(2E)-1-(5-Bromothiophen-2-yl)-3-(4-chloro­phen­yl)prop-2-en-1-one

Abstract

In the title compound, C₁₃H₈BrClOS, the thio­phene and phenyl rings are inclined by 40.69 (11)° to each other. The crystal structure is characterized by C—H⋯π inter­actions, which link the mol­ecules into broad layers parallel to (100). Short Br⋯Cl contacts [3.698 (1) Å] link these layers along [100].

Related literature  

For general background to chalcones, see: Chun et al. (2001 ▶); Horng et al. (2003 ▶); Lopez et al. (2001 ▶); Mei et al. (2003 ▶). For related structures, see: Vepuri et al. (2012 ▶); Li & Su (1993 ▶).

Experimental  

Crystal data  

• C₁₃H₈BrClOS

• M _r = 327.61

• Monoclinic,

• a = 15.235 (3) Å

• b = 13.959 (3) Å

• c = 5.9153 (11) Å

• β = 93.259 (3)°

• V = 1255.9 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 3.63 mm⁻¹

• T = 293 K

• 0.24 × 0.20 × 0.12 mm

Data collection  

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.770, T _max = 1.000

• 14247 measured reflections

• 3032 independent reflections

• 2204 reflections with I > 2σ(I)

• R _int = 0.023

Refinement  

• R[F ² > 2σ(F ²)] = 0.030

• wR(F ²) = 0.081

• S = 1.05

• 3032 reflections

• 154 parameters

• H-atom parameters constrained

• Δρ_max = 0.40 e Å⁻³

• Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg2 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯Cg2i	0.93	2.87	3.557 (3)	132
C16—H16⋯Cg2ii	0.93	2.96	3.480 (3)	117

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Chalcones are alpha beta unsaturated ketones, widely distributed in nature and are extensively studied for their biological activity (Chun et al., 2001; Horng et al., 2003; Lopez et al., 2001; Mei et al., 2003). We report here the crystal structure of a bromo derivative of hetero aryl chalcone which has shown aldose reductase inhibition in the virtual screening study conducted by us.

The titlecompound (2E)-1-(5-bromo-2-thienyl)-3-(4- chlorophenyl)prop-2-en-1-one, C₁₃H₈Br Cl O S, presents a five-membered thiophene ring (S3\C14\···C17) and a phenyl ring (C5\C6\···C10) at 40.69 (11)° to each other (Fig 1). All intermolecular bond lengths and angles are within normal ranges (Vepuri et al., 2012; Li & Su, 1993). The crystal structure is characterized by C—H···π interactions (C10—H10···Cg2; C16—H16···Cg2, Cg2 = C5->C10) (Table 1) which link molecules into broad 2D structures parallel to (100). There are in addition short intermolecular Br1···Cl2 contacts of 3.698 (1) Å, which link these structures along [100]. (Fig 2)

Experimental

A mixture of 2-acetyl-5-BromoThiophene (0.01 mole) and 4-chlorobenzaldehyde (0.01 mole) were stirred in ethanol (30 ml) and then an aqueous solution of potassium hydroxide (40%,15 ml)was added to it. The mixture was kept over night at room temperature and then it was poured into crushed ice and acidified with dilute hydrochloric acid. The precipiteted chalcone was filtered and crystallized from ethanol.

Refinement

All H atoms were positioned geometrically, with C—H = 0.93 Å for aromatic H and refined using a riding model with U_iso(H) = 1.2U_eq(C) for aromatic H.

Figures

Fig. 1.

The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2.

Crystal packing of the title compound. Dashed lines represent C-H···π and Br···Cl bonds.

Crystal data

C13H8BrClOS	F(000) = 648
Mr = 327.61	Dx = 1.733 Mg m−3
Monoclinic, P21/c	Melting point: 399 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 15.235 (3) Å	Cell parameters from 2202 reflections
b = 13.959 (3) Å	θ = 2.0–25.0°
c = 5.9153 (11) Å	µ = 3.63 mm−1
β = 93.259 (3)°	T = 293 K
V = 1255.9 (4) Å3	Plate, colourless
Z = 4	0.24 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3032 independent reflections
Radiation source: fine-focus sealed tube	2204 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω and φ scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −18→18
Tmin = 0.770, Tmax = 1.000	k = 0→16
14247 measured reflections	l = 0→7

