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

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

doi:10.1107/S1600536811026390

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1962

doi:10.1107/S1600536811026390

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1-Chloro-1-[(4-chlorophenyl)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, C₉H₈Cl₂N₂O, lie nearly on a plane (r.m.s. deviation = 0.110 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 [100].

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

C₉H₈Cl₂N₂O
M_r = 231.07
Monoclinic, P 2₁ /c
a = 5.7558 (4) Å
b = 23.3282 (17) Å
c = 7.4107 (6) Å
β = 96.976 (7)°
V = 987.69 (13) Å³
Z = 4
Cu Kα radiation
μ = 5.65 mm⁻¹
T = 100 K
0.35 × 0.05 × 0.03 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.243, T_max = 0.849
3486 measured reflections
1939 independent reflections
1640 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.070
wR(F²) = 0.208
S = 1.17
1939 reflections
133 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.28 e Å⁻³
Δρ_min = −0.54 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 (8)	2.26 (8)	3.029 (6)	150 (7)
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/S1600536811026390/xu5260sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026390/xu5260Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811026390/xu5260Isup3.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-chloro substituted compound (Scheme I, Fig. 1), the non-hydrogen atoms lie on a plane [r.m.s. deviation 0.110 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 0].

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-chloroaniline (1.20 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 C₉H₈Cl₂N₂O at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

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

Crystal data top

C₉H₈Cl₂N₂O	F(000) = 472
M_r = 231.07	D_x = 1.554 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 1477 reflections
a = 5.7558 (4) Å	θ = 3.8–74.1°
b = 23.3282 (17) Å	µ = 5.65 mm⁻¹
c = 7.4107 (6) Å	T = 100 K
β = 96.976 (7)°	Prism, yellow
V = 987.69 (13) Å³	0.35 × 0.05 × 0.03 mm
Z = 4

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1939 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1640 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.036
Detector resolution: 10.4041 pixels mm^-1	θ_max = 74.3°, θ_min = 3.8°
ω scans	h = −6→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −27→28
T_min = 0.243, T_max = 0.849	l = −9→9
3486 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.070	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.208	w = 1/[σ²(F_o²) + (0.0903P)² + 4.1934P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max = 0.002
1939 reflections	Δρ_max = 1.28 e Å⁻³
133 parameters	Δρ_min = −0.54 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0015 (7)

Crystal data top

C₉H₈Cl₂N₂O	V = 987.69 (13) Å³
M_r = 231.07	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 5.7558 (4) Å	µ = 5.65 mm⁻¹
b = 23.3282 (17) Å	T = 100 K
c = 7.4107 (6) Å	0.35 × 0.05 × 0.03 mm
β = 96.976 (7)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1939 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1640 reflections with I > 2σ(I)
T_min = 0.243, T_max = 0.849	R_int = 0.036
3486 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.070	0 restraints
wR(F²) = 0.208	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	Δρ_max = 1.28 e Å⁻³
1939 reflections	Δρ_min = −0.54 e Å⁻³
133 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.2378 (2)	0.21916 (5)	0.50652 (16)	0.0233 (4)
Cl2	0.7056 (2)	0.56866 (5)	0.85227 (16)	0.0253 (4)
O1	−0.2165 (6)	0.23416 (15)	0.2828 (5)	0.0272 (8)
N1	0.1754 (7)	0.33248 (18)	0.5054 (5)	0.0194 (9)
N2	0.3787 (7)	0.33782 (18)	0.6093 (5)	0.0204 (9)
H2	0.464 (14)	0.308 (3)	0.632 (10)	0.05 (2)*
C1	−0.2428 (9)	0.3362 (2)	0.2694 (8)	0.0290 (12)
H1A	−0.3553	0.3296	0.1612	0.044*
H1B	−0.1229	0.3634	0.2402	0.044*
H1C	−0.3244	0.3520	0.3669	0.044*
C2	−0.1284 (9)	0.2803 (2)	0.3310 (7)	0.0215 (10)
C3	0.0947 (9)	0.2835 (2)	0.4510 (6)	0.0193 (10)
C4	0.4510 (8)	0.3930 (2)	0.6690 (6)	0.0197 (10)
C5	0.6761 (9)	0.4003 (2)	0.7582 (7)	0.0235 (11)
H5	0.7773	0.3682	0.7794	0.028*
C6	0.7533 (9)	0.4543 (2)	0.8162 (6)	0.0226 (10)
H6	0.9070	0.4595	0.8768	0.027*
C7	0.6036 (9)	0.5004 (2)	0.7845 (6)	0.0195 (10)
C8	0.3792 (9)	0.4940 (2)	0.6972 (7)	0.0221 (10)
H8	0.2789	0.5263	0.6771	0.027*
C9	0.3016 (8)	0.4404 (2)	0.6392 (6)	0.0209 (10)
H9	0.1474	0.4356	0.5793	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0260 (7)	0.0181 (6)	0.0248 (6)	0.0025 (4)	−0.0012 (5)	0.0005 (4)
Cl2	0.0281 (7)	0.0178 (6)	0.0279 (6)	−0.0023 (5)	−0.0050 (5)	−0.0019 (4)
O1	0.0274 (19)	0.0194 (18)	0.033 (2)	−0.0044 (15)	−0.0023 (15)	−0.0029 (15)
N1	0.019 (2)	0.021 (2)	0.0179 (18)	−0.0010 (16)	−0.0002 (15)	0.0004 (16)
N2	0.021 (2)	0.018 (2)	0.021 (2)	−0.0031 (17)	−0.0028 (16)	−0.0005 (16)
C1	0.024 (3)	0.025 (3)	0.036 (3)	−0.003 (2)	−0.007 (2)	0.002 (2)
C2	0.021 (2)	0.020 (2)	0.024 (2)	−0.0049 (19)	0.0022 (19)	−0.0011 (19)
C3	0.021 (2)	0.018 (2)	0.019 (2)	0.0010 (18)	0.0013 (18)	0.0013 (18)
C4	0.024 (2)	0.020 (2)	0.016 (2)	−0.0012 (19)	0.0014 (18)	0.0006 (18)
C5	0.022 (2)	0.023 (3)	0.024 (2)	0.005 (2)	−0.0008 (19)	0.000 (2)
C6	0.018 (2)	0.027 (3)	0.021 (2)	0.003 (2)	−0.0032 (18)	−0.001 (2)
C7	0.024 (2)	0.015 (2)	0.019 (2)	−0.0017 (18)	−0.0001 (18)	−0.0013 (17)
C8	0.020 (2)	0.020 (2)	0.025 (2)	0.0015 (19)	−0.0023 (19)	−0.0008 (19)
C9	0.018 (2)	0.023 (2)	0.021 (2)	0.0008 (19)	−0.0002 (18)	−0.0001 (19)

