4-Chloro-N-methyl­benzamide

Yuan, J.; Liu, Y.-J.

doi:10.1107/S1600536812008641

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o937

doi:10.1107/S1600536812008641

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4-Chloro-N-methylbenzamide

Juan Yuan ^a and Yan-Ju Liu ^a ^*

^aPharmacy College, Henan University of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China
^*Correspondence e-mail: liuyanju886@163.com

(Received 8 February 2012; accepted 27 February 2012; online 3 March 2012)

There are two molecules in the asymmetric unit of the title compound, C₈H₈ClNO, which are linked in the crystal structure via N—H⋯O hydrogen bonds into chains along the b axis. C—H⋯O contacts also occur. The benzene ring makes dihedral angles of 5.9 (1) and 16.7 (1)°with the attached amide group in the two independent molecules.

Related literature

For applications of the title compound and background to the synthesis, see: Lee et al. (2009 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₈ClNO
M_r = 169.61
Triclinic, $[P \overline 1]$
a = 3.9420 (8) Å
b = 9.2250 (18) Å
c = 21.864 (4) Å
α = 96.46 (3)°
β = 90.34 (3)°
γ = 90.99 (3)°
V = 789.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 296 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.921, T_max = 0.959
3079 measured reflections
2887 independent reflections
1633 reflections with I > 2σ(I)
R_int = 0.047
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.188
S = 1.00
2887 reflections
199 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.86	2.07	2.876 (4)	157
N2—H2B⋯O1ⁱⁱ	0.86	2.06	2.887 (4)	160
C5—H5A⋯O2ⁱ	0.93	2.53	3.417 (5)	159
C9—H9A⋯O1ⁱⁱ	0.93	2.60	3.379 (5)	142
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+2, -z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812008641/bq2339sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008641/bq2339Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812008641/bq2339Isup3.cml

checkCIF report

Comment top

Benzamide derivatives exhibit interesting biological activities such as antibacterial and antifungal effects (Lee et al., 2009). We report here the crystal structure of the title compound 4-chloro-N-methylbenzamide, (I).

The molecular structure of (I) is shown in Fig. 1. The title compound was connected together via N—H···O intermolecular hydrogen bonds (Table 1), supported by a C—H···O contact, forming chains along b axis direction (Figure 2.).

The asymmetric unit contains two title molecules of 4-chloro-N-methylbenzamide. The rings of these molecules are planar with r.m.s. deviation of 0.0048 Å and 0.0034 Å. The dihedral angles of the planes A(C1—C6), B(C7/O1/N1/H1A), C(C9—C14), D(C15/O2/N2/H2B) are: A/B = 5.9 (1)°, C/D = 16.7 (1)° and A/C = 16.77 (16) °.

Related literature top

For applications of the title compound and background to the synthesis, see: Lee et al. (2009). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I) was prepared by a method reported in literature (Lee et al., 2009). The crystals were obtained by dissolving (I) (0.1 g) in methanol (30 ml) and evaporating the solvent slowly at room temperature for about 8 d.

Structure description top

For applications of the title compound and background to the synthesis, see: Lee et al. (2009). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I) showing N-H..O hydrogen-bonded chains along b axis. H atoms not involved in bonding are omitted for clarity.

