The title molecule adopts an s-cis configuration with respect to the C=O and C=C bonds. The dihedral angle between the indole ring system and the nitro-substituted benzene ring is 37.64 (16)°. In the crystal, molecules are linked by O—-H⋯O and N—H⋯O hydrogen bonds, forming chains along [010]. In addition, weak C—H⋯O, C—H⋯π and π–π interactions further link the structure into a three-dimensional network.
Keywords: chalcone, crystal structure, DFT, UV–vis, HOMO–LUMO, Hirshfeld surface
Abstract
The asymmetric unit of the title compound, 2C17H12N2O3·H2O comprises two molecules of (E)-3-(1H-indol-2-yl)-1-(4-nitrophenyl)prop-2-en-1-one and a water molecule. The main molecule adopts an s-cis configuration with respect to the C=O and C=C bonds. The dihedral angle between the indole ring system and the nitro-substituted benzene ring is 37.64 (16)°. In the crystal, molecules are linked by O—-H⋯O and N—H⋯O hydrogen bonds, forming chains along [010]. In addition, weak C—H⋯O, C—H⋯π and π–π interactions further link the structure into a three-dimensional network. The optimized structure was generated theoretically via a density functional theory (DFT) approach at the B3LYP/6–311 G++(d,p) basis level and the HOMO–LUMO behaviour was elucidated to determine the energy gap. The obtained values of 2.70 eV (experimental) and 2.80 eV (DFT) are desirable for optoelectronic applications. The intermolecular interactions were quantified and analysed using Hirshfeld surface analysis.
Chemical context
Chalcone compounds consist of open-chain flavanoids in which two aromatic rings are joined by a three carbon α,β-unsaturated carbonyl system (Thanigaimani et al., 2015 ▸). The design of the chalcone system such as donor–π–acceptor (D–π–A) plays a significant role in intramolecular charge–transfer transitions (ICT) in which optical excitation leads to the movement of charge from the donor group to the acceptor group. In addition, the chalcone bridge consists of two different double bonds, C=C and C=O, which contribute to the conjugation of charge transfer, leading to their excellent structural and spectroscopic properties (de Toledo et al., 2018 ▸). Furthermore, the non-linear optical (NLO) properties of chalcone molecules originate mainly from a strong donor–acceptor intramolecular interaction and delocalization of the π-electrons (Prabhu et al., 2015 ▸). Many researchers are currently investigating the nitro (NO2) group as an acceptor group because the decrease of the resonance effect leads to substantial changes in π-electron delocalization in the ring (Dobrowolski et al., 2009 ▸). In this work, the title chalcone compound was successfully synthesized and its crystal structure is reported herein.
Structural commentary
The molecular structure of the title compound is shown in Fig. 1 ▸ a. The structure was optimized with the Gaussian09W software package using the DFT method at the B3LYP/6-311G++(d,p) level, providing information about the geometry of the molecule. The optimized structure is shown in Fig. 1 ▸ b. The geometrical parameters are mostly within normal ranges, the slight deviations from the experimental values are due to the fact that the optimization is performed in isolated conditions, whereas the crystal environment and hydrogen-bonding interactions affect the results of the X-ray structure (Zainuri et al., 2017 ▸).
Figure 1.
(a) The molecular structure of the title compound showing 50% probability ellipsoids, (b) the optimized molecular structure and (c) a representation of the molecule showing the dihedral angle between the two chosen planes.
In the title compound, the enone group (O1/C9–C11) adopts an s-cis configuration with respect to the C11=O1 [1.209 (4) Å] and C9=C10 [1.310 (5) Å] bonds. The compound is twisted about the C10—C11 bond with C9—C10—C11—O1 torsion angle of −21.9 (6)°. The corresponding torsion angle obtained from the DFT study is 0.08°. In addition, the molecule is twisted about the C11—C12 bond with an O1—C11—C12—C13 torsion angle of 167.7 (4)° (calculated value 179.4°). The differences between the experimental and calculated values show that the intermolecular hydrogen bond involving the water molecule does not affect the planarity of the compound. A previous study (Zheng et al., 2016 ▸) reported that the intermolecular hydrogen bond present in the optimized structure stabilizes both the main molecule and the water molecule, which is why we claim that the hydrogen bond does affect the planar conformation in our optimized structure. In the experimental structure, a weak intermolecular hydrogen bond involving an O atom of the nitro group (Table 1 ▸) may be responsible for the distortion from planarity of the molecule. Furthermore, the twisted nature of this part of the molecule might also be expected because of the steric effects between the carbonyl group and the nitro-substituted benzene ring (Kozlowski et al., 2007 ▸).
