3,5-Dichloro-N-(2-methyl­but-3-yn-2-yl)benzamide

Ru, Z.-L.; Wang, G.-X.

doi:10.1107/S1600536809051228

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o8

doi:10.1107/S1600536809051228

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3,5-Dichloro-N-(2-methylbut-3-yn-2-yl)benzamide

Zong-Ling Ru ^a and Guo-Xi Wang ^a ^*

^aDepartment of Chemical & Environmental Engineering, Anyang Institute of Technology, Anyang 455000, People's Republic of China
^*Correspondence e-mail: aywgx@yahoo.com.cn

(Received 24 November 2009; accepted 27 November 2009; online 4 December 2009)

In the title compound, C₁₂H₁₁Cl₂NO, the amide group is twisted by a dihedral angle of 31.98 (2)° with respect to the benzene ring. In the crystal structure, molecules are linked via N—H⋯O hydrogen bonds, forming one-dimensional supramolecular chains.

Related literature

For the chemistry of halogenated aromatic amide derivatives, see: Cirilli et al. (1997 ).

Experimental

Crystal data

C₁₂H₁₁Cl₂NO
M_r = 256.12
Monoclinic, P 2₁ /c
a = 12.227 (2) Å
b = 10.898 (2) Å
c = 10.170 (2) Å
β = 111.08 (3)°
V = 1264.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 298 K
0.4 × 0.35 × 0.2 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.881, T_max = 0.940
12803 measured reflections
2890 independent reflections
2308 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.103
S = 1.07
2890 reflections
147 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1ⁱ	0.86	2.21	3.051 (3)	168
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809051228/xu2695sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051228/xu2695Isup2.hkl

checkCIF report

Comment top

Halogenated aromatic amide derivatives are an important class of chemical raw materials, which have found wide range of applications in agriculture as herbicides, in medicine as drugs, in coordination chemistry as ligand, and which are also used in industry. Recently, a series of halogenated aromatic amide compounds have been reported (Cirilli et al., 1997). As an extension of these work on the structural characterization, we report here the crystal structure of the title compound 3,5-dichloro-N-(2-methylbut-3-yn-2-yl)benzamide.

The crystal data show that in the title compound (Fig. 1), the amide group is rotated by 31.98 (2)° out of the plane of the benzene ring. All the bond length are within the normal range. The crystal packing is stabilized by N—H···O hydrogen bonds to form an infinite one-dimensional chain parallel to the c axis (Table 1).

Related literature top

For the chemistry of halogenated aromatic amide derivatives, see: Cirilli et al. (1997).

Experimental top

The purchased 3,5-dichloro-N-(2-methylbut-3-yn-2-yl)benzamide (3 mmol, 768 mg) was dissolved in chloroform (20 ml) and evaporated in the air, single crystals of the compound suitable for X-ray analysis were obtained from the solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

