supplementary materials


rz5065 scheme

Acta Cryst. (2013). E69, o1004-o1005    [ doi:10.1107/S1600536813014189 ]

(E)-1-(2-Aminophenyl)-3-(thiophen-2-yl)prop-2-en-1-one

S. Chantrapromma, P. Ruanwas, N. Boonnak and H.-K. Fun

Abstract top

The molecule of the title heteroaryl chalcone derivative, C13H11NOS, exists in a trans-configuaration and is almost planar with a dihedral angle of 3.73 (8)° between the phenyl and thiophene rings. An intramolecular N-H...O hydrogen bond generates an S(6) ring motif. In the crystal, two adjacent molecules are linked into a dimer in an anti-parallel face-to-face manner by a pair of C-H...O interactions. Neighboring dimers are further linked into chains along the c-axis direction by N-H...N hydrogen bonds.

Comment top

The basic structure of chalcones consists of two aromatic rings bound by an α,β-unsaturated carbonyl group, a unique template associated with various biological activities such as analgesic, anti-inflammatory, antibacterial (Go et al., 2005; Liu et al., 2008; Ni et al., 2004), anticancer and antioxidant (Shenvi et al., 2013) as well as tyrosinase inhibitory (Nerya et al., 2004) and fluorescence (Suwunwong et al., 2011) properties. The title compound (I) was synthesized and studied for antioxidant activity by the DPPH scavenging method (Molyneux, 2004). Our result showed that (I) exhibits a weakly antioxidant activity. It was also tested for antityrosinase activity but found to be inactive. Herein we report the crystal structure of (I).

The molecular structure of (I) exists in a trans configuration with respect to the C8C9 double bond [1.340 (2)°] as indicated by the torsion angle C7–C8–C9–C10 = 179.29 (15)° (Fig. 1). The whole molecule is almost planar, the interplanar angle between phenyl and thiophene rings being 3.73 (8)° (Fig. 2). The propenone unit (C7—C9/O1) is almost planar with the torsion angle O1–C7–C8–C9 = -7.8 (2)°. The mean plane through the propenone bridge makes the dihedral angles of 7.37 (10) and 3.66 (10)° with the phenyl and thiophene rings, respectively. Intramolecular N1—H1N1···O1 hydrogen bond between amino and enone groups (Fig. 1 and Table 1) generates S(6) ring motif (Bernstein et al., 1995). This intramolecular hydrogen bond helps to stabilize the planarity of the structure. However it may result in the prohibition of the α,β-unsaturated carbonyl moiety to be reactive. The bond distances in (I) agree with the literature values (Allen et al., 1987) and are comparable with those observed in related structures (Fun et al., 2011; Suwunwong et al., 2009).

In the crystal packing (Fig. 3), two adjacent molecules are linked in an anti-parallel face-to-face manner into a dimer by a pair of Cthiophene—H···O interactions and the neighboring dimers are further linked into chains along the c axis by N—H···N hydrogen bonds (Fig. 4 and Table 1).

Related literature top

For standard bond lengths, see: Allen et al. (1987). For graph-set notation, see: Bernstein et al. (1995). For related structures, see: Fun et al. (2011); Suwunwong et al. (2009). For background to and applications of chalcones, see: Go et al. (2005); Liu et al. (2008); Molyneux (2004); Nerya et al. (2004); Ni et al. (2004); Shenvi et al. (2013); Suwunwong et al. (2011). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer, (1986).

Experimental top

The title compound (I) was prepared by mixing 2-aminoacetophenone (0.40 g, 3 mmol) and 2-thiophenecarboxaldehyde (0.34 g, 3 mmol) in ethanol (30 ml). 30% NaOH aqueous solution (5 ml) was then added and the mixture was stirred at room temperature for 2 hr. The yellow solid formed was filtered and washed with distilled water. Yellow block-shaped single crystals of (I) suitable for x-ray structure determination were recrystallized from ethanol by slow evaporation at room temperature over a few weeks. M.p. 407–408 K.

