research communications
1-{(E)-[(2E)-3-(4-Methoxyphenyl)-1-phenylprop-2-en-1-ylidene]amino}-3-phenylurea: and Hirshfeld surface analysis
aDepartment of Physical Science, Faculty of Applied Sciences, Tunku Abdul Rahman University College, 50932 Setapak, Kuala Lumpur, Malaysia, bDepartment of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor Darul Ehsan, Malaysia, cDepartment of Chemistry, St. Francis Xavier University, PO Box 5000, Antigonish, NS B2G 2W5, Canada, dDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380 001, India, and eResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: edwardt@sunway.edu.my
The title compound, C23H21N3O2, is constructed about an almost planar disubstituted aminourea residue (r.m.s. deviation = 0.0201 Å), which features an intramolecular amine-N—H⋯N(imine) hydrogen bond. In the `all-trans' chain connecting this to the terminal methoxybenzene residue, the conformation about each of the imine and ethylene double bonds is E. In the crystal, amide-N—H⋯O(carbonyl) hydrogen bonds connect centrosymmetrically related molecules into dimeric aggregates, which also incorporate ethylene-C—H⋯O(amide) interactions. The dimers are linked by amine–phenyl-C—H⋯π(imine–phenyl) and methoxybenzene-C—H⋯π(amine–phenyl) interactions to generate a three-dimensional network. The importance of C—H⋯π interactions in the molecular packing is reflected in the relatively high contributions made by C⋯H/H⋯C contacts to the Hirshfeld surface, i.e. 31.6%.
CCDC reference: 1577439
1. Chemical context
via a three-carbon-atom α,β-unsaturated carbonyl system. These compounds have attracted much attention due to their diverse pharmacological and biological activities (Gaonkar & Vignesh, 2017), including their anti-cancer (Mahapatra et al., 2015), anti-malarial (Syahri et al., 2017), anti-inflammatory (Li et al., 2017), anti-microbial (Kumar et al., 2017), xanthine oxidase inhibitory (Xie et al., 2017) and aldol reductase inhibitory (Zhuang et al., 2017) properties. The present work is part of an on-going project on the synthesis of chalcone-derived their ultilization in the synthesis of new transition metal complexes and their investigation as anti-proliferative and anti-bacterial agents. In this context, crystal-structure determinations of a chalcone-derived thiosemicarbazone and a zinc complex have been published (Tan et al., 2015, 2017).
are natural or synthetic compounds comprising an open-chain flavonoid structure in which the two aromatic rings are connectedIn this contribution, a chalcone residue has been incorporated into a semicarbazide skeleton to form the title chalconesemicarbazone, (I). While chalconesemicarbazone derivatives have shown potential anti-convulsant (Sharma et al., 2014), anti-inflammatory (Singha et al., 2010) and anti-oxidant activities (Singhal et al., 2011), no crystal structures of chalconesemicarbazone derivatives have been published. Herein, the crystal and molecular structures of (I) have been determined and the study augmented by an analysis of the calculated Hirshfeld surfaces.
2. Structural commentary
The molecular structure of (I), Fig. 1, comprises a doubly substituted aminourea residue which is close to planar (r.m.s. deviation of CN3O = 0.0201 Å), owing in part to an intramolecular amine-N—H⋯N(imine) hydrogen bond, Table 1. The amine-bound phenyl ring is inclined to the CN3O plane, forming a dihedral angle of 46.88 (4)°. The imine/ethylene sequence of bonds, i.e. N3=C8—C9=C10—C11, has an all-trans conformation but the N3—C8—C9—C10 and C8—C9—C10—C11 torsion angles of 154.62 (12) and −169.19 (11)°, respectively, indicate some twisting in this residue, especially about the C8—C9 bond; the conformation about each of the double bonds is E. The imine-bound phenyl ring forms a dihedral angle of 63.30 (7)° with the C4N atoms of the imine/ethylene sequence, and the corresponding angle for the terminal methoxybenzene ring is significantly less, at 8.29 (13)°. The methoxy group is twisted out of the plane of the ring to which it is connected as seen in the value of the C17—O18—C14—C15 torsion angle of 15.55 (17)°.