Refinement

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0473P)2 + 0.2986P] where P = (Fo2 + 2Fc2)/3
2202 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.876810 (18)	0.34860 (2)	0.10591 (6)	0.06662 (15)
Cl2	0.03637 (5)	0.36156 (7)	0.68667 (14)	0.0719 (3)
S3	0.67904 (4)	0.34879 (5)	−0.04338 (10)	0.04481 (18)
O4	0.48985 (13)	0.37196 (16)	−0.1517 (3)	0.0642 (6)
C5	0.13007 (16)	0.37433 (18)	0.5358 (4)	0.0436 (6)
C6	0.12401 (15)	0.41523 (19)	0.3238 (4)	0.0466 (6)
H6	0.0705	0.4381	0.2626	0.056*
C7	0.19854 (15)	0.42171 (17)	0.2044 (4)	0.0421 (6)
H7	0.1943	0.4480	0.0598	0.051*
C8	0.28016 (15)	0.39015 (16)	0.2928 (4)	0.0369 (5)
C9	0.28356 (16)	0.35027 (16)	0.5098 (4)	0.0407 (6)
H9	0.3372	0.3292	0.5743	0.049*
C10	0.20961 (17)	0.34157 (16)	0.6295 (4)	0.0431 (6)
H10	0.2129	0.3138	0.7727	0.052*
C11	0.35582 (15)	0.39464 (17)	0.1545 (4)	0.0399 (5)
H11	0.3445	0.4112	0.0034	0.048*
C12	0.43893 (16)	0.37794 (19)	0.2184 (4)	0.0450 (6)
H12	0.4544	0.3669	0.3706	0.054*
C13	0.50768 (17)	0.37658 (18)	0.0522 (4)	0.0431 (6)
C14	0.59921 (15)	0.37793 (16)	0.1398 (4)	0.0371 (5)
C15	0.63572 (16)	0.40178 (19)	0.3477 (4)	0.0454 (6)
H15	0.6027	0.4194	0.4684	0.055*
C16	0.72770 (16)	0.39728 (19)	0.3626 (4)	0.0464 (6)
H16	0.7625	0.4121	0.4922	0.056*
C17	0.75950 (15)	0.36879 (17)	0.1654 (4)	0.0410 (6)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.03415 (18)	0.0911 (3)	0.0755 (2)	0.00978 (13)	0.01087 (14)	0.00945 (16)
Cl2	0.0432 (4)	0.1058 (7)	0.0687 (5)	−0.0075 (4)	0.0196 (3)	0.0045 (4)
S3	0.0374 (4)	0.0601 (4)	0.0373 (3)	0.0041 (3)	0.0062 (3)	−0.0034 (3)
O4	0.0443 (11)	0.1042 (17)	0.0438 (11)	0.0027 (10)	−0.0004 (8)	−0.0067 (10)
C5	0.0348 (13)	0.0501 (14)	0.0466 (14)	−0.0074 (11)	0.0069 (11)	−0.0050 (12)
C6	0.0318 (13)	0.0592 (17)	0.0483 (15)	0.0033 (11)	−0.0024 (10)	0.0017 (12)
C7	0.0377 (13)	0.0474 (14)	0.0407 (13)	0.0003 (11)	−0.0025 (10)	0.0034 (11)
C8	0.0344 (12)	0.0350 (12)	0.0411 (13)	−0.0037 (10)	0.0003 (10)	−0.0021 (10)
C9	0.0351 (13)	0.0433 (14)	0.0431 (14)	0.0022 (10)	−0.0029 (11)	−0.0003 (10)
C10	0.0452 (14)	0.0432 (14)	0.0408 (14)	−0.0018 (11)	0.0013 (11)	0.0006 (10)
C11	0.0367 (13)	0.0429 (13)	0.0400 (13)	−0.0018 (10)	0.0020 (10)	−0.0024 (10)
C12	0.0369 (14)	0.0580 (15)	0.0402 (13)	0.0007 (11)	0.0039 (11)	0.0015 (11)
C13	0.0367 (13)	0.0484 (14)	0.0441 (15)	0.0010 (11)	0.0017 (11)	0.0003 (11)
C14	0.0320 (12)	0.0393 (13)	0.0406 (13)	0.0014 (10)	0.0077 (10)	−0.0008 (10)
C15	0.0424 (14)	0.0525 (16)	0.0420 (14)	0.0038 (11)	0.0077 (11)	−0.0078 (11)
C16	0.0407 (14)	0.0555 (16)	0.0430 (14)	−0.0036 (12)	0.0004 (11)	−0.0066 (12)
C17	0.0300 (12)	0.0426 (13)	0.0507 (14)	−0.0018 (10)	0.0042 (10)	0.0034 (11)

