Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041736/sj2342sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041736/sj2342Isup2.hkl |
CCDC reference: 663852
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (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
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).
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%).
The hydrogen atoms were geometrically placed (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(carrier).
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).
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).
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.
Fig. 1. View of the molecular structure of (I) showing 50% displacement ellipsoids (arbitrary spheres for the H atoms). |
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) Å3 |
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 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 0.88 | w = 1/[σ2(Fo2) + (0.0578P)2] where P = (Fo2 + 2Fc2)/3 |
2942 reflections | (Δ/σ)max = 0.001 |
172 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
C13H8BrNO3S | γ = 85.316 (2)° |
Mr = 338.17 | V = 650.42 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.8098 (3) Å | Mo Kα radiation |
b = 10.7863 (8) Å | µ = 3.32 mm−1 |
c = 12.7709 (9) Å | T = 291 K |
α = 81.835 (1)° | 0.47 × 0.20 × 0.20 mm |
β = 83.714 (2)° |
Bruker SMART1000 CCD diffractometer | 2942 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 1946 reflections with I > 2σ(I) |
Tmin = 0.304, Tmax = 0.556 | Rint = 0.022 |
5268 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 0.88 | Δρmax = 0.52 e Å−3 |
2942 reflections | Δρmin = −0.45 e Å−3 |
172 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O2i | 0.93 | 2.50 | 3.157 (4) | 128 |
Symmetry code: (i) x−2, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C13H8BrNO3S |
Mr | 338.17 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 291 |
a, b, c (Å) | 4.8098 (3), 10.7863 (8), 12.7709 (9) |
α, β, γ (°) | 81.835 (1), 83.714 (2), 85.316 (2) |
V (Å3) | 650.42 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.32 |
Crystal size (mm) | 0.47 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.304, 0.556 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5268, 2942, 1946 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.093, 0.88 |
No. of reflections | 2942 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.52, −0.45 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97r.
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O2i | 0.93 | 2.50 | 3.157 (4) | 128 |
Symmetry code: (i) x−2, y−1, z. |
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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).