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Synthesis, characterization, and third-order
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nonlinear optical properties of a new neolignane
Cite this: RSC Adv., 2016, 6, 79215
Wesley F. Vaz,ab Jean M. F. Custodio,b Rafael G. Silveira,c Adailton N. Castro,b
Carlos E. M. Campos,d Murilo M. Anjos,e Guilherme R. Oliveira,e
Clodoaldo Valverde,bfg Bası́lio Baseiahi and Hamilton B. Napolitano*b

Recently, a wide number of pharmacological activities, such as anti-leishmanial, antioxidant and antitumor,
have been discovered for neolignane analogues. To provide a view of the non-linear optical behavior of the
third order of the crystal 2-(4-nitrophenoxy)-1-phenylethanone (NPH-PE) in the static and dynamic cases,
we calculated its linear polarizability (a) and second hyperpolarizability (g). We used a new supermolecule
approach combined with an iterative electrostatic system whose atoms of the neighboring molecules are
represented by point charges. A comprehensive investigation of NPH-PE is reported by single crystal X-ray
diffraction and FT-Raman and NMR spectroscopy. In addition, a combination of density functional theory
Received 8th June 2016
Accepted 29th July 2016
(DFT) with the CAM-B3LYP functional and the 6-311+G(d) basis set was used to calculate the molecular
structure optimization, the vibrational frequencies, and the intensity of the vibrational bands. Concerning
DOI: 10.1039/c6ra14961h
the values of the third-order optical nonlinearity, the second hyperpolarizability of the embedded molecule showed an increase of 125 058% in comparison with the corresponding result in the static case.

of the fact that this wide range of compounds exhibits biological
1. Introduction potential such as anti-leishmanial, antioxidant, and antitumor
The term “lignans” was rst introduced by Haworth1 and was activities3–5 as well as anti-schistosomiasis6 and anti-
assigned to plant products derived from carbon skeletons in mycobacterial7 properties. Recently, Hanusch et al.8 described
which the propenylbenzene units (C3–C6) 8.80 are linked by the genotoxicity and evaluated the cytotoxicity of the neolignan
carbons (b0 –b). However, due to increased understanding of analogue 2-(4-nitrophenoxy)-1-phenylethanone. In order to
various structures, this assignment become obsolete; lignoids better understand the results found by Hanusch, more detailed
now are subdivided into more groups, such as (a) lignans; (b) structural study of the analyzed compound is required. Among
neolignans; (c) alolignanas; (d) norlignanas; (e) oligolignóides; the available techniques and methodologies for this purpose,
and (f) heterolignóides.2 The structural study of neolignans has an important role is played by crystallographic analysis because
attracted attention in the scientic community recently, in view it evaluates the composition and chemical structure of the
compound.9 Moreover, the knowledge of the crystalline struc-
ture of an organic sample enables the calculation of its various
Instituto Federal de Educação, Ciência e Tecnologia de Mato Grosso, 78455-000, electrical properties.
Lucas do Rio Verde, MT, Brazil The fascination with new organic materials for nonlinear
Ciências Exatas e Tecnológicas, Universidade Estadual de Goiás, 459, 75001-970, optical (NLO) applications has widely stimulated their study in
Anápolis, GO, Brazil. E-mail:
the past 30 years; this interesting topic has been considered by
Departamento de Quı́mica, Universidade Federal de São Carlos, CEP: 13565-905, São
many researchers, such as Champagne and Bishop.10 Organic
Carlos, SP, Brazil
Departamento de Fı́sica, Universidade Federal de Santa Catarina, 88040-970,
molecules, especially polymers with high hyperpolarizability,
Florianópolis, SC, Brazil have raised great interest due to their applications in nonlinear
Instituto de Quı́mica, Universidade Federal de Goiás, Goiânia, GO, Brazil optical systems.11 Their relative ease of synthesis and manipula-
Escola Superior Associada de Goiânia (ESUP), 74840-090, Goiânia, GO, Brazil tion and their more efficient NLO have placed organic structures
Universidade Paulista (UNIP), 74845-090, Goiânia, GO, Brazil at the border of research and technological applications that have
Instituto de Fı́sica, Universidade Federal de Goiás, 74.690-900, Goiânia, GO, Brazil elicited much attention; even today, several studies have been
Departamento de Fı́sica, Universidade Federal da Paraı́ba, 58.051-970, João Pessoa, published related to chromophore synthesis in order to optimize
PB, Brazil
the non-linear optical properties of crystalline materials.12,13
† Electronic supplementary information (ESI) available. CCDC 1481520. For ESI
and crystallographic data in CIF or other electronic format see DOI:
Theoretical research has played an invaluable role in
10.1039/c6ra14961h increasing our understanding of experimental data, such as the

This journal is © The Royal Society of Chemistry 2016 RSC Adv., 2016, 6, 79215–79227 | 79215

829(1) Å (observed by TLC) and water (20 mL) was added. deposited in the Cambridge Structural Database32 under the The aim of this study is to determine the third order optical code CCDC 1481520. P21/c. therefore. a ¼ 90 90 and dried over anhydrous Na2SO4. Z Monoclinic. and other lographic information les of the C14H11NO4 molecule were optical equipment. representations. we can estimate data are shown in Table 1. and brine.104 mm1 1.412(6) Å.29(1)  under reduced pressure and the product was recrystallized with g ¼ 90 90 Volume 1216. Other atom densities at the corresponding distances from the schemes of embedding general/local eld theory to calculate c1 nuclei.80(12) Å3 1173.00 Reections collected/unique 6420/2258 [R(int) ¼ 0.71073 Å 1.77142 Å mixture was stirred until the starting material was consumed Crystal system.05 collected at room temperature using a Bruker APEX II CCD Final R indices [I > 2s(I)] 0.14–17 The incorporation of polarization for aromatic and methyl groups. in relation to the free- reasonable results compared with those of experiments. ing to the riding model (C–H bond lengths of 0. Recently. Experimental and computational procedures Synthesis and crystallization Table 1 Crystal data and structure refinement for NPH-PE To a suspension of K2CO3 (5 mmol) and 4-nitrophenol (1 mmol) Formula weight 257.u. tables and pictures were generated by the molecular interactions on the electrical properties. The crystal- devices. with made at each point between the atoms.61 Å3 a hexane–acetate mixture to obtain a light yellow solid in 80% Calculated density 1.43(2) 92.22–26 In this atom distributions.0930(5) Å 7.03181 diffractometer with graphite-monochromated MoKa radiation 79216 | RSC Adv. we calculate the NLO properties for the static and molecular density in its neighborhood.24 a. The integration of the dynamic cases.19.27 The studied compound crystallized in the mono- electrical properties of organic molecules.20 In from an attempt to dene the space occupied by a molecule in another recent work. washed with water. The structure was solved by direct methods and molecule approach. The relationships of structural properties are required in the design possible interactions of hydrogen were checked by PARST of optical materials for effective applications in photonic soware31 and studied from the Hirshfeld surface. b ¼ 13. electro-optics. This polarization clinic crystal system and space group P21/c.404 mg m3 1. such as silicon. 2016.4120(6) Å 11. the product b ¼ 13. a crystal in order to partition the crystal electron density into nique of polarization used here to estimate the non-linear molecular fragments. in dry butanone (30 mL) at 50  C was added a solution of phe. (l ¼ 0.5 Ueq] accord- Published on 22 August 2016. Molecular effects in the material medium modies the action of inter.96 A treated as point charges. charges and multipole moments. Temperature 293(2) K 100(2) K nacyl bromide (1. such as optical modulators. Absorption coefficient 0. leading to molecular charge reorganization. nonlinearities of the compound 2-(4-nitrophenoxy)-1- phenylethanone (NPH-PE).97  A and 0.160(3) Å was then extracted with ethyl acetate (30 mL  3). Downloaded by Northern Illinois University on 22/08/2016 13:53:18. The potential intermolecular interactions of NPH-PE were polarizability (g) in the static and dynamic cases.179(7) Å. All the hydrogen atoms were placed the dipole moment. 79215–79227 This journal is © The Royal Society of Chemistry 2016 . interactions are electrostatic in nature and takes long-range g ¼ a ¼ 90 and b ¼ 91. The resulting Wavelength 0.293] Crystallographic characterization Renement method Direct method Rietveld The X-ray diffraction data of the analyzed compound were Goodness-of-t on F2 1. using this method in an iterative process. We also calculate the energy of the HOMO and atomic deformation densities determines the net atomic LUMO through the MP2 method. The solvent was removed b ¼ 91. c ¼ 11. The organic c ¼ 11. The Hirshfeld surface arose materials with high susceptibility c3. rened by full-matrix least squares on F2 using SHELXL2014 can simulate the effect of the polarization of a medium on the soware. View Article Online RSC Advances Paper microscopic origin of molecular responses in NLO.21 the authors developed the same tech. 6. The super. was proposed that an unconventional blockade may allow This is a graphical tool for the visualization and understanding emission of light to reach antibunched passive devices made of of intermolecular interactions. 30) programs.028 3. This allows us to calculate the external electro- static potential and the interaction energy between molecules or 2.5 mmol/10 mL of butanone). To this end.33 A share in the charge density can be optical properties c1 and c2 of molecular crystals. respectively).0392 0. the linear polarizability and the second in calculated positions and rened with xed individual hyperpolarizability of a crystal surrounded by a polarizable displacement parameters [Uiso(H) ¼ 1.093(5) Å. 4 Unit cell dimensions a ¼ 8. domain constituted by other atoms of neighboring molecules. space group. we present an ab ini- tio study using the procedure of supermolecule polarization to Hirshfeld surface analysis calculate the linear polarizability (a) and second hyper.552 mm1 F(000) 536.399(3) Å layers were combined. it visualized and interpreted using Hirshfeld surface analysis.452 mg m3 yield.431 (19) .28 with the following procedure relies on the fact that the dominant intermolecular unit cell metrics: a ¼ 8..1 (ref. each of which closely resembles the paper.2 Ueq or 1. The main crystallographic electrostatic effects into account. HCl 10%. This entails the generation of well-localized bonded and c2 were also developed for molecular crystals.71073 Å).18 Reliable Mercury29 and Crystal Explorer v3.1790(7) Å 13.

