2,2-Dichloro-N-(3,5-dimethyl­phen­yl)­acetamide

Gowda, B.T.; Svoboda, I.; Foro, S.; Paulus, H.; Fuess, H.

doi:10.1107/S1600536807064914

organic compounds

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Volume 64| Part 1| January 2008| Page o209

https://doi.org/10.1107/S1600536807064914

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2,2-Dichloro-N-(3,5-dimethylphenyl)acetamide

B. Thimme Gowda,^a ^* Ingrid Svoboda,^b Sabine Foro,^b Helmut Paulus ^b and Hartmut Fuess ^b

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 18 November 2007; accepted 1 December 2007; online 6 December 2007)

The structure of the title compound, C₁₀H₁₁Cl₂NO, resembles those of 2,2-dichloro-N-phenylacetamide, 2,2-dichloro-N-(2-methylphenyl)acetamide, 2,2-dichloro-N-(3-methylphenyl)acetamide, 2,2-dichloro-N-(4-methylphenyl)acetamide, N-(3,5-dimethylphenyl)acetamide and other acetanilides, with similar bond parameters. The molecules in the title compound are linked into infinite chains through N—H⋯O and C—H⋯O hydrogen bonding.

Related literature

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

Experimental

Crystal data

C₁₀H₁₁Cl₂NO
M_r = 232.10
Monoclinic, P 2₁ /c
a = 11.412 (4) Å
b = 10.570 (4) Å
c = 9.163 (3) Å
β = 110.99 (2)°
V = 1031.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 297 (2) K
0.80 × 0.26 × 0.13 mm

Data collection

Stoe STADI-4 four-circle diffractometer
Absorption correction: ψ-sacn (North et al., 1968 ) T_min = 0.873, T_max = 0.927
1825 measured reflections
1825 independent reflections
1445 reflections with I > 2σ(I)
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.179
S = 1.07
1825 reflections
133 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6N⋯O5ⁱ	0.78 (4)	2.12 (4)	2.857 (4)	159 (4)
C3—H3⋯O5ⁱ	0.98	2.38	3.252 (4)	148
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: STADI4 (Stoe & Cie, 1987 ); cell refinement: STADI4; 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: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807064914/dn2290sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807064914/dn2290Isup2.hkl

checkCIF report

Comment top

In the present work, the structure of 2,2-dichloro-N- (3,5-dimethylphenyl)-acetamide (35DMPDCA) has been determined to explore the substituent effects on the structures of N-aromatic amides (Gowda et al., 2001, 2006, 2007). The structure of 35DMPDCA (Fig. 1) resembles those of 2,2-dichloro-N-(phenyl)acetamide (PDCA)(Gowda et al., 2001), 2,2-dichloro-N-(2-methylphenyl)acetamide (2MPDCA)(Gowda et al., 2006), 2,2-dichloro-N-(3-methylphenyl)-acetamide (3MPDCA) (Gowda et al., 2006), 2,2-dichloro-N-(4-methylphenyl)-acetamide (4MPDCA)(Gowda et al., 2001) and N-(3,5-dimethylphenyl)-acetamide (35DMPA)(Gowda et al., 2007). But the 35DMPDCA has a single molecule in its asymmetric unit, in contrast to two molecules observed in the asymmetric unit of 35DMPA. The bond parameters in 35DMPDCA are similar to those in PDCA, 2MPDCA, 3MPDCA, 4MPDCA, 35DMPA and other acetanilides (Gowda et al., 2001, 2006; 2007). The molecules in 35DMPDcA are linked into zigzag chains through N—H···O and C—H···O hydrogen bonding (Table 1 and Fig.2).

