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

Asiri, A.M.; Al-Youbi, A.O.; Zayed, M.E.M.; Ng, S.W.

doi:10.1107/S1600536811026407

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1963

doi:10.1107/S1600536811026407

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

Abdullah M. Asiri,^a,^b Abdulrahman O. Al-Youbi,^a Mohie E. M. Zayed ^a and Seik Weng Ng ^c,^a ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia, ^bThe Center of Excellence for Advanced Materials Research, King Abdul Aziz University, PO Box 8020 Jeddah, Saudi Arabia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 29 June 2011; accepted 3 July 2011; online 9 July 2011)

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, P 2₁ /n
a = 7.0628 (3) Å
b = 13.4182 (5) Å
c = 11.2884 (5) Å
β = 95.589 (4)°
V = 1064.72 (8) Å³
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[F² > 2σ(F²)] = 0.054
wR(F²) = 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

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) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811026407/xu5261sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026407/xu5261Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811026407/xu5261Isup3.cml

checkCIF report

Comment top

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].

Related literature top

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

Experimental top

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.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); 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).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₉H₈ClN₃O₃ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

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

Crystal data top

C₉H₈ClN₃O₃	F(000) = 496
M_r = 241.63	D_x = 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 top

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 monochromator	R_int = 0.020
Detector resolution: 10.4041 pixels mm^-1	θ_max = 74.4°, θ_min = 5.1°
ω scans	h = −8→5
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −16→16
T_min = 0.568, T_max = 0.857	l = −14→14
4113 measured reflections

Refinement top

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(F_o²) + (0.0849P)² + 0.8946P] where P = (F_o² + 2F_c²)/3
2105 reflections	(Δ/σ)_max = 0.001
150 parameters	Δρ_max = 1.21 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₉H₈ClN₃O₃	V = 1064.72 (8) Å³
M_r = 241.63	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 7.0628 (3) Å	µ = 3.19 mm⁻¹
b = 13.4182 (5) Å	T = 100 K
c = 11.2884 (5) Å	0.20 × 0.10 × 0.05 mm
β = 95.589 (4)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2105 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1839 reflections with I > 2σ(I)
T_min = 0.568, T_max = 0.857	R_int = 0.020
4113 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 1.21 e Å⁻³
2105 reflections	Δρ_min = −0.48 e Å⁻³
150 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₈ClN₃O₃
M_r	241.63
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	7.0628 (3), 13.4182 (5), 11.2884 (5)
β (°)	95.589 (4)
V (Å³)	1064.72 (8)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.19
Crystal size (mm)	0.20 × 0.10 × 0.05

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.568, 0.857
No. of measured, independent and observed [I > 2σ(I)] reflections	4113, 2105, 1839
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.152, 1.09
No. of reflections	2105
No. of parameters	150
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.21, −0.48

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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) x+1/2, −y+1/2, z+1/2.

Acknowledgements

We thank King Abdulaziz University and the University of Malaya for supporting this study.

References

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