Table 1. Hydrogen-bond geometry (Å, °).
Cg1 is the centroid of the N1/C1/C6–C8 ring.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O1W—H1OW⋯O1i | 0.88 (4) | 1.86 (4) | 2.723 (4) | 171 (4) |
| N1—H1A⋯O1W | 0.87 (3) | 2.06 (3) | 2.923 (4) | 170 (3) |
| C4—H4A⋯O2ii | 0.93 | 2.60 | 3.405 (6) | 146 |
| C9—H9A⋯Cg1iii | 0.93 | 2.87 | 3.518 (4) | 127 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
.
The overall conformation of the molecule can be described by the dihedral angle formed by the indole ring system (N1/C1–C8) and the nitro-substituted benzene (C12–C17) ring with a value of 37.64 (16)° (Fig. 1 ▸ c). The enone group (O1/C9–C11) with maximum deviation of 0.082 (3) Å at C11 forms dihedral angles of 21.5 (2) and 16.3 (2)° with the indole ring system and the nitro-substituted benzene ring, respectively.
Supramolecular features
In the crystal, four symmetry-related molecules are connected to each other via O—H⋯O and N—H⋯O hydrogen bonds involving the solvent water molecule. The water molecule is connected to the carbonyl group and indole ring system by intermolecular O1W—H1OW⋯O1i and N1—H1A⋯O1W hydrogen bonds (Table 1 ▸), forming chains extending along the b-axis direction (Fig. 2 ▸). In addition, weak C4—H4A⋯O2ii interactions (Table 1 ▸) link these chains into sheets parallel to the bc plane (Fig. 3 ▸ a). Furthermore, C9—H9A⋯Cg1 interactions (Cg1 is the centroid of the N1/C1/C6–C8 ring; Table 1 ▸, Fig. 3 ▸ b) are observed along the a-axis direction, completing the three-dimensional structure. Two of the anti-parallel molecules are linked by π–π stacking interactions (Fig. 3 ▸ a) involving the centroids (Cg2 and Cg3) of the C1–C6 and C12–C17 rings with a centroid–centroid distance Cg2⋯Cg3 (2-x, y, 1/2 - z) of 3.534 (3) Å. These π–π interactions further stabilize the crystal structure.
Figure 2.
The crystal packing of the title compound along the b axis showing the O—H⋯O and N—H⋯O hydrogen bonds as dotted lines.
Figure 3.
(a) A view of the crystal packing showing two of the chains linked by C—H⋯O interactions extending along c-axis direction. The π–π stacking interactions shown by grey lines further stabilize the crystal structure. (b) C—H⋯π interactions in the title compound. H atoms not involved in hydrogen-bonding interactions have been omitted for clarity.
Hirshfeld surface analysis
Analysis of the Hirshfeld surfaces provides a three-dimensional representation of intermolecular interactions. The Hirshfeld surfaces and related two-dimensional fingerprint (FP) plots were generated with CrystalExplorer3.1 (Wolff et al., 2012 ▸). In the FP plots, d i and d e are the distances from the Hirshfeld surface to the nearest atoms outside and inside the surface. The blue colour represents a low frequency of occurrence of a (d i, d e) pair and the full fingerprint is outlined in grey (Ternavisk et al., 2014 ▸). The water molecule and H⋯O interactions are visualized as bright-red spots on the Hirshfeld surface mapped over d norm with neighbouring molecules connected by O1W—H1OW⋯O1 and N1—H1A⋯O1 hydrogen bonds (Fig. 4 ▸). The fingerprint plots indicate the percentage contributions of the various intermolecular contacts (Fig. 5 ▸). The H⋯H contacts clearly make the most significant contribution (36.6%), whereas O⋯H/H⋯O and C⋯H/H⋯C contacts make contributions of 29.9 and 12.5%, respectively, to the Hirshfeld surface. The presence of O⋯H/H⋯O interactions is indicated by two symmetrical narrow spikes with d i + d e ∼1.7 Å arise specifically due to hydrogen-bonding interactions between the water H atom and the carbonyl oxygen. Furthermore, the existence of C⋯H/H⋯C interactions is shown by the pair of characteristics wings with the edge at d i + d e ∼2.9 Å, which is due to the contribution of C—H⋯π interaction. The 11.5% contribution of the C⋯C interactions arises from the π–π interaction, where the sum of d i and d e obtained is quite similar at 3.5 Å. Interestingly, the N⋯H contacts showed a 2.6% contribution elucidated by a butterfly fingerprint plot resulting from the N1—H1A⋯O1 interaction.