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

Data collection: STADI4 (Stoe & Cie, 1987); cell refinement: STADI4 (Stoe & Cie, 1987); 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: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

	Fig. 1. Molecular structure of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view showing the formation of the chain through N—H···O hydrogen bondings. H atoms not involved in H bonds have been omitted for clarity. H bonds are shown as dashed lines. [Symmetry code: (i) x, -y + 1/2, z + 1/2]

2,2-Dichloro-N-(3,5-dimethylphenyl)acetamide top

Crystal data top

C₁₀H₁₁Cl₂NO	F(000) = 480
M_r = 232.10	D_x = 1.494 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 44 reflections
a = 11.412 (4) Å	θ = 17.6–19.7°
b = 10.570 (4) Å	µ = 0.59 mm⁻¹
c = 9.163 (3) Å	T = 297 K
β = 110.99 (2)°	Prism, light yellow
V = 1031.9 (6) Å³	0.80 × 0.26 × 0.13 mm
Z = 4

Data collection top

Stoe STADI-4 four-circle diffractometer	1445 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 25.0°, θ_min = 1.9°
Profile fitted scans 2θ/ω=1/1	h = −13→12
Absorption correction: numerical (North et al., 1968)	k = 0→12
T_min = 0.873, T_max = 0.927	l = 0→10
1825 measured reflections	3 standard reflections every 120 min
1825 independent reflections	intensity decay: 1%

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.179	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0889P)² + 0.8161P] where P = (F_o² + 2F_c²)/3
1825 reflections	(Δ/σ)_max = 0.015
133 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₁₀H₁₁Cl₂NO	V = 1031.9 (6) Å³
M_r = 232.10	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.412 (4) Å	µ = 0.59 mm⁻¹
b = 10.570 (4) Å	T = 297 K
c = 9.163 (3) Å	0.80 × 0.26 × 0.13 mm
β = 110.99 (2)°

Data collection top

Stoe STADI-4 four-circle diffractometer	1445 reflections with I > 2σ(I)
Absorption correction: numerical (North et al., 1968)	R_int = 0.000
T_min = 0.873, T_max = 0.927	3 standard reflections every 120 min
1825 measured reflections	intensity decay: 1%
1825 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.179	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.62 e Å⁻³
1825 reflections	Δρ_min = −0.49 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.