4-Chloro-N-methylbenzamide top

Crystal data top

C₈H₈ClNO	Z = 4
M_r = 169.61	F(000) = 352
Triclinic, P1	D_x = 1.426 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.9420 (8) Å	Cell parameters from 25 reflections
b = 9.2250 (18) Å	θ = 9–12°
c = 21.864 (4) Å	µ = 0.42 mm⁻¹
α = 96.46 (3)°	T = 296 K
β = 90.34 (3)°	Block, colourless
γ = 90.99 (3)°	0.20 × 0.10 × 0.10 mm
V = 789.9 (3) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1633 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.047
Graphite monochromator	θ_max = 25.4°, θ_min = 1.9°
ω/2θ scans	h = −4→4
Absorption correction: ψ scan (North et al., 1968)	k = −11→0
T_min = 0.921, T_max = 0.959	l = −26→26
3079 measured reflections	3 standard reflections every 200 reflections
2887 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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.188	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.094P)²] where P = (F_o² + 2F_c²)/3
2887 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.29 e Å⁻³
2 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₈H₈ClNO	γ = 90.99 (3)°
M_r = 169.61	V = 789.9 (3) Å³
Triclinic, P1	Z = 4
a = 3.9420 (8) Å	Mo Kα radiation
b = 9.2250 (18) Å	µ = 0.42 mm⁻¹
c = 21.864 (4) Å	T = 296 K
α = 96.46 (3)°	0.20 × 0.10 × 0.10 mm
β = 90.34 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1633 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.047
T_min = 0.921, T_max = 0.959	3 standard reflections every 200 reflections
3079 measured reflections	intensity decay: 1%
2887 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	2 restraints
wR(F²) = 0.188	H-atom parameters constrained
S = 1.00	Δρ_max = 0.29 e Å⁻³
2887 reflections	Δρ_min = −0.25 e Å⁻³
199 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	1.2503 (4)	0.71959 (16)	1.02286 (5)	0.0971 (5)
N1	0.7112 (8)	0.7694 (3)	0.73236 (14)	0.0536 (8)
H1A	0.6619	0.6842	0.7424	0.064*
O1	0.9592 (8)	0.9833 (3)	0.75794 (13)	0.0748 (9)
C1	1.1009 (11)	0.9251 (5)	0.87664 (19)	0.0723 (13)
H1B	1.1381	1.0195	0.8667	0.087*
C2	1.1874 (12)	0.8941 (5)	0.9344 (2)	0.0751 (13)
H2A	1.2858	0.9658	0.9626	0.090*
C3	1.1290 (11)	0.7593 (5)	0.94995 (19)	0.0642 (11)
C4	0.9934 (12)	0.6541 (5)	0.9090 (2)	0.0732 (13)
H4A	0.9623	0.5610	0.9207	0.088*
C5	0.8993 (12)	0.6791 (4)	0.85058 (19)	0.0659 (12)
H5A	0.7988	0.6064	0.8231	0.079*
C6	0.9649 (9)	0.8253 (3)	0.83385 (16)	0.0478 (9)
C7	0.8729 (9)	0.8632 (4)	0.77223 (17)	0.0470 (9)
C8	0.6136 (11)	0.8043 (4)	0.67242 (18)	0.0625 (11)
H8A	0.4946	0.7224	0.6507	0.094*
H8B	0.8125	0.8266	0.6499	0.094*
H8C	0.4683	0.8872	0.6766	0.094*
Cl2	0.3429 (3)	0.77031 (14)	0.52328 (5)	0.0843 (5)
O2	−0.3948 (7)	0.5109 (3)	0.25934 (13)	0.0690 (8)
N2	−0.3020 (8)	0.7363 (3)	0.23575 (14)	0.0575 (9)
H2B	−0.2129	0.8209	0.2470	0.069*
C9	−0.0638 (11)	0.8149 (4)	0.36052 (18)	0.0615 (11)
H9A	−0.1235	0.8915	0.3386	0.074*
C10	0.0805 (11)	0.8473 (4)	0.41801 (18)	0.0626 (11)
H10A	0.1145	0.9435	0.4350	0.075*
C11	0.1731 (10)	0.7327 (4)	0.44960 (18)	0.0592 (10)
C12	0.1202 (10)	0.5922 (4)	0.42494 (18)	0.0608 (11)
H12A	0.1841	0.5163	0.4470	0.073*
C13	−0.0237 (10)	0.5619 (4)	0.36903 (18)	0.0593 (11)
H13A	−0.0589	0.4652	0.3528	0.071*
C14	−0.1232 (9)	0.6758 (3)	0.33430 (16)	0.0444 (8)
C15	−0.2870 (10)	0.6352 (4)	0.27428 (17)	0.0504 (9)
C16	−0.4602 (11)	0.7105 (4)	0.17627 (19)	0.0694 (12)
H16A	−0.4403	0.7968	0.1557	0.104*
H16B	−0.6957	0.6861	0.1809	0.104*
H16C	−0.3507	0.6312	0.1524	0.104*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1301 (12)	0.1145 (11)	0.0491 (7)	−0.0039 (8)	−0.0234 (7)	0.0221 (7)
N1	0.076 (2)	0.0421 (17)	0.0432 (18)	−0.0096 (15)	−0.0155 (15)	0.0103 (14)
O1	0.113 (2)	0.0438 (16)	0.069 (2)	−0.0172 (15)	−0.0122 (17)	0.0171 (14)
C1	0.102 (3)	0.062 (3)	0.053 (3)	−0.020 (2)	−0.011 (2)	0.012 (2)
C2	0.099 (3)	0.072 (3)	0.052 (3)	−0.032 (2)	−0.022 (2)	0.001 (2)
C3	0.072 (3)	0.072 (3)	0.051 (3)	0.015 (2)	−0.002 (2)	0.013 (2)
C4	0.116 (4)	0.052 (2)	0.053 (3)	−0.005 (2)	−0.010 (2)	0.015 (2)
C5	0.104 (3)	0.041 (2)	0.054 (3)	−0.004 (2)	−0.013 (2)	0.0096 (17)
C6	0.061 (2)	0.0419 (19)	0.039 (2)	−0.0028 (16)	−0.0064 (17)	0.0023 (15)
C7	0.058 (2)	0.0308 (18)	0.054 (2)	0.0032 (16)	−0.0016 (17)	0.0098 (15)
C8	0.080 (3)	0.061 (2)	0.048 (2)	0.005 (2)	−0.012 (2)	0.0118 (18)
Cl2	0.1028 (9)	0.1021 (10)	0.0483 (7)	0.0030 (7)	−0.0151 (6)	0.0110 (6)
O2	0.099 (2)	0.0387 (15)	0.068 (2)	−0.0151 (14)	−0.0110 (16)	0.0061 (13)
N2	0.085 (2)	0.0421 (17)	0.046 (2)	−0.0030 (15)	−0.0068 (16)	0.0078 (14)
C9	0.093 (3)	0.041 (2)	0.052 (3)	0.002 (2)	−0.015 (2)	0.0115 (17)
C10	0.102 (3)	0.037 (2)	0.049 (2)	0.001 (2)	−0.003 (2)	0.0020 (16)
C11	0.064 (3)	0.067 (3)	0.047 (2)	0.015 (2)	0.0010 (19)	0.0052 (19)
C12	0.079 (3)	0.053 (2)	0.054 (3)	0.011 (2)	−0.008 (2)	0.0194 (19)
C13	0.080 (3)	0.042 (2)	0.057 (3)	0.0145 (19)	0.003 (2)	0.0108 (18)
C14	0.052 (2)	0.0384 (19)	0.043 (2)	0.0040 (15)	0.0077 (16)	0.0034 (15)
C15	0.064 (2)	0.044 (2)	0.044 (2)	0.0031 (17)	0.0059 (18)	0.0069 (17)
C16	0.086 (3)	0.066 (3)	0.057 (3)	−0.007 (2)	−0.022 (2)	0.013 (2)

