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

In the title compound, C₁₃H₈BrNO₃S, the dihedral angles between the enone fragment and the adjacent thienyl (th) and benzene (bz) rings are 12.7 (2) and 2.8 (2)°, respectively. The dihedral angle between the th and bz ring systems is 13.20 (18)°. An acute C—H...O inter­action may help to consolidate the centrosymmetric crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.037
• wR factor = 0.093
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.93
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N1
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1    ..  O3      ..       3.21 Ang.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.926
            Tmax scaled      0.515 Tmin scaled      0.281

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

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

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S1. Comment

The title compound, (I), (Fig. 1), was prepared as part of our ongoing studies (Harrison et al., 2007) of the non-linear optical (NLO) properties (Uchida et al., 1998) and crystal structures of chalcone derivatives. Compound (I) is centrosymmetric, thus its second harmonic generation (SHG) response is zero.

The geometrical parameters for (I) mostly fall within their expected ranges (Allen et al., 1995). The C4—C3—Br1 angle of 126.5 (13)° is somewhat obtuse, perhaps due to steric repulsion between Br1 and H6 (H···Br = 2.72 Å), as also seen in related structures (Harrison et al., 2007). This may help to explain why Br1 is displaced from the C1—C4/S1 mean plane by 0.046 (4) Å.

The dihedral angles between the enone (C5/C6/C7/O1) fragment and its adjacent thienyl (C1—C4/S1) and benzene (C8—C13) rings in (I) are 12.7 (2)° and 2.8 (2)°, respectively. The dihedral angle between the thienyl and benzene ring systems is 13.20 (18)° A possible weak intermolecular C—H···O interaction (Table 1) resulting in [001] chains of molecules may help to establish the crystal packing in (I).

Related literature

For related structures and background, see: Harrison et al. (2007). For reference structural data, see: Allen et al. (1995). For general background, see: Uchida et al. (1998).

S2. Experimental

4-Nitrobenzaldehyde (1.51 g, 0.01 mol) in ethanol (20 ml) was mixed with 1-(3-bromo-2-thienyl)ethanone (2.05 ml, 0.01 mol) in 20 ml e thanol and the mixture was treated with 8 ml of 10% KOH solution at 283 K and stirred for 8 h. The precipitate obtained was filtered, washed with ethanol and dried. Pale yellow rods of (I) were grown from a 1:1 (v/v) solution of acetone and toluene by slow evaporation (m.p.: 452–54 K). Analysis for C₁₃H₈BrNO₃S: Found (calculated): C 46.11 (46.19); H 2.34 (2.38); N 4.09 (4.14); S 9.40% (9.48%).

S3. Refinement

The hydrogen atoms were geometrically placed (C—H = 0.93 Å) and refined as riding with U_iso(H) = 1.2U_eq(carrier).

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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: SHELXL97r.

Figures

Fig. 1. View of the molecular structure of (I) showing 50% displacement ellipsoids (arbitrary spheres for the H atoms).

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

Crystal data

C13H8BrNO3S	Z = 2
Mr = 338.17	F(000) = 336
Triclinic, P1	Dx = 1.727 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.8098 (3) Å	Cell parameters from 2053 reflections
b = 10.7863 (8) Å	θ = 2.3–27.2°
c = 12.7709 (9) Å	µ = 3.32 mm^−1
α = 81.835 (1)°	T = 291 K
β = 83.714 (2)°	Rod, pale yellow
γ = 85.316 (2)°	0.47 × 0.20 × 0.20 mm
V = 650.42 (8) Å^3

