3-[4-(Methyl­sulfan­yl)phen­yl]-1-(4-nitro­phen­yl)prop-2-en-1-one

Harrison, W.T.A.; Yathirajan, H.S.; Mithun, A.; Narayana, B.; Sarojini, B.K.

doi:10.1107/S160053680603710X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 10| October 2006| Pages o4508-o4509

https://doi.org/10.1107/S160053680603710X

3-[4-(Methylsulfanyl)phenyl]-1-(4-nitrophenyl)prop-2-en-1-one

William T. A. Harrison,^a ^* H. S. Yathirajan,^b A. Mithun,^c B. Narayana ^c and B. K. Sarojini ^d

^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, ^cDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, India, and ^dDepartment of Chemistry, P. A. College of Engineering, Nadupadavu, Mangalore 574 153, India
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 11 September 2006; accepted 12 September 2006; online 20 September 2006)

The geometrical parameters for the title compound, C₁₆H₁₃NO₂S, are normal. The non-centrosymmetric crystal packing, which is consistent with the non-zero second harmonic generation response, may be influenced by a weak intermolecular C—H⋯O interaction.

Comment

The title compound, (I) (Fig. 1), was prepared as part of our ongoing studies (Harrison et al., 2005 , 2006 ) of the non-linear optical (NLO) properties and crystal structures of chalcone derivatives. It is known that substitution at either benzene ring of the chalcone skeleton substantially affects the optical response (Uchida et al., 1998 ) and we are now exploring the role of the methylsulfanyl (H₃CS–) substituent (Butcher et al., 2006 ) in this process.

The non-centrosymmetric polar space group of (I) is consistent with its significant second harmonic generation (SHG) response of 0.6 times that of urea (Watson et al., 1993 ). The geometrical parameters for (I) fall within their expected ranges (Allen et al., 1987 ). The molecule of (I) is distinctly twisted about the C6—C7 and the C9—C10 bonds (Table 1). The dihedral angle between the benzene ring mean planes (C1–C6 and C10–C15) in (I) is 45.84 (4)°, which is significantly smaller than the equivalent value of 68.15 (6)° in 2-bromo-1-(4-methylphenyl)-3-[4-(methylsulfanyl)phenyl]prop-2-en-1-one (Butcher et al., 2006). The nitro group in (I) is well ordered and makes a dihedral angle of 12.94 (15)° with respect to the C10–C15 benzene ring. The C16 methyl group is almost in the plane of the C1–C6 benzene ring [deviation = 0.049 (4) Å].

A PLATON (Spek, 2003 ) analysis of the crystal structure of (I) indicates a possible intermolecular C—H⋯O interaction (Table 2) that might help to establish the crystal packing (Fig. 2). The C—H⋯O interaction forms extended chains of molecules propagating along [001]. Adjacent chains form pseudo-layers in (100), with all the molecules oriented in the same sense with respect to the polar axis.

Figure 1
Molecular structure of (I)

showing 50% displacement ellipsoids (arbitrary spheres for the H atoms).

Figure 2
Part of a (100) sheet of molecules in (I)

with C—H⋯O interactions shown as dashed lines.

Experimental

To a mixture of 4-(methylsulfanyl)benzaldehyde (1.52 g, 0.01 mol) and 4-nitroacetophenone (1.65 g, 0.01 mol) in ethanol (5 ml), a solution of potassium hydroxide (5%, 5 ml) was added slowly with stirring. The mixture was stirred at room temperature for 24 h. The precipitated solid was filtered off, washed with water, dried and recrystallized from an acetone–toluene (1:1 v/v) solvent mixture (yield 86%; m.p. 409 K). Analysis for C₁₆H₁₃NO₃S found (calculated) (%): C 64.15 (64.20), H 4.32 (4.38), N 4.66 (4.68).

Crystal data

C₁₆H₁₃NO₃S
M_r = 299.33
Orthorhombic, A b a 2
a = 13.7388 (4) Å
b = 33.5802 (8) Å
c = 5.9538 (2) Å
V = 2746.80 (14) Å³
Z = 8
D_x = 1.448 Mg m⁻³
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 120 (2) K
Plate, yellow
0.28 × 0.24 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer
ω and φ scans
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.936, T_max = 0.993
27858 measured reflections
3173 independent reflections
2811 reflections with I > 2σ(I)
R_int = 0.063
θ_max = 27.6°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.081
S = 1.06
3173 reflections
191 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0338P)² + 1.763P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ), 1416 Friedel pairs
Flack parameter: 0.04 (8)

Table 1
Selected torsion angles (°)

C5—C6—C7—C8	10.3 (3)
C7—C8—C9—O1	11.4 (3)
O1—C9—C10—C15	21.2 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O1ⁱ	0.95	2.60	3.278 (3)	129
Symmetry code: (i) x, y, z+1.