Geometric parameters (Å, º) top

Cl1—C3	1.741 (4)	Cl2—C11	1.737 (4)
N1—C7	1.311 (4)	O2—C15	1.224 (4)
N1—C8	1.436 (4)	N2—C15	1.327 (4)
N1—H1A	0.8600	N2—C16	1.433 (5)
O1—C7	1.227 (4)	N2—H2B	0.8600
C1—C6	1.339 (5)	C9—C14	1.360 (5)
C1—C2	1.368 (6)	C9—C10	1.376 (5)
C1—H1B	0.9300	C9—H9A	0.9300
C2—C3	1.342 (6)	C10—C11	1.379 (5)
C2—H2A	0.9300	C10—H10A	0.9300
C3—C4	1.345 (6)	C11—C12	1.359 (5)
C4—C5	1.373 (5)	C12—C13	1.343 (5)
C4—H4A	0.9300	C12—H12A	0.9300
C5—C6	1.456 (4)	C13—C14	1.423 (5)
C5—H5A	0.9300	C13—H13A	0.9300
C6—C7	1.474 (5)	C14—C15	1.467 (5)
C8—H8A	0.9600	C16—H16A	0.9600
C8—H8B	0.9600	C16—H16B	0.9600
C8—H8C	0.9600	C16—H16C	0.9600