Geometric parameters (Å, º) top

Cl1—C3	1.737 (5)	C2—C3	1.472 (7)
Cl2—C7	1.749 (5)	C4—C5	1.392 (7)
O1—C2	1.225 (6)	C4—C9	1.401 (7)
N1—C3	1.280 (6)	C5—C6	1.386 (7)
N1—N2	1.326 (6)	C5—H5	0.9500
N2—C4	1.407 (6)	C6—C7	1.382 (7)
N2—H2	0.85 (8)	C6—H6	0.9500
C1—C2	1.506 (7)	C7—C8	1.381 (7)
C1—H1A	0.9800	C8—C9	1.379 (7)
C1—H1B	0.9800	C8—H8	0.9500
C1—H1C	0.9800	C9—H9	0.9500

C3—N1—N2	121.8 (4)	C5—C4—N2	119.0 (4)
N1—N2—C4	118.4 (4)	C9—C4—N2	121.3 (4)
N1—N2—H2	119 (5)	C6—C5—C4	120.2 (5)
C4—N2—H2	123 (5)	C6—C5—H5	119.9
C2—C1—H1A	109.5	C4—C5—H5	119.9
C2—C1—H1B	109.5	C7—C6—C5	119.1 (5)
H1A—C1—H1B	109.5	C7—C6—H6	120.5
C2—C1—H1C	109.5	C5—C6—H6	120.5
H1A—C1—H1C	109.5	C6—C7—C8	121.5 (4)
H1B—C1—H1C	109.5	C6—C7—Cl2	118.7 (4)
O1—C2—C3	121.3 (5)	C8—C7—Cl2	119.8 (4)
O1—C2—C1	121.5 (4)	C9—C8—C7	119.6 (5)
C3—C2—C1	117.2 (4)	C9—C8—H8	120.2
N1—C3—C2	119.4 (4)	C7—C8—H8	120.2
N1—C3—Cl1	123.6 (4)	C8—C9—C4	119.8 (4)
C2—C3—Cl1	117.0 (4)	C8—C9—H9	120.1
C5—C4—C9	119.7 (5)	C4—C9—H9	120.1

C3—N1—N2—C4	−177.6 (4)	N2—C4—C5—C6	179.0 (4)
N2—N1—C3—C2	−178.0 (4)	C4—C5—C6—C7	0.1 (8)
N2—N1—C3—Cl1	0.4 (7)	C5—C6—C7—C8	0.2 (8)
O1—C2—C3—N1	−176.7 (5)	C5—C6—C7—Cl2	−178.2 (4)
C1—C2—C3—N1	3.6 (7)	C6—C7—C8—C9	−0.2 (8)
O1—C2—C3—Cl1	4.8 (7)	Cl2—C7—C8—C9	178.1 (4)
C1—C2—C3—Cl1	−174.9 (4)	C7—C8—C9—C4	−0.1 (7)
N1—N2—C4—C5	−171.9 (4)	C5—C4—C9—C8	0.5 (7)
N1—N2—C4—C9	7.6 (7)	N2—C4—C9—C8	−179.0 (4)
C9—C4—C5—C6	−0.5 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.85 (8)	2.26 (8)	3.029 (6)	150 (7)

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

Experimental details

Crystal data
Chemical formula	C₉H₈Cl₂N₂O
M_r	231.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	5.7558 (4), 23.3282 (17), 7.4107 (6)
β (°)	96.976 (7)
V (Å³)	987.69 (13)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	5.65
Crystal size (mm)	0.35 × 0.05 × 0.03

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.243, 0.849
No. of measured, independent and observed [I > 2σ(I)] reflections	3486, 1939, 1640
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.070, 0.208, 1.17
No. of reflections	1939
No. of parameters	133
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.28, −0.54

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 (8)	2.26 (8)	3.029 (6)	150 (7)

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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