21 MHz. were recorded at room temperature on a XPERT polarizability of long chains. Further measurements were performed at the computations.6 Hz. analytic harmonic frequency photons at room temperature and 100 K. 13C NMR (400. 2016. All spectra were recorded in the spectral window of 200 to 1800 cm1 with the same acquisition time (10 s). tt ¼ triple triplet and m ¼ multiplet.9 (C4).34 Thus. C6). 5. 2H). 2H). and second hyperpolarizability (g).21 MHz. 1. excitations to Rydberg states and PANalytical diffractometer equipped with an X'Celerator charge transfer excitations.97–8. range properties and is recommended as highly accurate for the C14H11NO4. 1H–1H COSY. Downloaded by Northern Illinois University on 22/08/2016 13:53:18. i. The procedures for the structural determination were structure is truly in a local minimum.91 (C2. allowing us to obtain a spectral resolution of 6 cm1. 128.58 (m..12 (C1). CDCl3.24 (m.67 (tt. they must be non- Raman radiation was dispersed with a grating and focused on centrosymmetric materials. 3Jortho ¼ 7. 2H).8 Å view of de vs. The sample was screened in potassium bromide (KBr) and the main absorbent groups were characterized.6–2. di. mp: 147  C to 148  C. Gaussian 09 package of programs. DEPT-135 NMR and advanced 2D NMR techniques such as gradient enhanced. 114. 298 K): d (ppm) 162.43 Karlsruhe. Rietveld analyses of the patterns were performed using distribution (PED) analysis using VEDA 4 soware42 and were GSASEXPGUI36. To conrm that the fully optimized geometry XRD1 beamline of Brazilian Synchrotron.81(C3. The synthesis and the experimental between parts of the same molecule. 134. Germany). 79215–79227 | 79217 . are reported in ppm with TMS (tetramethylsilane) as the internal reference). 1H). 125. with using density functional theory (DFT) as implemented in the ngerprint plots using the standard 0.35 and the molecular structure was given vibrational frequencies were carried out by potential energy by RNM. The assignments of the carried out using DASH. in NPH-PE were mapped as a function of de (the distance from The obtained solid was colorless. C5).41 was used for all the 40 kV and 45 mA. interactions found infrared and Raman spectra of C14H11NO4 are shown in Fig. 7.e. 7.82 (C8). C13). 1 (a) Synthesis of 2-(4-nitrophenoxy)-1-phenylethanone. using 7 and 12 keV was found in a local minimum.39 was employed throughout the calculations.08 (C14. 192. 6.11 As NPH-PE exhibits This journal is © The Royal Society of Chemistry 2016 RSC Adv. 2H). 7. 13C. The extended Gaussian basis set 6- detector using ltered Ka1 radiation from a Cu tube operating at 311+G(d) of Pople and co-workers40.6 Hz and 4Jmeta ¼ 1. rst collected with a 20 objective lens at room temperature using hyperpolarizability (b). The a PeakSeeker 785 (RAM – PRO – 785) Raman system with a diode essential requirement is that molecular (b) organic materials laser of 785 nm and 50 mW at the source. theoretical (black) and overlap of the IR and Raman observed in the region from 4000 to 400 cm1 using an FT-IR/ spectra of NPH-PE. This functional is a hybrid with improved long- XRPD patterns of 2-(4-nitrophenoxy)-1-phenylethanone. 8.7 mm glass absence of imaginary frequencies shows that the optimized capillary. (b) The experimental absorption spectrum in the solid state was experimental (red). supported by the animation option of Gaussview.03 (C9). linear polarizability (a)..03 (m. 1H NMR (400.2 (Bruker AXS GmbH.17–8.44 (s.37 and TOPAS version 4. 298 K) d (ppm) 6. IRAffinity-1 Shimadzu spectrophotometer. 30) soware. Infrared spectroscopy and assignments Fig. CDCl3. NMR spectroscopy characterization All NMR experiments were performed on a BRUKER DRX 400 MHz spectrometer with a BBO 5 mm probe at 298 K (all signals Published on 22 August 2016. The the surface to the nearest atom in the molecule itself) and di (the starting geometry used in the calculations was taken directly distance from the surface to the nearest atom in another from the X-ray data and was fully optimized without constraint molecule) by Crystal Explorer 3. using CDCl3 as the solvent. 2H). The were carried out in transmission mode using a 0.03 (m. The backscattered exhibit no inversion center.00 (C7). CAM-B3LYP. 129.00 (C11. 1H.51–7.38 (C12). Computational procedures Raman spectroscopy Molecules can be characterized by their electrical properties.97–7. and 1 H–13C correlation HSQC were employed. The splitting of proton and carbon resonances were reported as s ¼ singlet. All the measurements calculations were carried out at the same level of theory. 134. View Article Online Paper RSC Advances a Peltier-cooled charge-coupled device CCD detector. 142.38 Handy and co-workers' long range corrected version of B3LYP using the Coulomb- Powder diffraction attenuating method.1 (ref. 70. C10). Raman spectra of different regions of the sample surface were such as dipole moment (m).