Refinement top

Amino H atoms were located in difference maps and refined isotropically. The remaining H atoms were fixed geometrically and allowed to ride on their parent atoms, with d(C—H) = 0.93 Å for aromatic and 0.98 for CH. The Uiso values were constrained to be 1.2Ueq of the carrier atoms. Four outliers (1 5 4, 5 5 2, -1 5 5, -33 3 15) were omitted from the last refinement cycles.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009), Mercury (Macrae et al., 2006) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound showing 50% probability displacement ellipsoid. Intramolecular N—H···O hydrogen bond is drawn as dashed line.
[Figure 2] Fig. 2. The molecular structure of the title compound showing the approximate planarity of the molecule and the interplanar angle between phenyl and thophene rings.
[Figure 3] Fig. 3. The crystal packing of the title compound viewed along the b axis. Hydrogen bonds are drawn as dashed lines.
[Figure 4] Fig. 4. The crystal packing of the title compound, showing a chain of dimers running along the c axis. Hydrogen bonds are drawn as dashed lines.
(E)-1-(2-Aminophenyl)-3-(thiophen-2-yl)prop-2-en-1-one top
Crystal data top
C13H11NOSF(000) = 960
Mr = 229.30Dx = 1.395 Mg m3
Monoclinic, C2/cMelting point = 407–408 K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 24.9335 (4) ÅCell parameters from 3942 reflections
b = 5.0278 (1) Åθ = 1.8–32.5°
c = 18.6813 (3) ŵ = 0.27 mm1
β = 111.151 (1)°T = 100 K
V = 2184.13 (7) Å3Block, yellow
Z = 80.36 × 0.12 × 0.06 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3942 independent reflections
Radiation source: sealed tube2620 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
φ and ω scansθmax = 32.5°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
h = 3737
Tmin = 0.908, Tmax = 0.984k = 75
14827 measured reflectionsl = 2828
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0488P)2 + 2.0262P]
where P = (Fo2 + 2Fc2)/3
3942 reflections(Δ/σ)max = 0.001
153 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.45 e Å3
Crystal data top
C13H11NOSV = 2184.13 (7) Å3
Mr = 229.30Z = 8
Monoclinic, C2/cMo Kα radiation
a = 24.9335 (4) ŵ = 0.27 mm1
b = 5.0278 (1) ÅT = 100 K
c = 18.6813 (3) Å0.36 × 0.12 × 0.06 mm
β = 111.151 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3942 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
2620 reflections with I > 2σ(I)
Tmin = 0.908, Tmax = 0.984Rint = 0.036
14827 measured reflectionsθmax = 32.5°
Refinement top
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.127Δρmax = 0.39 e Å3
S = 1.04Δρmin = 0.45 e Å3
3942 reflectionsAbsolute structure: ?
153 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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 (Å2) top
xyzUiso*/Ueq
S10.071728 (19)0.24213 (9)0.38943 (3)0.02647 (13)
