(2E)-1-(4-Bromo­phen­yl)-3-(4-nitro­phen­yl)prop-2-en-1-one

Harrison, W.T.A.; Yathirajan, H.S.; Narayana, B.; Sreevidya, T.V.; Sunil, K.

doi:10.1107/S1600536806039900

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 11| November 2006| Pages o4829-o4831

https://doi.org/10.1107/S1600536806039900

(2E)-1-(4-Bromophenyl)-3-(4-nitrophenyl)prop-2-en-1-one

William T. A. Harrison,^a ^* H. S. Yathirajan,^b B. Narayana,^c T. V. Sreevidya ^c and K. Sunil ^c

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^cDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, India
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 18 September 2006; accepted 28 September 2006; online 4 October 2006)

In the approximately planar molecule of the title compound, C₁₅H₁₀BrNO₃, the dihedral angle between the two benzene rings is 4.97 (18)°. Intermolecular C—H⋯O interactions help to form chains of molecules in the crystal structure.

Comment

Chalcone derivatives show considerable promise as organic non-linear optical materials (Uchida et al., 1998 ). As part of our ongoing studies of these compounds (Harrison et al., 2006 ), the synthesis and structure of the title compound, (I) (Fig. 1), is presented here. Compound (I) is an isomer of the recently reported 3-(4-bromophenyl)-1-(4-nitrophenyl)prop-2-en-1-one [(II); Rosli et al., 2006 ], in which the bromo and nitro substituents are exchanged on the benzene rings.

The geometrical parameters for (I) fall within their expected ranges (Allen et al., 1987 ). The degree of twisting about the C6—C7 and C9—C10 bonds in (I) (Table 1) is almost the same, but in opposite senses. This results in the C1–C6 and C10–C15 benzene-ring mean planes in (I) being close to parallel [dihedral angle = 4.97 (18)°]. By comparison, in compound (II), the dihedral angles between the mean planes of the corresponding benzene rings in the two molecules of the asymmetric unit are 12.83 (7) and 41.15 (7)°. The well ordered nitro group in (I) is slightly twisted away from the C10–C15 benzene ring mean plane [dihedral angle = 3.4 (4)°].

A PLATON (Spek, 2003 ) analysis of (I) indicated two possible intermolecular C—H⋯O interactions (Table 2) that result in chains of molecules (Fig. 2) propagating in either [011] or [01 $[\overline{1}]$ ]. The graph-theory (Bernstein et al., 1995 ) notation for the closed loop that results is R₂²(12). Overall, the packing (Fig. 3) results in zigzag (100) sheets of (I). The packing in (II) is completely different: all molecules are aligned in approximately the same orientation, resulting in a layered structure in the centrosymmetric space group P $[\overline{1}]$ .

Figure 1
View of the molecular structure of (I)

showing 50% probability displacement ellipsoids.

Figure 2
Detail of (I)

, showing the C—H⋯O interactions (dashed lines) that link the molecules into [011] and [01 $[\overline{1}]$ ] chains. Atoms with the suffixes * and % are generated by the symmetry operations (x, y − 1, z + 1) and (x, y + 1, z − 1), respectively.

Figure 3
The unit cell contents of (I)

, viewed down [010]. H atoms have been omitted.

Experimental

A solution of potassium hydroxide (5%, 5 ml) was added slowly with stirring to a mixture of 4-nitrobenzaldehyde (1.51 g, 0.01 mol) and 4-bromoacetophenone (1.99 g, 0.01 mol) in ethanol (30 ml). The mixture was stirred at room temperature for 24 h. The precipitated solid was filtered, washed with water, dried and crystals of (I) were recrystallized from acetone by slow evaporation (yield: 68%; m.p. 439–441 K). Analysis found (calculated) for C₁₅H₁₀BrNO₃ (%): C 54.11 (54.24), H 3.04 (3.03), N 4.10 (4.22).