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	−0.00025 (11)	0.11758 (11)	0.14291 (16)	0.0946 (5)
Cl2	0.03634 (11)	0.35402 (11)	0.07162 (15)	0.0921 (5)
C3	0.0997 (3)	0.2384 (3)	0.2002 (4)	0.0532 (8)
H3	0.1084	0.2653	0.3059	0.064*
C4	0.2273 (3)	0.2054 (3)	0.1930 (3)	0.0471 (7)
O5	0.2424 (2)	0.1976 (3)	0.0688 (2)	0.0668 (7)
N6	0.3146 (2)	0.1846 (2)	0.3333 (3)	0.0460 (6)
H6N	0.300 (3)	0.199 (3)	0.408 (4)	0.055*
C7	0.4409 (3)	0.1498 (3)	0.3696 (3)	0.0442 (7)
C8	0.4852 (3)	0.1039 (3)	0.2593 (4)	0.0522 (8)
H8	0.4318	0.0955	0.1558	0.063*
C9	0.6106 (3)	0.0702 (3)	0.3040 (4)	0.0580 (8)
C10	0.6875 (3)	0.0818 (3)	0.4575 (4)	0.0602 (9)
H10	0.7713	0.0583	0.4866	0.072*
C11	0.6444 (3)	0.1270 (3)	0.5694 (4)	0.0574 (8)
C12	0.5203 (3)	0.1600 (3)	0.5236 (4)	0.0511 (8)
H12	0.4889	0.1899	0.5977	0.061*
C13	0.6583 (4)	0.0221 (5)	0.1825 (5)	0.0855 (13)
H13A	0.6346	0.0795	0.0956	0.120*
H13B	0.6229	−0.0598	0.1476	0.120*
H13C	0.7481	0.0155	0.2262	0.120*
C14	0.7311 (4)	0.1379 (4)	0.7388 (5)	0.0799 (12)
H14A	0.8149	0.1555	0.7434	0.112*	0.46 (5)
H14B	0.7304	0.0598	0.7920	0.112*	0.46 (5)
H14C	0.7029	0.2053	0.7883	0.112*	0.46 (5)
H14D	0.6839	0.1250	0.8057	0.112*	0.54 (5)
H14E	0.7684	0.2206	0.7571	0.112*	0.54 (5)
H14F	0.7959	0.0751	0.7609	0.112*	0.54 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0748 (8)	0.0835 (8)	0.1257 (11)	−0.0243 (5)	0.0362 (7)	−0.0154 (6)
Cl2	0.0778 (8)	0.0821 (8)	0.1134 (9)	0.0310 (6)	0.0306 (6)	0.0280 (6)
C3	0.0472 (16)	0.0593 (19)	0.0507 (16)	0.0001 (14)	0.0146 (13)	−0.0023 (14)
C4	0.0502 (17)	0.0486 (16)	0.0425 (15)	0.0020 (13)	0.0165 (13)	0.0035 (12)
O5	0.0634 (15)	0.0949 (19)	0.0436 (12)	0.0195 (13)	0.0211 (10)	0.0148 (12)
N6	0.0494 (14)	0.0508 (14)	0.0388 (13)	0.0056 (11)	0.0171 (11)	0.0011 (11)
C7	0.0463 (16)	0.0370 (14)	0.0482 (16)	0.0021 (11)	0.0156 (13)	0.0052 (11)
C8	0.0566 (19)	0.0501 (16)	0.0490 (16)	0.0047 (14)	0.0176 (14)	0.0033 (13)
C9	0.0567 (19)	0.0496 (17)	0.070 (2)	0.0057 (14)	0.0258 (17)	0.0038 (15)
C10	0.0480 (18)	0.0505 (17)	0.076 (2)	0.0062 (14)	0.0153 (16)	0.0040 (16)
C11	0.0530 (19)	0.0431 (16)	0.065 (2)	−0.0012 (13)	0.0074 (16)	0.0028 (14)
C12	0.0547 (19)	0.0457 (16)	0.0479 (16)	0.0013 (14)	0.0123 (14)	−0.0001 (13)
C13	0.080 (3)	0.096 (3)	0.089 (3)	0.027 (2)	0.041 (2)	−0.001 (2)
C14	0.065 (2)	0.072 (2)	0.074 (2)	0.0028 (19)	−0.0092 (19)	−0.0078 (19)