3. Supramolecular features
The most notable feature of the molecular packing of (I) is the presence of a centrosymmetric, eight-membered amide synthon, {⋯OCNH}2, Table 1. The resultant dimeric aggregate also incorporates two additional ethylene-C—H⋯O(amide) interactions, Fig. 2a, as well as methoxy-C—H⋯π(amine-phenyl) contacts, Table 1. The aggregates are assembled into a three-dimensional network via amine-phenyl-C—H⋯π(imine-phenyl) and methoxy-benzene-C—H⋯π(amine-phenyl) interactions, Fig. 2b.
4. Analysis of the Hirshfeld surface
The Hirshfeld surface was calculated for (I) in accord with a recent report on a related molecule (Tan et al., 2017) to provide more detailed information on the relative significance of the various intermolecular interactions. The donors and acceptors of intermolecular N—H⋯O and C—H⋯O interactions in (I) are viewed as the bright-red spots near the ethylene-H9, amide-H2N and carbonyl-O1 atoms on the Hirshfeld surface mapped over dnorm in Fig. 3a. The appearance of diminutive red spots near the N3 and C17 atoms, Fig. 3a, and the tiny faint-red spots near the C9 and H82 atoms in Fig. 3b, indicate the influence of short interatomic N3⋯C17 and C9⋯H82 contacts, Table 2. The donors and acceptors of intermolecular hydrogen bonds also appear as blue and red regions, respectively, around the participating atoms on the Hirshfeld surface mapped over the calculated electrostatic potential in Fig. 4. The involvement of the imine-phenyl (C81–C86) and amine-phenyl (C2–C7) rings as acceptors for C—H⋯π interactions are also evident through the light-red regions around these rings on the Hirshfeld surfaces in the views of Fig. 4. Referring to Fig. 5a, the concave region around the imine-phenyl ring on one side and the biconcave region around the amine-phenyl ring indicate their involvement in one and two C—H⋯π contacts, respectively. The short interatomic O⋯H/H⋯O contacts (Table 3) as well as N—H⋯O and C—H⋯O interactions about a reference molecule within shape-index mapped Hirshfeld surface, and the H⋯H, C⋯H/H⋯C and C⋯N/N⋯C contacts within the dnorm-mapped Hirshfeld surface are shown in Fig. 5b and c, respectively.
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The overall two dimensional fingerprint plot, Fig. 6a, and those delineated into H⋯H, C⋯H/H⋯C, O⋯H/H⋯O and N⋯H/H⋯N contacts (McKinnon et al., 2007) are illustrated in Fig. 6b–e, respectively; the relative contributions from different interatomic contacts to the Hirshfeld surfaces are summarized in Table 3. The presence of a small but, distinctive peak at de + di ∼ 2.3 Å in the fingerprint plot delineated into H⋯H contacts, and highlighted by a red arrow in Fig. 6b, results from the short interatomic H⋯H contact between symmetry-related imine-phenyl-H86 atoms, Table 2, whereas the flanking peaks, at the same de + di ∼ 2.3 Å distance correspond to short interatomic H⋯H contacts between methoxybenzene-H12 and methoxy-H17C atoms, Table 2.
The C⋯H/H⋯C contacts in the crystal make the second largest contribution, i.e. 31.6%, to the Hirshfeld surface of (I), Fig. 6c, which is due to the presence of a significant number of C—H⋯π interactions involving the imine- and amine-phenyl rings, as well as short interatomic C⋯H/H⋯C contacts, Table 3, between the atoms of the methoxy-phenyl and imine-phenyl rings, Fig. 5c. The pair of forceps-like long tips at de + di = 2.1 Å in the fingerprint plot delineated into O⋯H/H⋯O contacts, Fig. 6d, reflect the presence the N—H⋯O hydrogen bond; the pair of spikes corresponding to the C—H⋯O contacts and the points related to short interatomic O⋯H/H⋯O contacts, Table 2, are merged within the plot. Although the N⋯H/H⋯N contacts have a notable contribution of 4.2% to the Hirshfeld surface, Fig. 6e, as their interatomic distances are greater than their van der Waals separations, they do not make a specific contribution to the molecular packing. The participation of the methyl-C17 atom in two close interatomic contacts, Table 2, brings into close proximity the methyl-C17 and imine-N3 atoms, Table 2, but these are interspersed by the H17A and H17B atoms so are not surface contacts. Finally, the small contributions from other interatomic contacts summarized in Table 3 have a negligible effect on the structure.