Data collection

Bruker SMART1000 CCD diffractometer	2942 independent reflections
Radiation source: fine-focus sealed tube	1946 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −5→6
Tmin = 0.304, Tmax = 0.556	k = −13→13
5268 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H-atom parameters constrained
S = 0.88	w = 1/[σ^2(Fo^2) + (0.0578P)^2] where P = (Fo^2 + 2Fc^2)/3
2942 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.0465 (7)	−0.0063 (3)	0.1850 (3)	0.0619 (9)
H1	−0.1649	−0.0656	0.1728	0.074*
C2	0.0182 (7)	0.0077 (3)	0.2825 (3)	0.0562 (8)
H2	−0.0480	−0.0410	0.3449	0.067*
C3	0.1991 (6)	0.1054 (2)	0.2781 (2)	0.0438 (6)
C4	0.2717 (6)	0.1638 (2)	0.1766 (2)	0.0405 (6)
C5	0.4353 (6)	0.2710 (3)	0.1287 (2)	0.0429 (6)
C6	0.6144 (5)	0.3285 (2)	0.1915 (2)	0.0436 (6)
H6	0.6465	0.2897	0.2594	0.052*
C7	0.7316 (5)	0.4352 (2)	0.1531 (2)	0.0418 (6)
H7	0.6924	0.4718	0.0854	0.050*
C8	0.9171 (5)	0.5005 (2)	0.2077 (2)	0.0379 (6)
C9	0.9742 (6)	0.4615 (3)	0.3122 (2)	0.0455 (7)
H9	0.8929	0.3910	0.3499	0.055*
C10	1.1483 (6)	0.5251 (3)	0.3609 (2)	0.0493 (7)
H10	1.1874	0.4977	0.4305	0.059*
C11	1.2645 (5)	0.6309 (3)	0.3043 (2)	0.0428 (6)
C12	1.2194 (6)	0.6710 (3)	0.2003 (2)	0.0469 (7)
H12	1.3056	0.7402	0.1627	0.056*
C13	1.0438 (6)	0.6065 (2)	0.1525 (2)	0.0450 (7)
H13	1.0087	0.6338	0.0825	0.054*
N1	1.4441 (5)	0.7013 (3)	0.3579 (2)	0.0567 (7)
O1	0.4159 (5)	0.3103 (2)	0.03438 (16)	0.0642 (6)
O2	1.5621 (5)	0.7873 (2)	0.3064 (2)	0.0839 (8)
O3	1.4633 (7)	0.6687 (3)	0.4522 (2)	0.0973 (9)
S1	0.10966 (17)	0.09492 (7)	0.08705 (6)	0.0547 (2)
Br1	0.31076 (8)	0.14643 (3)	0.40507 (2)	0.06575 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.072 (2)	0.0503 (18)	0.068 (2)	−0.0251 (16)	−0.0080 (18)	−0.0111 (15)
C2	0.064 (2)	0.0501 (17)	0.0533 (18)	−0.0197 (15)	−0.0024 (16)	0.0021 (14)
C3	0.0521 (17)	0.0389 (15)	0.0404 (14)	−0.0049 (12)	−0.0086 (13)	−0.0020 (11)
C4	0.0452 (15)	0.0408 (15)	0.0373 (13)	−0.0064 (12)	−0.0091 (12)	−0.0058 (11)
C5	0.0481 (16)	0.0449 (15)	0.0362 (14)	−0.0084 (12)	−0.0066 (12)	−0.0028 (11)
C6	0.0471 (16)	0.0489 (16)	0.0360 (13)	−0.0125 (13)	−0.0099 (12)	0.0000 (12)
C7	0.0435 (15)	0.0479 (15)	0.0349 (13)	−0.0091 (12)	−0.0067 (12)	−0.0032 (11)
C8	0.0335 (14)	0.0453 (15)	0.0352 (13)	−0.0051 (11)	−0.0016 (11)	−0.0061 (11)
C9	0.0494 (16)	0.0515 (16)	0.0357 (13)	−0.0182 (13)	−0.0029 (12)	0.0014 (12)
C10	0.0528 (17)	0.0669 (19)	0.0299 (13)	−0.0190 (15)	−0.0053 (12)	−0.0029 (12)
C11	0.0397 (15)	0.0487 (16)	0.0434 (15)	−0.0099 (12)	−0.0052 (12)	−0.0138 (12)
C12	0.0491 (17)	0.0448 (15)	0.0465 (15)	−0.0143 (13)	−0.0026 (13)	−0.0004 (13)
C13	0.0520 (17)	0.0470 (16)	0.0354 (13)	−0.0101 (13)	−0.0069 (13)	0.0023 (12)
N1	0.0549 (15)	0.0652 (17)	0.0562 (16)	−0.0158 (13)	−0.0076 (13)	−0.0210 (13)
O1	0.0828 (15)	0.0770 (15)	0.0369 (11)	−0.0382 (12)	−0.0176 (10)	0.0057 (10)
O2	0.0899 (18)	0.0788 (17)	0.0910 (19)	−0.0497 (15)	−0.0119 (15)	−0.0111 (14)
O3	0.123 (2)	0.123 (2)	0.0597 (16)	−0.0572 (18)	−0.0285 (16)	−0.0191 (16)
S1	0.0668 (5)	0.0564 (5)	0.0468 (4)	−0.0211 (4)	−0.0110 (4)	−0.0137 (3)
Br1	0.0878 (3)	0.0755 (3)	0.03571 (17)	−0.02357 (19)	−0.01421 (15)	0.00301 (14)