Geometric parameters (Å, º) top

Cl1—C3	1.667 (3)	C10—C11	1.372 (5)
Cl2—C3	1.671 (3)	C10—H10	0.9300
C3—C4	1.522 (4)	C11—C12	1.371 (5)
C3—H3	0.9800	C11—C14	1.518 (5)
C4—O5	1.213 (4)	C12—H12	0.9300
C4—N6	1.333 (4)	C13—H13A	0.9600
N6—C7	1.407 (4)	C13—H13B	0.9600
N6—H6N	0.78 (4)	C13—H13C	0.9600
C7—C8	1.370 (4)	C14—H14A	0.9600
C7—C12	1.381 (4)	C14—H14B	0.9600
C8—C9	1.387 (5)	C14—H14C	0.9600
C8—H8	0.9300	C14—H14D	0.9600
C9—C10	1.370 (5)	C14—H14E	0.9600
C9—C13	1.493 (5)	C14—H14F	0.9600

C4—C3—Cl1	111.6 (2)	C7—C12—H12	119.3
C4—C3—Cl2	108.4 (2)	C9—C13—H13A	109.5
Cl1—C3—Cl2	105.31 (18)	C9—C13—H13B	109.5
C4—C3—H3	110.5	H13A—C13—H13B	109.5
Cl1—C3—H3	110.5	C9—C13—H13C	109.5
Cl2—C3—H3	110.5	H13A—C13—H13C	109.5
O5—C4—N6	125.8 (3)	H13B—C13—H13C	109.5
O5—C4—C3	121.0 (3)	C11—C14—H14A	109.5
N6—C4—C3	113.1 (3)	C11—C14—H14B	109.5
C4—N6—C7	128.3 (3)	H14A—C14—H14B	109.5
C4—N6—H6N	120 (3)	C11—C14—H14C	109.5
C7—N6—H6N	112 (3)	H14A—C14—H14C	109.5
C8—C7—C12	120.1 (3)	H14B—C14—H14C	109.5
C8—C7—N6	122.4 (3)	C11—C14—H14D	109.5
C12—C7—N6	117.6 (3)	H14A—C14—H14D	141.1
C7—C8—C9	119.2 (3)	H14B—C14—H14D	56.3
C7—C8—H8	120.4	H14C—C14—H14D	56.3
C9—C8—H8	120.4	C11—C14—H14E	109.5
C10—C9—C8	119.6 (3)	H14A—C14—H14E	56.3
C10—C9—C13	121.7 (3)	H14B—C14—H14E	141.1
C8—C9—C13	118.7 (3)	H14C—C14—H14E	56.3
C9—C10—C11	121.9 (3)	H14D—C14—H14E	109.5
C9—C10—H10	119.0	C11—C14—H14F	109.5
C11—C10—H10	119.0	H14A—C14—H14F	56.3
C12—C11—C10	117.9 (3)	H14B—C14—H14F	56.3
C12—C11—C14	121.2 (4)	H14C—C14—H14F	141.1
C10—C11—C14	121.0 (3)	H14D—C14—H14F	109.5
C11—C12—C7	121.4 (3)	H14E—C14—H14F	109.5
C11—C12—H12	119.3

Cl1—C3—C4—O5	73.5 (4)	C7—C8—C9—C10	0.8 (5)
Cl2—C3—C4—O5	−42.1 (4)	C7—C8—C9—C13	−179.2 (3)
Cl1—C3—C4—N6	−105.2 (3)	C8—C9—C10—C11	−0.6 (5)
Cl2—C3—C4—N6	139.3 (2)	C13—C9—C10—C11	179.4 (4)
O5—C4—N6—C7	0.0 (5)	C9—C10—C11—C12	0.5 (5)
C3—C4—N6—C7	178.5 (3)	C9—C10—C11—C14	179.5 (3)
C4—N6—C7—C8	−15.4 (5)	C10—C11—C12—C7	−0.8 (5)
C4—N6—C7—C12	166.3 (3)	C14—C11—C12—C7	−179.8 (3)
C12—C7—C8—C9	−1.1 (5)	C8—C7—C12—C11	1.1 (5)
N6—C7—C8—C9	−179.3 (3)	N6—C7—C12—C11	179.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6N···O5ⁱ	0.78 (4)	2.12 (4)	2.857 (4)	159 (4)
C3—H3···O5ⁱ	0.98	2.38	3.252 (4)	148

Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁Cl₂NO
M_r	232.10
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	297
a, b, c (Å)	11.412 (4), 10.570 (4), 9.163 (3)
β (°)	110.99 (2)
V (Å³)	1031.9 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.59
Crystal size (mm)	0.80 × 0.26 × 0.13

Data collection
Diffractometer	Stoe STADI-4 four-circle diffractometer
Absorption correction	Numerical (North et al., 1968)
T_min, T_max	0.873, 0.927
No. of measured, independent and observed [I > 2σ(I)] reflections	1825, 1825, 1445
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.179, 1.07
No. of reflections	1825
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)	0.62, −0.49

Computer programs: STADI4 (Stoe & Cie, 1987), REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6N···O5ⁱ	0.78 (4)	2.12 (4)	2.857 (4)	159 (4)
C3—H3···O5ⁱ	0.98	2.38	3.252 (4)	148.2

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for extensions of his research fellowship.

References

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gowda, B. T., Kožíšek, J., Tokarčík, M. & Fuess, H. (2007). Acta Cryst. E63, o2711. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gowda, B. T., Paulus, H. & Fuess, H. (2001). Z. Naturforsch. Teil A, 56, 386–394. CAS Google Scholar
Gowda, B. T., Paulus, H., Kozisek, J., Tokarcik, M. & Fuess, H. (2006). Z. Naturforsch. Teil A, 61, 675–682. CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Shilpa & Gowda, B. T. (2007). Z. Naturforsch. Teil A, 62, 84–90. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (1987). STADI4 and REDU4. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar