1-Chloro-1-[(Z)-2-phenyl­hydrazin-1-yl­idene]propan-2-one

Abstract

The title compound, C₉H₉ClN₂O, is close to planar (r.m.s. deviation for the non-H atoms = 0.0446 Å); it exists in a cis conformation with respect to the C=N double bond. In the crystal, the ketone O atom accepts both N—H⋯O and C—H⋯O hydrogen bonds, which leads to [010] infinite chains incorporating R ₂ ¹(6) loops. The crystal structure also features a C—H⋯π inter­action.

Related literature  

For synthetic applications of hydrazonoyl chlorides, see: Abdel-Aziz & Mekawey (2009 ▶). For graph-set descriptors of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures. see: Asiri et al. (2011a ▶,b ▶). For a historical perspective on the synthesis, see: Dieckmann & Platz (1905 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental  

Crystal data  

• C₉H₉ClN₂O

• M _r = 196.63

• Monoclinic,

• a = 7.2681 (14) Å

• b = 12.361 (2) Å

• c = 10.704 (2) Å

• β = 101.158 (3)°

• V = 943.5 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.36 mm⁻¹

• T = 100 K

• 0.37 × 0.21 × 0.10 mm

Data collection  

• Bruker APEX DUO CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.877, T _max = 0.963

• 8906 measured reflections

• 2722 independent reflections

• 2225 reflections with I > 2σ(I)

• R _int = 0.030

Refinement  

• R[F ² > 2σ(F ²)] = 0.049

• wR(F ²) = 0.148

• S = 1.06

• 2722 reflections

• 124 parameters

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

• Δρ_max = 0.86 e Å⁻³

• Δρ_min = −0.37 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812028759/hb6870Isup3.cml

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

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

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1i	0.99 (3)	2.01 (3)	2.948 (2)	157 (2)
C1—H1A⋯O1i	0.95	2.45	3.237 (3)	140
C9—H9B⋯Cg1ii	0.98	2.68	3.560 (2)	149

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

As part of our ongoing studies of the synthetic chemistry of hydrazonoyl chlorides (Abdel-Aziz & Mekawey, 2009), the title compound was prepared and its crystal structure is now reported.

The asymmetric unit of the title compound is shown in Fig. 1. All of the non-H atoms lie nearly on a plane with r.m.s. deviation of 0.0446 Å. The molecule exists in cis configuration with respect to the C7═N2 double bond. Bond lengths and angles are comparable to those in related structures (Asiri et al., 2011a,b).

In the crystal (Fig. 2), molecules are linked by N1—H1N1···O1 and C1—H1A···O1 hydrogen bonds (Table 1), generating R₂¹(6) loops (Bernstein et al., 1995) and forming infinite wave-like chains along [010]. The packing also features a C—H···π interaction (Table 1), involving Cg1, which is the centroid of C1–C6 ring.

Experimental

The title compound was prepared by the coupling reaction of 3-chloro-2,4-pentanedione and the diazonium salt of aniline at 0–5 °C (Dieckmann & Platz, 1905). Yellow blocks were recrystallised from ethanol solution.

Refinement

The atom H1N1 was located in a difference fourier map and refined freely [N1—H1N1 = 1.00 (3) Å]. The remaining H atoms were positioned geometrically [C—H = 0.95 and 0.98 Å] and refined using a riding model with U_iso(H) = 1.2 or 1.5U_eq(C). A rotating group model was applied to the methyl group. Five outliers, (102), (213), (113), (315) and (011) were omitted in the final refinement.

Figures

Fig. 1.

The molecular structure of the title compound with 50% probability displacement ellipsoids.

Fig. 2.

The crystal packing of the title compound. The dashed lines represent the hydrogen bonds. For clarity sake, hydrogen atoms not involved in hydrogen bonding have been omitted.

