symmetry code: (i) .

supplementary crystallographic information

Comment

We have previously reported the synthesis of ethyl (Z)-2-chloro-2-(2-phenylhydrazin-1-ylidene) acetate by the reaction of benzenediazonium chloride with ethyl 2-chloro-3-oxobutanoate (Asiri et al., 2010). The compound is an ester. In the present study, the use of a substituted benzenediazonium chloride and the methyl ester (instead of the ethyl ester) afforded a 1-chloro-1-(arylhydrazono)-2-propanone. Such ketones are intermediates in the synthesis of pyrazoles (Sayed et al., 2002) and other heterocycles (Benincori et al., 1990). In the 4-nitro substituted compound (Scheme I, Fig. 1), the non-hydrogen atoms lie on a plane [r.m.s. deviation 0.111 Å] (Scheme I, Fig. 1). The C_aryl–N(H)–N═ C(S)═O portion adopts an extended zigzag conformation. Adjacent molecules are linked by an N–H···O_carbonyl hydrogen bond to form a chain running [1 0 1].

Experimental

To a stirred solution of methyl 2-chloro-3-oxobutanoate (1.64 g, 10 mmol) in ethanol (100 ml) was added sodium acetate trihydrate (1.30 g, 10 mmol). The mixture was chilled to 273 K and then treated with a cold solution of p-nitrobenzenediazonium chloride, prepared by diazotizing p-nitroaniline (1.38 g, 10 mmol) dissolved in 6M hydrochloric acid (6 ml) with a solution of sodium nitrite (0.70 g, 10 mmol) in water (10 ml). The addition of the diazonium salt solution was carried out with rapid stirring over a period of 20 min. The reaction mixture was stirred for further 15 min. and left for 3 h in refrigerator. The resulting solid was collected by filtration and washed thoroughly with water. The crude product was crystallized from ethanol to give the corresponding hydrazonoyl chloride.

Refinement

Carbon-bound H-atoms were placed in calculated positions [C—H 0.95 to 0.98 Å, U_iso(H) 1.2 to 1.5U_eq(C)] and were included in the refinement in the riding model approximation.

The amino H-atom was located in a difference Fourier map, and was freely refined.

The final difference Fourier map had a peak in the vicinity of H6.

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of C9H8ClN3O3 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C9H8ClN3O3	F(000) = 496
Mr = 241.63	Dx = 1.507 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 1647 reflections
a = 7.0628 (3) Å	θ = 3.3–74.3°
b = 13.4182 (5) Å	µ = 3.19 mm−1
c = 11.2884 (5) Å	T = 100 K
β = 95.589 (4)°	Prism, yellow
V = 1064.72 (8) Å3	0.20 × 0.10 × 0.05 mm
Z = 4

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	2105 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1839 reflections with I > 2σ(I)
Mirror	Rint = 0.020
Detector resolution: 10.4041 pixels mm-1	θmax = 74.4°, θmin = 5.1°
ω scans	h = −8→5
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −16→16
Tmin = 0.568, Tmax = 0.857	l = −14→14
4113 measured reflections

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0849P)2 + 0.8946P] where P = (Fo2 + 2Fc2)/3
2105 reflections	(Δ/σ)max = 0.001
150 parameters	Δρmax = 1.21 e Å−3
0 restraints	Δρmin = −0.48 e Å−3

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

	x	y	z	Uiso*/Ueq
Cl1	0.63780 (10)	0.29860 (4)	0.39614 (6)	0.0299 (2)
O1	0.4446 (3)	0.25504 (13)	0.15943 (16)	0.0275 (4)
O2	0.8827 (3)	−0.34157 (14)	0.6658 (2)	0.0369 (5)
O3	1.0132 (3)	−0.25969 (16)	0.81885 (18)	0.0383 (5)
N1	0.6623 (3)	0.10048 (16)	0.37953 (18)	0.0213 (5)
N2	0.7385 (3)	0.09908 (17)	0.49160 (19)	0.0226 (5)
H2	0.753 (5)	0.154 (3)	0.528 (3)	0.042 (10)*
N3	0.9267 (3)	−0.26356 (18)	0.7182 (2)	0.0300 (5)
C1	0.5294 (4)	0.0846 (2)	0.1360 (2)	0.0304 (6)
H1A	0.4572	0.0912	0.0578	0.046*
H1B	0.4743	0.0311	0.1808	0.046*
H1C	0.6622	0.0686	0.1258	0.046*
C2	0.5211 (4)	0.1804 (2)	0.2026 (2)	0.0251 (6)
C3	0.6129 (4)	0.18280 (19)	0.3275 (2)	0.0224 (5)
C4	0.7818 (3)	0.00828 (19)	0.5472 (2)	0.0209 (5)
C5	0.8644 (4)	0.0084 (2)	0.6644 (2)	0.0246 (5)
H5	0.8885	0.0696	0.7054	0.030*
C6	0.9115 (4)	−0.0816 (2)	0.7210 (2)	0.0250 (5)
H6	0.9677	−0.0825	0.8009	0.030*
C7	0.8754 (4)	−0.16926 (19)	0.6594 (2)	0.0237 (5)
C8	0.7916 (4)	−0.17086 (19)	0.5427 (2)	0.0241 (5)
H8	0.7668	−0.2324	0.5026	0.029*
C9	0.7449 (4)	−0.08185 (19)	0.4860 (2)	0.0229 (5)
H9	0.6882	−0.0815	0.4061	0.027*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0424 (4)	0.0166 (4)	0.0299 (4)	0.0005 (2)	0.0002 (3)	0.0006 (2)
O1	0.0353 (10)	0.0225 (9)	0.0246 (9)	0.0050 (8)	0.0026 (8)	0.0069 (7)
O2	0.0469 (12)	0.0195 (10)	0.0448 (12)	0.0028 (9)	0.0070 (10)	0.0060 (9)
O3	0.0513 (13)	0.0354 (11)	0.0272 (10)	0.0140 (10)	−0.0015 (9)	0.0142 (9)
N1	0.0244 (10)	0.0193 (10)	0.0202 (10)	0.0008 (8)	0.0019 (8)	0.0023 (8)
N2	0.0300 (11)	0.0183 (10)	0.0195 (10)	0.0001 (9)	0.0014 (8)	−0.0007 (9)
N3	0.0329 (12)	0.0262 (12)	0.0322 (12)	0.0067 (10)	0.0099 (10)	0.0094 (10)
C1	0.0410 (15)	0.0266 (14)	0.0233 (12)	0.0013 (12)	0.0021 (11)	−0.0004 (11)
C2	0.0279 (12)	0.0229 (12)	0.0253 (13)	0.0009 (10)	0.0066 (10)	0.0058 (10)
C3	0.0265 (12)	0.0169 (11)	0.0244 (12)	0.0022 (10)	0.0062 (10)	0.0026 (10)
C4	0.0214 (11)	0.0179 (12)	0.0242 (12)	0.0006 (9)	0.0060 (9)	0.0034 (10)
C5	0.0291 (12)	0.0206 (13)	0.0245 (12)	−0.0018 (10)	0.0046 (10)	−0.0028 (10)
C6	0.0259 (12)	0.0297 (14)	0.0193 (11)	0.0032 (10)	0.0016 (9)	0.0044 (10)
C7	0.0266 (12)	0.0197 (13)	0.0254 (13)	0.0052 (10)	0.0059 (10)	0.0097 (10)
C8	0.0287 (12)	0.0186 (12)	0.0259 (13)	−0.0007 (10)	0.0071 (10)	−0.0007 (10)
C9	0.0275 (12)	0.0198 (12)	0.0214 (12)	−0.0009 (10)	0.0027 (9)	0.0002 (10)

