2-(4-Chloro­anilino)-1-(4-chloro­phen­yl)ethanone

Fun, H.-K.; Quah, C.K.; Vijesh, A.M.; Isloor, A.M.; Arulmoli, T.

doi:10.1107/S1600536811048276

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3373

https://doi.org/10.1107/S1600536811048276

Open

access

2-(4-Chloroanilino)-1-(4-chlorophenyl)ethanone

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § A. M. Vijesh,^b,^c A. M. Isloor ^c and T. Arulmoli ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bSeQuent Scientific Ltd, No. 120 A & B, Industrial Area, Baikampady, New Mangalore, Karnataka 575 011, India, and, Medicinal Chemistry Division, Department of Chemistry, National Institute of Technology-Karnataka, Surathkal, Mangalore 575 025, India, and ^cMedicinal Chemistry Division, Department of Chemistry, National Institute of Technology-Karnataka, Surathkal, Mangalore 575 025, India
^*Correspondence e-mail: hkfun@usm.my

(Received 11 November 2011; accepted 14 November 2011; online 19 November 2011)

In the title compound, C₁₄H₁₁Cl₂NO, the benzene rings form a dihedral angle of 3.14 (6)°. Overall, the molecule is close to being planar (r.m.s. deviation for all the non-H atoms = 0.054 Å). No significant directional intermolecular interactions are observed in the crystal structure.

Related literature

For general background to amine derivatives, see: Sridharan et al. (2006 ). For bond-length data, see: Allen et al. (1987 ). For related structures, see: Fun et al. (2010 , 2011 ).

Experimental

Crystal data

C₁₄H₁₁Cl₂NO
M_r = 280.14
Triclinic, $[P \overline 1]$
a = 5.7286 (3) Å
b = 7.4225 (5) Å
c = 15.4274 (9) Å
α = 85.337 (1)°
β = 89.772 (1)°
γ = 82.519 (1)°
V = 648.23 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 296 K
0.55 × 0.26 × 0.15 mm

Data collection

Bruker SMART APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.776, T_max = 0.931
14634 measured reflections
4406 independent reflections
3279 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.121
S = 1.05
4406 reflections
167 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811048276/hb6501sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048276/hb6501Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811048276/hb6501Isup3.cml

checkCIF report

Comment top

1-(4-Chlorophenyl)-2-[(4-chlorophenyl)amino]ethanone is a derivative of an amine formed by the reaction between an amine and phenacyl bromide. It finds applications in the field of synthetic chemistry and is a key intermediate in indole synthesis (Sridharan et al., 2006). Keeping this in view, the title compound was synthesized to study its crystal structure.

The molecular structure is shown in Fig. 1. The phenyl rings (C1-C6 and C9-C14) form a dihedral angle of 3.14 (6) °. Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to related structures (Fun et al., 2010, 2011). No significant hydrogen bond is observed in this compound.

Related literature top

For general background to amine derivatives, see: Sridharan et al. (2006). For bond-length data, see: Allen et al. (1987). For related structures, see: Fun et al. (2010, 2011).

Experimental top

The mixture of 4-chloroaniline (1.0 g, 0.0078 mol) potassium carbonate (0.95 g, 0.0069 mol) and 2-bromo-1-(4-chlorophenyl)ethanone (1.83 g, 0.0078 mol) in dimethyl formamide (10 ml) was stirred at room temperature for 2 h. On cooling, colorless needle-shaped crystals 2-(4-chlorophenyl)- 2-oxoethyl 2-methylbenzoate begins to separate. It was collected by filtration and recrystallized from hot ethanol as colourless needles. Yield: 1.85 g, 84.5 %, m.p.: 427-428 K.

Structure description top

For general background to amine derivatives, see: Sridharan et al. (2006). For bond-length data, see: Allen et al. (1987). For related structures, see: Fun et al. (2010, 2011).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids for non-H atoms.

