N-(2,4-Dichloro­phen­yl)benzamide

Abstract

The conformations of the N—H and C=O bonds in the structure of the title compound, C₁₃H₉Cl₂NO, are anti to each other, similar to that observed in N-phenyl­benzamide, N-(2-chloro­phen­yl)benzamide, N-(4-chloro­phen­yl)benzamide, N-(2,3-dichloro­phen­yl)benzamide, N-(2,6-dichloro­phen­yl)benzamide and other benzanilides. The amide –NHCO– group forms a dihedral angle of 33.0 (2)° with the benzoyl ring, while the rings are almost coplanar, making a dihedral angle of 2.6 (2)°). The mol­ecules are linked by N—H⋯O hydrogen bonds into infinite chains running along the b axis.

Related literature

For related literature, see: Gowda et al. (2003 ▶, 2007a ▶,b ▶, 2008a ▶,b ▶).

Experimental

Crystal data

• C₁₃H₉Cl₂NO

• M _r = 266.11

• Monoclinic,

• a = 11.7388 (6) Å

• b = 4.7475 (2) Å

• c = 22.8630 (11) Å

• β = 106.360 (4)°

• V = 1222.56 (10) ų

• Z = 4

• Mo Kα radiation

• μ = 0.51 mm⁻¹

• T = 295 (2) K

• 0.33 × 0.06 × 0.03 mm

Data collection

• Oxford Diffraction Xcalibur diffractometer

• Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2007 ▶), based on expressions derived by Clark & Reid (1995 ▶)] T _min = 0.905, T _max = 0.987

• 11465 measured reflections

• 2311 independent reflections

• 1209 reflections with I > 2σ(I)

• R _int = 0.060

Refinement

• R[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 0.089

• S = 1.06

• 2311 reflections

• 157 parameters

• 1 restraint

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

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2002 ▶); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2003 ▶) and WinGX (Farrugia, 1999 ▶).

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	0.805 (16)	2.178 (19)	2.899 (2)	149 (2)

Symmetry code: (i) .

supplementary crystallographic information

Comment

In the present work, the structure of N-(2,4-dichlorophenyl)-benzamide (N24DCPBA) has been determined to study the effect of substituents on the structures of benzanilides (Gowda et al., 2003, 2007a,b, 2008a,b). The conformations of the N—H and C=O bonds in the structure of N24DCPBA (Fig.1) are anti to each other, similar to that observed in N-(phenyl)-benzamide (NPBA) (Gowda et al., 2003), N-(2-chlorophenyl)-benzamide (N2CPBA), N-(4-chlorophenyl)-benzamide (N4CPBA), N-(2,3-dichlorophenyl)-benzamide(N23DCPBA), N-(2,6-dichlorophenyl)-benzamide (N26DCPBA) and other benzanilides (Gowda et al., 2007a,b, 2008a,b). The bond parameters in N24DCPBA are similar to those in NPBA, N2CPBA, N4CPBA, N23DCPBA, N26DCPBA and other benzanilides. The amide group –NHCO– forms the dihedral angle of 33.0 (2)° with the benzoyl ring, while the benzoyl and aniline rings are almost coplanar, with the dihedral angle of 2.6 (2)°). Part of the crystal structure of the title compound with infinite molecular chains running in the [010] direction is shown in Fig. 2. The chains are generated by N—H···O(i) hydrogen bonds (Table 1) [symmetry operation (i): x,y - 1,z].

Experimental

The title compound was prepared according to the literature method (Gowda et al., 2003). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra. Single crystals of the title compound were obtained from an ethanolic solution and used for X-ray diffraction studies at room temperature.

Refinement

H atoms attached to C atoms were placed in calculated positions and subsequently treated as riding with C–H distance 0.93 Å. H atom of the amide group was refined with the N—H distance restrained to 0.81 (2) Å. The U_iso(H) values were set at 1.2 U_eq(C,N).

Figures

Fig. 1.

Molecular structure of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2.

Part of the crystal structure of the title compound with infinite molecular chains running in the [010] direction. The chains are generated by N—H···O(i) hydrogen bonds.[Symmetry operation (i): x,y - 1,z]. H atoms not involved in intermolecular bonding have been omitted.

