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

Abstract

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,

• a = 5.7558 (4) Å

• b = 23.3282 (17) Å

• c = 7.4107 (6) Å

• β = 96.976 (7)°

• V = 987.69 (13) ų

• 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[F ² > 2σ(F ²)] = 0.070

• wR(F ²) = 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

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/S1600536811026390/xu5260Isup3.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 (8)	2.26 (8)	3.029 (6)	150 (7)

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-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].

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-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.

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 H1b.

Omitted from the refinement were (-3 5 1), (-3 13 1), (-3 4 2) and (-3 3 3).

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of C9H8Cl2N2O at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C9H8Cl2N2O	F(000) = 472
Mr = 231.07	Dx = 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

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	Rint = 0.036
Detector resolution: 10.4041 pixels mm-1	θmax = 74.3°, θmin = 3.8°
ω scans	h = −6→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −27→28
Tmin = 0.243, Tmax = 0.849	l = −9→9
3486 measured reflections

Refinement

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(Fo2) + (0.0903P)2 + 4.1934P] where P = (Fo2 + 2Fc2)/3
S = 1.17	(Δ/σ)max = 0.002
1939 reflections	Δρmax = 1.28 e Å−3
133 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) x+1, −y+1/2, z+1/2.