3 (4 Meth­oxy­phen­yl) 1 (4 nitro­phen­yl)prop 2 en 1 one

organic papers

o896

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

3-(4-Methoxyphenyl)-1-(4-nitrophenyl)prop-2-en-1-one

P. S. Patil,aJeannie Bee-Jan Teh,b Hoong-Kun Fun,b* Ibrahim Abdul Razakb and S. M. Dharmaprakasha

a_{Department of Studies in Physics, Mangalore}

University, Mangalagangotri, Mangalore 574 199, India, andb_{X-ray Crystallography Unit,} School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 100 K

Mean(C–C) = 0.002 A˚

Rfactor = 0.035

wRfactor = 0.096

Data-to-parameter ratio = 11.8

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 25 January 2006 Accepted 30 January 2006

#2006 International Union of Crystallography All rights reserved

The enone group and the benzene rings of the title compound, C16H13NO4, are each planar. In the crystal structure,

inter-molecular C—H O interactions form chains along theaaxis.

Comment

In the last two decades, much effort has been focused on the discovery of new organic materials which exhibit large non-linear optical (NLO) properties (Chemla & Zyss, 1987) and would thus have applications in the field of opto-electronics and photonics. In order to obtain second-order NLO single crystals, the main requirements are the choice of molecules with a large hyperpolarizability () and the alignment of these molecules in a non-centrosymmetric space group with optimal orientation in the crystal structure. Among the many known organic NLO materials, chalcone derivatives are interesting as they exhibit extremely high and fast non-linearity (Fichou et al., 1988; Uchidaet al., 1998; Gotoet al., 1991; Zhaoet al., 2000) and show a preference to crystallize as non-centrosymmetric structures. In this connection we synthesized the title compound, (I), as a potential second-order NLO material and, in order to obtain detailed information on its crystal structure, an X-ray crystal structure determination of (I) has been carried out.

The non-centrosymmetric space group of (I) is consistent with the non-zero SHG signal observed. Our measurements of the SHG conversion efficiency of (I) show that it is five times that of urea.

attached at C3 is twisted away from the C1–C6 benzene ring, with torsion angles O1—N1—C3—C2 of 10.9 (2) _{and O2—} N1—C3—C4 of 11.7 (2)_{. Meanwhile, the methoxy group} attached at C13 is coplanar with the C10–C15 benzene ring.

In the molecular structure of (I), each of the C5–H5A O3 and C9–H9A O3 interactions generates an S(5) ring motif (Bernsteinet al., 1995). The crystal structure is stabilized by C—H O interactions (Table 1), which form molecular chains along theaaxis (Fig. 2).

Experimental

Compound (I) was prepared by the condensation of 4-methoxy-benzaldehyde (0.01 mol) with 4-nitroacetophenone (0.01 mol) in ethanol (60 ml) in the presence of NaOH (5 ml, 30%). After stirring for 2 h, the contents of the flask were poured into ice-cold water, and the resulting crude solid was collected by filtration. The compound was dried and recrystallized from acetone. Crystals suitable for X-ray

diffraction study were grown by slow evaporation of an acetone solution. The SHG measurements were carried out by the classical powder technique (Kurtz & Perry, 1968) using a pulsed Nd:YAG laser (1.064mm, 10 ns, 5 mJ).

Crystal data

C16H13NO4

Mr= 283.27

Orthorhombic,P212121

a= 3.8765 (1) A˚

b= 12.9341 (2) A˚

c= 25.9060 (5) A˚

V= 1298.90 (5) A˚3

Z= 4

Dx= 1.449 Mg m

3

MoKradiation Cell parameters from 9254

reflections

= 1.8–30.0

= 0.11 mm1

T= 100.0 (1) K Block, yellow 0.790.420.17 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer

!scans

Absorption correction: multi-scan (SADABS; Bruker, 2005)

Tmin= 0.813,Tmax= 0.982

15897 measured reflections

2247 independent reflections 2164 reflections withI> 2(I)

Rint= 0.028

max= 30.0

h=5!5

k=18!18

l=35!35

Refinement

Refinement onF2

R[F2_{> 2(F}2_{)] = 0.035}

wR(F2) = 0.096

S= 1.06 2247 reflections 190 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0585P)2

+ 0.3408P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001

max= 0.32 e A˚

3

min=0.22 e A˚

3

Table 1

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

C5—H5 O3 0.93 2.42 2.746 (2) 100 C9—H9 O3 0.93 2.41 2.781 (2) 104 C12—H12 O3i

0.93 2.54 3.470 (2) 175

Symmetry code: (i)x1 2;yþ

1 2;zþ1.

H atoms were placed in calculated positions, with C—H distances of 0.93 or 0.96 A˚ . TheUiso(H) values were constrained to be 1.5Ueqof

the carrier atom for methyl H atoms and 1.2Ueqfor the remaining H

atoms. In the absence of significant anomalous dispersion effects, Friedel pairs were merged before the final refinement.

Data collection:APEX2(Bruker, 2005); cell refinement:APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL,PARST(Nardelli, 1995) andPLATON(Spek, 2003).

The authors thank the Malaysian Government and Universiti Sains Malaysia for the Scientific Advancement Grant Allocation (SAGA) grant No.304/PFIZIK/653003/A118 and the USM short-term grant No. 304/PFIZIK/635028.

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.

organic papers

Acta Cryst.(2006). E62, o896–o898 Patilet al. _C16H13NO4

o897

Figure 1

The structure of (I), showing 50% probability displacement ellipsoids and the atomic numbering. Dashed lines represent hydrogen bonds.

Figure 2

Bernstein, J., Davis, R. E., Shimoni, L. & Chang N.-L. (1995).Angew. Chem. Int. Ed. Engl.34, 1555–1573.

Bruker (2005).APEX2(Version 1.27),SAINTandSADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Chemla, D. S. & Zyss, J. (1987). Nonlinear Optical Properties of Organic Molecules & Crystals, Vol. 1 and 2. New York: Academic Press.

Fichou, D., Watanabe, T., Takeda, T., Miyata, S., Goto, Y. & Nakayama, M. (1988).Jpn J. Appl. Phys.27, L429–L430.

Goto, Y., Hayashi, A., Kimura, Y. & Nakayama, M. (1991).J. Cryst. Growth,

108, 688–698.

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Acta Cryst.E62, o893–o895.

Ravishankar, T., Chinnakali, K., Nanjundan, S., Selvam, P., Fun, H.-K. & Yu, X. -L. (2005).Acta Cryst.E61, o405–o407.

Sathiya Moorthi, S., Chinnakali, K., Nanjundan, S., Radhika, R., Fun, H.-K. & Yu, X.-L. (2005).Acta Cryst.E61, o480–o482.

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Sathiya Moorthi, S., Chinnakali, K., Nanjundan, S., Unnithan, C. S., Fun, H.-K. & Yu, X.-L. (2005).Acta Cryst.E61, o483–o485.

Sheldrick, G. M. (1998).SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.

Teh, J. B. J., Patil, P. S., Fun, H.-K. Razak, I. A., & Dharmaprakash, S. M. (2006).Acta Cryst.E62, o890–o892.

Uchida, T., Kozawa, K., Sakai, T., Aoki, M., Yoguchi, H., Abdureyim, A. & Watanebe, Y. (1998).Mol. Cryst. Liq. Cryst.314, 135–140.

Zhao, B., Lu, W.-Q., Zhou, Z.-H. & Wu, Y. (2000).J. Mater. Chem.10, 1513– 1517.

organic papers

supporting information

sup-1 Acta Cryst. (2006). E62, o896–o898

supporting information

Acta Cryst. (2006). E62, o896–o898 [https://doi.org/10.1107/S1600536806003564]

3-(4-Methoxyphenyl)-1-(4-nitrophenyl)prop-2-en-1-one

P. S. Patil, Jeannie Bee-Jan Teh, Hoong-Kun Fun, Ibrahim Abdul Razak and S. M. Dharmaprakash

3-(4-Methoxyphenyl)-1-(4-nitrophenyl)prop-2-en-1-one

Crystal data

C16H13NO4

Mr = 283.27

Orthorhombic, P212121

Hall symbol: P 2ac 2ab a = 3.8765 (1) Å b = 12.9341 (2) Å c = 25.9060 (5) Å V = 1298.90 (5) Å3

Z = 4

F(000) = 592 Dx = 1.449 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 9254 reflections θ = 1.8–30.0°

µ = 0.11 mm−1

T = 100 K Block, yellow

0.79 × 0.42 × 0.17 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

Detector resolution: 8.33 pixels mm-1

ω scans

Absorption correction: multi-scan (SADABS; Bruker, 2005) Tmin = 0.813, Tmax = 0.982

15897 measured reflections 2247 independent reflections 2164 reflections with I > 2σ(I) Rint = 0.028

θmax = 30.0°, θmin = 1.8°

h = −5→5 k = −18→18 l = −35→35

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.035}

wR(F2_{) = 0.096}

S = 1.06 2247 reflections 190 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.0585P)2 + 0.3408P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.32 e Å−3

Δρmin = −0.22 e Å−3

Special details

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sup-2 Acta Cryst. (2006). E62, o896–o898

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

O1 0.6403 (4) −0.27796 (9) 0.22026 (4) 0.0251 (3)

O2 0.4397 (5) −0.39845 (8) 0.27006 (5) 0.0376 (4)

O3 −0.3158 (3) −0.04627 (8) 0.42950 (4) 0.0194 (2)

O4 −0.3233 (3) 0.60111 (7) 0.41986 (4) 0.0189 (2)

N1 0.4760 (4) −0.30697 (9) 0.25816 (5) 0.0199 (3)

C1 0.1437 (4) −0.05452 (10) 0.30714 (5) 0.0159 (3)

H1 0.1280 0.0141 0.2967 0.019*

C2 0.2986 (4) −0.12702 (10) 0.27478 (5) 0.0165 (3)

H2 0.3894 −0.1077 0.2430 0.020*

C3 0.3133 (4) −0.22904 (10) 0.29147 (5) 0.0155 (3)

C4 0.1855 (5) −0.26107 (10) 0.33886 (5) 0.0179 (3)

H4 0.1999 −0.3299 0.3491 0.022*

C5 0.0361 (4) −0.18755 (10) 0.37044 (5) 0.0173 (3)

H5 −0.0500 −0.2072 0.4025 0.021*

C6 0.0119 (4) −0.08409 (10) 0.35511 (5) 0.0142 (3)

C7 −0.1647 (4) −0.01081 (10) 0.39167 (5) 0.0150 (3)

C8 −0.1495 (4) 0.10163 (10) 0.38147 (5) 0.0161 (3)

H8 −0.0253 0.1272 0.3535 0.019*

C9 −0.3188 (4) 0.16629 (10) 0.41335 (5) 0.0154 (3)

H9 −0.4474 0.1350 0.4393 0.018*

C10 −0.3266 (4) 0.27903 (10) 0.41244 (5) 0.0147 (3)

C11 −0.4791 (4) 0.32974 (10) 0.45424 (5) 0.0156 (3)

H11 −0.5821 0.2903 0.4800 0.019*

C12 −0.4829 (4) 0.43672 (10) 0.45886 (5) 0.0159 (3)

H12 −0.5812 0.4685 0.4875 0.019*

C13 −0.3360 (4) 0.49509 (10) 0.41952 (5) 0.0152 (3)

C14 −0.1888 (4) 0.44696 (10) 0.37629 (5) 0.0169 (3)

H14 −0.0966 0.4868 0.3498 0.020*

C15 −0.1805 (4) 0.34024 (10) 0.37303 (5) 0.0165 (3)

H15 −0.0780 0.3086 0.3447 0.020*

C16 −0.4742 (5) 0.65134 (11) 0.46364 (6) 0.0210 (3)