(iv) we returned to item Fig. stabilized by nonclassical hydrogen bonds. described by its charge distribution in a vacuum. we with 3240 atoms).y. using the 6-311+G(d) including 30 atoms. y + 1. therefore. (1) 3 we then calculated the partial atomic charges (ChelpG) for one qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi isolated molecule of the asymmetric unit. we took the unit cell of the NPH. consisting of four asymmetric units. Interactions are drawn as dashed lines. (iii) we calculated the static electric properties (dipole hgi ¼ g þ gijij þ gijji : (3) 15 ij¼x. (i) hai ¼ axx þ ayy þ azz .z iijj moment and second hyperpolarizability) and the new partial atomic charges of the asymmetric unit. These calcu- PE molecule. by repli.. 7  7  7 (343 unit cells with 41 160 atoms) and the 9  9  9 moment. C6–H6/O4. a supermolecule approach was developed to detect molecular properties was achieved. C13–H13/O1 [symmetry code: x. (2) each corresponding atom in the generated unit cells. we the polarization effects of the crystalline environment upon the calculated the linear and nonlinear electrical properties for electrical properties of NPH-PE. with 15 000 atoms). 6. used a larger arrangement (9  9  9) to ensure a stable dipole Published on 22 August 2016. and hydrogen atoms are shown as spheres of arbitrary radii. we replaced the atom by its partial atomic charge. (ii) in the position of m¼ mx 2 þ my 2 þ mz 2 . This method was used in the both the static and dynamic cases via the MP2 and Density experimental geometry of the asymmetric unit of NPH-PE. Downloaded by Northern Illinois University on 22/08/2016 13:53:18. View Article Online RSC Advances Paper a centrosymmetric crystal structure. the values of average linear polarizability Each atomic conguration around the isolated NPH-PE mole. 79215–79227 This journal is © The Royal Society of Chemistry 2016 . program. basis set employing the nite eld (FF) method. In this study. View normal to (100). Functional Theory (CAM-B3LYP) levels. respectively: potential (ChelpG) obtained with the 6-311+G(d) basis set at the 1  MP2 level. hai. (b) The crystal packing of NPH-PE. Here. C6–H6/O3 [symmetry code: x + 1. the total dipole moment m and the second average hyper- cule is treated as a point charge. calculated in 1 X  item (i). In each iterative process. To this end. z  1/2]. Initially. 5  5  5 (125 unit cells. All bonds are in the normal range. we initiated it (step polarizability hgi have been calculated through the following 0) with the isolated molecule via a t of the electrostatic expressions. including C10–H10/O4. z]. 2016. lations show that a set of 5  5  5 unit cells guarantees fast cating it in all three axes. +y  1/2. 2 (a) ORTEP diagram of ellipsoids at the 30% probability level with the atomic numbering scheme for NPH-PE. 79218 | RSC Adv. All calculations were performed using the Gaussian 09 conguration (729 unit cells with 87 480 atoms) were obtained. its rst hyperpolarizability (ii) and repeated the procedure until convergence in the electric is null. the settings 3  3  3 (27 unit cells convergence of the dipole moment of the crystal.

Consequently. with cell parameters symmetry code: x + 1. This can be conrmed On average. The C7–O2 bond shows a lower free capacity of rotation when compared with other heteroatoms. D–H/A ¼ 164. y + 1.01 crystals. and V is the volume of the unit C07–O02 1. even considering the The crystalline arrangement of the analyzed compound is size of the atom and its electronegativity.07 cð3Þ ¼ hgi.91 C04–N01–O04 118. C06–C01 1. 79215–79227 | 79219 . 2016. forming the two-dimensional arrangement shown in parameters (bond lengths and bond angles) were compared Fig.09 polarizability are given in Table 5. 6. the third-order C01–O02 1.498 Å. nal indices R1 ¼ z  1/2] and C6–H6/O3 [D/A ¼ 3.2274 1.04 C11–C10 1.2169 C03–C04–C05 121.98 119. similar to a micelle.3836 1.432 Å.432 135. such as sulfur.3704 1.18 C04–N01–O03 118. 30 (8.44 NPH-PE crystallizes in the mono.3491 C07–O02–C01 118.3855 1. y.3802 1. D–H/A ¼ 135.80 120. and goodness-of-t (S) ¼ 1.3923 1. +y  1/2.3984 C05–C04–N01 119. This journal is © The Royal Society of Chemistry 2016 RSC Adv.3763 C06–C01–C02 120.80 120. D–H/A ¼ 165.3764 1.3699 1. View Article Online Paper RSC Advances We used Kleinmann symmetry.3814 C01–C02–C03 120.30 117.3880 C13–C12–C11 120.4812 1.3902 C14–C13–C12 119. +y  1/2. The data for the nal structural interactions.82 bound to a six-membered substituted aromatic ring.54 a vacuum. showing four molecules and symmetry code: –x + 1. (5) 30 V C14–C09 1. C6–H6/O4 [D/A ¼ a ¼ 8. An angle of 3.32 compounds constituted by ketones containing a keto group C08–C09–C14 117.04 120.954 2.09 rings in the packing conrms the planarity of the structure.5246 O01–C08–C07 120.85418782  1012 F C08–C07 1. j standing for x. which shows the interaction maps of the part of the theoretical values is very good.431(19) and g ¼ 90 . we can use the following relationship: C12–C11 1.4648 C02–C03–C04 118.74 124.179(7) Å.60 121. The ellipsoid displacement interactions are related by C13–H13/O1 [D/A ¼ 3.33 120. (6) N01–O03 1. c ¼ 11. C10–C09 1.3873 1.3840 1. formation of an empty space between the molecules of the layer clear distances and bond angles were calculated in this work.3821 1.71 between the planes of the aromatic C10–H10/O4(ii) 0.38 Next.54 and symmetry code: x.70 115.09 and clinic centrosymmetric space group P21/c. The experimental quantity. z) of the linear C08–O01 1.73 120.97 ð1Þ aij cij ¼ . 3.94 m1) is the vacuum permittivity. the correlation between the experimental and by Fig.0392. therefore. 91.36 119.28 119. C10–H10/O4 [D/A ¼ 3.72 3.56 C6–H6/O3(ii) 0.07 117.50 with N standing for the number of atoms in the unit cell.3947 C10–C09–C14 119. 2.3868 O02–C01–C06 124.29 C06–C05 1.56 and symmetry code: x + 1. z. (ii) x + 1. while the geometry was optimized for the free molecule in C13–H13/O1(i) 0. Results and discussion C08–C09–C10 123. non-classical interactions already discussed contribute to the The roots of the mean squared errors (RMSE) for internu.711 3. as shown in different biological activities are observed between sulfurated Table 3.498 165. y + 1.162 Å. z] inter- packing of NPH-PE are presented in Fig.40 119.3618 1.670 3.927 2. z  1/2]. with RMSEs of 0. a ¼ 90 .52 124.81 Crystallographic structure O04–N01–O03 122. In general.3733 1. the similar.4944 C09–C08–O01 120.27 C09–C08 1.4542 1.2271 1. V ¼ 1216.5 for the angles.5041 1.78 cell (see Table 1)..3873 C12–C11–C10 119.80(12) Å3.61 C03–C02 1. +y  1/2. 2(b). Downloaded by Northern Illinois University on 22/08/2016 13:53:18. The linear periodicity along the b axis is sustained by and oxygenated analogues. z  1/2. a Symmetry codes: (i) x.412(6) Å.927 2.4182 1.162 148. plot of the asymmetric unit (with labeling) and the crystal D–H/A ¼ 148. large deviations between these D–H/A d(D–H) d(H/A) d(D/A) d(D–H/A) ( ) measures exist because the X-ray results are in the solid phase. The portions formed by the aforementioned renements are shown in Table 1.97 where the components aij (i.61 119.572 164. The C6–H6/O4(ii) 0.2175 C04–C05–C06 119.2034 C09–C08–C07 119.32 Published on 22 August 2016. the results were very In addition to stabilizing the crystalline arrangement.46 The neolignane analogue NPH-PE belongs to the class of C03–C04–N01 118. The X-ray geometry actions.74 121.91 119.993 2.56 120.67 117. z  1/2] non-classical in the asymmetric unit. 2(b).49 V N01–O04 1. to estimate the linear macroscopic parameter c1 of the C13–C12 1. +y  1/2.12 C02–C01 1.81 117.17 electric susceptibility c3.3948 C11–C10–C09 119.3900 1.40 122.21 N C04–N01 1.3943 O02–C01–C02 114.77 108.30 0. depicted in Fig.2045 1.093(5) Å.61 120.568 3. C04–C03 1.272 3. with fully optimized geometric parameters. is related to the second hyper.028. b ¼ 3. stabilized by three non-classical hydrogen bonds.4019 C08–C07–O02 107. only the hgi in the Table 2 The calculated and experimental geometric parameters for static case is reduced to NPH-PE 1   Bond distance hgi ¼ gxxxx þ gyyyy þ gzzzz þ 2 gxxyy þ gxxzz þ gyyzz : (4) 5 (Å) X-ray DFT Bond angle ( ) X-ray DFT C14–C13 1. b ¼ 13. Large discrepancies between the theoretical and the experimental bond distances and angles Table 3 Non-classical hydrogen bonds of NPH-PEa were not observed.3842 C09–C14–C13 120.27 119.3907 C05–C06–C01 119.58 polarizability by the expression C05–C04 1.572 Å.0024 Å for the distances and 15.90 119.3 optimized and experimental geometry parameters are pre- sented in Table 2.