Figure 4.
Hirshfeld surface of the title compound mapped over d norm.
Figure 5.
Fingerprint plots of the intermolecular interactions showing the percentage contributions to the total Hirshfeld surface.
The presence of the C—H⋯π interactions can be seen in the pale-orange spot inside the circle of black arrows on the Hirshfeld surface mapped over d e in (Fig. 6 ▸ a). With the shape-indexed mapping, the C—H⋯π interactions can be observed as a bright-red spot identified with black arrows in Fig. 6 ▸ b. The blue spots near the ring represent the reciprocal C—H⋯π interactions.
Figure 6.
Graphical view of the Hirshfeld surfaces for the title compound (a) mapped over d e with a pale-orange spot and (b) mapped over shape-index with a bright-red spot, both inside the black arrows, signifying the involvement of the C—H⋯π interactions.
Frontier molecular orbital and UV–vis studies
Frontier molecular orbital analysis is a vital tool in the development of molecular electronic properties. The energy gap (E g) between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) is a crucial factor in elucidating the molecular electrical transport properties. In the present study, the HOMO and LUMO were computed at the DFT/B3LYP/6-311G++(d,p) theoretical level and the respective plots of the frontier molecular orbital are illustrated in Fig. 7 ▸. At a specific separation between donor and acceptor, charge transfer may occur in the ground state if the HOMO of the donor lies energetically above the LUMO of the acceptor (Caruso et al., 2014 ▸). As can be seen from Fig. 7 ▸, the charge at the HOMO state is more localized at the indole group and enone moiety while charge is accumulated entirely at the nitro-substituted phenyl ring and the enone moiety in the LUMO state. The results reveal that the intramolecular charge transfer (ICT) occurred from the electron-donor groups to the electron-acceptor groups through the enone moiety. The carbon–carbon double bond connecting the donor and acceptor groups is responsible for the charge movement through π-conjugation, triggering electronic delocalization within the molecule (Prabhu et al., 2015 ▸). The energy gap of 2.80 eV obtained from the DFT calculations indicates strong chemical reactivity and weaker kinetic stability, which increase the polarizability and NLO properties (Maidur et al., 2018 ▸).
Figure 7.
Molecular orbitals showing electronic transition between HOMO–LUMO of the title compound.
The absorption spectrum of the title compound was carried out in acetonitrile with a concentration of 10−4 M. The absorption spectrum comprises of four major bands (Fig. 8 ▸). The strongest band occurs in the region of 396 nm, which was assigned to π–π* transition. This sharp peak is suspected to arise from the indole ring and carbonyl group (C=O). The second strong UV–vis band is observed at 269 nm and is mainly attributed to the electron-withdrawing substituent of the nitro group (Pavia et al., 2001 ▸). The energy gap of the title compound was calculated from the UV–vis absorption edge at 461 nm (Fig. 8 ▸), giving an energy band gap value of 2.70 eV, comparable with the HOMO–LUMO energy gap obtained from the DFT study. This band gap is similar to those in reported studies (D’silva et al., 2011 ▸) and within the energy-gap range for semiconducting materials (Emmanuel et al., 2002 ▸).
Figure 8.
The UV–vis absorption spectrum of the title compound.
Database survey
A search of the Cambridge Structural Database (Version 5.39, last update November 2017; Groom et al., 2016 ▸) revealed closely related compounds that differ in the donor substituents: 1-(4-nitrophenyl)-3-(pyren-1-yl)prop-2-en-1-one (Yu et al., 2017 ▸), 3-(2-furyl)-1-(4-nitrophenyl)prop-2-en-1-one) (Patil et al., 2006 ▸) and 1-(4-nitrophenyl)-3-(2-thienyl)prop-2-en-1-one (Teh et al., 2006 ▸) with pyrene, furan and thiophene donor substituent rings. Other related compounds include (2E)-3-(2-methylphenyl)-1-(4-nitrophenyl)prop-2-en-1-one (Prabhu et al., 2015 ▸) and 3-(4-methoxyphenyl)-1-(4-nitrophenyl)prop-2-en-1-one (Patil et al., 2006 ▸).
Synthesis and crystallization
The title compound was synthesized via a Claisen–Schmidt condensation reaction. A mixture of 1-(4-nitrophenyl)ethanone (0.5 mmol) and indole-2-carboxaldehyde (0.5 mmol) was dissolved in methanol (20 mL). Sodium hydroxide (NaOH) solution was then added dropwise under vigorous stirring. The reaction mixture was stirred for 5–6 h at room temperature. The final precipitate was filtered, washed with distilled water and recrystallized by slow evaporation from acetone solution to obtain orange plate-shaped crystals.
Refinement
Crystal data collection and structure refinement details are summarized in Table 2 ▸. All C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and refined using a riding model with U iso(H) = 1.2U eq(C). The water O atom was refined with half-occupancy. The O- and N-bound H atoms were located from difference-Fourier maps and refined freely.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | 2C17H12N2O3·H2O |
| M r | 602.59 |
| Crystal system, space group | Monoclinic, C2/c |
| Temperature (K) | 296 |
| a, b, c (Å) | 14.835 (7), 6.453 (2), 28.000 (11) |
| β (°) | 93.505 (10) |
| V (Å3) | 2675.4 (18) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.11 |
| Crystal size (mm) | 0.83 × 0.31 × 0.04 |
| Data collection | |
| Diffractometer | Bruker APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Bruker, 2009 ▸) |
| T min, T max | 0.638, 0.955 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 36005, 2369, 1263 |
| R int | 0.129 |
| (sin θ/λ)max (Å−1) | 0.595 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.061, 0.190, 1.07 |
| No. of reflections | 2369 |
| No. of parameters | 213 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.22, −0.19 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018014329/lh5883sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018014329/lh5883Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989018014329/lh5883Isup3.cml
CCDC reference: 1846181
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Crystal data
| 2C17H12N2O3·H2O | F(000) = 1256 |
| Mr = 602.59 | Dx = 1.496 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 14.835 (7) Å | Cell parameters from 1566 reflections |
| b = 6.453 (2) Å | θ = 2.9–19.5° |
| c = 28.000 (11) Å | µ = 0.11 mm−1 |
| β = 93.505 (10)° | T = 296 K |
| V = 2675.4 (18) Å3 | Plate, orange |
| Z = 4 | 0.83 × 0.31 × 0.04 mm |
Data collection
| Bruker APEXII CCD diffractometer | 1263 reflections with I > 2σ(I) |
| φ and ω scans | Rint = 0.129 |
| Absorption correction: multi-scan (SADABS; Bruker, 2009) | θmax = 25.0°, θmin = 2.8° |
| Tmin = 0.638, Tmax = 0.955 | h = −17→17 |
| 36005 measured reflections | k = −7→7 |
| 2369 independent reflections | l = −33→33 |
Refinement
| Refinement on F2 | Hydrogen site location: mixed |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.061 | w = 1/[σ2(Fo2) + (0.0548P)2 + 3.4801P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.190 | (Δ/σ)max < 0.001 |
| S = 1.07 | Δρmax = 0.22 e Å−3 |
| 2369 reflections | Δρmin = −0.19 e Å−3 |
| 213 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.0010 (4) |
Special details
| Experimental. The following wavelength and cell were deduced by SADABS from the direction cosines etc. They are given here for emergency use only: CELL 0.71150 6.604 8.276 28.665 93.349 89.966 113.537 |
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| N1 | 0.8500 (2) | 0.5670 (5) | 0.21045 (11) | 0.0608 (8) | |
| H1A | 0.892 (2) | 0.494 (6) | 0.2257 (13) | 0.071 (12)* | |
| N2 | 1.1251 (3) | 0.4606 (7) | 0.48886 (12) | 0.0826 (11) | |
| O1 | 0.98111 (17) | 1.0824 (4) | 0.33010 (9) | 0.0713 (8) | |
| O2 | 1.1071 (3) | 0.2810 (6) | 0.49214 (12) | 0.1143 (13) | |
| O3 | 1.1754 (2) | 0.5484 (6) | 0.51669 (11) | 0.1137 (12) | |
| C1 | 0.8028 (2) | 0.5110 (6) | 0.16995 (12) | 0.0579 (9) | |
| C2 | 0.8031 (3) | 0.3301 (6) | 0.14546 (14) | 0.0712 (11) | |
| H2A | 0.8396 | 0.2200 | 0.1559 | 0.085* | |
| C3 | 0.7485 (3) | 0.3159 (7) | 0.10529 (15) | 0.0802 (12) | |
| H3A | 0.7470 | 0.1935 | 0.0877 | 0.096* | |
| C4 | 0.6954 (3) | 0.4782 (8) | 0.09007 (15) | 0.0802 (12) | |
| H4A | 0.6584 | 0.4637 | 0.0622 | 0.096* | |
| C5 | 0.6950 (3) | 0.6569 (7) | 0.11385 (14) | 0.0750 (12) | |
| H5A | 0.6590 | 0.7666 | 0.1025 | 0.090* | |
| C6 | 0.7487 (2) | 0.6766 (6) | 0.15553 (13) | 0.0620 (10) | |
| C7 | 0.7659 (2) | 0.8323 (6) | 0.18888 (13) | 0.0613 (10) | |
| H7A | 0.7388 | 0.9623 | 0.1884 | 0.074* | |
| C8 | 0.8281 (2) | 0.7644 (6) | 0.22200 (12) | 0.0569 (9) | |
| C9 | 0.8692 (2) | 0.8667 (6) | 0.26162 (12) | 0.0586 (10) | |
| H9A | 0.8545 | 1.0055 | 0.2656 | 0.070* | |
| C10 | 0.9266 (2) | 0.7848 (6) | 0.29370 (12) | 0.0603 (10) | |
| H10A | 0.9386 | 0.6439 | 0.2913 | 0.072* | |
| C11 | 0.9717 (2) | 0.8965 (6) | 0.33203 (12) | 0.0574 (9) | |
| C12 | 1.0089 (2) | 0.7823 (5) | 0.37368 (12) | 0.0560 (9) | |
| C13 | 0.9864 (3) | 0.5825 (6) | 0.38163 (13) | 0.0678 (11) | |
| H13A | 0.9450 | 0.5162 | 0.3605 | 0.081* | |
| C14 | 1.0231 (3) | 0.4790 (6) | 0.41952 (13) | 0.0694 (11) | |
| H14A | 1.0072 | 0.3421 | 0.4249 | 0.083* | |
| C15 | 1.0831 (2) | 0.5757 (6) | 0.44943 (12) | 0.0634 (10) | |
| C16 | 1.1064 (3) | 0.7740 (7) | 0.44334 (14) | 0.0729 (11) | |
| H16A | 1.1475 | 0.8391 | 0.4648 | 0.088* | |
| C17 | 1.0683 (3) | 0.8770 (6) | 0.40510 (13) | 0.0668 (11) | |
| H17A | 1.0832 | 1.0152 | 0.4004 | 0.080* | |
| O1W | 1.0000 | 0.3138 (6) | 0.2500 | 0.0710 (11) | |
| H1OW | 1.012 (3) | 0.237 (6) | 0.2254 (14) | 0.094 (15)* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.061 (2) | 0.063 (2) | 0.0561 (19) | 0.0041 (17) | −0.0096 (16) | 0.0024 (16) |