H16C −0.4514 0.7249 0.4600 0.032*

H16A −0.3583 0.6293 0.4945 0.032*

H16B −0.7142 0.6335 0.4658 0.032*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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sup-3 Acta Cryst. (2006). E62, o896–o898

O3 0.0238 (6) 0.0180 (4) 0.0163 (4) −0.0009 (5) 0.0034 (5) −0.0002 (3) O4 0.0245 (6) 0.0132 (4) 0.0190 (5) 0.0006 (5) 0.0037 (5) −0.0012 (3) N1 0.0226 (6) 0.0179 (5) 0.0191 (6) 0.0016 (6) 0.0007 (6) −0.0037 (4) C1 0.0192 (7) 0.0132 (5) 0.0153 (6) −0.0003 (6) 0.0000 (6) 0.0008 (4) C2 0.0194 (7) 0.0159 (5) 0.0142 (5) −0.0011 (6) 0.0012 (6) −0.0004 (4) C3 0.0156 (6) 0.0140 (5) 0.0167 (6) −0.0004 (6) −0.0003 (6) −0.0032 (4) C4 0.0210 (7) 0.0134 (5) 0.0194 (6) −0.0003 (6) 0.0009 (6) 0.0007 (5) C5 0.0209 (7) 0.0157 (5) 0.0154 (6) −0.0003 (6) 0.0022 (6) 0.0016 (4) C6 0.0132 (6) 0.0138 (5) 0.0155 (5) −0.0005 (5) −0.0016 (5) −0.0005 (4) C7 0.0152 (6) 0.0152 (5) 0.0147 (6) −0.0003 (6) −0.0015 (6) −0.0012 (4) C8 0.0173 (7) 0.0144 (5) 0.0165 (6) 0.0003 (6) 0.0003 (5) 0.0006 (4) C9 0.0149 (6) 0.0161 (5) 0.0150 (6) 0.0002 (6) −0.0011 (6) 0.0002 (4) C10 0.0134 (6) 0.0152 (5) 0.0155 (6) 0.0012 (6) −0.0013 (6) −0.0007 (4) C11 0.0155 (6) 0.0162 (5) 0.0151 (6) 0.0012 (6) 0.0012 (6) 0.0011 (4) C12 0.0163 (6) 0.0171 (6) 0.0143 (5) 0.0017 (6) 0.0010 (6) −0.0015 (4) C13 0.0156 (6) 0.0139 (5) 0.0163 (6) 0.0009 (6) −0.0009 (6) −0.0005 (4) C14 0.0189 (7) 0.0165 (5) 0.0152 (6) −0.0002 (6) 0.0020 (6) 0.0012 (4) C15 0.0175 (6) 0.0175 (6) 0.0145 (6) 0.0018 (6) 0.0006 (6) −0.0010 (4) C16 0.0233 (8) 0.0167 (6) 0.0232 (6) −0.0005 (7) 0.0051 (7) −0.0042 (5)

Geometric parameters (Å, º)

O1—N1 1.2292 (18) C8—C9 1.346 (2)

O2—N1 1.2307 (16) C8—H8 0.93

O3—C7 1.2304 (18) C9—C10 1.4587 (17)

O4—C13 1.3722 (15) C9—H9 0.93

O4—C16 1.4320 (17) C10—C11 1.3972 (18)

N1—C3 1.4690 (18) C10—C15 1.4106 (19)

C1—C2 1.3939 (19) C11—C12 1.3889 (17)

C1—C6 1.3969 (18) C11—H11 0.93

C1—H1 0.93 C12—C13 1.3903 (19)

C2—C3 1.3898 (18) C12—H12 0.93

C2—H2 0.93 C13—C14 1.4028 (19)

C3—C4 1.387 (2) C14—C15 1.3833 (18)

C4—C5 1.382 (2) C14—H14 0.93

C4—H4 0.93 C15—H15 0.93

C5—C6 1.3990 (17) C16—H16C 0.96

C5—H5 0.93 C16—H16A 0.96

C6—C7 1.5048 (19) C16—H16B 0.96

C7—C8 1.4793 (18)