A handful of reflections weakly violated the h00 (h ≠ 2n) systematic absence condition for the space group Aba2. Attempts to develop a model in lower-symmetry space groups were not successful. The H atoms were positioned geometrically (C—H = 0.95–0.98 Å) and refined as riding, with U_iso(H) = 1.2U_eq(carrier) or 1.5U_eq(methyl). The methyl group was allowed to rotate but not to tip to best fit the electron density.

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/S160053680603710X/lh2179sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680603710X/lh2179Isup2.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.

3-[4-(Methylsulfanyl)phenyl]-1-(4-nitrophenyl)prop-2-en-1-one top

Crystal data top

C₁₆H₁₃NO₃S	F(000) = 1248
M_r = 299.33	D_x = 1.448 Mg m⁻³
Orthorhombic, Aba2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: A 2 -2ac	Cell parameters from 6217 reflections
a = 13.7388 (4) Å	θ = 2.9–27.5°
b = 33.5802 (8) Å	µ = 0.25 mm⁻¹
c = 5.9538 (2) Å	T = 120 K
V = 2746.80 (14) Å³	Plate, yellow
Z = 8	0.28 × 0.24 × 0.03 mm

Data collection top

Nonius KappaCCD diffractometer	3173 independent reflections
Radiation source: fine-focus sealed tube	2811 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
ω and φ scans	θ_max = 27.6°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −17→17
T_min = 0.936, T_max = 0.993	k = −43→43
27858 measured reflections	l = −7→7

Refinement top

Refinement on F²	Secondary atom site location: none
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0338P)² + 1.763P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
3173 reflections	Δρ_max = 0.29 e Å⁻³
191 parameters	Δρ_min = −0.21 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1416 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (8)

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.

