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

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

doi:10.1107/S1600536811026389

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1961

doi:10.1107/S1600536811026389

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1-Chloro-1-[(4-methoxyphenyl)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, C₁₀H₁₁ClN₂O₂, lie nearly on a plane (r.m.s. deviation = 0.150 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 [201].

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

C₁₀H₁₁ClN₂O₂
M_r = 226.66
Monoclinic, P 2₁ /c
a = 5.8873 (3) Å
b = 25.0467 (10) Å
c = 7.3041 (3) Å
β = 99.016 (4)°
V = 1063.74 (8) Å³
Z = 4
Cu Kα radiation
μ = 3.05 mm⁻¹
T = 100 K
0.35 × 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 = 0.415, T_max = 0.863
3802 measured reflections
2090 independent reflections
1776 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.102
S = 1.05
2090 reflections
142 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.87 (3)	2.22 (3)	3.021 (2)	153 (2)
Symmetry code: (i) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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/S1600536811026389/xu5259sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026389/xu5259Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811026389/xu5259Isup3.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-methoxy substituted compound (Scheme I, Fig. 1), the non-hydrogen atoms lie on a plane [r.m.s. deviation 0.150 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 [2 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-methoxyaniline (1.23 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 C₁₀H₁₁N₂O₂ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

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

Crystal data top

C₁₀H₁₁ClN₂O₂	F(000) = 472
M_r = 226.66	D_x = 1.415 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 1678 reflections
a = 5.8873 (3) Å	θ = 3.5–74.0°
b = 25.0467 (10) Å	µ = 3.05 mm⁻¹
c = 7.3041 (3) Å	T = 100 K
β = 99.016 (4)°	Prism, yellow
V = 1063.74 (8) Å³	0.35 × 0.10 × 0.05 mm
Z = 4

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2090 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1776 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.026
Detector resolution: 10.4041 pixels mm^-1	θ_max = 74.2°, θ_min = 3.5°
ω scan	h = −5→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −20→31
T_min = 0.415, T_max = 0.863	l = −8→7
3802 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0508P)² + 0.2595P] where P = (F_o² + 2F_c²)/3
2090 reflections	(Δ/σ)_max = 0.001
142 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₀H₁₁ClN₂O₂	V = 1063.74 (8) Å³
M_r = 226.66	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 5.8873 (3) Å	µ = 3.05 mm⁻¹
b = 25.0467 (10) Å	T = 100 K
c = 7.3041 (3) Å	0.35 × 0.10 × 0.05 mm
β = 99.016 (4)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2090 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1776 reflections with I > 2σ(I)
T_min = 0.415, T_max = 0.863	R_int = 0.026
3802 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.25 e Å⁻³
2090 reflections	Δρ_min = −0.30 e Å⁻³
142 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.79949 (8)	0.222023 (16)	0.49001 (6)	0.02053 (15)
O1	0.3432 (2)	0.23571 (5)	0.2668 (2)	0.0248 (3)
O2	1.2583 (2)	0.53251 (5)	0.8487 (2)	0.0247 (3)
N1	0.7372 (3)	0.32750 (6)	0.4928 (2)	0.0162 (3)
N2	0.9408 (3)	0.33231 (6)	0.5974 (2)	0.0165 (3)
H2	1.023 (4)	0.3046 (10)	0.634 (4)	0.038 (7)*
C1	0.3119 (3)	0.33074 (8)	0.2551 (3)	0.0240 (4)
H1A	0.3295	0.3380	0.1263	0.036*
H1B	0.3820	0.3597	0.3348	0.036*
H1C	0.1481	0.3282	0.2646	0.036*
C2	0.4288 (3)	0.27892 (7)	0.3161 (3)	0.0184 (4)
C3	0.6546 (3)	0.28185 (7)	0.4355 (3)	0.0168 (4)
C4	1.0117 (3)	0.38372 (7)	0.6642 (2)	0.0155 (4)
C5	1.2413 (3)	0.39119 (7)	0.7442 (3)	0.0182 (4)
H5	1.3455	0.3620	0.7566	0.022*
C6	1.3153 (3)	0.44152 (7)	0.8052 (3)	0.0202 (4)
H6	1.4710	0.4467	0.8599	0.024*
C7	1.1642 (3)	0.48447 (7)	0.7872 (3)	0.0179 (4)
C8	0.9350 (3)	0.47698 (7)	0.7091 (3)	0.0185 (4)
H8	0.8307	0.5062	0.6972	0.022*
C9	0.8601 (3)	0.42636 (7)	0.6485 (3)	0.0186 (4)
H9	0.7037	0.4210	0.5960	0.022*
C10	1.1081 (4)	0.57745 (7)	0.8382 (3)	0.0242 (4)
H10A	1.1951	0.6090	0.8875	0.036*
H10B	0.9851	0.5704	0.9112	0.036*
H10C	1.0408	0.5838	0.7086	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0247 (3)	0.0108 (2)	0.0250 (3)	0.00228 (17)	0.00048 (18)	0.00008 (17)
O1	0.0238 (7)	0.0152 (7)	0.0340 (8)	−0.0046 (6)	−0.0002 (6)	−0.0032 (6)
O2	0.0255 (7)	0.0124 (6)	0.0348 (8)	−0.0011 (6)	0.0000 (6)	−0.0050 (6)
N1	0.0174 (7)	0.0134 (7)	0.0174 (8)	−0.0007 (6)	0.0016 (6)	0.0004 (6)
N2	0.0169 (8)	0.0101 (7)	0.0211 (8)	−0.0006 (6)	−0.0010 (6)	−0.0004 (6)
C1	0.0216 (10)	0.0160 (9)	0.0321 (11)	0.0011 (8)	−0.0032 (8)	−0.0006 (8)
C2	0.0185 (9)	0.0147 (9)	0.0214 (9)	−0.0011 (7)	0.0018 (7)	−0.0002 (7)
C3	0.0179 (9)	0.0107 (9)	0.0220 (9)	0.0013 (7)	0.0035 (7)	0.0007 (7)
C4	0.0190 (9)	0.0113 (8)	0.0162 (9)	−0.0007 (7)	0.0033 (7)	−0.0003 (7)
C5	0.0181 (9)	0.0120 (9)	0.0241 (10)	0.0018 (7)	0.0020 (7)	−0.0006 (7)
C6	0.0167 (9)	0.0172 (9)	0.0260 (10)	0.0009 (7)	0.0014 (7)	−0.0022 (8)
C7	0.0241 (10)	0.0116 (9)	0.0180 (9)	−0.0014 (7)	0.0035 (7)	−0.0014 (7)
C8	0.0207 (9)	0.0127 (9)	0.0221 (9)	0.0044 (7)	0.0029 (7)	0.0014 (7)
C9	0.0172 (9)	0.0169 (9)	0.0213 (9)	0.0018 (7)	0.0019 (7)	−0.0006 (8)
C10	0.0355 (11)	0.0102 (9)	0.0268 (11)	0.0010 (8)	0.0047 (9)	−0.0005 (8)