second and third contours with the initial levels of 2. respectively. 2016. H6. 2(b). 4(a) shows the rst p-stacking interaction. 5 The Hirshfeld surface dnorm map of NPH-PE for visualizing intercontacts. We can note the absence of interac- shows the Hirshfeld surface dnorm45 of NPH-PE.0. Cg1/Cg2(ii). and white and blue Fig. y. (ii) 4.296 Å. As an Each interaction is described by three map contour levels. z]. z  1/2].0 and opacity 0. C6–H6/O3 [symmetry code: x + 1. and the second p-stacking interaction. alternating to form the three-dimensional arrangement of NPH-PE layer formed by four molecules. where the layer tions in the empty space.0 with opacity 0. 79215–79227 This journal is © The Royal Society of Chemistry 2016 . including C10–H10/O4.0 and 6. this analysis highlights the areas of the rst.] 79220 | RSC Adv. is stabilized by bifurcated non-classical interactions involving There are no non-classical hydrogen bonds responsible for the C6. Fig. H-bond acceptors and hydrophobic Hirshfeld surface analysis is an excellent tool for qualitative groups. red and green. The interactions are drawn as dashed lines. 6.2. The first contour is represented by an initial level of 2. Fig. +y  1/2. This picture shows the regions [symmetry codes: (i) ¼ (ii) ¼ 1  x. The layers are C13–H13/O1 around the H-bond acceptor regions. This stability is classical interactions around the H-bond donor regions and achieved by p-stacking (or p–p) interactions. represented by blue. non-classical hydrogen bonds and p–p interactions. H-bond acceptors and hydrophobic groups are represented by blue. Cg1 and Cg2 represent the centroids of the aromatic rings. C13–H13/O1 [symmetry Fig. Downloaded by Northern Illinois University on 22/08/2016 13:53:18. [Cg1/Cg2 ¼ (i) 3. code: x. respectively. Fig.961 Å. respectively. Red indi- connected via the centroids Cg1 (the aromatic ring closest to the cates the region of highest interaction. the second nitro group) and Cg2 (the aromatic ring closest to the carbonyl contour level is 4. 1  z]. O3 and O4 atoms (b) and C10–H10/O4 non- the crystal packing represented in Fig. showing the layer stabilized by non-classical hydrogen bonds. establishing the crystal packing of NPH-PE. y + 1. red and green colors. indicated by arrows..8. with a distance of 4.296 Å. analysis of the intermolecular contacts of crystal packing. of the H-bond donors. View Article Online RSC Advances Paper Published on 22 August 2016.5 and the third contour has an initial level of 6. Cg1/ Cg2(i). 3 Interaction maps and hotspots for the NPH-PE arrangement. (b) Hirshfeld surface shape index showing the complementary patches where p–p interactions occur. C6–H6/O4. 5 4. being additional methodology. with a distance of 3. The regions of H-bond donors.0. group).961 Å. 4 (a) Representation of p–p interactions by dotted lines.0 and opacity 0.

in addition to indicating classical. (e) C/O. 7(b) and (c)]. As an intermolecular and correspond to hydrogen-bond donors. (b) H/H. shape. Rietveld analysis gave distance from the surface to the nearest atom exterior to the no satisfactory tting or records for the NPH-PE compound [see surface) against di contacts (abscissa – distance from the surface Table 1 and Fig. This journal is © The Royal Society of Chemistry 2016 RSC Adv. Downloaded by Northern Illinois University on 22/08/2016 13:53:18. The signicant overlap of molecules of NPH- described by the Hirshfeld surface shape index. The Hirshfeld surface shape index can be used to by the green region in images 6(a) and (f). using the Rietveld method supports the NPH-PE crystallo- combined with the second blue triangle. 6. X-ray powder patterns identify additional empty (red) and lled (blue) regions where of NPH-PE samples were collected at three different wave- two molecules meet. 6. this mist of the pattern built with CIF and experi- graphics. 7(a)]. Note the two triangular shapes above the lengths and two different temperatures. (f) C/C. di is the closest internal distance from a given point on the Hirshfeld surface. 4(b). 4(b). As pref- type of interaction present in the molecule. non-classical and and molecular conformation of NPH-PE in powder form. 6. Next. The rst red triangle. indicating the presence of p–p interactions. C/H and H/H contacts) can also be quantitatively described by PLATON soware46 and qualitatively observed in Fig. indicate regions of weaker interactions. Hirshfeld surface analysis also provides Although Fig. (c) O/H. 79215–79227 | 79221 . The outline of the full fingerprint is shown in gray. XRPD measurements were performed to verify the packing Finally. (d) C/H. but with no success. and de is the closest external contact. as can be seen PE results in greater contact in de ¼ di ¼ 1. p–p interactions. as mental patterns suggests a polymorphic susceptibility of the shown in Fig. 7(b)]. many attempts to nd a better to the nearest atom interior to the surface) in a two-dimensional structural solution using DASH and the molecular structure graph in order to represent the percentage contribution of each given by RNM were carried out. forms a “bowtie” graphic structure. 7(a) shows good visual agreement between the a unique identication for each molecule.. Such interactions are interactions (C/C. The upper spikes are in regions where de > di NPH-PE compound [Fig.8 Å. View Article Online Paper RSC Advances Published on 22 August 2016. It is represented in Fig. Hirshfeld surface analysis plays an important role indicate hydrogen-bond acceptors (di > de). 6 Fingerprint of NPH-PE. Structural renement Cg1 and Cg2 centroids in Fig. calculated pattern (obtained using CIF from single crystal Fingerprints are the combination of de contacts (ordinate – analysis) and the experimental patterns. the lower spikes contact tool.47 The hydrogen erential orientation is not expected using capillaries as sample bonds (O/H contacts) are responsible for the ngerprints of holders. (a) Total interactions. called a ngerprint. 2016. also in powder form [Fig. they are also recognized as a pair of sharp spikes. Fig.45 Hydrophobic in the description of p–p interactions.

13%.53 axz 6. with an increase of 6. The polarization effect of the 311+G(d).97%. showing that the trostatic polarization arrangement are favourable due to the fast polarization effect causes an increase of 13. View Article Online RSC Advances Paper Table 4 MP2/6-311+G(d) results for the components of the dipole moment (in D) as a function of the number of iterative processes 0 1 2 3 4 5 6 7 mx 0.00 9. (b) calculated (CIF) and experimental XRPD patterns of NPH-PE a minor inuence from the polarization of the crystalline envi- collected with different excitation energies at room temperature and ronment. The results for (g) in the static case were obtained using CAM-B3LYP/6-311+G(d).52 36.21 0.07 9.58 17.57 17. crystalline environment has the smallest inuence on the gxxxx followed by the respective number of iterations.08 9.13% in the average convergence of the iterative process to obtain the dipole moment second hyperpolarizability when compared with the case of the and the linear polarizability of the crystal. Table 4 shows the results of this property for NPH-PE.22 6.48 36.13 0.64% increase to the total dipole moment upon passing from the isolated molecule to the embedded one.18 3.18 azz 23.15 ayy 35. with an increase of 11.02 24.10 Published on 22 August 2016.22%.68 8.08 9. and the ayy component provides the greater contribution to this result.16 3.32 0.85 my 7. comes from the component gyyyy.10 9.10 9.15 4.37 8. showing a small increase of 1.09 24.36 17.14 4.06 26.17 3.06 26..13 m 7.15 4.18 3.53 36. The higher contribution to the total dipole moment (m) originates from the my component.20 6.02 6.06 9.85 0.79 0. The mz component shows the greatest inuence arising from polar- ization of the crystalline environment: it shows a decrease of 46.22 6. 7 (a) Overlapping of NPH-PE structure by DRX (black) and DRXP of the isolated molecule – see Table 5. 79222 | RSC Adv.53 36.34% compared with the case of the isolated molecule.56% in the average linear polarizability of the embedded molecule compared with the case Fig.09 hai 25. The results of the linear polarizability a suffer variations due to polarization effects of the crystalline environment throughout the iterative process: we note an increase in the results of all components of a. 6.53 36.85 0.08 24. demonstrating that the polarization effect carries a 22.85 0.95 26.06 26.87 4.16 0. The highest contribution to the result of g rst performed at the MP2 level using the basic feature base 6.10 D.15 6.58 17. component. Downloaded by Northern Illinois University on 22/08/2016 13:53:18.17%.10 9. with an increase of 17.22 ayz 2.13 0.15 4.66 25. This calculation was isolated molecule.09 24.22 6.39 (in 1036 esu).21 6. Table 5 MP2/6-311+G(d) results for the linear polarizability (in 1024 esu) as a function of the number of iterations 0 1 2 3 4 5 6 7 axx 17.13 4.08 9.07 24.83 36.72 9.07 4.51 17.84 3.56 17.18 3.42 8. The component azz receives (blue).14 0.32 36.13 0.04 26. 2016.09 24. the difference between both patterns).06 26.06 (in 1024 esu).98 9. the greatest inuence comes from the gyyzz component.58 axy 3.06 We analyzed these results by considering the cases of the isolated and embedded molecule via MP2: we note that they converge to 9. The values of the average linear polarizability via MP2 converge to 26. whereas the greatest low temperature (100 K).07 3.58 17.85 0. molecule converge to 29. (c) experimental (symbols) and theoretical (red line) XRPD patterns of NPH-PE with 7 keV at 100 K (the gray line is inuence affects the component ayz.80 24. The results of the second hyperpolarizability (g) representing a non-linear response can be seen in Table 6. 79215–79227 This journal is © The Royal Society of Chemistry 2016 .82 0.09 mz 0. The results indi- cate that the polarization effects of the crystalline environment contribute to a small increase of 1.85 0. The Electrical properties values of the average second hyperpolarizability of the embedded The applicability of the supermolecule approach and the elec.

0. u. 0)i. Fig.30 12.39 12.0428 a. When comparing the values of the second hyperpolarizability for the isolated molecule in the static case. 0)i hg(u. u.38 11.08 a.60 hgi 25.39 29.43 gyyyy 54.19%) and [13. l ¼ 569.08 a. 0)i Isolated 26.31 12. which is 35. l ¼ 1064 nm u ¼ 0.89 29. 0.60 14. u.u.88 62. 0.38 29. 0)i.27 11.u.72 60.31 12. Frontier molecular orbitals hg(0. In the work of Senthil et al.0239 (0. 79215–79227 | 79223 .11 37. for the frequency values a.98 28.77%)].39 Fig. 0)i hg(2u.57 4.27 12.97 28. u ¼ 0. 0. 0. we found an increase of 2113%. u.53 29.50 4. u.0239 a. View Article Online Paper RSC Advances Table 6 CAM-B3LYP/6-311+G(d) results for the second hyper- polarizability (in 1036 esu) in the static case as a function of the number of iterations 0 1 2 3 4 5 6 7 gxxxx 10.58 4.92 11. these values are very signicant Fig. In the case of the embedded molecule. tions (Table 7).u. Now.49 A small HOMO–LUMO gap automatically means small excitation Table 7 CAM-B3LYP/6-311+G(d) results of components of the second hyperpolarizability (in 1036 esu) u ¼ 0.32 62.89 36 748 This journal is © The Royal Society of Chemistry 2016 RSC Adv.43 11.59 14.80%)]. as displayed in Table 7.u. Downloaded by Northern Illinois University on 22/08/2016 13:53:18.08 a. with the dynamic cases.0428 The difference in energy of the HOMO and LUMO is an a.42% smaller.62 40. 0)i for u ¼ 0. u. 0)i]. 6. u.56 4. u.0428 a. u. The value found in our case. 0. 0)i hg(2u.u. gyyzz 12. u. 0)i corresponds to the Kerr effect.16 12.81% (12.. u ¼ 0.27 11. u. with those for the static case. hg(u. and u ¼ 0. 0)i and hg(2u.46 14. l ¼ 1907 nm u ¼ 0.10 a. 8 Dynamic evolution of the calculated values of the linear polarizability (in 1024 esu) and second hyperpolarizability (hg(u. u. 0)i for the argued could be a possible candidate material for photonic isolated and embedded NPH-PE molecules. u. 0. For the highest value of the frequency considered. u. 8).05%) and [11. u. u. u. where both are consid- Relating dynamic second hyperpolarizability ered as embedded systems. optical switches. 0. u.. u.u. u. they frequency-dependent descriptions of the second hyper- employed the stilbazolium crystal. u.47% larger than that exhibited by the isolated molecule for the same frequency (see Fig.83 10.78 49.5 nm ABC hg(u.36 574.56 45. 0)i.94 Embedded 30. u.27 gxxzz 4.34 29.23 4.39 29..31 gxxyy 9.39% (14. (44. this value becomes 4722. an increase of 125 058% was observed. 0. 0.08 a. 0)i and [hg(2u.42 11.20 62.42 11.u. respectively. This is a very striking result because in a recent The value hg(2u.03 14.20% (55.u.. u. 0)i corresponds to a dc-electric eld experiment by Senthil et al. whereas the second hyperpolarizability that was 4400% smaller than the value hg(u.58 4.46 14.31 62. and when we compared the values of hg(2u.56 14.29 62.37 61. it shows similar behaviors of the linear polarizability and second hyperpolarizability. u. because when comparing them with those of the isolated NPH- 0)i in 1036 esu) of NPH-PE with respective values of frequencies. 0.19 29.77 11.21 11.20% important index for the chemical stability of molecules. 8 stands for the dispersion curves of the isolated and embedded molecules as a function of the frequency u: in both cases. 0)i hg(u.43 11. which the authors have polarizability are hg(u.. and optical power limiting applica- three frequency standards are u ¼ 0.).58 Published on 22 August 2016..27 11.u.25 11.0239 a.32 gzzzz 11. we observe an increase of 3.. when we compare hg(2u.48 the authors found a value for the induced second-harmonic generation (EFISH). A greater value of the second hyperpolarizability hg(2u. 9 LUMO–HOMO of the isolated molecule. 2016.31 12.27 33. u.19 11. 0)i hg(2u.. PE molecule in the static case.68 33.u..58 4. 0)i was found for the frequency u ¼ 0. u.. the embedded molecule presents the value of second hyperpolarizability hg(u.u. the devices.60 14. the results are 4.