C13—O4—C16 116.35 (11) C8—C9—C10 128.41 (14)

O1—N1—O2 123.56 (13) C8—C9—H9 115.8

O1—N1—C3 118.83 (12) C10—C9—H9 115.8

O2—N1—C3 117.61 (13) C11—C10—C15 117.86 (12)

C2—C1—C6 120.56 (12) C11—C10—C9 117.74 (12)

C2—C1—H1 119.7 C15—C10—C9 124.36 (13)

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sup-4 Acta Cryst. (2006). E62, o896–o898

C3—C2—C1 117.99 (13) C12—C11—H11 118.7

C3—C2—H2 121.0 C10—C11—H11 118.7

C1—C2—H2 121.0 C11—C12—C13 118.26 (13)

C4—C3—C2 122.97 (13) C11—C12—H12 120.9

C4—C3—N1 117.92 (12) C13—C12—H12 120.9

C2—C3—N1 119.10 (12) O4—C13—C12 123.55 (12)

C5—C4—C3 117.92 (12) O4—C13—C14 115.72 (12)

C5—C4—H4 121.0 C12—C13—C14 120.73 (12)

C3—C4—H4 121.0 C15—C14—C13 120.07 (13)

C4—C5—C6 121.22 (13) C15—C14—H14 120.0

C4—C5—H5 119.4 C13—C14—H14 120.0

C6—C5—H5 119.4 C14—C15—C10 120.43 (13)

C1—C6—C5 119.34 (12) C14—C15—H15 119.8

C1—C6—C7 123.64 (11) C10—C15—H15 119.8

C5—C6—C7 117.02 (12) O4—C16—H16C 109.5

O3—C7—C8 121.86 (13) O4—C16—H16A 109.5

O3—C7—C6 118.89 (12) H16C—C16—H16A 109.5

C8—C7—C6 119.25 (12) O4—C16—H16B 109.5

C9—C8—C7 118.80 (13) H16C—C16—H16B 109.5

C9—C8—H8 120.6 H16A—C16—H16B 109.5

C7—C8—H8 120.6

C6—C1—C2—C3 0.8 (2) O3—C7—C8—C9 −2.9 (2)

C1—C2—C3—C4 −0.9 (2) C6—C7—C8—C9 177.61 (14)

C1—C2—C3—N1 −179.86 (14) C7—C8—C9—C10 176.69 (16)

O1—N1—C3—C4 −168.12 (15) C8—C9—C10—C11 −170.57 (16)

O2—N1—C3—C4 11.7 (2) C8—C9—C10—C15 7.2 (3)

O1—N1—C3—C2 10.9 (2) C15—C10—C11—C12 −1.8 (2)

O2—N1—C3—C2 −169.24 (17) C9—C10—C11—C12 176.15 (16)

C2—C3—C4—C5 0.3 (3) C10—C11—C12—C13 1.6 (3)

N1—C3—C4—C5 179.28 (15) C16—O4—C13—C12 −0.4 (2)

C3—C4—C5—C6 0.4 (2) C16—O4—C13—C14 179.69 (14)

C2—C1—C6—C5 −0.1 (2) C11—C12—C13—O4 −179.77 (16)

C2—C1—C6—C7 −178.79 (15) C11—C12—C13—C14 0.2 (2)

C4—C5—C6—C1 −0.5 (2) O4—C13—C14—C15 178.26 (16)

C4—C5—C6—C7 178.26 (15) C12—C13—C14—C15 −1.7 (3)

C1—C6—C7—O3 169.65 (15) C13—C14—C15—C10 1.5 (3)

C5—C6—C7—O3 −9.1 (2) C11—C10—C15—C14 0.2 (2)

C1—C6—C7—C8 −10.9 (2) C9—C10—C15—C14 −177.57 (16)

C5—C6—C7—C8 170.42 (15)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

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sup-5 Acta Cryst. (2006). E62, o896–o898

C9—H9···O3 0.93 2.41 2.781 (2) 104

C12—H12···O3i _{0.93 2.54 3.470 (2) 175}