Crystal data

C9H9ClN2O	F(000) = 408
Mr = 196.63	Dx = 1.384 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3613 reflections
a = 7.2681 (14) Å	θ = 2.5–30.0°
b = 12.361 (2) Å	µ = 0.36 mm−1
c = 10.704 (2) Å	T = 100 K
β = 101.158 (3)°	Block, yellow
V = 943.5 (3) Å3	0.37 × 0.21 × 0.10 mm
Z = 4

Data collection

Bruker APEX DUO CCD diffractometer	2722 independent reflections
Radiation source: fine-focus sealed tube	2225 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 30.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.877, Tmax = 0.963	k = −17→14
8906 measured reflections	l = −15→13

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)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.148	w = 1/[σ2(Fo2) + (0.0802P)2 + 0.7657P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
2722 reflections	Δρmax = 0.86 e Å−3
124 parameters	Δρmin = −0.37 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.008 (3)

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cl1	−0.00357 (7)	0.01567 (4)	0.18248 (4)	0.02310 (16)
O1	0.0096 (2)	0.24567 (12)	0.25220 (13)	0.0275 (3)
N1	0.1947 (2)	−0.08946 (14)	0.41978 (16)	0.0235 (4)
N2	0.1820 (2)	0.01726 (13)	0.42826 (16)	0.0220 (3)
C1	0.2872 (3)	−0.26204 (17)	0.51547 (19)	0.0230 (4)
H1A	0.2243	−0.2962	0.4397	0.028*
C2	0.3780 (3)	−0.32397 (18)	0.6175 (2)	0.0265 (4)
H2A	0.3769	−0.4006	0.6112	0.032*
C3	0.4705 (3)	−0.27448 (19)	0.72882 (19)	0.0278 (4)
H3A	0.5321	−0.3169	0.7985	0.033*
C4	0.4715 (3)	−0.16205 (19)	0.7370 (2)	0.0277 (4)
H4A	0.5349	−0.1281	0.8128	0.033*
C5	0.3816 (3)	−0.09862 (18)	0.63614 (19)	0.0250 (4)
H5A	0.3831	−0.0220	0.6428	0.030*
C6	0.2890 (3)	−0.14930 (17)	0.52499 (18)	0.0216 (4)
C7	0.0985 (3)	0.07370 (17)	0.33405 (18)	0.0225 (4)
C8	0.0876 (3)	0.19245 (16)	0.34351 (18)	0.0221 (4)
C9	0.1800 (3)	0.24284 (17)	0.46791 (19)	0.0256 (4)
H9A	0.1471	0.3197	0.4678	0.038*
H9B	0.3164	0.2353	0.4787	0.038*
H9C	0.1367	0.2063	0.5382	0.038*
H1N1	0.129 (4)	−0.130 (2)	0.344 (3)	0.032 (7)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0330 (3)	0.0140 (2)	0.0192 (2)	0.00383 (16)	−0.00273 (17)	−0.00116 (15)
O1	0.0323 (8)	0.0238 (7)	0.0241 (7)	0.0020 (6)	−0.0001 (6)	0.0020 (6)
N1	0.0275 (8)	0.0211 (8)	0.0202 (8)	0.0017 (6)	0.0006 (6)	0.0010 (6)
N2	0.0214 (7)	0.0211 (8)	0.0235 (8)	0.0000 (6)	0.0040 (6)	0.0013 (6)
C1	0.0220 (9)	0.0246 (10)	0.0210 (8)	−0.0009 (7)	0.0010 (7)	0.0004 (7)
C2	0.0271 (9)	0.0252 (10)	0.0268 (10)	0.0011 (8)	0.0041 (8)	0.0040 (8)
C3	0.0270 (10)	0.0324 (11)	0.0222 (9)	0.0008 (8)	0.0000 (7)	0.0064 (8)
C4	0.0280 (10)	0.0326 (11)	0.0206 (9)	−0.0028 (8)	−0.0005 (7)	0.0000 (8)
C5	0.0274 (9)	0.0234 (10)	0.0234 (9)	−0.0017 (7)	0.0027 (7)	0.0002 (7)
C6	0.0207 (8)	0.0234 (9)	0.0208 (9)	0.0004 (7)	0.0040 (7)	0.0035 (7)
C7	0.0237 (9)	0.0233 (10)	0.0196 (8)	0.0003 (7)	0.0019 (7)	−0.0002 (7)
C8	0.0211 (8)	0.0240 (10)	0.0212 (9)	0.0000 (7)	0.0039 (7)	0.0005 (7)
C9	0.0283 (10)	0.0240 (10)	0.0227 (9)	−0.0004 (7)	0.0002 (7)	−0.0018 (7)