Crystal data

C₁₅H₁₀BrNO₃
M_r = 332.15
Orthorhombic, P n a 2₁
a = 43.007 (3) Å
b = 5.9744 (4) Å
c = 5.1137 (3) Å
V = 1313.92 (15) Å³
Z = 4
D_x = 1.679 Mg m⁻³
Mo Kα radiation
μ = 3.13 mm⁻¹
T = 120 (2) K
Slab, light yellow
0.48 × 0.34 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer
ω and φ scans
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.315, T_max = 0.634
9881 measured reflections
2833 independent reflections
2452 reflections with I > 2σ(I)
R_int = 0.034
θ_max = 27.6°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.058
S = 1.02
2833 reflections
181 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0103P)² + 0.5147P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Absolute structure: Flack (1983 ), 1143 Friedel pairs
Flack parameter: 0.039 (9)

Table 1
Selected torsion angles (°)

C1—C6—C7—O1	9.1 (4)
C8—C9—C10—C11	−9.3 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O1ⁱ	0.95	2.51	3.218 (3)	131
C15—H15⋯O3ⁱⁱ	0.95	2.46	3.296 (3)	146
Symmetry codes: (i) x, y-1, z+1; (ii) x, y+1, z-1.

The H atoms were positioned geometrically (C—H = 0.95 Å) and refined as riding, with U_iso(H) = 1.2U_eq(carrier).

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806039900/bm2006sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806039900/bm2006Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

(2E)-1-(4-Bromophenyl)-3-(4-nitrophenyl)prop-2-en-1-one top

Crystal data top

C₁₅H₁₀BrNO₃	D_x = 1.679 Mg m⁻³
M_r = 332.15	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 1807 reflections
a = 43.007 (3) Å	θ = 2.9–27.5°
b = 5.9744 (4) Å	µ = 3.13 mm⁻¹
c = 5.1137 (3) Å	T = 120 K
V = 1313.92 (15) Å³	Slab, light yellow
Z = 4	0.48 × 0.34 × 0.16 mm
F(000) = 664

Data collection top

Nonius KappaCCD diffractometer	2833 independent reflections
Radiation source: fine-focus sealed tube	2452 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ω and φ scans	θ_max = 27.6°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −55→51
T_min = 0.315, T_max = 0.634	k = −7→7
9881 measured reflections	l = −6→6