2-(4-Chloroanilino)-1-(4-chlorophenyl)ethanone top

Crystal data top

C₁₄H₁₁Cl₂NO	Z = 2
M_r = 280.14	F(000) = 288
Triclinic, P1	D_x = 1.435 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7286 (3) Å	Cell parameters from 5676 reflections
b = 7.4225 (5) Å	θ = 2.7–31.5°
c = 15.4274 (9) Å	µ = 0.49 mm⁻¹
α = 85.337 (1)°	T = 296 K
β = 89.772 (1)°	Needle, colorless
γ = 82.519 (1)°	0.55 × 0.26 × 0.15 mm
V = 648.23 (7) Å³

Data collection top

Bruker SMART APEXII DUO CCD diffractometer	4406 independent reflections
Radiation source: fine-focus sealed tube	3279 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
φ and ω scans	θ_max = 31.9°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
T_min = 0.776, T_max = 0.931	k = −10→10
14634 measured reflections	l = −22→22

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0546P)² + 0.1078P] where P = (F_o² + 2F_c²)/3
4406 reflections	(Δ/σ)_max = 0.001
167 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₄H₁₁Cl₂NO	γ = 82.519 (1)°
M_r = 280.14	V = 648.23 (7) Å³
Triclinic, P1	Z = 2
a = 5.7286 (3) Å	Mo Kα radiation
b = 7.4225 (5) Å	µ = 0.49 mm⁻¹
c = 15.4274 (9) Å	T = 296 K
α = 85.337 (1)°	0.55 × 0.26 × 0.15 mm
β = 89.772 (1)°

Data collection top

Bruker SMART APEXII DUO CCD diffractometer	4406 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3279 reflections with I > 2σ(I)
T_min = 0.776, T_max = 0.931	R_int = 0.017
14634 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.29 e Å⁻³
4406 reflections	Δρ_min = −0.31 e Å⁻³
167 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.53272 (7)	0.38195 (5)	0.30213 (2)	0.06177 (13)
Cl2	1.09875 (12)	0.23470 (8)	−0.52931 (3)	0.0986 (2)
O1	1.46099 (17)	0.11247 (15)	−0.11538 (6)	0.0595 (3)
N1	1.1416 (2)	0.20038 (17)	0.00358 (7)	0.0479 (3)
C1	1.0802 (2)	0.20624 (16)	0.15684 (7)	0.0414 (2)
H1A	1.2343	0.1513	0.1664	0.050*
C2	0.9398 (2)	0.24941 (18)	0.22701 (8)	0.0450 (3)
H2A	0.9990	0.2233	0.2833	0.054*
C3	0.7107 (2)	0.33154 (16)	0.21332 (8)	0.0418 (2)
C4	0.6222 (2)	0.37011 (17)	0.13004 (8)	0.0448 (3)
H4A	0.4682	0.4259	0.1213	0.054*
C5	0.7621 (2)	0.32599 (17)	0.05920 (8)	0.0428 (2)
H5A	0.7008	0.3513	0.0032	0.051*
C6	0.99495 (19)	0.24365 (14)	0.07159 (7)	0.0363 (2)
C7	1.0671 (2)	0.23121 (16)	−0.08528 (7)	0.0392 (2)
H7A	1.0121	0.3597	−0.0986	0.047*
H7B	0.9371	0.1631	−0.0946	0.047*
C8	1.2670 (2)	0.17276 (15)	−0.14502 (7)	0.0399 (2)
C9	1.2203 (2)	0.19003 (15)	−0.24018 (7)	0.0392 (2)
C10	1.3956 (2)	0.12290 (19)	−0.29565 (9)	0.0519 (3)
H10A	1.5399	0.0686	−0.2726	0.062*
C11	1.3597 (3)	0.1352 (2)	−0.38450 (9)	0.0623 (4)
H11A	1.4780	0.0889	−0.4212	0.075*
C12	1.1463 (3)	0.2168 (2)	−0.41788 (9)	0.0583 (4)
C13	0.9689 (3)	0.2858 (2)	−0.36467 (9)	0.0592 (4)
H13A	0.8257	0.3412	−0.3883	0.071*
C14	1.0057 (2)	0.27170 (19)	−0.27579 (8)	0.0497 (3)
H14A	0.8861	0.3172	−0.2394	0.060*
H1N1	1.266 (3)	0.146 (2)	0.0124 (11)	0.058 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0600 (2)	0.0724 (2)	0.0522 (2)	−0.00031 (16)	0.01890 (15)	−0.01462 (16)
Cl2	0.1357 (5)	0.1203 (4)	0.03485 (19)	0.0016 (4)	−0.0021 (2)	−0.0062 (2)
O1	0.0450 (5)	0.0820 (7)	0.0464 (5)	0.0127 (5)	−0.0019 (4)	−0.0088 (5)
N1	0.0406 (5)	0.0649 (7)	0.0342 (5)	0.0077 (5)	0.0009 (4)	−0.0032 (4)
C1	0.0368 (5)	0.0484 (6)	0.0370 (5)	0.0015 (4)	−0.0030 (4)	−0.0028 (4)
C2	0.0460 (6)	0.0537 (7)	0.0343 (5)	−0.0022 (5)	−0.0024 (4)	−0.0050 (5)
C3	0.0422 (6)	0.0426 (6)	0.0409 (5)	−0.0038 (4)	0.0072 (4)	−0.0075 (4)
C4	0.0354 (5)	0.0496 (6)	0.0472 (6)	0.0009 (5)	0.0017 (4)	−0.0003 (5)
C5	0.0382 (5)	0.0511 (6)	0.0370 (5)	−0.0008 (5)	−0.0029 (4)	0.0007 (4)
C6	0.0370 (5)	0.0370 (5)	0.0346 (5)	−0.0034 (4)	0.0006 (4)	−0.0028 (4)
C7	0.0390 (5)	0.0440 (6)	0.0342 (5)	−0.0033 (4)	0.0020 (4)	−0.0044 (4)
C8	0.0402 (5)	0.0407 (5)	0.0382 (5)	−0.0017 (4)	0.0028 (4)	−0.0051 (4)
C9	0.0424 (5)	0.0389 (5)	0.0360 (5)	−0.0036 (4)	0.0041 (4)	−0.0042 (4)
C10	0.0497 (7)	0.0587 (7)	0.0442 (6)	0.0056 (6)	0.0078 (5)	−0.0063 (5)
C11	0.0715 (9)	0.0697 (9)	0.0429 (7)	0.0045 (7)	0.0163 (6)	−0.0099 (6)
C12	0.0788 (10)	0.0608 (8)	0.0348 (6)	−0.0071 (7)	0.0034 (6)	−0.0044 (5)
C13	0.0592 (8)	0.0745 (9)	0.0408 (6)	0.0020 (7)	−0.0048 (6)	−0.0024 (6)
C14	0.0463 (6)	0.0611 (8)	0.0393 (6)	0.0028 (5)	0.0028 (5)	−0.0056 (5)

Geometric parameters (Å, º) top

Cl1—C3	1.7406 (12)	C5—H5A	0.9300
Cl2—C12	1.7332 (14)	C7—C8	1.5091 (15)
O1—C8	1.2187 (14)	C7—H7A	0.9700
N1—C6	1.3738 (15)	C7—H7B	0.9700
N1—C7	1.4290 (15)	C8—C9	1.4855 (16)
N1—H1N1	0.780 (17)	C9—C10	1.3860 (16)
C1—C2	1.3798 (16)	C9—C14	1.3921 (17)
C1—C6	1.3985 (15)	C10—C11	1.3808 (19)
C1—H1A	0.9300	C10—H10A	0.9300
C2—C3	1.3823 (17)	C11—C12	1.374 (2)
C2—H2A	0.9300	C11—H11A	0.9300
C3—C4	1.3774 (17)	C12—C13	1.377 (2)
C4—C5	1.3881 (17)	C13—C14	1.3817 (18)
C4—H4A	0.9300	C13—H13A	0.9300
C5—C6	1.4000 (16)	C14—H14A	0.9300

C6—N1—C7	122.77 (10)	N1—C7—H7B	109.5
C6—N1—H1N1	120.3 (13)	C8—C7—H7B	109.5
C7—N1—H1N1	116.5 (13)	H7A—C7—H7B	108.1
C2—C1—C6	121.18 (10)	O1—C8—C9	121.31 (11)
C2—C1—H1A	119.4	O1—C8—C7	120.43 (10)
C6—C1—H1A	119.4	C9—C8—C7	118.26 (10)
C1—C2—C3	119.77 (11)	C10—C9—C14	118.66 (11)
C1—C2—H2A	120.1	C10—C9—C8	119.16 (11)
C3—C2—H2A	120.1	C14—C9—C8	122.18 (10)
C4—C3—C2	120.29 (11)	C11—C10—C9	121.18 (13)
C4—C3—Cl1	120.13 (9)	C11—C10—H10A	119.4
C2—C3—Cl1	119.56 (9)	C9—C10—H10A	119.4
C3—C4—C5	120.22 (11)	C12—C11—C10	118.92 (13)
C3—C4—H4A	119.9	C12—C11—H11A	120.5
C5—C4—H4A	119.9	C10—C11—H11A	120.5
C4—C5—C6	120.41 (10)	C11—C12—C13	121.39 (13)
C4—C5—H5A	119.8	C11—C12—Cl2	119.56 (12)
C6—C5—H5A	119.8	C13—C12—Cl2	119.05 (12)
N1—C6—C1	119.28 (10)	C12—C13—C14	119.30 (13)
N1—C6—C5	122.59 (10)	C12—C13—H13A	120.4
C1—C6—C5	118.13 (10)	C14—C13—H13A	120.4
N1—C7—C8	110.63 (10)	C13—C14—C9	120.55 (12)
N1—C7—H7A	109.5	C13—C14—H14A	119.7
C8—C7—H7A	109.5	C9—C14—H14A	119.7

C6—C1—C2—C3	−0.17 (19)	O1—C8—C9—C10	5.16 (19)
C1—C2—C3—C4	0.11 (19)	C7—C8—C9—C10	−174.56 (11)
C1—C2—C3—Cl1	178.85 (10)	O1—C8—C9—C14	−174.82 (13)
C2—C3—C4—C5	0.29 (19)	C7—C8—C9—C14	5.46 (17)
Cl1—C3—C4—C5	−178.44 (10)	C14—C9—C10—C11	−0.3 (2)
C3—C4—C5—C6	−0.64 (19)	C8—C9—C10—C11	179.70 (13)
C7—N1—C6—C1	178.89 (11)	C9—C10—C11—C12	0.5 (2)
C7—N1—C6—C5	−1.74 (19)	C10—C11—C12—C13	−0.1 (3)
C2—C1—C6—N1	179.23 (12)	C10—C11—C12—Cl2	179.61 (12)
C2—C1—C6—C5	−0.16 (18)	C11—C12—C13—C14	−0.3 (3)
C4—C5—C6—N1	−178.81 (12)	Cl2—C12—C13—C14	179.92 (12)
C4—C5—C6—C1	0.57 (18)	C12—C13—C14—C9	0.5 (2)
C6—N1—C7—C8	179.16 (11)	C10—C9—C14—C13	−0.2 (2)
N1—C7—C8—O1	−1.37 (17)	C8—C9—C14—C13	179.82 (13)
N1—C7—C8—C9	178.35 (10)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁Cl₂NO
M_r	280.14
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.7286 (3), 7.4225 (5), 15.4274 (9)
α, β, γ (°)	85.337 (1), 89.772 (1), 82.519 (1)
V (Å³)	648.23 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.55 × 0.26 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII DUO CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.776, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	14634, 4406, 3279
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.744

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.121, 1.05
No. of reflections	4406
No. of parameters	167
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.31

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

Acknowledgements

HKF and CKQ thank Universiti Sains Malysia (USM) for the Research University Grant (No. 1001/PFIZIK/811160). AMI is thankful to the Department of Atomic Energy, Board for Research in Nuclear Sciences, Government of India, for the Young scientist award. AMV is thankful to the management of SeQuent Scientific Ltd, New Mangalore, India, for their invaluable support and allocation of resources for this work.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fun, H.-K., Quah, C. K., Shetty, S. & Kalluraya, B. (2010). Acta Cryst. E66, o3131. Web of Science CSD CrossRef IUCr Journals Google Scholar
Fun, H.-K., Quah, C. K., Vijesh, A. M., Isloor, A. M. & Arulmoli, T. (2011). Acta Cryst. E67, o3351. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sridharan, V., Perumal, S., Avendano, C. & Menendez, J. C. (2006). Synlett, pp. 91–95. Google Scholar