O10.21891 (5)0.4157 (2)0.59945 (7)0.0243 (3)
N10.22281 (6)0.7977 (3)0.69701 (8)0.0196 (3)
H1N10.2382 (8)0.721 (4)0.6700 (11)0.021 (5)*
H2N10.2361 (9)0.944 (5)0.7198 (12)0.037 (6)*
C10.13438 (6)0.5801 (3)0.61394 (9)0.0157 (3)
C20.16405 (7)0.7756 (3)0.66901 (9)0.0161 (3)
C30.13202 (7)0.9494 (3)0.69732 (9)0.0193 (3)
H3A0.15161.07910.73460.023*
C40.07321 (7)0.9354 (3)0.67233 (10)0.0210 (3)
H4A0.05261.05600.69190.025*
C50.04342 (7)0.7438 (3)0.61801 (10)0.0214 (3)
H5A0.00270.73370.60070.026*
C60.07387 (7)0.5711 (3)0.59021 (9)0.0197 (3)
H6A0.05350.44080.55370.024*
C70.16602 (7)0.3989 (3)0.58064 (9)0.0166 (3)
C80.13517 (7)0.1944 (3)0.52357 (9)0.0176 (3)
H8A0.09550.16130.51260.021*
C90.16398 (7)0.0568 (3)0.48761 (9)0.0181 (3)
H9A0.20340.10210.50100.022*
C100.14298 (7)0.1511 (3)0.43121 (9)0.0186 (3)
C110.17609 (7)0.3053 (3)0.40209 (10)0.0210 (3)
H11A0.21660.28640.41760.025*
C120.14450 (8)0.4928 (4)0.34746 (10)0.0267 (4)
H12A0.16130.61490.32280.032*
C130.08760 (8)0.4801 (4)0.33398 (10)0.0275 (4)
H13A0.05960.58970.29810.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0228 (2)0.0244 (2)0.0278 (2)0.00019 (17)0.00385 (17)0.00763 (19)
O10.0191 (6)0.0249 (6)0.0278 (7)0.0020 (5)0.0071 (5)0.0082 (5)
N10.0185 (7)0.0191 (7)0.0187 (7)0.0015 (5)0.0035 (6)0.0039 (6)
C10.0186 (7)0.0133 (6)0.0144 (7)0.0012 (6)0.0050 (6)0.0004 (6)
C20.0203 (7)0.0143 (6)0.0125 (7)0.0003 (6)0.0043 (6)0.0027 (6)
C30.0265 (8)0.0151 (7)0.0144 (7)0.0006 (6)0.0054 (6)0.0005 (6)
C40.0265 (8)0.0185 (7)0.0195 (8)0.0037 (6)0.0100 (7)0.0003 (6)
C50.0180 (7)0.0224 (7)0.0241 (8)0.0004 (7)0.0078 (6)0.0015 (7)
C60.0218 (8)0.0172 (7)0.0186 (8)0.0024 (6)0.0056 (6)0.0020 (6)
C70.0195 (8)0.0144 (7)0.0151 (7)0.0004 (6)0.0055 (6)0.0012 (6)
C80.0190 (7)0.0149 (7)0.0180 (7)0.0012 (6)0.0057 (6)0.0003 (6)
C90.0201 (8)0.0163 (7)0.0172 (7)0.0020 (6)0.0060 (6)0.0001 (6)
C100.0241 (8)0.0151 (7)0.0179 (8)0.0014 (6)0.0090 (6)0.0003 (6)
C110.0252 (8)0.0202 (8)0.0228 (8)0.0027 (6)0.0148 (7)0.0014 (6)
C120.0443 (11)0.0195 (8)0.0221 (9)0.0013 (8)0.0191 (8)0.0029 (7)
C130.0384 (10)0.0205 (8)0.0192 (8)0.0038 (7)0.0050 (7)0.0055 (7)
Geometric parameters (Å, º) top
S1—C131.7195 (19)C5—C61.373 (2)
S1—C101.7245 (17)C5—H5A0.9500
O1—C71.2392 (19)C6—H6A0.9500
N1—C21.371 (2)C7—C81.481 (2)
N1—H1N10.83 (2)C8—C91.340 (2)
N1—H2N10.86 (2)C8—H8A0.9500
C1—C61.412 (2)C9—C101.442 (2)
C1—C21.422 (2)C9—H9A0.9500
C1—C71.481 (2)C10—C111.380 (2)
C2—C31.409 (2)C11—C121.404 (2)
C3—C41.371 (2)C11—H11A0.9500
C3—H3A0.9500C12—C131.350 (3)
C4—C51.402 (2)C12—H12A0.9500
C4—H4A0.9500C13—H13A0.9500
C13—S1—C1091.94 (9)O1—C7—C1120.84 (14)
C2—N1—H1N1113.2 (13)O1—C7—C8118.34 (14)
C2—N1—H2N1115.3 (14)C1—C7—C8120.82 (14)
H1N1—N1—H2N1122 (2)C9—C8—C7119.10 (15)
C6—C1—C2117.86 (14)C9—C8—H8A120.4
C6—C1—C7121.29 (14)C7—C8—H8A120.4