Geometric parameters (Å, º) top

Cl1—C3	1.7395 (18)	C4—C9	1.385 (2)
O1—C2	1.224 (2)	C4—C5	1.398 (3)
O2—C7	1.371 (2)	C5—C6	1.384 (3)
O2—C10	1.426 (2)	C5—H5	0.9500
N1—C3	1.287 (2)	C6—C7	1.389 (3)
N1—N2	1.322 (2)	C6—H6	0.9500
N2—C4	1.417 (2)	C7—C8	1.393 (3)
N2—H2	0.87 (3)	C8—C9	1.392 (3)
C1—C2	1.503 (2)	C8—H8	0.9500
C1—H1A	0.9800	C9—H9	0.9500
C1—H1B	0.9800	C10—H10A	0.9800
C1—H1C	0.9800	C10—H10B	0.9800
C2—C3	1.473 (3)	C10—H10C	0.9800

C7—O2—C10	117.36 (15)	C6—C5—H5	120.3
C3—N1—N2	122.09 (16)	C4—C5—H5	120.3
N1—N2—C4	118.27 (15)	C5—C6—C7	120.67 (18)
N1—N2—H2	121.2 (18)	C5—C6—H6	119.7
C4—N2—H2	120.3 (18)	C7—C6—H6	119.7
C2—C1—H1A	109.5	O2—C7—C6	115.38 (17)
C2—C1—H1B	109.5	O2—C7—C8	124.65 (17)
H1A—C1—H1B	109.5	C6—C7—C8	119.96 (17)
C2—C1—H1C	109.5	C9—C8—C7	119.43 (17)
H1A—C1—H1C	109.5	C9—C8—H8	120.3
H1B—C1—H1C	109.5	C7—C8—H8	120.3
O1—C2—C3	120.66 (17)	C4—C9—C8	120.53 (18)
O1—C2—C1	121.88 (18)	C4—C9—H9	119.7
C3—C2—C1	117.45 (16)	C8—C9—H9	119.7
N1—C3—C2	119.81 (16)	O2—C10—H10A	109.5
N1—C3—Cl1	122.97 (15)	O2—C10—H10B	109.5
C2—C3—Cl1	117.21 (13)	H10A—C10—H10B	109.5
C9—C4—C5	119.98 (17)	O2—C10—H10C	109.5
C9—C4—N2	121.38 (17)	H10A—C10—H10C	109.5
C5—C4—N2	118.63 (16)	H10B—C10—H10C	109.5
C6—C5—C4	119.42 (17)

C3—N1—N2—C4	−175.92 (16)	C4—C5—C6—C7	−0.2 (3)
N2—N1—C3—C2	−178.79 (16)	C10—O2—C7—C6	−178.14 (16)
N2—N1—C3—Cl1	0.3 (3)	C10—O2—C7—C8	2.5 (3)
O1—C2—C3—N1	−176.92 (18)	C5—C6—C7—O2	−178.62 (17)
C1—C2—C3—N1	4.3 (3)	C5—C6—C7—C8	0.8 (3)
O1—C2—C3—Cl1	3.9 (3)	O2—C7—C8—C9	178.87 (17)
C1—C2—C3—Cl1	−174.89 (14)	C6—C7—C8—C9	−0.5 (3)
N1—N2—C4—C9	10.9 (3)	C5—C4—C9—C8	1.1 (3)
N1—N2—C4—C5	−167.94 (16)	N2—C4—C9—C8	−177.73 (17)
C9—C4—C5—C6	−0.7 (3)	C7—C8—C9—C4	−0.5 (3)
N2—C4—C5—C6	178.08 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.87 (3)	2.22 (3)	3.021 (2)	153 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁ClN₂O₂
M_r	226.66
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	5.8873 (3), 25.0467 (10), 7.3041 (3)
β (°)	99.016 (4)
V (Å³)	1063.74 (8)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.05
Crystal size (mm)	0.35 × 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	0.415, 0.863
No. of measured, independent and observed [I > 2σ(I)] reflections	3802, 2090, 1776
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.102, 1.05
No. of reflections	2090
No. of parameters	142
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.30

Computer programs: CrysAlis PRO (Agilent, 2010), 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	0.87 (3)	2.22 (3)	3.021 (2)	153 (2)

Symmetry code: (i) x+1, −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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