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

	x	y	z	U_iso*/U_eq
C1	0.33886 (12)	0.58404 (5)	0.0329 (4)	0.0197 (4)
H1	0.3126	0.5828	−0.1146	0.024*
C2	0.34598 (13)	0.62074 (6)	0.1380 (3)	0.0209 (4)
H2	0.3246	0.6442	0.0633	0.025*
C3	0.38469 (12)	0.62311 (6)	0.3537 (3)	0.0187 (4)
C4	0.41536 (13)	0.58797 (5)	0.4603 (3)	0.0201 (4)
H4	0.4422	0.5892	0.6072	0.024*
C5	0.40679 (13)	0.55163 (6)	0.3533 (4)	0.0207 (4)
H5	0.4271	0.5281	0.4288	0.025*
C6	0.36880 (14)	0.54878 (6)	0.1360 (4)	0.0201 (4)
C7	0.36326 (12)	0.51127 (5)	0.0127 (4)	0.0215 (4)
H7	0.3467	0.5129	−0.1420	0.026*
C8	0.37921 (13)	0.47485 (6)	0.0965 (3)	0.0222 (4)
H8	0.3892	0.4717	0.2534	0.027*
C9	0.38153 (13)	0.43940 (6)	−0.0505 (4)	0.0229 (4)
C10	0.38089 (13)	0.39913 (6)	0.0592 (3)	0.0208 (4)
C11	0.34357 (13)	0.39365 (6)	0.2756 (3)	0.0218 (4)
H11	0.3219	0.4160	0.3597	0.026*
C12	0.33801 (13)	0.35585 (6)	0.3683 (3)	0.0231 (4)
H12	0.3103	0.3518	0.5128	0.028*
C13	0.37387 (15)	0.32407 (6)	0.2449 (4)	0.0227 (4)
C14	0.41321 (13)	0.32839 (5)	0.0330 (4)	0.0229 (4)
H14	0.4383	0.3061	−0.0464	0.028*
C15	0.41513 (13)	0.36617 (6)	−0.0604 (3)	0.0230 (4)
H15	0.4401	0.3697	−0.2078	0.028*
C16	0.34877 (16)	0.70446 (6)	0.3191 (4)	0.0304 (5)
H16A	0.3535	0.7308	0.3888	0.046*
H16B	0.2804	0.6984	0.2866	0.046*
H16C	0.3862	0.7042	0.1790	0.046*
N1	0.36971 (13)	0.28424 (5)	0.3491 (3)	0.0287 (4)
O1	0.38403 (11)	0.44190 (4)	−0.2549 (3)	0.0295 (3)
O2	0.31977 (12)	0.28024 (4)	0.5189 (3)	0.0416 (4)
O3	0.41585 (12)	0.25723 (4)	0.2606 (3)	0.0373 (4)
S1	0.39700 (3)	0.667528 (13)	0.50812 (10)	0.02260 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0198 (8)	0.0229 (9)	0.0163 (9)	−0.0008 (6)	0.0022 (8)	0.0003 (9)
C2	0.0199 (9)	0.0219 (10)	0.0209 (10)	0.0015 (7)	−0.0007 (8)	0.0037 (8)
C3	0.0163 (8)	0.0199 (9)	0.0200 (9)	0.0006 (7)	0.0021 (7)	−0.0015 (8)
C4	0.0210 (8)	0.0229 (9)	0.0165 (11)	0.0006 (7)	−0.0006 (7)	0.0003 (8)
C5	0.0215 (9)	0.0217 (10)	0.0187 (10)	0.0034 (7)	0.0006 (8)	0.0025 (8)
C6	0.0191 (9)	0.0209 (10)	0.0202 (10)	0.0002 (7)	0.0016 (8)	−0.0012 (8)
C7	0.0212 (8)	0.0256 (9)	0.0176 (8)	−0.0002 (7)	−0.0003 (9)	−0.0015 (10)
C8	0.0229 (10)	0.0238 (10)	0.0199 (10)	−0.0002 (8)	−0.0011 (8)	−0.0022 (8)
C9	0.0186 (9)	0.0259 (10)	0.0243 (11)	−0.0009 (7)	−0.0009 (7)	−0.0035 (8)
C10	0.0175 (9)	0.0233 (9)	0.0217 (12)	−0.0020 (7)	−0.0030 (7)	−0.0024 (8)
C11	0.0185 (9)	0.0265 (10)	0.0204 (10)	0.0013 (7)	−0.0016 (8)	−0.0053 (8)
C12	0.0222 (9)	0.0286 (11)	0.0186 (10)	−0.0009 (8)	−0.0003 (8)	−0.0012 (8)
C13	0.0242 (9)	0.0227 (10)	0.0213 (10)	−0.0017 (8)	−0.0042 (8)	−0.0014 (8)
C14	0.0242 (9)	0.0223 (9)	0.0223 (11)	0.0014 (7)	−0.0029 (9)	−0.0051 (9)
C15	0.0218 (9)	0.0275 (11)	0.0197 (10)	−0.0020 (8)	0.0013 (7)	−0.0038 (8)
C16	0.0391 (12)	0.0203 (10)	0.0319 (13)	0.0037 (9)	−0.0054 (10)	0.0007 (9)
N1	0.0340 (9)	0.0258 (10)	0.0262 (10)	−0.0005 (7)	−0.0052 (8)	0.0000 (8)
O1	0.0413 (9)	0.0276 (8)	0.0197 (8)	−0.0001 (6)	0.0023 (7)	−0.0022 (6)
O2	0.0547 (9)	0.0352 (8)	0.0350 (8)	0.0026 (7)	0.0094 (10)	0.0107 (9)
O3	0.0524 (9)	0.0210 (8)	0.0385 (9)	0.0061 (7)	−0.0038 (8)	−0.0040 (7)
S1	0.0248 (2)	0.0203 (2)	0.0227 (2)	0.00036 (18)	−0.0015 (2)	−0.0021 (2)

Geometric parameters (Å, º) top

C1—C2	1.386 (3)	C10—C15	1.398 (3)
C1—C6	1.395 (3)	C10—C11	1.399 (3)
C1—H1	0.9500	C11—C12	1.386 (3)
C2—C3	1.392 (3)	C11—H11	0.9500
C2—H2	0.9500	C12—C13	1.386 (3)
C3—C4	1.405 (3)	C12—H12	0.9500
C3—S1	1.760 (2)	C13—C14	1.380 (3)
C4—C5	1.382 (3)	C13—N1	1.475 (3)
C4—H4	0.9500	C14—C15	1.386 (3)
C5—C6	1.398 (3)	C14—H14	0.9500
C5—H5	0.9500	C15—H15	0.9500
C6—C7	1.460 (3)	C16—S1	1.801 (2)
C7—C8	1.339 (3)	C16—H16A	0.9800
C7—H7	0.9500	C16—H16B	0.9800
C8—C9	1.478 (3)	C16—H16C	0.9800
C8—H8	0.9500	N1—O3	1.225 (2)
C9—O1	1.220 (2)	N1—O2	1.229 (3)
C9—C10	1.502 (3)