3,5-Dichloro-N-(2-methylbut-3-yn-2-yl)benzamide top

Crystal data top

C₁₂H₁₁Cl₂NO	F(000) = 528
M_r = 256.12	D_x = 1.345 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2308 reflections
a = 12.227 (2) Å	θ = 3.6–27.5°
b = 10.898 (2) Å	µ = 0.49 mm⁻¹
c = 10.170 (2) Å	T = 298 K
β = 111.08 (3)°	Block, colourless
V = 1264.5 (4) Å³	0.4 × 0.35 × 0.2 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	2890 independent reflections
Radiation source: fine-focus sealed tube	2308 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.6°
ω scans	h = −15→15
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
T_min = 0.881, T_max = 0.940	l = −13→13
12803 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0378P)² + 0.5464P] where P = (F_o² + 2F_c²)/3
2890 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.28 e Å⁻³
1 restraint	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₂H₁₁Cl₂NO	V = 1264.5 (4) Å³
M_r = 256.12	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.227 (2) Å	µ = 0.49 mm⁻¹
b = 10.898 (2) Å	T = 298 K
c = 10.170 (2) Å	0.4 × 0.35 × 0.2 mm
β = 111.08 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2890 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2308 reflections with I > 2σ(I)
T_min = 0.881, T_max = 0.940	R_int = 0.031
12803 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	1 restraint
wR(F²) = 0.103	H-atom parameters constrained
S = 1.07	Δρ_max = 0.28 e Å⁻³
2890 reflections	Δρ_min = −0.29 e Å⁻³
147 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
Cl1	0.50021 (8)	0.45984 (9)	0.16860 (9)	0.0697 (3)
Cl2	0.35913 (8)	0.74552 (7)	0.50663 (10)	0.0644 (3)
O1	0.20562 (18)	0.29208 (18)	0.52618 (18)	0.0477 (5)
C1	0.2939 (2)	0.5093 (2)	0.4506 (3)	0.0376 (6)
H1A	0.2532	0.5195	0.5115	0.045*
C7	0.2183 (2)	0.2973 (2)	0.4121 (2)	0.0349 (5)
C5	0.3539 (2)	0.3825 (2)	0.2953 (3)	0.0387 (6)
H5A	0.3524	0.3081	0.2499	0.046*
C6	0.2908 (2)	0.3977 (2)	0.3837 (2)	0.0334 (5)
N1	0.1679 (2)	0.2190 (2)	0.3067 (2)	0.0420 (5)
H1B	0.1830	0.2271	0.2308	0.050*
C3	0.4220 (2)	0.5918 (3)	0.3399 (3)	0.0433 (6)
H3A	0.4660	0.6565	0.3253	0.052*
C2	0.3579 (2)	0.6049 (2)	0.4260 (3)	0.0399 (6)
C4	0.4190 (2)	0.4799 (3)	0.2760 (3)	0.0415 (6)
C8	0.0882 (3)	0.1195 (2)	0.3123 (3)	0.0444 (6)
C11	−0.0141 (3)	0.1721 (3)	0.3361 (3)	0.0543 (8)
C10	0.0456 (3)	0.0569 (3)	0.1680 (3)	0.0680 (10)
H10A	0.0071	0.1160	0.0963	0.102*
H10B	−0.0083	−0.0075	0.1667	0.102*
H10C	0.1114	0.0228	0.1503	0.102*
C12	−0.0996 (4)	0.2091 (4)	0.3488 (5)	0.0849 (12)
H12	−0.1710	0.2530	0.3603	0.102*
C9	0.1506 (3)	0.0267 (3)	0.4266 (4)	0.0707 (10)
H9A	0.1726	0.0653	0.5173	0.106*
H9B	0.2194	−0.0029	0.4124	0.106*
H9C	0.0990	−0.0409	0.4222	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0835 (6)	0.0804 (6)	0.0687 (5)	−0.0018 (5)	0.0559 (5)	0.0028 (4)
Cl2	0.0809 (6)	0.0369 (4)	0.0803 (6)	−0.0041 (4)	0.0351 (5)	−0.0126 (4)
O1	0.0674 (13)	0.0510 (11)	0.0302 (9)	−0.0099 (10)	0.0240 (9)	−0.0033 (8)
C1	0.0375 (14)	0.0413 (14)	0.0341 (13)	0.0005 (11)	0.0129 (11)	−0.0027 (10)
C7	0.0394 (13)	0.0373 (13)	0.0280 (12)	−0.0003 (10)	0.0119 (10)	−0.0009 (10)
C5	0.0443 (14)	0.0413 (14)	0.0314 (12)	−0.0004 (11)	0.0147 (11)	−0.0025 (10)
C6	0.0329 (12)	0.0388 (13)	0.0259 (11)	−0.0012 (10)	0.0074 (9)	−0.0004 (10)
N1	0.0537 (14)	0.0465 (13)	0.0299 (11)	−0.0158 (10)	0.0199 (10)	−0.0063 (9)
C3	0.0435 (15)	0.0432 (15)	0.0422 (14)	−0.0038 (12)	0.0143 (12)	0.0073 (12)
C2	0.0427 (14)	0.0345 (13)	0.0397 (14)	0.0020 (11)	0.0114 (11)	−0.0016 (10)
C4	0.0428 (15)	0.0511 (16)	0.0343 (13)	0.0021 (12)	0.0186 (11)	0.0052 (11)
C8	0.0569 (17)	0.0405 (15)	0.0376 (14)	−0.0128 (12)	0.0193 (13)	−0.0036 (11)
C11	0.060 (2)	0.0516 (18)	0.0552 (18)	−0.0166 (15)	0.0249 (15)	−0.0028 (14)
C10	0.091 (3)	0.066 (2)	0.0528 (19)	−0.0371 (19)	0.0325 (18)	−0.0231 (16)
C12	0.070 (3)	0.078 (3)	0.114 (3)	−0.013 (2)	0.042 (2)	−0.013 (2)
C9	0.089 (3)	0.0462 (19)	0.070 (2)	−0.0042 (17)	0.020 (2)	0.0103 (16)

