2,2-Dichloro-N-(2,5-dichloro­phen­yl)acetamide

Abstract

The conformation of the N—H bond in the title compound, C₈H₅Cl₄NO, is syn to the 2-chloro substituent and anti to the 5-chloro substituent in the aromatic ring. The bond parameters are similar to those in 2,2-dichloro-N-phenyl­acetamide and other acetanilides. In the crystal structure, the mol­ecules are linked into chains through N—H⋯O hydrogen bonding.

Related literature

For related literature, see: Gowda et al. (2001 ▶, 2006 ▶, 2007a ▶,b ▶,c ▶); Shilpa & Gowda (2007 ▶).

Experimental

Crystal data

• C₈H₅Cl₄NO

• M _r = 272.93

• Monoclinic,

• a = 4.6977 (4) Å

• b = 11.509 (2) Å

• c = 19.888 (3) Å

• β = 95.23 (1)°

• V = 1070.8 (3) ų

• Z = 4

• Cu Kα radiation

• μ = 9.77 mm⁻¹

• T = 299 (2) K

• 0.60 × 0.08 × 0.05 mm

Data collection

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: ψ scan (North et al., 1968 ▶ T _min = 0.367, T _max = 0.591

• 4168 measured reflections

• 1917 independent reflections

• 1420 reflections with I > 2σ(I)

• R _int = 0.116

• 3 standard reflections frequency: 120 min intensity decay: 2.0%

Refinement

• R[F ² > 2σ(F ²)] = 0.073

• wR(F ²) = 0.217

• S = 1.03

• 1917 reflections

• 131 parameters

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

• Δρ_max = 0.80 e Å⁻³

• Δρ_min = −0.72 e Å⁻³

Data collection: CAD-4-PC Version (Enraf–Nonius, 1996 ▶); cell refinement: CAD-4-PC Version; data reduction: REDU4 (Stoe & Cie, 1987 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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
N1—H1N⋯O1i	0.98 (6)	1.90 (6)	2.851 (4)	162 (4)

Symmetry code: (i) .

supplementary crystallographic information

Comment

In the present work, the structure of N-(2,5-dichlorophenyl)-2,2- dichloroacetamide (25DCPDCA) has been determined to study the effect of substituents on the structures of N-aromatic amides (Gowda et al., 2001, 2006; 2007a, b</i, c</i). The conformation of the N—H bond in 25DCPDCA is syn to the 2-chloro substituent and anti to the 5-chloro substituent in the aromatic ring (Fig. 1), in contrast to syn conformation observed with respect to both the 2- and 3-chloro substituents in N-(2,3-dichlorophenyl)-2,2-dichloroacetamide (23DCPDCA) (Gowda et al., 2007c), 2-chloro substituent in N-(2-chlorophenyl)-2,2-dichloroacetamide (2CPDCA)(Gowda et al., 2001), 3-chloro substituent in N-(3,4-dichlorophenyl)-2,2-dichloroacetamide (34DCPDCA)(Gowda et al., 2007b),and 2- and 3-chloro substituents in N-(2,3-dichlorophenyl)-acetamide (23DCPA)(Gowda et al., 2007a), and anti conformation observed with respect to the 3-chloro substituent in the N-(3-chlorophenyl)-2,2-dichloroacetamide (3CPDCA)(Gowda et al., 2006). The bond parameters in 25DCPDCA are similar to those in N-(phenyl)-2,2-dichloroacetamide, 2CPDCA, 3CPDCA, 23DCPDCA, 34DCPDCA, 23DCPA and other acetanilides (Gowda et al., 2001, 2006; 2007a, b</i, b</i). The molecules in 25DCPDCA are linked into chains through N—H···O hydrogen bonding (Table 1 and Fig.2).

Experimental

The title compound was prepared according to the literature method (Shilpa and Gowda, 2007). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra (Shilpa and Gowda, 2007). Single crystals of the title compound were obtained from an ethanolic solution and used for X-ray diffraction studies at room temperature.

Refinement

The H atoms bonded to C were positioned with idealized geometry using a riding model with C—H = 0.93–0.98 Å. The NH atom was located in difference map and its coordinates were refined. U_iso(H) values were set equal to 1.2 U_eq of the parent atom.