Geometric parameters (Å, °)

Cl1—C3	1.737 (3)	C1—H1C	0.9800
O1—C2	1.217 (3)	C2—C3	1.494 (4)
O2—N3	1.227 (3)	C4—C5	1.393 (4)
O3—N3	1.238 (3)	C4—C9	1.405 (4)
N1—C3	1.283 (3)	C5—C6	1.391 (4)
N1—N2	1.326 (3)	C5—H5	0.9500
N2—C4	1.391 (3)	C6—C7	1.377 (4)
N2—H2	0.85 (4)	C6—H6	0.9500
N3—C7	1.458 (3)	C7—C8	1.391 (4)
C1—C2	1.493 (4)	C8—C9	1.380 (4)
C1—H1A	0.9800	C8—H8	0.9500
C1—H1B	0.9800	C9—H9	0.9500
C3—N1—N2	121.0 (2)	N2—C4—C5	118.7 (2)
N1—N2—C4	119.6 (2)	N2—C4—C9	120.7 (2)
N1—N2—H2	118 (3)	C5—C4—C9	120.6 (2)
C4—N2—H2	122 (3)	C6—C5—C4	119.6 (2)
O2—N3—O3	123.9 (2)	C6—C5—H5	120.2
O2—N3—C7	118.7 (2)	C4—C5—H5	120.2
O3—N3—C7	117.4 (2)	C7—C6—C5	119.1 (2)
C2—C1—H1A	109.5	C7—C6—H6	120.5
C2—C1—H1B	109.5	C5—C6—H6	120.5
H1A—C1—H1B	109.5	C6—C7—C8	122.1 (2)
C2—C1—H1C	109.5	C6—C7—N3	119.1 (2)
H1A—C1—H1C	109.5	C8—C7—N3	118.8 (2)
H1B—C1—H1C	109.5	C9—C8—C7	119.1 (2)
O1—C2—C1	123.0 (2)	C9—C8—H8	120.4
O1—C2—C3	119.7 (2)	C7—C8—H8	120.4
C1—C2—C3	117.3 (2)	C8—C9—C4	119.5 (2)
N1—C3—C2	119.1 (2)	C8—C9—H9	120.2
N1—C3—Cl1	123.7 (2)	C4—C9—H9	120.2
C2—C3—Cl1	117.12 (18)
C3—N1—N2—C4	176.8 (2)	C5—C6—C7—C8	−0.6 (4)
N2—N1—C3—C2	−177.8 (2)	C5—C6—C7—N3	179.3 (2)
N2—N1—C3—Cl1	−0.4 (3)	O2—N3—C7—C6	175.2 (2)
O1—C2—C3—N1	167.5 (2)	O3—N3—C7—C6	−4.9 (4)
C1—C2—C3—N1	−12.9 (4)	O2—N3—C7—C8	−4.9 (4)
O1—C2—C3—Cl1	−10.0 (3)	O3—N3—C7—C8	175.0 (2)
C1—C2—C3—Cl1	169.63 (19)	C6—C7—C8—C9	0.8 (4)
N1—N2—C4—C5	179.0 (2)	N3—C7—C8—C9	−179.1 (2)
N1—N2—C4—C9	−0.3 (3)	C7—C8—C9—C4	−0.3 (4)
N2—C4—C5—C6	−179.0 (2)	N2—C4—C9—C8	179.2 (2)
C9—C4—C5—C6	0.3 (4)	C5—C4—C9—C8	−0.2 (4)
C4—C5—C6—C7	0.1 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1i	0.85 (4)	2.26 (4)	3.000 (3)	145 (3)

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