35 0.72 0.97 0.69 0.28 5.01 2.08 0.59 55.91 968.17 0.13 0.21 6.54 1102.34 876(m) r C1C2C6 + r C3C4C5 + r NO2 37 957.95 G C5C6C1O2 3 45.42 1075.13 837.05 u CH R2 33 874.85 492.22 0.26 u CH R2 + u NO2 27 700.54 1.05 1.86 0.41 42.57 712..35 2.92 869.18 0.04 0.01 0.48 2.65 6.06 1.35 4.24 627.94 497(vw) G H3C3C1C6 + r C7O2C1 509(vw) + G H3C3C4N1 21 554.04 1022.13 4.03 0.40 G CHR2 + G C6C5C7N1 20 513.04 G C7C8C9C14 + G C6C1O2C7 + G C1O2C7C8 10 187.11 847(vw) r NO2 + r C8C7O2 36 907.39 G C3C4C5C6 + G O3C4O4N1 13 326.93 40.18 101.19 667.59 0.36 r C6H8C8 + r C2H3C3 53 1218.76 1097.75 r C5C7N1 32 835.32 2.12 3.29 G H12C12C11C10 + G H7C7O2C1 18 453.07 G C9C14C13C12 12 306.15 1143.56 7.07 989.04 1.42 0.14 u CH R1 + u CH R2 35 879.05 G C11C12C13C14 9 173.91 7.43 6.72 G C9C8C7O2 2 25.25 5.18 0.99 1.12 967.29 r C8O2C1 24 639.40 0.22 0.87 0.78 0. 6.27 138.76 19.01 49.01 0.81 612.81 946.20 800. Downloaded by Northern Illinois University on 22/08/2016 13:53:18. 2016.83 4.72 842.57 0.29 0.31 1.35 581(vw) G H14C14C13C12 + r CH2 23 635.31 2.84 484.65 3.04 46.06 0.85 75.77 2.12 12.34 22.71 n CH2–O + r CH R2 49 1145.79 0.92 15.51 418. experimental and calculated wave numbers in cm1 of NPH-PE at CAM-B3LYP/6-311+G(d) Unscaled Scaled Scaled ARaman.00 676(w) R1 deformation + R2 deformation + r NO2 28 710.01 t H2C2H3C3 40 1010.02 0. scattering activities Raman IR and Raman assignments 1 21.45 162.37 3.42 u CH R1 + r CH2 31 807.85 0.84 838.73 0. Raman Mode no IR freq.60 1000.83 10.82 613(w) R1 deformation 25 655.66 680.54 750 cm (vs) 1.69 0. 79215–79227 This journal is © The Royal Society of Chemistry 2016 .72 448(w) G H7C7O2C1 19 505.97 33.18 G C9C8C7O2 + G C6C1O2C7 Published on 22 August 2016.92 1208.70 6.99 0.64 531.05 0.81 44. + G C7C8C9C14 7 144.27 749.11 5.17 1.43 999(m) r C12C11C10 43 1033.37 1.22 135.34 1069(vw) r C13C14 + r C10C11 47 1122.46 0.55 0. View Article Online RSC Advances Paper Table 8 Vibrational assignments.47 0.07 u CH R1 + r CH2 42 1032.47 583. r CH2 46 1067.57 993.29 0.87 11.99 671.44 0.85 311(w) G C1C6C5C4 + G O3C4O4N1 14 392.86 313.08 293.91 4.27 2.81 G out C8C14C9C10 + G C6C1O2C7 11 249.02 u CH R1 29 743.91 1161.97 846(vs) 0.58 20.91 u C1O2C7 + u C4N1O3 + u NO2 30 782.39 630(w) G H6C6C1C2 26 697.28 G N1C4C3C5 + G C9C8C7O2 15 413.70 1.16 G H11C11H10C10 + r CH2 38 987.42 39.56 43.32 24.37 1070(vs) 2.08 1166.56 106.67 0.17 916.97 G C1O2C7C8 + G C9C8C7O2 8 158.39 166.34 4.76 773.07 975(vw) n CH2–C]O + r C13C14C9 41 1012.10 17.34 0.04 r H12C12 + H11C11 + r H13C13H14C14 52 1211.90 0. IR freq.25 r C12C11 + r C11C10 + r C13C14 48 1138.94 970.27 1168(w) r CH R1 + r CH R2 1188(vw) 54 1261.01 151.00 G C13C14C11C10 16 432 413.81 r CH R2 50 1150.54 376.02 G C6C1O2C7 6 111.26 0.68 0.79 61 42.61 G O4C4O3N1 + G C1C6C5C4 5 57.67 4.75 1232(m) n C9C]O + u CH2 79224 | RSC Adv.83 239.59 10.17 1107(s) r C2C3 + r C8C10 + n C4–NO2 51 1193.33 8.64 42.00 1.53 1.74 534(vw) G H7C7O2C1 550(vw) 565(vw) 22 609.06 G C2C3C5C6 17 436.09 r CH2 44 1036.94 2.61 608.98 0.55 37.96 1091.09 u CH R1 + u CH R2 34 874.96 0.35 434.73 396.27 t H5C5H6C6 39 1010.03 2.a I infrared FT-IRb Raman freq.02 G O1C7C9C8 4 48.50 t CH R1.92 295.32 988.90 180.79 r CH R2 45 1044.

72 32.44 r CH R1 61 1430.81 3059. respectively.62 7.3310 eV.27 1494.92 22.02 5.958 (ref.56 390.77 6.27 n O2C1 + n asym C R1 + r CH R2 59 1366.37 1695(m) n C]O 74 3036.23 1582(w) n asym NO2 69 1663. Downloaded by Northern Illinois University on 22/08/2016 13:53:18. while the aromatic CH embedded molecule is 0.95 0.85 1445.50 t CH2 56 1320.35 63. the DFT scaled The vibrational.52 42. View Article Online Paper RSC Advances Table 8 (Contd.75 1487.91 2909.50 1622. The aromatic CH 311+G(d) for NPH-PE.33 48. Fig.70 1607. two strong bands.3699 eV.37 159.17 3.35 0. this is in good agreement with the calculations were made for an isolated molecule in a vacuum. respectively. IR freq.39 1437(vw) r CH2 + n C5C6 + n C2C3 64 1505. 9 represents the distribution of energy levels equal to 0. so presented in Fig.60 n CH R1 79 3220.67 3116. The band gap of the isolated molecule tions occur in pairs at 1600 cm1 and 1475 cm1.36 3094. therefore.67 n H13C13 + n H14C14 82 3234. 9.74 136. these bands can be used to isolated molecule is 0.46 59. the HOMO stretching vibrations occur at frequencies greater than 3000 orbital of the isolated molecule is 0. Therefore.95 5.34 117.24 203.28 n CH R1 80 3227.28 1442.41 1234(vs) 15. b Intensity.44 5.32 n H6C6 84 3252.65 1656(vw) n R2 + n asym NO2 73 1827. it ranges of 1246 to 1378 cm1 and 2909 to 2949 cm1.62 1246.13 n CH R1 77 3201. The LUMO orbital of the bending occurs at 900 to 690 cm1.48 46. will be more polarizable than hard tional frequencies.91 15.70 3114.06 2.68 11.64 n asym C14C9C10 + n asym C11C12C13 70 1677.14 1313.80 193.50 and a proper scaling factor for CAM-B3LYP molecules.62 1265.35 1282.25 1284. respec- was possible to characterize the main absorbing/scattering tively.17 1378.02 10.33 n C8C7 + n C13C14 + n C11C10 65 1508.84 1594(s) n asym C2C3C4 + n asym C1C6C5 71 1683. As can be seen in Fig.85 n sym CH2 75 3079 2949. Raman and NMR characterizations occurring in the 3000 to 2840 cm1 range. 60 1371.86 1628(vw) n sym R1 72 1693.44 144. characteristics of the methylene group.0410 eV.14 65.13 n asym C R1 + r CH R2 58 1341. an asymmetric C–O–C stretch near 1250 cm1 Table 8 shows the IR intensities. ) Unscaled Scaled Scaled ARaman.56 9.27 3085.39 1593. 6.85 1380(vw) u CH2 63 1480.69 58. These values indicate that this compound has high be seen by examining Table 8. and 1452 cm1 and 2906 to 2929 cm1 in the IR spec- groups.82 2929(vw) 22.958.03 1284. Raman Mode no IR freq. 1. theoretical and experimental frequencies in the frequencies obtained in this work show these absorptions in the infrared and Raman range show good agreement.21 2906(vw) 80.0389 eV. respectively.49 9. The IR and Raman spectra are cm1 and 1070 in the IR.3814 eV. 51) was used to obtain more coherent values and the HOMO–LUMO orbitals used at the theory level MP2/6.53 10.00 r CH2 66 1552.15 1308. whereas that of the embedded molecule is show good agreement with those obtained in this work.29 191.92 164. DFT calculations overestimate the vibra- molecules.05 22.57 n H3C3 + n H2C2 81 3230. 2016.63 11.19 1418.15 252.67 1.56 1750.30 43. these bands appear at frequencies for the optimized geometries and the proposed 1265 cm1 and 1091 cm1 in the DFT.68 6.52 3. the calculated vibrational and a symmetric stretch near 1040 cm1.93 1613.a Iinfrared FT-IRb Raman freq. The methylene group has a characteristic bending absorp- tion of approximately 1465 cm1 and stretch absorptions Infrared.98 77.06 40. and 1234 vibrational assignments. to compare to the experimental data. nally.66 31.27 1331(vs) 1342(vs) n NO2 62 1439.13 1330(vs) 458.3404 eV and that of the cm1.75 n H5C5 83 3250.22 201. with a small gap. chemical stability and high excitation energy.24 1593(vs) 18.36 50.06 13.91 3076. energies to the manifold of excited states.98 109. Aryl ethers give rise to while the experiments were performed using a solid sample.53 4.66 1297(m) n asym C R2 + u CH2 Published on 22 August 2016.40 n H3C3 a Scale factor = 0.52 These values energy is 0.20 25.27 4. in the 3050 to 3010 cm1 range. The band in the 1700 to This journal is © The Royal Society of Chemistry 2016 RSC Adv.11 1264(m) n asym CH2O2C1 + n C3C4 57 1338.67 1452(s) 3.10 n asym CH2 76 3193.13 n CH R1 78 3210.92 3067.78 1562.35 3098. The observed discrepancies are justied because the trum.. the ring stretch absorp- molecule is 0. scattering activities Raman IR and Raman assignments 55 1301. 79215–79227 | 79225 .92 3092.51 7.80 194. whereas that of the embedded assign ring substitution and.46 1510(vw) r C5C6 + r C2C3 68 1630. as can 0.16 1499(vw) n C7O2 + n C10C14C9 + C11C12C13 67 1560.95 6.30 123.