Figures

Fig. 1.

Molecular structure of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.

Fig. 2.

Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

Crystal data

C8H5Cl4NO	F000 = 544
Mr = 272.93	Dx = 1.693 Mg m−3
Monoclinic, P21/c	Cu Kα radiation λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 4.6977 (4) Å	θ = 7.7–20.2º
b = 11.509 (2) Å	µ = 9.77 mm−1
c = 19.888 (3) Å	T = 299 (2) K
β = 95.23 (1)º	Needle, colourless
V = 1070.8 (3) Å3	0.60 × 0.08 × 0.05 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.116
Radiation source: fine-focus sealed tube	θmax = 67.0º
Monochromator: graphite	θmin = 4.4º
T = 299(2) K	h = 0→5
ω/2θ scans	k = −13→12
Absorption correction: ψ scan(North et al., 1968	l = −23→23
Tmin = 0.367, Tmax = 0.591	3 standard reflections
4168 measured reflections	every 120 min
1917 independent reflections	intensity decay: 2.0%
1420 reflections with I > 2σ(I)

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.073	w = 1/[σ2(Fo2) + (0.144P)2 + 0.518P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.217	(Δ/σ)max = 0.033
S = 1.03	Δρmax = 0.80 e Å−3
1917 reflections	Δρmin = −0.72 e Å−3
131 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0038 (10)
Secondary atom site location: difference Fourier map

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.

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
C1	0.3994 (8)	0.7062 (3)	0.43590 (17)	0.0324 (8)
C2	0.2953 (8)	0.8112 (3)	0.45736 (19)	0.0367 (8)
C3	0.3981 (10)	0.8573 (3)	0.5194 (2)	0.0439 (10)
H3	0.3256	0.9273	0.5337	0.053*
C4	0.6063 (10)	0.8001 (4)	0.55998 (19)	0.0440 (9)
H4	0.6764	0.8313	0.6014	0.053*
C5	0.7093 (9)	0.6956 (4)	0.53810 (19)	0.0389 (9)
C6	0.6085 (8)	0.6475 (3)	0.47678 (18)	0.0345 (8)
H6	0.6797	0.5768	0.4630	0.041*
C7	0.4478 (8)	0.6066 (3)	0.33005 (18)	0.0344 (8)
C8	0.2734 (8)	0.5542 (4)	0.26817 (19)	0.0411 (9)
H8	0.0932	0.5238	0.2822	0.049*
N1	0.2888 (7)	0.6573 (3)	0.37354 (16)	0.0379 (7)
H1N	0.080 (12)	0.653 (4)	0.365 (2)	0.045*
O1	0.7058 (6)	0.5995 (4)	0.33605 (15)	0.0578 (10)
Cl1	0.0411 (3)	0.88522 (9)	0.40600 (6)	0.0526 (4)
Cl2	0.9670 (3)	0.62104 (10)	0.58918 (5)	0.0529 (4)
Cl3	0.4607 (4)	0.4414 (2)	0.23486 (12)	0.1290 (11)
Cl4	0.1977 (5)	0.66320 (18)	0.20858 (7)	0.0964 (8)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0219 (16)	0.0374 (17)	0.0371 (17)	−0.0020 (15)	−0.0014 (13)	−0.0001 (14)
C2	0.0262 (18)	0.0368 (18)	0.047 (2)	0.0029 (15)	0.0014 (15)	0.0014 (15)
C3	0.043 (2)	0.0387 (19)	0.050 (2)	0.0025 (19)	0.0064 (19)	−0.0080 (17)
C4	0.044 (2)	0.049 (2)	0.0380 (19)	−0.002 (2)	−0.0037 (17)	−0.0059 (16)
C5	0.0312 (19)	0.046 (2)	0.0383 (18)	−0.0034 (17)	−0.0028 (15)	0.0030 (15)
C6	0.0234 (18)	0.0380 (17)	0.0415 (19)	0.0014 (16)	0.0002 (15)	−0.0038 (15)
C7	0.0174 (17)	0.0484 (19)	0.0366 (18)	−0.0005 (15)	−0.0015 (14)	−0.0015 (15)
C8	0.0202 (17)	0.059 (2)	0.0424 (19)	−0.0010 (18)	−0.0059 (15)	−0.0060 (18)
N1	0.0157 (14)	0.0525 (17)	0.0442 (17)	0.0034 (15)	−0.0044 (12)	−0.0095 (14)
O1	0.0155 (14)	0.104 (3)	0.0529 (18)	0.0009 (16)	−0.0025 (12)	−0.0211 (16)
Cl1	0.0420 (7)	0.0528 (6)	0.0619 (7)	0.0160 (5)	−0.0019 (5)	0.0066 (4)
Cl2	0.0484 (7)	0.0613 (7)	0.0456 (6)	0.0052 (5)	−0.0138 (5)	0.0056 (4)
Cl3	0.0671 (10)	0.1554 (19)	0.1553 (17)	0.0449 (12)	−0.0398 (11)	−0.1137 (16)
Cl4	0.1098 (15)	0.1129 (13)	0.0588 (9)	−0.0326 (12)	−0.0344 (9)	0.0310 (8)

