3-(4-Bromo­anilino)-3-(4-chloro­phen­yl)-1-phenyl­propan-1-one

Pourayoubi, M.; Shobeiri, Z.; Bruno, G.; Amiri Rudbari, H.

doi:10.1107/S1600536811036932

3-(4-Bromoanilino)-3-(4-chlorophenyl)-1-phenylpropan-1-one

M. Pourayoubi, Z. Shobeiri, G. Bruno and H. Amiri Rudbari

The asymmetric C atom in the title compound, C₂₁H₁₇BrClNO, is in a slightly distorted tetrahedral environment and the NH unit adopts a gauche orientation with respect to the CO group. In the crystal, pairs of intermolecular N—H

O hydrogen bonds form centrosymmetric dimers.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811036932/qm2027sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811036932/qm2027Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536811036932/qm2027Isup3.cml Supplementary material

CCDC reference: 850560

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.003 Å
R factor = 0.033
wR factor = 0.084
Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT793_ALERT_4_G The Model has Chirality at C9      (Verify) ....          S
PLAT960_ALERT_3_G Number of Intensities with I .LT. - 2*sig(I) ...          2

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

β-Amino ketones, of the formula [R¹]CH[NHR²][CH₂C(O)R³], such as the title compound have attracted attention because of their roles as important intermediates for the synthesis of natural products and chiral auxiliaries (Scettri et al., 2008). In the previous work, the structure determination of 3-(4-bromophenylamino)-1-phenyl-3-p-tolylpropan-1-one (Shobeiri et al., 2011) has been investigated. Here, we report the synthesis and crystal structure of the title molecule, [4-Cl—C₆H₄]CH[NHC₆H₄-4-Br][CH₂C(O)C₆H₅]. The asymmetric C atom has a slightly distorted tetrahedral configuration (Fig 1) with the bond angles in the range of 107.92 (16)° [N(1)—C(9)—C(8)] to 114.69 (16)° [N(1)—C(9)—C(10)]. In the crystal, pairs of intermolecular N—H···O(C) hydrogen bonds (Table 1) form centrosymmetric dimers as R₂²(12) rings (for graph-set notation, see Bernstein et al., 1995). A view of crystal packing is shown in Fig. 2.

Related literature top

For background to β-amino ketones, see: Scettri et al. (2008). For related structures, see: Shobeiri et al. (2011); Zhang et al. (2008). For hydrogen-bond motifs and their graph-set notation, see: Bernstein et al. (1995).

Experimental top

To a magnetically stirred mixture of 3-(4-chlorophenyl)-1-phenylprop-2-en-1-one (0.24 g, 1.0 mmol) and Ag₃PW₁₂O₄₀ (0.32 g, 0.10 mmol) as catalyst, in ethanol (5 ml), 4-bromoaniline (0.20 g, 1.2 mmol) was added at room temperature. The reaction completion was monitored by thin layer chromatography (TLC). The catalyst Ag₃PW₁₂O₄₀ was collected by centrifugation. The reaction mixture was extracted with distilled water and ether (2×10 ml). The combined organic layer was evaporated to obtain crude product which was washed with hexane to give pure product. Single crystals of the product were obtained from a solution of CHCl₃/CH₃OH at room temperature.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. An ORTEP-style plot of title compound with labeling. Ellipsoids are given at the 50% probability level.
	Fig. 2. Part of the crystal packing of the title compound showing a centrosymmetric H-bonded (dashed lines) dimer. Only H atoms involving in hydrogen bonds are shown.

3-(4-Bromoanilino)-3-(4-chlorophenyl)-1-phenylpropan-1-one top

Crystal data top

C₂₁H₁₇BrClNO	F(000) = 840
M_r = 414.72	D_x = 1.506 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9986 reflections
a = 10.6571 (4) Å	θ = 2.4–23.8°
b = 17.2432 (6) Å	µ = 2.40 mm⁻¹
c = 10.8602 (4) Å	T = 296 K
β = 113.571 (2)°	Irregular, colorless
V = 1829.19 (12) Å³	0.35 × 0.31 × 0.11 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3983 independent reflections
Radiation source: fine-focus sealed tube	3274 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
φ and ω scans	θ_max = 27.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −13→13
T_min = 0.589, T_max = 0.746	k = −22→22
69312 measured reflections	l = −13→13

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0314P)² + 1.4336P] where P = (F_o² + 2F_c²)/3
3983 reflections	(Δ/σ)_max = 0.001
230 parameters	Δρ_max = 0.71 e Å⁻³
0 restraints	Δρ_min = −0.86 e Å⁻³

Crystal data top

C₂₁H₁₇BrClNO	V = 1829.19 (12) Å³
M_r = 414.72	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.6571 (4) Å	µ = 2.40 mm⁻¹
b = 17.2432 (6) Å	T = 296 K
c = 10.8602 (4) Å	0.35 × 0.31 × 0.11 mm
β = 113.571 (2)°

Data collection top

Bruker APEXII CCD diffractometer	3983 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	3274 reflections with I > 2σ(I)
T_min = 0.589, T_max = 0.746	R_int = 0.036
69312 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.71 e Å⁻³
3983 reflections	Δρ_min = −0.86 e Å⁻³
230 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Br	−0.04722 (3)	0.80334 (2)	−0.19048 (3)	0.06568 (12)
Cl	−0.16806 (9)	0.56173 (4)	0.49694 (7)	0.0721 (2)
O1	0.17572 (18)	1.03398 (10)	0.6206 (2)	0.0634 (5)
N1	0.08682 (19)	0.90054 (10)	0.38597 (18)	0.0371 (4)
C18	−0.0066 (2)	0.83266 (15)	−0.0093 (2)	0.0450 (5)
C17	0.0762 (3)	0.78643 (15)	0.0933 (2)	0.0494 (6)
H17	0.1118	0.7409	0.0743	0.059*
C16	0.1072 (2)	0.80736 (13)	0.2259 (2)	0.0450 (5)
H16	0.1635	0.7757	0.2953	0.054*
C21	0.0549 (2)	0.87508 (12)	0.2558 (2)	0.0351 (4)
C9	0.1518 (2)	0.85036 (11)	0.5014 (2)	0.0341 (4)
H9	0.2417	0.8351	0.5049	0.041*
C8	0.1731 (2)	0.89759 (12)	0.6286 (2)	0.0385 (5)
H8A	0.0848	0.9064	0.6323	0.046*
H8B	0.2281	0.8673	0.7069	0.046*
C7	0.2419 (2)	0.97478 (12)	0.6350 (2)	0.0389 (5)
C6	0.3887 (2)	0.97840 (12)	0.65830 (19)	0.0358 (4)
C5	0.4741 (2)	0.91441 (13)	0.6986 (2)	0.0405 (5)
H5	0.4400	0.8672	0.7132	0.049*
C4	0.6101 (2)	0.92042 (15)	0.7171 (2)	0.0498 (6)
H4	0.6673	0.8774	0.7450	0.060*
C3	0.6605 (2)	0.98986 (17)	0.6944 (3)	0.0556 (6)
H3	0.7514	0.9934	0.7053	0.067*
C20	−0.0291 (2)	0.92111 (13)	0.1491 (2)	0.0437 (5)
H20	−0.0654	0.9667	0.1670	0.052*
C19	−0.0594 (2)	0.90066 (15)	0.0179 (2)	0.0486 (5)
H19	−0.1149	0.9323	−0.0520	0.058*
C10	0.0717 (2)	0.77732 (11)	0.5009 (2)	0.0336 (4)
C11	0.1383 (2)	0.70874 (13)	0.5539 (2)	0.0455 (5)
H11	0.2335	0.7072	0.5888	0.055*
C12	0.0668 (3)	0.64243 (14)	0.5562 (3)	0.0538 (6)
H12	0.1129	0.5967	0.5926	0.065*
C13	−0.0743 (3)	0.64527 (13)	0.5035 (2)	0.0460 (5)
C14	−0.1434 (2)	0.71292 (14)	0.4522 (2)	0.0460 (5)
H14	−0.2385	0.7144	0.4188	0.055*
C15	−0.0702 (2)	0.77871 (12)	0.4507 (2)	0.0409 (5)
H15	−0.1166	0.8246	0.4156	0.049*
C2	0.5775 (3)	1.05403 (16)	0.6559 (3)	0.0565 (6)
H2	0.6125	1.1010	0.6417	0.068*
C1	0.4420 (2)	1.04882 (13)	0.6382 (2)	0.0463 (5)
H1	0.3862	1.0924	0.6129	0.056*
H	0.031 (3)	0.9290 (15)	0.396 (3)	0.046 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.04927 (16)	0.1060 (3)	0.03996 (14)	−0.00352 (14)	0.01597 (11)	−0.00835 (13)
Cl	0.0956 (5)	0.0517 (4)	0.0638 (4)	−0.0335 (4)	0.0266 (4)	0.0014 (3)
O1	0.0462 (10)	0.0427 (9)	0.0988 (15)	0.0070 (8)	0.0262 (10)	−0.0028 (9)
N1	0.0382 (9)	0.0331 (9)	0.0392 (9)	0.0026 (8)	0.0145 (8)	0.0021 (7)
C18	0.0366 (11)	0.0616 (14)	0.0372 (11)	−0.0081 (10)	0.0153 (9)	−0.0005 (10)
C17	0.0552 (14)	0.0516 (13)	0.0476 (13)	0.0056 (11)	0.0271 (11)	−0.0006 (11)
C16	0.0483 (12)	0.0469 (13)	0.0403 (11)	0.0105 (10)	0.0183 (10)	0.0080 (10)
C21	0.0319 (10)	0.0349 (10)	0.0376 (10)	−0.0048 (8)	0.0129 (8)	0.0024 (8)
C9	0.0296 (9)	0.0346 (10)	0.0368 (10)	0.0004 (8)	0.0117 (8)	0.0005 (8)
C8	0.0347 (10)	0.0433 (11)	0.0375 (11)	−0.0052 (9)	0.0144 (9)	−0.0027 (9)
C7	0.0371 (11)	0.0393 (11)	0.0370 (10)	−0.0010 (9)	0.0114 (9)	−0.0042 (9)
C6	0.0348 (10)	0.0375 (11)	0.0324 (10)	−0.0048 (8)	0.0106 (8)	−0.0037 (8)
C5	0.0361 (10)	0.0406 (11)	0.0395 (11)	−0.0032 (9)	0.0094 (9)	0.0001 (9)
C4	0.0366 (11)	0.0565 (14)	0.0495 (13)	0.0017 (10)	0.0100 (10)	−0.0039 (11)
C3	0.0380 (12)	0.0771 (18)	0.0495 (14)	−0.0132 (12)	0.0151 (10)	−0.0062 (13)
C20	0.0407 (11)	0.0390 (11)	0.0453 (12)	0.0026 (9)	0.0107 (10)	0.0040 (9)
C19	0.0398 (11)	0.0565 (14)	0.0406 (12)	0.0000 (10)	0.0068 (9)	0.0100 (10)
C10	0.0356 (10)	0.0316 (10)	0.0327 (9)	−0.0010 (8)	0.0127 (8)	−0.0009 (8)
C11	0.0405 (12)	0.0405 (12)	0.0484 (13)	0.0045 (9)	0.0104 (10)	0.0056 (10)
C12	0.0652 (16)	0.0361 (12)	0.0516 (14)	0.0019 (11)	0.0143 (12)	0.0081 (10)
C13	0.0624 (15)	0.0373 (12)	0.0386 (11)	−0.0157 (10)	0.0206 (11)	−0.0041 (9)
C14	0.0410 (12)	0.0478 (13)	0.0486 (13)	−0.0085 (10)	0.0173 (10)	−0.0052 (10)
C15	0.0363 (11)	0.0341 (10)	0.0493 (12)	0.0005 (8)	0.0141 (9)	0.0003 (9)
C2	0.0559 (15)	0.0589 (16)	0.0519 (14)	−0.0240 (13)	0.0186 (12)	0.0009 (12)
C1	0.0491 (13)	0.0408 (12)	0.0441 (12)	−0.0060 (10)	0.0134 (10)	0.0007 (10)

Geometric parameters (Å, º) top

Br—C18	1.906 (2)	C5—C4	1.385 (3)
Cl—C13	1.738 (2)	C5—H5	0.9300
O1—C7	1.215 (3)	C4—C3	1.374 (4)
N1—C21	1.386 (3)	C4—H4	0.9300
N1—C9	1.451 (3)	C3—C2	1.374 (4)
N1—H	0.81 (3)	C3—H3	0.9300
C18—C17	1.367 (3)	C20—C19	1.375 (3)
C18—C19	1.382 (4)	C20—H20	0.9300
C17—C16	1.391 (3)	C19—H19	0.9300
C17—H17	0.9300	C10—C11	1.381 (3)
C16—C21	1.387 (3)	C10—C15	1.388 (3)
C16—H16	0.9300	C11—C12	1.380 (3)
C21—C20	1.395 (3)	C11—H11	0.9300
C9—C10	1.520 (3)	C12—C13	1.379 (4)
C9—C8	1.540 (3)	C12—H12	0.9300
C9—H9	0.9800	C13—C14	1.373 (3)
C8—C7	1.507 (3)	C14—C15	1.381 (3)
C8—H8A	0.9700	C14—H14	0.9300
C8—H8B	0.9700	C15—H15	0.9300
C7—C6	1.483 (3)	C2—C1	1.381 (4)
C6—C5	1.385 (3)	C2—H2	0.9300
C6—C1	1.394 (3)	C1—H1	0.9300

C21—N1—C9	121.99 (17)	C3—C4—C5	120.0 (2)
C21—N1—H	115.5 (18)	C3—C4—H4	120.0
C9—N1—H	111.7 (18)	C5—C4—H4	120.0
C17—C18—C19	120.4 (2)	C2—C3—C4	120.4 (2)
C17—C18—Br	119.53 (19)	C2—C3—H3	119.8
C19—C18—Br	120.11 (17)	C4—C3—H3	119.8
C18—C17—C16	120.1 (2)	C19—C20—C21	121.5 (2)
C18—C17—H17	119.9	C19—C20—H20	119.3
C16—C17—H17	119.9	C21—C20—H20	119.3
C21—C16—C17	120.6 (2)	C20—C19—C18	119.5 (2)
C21—C16—H16	119.7	C20—C19—H19	120.3
C17—C16—H16	119.7	C18—C19—H19	120.3
N1—C21—C16	123.20 (19)	C11—C10—C15	118.5 (2)
N1—C21—C20	118.79 (19)	C11—C10—C9	120.90 (19)
C16—C21—C20	117.9 (2)	C15—C10—C9	120.61 (18)
N1—C9—C10	114.69 (16)	C12—C11—C10	121.4 (2)
N1—C9—C8	107.92 (16)	C12—C11—H11	119.3
C10—C9—C8	108.81 (16)	C10—C11—H11	119.3
N1—C9—H9	108.4	C13—C12—C11	118.8 (2)
C10—C9—H9	108.4	C13—C12—H12	120.6
C8—C9—H9	108.4	C11—C12—H12	120.6
C7—C8—C9	113.74 (17)	C14—C13—C12	121.2 (2)
C7—C8—H8A	108.8	C14—C13—Cl	118.75 (19)
C9—C8—H8A	108.8	C12—C13—Cl	120.06 (19)
C7—C8—H8B	108.8	C13—C14—C15	119.3 (2)
C9—C8—H8B	108.8	C13—C14—H14	120.4
H8A—C8—H8B	107.7	C15—C14—H14	120.4
O1—C7—C6	120.3 (2)	C14—C15—C10	120.9 (2)
O1—C7—C8	119.32 (19)	C14—C15—H15	119.6
C6—C7—C8	120.35 (18)	C10—C15—H15	119.6
C5—C6—C1	119.1 (2)	C3—C2—C1	120.0 (2)
C5—C6—C7	122.37 (19)	C3—C2—H2	120.0
C1—C6—C7	118.56 (19)	C1—C2—H2	120.0
C4—C5—C6	120.2 (2)	C2—C1—C6	120.2 (2)
C4—C5—H5	119.9	C2—C1—H1	119.9
C6—C5—H5	119.9	C6—C1—H1	119.9

C19—C18—C17—C16	0.4 (4)	C16—C21—C20—C19	−0.2 (3)
Br—C18—C17—C16	179.65 (18)	C21—C20—C19—C18	0.6 (3)
C18—C17—C16—C21	0.0 (4)	C17—C18—C19—C20	−0.7 (4)
C9—N1—C21—C16	−14.4 (3)	Br—C18—C19—C20	−179.93 (17)
C9—N1—C21—C20	168.47 (19)	N1—C9—C10—C11	145.8 (2)
C17—C16—C21—N1	−177.2 (2)	C8—C9—C10—C11	−93.3 (2)
C17—C16—C21—C20	−0.1 (3)	N1—C9—C10—C15	−36.2 (3)
C21—N1—C9—C10	−59.1 (2)	C8—C9—C10—C15	84.8 (2)
C21—N1—C9—C8	179.46 (17)	C15—C10—C11—C12	0.8 (3)
N1—C9—C8—C7	−50.4 (2)	C9—C10—C11—C12	178.8 (2)
C10—C9—C8—C7	−175.40 (17)	C10—C11—C12—C13	0.3 (4)
C9—C8—C7—O1	109.1 (2)	C11—C12—C13—C14	−1.5 (4)
C9—C8—C7—C6	−70.7 (2)	C11—C12—C13—Cl	176.77 (19)
O1—C7—C6—C5	168.4 (2)	C12—C13—C14—C15	1.5 (4)
C8—C7—C6—C5	−11.8 (3)	Cl—C13—C14—C15	−176.77 (18)
O1—C7—C6—C1	−11.9 (3)	C13—C14—C15—C10	−0.4 (3)
C8—C7—C6—C1	167.93 (19)	C11—C10—C15—C14	−0.7 (3)
C1—C6—C5—C4	−0.7 (3)	C9—C10—C15—C14	−178.8 (2)
C7—C6—C5—C4	179.0 (2)	C4—C3—C2—C1	−0.7 (4)
C6—C5—C4—C3	−0.6 (4)	C3—C2—C1—C6	−0.5 (4)
C5—C4—C3—C2	1.3 (4)	C5—C6—C1—C2	1.2 (3)
N1—C21—C20—C19	177.1 (2)	C7—C6—C1—C2	−178.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H···O1ⁱ	0.81 (3)	2.23 (3)	2.992 (3)	156 (2)

Symmetry code: (i) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₇BrClNO
M_r	414.72
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	10.6571 (4), 17.2432 (6), 10.8602 (4)
β (°)	113.571 (2)
V (Å³)	1829.19 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.40
Crystal size (mm)	0.35 × 0.31 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.589, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	69312, 3983, 3274
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.084, 1.03
No. of reflections	3983
No. of parameters	230
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.86

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008).