Crystal data

C13H9Cl2NO	F000 = 544
Mr = 266.11	Dx = 1.446 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2675 reflections
a = 11.7388 (6) Å	θ = 3.5–29.1º
b = 4.7475 (2) Å	µ = 0.51 mm−1
c = 22.8630 (11) Å	T = 295 (2) K
β = 106.360 (4)º	Needle, colorless
V = 1222.56 (10) Å3	0.33 × 0.06 × 0.03 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur diffractometer	2311 independent reflections
Monochromator: graphite	1209 reflections with I > 2σ(I)
Detector resolution: 10.434 pixels mm-1	Rint = 0.060
T = 295(2) K	θmax = 25.7º
ω scans with κ offsets	θmin = 5.1º
Absorption correction: analytical[CrysAlis RED (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]	h = −14→14
Tmin = 0.905, Tmax = 0.987	k = −5→5
11465 measured reflections	l = −27→27

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)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.089	[exp(3(sinθ/λ)2)]/ [σ2(Fo2) + (0.0389P)2] where P = 0.33333Fo2 + 0.66667Fc2
S = 1.06	(Δ/σ)max = 0.002
2311 reflections	Δρmax = 0.21 e Å−3
157 parameters	Δρmin = −0.16 e Å−3
1 restraint	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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	1.0522 (2)	0.6218 (5)	0.12848 (10)	0.0496 (6)
C2	1.1434 (2)	0.5105 (5)	0.18272 (10)	0.0528 (6)
C3	1.2566 (3)	0.6149 (6)	0.19551 (12)	0.0702 (7)
H3	1.2743	0.7524	0.1704	0.084*
C4	1.3453 (3)	0.5182 (7)	0.24537 (14)	0.0849 (9)
H4	1.4223	0.5874	0.2533	0.102*
C5	1.3184 (4)	0.3218 (8)	0.28242 (14)	0.0893 (10)
H5	1.3774	0.2567	0.316	0.107*
C6	1.2056 (4)	0.2184 (6)	0.27103 (12)	0.0877 (10)
H6	1.1882	0.0849	0.297	0.105*
C7	1.1172 (3)	0.3122 (5)	0.22083 (11)	0.0677 (7)
H7	1.0405	0.2413	0.213	0.081*
C8	0.8686 (2)	0.4974 (4)	0.04960 (9)	0.0457 (6)
C9	0.8747 (2)	0.6864 (4)	0.00429 (10)	0.0518 (6)
H9	0.9462	0.7762	0.0064	0.062*
C10	0.7767 (2)	0.7427 (5)	−0.04370 (10)	0.0597 (7)
H10	0.7814	0.8708	−0.0737	0.072*
C11	0.6721 (2)	0.6086 (6)	−0.04695 (11)	0.0611 (7)
C12	0.6630 (2)	0.4146 (5)	−0.00389 (11)	0.0610 (7)
H12	0.5919	0.3208	−0.0071	0.073*
C13	0.7617 (2)	0.3632 (5)	0.04400 (10)	0.0510 (6)
N1	0.96721 (19)	0.4383 (4)	0.09966 (8)	0.0513 (5)
H1N	0.972 (2)	0.276 (4)	0.1100 (10)	0.062*
O1	1.05520 (15)	0.8645 (3)	0.11131 (7)	0.0687 (5)
Cl1	0.75028 (6)	0.12644 (14)	0.09989 (3)	0.0705 (2)
Cl2	0.54660 (7)	0.6883 (2)	−0.10654 (3)	0.1010 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0601 (15)	0.0357 (14)	0.0511 (13)	0.0050 (13)	0.0128 (12)	−0.0020 (11)
C2	0.0646 (18)	0.0412 (13)	0.0492 (13)	0.0076 (13)	0.0102 (12)	−0.0042 (11)
C3	0.0695 (19)	0.0686 (18)	0.0653 (17)	0.0051 (16)	0.0073 (14)	0.0003 (13)
C4	0.071 (2)	0.099 (2)	0.073 (2)	0.0125 (19)	0.0002 (17)	−0.0152 (19)
C5	0.100 (3)	0.089 (2)	0.0600 (19)	0.036 (2)	−0.0077 (18)	−0.0101 (17)
C6	0.131 (3)	0.072 (2)	0.0491 (16)	0.016 (2)	0.0083 (18)	0.0054 (14)
C7	0.093 (2)	0.0550 (17)	0.0504 (14)	0.0032 (15)	0.0121 (14)	0.0012 (12)
C8	0.0541 (16)	0.0349 (12)	0.0482 (13)	0.0057 (12)	0.0146 (11)	−0.0021 (11)
C9	0.0556 (15)	0.0437 (14)	0.0557 (14)	0.0016 (12)	0.0150 (12)	0.0043 (11)
C10	0.0700 (19)	0.0588 (15)	0.0510 (14)	0.0114 (14)	0.0184 (13)	0.0099 (12)
C11	0.0547 (17)	0.0721 (17)	0.0526 (14)	0.0143 (15)	0.0086 (12)	−0.0020 (14)
C12	0.0549 (16)	0.0659 (17)	0.0645 (16)	−0.0021 (13)	0.0205 (13)	−0.0069 (14)
C13	0.0566 (16)	0.0454 (13)	0.0541 (14)	0.0010 (13)	0.0204 (12)	−0.0024 (11)
N1	0.0636 (13)	0.0342 (11)	0.0531 (11)	0.0008 (11)	0.0117 (10)	0.0065 (9)
O1	0.0800 (12)	0.0347 (10)	0.0776 (11)	−0.0009 (9)	−0.0003 (9)	0.0063 (8)
Cl1	0.0783 (5)	0.0633 (4)	0.0772 (4)	−0.0034 (4)	0.0339 (4)	0.0109 (3)
Cl2	0.0706 (5)	0.1426 (8)	0.0752 (5)	0.0183 (5)	−0.0033 (4)	0.0119 (4)

Geometric parameters (Å, °)

C1—O1	1.221 (2)	C8—C13	1.380 (3)
C1—N1	1.348 (3)	C8—C9	1.388 (3)
C1—C2	1.488 (3)	C8—N1	1.408 (3)
C2—C3	1.371 (3)	C9—C10	1.374 (3)
C2—C7	1.375 (3)	C9—H9	0.93
C3—C4	1.387 (4)	C10—C11	1.366 (3)
C3—H3	0.93	C10—H10	0.93
C4—C5	1.356 (4)	C11—C12	1.374 (3)
C4—H4	0.93	C11—Cl2	1.743 (2)
C5—C6	1.366 (5)	C12—C13	1.374 (3)
C5—H5	0.93	C12—H12	0.93
C6—C7	1.387 (4)	C13—Cl1	1.735 (2)
C6—H6	0.93	N1—H1N	0.805 (16)
C7—H7	0.93
O1—C1—N1	122.5 (2)	C13—C8—C9	117.8 (2)
O1—C1—C2	121.6 (2)	C13—C8—N1	120.1 (2)
N1—C1—C2	115.9 (2)	C9—C8—N1	122.2 (2)
C3—C2—C7	119.3 (2)	C10—C9—C8	120.9 (2)
C3—C2—C1	118.4 (2)	C10—C9—H9	119.5
C7—C2—C1	122.3 (2)	C8—C9—H9	119.5
C2—C3—C4	120.9 (3)	C11—C10—C9	119.4 (2)
C2—C3—H3	119.6	C11—C10—H10	120.3
C4—C3—H3	119.6	C9—C10—H10	120.3
C5—C4—C3	119.2 (3)	C10—C11—C12	121.6 (2)
C5—C4—H4	120.4	C10—C11—Cl2	119.3 (2)
C3—C4—H4	120.4	C12—C11—Cl2	119.1 (2)
C4—C5—C6	120.8 (3)	C13—C12—C11	118.1 (2)
C4—C5—H5	119.6	C13—C12—H12	120.9
C6—C5—H5	119.6	C11—C12—H12	120.9
C5—C6—C7	120.1 (3)	C12—C13—C8	122.2 (2)
C5—C6—H6	119.9	C12—C13—Cl1	118.62 (19)
C7—C6—H6	119.9	C8—C13—Cl1	119.18 (17)
C2—C7—C6	119.7 (3)	C1—N1—C8	126.45 (18)
C2—C7—H7	120.2	C1—N1—H1N	119.5 (18)
C6—C7—H7	120.2	C8—N1—H1N	114.0 (18)
O1—C1—C2—C3	−31.9 (3)	C9—C10—C11—C12	−1.2 (4)
N1—C1—C2—C3	147.8 (2)	C9—C10—C11—Cl2	178.01 (17)
O1—C1—C2—C7	146.7 (2)	C10—C11—C12—C13	1.7 (4)
N1—C1—C2—C7	−33.6 (3)	Cl2—C11—C12—C13	−177.46 (18)
C7—C2—C3—C4	1.6 (4)	C11—C12—C13—C8	−0.6 (3)
C1—C2—C3—C4	−179.8 (2)	C11—C12—C13—Cl1	178.13 (19)
C2—C3—C4—C5	−1.3 (4)	C9—C8—C13—C12	−1.0 (3)
C3—C4—C5—C6	0.2 (4)	N1—C8—C13—C12	179.8 (2)
C4—C5—C6—C7	0.5 (4)	C9—C8—C13—Cl1	−179.73 (16)
C3—C2—C7—C6	−0.8 (4)	N1—C8—C13—Cl1	1.0 (3)
C1—C2—C7—C6	−179.4 (2)	O1—C1—N1—C8	−3.9 (4)
C5—C6—C7—C2	−0.2 (4)	C2—C1—N1—C8	176.4 (2)
C13—C8—C9—C10	1.6 (3)	C13—C8—N1—C1	−145.5 (2)
N1—C8—C9—C10	−179.2 (2)	C9—C8—N1—C1	35.3 (3)
C8—C9—C10—C11	−0.5 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.805 (16)	2.178 (19)	2.899 (2)	149 (2)

Symmetry codes: (i) x, y−1, z.