Geometric parameters (Å, °)

C1—C2	1.386 (5)	C5—Cl2	1.735 (4)
C1—C6	1.392 (5)	C6—H6	0.9300
C1—N1	1.417 (5)	C7—O1	1.209 (5)
C2—C3	1.389 (6)	C7—N1	1.328 (5)
C2—Cl1	1.724 (4)	C7—C8	1.538 (5)
C3—C4	1.377 (6)	C8—Cl3	1.734 (4)
C3—H3	0.9300	C8—Cl4	1.740 (4)
C4—C5	1.381 (6)	C8—H8	0.9800
C4—H4	0.9300	N1—H1N	0.98 (6)
C5—C6	1.383 (5)
C2—C1—C6	119.6 (3)	C5—C6—C1	119.2 (3)
C2—C1—N1	120.3 (3)	C5—C6—H6	120.4
C6—C1—N1	120.1 (3)	C1—C6—H6	120.4
C1—C2—C3	120.2 (4)	O1—C7—N1	125.7 (4)
C1—C2—Cl1	119.6 (3)	O1—C7—C8	120.5 (4)
C3—C2—Cl1	120.2 (3)	N1—C7—C8	113.8 (3)
C4—C3—C2	120.6 (4)	C7—C8—Cl3	110.3 (3)
C4—C3—H3	119.7	C7—C8—Cl4	108.9 (3)
C2—C3—H3	119.7	Cl3—C8—Cl4	111.0 (2)
C3—C4—C5	118.8 (4)	C7—C8—H8	108.9
C3—C4—H4	120.6	Cl3—C8—H8	108.9
C5—C4—H4	120.6	Cl4—C8—H8	108.9
C4—C5—C6	121.7 (4)	C7—N1—C1	124.1 (3)
C4—C5—Cl2	119.5 (3)	C7—N1—H1N	119 (3)
C6—C5—Cl2	118.9 (3)	C1—N1—H1N	117 (3)
C6—C1—C2—C3	−0.3 (6)	C2—C1—C6—C5	−0.2 (6)
N1—C1—C2—C3	178.1 (4)	N1—C1—C6—C5	−178.7 (3)
C6—C1—C2—Cl1	178.8 (3)	O1—C7—C8—Cl3	25.6 (5)
N1—C1—C2—Cl1	−2.8 (5)	N1—C7—C8—Cl3	−154.3 (3)
C1—C2—C3—C4	0.7 (6)	O1—C7—C8—Cl4	−96.5 (4)
Cl1—C2—C3—C4	−178.3 (3)	N1—C7—C8—Cl4	83.6 (4)
C2—C3—C4—C5	−0.6 (7)	O1—C7—N1—C1	−3.3 (7)
C3—C4—C5—C6	0.0 (7)	C8—C7—N1—C1	176.5 (3)
C3—C4—C5—Cl2	−178.8 (3)	C2—C1—N1—C7	138.6 (4)
C4—C5—C6—C1	0.4 (6)	C6—C1—N1—C7	−43.0 (6)
Cl2—C5—C6—C1	179.2 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.98 (6)	1.90 (6)	2.851 (4)	162 (4)

Symmetry codes: (i) x−1, y, z.