| N2 | 0.090 (3) | 0.093 (3) | 0.063 (2) | 0.004 (2) | −0.010 (2) | 0.008 (2) |
| O1 | 0.0864 (19) | 0.0584 (17) | 0.0674 (17) | −0.0039 (14) | −0.0090 (14) | 0.0005 (13) |
| O2 | 0.153 (3) | 0.089 (2) | 0.096 (2) | −0.002 (2) | −0.032 (2) | 0.025 (2) |
| O3 | 0.128 (3) | 0.128 (3) | 0.079 (2) | −0.006 (2) | −0.043 (2) | 0.007 (2) |
| C1 | 0.056 (2) | 0.064 (2) | 0.053 (2) | −0.0047 (18) | −0.0023 (17) | 0.0009 (19) |
| C2 | 0.079 (3) | 0.064 (3) | 0.069 (3) | −0.002 (2) | −0.001 (2) | −0.008 (2) |
| C3 | 0.081 (3) | 0.084 (3) | 0.076 (3) | −0.014 (3) | 0.006 (2) | −0.018 (2) |
| C4 | 0.065 (3) | 0.106 (3) | 0.068 (3) | −0.011 (3) | −0.008 (2) | −0.015 (3) |
| C5 | 0.067 (3) | 0.087 (3) | 0.069 (3) | 0.004 (2) | −0.014 (2) | −0.003 (2) |
| C6 | 0.057 (2) | 0.067 (2) | 0.060 (2) | −0.004 (2) | −0.0039 (18) | 0.002 (2) |
| C7 | 0.061 (2) | 0.056 (2) | 0.066 (2) | 0.0046 (18) | −0.0078 (19) | 0.005 (2) |
| C8 | 0.057 (2) | 0.056 (2) | 0.057 (2) | −0.0013 (18) | −0.0010 (18) | −0.0047 (18) |
| C9 | 0.057 (2) | 0.060 (2) | 0.058 (2) | −0.0015 (17) | −0.0025 (18) | −0.0025 (18) |
| C10 | 0.065 (2) | 0.056 (2) | 0.059 (2) | 0.0033 (18) | −0.0023 (19) | −0.0037 (19) |
| C11 | 0.055 (2) | 0.058 (2) | 0.058 (2) | 0.0012 (18) | −0.0013 (18) | −0.0020 (19) |
| C12 | 0.056 (2) | 0.055 (2) | 0.056 (2) | 0.0008 (18) | −0.0019 (18) | −0.0055 (18) |
| C13 | 0.072 (3) | 0.065 (2) | 0.064 (2) | −0.008 (2) | −0.015 (2) | 0.002 (2) |
| C14 | 0.077 (3) | 0.065 (3) | 0.064 (2) | −0.006 (2) | −0.006 (2) | 0.002 (2) |
| C15 | 0.068 (2) | 0.070 (3) | 0.051 (2) | 0.004 (2) | −0.0066 (19) | 0.000 (2) |
| C16 | 0.079 (3) | 0.076 (3) | 0.062 (2) | −0.010 (2) | −0.012 (2) | −0.007 (2) |
| C17 | 0.072 (2) | 0.064 (2) | 0.063 (2) | −0.008 (2) | −0.010 (2) | −0.005 (2) |
| O1W | 0.091 (3) | 0.055 (2) | 0.065 (3) | 0.000 | −0.012 (2) | 0.000 |
Geometric parameters (Å, º)
| N1—C1 | 1.345 (4) | C7—H7A | 0.9300 |
| N1—C8 | 1.359 (4) | C8—C9 | 1.399 (5) |
| N1—H1A | 0.87 (4) | C9—C10 | 1.310 (5) |
| N2—O3 | 1.189 (4) | C9—H9A | 0.9300 |
| N2—O2 | 1.194 (4) | C10—C11 | 1.426 (5) |
| N2—C15 | 1.440 (5) | C10—H10A | 0.9300 |
| O1—C11 | 1.209 (4) | C11—C12 | 1.459 (5) |
| C1—C2 | 1.354 (5) | C12—C17 | 1.353 (5) |
| C1—C6 | 1.382 (5) | C12—C13 | 1.353 (5) |
| C2—C3 | 1.348 (5) | C13—C14 | 1.341 (5) |
| C2—H2A | 0.9300 | C13—H13A | 0.9300 |
| C3—C4 | 1.363 (6) | C14—C15 | 1.338 (5) |
| C3—H3A | 0.9300 | C14—H14A | 0.9300 |
| C4—C5 | 1.332 (5) | C15—C16 | 1.339 (5) |
| C4—H4A | 0.9300 | C16—C17 | 1.354 (5) |
| C5—C6 | 1.378 (5) | C16—H16A | 0.9300 |
| C5—H5A | 0.9300 | C17—H17A | 0.9300 |
| C6—C7 | 1.385 (5) | O1W—H1OW | 0.88 (4) |
| C7—C8 | 1.341 (4) | ||
| C1—N1—C8 | 109.4 (3) | N1—C8—C9 | 122.2 (3) |
| C1—N1—H1A | 126 (2) | C10—C9—C8 | 126.0 (4) |
| C8—N1—H1A | 124 (2) | C10—C9—H9A | 117.0 |
| O3—N2—O2 | 123.1 (4) | C8—C9—H9A | 117.0 |
| O3—N2—C15 | 118.8 (4) | C9—C10—C11 | 124.6 (3) |
| O2—N2—C15 | 118.1 (4) | C9—C10—H10A | 117.7 |
| N1—C1—C2 | 129.9 (4) | C11—C10—H10A | 117.7 |
| N1—C1—C6 | 107.6 (3) | O1—C11—C10 | 121.2 (3) |
| C2—C1—C6 | 122.6 (3) | O1—C11—C12 | 119.9 (3) |
| C3—C2—C1 | 117.4 (4) | C10—C11—C12 | 118.9 (3) |
| C3—C2—H2A | 121.3 | C17—C12—C13 | 118.7 (4) |
| C1—C2—H2A | 121.3 | C17—C12—C11 | 119.4 (3) |
| C2—C3—C4 | 121.0 (4) | C13—C12—C11 | 121.9 (3) |
| C2—C3—H3A | 119.5 | C14—C13—C12 | 120.8 (4) |
| C4—C3—H3A | 119.5 | C14—C13—H13A | 119.6 |
| C5—C4—C3 | 122.0 (4) | C12—C13—H13A | 119.6 |
| C5—C4—H4A | 119.0 | C15—C14—C13 | 119.0 (4) |
| C3—C4—H4A | 119.0 | C15—C14—H14A | 120.5 |
| C4—C5—C6 | 118.9 (4) | C13—C14—H14A | 120.5 |
| C4—C5—H5A | 120.6 | C14—C15—C16 | 122.2 (4) |
| C6—C5—H5A | 120.6 | C14—C15—N2 | 118.6 (4) |
| C5—C6—C1 | 118.1 (4) | C16—C15—N2 | 119.2 (4) |
| C5—C6—C7 | 135.3 (4) | C15—C16—C17 | 118.2 (4) |
| C1—C6—C7 | 106.5 (3) | C15—C16—H16A | 120.9 |
| C8—C7—C6 | 108.6 (3) | C17—C16—H16A | 120.9 |
| C8—C7—H7A | 125.7 | C12—C17—C16 | 121.0 (4) |
| C6—C7—H7A | 125.7 | C12—C17—H17A | 119.5 |
| C7—C8—N1 | 107.8 (3) | C16—C17—H17A | 119.5 |
| C7—C8—C9 | 130.0 (4) | ||
| C8—N1—C1—C2 | 179.9 (4) | C8—C9—C10—C11 | 175.8 (3) |
| C8—N1—C1—C6 | −0.6 (4) | C9—C10—C11—O1 | −21.9 (6) |
| N1—C1—C2—C3 | −179.9 (4) | C9—C10—C11—C12 | 159.5 (4) |
| C6—C1—C2—C3 | 0.6 (6) | O1—C11—C12—C17 | −13.1 (5) |
| C1—C2—C3—C4 | 0.2 (6) | C10—C11—C12—C17 | 165.5 (3) |
| C2—C3—C4—C5 | 0.0 (7) | O1—C11—C12—C13 | 167.7 (4) |
| C3—C4—C5—C6 | −1.2 (6) | C10—C11—C12—C13 | −13.7 (5) |
| C4—C5—C6—C1 | 1.9 (6) | C17—C12—C13—C14 | −0.9 (6) |
| C4—C5—C6—C7 | 179.8 (4) | C11—C12—C13—C14 | 178.3 (4) |
| N1—C1—C6—C5 | 178.7 (3) | C12—C13—C14—C15 | −0.4 (6) |
| C2—C1—C6—C5 | −1.7 (6) | C13—C14—C15—C16 | 1.3 (6) |
| N1—C1—C6—C7 | 0.2 (4) | C13—C14—C15—N2 | −177.3 (4) |
| C2—C1—C6—C7 | 179.8 (3) | O3—N2—C15—C14 | −176.8 (4) |
| C5—C6—C7—C8 | −177.8 (4) | O2—N2—C15—C14 | 2.8 (6) |
| C1—C6—C7—C8 | 0.3 (4) | O3—N2—C15—C16 | 4.5 (6) |
| C6—C7—C8—N1 | −0.6 (4) | O2—N2—C15—C16 | −176.0 (4) |
| C6—C7—C8—C9 | 177.6 (4) | C14—C15—C16—C17 | −0.9 (6) |
| C1—N1—C8—C7 | 0.7 (4) | N2—C15—C16—C17 | 177.8 (4) |
| C1—N1—C8—C9 | −177.7 (3) | C13—C12—C17—C16 | 1.4 (6) |
| C7—C8—C9—C10 | 176.4 (4) | C11—C12—C17—C16 | −177.9 (4) |
| N1—C8—C9—C10 | −5.5 (6) | C15—C16—C17—C12 | −0.5 (6) |
Hydrogen-bond geometry (Å, º)
Cg1 is the centroid of the N1/C1/C6–C8 ring.
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1OW···O1i | 0.88 (4) | 1.86 (4) | 2.723 (4) | 171 (4) |
| N1—H1A···O1W | 0.87 (3) | 2.06 (3) | 2.923 (4) | 170 (3) |
| C4—H4A···O2ii | 0.93 | 2.60 | 3.405 (6) | 146 |
| C9—H9A···Cg1iii | 0.93 | 2.87 | 3.518 (4) | 127 |
Symmetry codes: (i) −x+2, y−1, −z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+3/2, y+1/2, −z+1/2.
Funding Statement
This work was funded by Ministry of Higher Education, Malaysia grants 203.PFIZIK.6711572 and 304.PFIZIK.6313336.
References
- Brandenburg, K. B. M. (2009). DIAMOND. University of Bonn, Germany.
- Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
- Caruso, F., Atalla, V., Ren, X., Rubio, A., Scheffler, M. & Rinke, P. (2014). Phys. Rev. B, 90, 085141.
- Dobrowolski, M. A., Krygowski, T. M. & Cyranski, M. K. (2009). Croat. Chem. Acta, 82, 139–147.
- D’silva, E. D., Podagatlapalli, G. K., Rao, S. V., Rao, D. N. & Dharmaprakash, S. M. (2011). Cryst. Growth Des. 11, 5362–5369.
- Emmanuel, R. & Borge, V. (2002). In Optoelectronics. New York: Cambridge University, Press.
- Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst B72, 171–179. [DOI] [PMC free article] [PubMed]
- Kozlowski, D., Trouillas, P., Calliste, C., Marsal, P., Lazzaroni, R. & Duroux, J.-L. (2007). J. Phys. Chem. A, 111, 1138–1145. [DOI] [PubMed]
- Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.
- Maidur, S. R., Jahagirdar, J. R., Patil, P. S., Chia, T. S. & Quah, C. K. (2018). Opt. Mater. 75, 580–594.
- Patil, P. S., Teh, J. B.-J., Fun, H.-K., Razak, I. A. & Dharmaprakash, S. M. (2006). Acta Cryst. E62, o2397–o2398.
- Pavia, D. L., Lampman, G. M. & Kriz, G. S. (2001). Introduction to Spectroscopy, 3rd ed, pp. 378–379. Australia: Brooks/Cole-Thomson Learning.
- Prabhu, S. R., Jayarama, A., Upadhyaya, V., Bhat, K. S. & Ng, S. W. (2015). Mol. Cryst. Liq. Cryst. 607, 200–214.
- Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
- Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.
- Spek, A. L. (2009). Acta Cryst. D65, 148–155. [DOI] [PMC free article] [PubMed]
- Teh, J. B.-J., Patil, P. S., Fun, H.-K., Razak, I. A. & Dharmaprakash, S. M. (2006). Acta Cryst. E62, o3957–o3958.
- Ternavisk, R. R., Camargo, A. J., Machado, F. B. C., Rocco, J. A. F. F., Aquino, G. L. B., Silva, V. H. C. & Napolitano, H. B. (2014). J. Mol. Model. 20, 2526–2536. [DOI] [PubMed]
- Thanigaimani, K., Arshad, S., Khalib, N. C., Razak, I. A., Arunagiri, C., Subashini, A., Sulaiman, S. F., Hashim, N. S. & Ooi, K. L. (2015). Spectrochim. Acta A, 149, 90–102. [DOI] [PubMed]
- Toledo, T. A. de, da Costa, R. C., Bento, R. R. F., Al-Maqtari, H. M., Jamalis, J. & Pizani, P. S. (2018). J. Mol. Struct. 1155, 634–645.
- Wolff, S. K., Grimwood, D. J., McKinnon, J. J., Turner, M. J., Jayatilaka, D. & Spackman, M. A. (2012). Crystal Explorer. University of Western Australia, Perth.
- Yu, F., Wang, M., Sun, H., Shan, Y., Du, M., Khan, A., Usman, R., Zhang, W., Shan, H. & Xu, C. (2017). RSC Adv. 7, 8491–8503.
- Zainuri, D. A., Arshad, S., Khalib, N. C., Razak, A. I., Pillai, R. R., Sulaiman, F., Hashim, N. S., Ooi, K. L., Armaković, S., Armaković, S. J., Panicker, Y. & Van Alsenoy, C. (2017). J. Mol. Struct. 1128, 520–533.
- Zheng, Y.-Z., Zhou, Y., Liang, Q., Chen, D.-F., Guo, R. & Lai, R. C. (2016). Sci. Rep. 6, 34647. [DOI] [PMC free article] [PubMed]
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018014329/lh5883sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018014329/lh5883Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989018014329/lh5883Isup3.cml
CCDC reference: 1846181
Additional supporting information: crystallographic information; 3D view; checkCIF report