C2—C1—C6	122.4 (2)	C15—C10—C9	119.33 (17)
C2—C1—H1	118.8	C11—C10—C9	121.39 (17)
C6—C1—H1	118.8	C12—C11—C10	120.48 (18)
C1—C2—C3	119.60 (19)	C12—C11—H11	119.8
C1—C2—H2	120.2	C10—C11—H11	119.8
C3—C2—H2	120.2	C13—C12—C11	118.31 (19)
C2—C3—C4	118.92 (18)	C13—C12—H12	120.8
C2—C3—S1	124.52 (16)	C11—C12—H12	120.8
C4—C3—S1	116.55 (15)	C14—C13—C12	122.88 (18)
C5—C4—C3	120.52 (18)	C14—C13—N1	119.64 (17)
C5—C4—H4	119.7	C12—C13—N1	117.48 (19)
C3—C4—H4	119.7	C13—C14—C15	118.07 (19)
C4—C5—C6	121.26 (18)	C13—C14—H14	121.0
C4—C5—H5	119.4	C15—C14—H14	121.0
C6—C5—H5	119.4	C14—C15—C10	120.96 (19)
C1—C6—C5	117.31 (19)	C14—C15—H15	119.5
C1—C6—C7	119.72 (19)	C10—C15—H15	119.5
C5—C6—C7	122.93 (18)	S1—C16—H16A	109.5
C8—C7—C6	126.3 (2)	S1—C16—H16B	109.5
C8—C7—H7	116.8	H16A—C16—H16B	109.5
C6—C7—H7	116.8	S1—C16—H16C	109.5
C7—C8—C9	121.26 (19)	H16A—C16—H16C	109.5
C7—C8—H8	119.4	H16B—C16—H16C	109.5
C9—C8—H8	119.4	O3—N1—O2	124.16 (18)
O1—C9—C8	122.38 (19)	O3—N1—C13	118.04 (19)
O1—C9—C10	119.72 (18)	O2—N1—C13	117.80 (17)
C8—C9—C10	117.90 (17)	C3—S1—C16	102.82 (10)
C15—C10—C11	119.24 (17)

C6—C1—C2—C3	0.3 (3)	C8—C9—C10—C11	23.6 (3)
C1—C2—C3—C4	−0.3 (3)	C15—C10—C11—C12	−1.8 (3)
C1—C2—C3—S1	−179.35 (14)	C9—C10—C11—C12	175.91 (16)
C2—C3—C4—C5	−0.3 (3)	C10—C11—C12—C13	2.6 (3)
S1—C3—C4—C5	178.83 (14)	C11—C12—C13—C14	−1.1 (3)
C3—C4—C5—C6	0.9 (3)	C11—C12—C13—N1	178.38 (16)
C2—C1—C6—C5	0.2 (3)	C12—C13—C14—C15	−1.1 (3)
C2—C1—C6—C7	−177.38 (16)	N1—C13—C14—C15	179.42 (16)
C4—C5—C6—C1	−0.8 (3)	C13—C14—C15—C10	1.9 (3)
C4—C5—C6—C7	176.70 (17)	C11—C10—C15—C14	−0.5 (3)
C1—C6—C7—C8	−172.30 (18)	C9—C10—C15—C14	−178.24 (17)
C5—C6—C7—C8	10.3 (3)	C14—C13—N1—O3	12.0 (3)
C6—C7—C8—C9	−173.50 (18)	C12—C13—N1—O3	−167.51 (18)
C7—C8—C9—O1	11.4 (3)	C14—C13—N1—O2	−167.74 (19)
C7—C8—C9—C10	−168.69 (17)	C12—C13—N1—O2	12.8 (3)
O1—C9—C10—C15	21.2 (3)	C2—C3—S1—C16	0.09 (18)
C8—C9—C10—C15	−158.66 (17)	C4—C3—S1—C16	−179.01 (14)
O1—C9—C10—C11	−156.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1ⁱ	0.95	2.60	3.278 (3)	129

Symmetry code: (i) x, y, 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 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
Butcher, R. J., Yathirajan, H. S., Anilkumar, H. G., Sarojini, B. K. & Narayana, B. (2006). Acta Cryst. E62, o1659–o1661. Web of Science CSD CrossRef IUCr Journals 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. & Anilkumar, H. G. (2005). Acta Cryst. C61, o728–o730. Web of Science CSD CrossRef CAS 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
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
Watson, G. J. R., Turner, A. B. & Allen, S. (1993). Organic Materials for Non-linear Optics III, edited by G. J. Ashwell & D Bloor. RSC Special Publication No. 137, pp 112–117. Cambridge: Royal Society of Chemistry. Google Scholar

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