De Oliveira.958. J. L. J.97 to 8. Barata.. Adv.. E. M. spectra. Phys. N. 13C. Dos Anjos and L. 9. 1–9. Hanusch. Z. Jardim. Varga and S. Zhou. C. behaving as a two level quantum system tively. Rep. In the IR ties. this is an interesting issue that can be explored through intensity of the NO2 scissors band obtained from calculations is the Jaynes–Cummings model. L. K. C.. Haworth. Phillipson.44 ppm for 2H was assigned to the methylene C7 carbon. 94. T. In the 2 C. Karat and B. 448. 5362– calculations for the values of the third-order optical 5369. Growth. 12 J. 2003. C–O). J. C. L. In our DFT scaled frequencies. 1994. option to obtain the vibrational spectra. P. S. S. 589–595. Machado. 56. L. 2001. which led to better convergence with the experimental results. C. A. of the experimental and computed vibrational wavenumbers. 8. Y. this band appears at 712 cm1 and 750 cm1 The authors gratefully acknowledge the nancial support of the in the IR spectra. The comparison of the predicted bands with the experimental 2015. For this 126. Pierce. R. M. 7. spectra of the molecule were recorded and assigned with the aid 8 A. Conclusions 6 C. Soc. 0. and that in the IR spectra is 846 cm1. Indira. Kovalchuk. Kónya. 2000. 10. we have presented the results of computational S.. Simões. 5 K. The structure proposed by MNR is consistent with the data 217–223. Fitoterapia. V. B. V.. T. Rao and In addition. M. O. 10 I. The theoretical 9 M. and quaternary L. respec. 1998. and aromatic carbons were ao medicamento. the vibrational FT-IR and Raman 2012. proposed in 1963. de Souza. In aromatic compounds. R. estimated the IR and Raman vibrational spectra.53 The eld. 577–582. via its HOMO– Published on 22 August 2016. Song. Barata. Phytomedicine. Gosmann. M. M. Rev. 91. H. Ind. G. Bentley. Dharmaprakash. 6th edn. E. D. 0. Ferri. National Council of Science and Technology (CNPq). 11 J. these bands are at 1593 cm1 and 1330 cm1. D. Peng. G. were assigned to H3 and H5. 2016. Huang. C. Barroso. S. Tackx.97 to 7. P. 7. Pharm. P. L. Santos. Editora da UFRGS. Mentz and P. and H13 and H11. Chen. The The structure of NPH-PE can be conrmed by complete authors are also grateful to organizers of the 3rd Edition of the assignment of all the 1H and 13C signals with the help of School of Crystallization and Crystallography for Latin America different 1D (1H. P. 7. R. the signals from the COSY spectrum enabled determination of 4 X. 2007. Silva and M. L. L. Z.. C–NO2. Also. the position of the neighboring protons in each aromatic ring. D. Four regions of LDRX-UFSC and at the XRD1 beam line of Brazilian multiplets at 6. Santos and I. 13 E. respectively.51 to 7. Phytochemistry. LUMO energy levels. Li.6 Hz and 5J ¼ 1. 13 C NMR spectrum. 454– 459. E. obtained by other techniques. Growth Des. reason. new insights could be cm1 (asymmetric) and 1355 to 1315 cm1 (symmetric). A. H14 and H10. Bishop. Cryst. Florianópolis. and and S.. e. A. The obtained from investigations of the inuences of different non- bands at 1562 cm1 and 1313 cm1 in this paper are assigned to linear crystals in the time evolution of the mentioned proper- the asymmetric and symmetric modes. the wagging mode u NO2 is assigned at Acknowledgements 740  50 cm1 with a moderate to strong intensity.. 2011. Farmacognosia: da planta carbons (C]O. XRPD measurements were carried out at with 11 integrated protons were obtained. Soares.03. all with integrals of 2H. The compound NPH-PE was crystallized in the centrosymmetric 7 P. Cro. De Sabóia-Morais. S. O. Chem. R. Petrovick. A. Champagne and D. Brazil.17 to Synchrotron-LNLS (proposal 20150198). X. 0)i of the embedded spectra of nitro compounds are due to the NO2 stretching molecule in comparison with the value obtained for the second vibrations. J. 6. Palazzo. Chem. G. In the 1H NMR spectrum. the functional CAM-B3LYP proved to be a good 242. Lou. Li. space group P21/c. 79226 | RSC Adv. The spectroscopic data are consistent with the crystal structure. Adant. L.. M. L. M. 38. respectively. u. H2 and H6.03. u. Downloaded by Northern Illinois University on 22/08/2016 13:53:18. Braz. An important result gation of C]O with the phenyl mode. results shows an acceptable general agreement. which give two strong bands. when one considers the molecule. Minarini. As a future perspective. with the X-ray results. Chem. 11. Alves. The HSQC spectrum allowed unambiguous assignment of the 3 L. and the triple triplet with an integral of 1H and 3J ¼ 1 R. 41–92. 6 signal regions fruitful discussions. The NO2 scissors occur at higher wavenumbers (850  60 interacting with a single mode of a quantized electromagnetic cm1) when conjugated to C]C or aromatic molecules.6 Hz was assigned to the proton of C12. D. The most characteristic bands in the second hyperpolarizability hg(2u. 4. 0)i for the embedded molecule in group with an aromatic ring presents two bands: 1550 to 1490 the static case. Ikejima and S. Rao. 2002. In addition. P. View Article Online RSC Advances Paper 1680 cm1 range in the IR spectrum is assigned as the conju. 1942. the theoretical results were scaled by a factor of 0. Schekel. 209–214. C. S. PLoS One. Paine 1 H signals which are directly connected to the 13C signals. Chem. J. M. 79215–79227 This journal is © The Royal Society of Chemistry 2016 . Liu. Antus. D'silva. 33.24. and 8. including the structure X-rays. Bredas. G. E. N. 55. Crystallogr. and DFT analysis showed good agreement C. Cryst.54–57 equal to 842 cm1.g. D. DEPT-135) and 2D NMR experiments (ECRISLA-2015) for X-ray single crystal data collection and (COSY and HSQC). Conjugation of a nitro hyperpolarizability hg(0. 2011. Sarojini. V. assigned together with the analysis of the DEPT-135 spectrum. Podagatlapalli. 259–263. Persoons and B.58. P. L. 243–278. J. T. nonlinearity of the compound NPH-PE. calculations using CAM-B3LYP/6-311+G(d) systematically over. 539–552. Drug Dev. S. 10 signals were obtained. 2013. the calculated value of emerging from this study is the increase of 125 058% in the this mode is 1750 cm1. L. R. L. N. The References singlet signal at 5. 8. Soc.