Refinement top

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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.058	w = 1/[σ²(F_o²) + (0.0103P)² + 0.5147P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2833 reflections	Δρ_max = 0.42 e Å⁻³
181 parameters	Δρ_min = −0.37 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1143 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.039 (9)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.32687 (6)	0.5698 (5)	−0.0869 (5)	0.0226 (6)
H1	0.3347	0.7145	−0.1261	0.027*
C2	0.30283 (6)	0.4845 (4)	−0.2341 (5)	0.0231 (6)
H2	0.2941	0.5690	−0.3731	0.028*
C3	0.29161 (6)	0.2713 (5)	−0.1749 (5)	0.0231 (6)
C4	0.30431 (6)	0.1460 (5)	0.0239 (5)	0.0242 (6)
H4	0.2965	0.0007	0.0607	0.029*
C5	0.32863 (6)	0.2330 (4)	0.1705 (6)	0.0241 (7)
H5	0.3376	0.1459	0.3063	0.029*
C6	0.33999 (5)	0.4475 (4)	0.1197 (8)	0.0192 (4)
C7	0.36493 (6)	0.5567 (5)	0.2803 (5)	0.0224 (6)
C8	0.38183 (6)	0.4199 (5)	0.4754 (5)	0.0223 (6)
H8	0.3763	0.2671	0.4973	0.027*
C9	0.40457 (5)	0.5046 (4)	0.6208 (8)	0.0205 (5)
H9	0.4102	0.6560	0.5890	0.025*
C10	0.42189 (6)	0.3854 (4)	0.8269 (5)	0.0180 (5)
C11	0.41295 (6)	0.1732 (4)	0.9179 (5)	0.0207 (6)
H11	0.3953	0.1017	0.8434	0.025*
C12	0.42930 (5)	0.0672 (4)	1.1133 (8)	0.0200 (5)
H12	0.4233	−0.0769	1.1733	0.024*
C13	0.45468 (5)	0.1749 (4)	1.2203 (5)	0.0164 (5)
C14	0.46438 (5)	0.3842 (4)	1.1389 (8)	0.0195 (5)
H14	0.4819	0.4547	1.2162	0.023*
C15	0.44770 (6)	0.4884 (4)	0.9408 (5)	0.0202 (6)
H15	0.4540	0.6323	0.8817	0.024*
N1	0.47161 (5)	0.0649 (4)	1.4359 (4)	0.0193 (5)
O1	0.37058 (4)	0.7549 (3)	0.2512 (4)	0.0333 (5)
O2	0.49310 (4)	0.1664 (3)	1.5394 (4)	0.0244 (4)
O3	0.46321 (4)	−0.1244 (3)	1.5005 (4)	0.0251 (4)
Br1	0.258082 (5)	0.14848 (4)	−0.36943 (8)	0.02868 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0198 (12)	0.0203 (13)	0.0277 (15)	0.0006 (11)	0.0010 (12)	0.0023 (12)
C2	0.0216 (12)	0.0257 (14)	0.0220 (13)	0.0017 (11)	−0.0006 (11)	0.0021 (12)
C3	0.0197 (13)	0.0262 (14)	0.0233 (14)	0.0016 (11)	−0.0001 (11)	−0.0051 (12)
C4	0.0222 (13)	0.0224 (13)	0.0280 (13)	0.0008 (11)	0.0011 (11)	−0.0004 (12)
C5	0.0246 (11)	0.0209 (12)	0.027 (2)	0.0044 (10)	−0.0038 (12)	0.0011 (13)
C6	0.0152 (9)	0.0211 (11)	0.0213 (11)	0.0035 (9)	0.0018 (15)	0.0013 (17)
C7	0.0155 (12)	0.0252 (14)	0.0264 (14)	0.0031 (11)	0.0002 (11)	0.0019 (13)
C8	0.0193 (12)	0.0201 (14)	0.0276 (14)	0.0000 (11)	0.0008 (11)	0.0029 (12)
C9	0.0181 (10)	0.0194 (11)	0.0238 (12)	0.0001 (8)	0.0027 (16)	0.0028 (18)
C10	0.0165 (12)	0.0172 (13)	0.0202 (13)	0.0025 (10)	0.0040 (10)	0.0003 (11)
C11	0.0171 (12)	0.0209 (14)	0.0243 (14)	−0.0027 (10)	0.0002 (11)	−0.0002 (12)
C12	0.0214 (10)	0.0155 (10)	0.0232 (12)	−0.0007 (9)	0.0012 (15)	−0.0009 (16)
C13	0.0171 (11)	0.0178 (13)	0.0143 (11)	0.0032 (10)	0.0026 (9)	0.0019 (10)
C14	0.0180 (9)	0.0199 (12)	0.0206 (11)	−0.0028 (8)	0.0017 (18)	−0.0036 (16)
C15	0.0205 (12)	0.0164 (13)	0.0236 (14)	−0.0009 (10)	−0.0003 (11)	0.0030 (11)
N1	0.0202 (10)	0.0190 (11)	0.0186 (11)	−0.0004 (9)	0.0003 (9)	−0.0001 (10)
O1	0.0304 (10)	0.0221 (10)	0.0473 (12)	−0.0069 (9)	−0.0132 (10)	0.0093 (10)
O2	0.0241 (9)	0.0239 (10)	0.0253 (10)	−0.0015 (8)	−0.0062 (7)	0.0004 (8)
O3	0.0292 (10)	0.0207 (10)	0.0254 (10)	−0.0034 (8)	0.0008 (8)	0.0090 (8)
Br1	0.02627 (12)	0.03238 (14)	0.02741 (13)	−0.00336 (11)	−0.00592 (16)	−0.0030 (2)

Geometric parameters (Å, º) top

C1—C2	1.377 (4)	C9—C10	1.474 (4)
C1—C6	1.403 (4)	C9—H9	0.9500
C1—H1	0.9500	C10—C15	1.396 (3)
C2—C3	1.395 (4)	C10—C11	1.404 (3)
C2—H2	0.9500	C11—C12	1.377 (4)
C3—C4	1.375 (4)	C11—H11	0.9500
C3—Br1	1.899 (3)	C12—C13	1.380 (4)
C4—C5	1.388 (4)	C12—H12	0.9500
C4—H4	0.9500	C13—C14	1.382 (3)
C5—C6	1.396 (3)	C13—N1	1.476 (3)
C5—H5	0.9500	C14—C15	1.389 (4)
C6—C7	1.500 (4)	C14—H14	0.9500
C7—O1	1.218 (3)	C15—H15	0.9500
C7—C8	1.481 (4)	N1—O2	1.226 (3)
C8—C9	1.329 (4)	N1—O3	1.232 (3)
C8—H8	0.9500