Geometric parameters (Å, º)

Br1—C17	1.863 (2)	C9—C10	1.370 (3)
Cl2—C5	1.735 (3)	C9—H9	0.9300
S3—C17	1.713 (3)	C10—H10	0.9300
S3—C14	1.723 (2)	C11—C12	1.321 (3)
O4—C13	1.223 (3)	C11—H11	0.9300
C5—C6	1.376 (4)	C12—C13	1.477 (3)
C5—C10	1.381 (4)	C12—H12	0.9300
C6—C7	1.374 (3)	C13—C14	1.460 (3)
C6—H6	0.9300	C14—C15	1.362 (3)
C7—C8	1.393 (3)	C15—C16	1.400 (3)
C7—H7	0.9300	C15—H15	0.9300
C8—C9	1.397 (3)	C16—C17	1.348 (3)
C8—C11	1.452 (3)	C16—H16	0.9300
C17—S3—C14	90.57 (12)	C12—C11—H11	116.2
C6—C5—C10	121.0 (2)	C8—C11—H11	116.2
C6—C5—Cl2	119.8 (2)	C11—C12—C13	121.1 (2)
C10—C5—Cl2	119.2 (2)	C11—C12—H12	119.5
C7—C6—C5	118.8 (2)	C13—C12—H12	119.5
C7—C6—H6	120.6	O4—C13—C14	120.3 (2)
C5—C6—H6	120.6	O4—C13—C12	122.1 (2)
C6—C7—C8	122.2 (2)	C14—C13—C12	117.6 (2)
C6—C7—H7	118.9	C15—C14—C13	131.0 (2)
C8—C7—H7	118.9	C15—C14—S3	111.04 (18)
C7—C8—C9	117.2 (2)	C13—C14—S3	117.92 (18)
C7—C8—C11	119.7 (2)	C14—C15—C16	113.7 (2)
C9—C8—C11	123.1 (2)	C14—C15—H15	123.2
C10—C9—C8	121.4 (2)	C16—C15—H15	123.2
C10—C9—H9	119.3	C17—C16—C15	111.5 (2)
C8—C9—H9	119.3	C17—C16—H16	124.3
C9—C10—C5	119.4 (2)	C15—C16—H16	124.3
C9—C10—H10	120.3	C16—C17—S3	113.23 (19)
C5—C10—H10	120.3	C16—C17—Br1	127.2 (2)
C12—C11—C8	127.6 (2)	S3—C17—Br1	119.61 (14)
C10—C5—C6—C7	1.0 (4)	C11—C12—C13—C14	167.3 (2)
Cl2—C5—C6—C7	−177.9 (2)	O4—C13—C14—C15	164.8 (3)
C5—C6—C7—C8	−1.4 (4)	C12—C13—C14—C15	−17.0 (4)
C6—C7—C8—C9	0.6 (4)	O4—C13—C14—S3	−12.8 (3)
C6—C7—C8—C11	177.1 (2)	C12—C13—C14—S3	165.31 (18)
C7—C8—C9—C10	0.7 (3)	C17—S3—C14—C15	0.3 (2)
C11—C8—C9—C10	−175.7 (2)	C17—S3—C14—C13	178.47 (19)
C8—C9—C10—C5	−1.1 (4)	C13—C14—C15—C16	−177.6 (2)
C6—C5—C10—C9	0.2 (4)	S3—C14—C15—C16	0.2 (3)
Cl2—C5—C10—C9	179.09 (18)	C14—C15—C16—C17	−0.8 (3)
C7—C8—C11—C12	171.9 (3)	C15—C16—C17—S3	1.0 (3)
C9—C8—C11—C12	−11.8 (4)	C15—C16—C17—Br1	−177.94 (19)
C8—C11—C12—C13	174.2 (2)	C14—S3—C17—C16	−0.8 (2)
C11—C12—C13—O4	−14.5 (4)	C14—S3—C17—Br1	178.26 (15)

Hydrogen-bond geometry (Å, º)

Cg2 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···Cg2i	0.93	2.87	3.557 (3)	132
C16—H16···Cg2ii	0.93	2.96	3.480 (3)	117

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