Geometric parameters (Å, º)

C1—C2	1.347 (5)	C7—H7	0.9300
C1—S1	1.692 (3)	C8—C9	1.392 (4)
C1—H1	0.9300	C8—C13	1.402 (3)
C2—C3	1.412 (4)	C9—C10	1.374 (4)
C2—H2	0.9300	C9—H9	0.9300
C3—C4	1.379 (4)	C10—C11	1.385 (4)
C3—Br1	1.884 (3)	C10—H10	0.9300
C4—C5	1.475 (4)	C11—C12	1.373 (4)
C4—S1	1.732 (3)	C11—N1	1.474 (3)
C5—O1	1.229 (3)	C12—C13	1.377 (4)
C5—C6	1.467 (4)	C12—H12	0.9300
C6—C7	1.329 (3)	C13—H13	0.9300
C6—H6	0.9300	N1—O2	1.202 (3)
C7—C8	1.469 (3)	N1—O3	1.218 (4)
C2—C1—S1	113.2 (2)	C9—C8—C7	122.8 (2)
C2—C1—H1	123.4	C13—C8—C7	119.0 (2)
S1—C1—H1	123.4	C10—C9—C8	121.2 (2)
C1—C2—C3	111.5 (3)	C10—C9—H9	119.4
C1—C2—H2	124.2	C8—C9—H9	119.4
C3—C2—H2	124.2	C9—C10—C11	118.7 (2)
C4—C3—C2	114.0 (3)	C9—C10—H10	120.7
C4—C3—Br1	126.50 (19)	C11—C10—H10	120.7
C2—C3—Br1	119.5 (2)	C12—C11—C10	122.0 (2)
C3—C4—C5	136.2 (2)	C12—C11—N1	119.5 (2)
C3—C4—S1	109.11 (19)	C10—C11—N1	118.5 (2)
C5—C4—S1	114.60 (19)	C11—C12—C13	118.7 (2)
O1—C5—C6	121.4 (2)	C11—C12—H12	120.7
O1—C5—C4	117.6 (2)	C13—C12—H12	120.7
C6—C5—C4	121.0 (2)	C12—C13—C8	121.2 (2)
C7—C6—C5	121.0 (2)	C12—C13—H13	119.4
C7—C6—H6	119.5	C8—C13—H13	119.4
C5—C6—H6	119.5	O2—N1—O3	123.8 (3)
C6—C7—C8	126.0 (2)	O2—N1—C11	118.5 (3)
C6—C7—H7	117.0	O3—N1—C11	117.7 (3)
C8—C7—H7	117.0	C1—S1—C4	92.20 (14)
C9—C8—C13	118.2 (2)
S1—C1—C2—C3	0.8 (4)	C7—C8—C9—C10	−179.8 (3)
C1—C2—C3—C4	−0.6 (4)	C8—C9—C10—C11	0.9 (5)
C1—C2—C3—Br1	178.1 (2)	C9—C10—C11—C12	−2.5 (5)
C2—C3—C4—C5	176.2 (3)	C9—C10—C11—N1	178.1 (3)
Br1—C3—C4—C5	−2.5 (5)	C10—C11—C12—C13	2.7 (5)
C2—C3—C4—S1	0.2 (3)	N1—C11—C12—C13	−177.9 (3)
Br1—C3—C4—S1	−178.44 (16)	C11—C12—C13—C8	−1.3 (4)
C3—C4—C5—O1	−167.6 (3)	C9—C8—C13—C12	−0.2 (4)
S1—C4—C5—O1	8.2 (4)	C7—C8—C13—C12	180.0 (3)
C3—C4—C5—C6	12.4 (5)	C12—C11—N1—O2	−5.0 (4)
S1—C4—C5—C6	−171.8 (2)	C10—C11—N1—O2	174.4 (3)
O1—C5—C6—C7	9.2 (4)	C12—C11—N1—O3	174.8 (3)
C4—C5—C6—C7	−170.7 (3)	C10—C11—N1—O3	−5.8 (4)
C5—C6—C7—C8	−179.1 (2)	C2—C1—S1—C4	−0.6 (3)
C6—C7—C8—C9	−5.4 (5)	C3—C4—S1—C1	0.2 (2)
C6—C7—C8—C13	174.4 (3)	C5—C4—S1—C1	−176.7 (2)
C13—C8—C9—C10	0.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2^i	0.93	2.50	3.157 (4)	128

Symmetry code: (i) x−2, y−1, z.