C2—C1—C6	121.4 (2)	C8—C9—C10	126.0 (2)
C2—C1—H1	119.3	C8—C9—H9	117.0
C6—C1—H1	119.3	C10—C9—H9	117.0
C1—C2—C3	118.6 (3)	C15—C10—C11	118.5 (2)
C1—C2—H2	120.7	C15—C10—C9	119.2 (2)
C3—C2—H2	120.7	C11—C10—C9	122.3 (2)
C4—C3—C2	121.3 (2)	C12—C11—C10	121.1 (2)
C4—C3—Br1	118.6 (2)	C12—C11—H11	119.5
C2—C3—Br1	120.1 (2)	C10—C11—H11	119.5
C3—C4—C5	119.6 (3)	C11—C12—C13	118.5 (2)
C3—C4—H4	120.2	C11—C12—H12	120.8
C5—C4—H4	120.2	C13—C12—H12	120.8
C4—C5—C6	120.5 (3)	C12—C13—C14	122.8 (3)
C4—C5—H5	119.8	C12—C13—N1	118.6 (2)
C6—C5—H5	119.8	C14—C13—N1	118.6 (2)
C5—C6—C1	118.5 (3)	C13—C14—C15	118.0 (2)
C5—C6—C7	123.2 (3)	C13—C14—H14	121.0
C1—C6—C7	118.3 (2)	C15—C14—H14	121.0
O1—C7—C8	121.4 (2)	C14—C15—C10	121.2 (2)
O1—C7—C6	119.9 (2)	C14—C15—H15	119.4
C8—C7—C6	118.7 (2)	C10—C15—H15	119.4
C9—C8—C7	121.9 (2)	O2—N1—O3	124.0 (2)
C9—C8—H8	119.1	O2—N1—C13	118.3 (2)
C7—C8—H8	119.1	O3—N1—C13	117.7 (2)

C6—C1—C2—C3	−0.3 (4)	C8—C9—C10—C15	172.2 (3)
C1—C2—C3—C4	−0.7 (4)	C8—C9—C10—C11	−9.3 (5)
C1—C2—C3—Br1	179.1 (2)	C15—C10—C11—C12	−0.6 (4)
C2—C3—C4—C5	0.5 (4)	C9—C10—C11—C12	−179.0 (3)
Br1—C3—C4—C5	−179.4 (2)	C10—C11—C12—C13	0.5 (4)
C3—C4—C5—C6	0.8 (4)	C11—C12—C13—C14	−0.2 (4)
C4—C5—C6—C1	−1.8 (4)	C11—C12—C13—N1	178.0 (2)
C4—C5—C6—C7	176.3 (2)	C12—C13—C14—C15	−0.1 (4)
C2—C1—C6—C5	1.5 (4)	N1—C13—C14—C15	−178.2 (2)
C2—C1—C6—C7	−176.7 (2)	C13—C14—C15—C10	0.0 (4)
C5—C6—C7—O1	−169.1 (3)	C11—C10—C15—C14	0.3 (4)
C1—C6—C7—O1	9.1 (4)	C9—C10—C15—C14	178.8 (3)
C5—C6—C7—C8	9.9 (4)	C12—C13—N1—O2	−176.2 (2)
C1—C6—C7—C8	−172.0 (2)	C14—C13—N1—O2	2.0 (3)
O1—C7—C8—C9	−2.4 (4)	C12—C13—N1—O3	3.9 (3)
C6—C7—C8—C9	178.7 (3)	C14—C13—N1—O3	−177.9 (2)
C7—C8—C9—C10	177.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O1ⁱ	0.95	2.51	3.218 (3)	131
C15—H15···O3ⁱⁱ	0.95	2.46	3.296 (3)	146

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

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton) for the data collection. BKS thanks AICTE, Government of India, New Delhi, for financial assistance under the `Career Award for Young Teachers' scheme.

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
Bernstein, J., Davies, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2003). SADABS, Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harrison, W. T. A., Yathirajan, H. S., Sarojini, B. K., Narayana, B. & Vijaya Raj, K. K. (2006). Acta Cryst. E62, o1578–o1579. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Rosli, M. M., Patil, P. S., Fun, H.-K., Razak, I. A. & Dharmaprakash, S. M. (2006). Acta Cryst. E62, o1466–o1468. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Uchida, T., Kozawa, K., Sakai, T., Aoki, M., Yoguchi, H., Abduryim, A. & Watanabe, Y. (1998). Mol. Cryst. Liq. Cryst. 315, 135–140. Web of Science CrossRef Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.