5. Database survey
The title compound was prepared from the dehydrogenation reaction of 4-phenylsemicarbazide and 4-methoxychalcone. A search of the Cambridge Structural Database (Groom et al., 2016) revealed no direct precedents for this type of molecule. The most closely related structure is one where the ethylene bond is incorporated within a five-membered pyrazolone ring (Chai et al., 2005). Here, the intramolecular amine-N—H⋯N(imine) hydrogen bond persists in each of the two independent molecules comprising the as do the E-conformations about the two analogous double bonds in the molecule. However, there is considerable twisting about the equivalent bonds to C8—C9 in (I), i.e. the N—C—C—C torsion angles are 130.3 (6) and 136.0 (6)°, cf. 154.62 (12)° in (I), an observation attributed to the need to reduce between the rings in the molecules.
6. Synthesis and crystallization
Analytical grade reagents were used as procured without further purification. 4-Phenylsemicarbazide (1.51 g, 0.01 mol) and 4-methoxychalcone (2.38 g, 0.01 mol) were dissolved separately in hot absolute ethanol (30 ml) and mixed with stirring. A few drops of concentrated hydrochloric acid were added as a catalyst. The reaction mixture was heated and stirred for about 20 min., then stirred for a further 30 min. at room temperature. The resulting yellow precipitate was filtered, washed with cold ethanol and dried in vacuo; yield: 75%. Single crystals were grown at room temperature from the slow evaporation of mixed ethanol and acetonitrile solvents (1:1 v/v; 20 ml), m.p. 407 K. IR (cm−1): 3336 ν(N—H), 1679 ν(C=O), 1526 ν(C=N), 1242 ν(C—N), 1025 ν(C=S). MS (m/z): 371.25 [M+1]+.
7. Refinement
Crystal data, data collection and structure . The carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2–1.5Ueq(C). The nitrogen-bound H atoms were located in a difference-Fourier map but were refined with a distance restraint of N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.2Ueq(N).
details are summarized in Table 4
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Supporting information
CCDC reference: 1577439
https://doi.org/10.1107/S2056989017014128/hb7709sup1.cif
contains datablock . DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017014128/hb7709Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989017014128/hb7709Isup3.cml
Data collection: CrysAlis PRO (Agilent, 2011); cell
CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C23H21N3O2 | F(000) = 784 |
Mr = 371.43 | Dx = 1.298 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.5418 Å |
a = 9.2879 (2) Å | Cell parameters from 12038 reflections |
b = 21.9137 (3) Å | θ = 4.0–71.3° |
c = 9.6740 (2) Å | µ = 0.68 mm−1 |
β = 105.187 (2)° | T = 100 K |
V = 1900.21 (6) Å3 | Slab (cut), light-yellow |
Z = 4 | 0.31 × 0.29 × 0.16 mm |
Oxford Diffraction Xcaliber Eos Gemini diffractometer | 3678 independent reflections |
Radiation source: fine-focus sealed tube | 3380 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 16.1952 pixels mm-1 | θmax = 71.4°, θmin = 4.0° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −26→26 |
Tmin = 0.904, Tmax = 1.000 | l = −11→11 |
25449 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0583P)2 + 0.6586P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
3678 reflections | Δρmax = 0.22 e Å−3 |
260 parameters | Δρmin = −0.24 e Å−3 |
2 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 1.01879 (9) | 0.56831 (4) | 0.59686 (10) | 0.0282 (2) | |
O18 | 0.65222 (10) | 0.14747 (4) | 0.28503 (10) | 0.0303 (2) | |
N1 | 0.81663 (12) | 0.63230 (5) | 0.54527 (11) | 0.0253 (2) | |
H1N | 0.7293 (12) | 0.6365 (7) | 0.4858 (14) | 0.030* | |
N2 | 0.80445 (11) | 0.53742 (5) | 0.44127 (11) | 0.0230 (2) | |
H2N | 0.8494 (16) | 0.5033 (5) | 0.4302 (16) | 0.028* | |
N3 | 0.65679 (11) | 0.55029 (5) | 0.37877 (11) | 0.0224 (2) | |
C1 | 0.88811 (13) | 0.57941 (6) | 0.53281 (13) | 0.0227 (3) | |
C2 | 0.86973 (13) | 0.67870 (6) | 0.64749 (13) | 0.0234 (3) | |
C3 | 0.94222 (14) | 0.66456 (6) | 0.78919 (14) | 0.0267 (3) | |
H3 | 0.9657 | 0.6234 | 0.8168 | 0.032* | |
C4 | 0.97992 (14) | 0.71113 (7) | 0.88961 (14) | 0.0314 (3) | |
H4 | 1.0300 | 0.7017 | 0.9861 | 0.038* | |
C5 | 0.94507 (14) | 0.77139 (7) | 0.85028 (15) | 0.0337 (3) | |
H5 | 0.9688 | 0.8029 | 0.9200 | 0.040* | |
C6 | 0.87558 (14) | 0.78537 (6) | 0.70894 (16) | 0.0312 (3) | |
H6 | 0.8527 | 0.8266 | 0.6816 | 0.037* | |
C7 | 0.83916 (13) | 0.73922 (6) | 0.60681 (14) | 0.0263 (3) | |
H7 | 0.7935 | 0.7490 | 0.5095 | 0.032* | |
C8 | 0.57139 (13) | 0.50863 (5) | 0.30443 (12) | 0.0215 (3) | |
C9 | 0.61677 (13) | 0.44598 (6) | 0.28545 (13) | 0.0221 (3) | |
H9 | 0.7195 | 0.4382 | 0.2945 | 0.026* | |
C10 | 0.52152 (13) | 0.39879 (6) | 0.25590 (12) | 0.0223 (3) | |
H10 | 0.4180 | 0.4081 | 0.2305 | 0.027* | |
C11 | 0.56261 (13) | 0.33419 (6) | 0.25920 (12) | 0.0216 (3) | |
C12 | 0.45125 (13) | 0.28994 (6) | 0.21358 (13) | 0.0239 (3) | |
H12 | 0.3505 | 0.3026 | 0.1776 | 0.029* | |
C13 | 0.48453 (14) | 0.22853 (6) | 0.21976 (13) | 0.0253 (3) | |
H13 | 0.4078 | 0.1994 | 0.1850 | 0.030* | |
C14 | 0.63070 (14) | 0.20925 (6) | 0.27707 (13) | 0.0232 (3) | |
C15 | 0.74391 (14) | 0.25212 (6) | 0.32357 (13) | 0.0253 (3) | |
H15 | 0.8441 | 0.2392 | 0.3619 | 0.030* | |
C16 | 0.70944 (14) | 0.31380 (6) | 0.31361 (13) | 0.0247 (3) | |
H16 | 0.7872 | 0.3429 | 0.3444 | 0.030* | |
C17 | 0.78852 (18) | 0.12581 (7) | 0.37548 (15) | 0.0384 (4) | |
H17A | 0.8711 | 0.1373 | 0.3351 | 0.058* | |
H17B | 0.7845 | 0.0813 | 0.3829 | 0.058* | |
H17C | 0.8041 | 0.1439 | 0.4709 | 0.058* | |
C81 | 0.41306 (13) | 0.52769 (5) | 0.24448 (13) | 0.0222 (3) | |
C82 | 0.33269 (14) | 0.55311 (6) | 0.33371 (14) | 0.0259 (3) | |
H82 | 0.3795 | 0.5587 | 0.4327 | 0.031* | |
C83 | 0.18453 (15) | 0.57034 (6) | 0.27873 (15) | 0.0299 (3) | |
H83 | 0.1298 | 0.5865 | 0.3408 | 0.036* | |
C84 | 0.11639 (14) | 0.56408 (6) | 0.13362 (16) | 0.0314 (3) | |
H84 | 0.0157 | 0.5765 | 0.0960 | 0.038* | |
C85 | 0.19547 (15) | 0.53967 (7) | 0.04391 (15) | 0.0345 (3) | |
H85 | 0.1494 | 0.5357 | −0.0557 | 0.041* | |
C86 | 0.34221 (15) | 0.52092 (6) | 0.09928 (14) | 0.0298 (3) | |
H86 | 0.3950 | 0.5033 | 0.0374 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0186 (4) | 0.0265 (5) | 0.0361 (5) | 0.0021 (3) | 0.0011 (4) | −0.0090 (4) |
O18 | 0.0325 (5) | 0.0216 (5) | 0.0364 (5) | 0.0031 (4) | 0.0085 (4) | 0.0038 (4) |
N1 | 0.0203 (5) | 0.0252 (5) | 0.0256 (5) | 0.0034 (4) | −0.0024 (4) | −0.0063 (4) |
N2 | 0.0192 (5) | 0.0194 (5) | 0.0281 (5) | 0.0018 (4) | 0.0019 (4) | −0.0027 (4) |
N3 | 0.0190 (5) | 0.0224 (5) | 0.0239 (5) | 0.0002 (4) | 0.0022 (4) | 0.0004 (4) |
C1 | 0.0200 (6) | 0.0234 (6) | 0.0241 (6) | −0.0006 (5) | 0.0047 (5) | −0.0016 (5) |
C2 | 0.0157 (5) | 0.0270 (6) | 0.0266 (6) | 0.0003 (5) | 0.0039 (5) | −0.0074 (5) |
C3 | 0.0189 (6) | 0.0330 (7) | 0.0274 (6) | 0.0020 (5) | 0.0045 (5) | −0.0030 (5) |
C4 | 0.0196 (6) | 0.0488 (8) | 0.0244 (6) | −0.0017 (6) | 0.0035 (5) | −0.0097 (6) |
C5 | 0.0218 (6) | 0.0415 (8) | 0.0379 (7) | −0.0047 (6) | 0.0082 (5) | −0.0211 (6) |
C6 | 0.0224 (6) | 0.0273 (7) | 0.0444 (8) | 0.0006 (5) | 0.0099 (6) | −0.0113 (6) |
C7 | 0.0194 (6) | 0.0286 (7) | 0.0291 (6) | 0.0025 (5) | 0.0034 (5) | −0.0050 (5) |
C8 | 0.0219 (6) | 0.0215 (6) | 0.0207 (6) | −0.0009 (5) | 0.0046 (4) | 0.0003 (4) |
C9 | 0.0192 (6) | 0.0236 (6) | 0.0223 (6) | 0.0013 (5) | 0.0034 (4) | −0.0008 (4) |
C10 | 0.0185 (6) | 0.0254 (6) | 0.0213 (6) | 0.0010 (5) | 0.0023 (4) | 0.0000 (5) |
C11 | 0.0212 (6) | 0.0231 (6) | 0.0200 (6) | −0.0004 (5) | 0.0047 (4) | −0.0001 (4) |
C12 | 0.0195 (6) | 0.0256 (6) | 0.0257 (6) | −0.0001 (5) | 0.0044 (5) | 0.0031 (5) |
C13 | 0.0236 (6) | 0.0237 (6) | 0.0284 (6) | −0.0044 (5) | 0.0066 (5) | 0.0020 (5) |
C14 | 0.0290 (6) | 0.0210 (6) | 0.0214 (6) | 0.0016 (5) | 0.0096 (5) | 0.0022 (4) |
C15 | 0.0214 (6) | 0.0278 (6) | 0.0256 (6) | 0.0040 (5) | 0.0041 (5) | −0.0014 (5) |
C16 | 0.0211 (6) | 0.0240 (6) | 0.0278 (6) | −0.0024 (5) | 0.0042 (5) | −0.0038 (5) |
C17 | 0.0510 (9) | 0.0276 (7) | 0.0311 (7) | 0.0153 (6) | 0.0012 (6) | −0.0011 (6) |
C81 | 0.0214 (6) | 0.0155 (5) | 0.0283 (6) | −0.0018 (4) | 0.0036 (5) | 0.0007 (5) |
C82 | 0.0294 (7) | 0.0212 (6) | 0.0270 (6) | 0.0012 (5) | 0.0073 (5) | 0.0036 (5) |
C83 | 0.0305 (7) | 0.0228 (6) | 0.0400 (7) | 0.0032 (5) | 0.0159 (6) | 0.0043 (5) |
C84 | 0.0200 (6) | 0.0262 (6) | 0.0448 (8) | 0.0016 (5) | 0.0028 (6) | 0.0028 (6) |
C85 | 0.0278 (7) | 0.0371 (8) | 0.0321 (7) | 0.0023 (6) | −0.0034 (5) | −0.0046 (6) |
C86 | 0.0250 (7) | 0.0329 (7) | 0.0294 (7) | 0.0023 (5) | 0.0035 (5) | −0.0056 (5) |
O1—C1 | 1.2338 (15) | C10—H10 | 0.9500 |
O18—C14 | 1.3677 (15) | C11—C16 | 1.4002 (17) |
O18—C17 | 1.4189 (17) | C11—C12 | 1.4020 (17) |
N1—C1 | 1.3566 (16) | C12—C13 | 1.3787 (18) |
N1—C2 | 1.4140 (16) | C12—H12 | 0.9500 |
N1—H1N | 0.868 (9) | C13—C14 | 1.3909 (17) |
N2—C1 | 1.3691 (16) | C13—H13 | 0.9500 |
N2—N3 | 1.3754 (14) | C14—C15 | 1.3937 (18) |
N2—H2N | 0.877 (9) | C15—C16 | 1.3865 (18) |
N3—C8 | 1.2964 (16) | C15—H15 | 0.9500 |
C2—C7 | 1.3914 (18) | C16—H16 | 0.9500 |
C2—C3 | 1.3945 (18) | C17—H17A | 0.9800 |
C3—C4 | 1.3891 (19) | C17—H17B | 0.9800 |
C3—H3 | 0.9500 | C17—H17C | 0.9800 |
C4—C5 | 1.389 (2) | C81—C86 | 1.3943 (18) |
C4—H4 | 0.9500 | C81—C82 | 1.3964 (18) |
C5—C6 | 1.385 (2) | C82—C83 | 1.3913 (19) |
C5—H5 | 0.9500 | C82—H82 | 0.9500 |
C6—C7 | 1.3923 (18) | C83—C84 | 1.387 (2) |
C6—H6 | 0.9500 | C83—H83 | 0.9500 |
C7—H7 | 0.9500 | C84—C85 | 1.383 (2) |
C8—C9 | 1.4616 (17) | C84—H84 | 0.9500 |
C8—C81 | 1.4922 (17) | C85—C86 | 1.3896 (19) |
C9—C10 | 1.3422 (17) | C85—H85 | 0.9500 |
C9—H9 | 0.9500 | C86—H86 | 0.9500 |
C10—C11 | 1.4643 (17) | ||
C14—O18—C17 | 117.36 (10) | C12—C11—C10 | 119.68 (11) |
C1—N1—C2 | 125.97 (10) | C13—C12—C11 | 121.53 (11) |
C1—N1—H1N | 115.3 (11) | C13—C12—H12 | 119.2 |
C2—N1—H1N | 118.7 (11) | C11—C12—H12 | 119.2 |
C1—N2—N3 | 118.57 (10) | C12—C13—C14 | 119.87 (11) |
C1—N2—H2N | 116.4 (10) | C12—C13—H13 | 120.1 |
N3—N2—H2N | 125.0 (10) | C14—C13—H13 | 120.1 |
C8—N3—N2 | 119.61 (10) | O18—C14—C13 | 115.85 (11) |
O1—C1—N1 | 124.31 (11) | O18—C14—C15 | 124.21 (11) |
O1—C1—N2 | 120.62 (11) | C13—C14—C15 | 119.94 (11) |
N1—C1—N2 | 115.07 (10) | C16—C15—C14 | 119.58 (11) |
C7—C2—C3 | 120.00 (12) | C16—C15—H15 | 120.2 |
C7—C2—N1 | 118.66 (11) | C14—C15—H15 | 120.2 |
C3—C2—N1 | 121.19 (12) | C15—C16—C11 | 121.45 (12) |
C4—C3—C2 | 119.51 (13) | C15—C16—H16 | 119.3 |
C4—C3—H3 | 120.2 | C11—C16—H16 | 119.3 |
C2—C3—H3 | 120.2 | O18—C17—H17A | 109.5 |
C5—C4—C3 | 120.59 (13) | O18—C17—H17B | 109.5 |
C5—C4—H4 | 119.7 | H17A—C17—H17B | 109.5 |
C3—C4—H4 | 119.7 | O18—C17—H17C | 109.5 |
C6—C5—C4 | 119.72 (12) | H17A—C17—H17C | 109.5 |
C6—C5—H5 | 120.1 | H17B—C17—H17C | 109.5 |
C4—C5—H5 | 120.1 | C86—C81—C82 | 118.53 (11) |
C5—C6—C7 | 120.25 (13) | C86—C81—C8 | 121.24 (11) |
C5—C6—H6 | 119.9 | C82—C81—C8 | 120.23 (11) |
C7—C6—H6 | 119.9 | C83—C82—C81 | 120.48 (12) |
C2—C7—C6 | 119.87 (12) | C83—C82—H82 | 119.8 |
C2—C7—H7 | 120.1 | C81—C82—H82 | 119.8 |
C6—C7—H7 | 120.1 | C84—C83—C82 | 120.22 (12) |
N3—C8—C9 | 125.20 (11) | C84—C83—H83 | 119.9 |
N3—C8—C81 | 114.57 (11) | C82—C83—H83 | 119.9 |
C9—C8—C81 | 120.09 (10) | C85—C84—C83 | 119.78 (12) |
C10—C9—C8 | 123.70 (11) | C85—C84—H84 | 120.1 |
C10—C9—H9 | 118.2 | C83—C84—H84 | 120.1 |
C8—C9—H9 | 118.2 | C84—C85—C86 | 120.07 (13) |
C9—C10—C11 | 125.93 (11) | C84—C85—H85 | 120.0 |
C9—C10—H10 | 117.0 | C86—C85—H85 | 120.0 |
C11—C10—H10 | 117.0 | C85—C86—C81 | 120.88 (13) |
C16—C11—C12 | 117.59 (11) | C85—C86—H86 | 119.6 |
C16—C11—C10 | 122.64 (11) | C81—C86—H86 | 119.6 |
C1—N2—N3—C8 | −172.44 (11) | C10—C11—C12—C13 | −177.65 (11) |
C2—N1—C1—O1 | −10.4 (2) | C11—C12—C13—C14 | 2.34 (19) |
C2—N1—C1—N2 | 169.88 (12) | C17—O18—C14—C13 | −163.67 (12) |
N3—N2—C1—O1 | 176.21 (11) | C17—O18—C14—C15 | 15.55 (17) |
N3—N2—C1—N1 | −4.07 (16) | C12—C13—C14—O18 | 177.07 (11) |
C1—N1—C2—C7 | 144.18 (13) | C12—C13—C14—C15 | −2.19 (18) |
C1—N1—C2—C3 | −40.29 (19) | O18—C14—C15—C16 | −178.53 (11) |
C7—C2—C3—C4 | 1.68 (19) | C13—C14—C15—C16 | 0.66 (18) |
N1—C2—C3—C4 | −173.79 (11) | C14—C15—C16—C11 | 0.76 (19) |