C7—N1—C8	122.2 (3)	C15—N2—C16	122.8 (3)
C7—N1—H1A	118.9	C15—N2—H2B	118.6
C8—N1—H1A	118.9	C16—N2—H2B	118.6
C6—C1—C2	122.7 (4)	C14—C9—C10	123.0 (3)
C6—C1—H1B	118.6	C14—C9—H9A	118.5
C2—C1—H1B	118.6	C10—C9—H9A	118.5
C3—C2—C1	119.4 (4)	C9—C10—C11	117.9 (4)
C3—C2—H2A	120.3	C9—C10—H10A	121.0
C1—C2—H2A	120.3	C11—C10—H10A	121.0
C2—C3—C4	120.7 (4)	C12—C11—C10	121.0 (4)
C2—C3—Cl1	119.0 (3)	C12—C11—Cl2	120.0 (3)
C4—C3—Cl1	120.2 (3)	C10—C11—Cl2	118.9 (3)
C3—C4—C5	122.5 (4)	C13—C12—C11	120.5 (4)
C3—C4—H4A	118.8	C13—C12—H12A	119.7
C5—C4—H4A	118.8	C11—C12—H12A	119.7
C4—C5—C6	116.6 (4)	C12—C13—C14	120.9 (4)
C4—C5—H5A	121.7	C12—C13—H13A	119.6
C6—C5—H5A	121.7	C14—C13—H13A	119.6
C1—C6—C5	118.1 (4)	C9—C14—C13	116.7 (4)
C1—C6—C7	121.1 (3)	C9—C14—C15	125.2 (3)
C5—C6—C7	120.8 (3)	C13—C14—C15	118.1 (3)
O1—C7—N1	120.1 (3)	O2—C15—N2	121.1 (4)
O1—C7—C6	118.8 (3)	O2—C15—C14	121.2 (3)
N1—C7—C6	121.1 (3)	N2—C15—C14	117.6 (3)
N1—C8—H8A	109.5	N2—C16—H16A	109.5
N1—C8—H8B	109.5	N2—C16—H16B	109.5
H8A—C8—H8B	109.5	H16A—C16—H16B	109.5
N1—C8—H8C	109.5	N2—C16—H16C	109.5
H8A—C8—H8C	109.5	H16A—C16—H16C	109.5
H8B—C8—H8C	109.5	H16B—C16—H16C	109.5

C6—C1—C2—C3	−1.4 (7)	C14—C9—C10—C11	1.1 (6)
C1—C2—C3—C4	1.4 (7)	C9—C10—C11—C12	−0.7 (6)
C1—C2—C3—Cl1	178.3 (4)	C9—C10—C11—Cl2	−177.9 (3)
C2—C3—C4—C5	−1.9 (7)	C10—C11—C12—C13	0.1 (6)
Cl1—C3—C4—C5	−178.8 (4)	Cl2—C11—C12—C13	177.3 (3)
C3—C4—C5—C6	2.2 (7)	C11—C12—C13—C14	0.2 (6)
C2—C1—C6—C5	1.7 (7)	C10—C9—C14—C13	−0.9 (6)
C2—C1—C6—C7	179.6 (4)	C10—C9—C14—C15	177.7 (4)
C4—C5—C6—C1	−2.0 (6)	C12—C13—C14—C9	0.2 (6)
C4—C5—C6—C7	−179.9 (4)	C12—C13—C14—C15	−178.4 (4)
C8—N1—C7—O1	−3.2 (6)	C16—N2—C15—O2	3.7 (6)
C8—N1—C7—C6	179.0 (3)	C16—N2—C15—C14	−179.0 (3)
C1—C6—C7—O1	8.5 (6)	C9—C14—C15—O2	−164.7 (4)
C5—C6—C7—O1	−173.6 (4)	C13—C14—C15—O2	13.9 (5)
C1—C6—C7—N1	−173.6 (4)	C9—C14—C15—N2	18.0 (6)
C5—C6—C7—N1	4.3 (5)	C13—C14—C15—N2	−163.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	2.07	2.876 (4)	157
N2—H2B···O1ⁱⁱ	0.86	2.06	2.887 (4)	160
C5—H5A···O2ⁱ	0.93	2.53	3.417 (5)	159
C9—H9A···O1ⁱⁱ	0.93	2.60	3.379 (5)	142

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

Experimental details

Crystal data
Chemical formula	C₈H₈ClNO
M_r	169.61
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	3.9420 (8), 9.2250 (18), 21.864 (4)
α, β, γ (°)	96.46 (3), 90.34 (3), 90.99 (3)
V (Å³)	789.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.42
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.921, 0.959
No. of measured, independent and observed [I > 2σ(I)] reflections	3079, 2887, 1633
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.188, 1.00
No. of reflections	2887
No. of parameters	199
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.25

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.8600	2.0700	2.876 (4)	157.00
N2—H2B···O1ⁱⁱ	0.8600	2.0600	2.887 (4)	160.00
C5—H5A···O2ⁱ	0.9300	2.5300	3.417 (5)	159.00
C9—H9A···O1ⁱⁱ	0.9300	2.6000	3.379 (5)	142.00

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

Acknowledgements

This study was supported by the Science and Technology Department of Henan Province (102102310321) and the Doctoral Research Fund of Henan Chinese Medicine (BSJJ2009–38). The authors thank the Center of Testing and Analysis, Nanjing University for the data collection.

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