C2—C1—C7120.81 (14)C8—C9—C10128.46 (15)
N1—C2—C3118.61 (14)C8—C9—H9A115.8
N1—C2—C1122.50 (14)C10—C9—H9A115.8
C3—C2—C1118.88 (14)C11—C10—C9125.77 (15)
C4—C3—C2121.45 (15)C11—C10—S1109.74 (12)
C4—C3—H3A119.3C9—C10—S1124.49 (12)
C2—C3—H3A119.3C10—C11—C12113.91 (16)
C3—C4—C5120.26 (15)C10—C11—H11A123.0
C3—C4—H4A119.9C12—C11—H11A123.0
C5—C4—H4A119.9C13—C12—C11112.33 (16)
C6—C5—C4119.19 (15)C13—C12—H12A123.8
C6—C5—H5A120.4C11—C12—H12A123.8
C4—C5—H5A120.4C12—C13—S1112.06 (13)
C5—C6—C1122.36 (15)C12—C13—H13A124.0
C5—C6—H6A118.8S1—C13—H13A124.0
C1—C6—H6A118.8
C6—C1—C2—N1178.64 (14)C2—C1—C7—C8179.69 (14)
C7—C1—C2—N13.6 (2)O1—C7—C8—C97.8 (2)
C6—C1—C2—C30.2 (2)C1—C7—C8—C9171.71 (14)
C7—C1—C2—C3177.97 (14)C7—C8—C9—C10179.29 (15)
N1—C2—C3—C4179.23 (15)C8—C9—C10—C11172.66 (17)
C1—C2—C3—C40.7 (2)C8—C9—C10—S17.8 (3)
C2—C3—C4—C50.7 (2)C13—S1—C10—C110.44 (13)
C3—C4—C5—C60.1 (3)C13—S1—C10—C9179.13 (15)
C4—C5—C6—C10.5 (3)C9—C10—C11—C12179.72 (16)
C2—C1—C6—C50.4 (2)S1—C10—C11—C120.15 (18)
C7—C1—C6—C5177.38 (15)C10—C11—C12—C130.9 (2)
C6—C1—C7—O1176.95 (15)C11—C12—C13—S11.2 (2)
C2—C1—C7—O10.8 (2)C10—S1—C13—C120.96 (15)
C6—C1—C7—C82.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···O10.83 (2)1.97 (2)2.6253 (18)135.6 (19)
N1—H2N1···N1i0.86 (2)2.34 (2)3.184 (2)169 (2)
C11—H11A···O1ii0.952.563.278 (2)133
Symmetry codes: (i) x+1/2, y+1/2, z+3/2; (ii) x+1/2, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaC13H11NOS
Mr229.30
Crystal system, space groupMonoclinic, C2/c
Temperature (K)100
a, b, c (Å)24.9335 (4), 5.0278 (1), 18.6813 (3)
β (°) 111.151 (1)
V3)2184.13 (7)
Z8
Radiation typeMo Kα
µ (mm1)0.27
Crystal size (mm)0.36 × 0.12 × 0.06
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.908, 0.984
No. of measured, independent and
observed [I > 2σ(I)] reflections
14827, 3942, 2620
Rint0.036
(sin θ/λ)max1)0.756
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.127, 1.04
No. of reflections3942
No. of parameters153
No. of restraints0
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.39, 0.45

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009), Mercury (Macrae et al., 2006) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···O10.83 (2)1.97 (2)2.6253 (18)135.6 (19)
N1—H2N1···N1i0.86 (2)2.34 (2)3.184 (2)169 (2)
C11—H11A···O1ii0.952.563.278 (2)133
Symmetry codes: (i) x+1/2, y+1/2, z+3/2; (ii) x+1/2, y+1/2, z+1.
Acknowledgements top

Financial support from the Thailand Research Fund through the Royal Golden Jubilee PhD Program (grant No. PHD/0314/2552) is gratefully acknowledged. The authors extend their appreciation to Prince of Songkla University, the Deanship of Scientific Research at King Saud University and Universiti Sains Malaysia for the APEX DE2012 grant No. 1002/PFIZIK/910323.

references
References top

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