Geometric parameters (Å, º) top

Cl1—C4	1.734 (3)	C3—C2	1.377 (4)
Cl2—C2	1.736 (3)	C3—H3A	0.9300
O1—C7	1.226 (3)	C8—C11	1.472 (4)
C1—C2	1.380 (4)	C8—C9	1.522 (4)
C1—C6	1.387 (3)	C8—C10	1.531 (4)
C1—H1A	0.9300	C11—C12	1.171 (5)
C7—N1	1.335 (3)	C10—H10A	0.9600
C7—C6	1.500 (3)	C10—H10B	0.9600
C5—C4	1.383 (4)	C10—H10C	0.9600
C5—C6	1.390 (3)	C12—H12	1.0386
C5—H5A	0.9300	C9—H9A	0.9600
N1—C8	1.473 (3)	C9—H9B	0.9600
N1—H1B	0.8600	C9—H9C	0.9600
C3—C4	1.375 (4)

C2—C1—C6	119.3 (2)	C3—C4—Cl1	119.0 (2)
C2—C1—H1A	120.3	C5—C4—Cl1	118.8 (2)
C6—C1—H1A	120.3	C11—C8—N1	109.4 (2)
O1—C7—N1	123.5 (2)	C11—C8—C9	110.8 (3)
O1—C7—C6	120.1 (2)	N1—C8—C9	111.2 (2)
N1—C7—C6	116.5 (2)	C11—C8—C10	108.4 (3)
C4—C5—C6	118.8 (2)	N1—C8—C10	107.0 (2)
C4—C5—H5A	120.6	C9—C8—C10	109.9 (3)
C6—C5—H5A	120.6	C12—C11—C8	175.9 (4)
C1—C6—C5	119.9 (2)	C8—C10—H10A	109.5
C1—C6—C7	117.3 (2)	C8—C10—H10B	109.5
C5—C6—C7	122.8 (2)	H10A—C10—H10B	109.5
C7—N1—C8	124.0 (2)	C8—C10—H10C	109.5
C7—N1—H1B	118.0	H10A—C10—H10C	109.5
C8—N1—H1B	118.0	H10B—C10—H10C	109.5
C4—C3—C2	117.9 (2)	C11—C12—H12	172.7
C4—C3—H3A	121.0	C8—C9—H9A	109.5
C2—C3—H3A	121.0	C8—C9—H9B	109.5
C3—C2—C1	121.8 (2)	H9A—C9—H9B	109.5
C3—C2—Cl2	118.9 (2)	C8—C9—H9C	109.5
C1—C2—Cl2	119.3 (2)	H9A—C9—H9C	109.5
C3—C4—C5	122.2 (2)	H9B—C9—H9C	109.5

C2—C1—C6—C5	1.4 (4)	C4—C3—C2—Cl2	−179.4 (2)
C2—C1—C6—C7	−179.0 (2)	C6—C1—C2—C3	−2.0 (4)
C4—C5—C6—C1	0.0 (4)	C6—C1—C2—Cl2	178.54 (19)
C4—C5—C6—C7	−179.6 (2)	C2—C3—C4—C5	0.3 (4)
O1—C7—C6—C1	−30.5 (4)	C2—C3—C4—Cl1	−179.2 (2)
N1—C7—C6—C1	147.8 (2)	C6—C5—C4—C3	−0.9 (4)
O1—C7—C6—C5	149.1 (2)	C6—C5—C4—Cl1	178.65 (19)
N1—C7—C6—C5	−32.6 (4)	C7—N1—C8—C11	59.8 (4)
O1—C7—N1—C8	2.1 (4)	C7—N1—C8—C9	−63.0 (4)
C6—C7—N1—C8	−176.2 (2)	C7—N1—C8—C10	177.0 (3)
C4—C3—C2—C1	1.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.86	2.21	3.051 (3)	168

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₁Cl₂NO
M_r	256.12
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.227 (2), 10.898 (2), 10.170 (2)
β (°)	111.08 (3)
V (Å³)	1264.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.4 × 0.35 × 0.2

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.881, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	12803, 2890, 2308
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.103, 1.07
No. of reflections	2890
No. of parameters	147
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.29

Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.86	2.21	3.051 (3)	167.7

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

This work was supported by a start-up grant from Anyang Institute of Technology, China.

References

Cirilli, R., Gaparrini, F., Villani, C., Gavuzzo, E. & Cirilli, M. (1997). Acta Cryst. C53, 1937–1939. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar