Methyl 2-[2-(2,6-dichloro­anilino)­phenyl]­acetate

Saleem, R.; Shabir, G.; Hanif, M.; Qadeer, G.; Wong, W.-Y.

doi:10.1107/S1600536808038336

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2400

doi:10.1107/S1600536808038336

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Methyl 2-[2-(2,6-dichloroanilino)phenyl]acetate

Rashid Saleem,^a Ghulam Shabir,^b Muhammad Hanif,^b Ghulam Qadeer ^b ^* and Wai-Yeung Wong ^c

^aDepartment of Chemistry, University of Engineering and Technology, Lahore, Pakistan, ^bDepartment of Chemistry, Quaid-I-Azam Univeristy, Islamabad 45320, Pakistan, and ^cDepartment of Chemistry, Hong Kong Baptist University, Waterloo Road, Kowloon Tong, Hong Kong, People's Republic of China
^*Correspondence e-mail: qadeerqau@yahoo.com

(Received 12 November 2008; accepted 17 November 2008; online 20 November 2008)

In the title compound, C₁₅H₁₃Cl₂NO₂, the dihedral angle between the aromatic rings is 63.80 (12)°. The conformation may be stabilized by a weak N—H⋯O hydrogen bond. In the crystal structure, a short C—Cl⋯π interaction occurs, with a Cl⋯π separation of 3.5706 (13) Å.

Related literature

For general background, see: Hashem et al. (2007 ); Husain et al. (2005 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₅H₁₃Cl₂NO₂
M_r = 310.16
Monoclinic, P 2₁ /n
a = 4.9319 (4) Å
b = 20.0288 (14) Å
c = 14.5542 (10) Å
β = 97.711 (1)°
V = 1424.66 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 173 (2) K
0.38 × 0.24 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.850, T_max = 1.000 (expected range = 0.776–0.913)
8526 measured reflections
3423 independent reflections
2777 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.171
S = 1.04
3423 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.88	2.64	3.152 (2)	118

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2007 ); data reduction: SAINT; 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, PARST (Nardelli, 1995 ) and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808038336/pv2122sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808038336/pv2122Isup2.hkl

checkCIF report

Comment top

Esters are important intermediates in heterocyclic chemistry and have been used for the synthesis of various biologically active five-membered heterocyles such as butenolides, pyrrolones (Husain et al., 2005), oxadiazoles and triazoles (Hashem et al., 2007). In view of the versatility of these compounds, we have synthesized the title compound and report herein its crystal structure.

In the title compound (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The planar ester group (O1/O2/C13/C14/C15) is oriented with respect to the plane of the benzene ring (C7–C12) at an angle 41.33 (2)°. There is a short intramolecular N—H···O hydrogen bond (Table 1) and a π-ring interaction of the type C—Cl···Cg with Cl1···Cg1 (centroid of C1–C6 ring) perpendicular distance 3.5706 (13) Å.

Related literature top

For general background, see: Hashem et al. (2007); Husain et al.(2005). For bond-length data, see: Allen et al. (1987).

Experimental top

A mixture of 2-(2,6-dichlorophenylamino)benzoic acid (2.81 g, 10 mmol) and absolute methanol (50 ml) in the presence of a few drops of sulfuric acid was refluxed for 5 h. The excess of the solvent was removed by distillation. The solid residue was filltered off, washed with water and recystallized from ethanol (30%) to give the title compound. Suitable single crystals of the title compound were obtained by slow evaporation of an ethanol solution at room temperature. (Yield, 88%; m.p. 331–332 K)

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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), PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme; thermal ellipsoids have been plotted at 50% probability level.
	Fig. 2. The formation of the title compound.

Methyl 2-[2-(2,6-dichloroanilino)phenyl]acetate top

Crystal data top

C₁₅H₁₃Cl₂NO₂	F(000) = 640
M_r = 310.16	D_x = 1.446 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 331 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 4.9319 (4) Å	Cell parameters from 9949 reflections
b = 20.0288 (14) Å	θ = 2.4–28.3°
c = 14.5542 (10) Å	µ = 0.46 mm⁻¹
β = 97.711 (1)°	T = 173 K
V = 1424.66 (18) Å³	Block, pale yellow
Z = 4	0.38 × 0.24 × 0.20 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	3423 independent reflections
Radiation source: fine-focus sealed tube	2777 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω and ϕ scans	θ_max = 28.3°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→6
T_min = 0.850, T_max = 1.000	k = −26→26
8526 measured reflections	l = −19→15

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.171	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.1042P)² + 0.5254P] where P = (F_o² + 2F_c²)/3
3423 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

C₁₅H₁₃Cl₂NO₂	V = 1424.66 (18) Å³
M_r = 310.16	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.9319 (4) Å	µ = 0.46 mm⁻¹
b = 20.0288 (14) Å	T = 173 K
c = 14.5542 (10) Å	0.38 × 0.24 × 0.20 mm
β = 97.711 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3423 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2777 reflections with I > 2σ(I)
T_min = 0.850, T_max = 1.000	R_int = 0.020
8526 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.171	H-atom parameters constrained
S = 1.04	Δρ_max = 0.62 e Å⁻³
3423 reflections	Δρ_min = −0.52 e Å⁻³
181 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
C1	0.8063 (4)	0.18670 (11)	0.42183 (15)	0.0459 (5)
C2	0.9559 (6)	0.23352 (14)	0.47685 (18)	0.0592 (7)
H2A	0.9401	0.2361	0.5411	0.071*
C3	1.1298 (6)	0.27691 (13)	0.4384 (2)	0.0646 (7)
H3A	1.2365	0.3084	0.4764	0.077*
C4	1.1462 (6)	0.27396 (11)	0.3451 (2)	0.0572 (6)
H4A	1.2586	0.3046	0.3178	0.069*
C5	0.9985 (5)	0.22618 (10)	0.29100 (16)	0.0454 (5)
C6	0.8295 (4)	0.17922 (9)	0.32730 (13)	0.0386 (4)
C7	0.6955 (4)	0.06202 (9)	0.29122 (13)	0.0360 (4)
C8	0.8988 (5)	0.03457 (12)	0.35515 (15)	0.0468 (5)
H8A	1.0348	0.0624	0.3879	0.056*
C9	0.9027 (6)	−0.03407 (14)	0.37114 (18)	0.0614 (7)
H9A	1.0410	−0.0529	0.4153	0.074*
C10	0.7088 (7)	−0.07451 (13)	0.3237 (2)	0.0676 (8)
H10A	0.7142	−0.1213	0.3347	0.081*
C11	0.5040 (5)	−0.04753 (12)	0.25957 (19)	0.0549 (6)
H11A	0.3696	−0.0759	0.2271	0.066*
C12	0.4948 (4)	0.02126 (10)	0.24258 (14)	0.0388 (4)
C13	0.2660 (4)	0.04998 (12)	0.17557 (15)	0.0434 (5)
H13A	0.1975	0.0907	0.2033	0.052*
H13B	0.1140	0.0173	0.1670	0.052*
C14	0.3438 (4)	0.06753 (10)	0.08154 (14)	0.0374 (4)
C15	0.1597 (4)	0.09199 (12)	−0.07671 (14)	0.0433 (5)
H15A	−0.0226	0.0958	−0.1125	0.065*
H15B	0.2626	0.0566	−0.1032	0.065*
H15C	0.2570	0.1345	−0.0789	0.065*
Cl1	0.57692 (13)	0.13766 (4)	0.47192 (4)	0.0602 (2)
Cl2	1.01835 (17)	0.22543 (3)	0.17271 (4)	0.0654 (2)
N1	0.6851 (4)	0.13126 (8)	0.27114 (12)	0.0425 (4)
H1A	0.5820	0.1447	0.2205	0.051*
O1	0.5844 (3)	0.07442 (10)	0.06748 (12)	0.0591 (5)
O2	0.1341 (3)	0.07623 (9)	0.01586 (12)	0.0550 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0417 (11)	0.0525 (12)	0.0422 (11)	0.0138 (9)	0.0005 (8)	−0.0030 (9)
C2	0.0595 (15)	0.0663 (15)	0.0479 (12)	0.0187 (12)	−0.0069 (10)	−0.0198 (11)
C3	0.0656 (16)	0.0500 (13)	0.0718 (17)	0.0071 (11)	−0.0138 (13)	−0.0208 (12)
C4	0.0564 (14)	0.0363 (10)	0.0754 (17)	−0.0006 (9)	−0.0040 (12)	−0.0007 (10)
C5	0.0512 (12)	0.0358 (9)	0.0473 (11)	0.0055 (8)	−0.0006 (9)	0.0021 (8)
C6	0.0373 (10)	0.0373 (9)	0.0385 (10)	0.0064 (7)	−0.0048 (7)	−0.0008 (7)
C7	0.0370 (9)	0.0388 (9)	0.0331 (9)	0.0030 (7)	0.0075 (7)	0.0035 (7)
C8	0.0460 (11)	0.0554 (12)	0.0386 (10)	0.0100 (9)	0.0045 (8)	0.0072 (9)
C9	0.0735 (17)	0.0627 (15)	0.0506 (13)	0.0289 (13)	0.0176 (12)	0.0193 (11)
C10	0.097 (2)	0.0419 (12)	0.0690 (17)	0.0124 (13)	0.0313 (16)	0.0124 (11)
C11	0.0661 (15)	0.0420 (11)	0.0606 (14)	−0.0056 (10)	0.0230 (12)	0.0000 (10)
C12	0.0384 (10)	0.0412 (10)	0.0385 (10)	−0.0019 (7)	0.0111 (8)	0.0003 (7)
C13	0.0311 (9)	0.0565 (12)	0.0430 (11)	−0.0068 (8)	0.0073 (8)	−0.0036 (9)
C14	0.0286 (9)	0.0407 (9)	0.0436 (10)	−0.0040 (7)	0.0075 (7)	−0.0060 (8)
C15	0.0329 (10)	0.0601 (12)	0.0359 (10)	−0.0045 (8)	0.0005 (7)	0.0023 (8)
Cl1	0.0537 (4)	0.0771 (4)	0.0521 (4)	0.0141 (3)	0.0159 (3)	0.0074 (3)
Cl2	0.0911 (5)	0.0551 (4)	0.0509 (4)	−0.0072 (3)	0.0123 (3)	0.0118 (2)
N1	0.0489 (10)	0.0383 (8)	0.0363 (8)	−0.0016 (7)	−0.0084 (7)	0.0037 (6)
O1	0.0273 (7)	0.1015 (14)	0.0486 (9)	−0.0057 (7)	0.0057 (6)	0.0102 (9)
O2	0.0413 (8)	0.0703 (11)	0.0532 (10)	−0.0023 (7)	0.0060 (7)	−0.0026 (8)

Geometric parameters (Å, º) top

C1—C2	1.381 (3)	C9—C10	1.367 (5)
C1—C6	1.404 (3)	C9—H9A	0.9500
C1—Cl1	1.731 (3)	C10—C11	1.390 (4)
C2—C3	1.390 (4)	C10—H10A	0.9500
C2—H2A	0.9500	C11—C12	1.399 (3)
C3—C4	1.371 (4)	C11—H11A	0.9500
C3—H3A	0.9500	C12—C13	1.503 (3)
C4—C5	1.383 (3)	C13—C14	1.511 (3)
C4—H4A	0.9500	C13—H13A	0.9900
C5—C6	1.406 (3)	C13—H13B	0.9900
C5—Cl2	1.738 (2)	C14—O1	1.239 (2)
C6—N1	1.393 (3)	C14—O2	1.322 (3)
C7—C8	1.387 (3)	C15—O2	1.406 (3)
C7—C12	1.400 (3)	C15—H15A	0.9800
C7—N1	1.417 (2)	C15—H15B	0.9800
C8—C9	1.394 (4)	C15—H15C	0.9800
C8—H8A	0.9500	N1—H1A	0.8800

C2—C1—C6	122.2 (2)	C9—C10—H10A	119.8
C2—C1—Cl1	118.01 (19)	C11—C10—H10A	119.8
C6—C1—Cl1	119.72 (17)	C10—C11—C12	120.3 (2)
C1—C2—C3	120.1 (2)	C10—C11—H11A	119.8
C1—C2—H2A	120.0	C12—C11—H11A	119.8
C3—C2—H2A	120.0	C11—C12—C7	118.7 (2)
C4—C3—C2	119.5 (2)	C11—C12—C13	119.7 (2)
C4—C3—H3A	120.2	C7—C12—C13	121.54 (18)
C2—C3—H3A	120.2	C12—C13—C14	114.64 (16)
C3—C4—C5	119.8 (3)	C12—C13—H13A	108.6
C3—C4—H4A	120.1	C14—C13—H13A	108.6
C5—C4—H4A	120.1	C12—C13—H13B	108.6
C4—C5—C6	122.8 (2)	C14—C13—H13B	108.6
C4—C5—Cl2	118.4 (2)	H13A—C13—H13B	107.6
C6—C5—Cl2	118.79 (16)	O1—C14—O2	122.7 (2)
N1—C6—C1	123.1 (2)	O1—C14—C13	122.73 (18)
N1—C6—C5	121.52 (19)	O2—C14—C13	114.61 (16)
C1—C6—C5	115.29 (19)	O2—C15—H15A	109.5
C8—C7—C12	120.44 (19)	O2—C15—H15B	109.5
C8—C7—N1	121.95 (19)	H15A—C15—H15B	109.5
C12—C7—N1	117.59 (17)	O2—C15—H15C	109.5
C7—C8—C9	119.7 (2)	H15A—C15—H15C	109.5
C7—C8—H8A	120.1	H15B—C15—H15C	109.5
C9—C8—H8A	120.1	C6—N1—C7	123.53 (16)
C10—C9—C8	120.5 (2)	C6—N1—H1A	118.2
C10—C9—H9A	119.8	C7—N1—H1A	118.2
C8—C9—H9A	119.8	C14—O2—C15	124.07 (17)
C9—C10—C11	120.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.88	2.64	3.152 (2)	118

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃Cl₂NO₂
M_r	310.16
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	4.9319 (4), 20.0288 (14), 14.5542 (10)
β (°)	97.711 (1)
V (Å³)	1424.66 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.38 × 0.24 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.850, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8526, 3423, 2777
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.171, 1.04
No. of reflections	3423
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.52

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.88	2.636	3.152 (2)	118

Acknowledgements

The authors gratefully acknowledge funds from the Higher Education Commission, Islamabad, Pakistan.

References

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