C2—C3—C4—C5 | 0.48 (19) | C12—C11—C16—C15 | −0.63 (18) |
C3—C4—C5—C6 | −1.7 (2) | C10—C11—C16—C15 | 175.98 (12) |
C4—C5—C6—C7 | 0.7 (2) | N3—C8—C81—C86 | 127.82 (13) |
C3—C2—C7—C6 | −2.62 (19) | C9—C8—C81—C86 | −56.24 (16) |
N1—C2—C7—C6 | 172.96 (11) | N3—C8—C81—C82 | −51.92 (16) |
C5—C6—C7—C2 | 1.42 (19) | C9—C8—C81—C82 | 124.02 (12) |
N2—N3—C8—C9 | 3.18 (18) | C86—C81—C82—C83 | 0.97 (18) |
N2—N3—C8—C81 | 178.88 (10) | C8—C81—C82—C83 | −179.28 (11) |
N3—C8—C9—C10 | 154.62 (12) | C81—C82—C83—C84 | −1.90 (19) |
C81—C8—C9—C10 | −20.85 (18) | C82—C83—C84—C85 | 1.1 (2) |
C8—C9—C10—C11 | −169.19 (11) | C83—C84—C85—C86 | 0.6 (2) |
C9—C10—C11—C16 | 9.05 (19) | C84—C85—C86—C81 | −1.6 (2) |
C9—C10—C11—C12 | −174.41 (12) | C82—C81—C86—C85 | 0.76 (19) |
C16—C11—C12—C13 | −0.93 (18) | C8—C81—C86—C85 | −178.98 (12) |
Cg1 and Cg2 are the centroids of the C2–C7 and C81–C86 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N3 | 0.87 (1) | 2.18 (2) | 2.6029 (15) | 110 (1) |
N2—H2N···O1i | 0.88 (1) | 2.05 (1) | 2.9184 (14) | 171 (1) |
C9—H9···O1i | 0.95 | 2.39 | 3.2913 (15) | 159 |
C15—H15···Cg1i | 0.95 | 2.88 | 3.5125 (14) | 125 |
C6—H6···Cg2ii | 0.95 | 2.92 | 3.8296 (14) | 161 |
C12—H12···Cg1iii | 0.95 | 2.75 | 3.4715 (14) | 133 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1, −y+1, −z+1. |
Contact | Percentage contribution |
H···H | 50.2 |
C···H/H···C | 31.6 |
O···H/H···O | 10.7 |
N···H/H···N | 4.2 |
N···O /O···N | 0.9 |
C···O/O···C | 0.9 |
C···C | 0.8 |
C···N/N···C | 0.7 |
Contact | Distance | Symmetry operation |
C17···N3 | 3.1147 (18) | 3/2 - x, -1/2 + y, 1/2 - z |
C9···H82 | 2.72 | 1 - x, 1 - y, 1 - z |
H86···H86 | 2.26 | 1 - x, 1 - y, -z |
H12···H17C | 2.26 | -1/2 + x, 1/2 - y, -1/2 + z |
O1···H16 | 2.61 | 2 - x, 1 - y, 1 - z |
O18···H84 | 2.67 | 1/2 - x, -1/2 + y, 1/2 - z |
C8···H82 | 2.87 | 1 - x, 1 - y, 1 - z |
C12···H17C | 2.79 | -1/2 + x, 1/2 - y, - 1/2 + z |
Footnotes
‡Additional correspondence author, e-mail: thahira@upm.edu.my.
Acknowledgements
We thank the staff of the University of Malaya's X-ray diffraction laboratory for the data collection.
Funding information
The authors are grateful for support from the Universiti Putra Malaysia, under their Research University Grant Scheme (RUGS Nos 9199834 and 9174000) and to the Malaysian Ministry of Science, Technology and Innovation (grants No. 09–02-04–0752-EA001 and 01-01-16-1833FR).
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