Geometric parameters (Å, º)

Cl1—C7	1.798 (2)	C3—C4	1.392 (3)
O1—C8	1.223 (2)	C3—H3A	0.9500
N1—N2	1.327 (2)	C4—C5	1.391 (3)
N1—C6	1.409 (2)	C4—H4A	0.9500
N1—H1N1	1.00 (3)	C5—C6	1.397 (3)
N2—C7	1.279 (3)	C5—H5A	0.9500
C1—C2	1.392 (3)	C7—C8	1.475 (3)
C1—C6	1.397 (3)	C8—C9	1.505 (3)
C1—H1A	0.9500	C9—H9A	0.9800
C2—C3	1.391 (3)	C9—H9B	0.9800
C2—H2A	0.9500	C9—H9C	0.9800
N2—N1—C6	119.79 (17)	C4—C5—H5A	120.5
N2—N1—H1N1	121.9 (15)	C6—C5—H5A	120.5
C6—N1—H1N1	118.0 (15)	C5—C6—C1	120.37 (18)
C7—N2—N1	121.15 (18)	C5—C6—N1	121.67 (18)
C2—C1—C6	119.68 (19)	C1—C6—N1	117.96 (18)
C2—C1—H1A	120.2	N2—C7—C8	120.84 (18)
C6—C1—H1A	120.2	N2—C7—Cl1	122.96 (16)
C3—C2—C1	120.5 (2)	C8—C7—Cl1	116.16 (14)
C3—C2—H2A	119.8	O1—C8—C7	120.24 (18)
C1—C2—H2A	119.8	O1—C8—C9	122.88 (19)
C2—C3—C4	119.25 (19)	C7—C8—C9	116.87 (17)
C2—C3—H3A	120.4	C8—C9—H9A	109.5
C4—C3—H3A	120.4	C8—C9—H9B	109.5
C5—C4—C3	121.2 (2)	H9A—C9—H9B	109.5
C5—C4—H4A	119.4	C8—C9—H9C	109.5
C3—C4—H4A	119.4	H9A—C9—H9C	109.5
C4—C5—C6	119.0 (2)	H9B—C9—H9C	109.5
C6—N1—N2—C7	179.46 (17)	N2—N1—C6—C5	−4.6 (3)
C6—C1—C2—C3	0.0 (3)	N2—N1—C6—C1	175.28 (17)
C1—C2—C3—C4	−0.1 (3)	N1—N2—C7—C8	−178.98 (17)
C2—C3—C4—C5	0.2 (3)	N1—N2—C7—Cl1	−1.3 (3)
C3—C4—C5—C6	−0.1 (3)	N2—C7—C8—O1	179.02 (17)
C4—C5—C6—C1	−0.1 (3)	Cl1—C7—C8—O1	1.2 (2)
C4—C5—C6—N1	179.75 (18)	N2—C7—C8—C9	0.5 (3)
C2—C1—C6—C5	0.1 (3)	Cl1—C7—C8—C9	−177.33 (13)
C2—C1—C6—N1	−179.73 (17)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1i	0.99 (3)	2.01 (3)	2.948 (2)	157 (2)
C1—H1A···O1i	0.95	2.45	3.237 (3)	140
C9—H9B···Cg1ii	0.98	2.68	3.560 (2)	149

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