L. 25 T. vol. L. Theor. Pidcock. Stadnicka and B. 16. 1984. J. C. Theory 42 M. 104109. J. 10. 60. 17.-R. Los Alamos National Laboratory Report. Hratchian. Version 5. H. Granadeiro. J. Pople. K. 1000–1006. 2009. Champagne. G. Fox. 56 C. Appl. C: Struct. J. Lampman. J. 47 M. J. C. R. Georg. 80. 129–138. M. Phys. Cambridge Crystallogr. System (GSAS). Chem.. in molecular crystals. View Article Online Paper RSC Advances 14 C. 2014. Braz. 148–155. G. 2013. Fonseca. J. Santos. 2015. S. H. Baseia. 122–130. Phys. 25705–25713. C. Cioslowski and 19 D. Hirshfeld. Taylor. Iyengar. K. J. M. N. 49 H. K. Nakai. Gaussian Inc. CrystEngComm. A. 2002. G. a. Barnes. Chemla and J. N. David. Shields. Ehara. 467– D. Macrae. 2009. 210–213. N. Gordon and Breach. P. 26 T. K. 2006. D. L. A. Anjos. ed. 16 T. Basel. Baseia. Daniels. tools for visualizing and exploring intermolecular interactions 27 G. Martin. Handy. Schlegel. 2114–2124. Dennington. Grimwood. 139. B. M. S. Champagne. Organic Nonlinear Optical Materials. 57 C. Napolitano. J. Zheng. A. Chem. J. 89– 36 A. J. P. GaussView. P. A. Spackman. Jaynes and F. J. University of Western Australia. 56112–56127. Acta. 5th edn. B. Wolff. Gomperts. CrystEngComm. Montgomery Jr. Adamo. 15. M. A. Sonnenberg. Sklenar and J. S. Ortiz. Shawnee Mission. R. Bakken. 17. J. S. 2001. Hasegawa. Chem. Opt. Novel 2014. pp. D. J. A.. Phys. J. Cengage Learning. Bearpark. Sect. 53. O. Phys. Crystallogr. 366. S. Hada. R. Groom and F.. J. Chem. Chem. S. Heyd. 1996. 133. 393.. 60. H. Pinto. 301–307. Oomens and I. L. 34 F. S. E. Adv. M. 1995. Chem. G. J. Voth. R.. Acta Crystallogr. Larson and R. 1977. S. Seidler. Santos. X. Rossi-Bergmann 2013. Semichem Inc. Scalmani. Phys. 52 D. 2014. Kudin. Canuto. C. 2004. 39 T. Farkas. J. Austin.. 2010. J. Chem. M. Cole. 51–57. 24 T. crystal structure determination from powder diffraction data. Sabino. Binkley. A. R. Lalama. Compagnon. J. Crystallogr. 71.. Normand. H. J. 2001. Toby. Tomasi. Ohio.1). 54 E. 46 A. Chambert. J. R. J. R. KS. Acta Crystallogr. Commun. E. M. Chem. W. J. 55 C. vol. 1979. S. Bloino. van de Streek. McCabe. 15. 32 C. Jäger.. Allen.. Soc. G. 29 C. Radom. Towler and J. R. 1976. Acta Crystallogr. 2. M. E. Staroverov. 025012. J. McKinnon. K. S. Proc. J. Krishnan. D.. K. Seidler. Turner. Warsaw. Appl. H. Gunter. 031803. 30 S. 4. McKinnon. A. 72. R. Motherwell and R. 51 L. 2012. 2006.. C. M. Crystal Explorer (version 484. Peralta. 11.. Mason. Yanai. 23 T. Phys. F. 2015.. 234503. Jamroz. J. 20 S. J.. M. 43 R. Published on 22 August 2016. C. 2009. K. Nogueira and C. Kobayashi. M. Florsheimer and P. A. V. Mitchell. G. This journal is © The Royal Society of Chemistry 2016 RSC Adv. H. Savona and D. Seidler. I. Cummings. Appl. Phys. Edgington. Spek. K. Lett. 44 M. 86–74. Ogliaro. T. Cossi. Pavia. Stadnicka and B.. W. Quantum Chem. Wallingford CT. S. 4. L. 17 K.. Fonseca. Nardelli. R. Valverde.. 141. Int. 2016. G. 2009. Nakatsuji. T. Brothers.. Sohn and R. 2007. J. Keith and J. Scott and L. B. D. E. Phys. K. 15 A. Cambridge. K. Vibrational Energy Distribution Analysis VEDA Comput. J. A. L.. 38 M. 2014.. Tew and N. 65. Valverde and B. Castro. A. Binkley and J.. Varghese. M. R. Pople. Fukuda. Salvador. 641–642. Avelar and B. 2015. B. 20. D. M. UK. P. M. a. Caricato. Gonçalves and B. Lett. McKinnon. 390. Scuseria. V. Maginn. Baseia. 45 J. R. Bioorg. Yohannan Panicker. J. Mater. 171568–171571. R. Chem. Castro and B. Chem. R. M. J. Pomelli. Georg. H. Ö. D. Jaramillo. V. P. Rev. Ferretti. Shankland. Georg and 40 R. 19546–19556. A. 2015. Chem. F. E.. Chem. A. J. G. Stadnicka and B. C.. M. J. A. Baseia. Raju. Hulliger. B. Phys. 1987. R. 2004. G. 2016. 16513. C. 35 W. S. S. H. Kumar and P. 41 H. Senthil. Vreven. G. Phys. N. O. Chem. Rega. L. 2016. L. Phys. Opt. 4. 2014. J. T. Raj. A. K. T. E. 2001. vol. W. 7337–7343. 28 P. Stratmann. F. V. Crystals. 3–8. Crystallogr. Downloaded by Northern Illinois University on 22/08/2016 13:53:18. Kriz and J. Spackman and A. in M. A. H. Phys. J. Singer. 89. Knox. C. Med. RSC Adv. D: Biol. 653. 650. Valverde. Honda. Cammi. J. Lett. Klene. J. 79215–79227 | 79227 . Vyvyan.. Spackman and J. Phys. 429. 22 T. Zakrzewski. V. 662–671. Chem. Taylor. Von Dreele. C. Li. 50 A.. Millam. V. 143. J. 1963. Valverde. 2014. Trucks... 2010. Champagne. J. J. Pauer. J. Phys. M.. Rendell. Cross. H. 21 O. Seidler. L. Int. Crystallogr. J. Sect.. Almeida.. Barata. Y. 48 K. G. Phys. 51. Castro. A. T. Dannenberg. 2011. 114105. Chem. Dapprich. 144103. S. Jayatilaka and M. Angew. 437–468. J. 2009. Chem. T. Spackman and D. Aveniente. Cheeseman. E.. Petersson. A. 28. B. V. Crystallogr. Champagne. Sheldrick. Coutinho and S. Millam. B. K. F. L. A: Found. 659. Oliveira. Foresman. pp. Ochterski. D. Bosshard. 446. Gerace and V. Nonlinear Optical Properties of Organic Molecules and J. Phys. Chem.. General Structure Analysis 109. T. 6. Sect. J. Gerace. Schindler. Aravindan. 34. Small. G. Castro and H. S. A. 453–457. Raghavachari. Kalainathan. IEEE. Introduction to Spectroscopy. J. Burant. Data Centre. J. Robb. and L. Jayatilaka. Allouche. Mennucci. Ed. 549–559. 16502– 31 M. Zyss. Seidler and B. LAUR. R. 39. Phys. 100.. L. D. A. 1980. Champagne. 171–181. 34. 378–392. 2016. 19–32. Sabino. Phys. DASH: a program for 53 A. Chem. Barone. B. Yazyev. Nakajima. A. J. 18 H. 3. 4045–4055. A. M. I. 6. D. Schlegel. Toyota. P. J. 2015. 2004. Seeger and J. 37 B. pp. 2004. H. G. Savona. Academic Press. Kitao. W. Morokuma. Chem. E. Chim. 33 M. 44. F. 119–123. N. Frisch. S. B. J. Simon. Stadnicka and B. Izmaylov. E. M. Ishida. New J. P.