1-{(E)-[(2E)-3-(4-Meth­oxy­phen­yl)-1-phenyl­prop-2-en-1-yl­idene]amino}-3-phenyl­urea: crystal structure and Hirshfeld surface analysis

Tan, M.Y.; Crouse, K.A.; Ravoof, T.B.S.A.; Jotani, M.M.; Tiekink, E.R.T.

doi:10.1107/S2056989017014128

research communications

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ISSN: 2056-9890

Volume 73| Part 11| November 2017| Pages 1607-1611

https://doi.org/10.1107/S2056989017014128

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1-{(E)-[(2E)-3-(4-Methoxyphenyl)-1-phenylprop-2-en-1-ylidene]amino}-3-phenylurea: crystal structure and Hirshfeld surface analysis

Ming Yueh Tan,^a Karen A. Crouse,^b,^c Thahira B. S. A. Ravoof,^b ‡ Mukesh M. Jotani ^d and Edward R. T. Tiekink ^e ^*

^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

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 27 September 2017; accepted 30 September 2017; online 6 October 2017)

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%.

Keywords: crystal structure; urea derivative; hydrogen bonding; Hirshfeld surface analysis.

CCDC reference: 1577439

1. Chemical context

Chalcones are natural or synthetic compounds comprising an open-chain flavonoid structure in which the two aromatic rings are connected 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 Schiff bases, 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 ).

In 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)°.

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1.

Figure 1
The molecular structure of (I)

, showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.

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.

Figure 2
The molecular packing in (I)

: (a) a view of the supramolecular dimer sustained by amine-N—H⋯O(carbonyl) hydrogen bonds and supported by ethylene-C—H⋯O(amide) interactions, shown as blue and orange dashed lines, respectively, and (b) a view of the unit-cell contents shown in projection down the c axis. The C—H⋯π interactions are shown as purple dashed lines.

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 d_norm 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 d_norm-mapped Hirshfeld surface are shown in Fig. 5b and c, respectively.

Table 2
Summary of short interatomic contacts (Å) in (I)

Contact	Distance	Symmetry operation
C17⋯N3	3.1147 (18)	$[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
C9⋯H82	2.72	1 − x, 1 − y, 1 − z
H86⋯H86	2.26	1 − x, 1 − y, −z
H12⋯H17C	2.26	− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z
O1⋯H16	2.61	2 − x, 1 − y, 1 − z
O18⋯H84	2.67	$[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
C8⋯H82	2.87	1 − x, 1 − y, 1 − z
C12⋯H17C	2.79	− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z

Table 3
Percentage contributions of interatomic contacts to the Hirshfeld surface for (I)

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

Figure 3
Two views of the Hirshfeld surface for (I)

mapped over d_norm in the ranges (a) −0.225 to +1.332 a.u. and (b) −0.110 to +1.332 a.u.

Figure 4
Two views of the Hirshfeld surface for (I)

mapped over the electrostatic potential in the range −0.095 to +0.108 a.u. The red and blue regions represent negative and positive electrostatic potentials, respectively.

Figure 5
Views of the Hirshfeld surfaces about a reference molecule mapped over (a) the shape-index property showing C—H⋯π/π⋯H—C interactions involving the C6 atom with the imine–phenyl C81–C86 ring (black dotted lines) and the C12 and C15 atoms with the amine–phenyl C2–C7 rings by red and white dotted lines, respectively, (b) the shape-index property about a reference molecule showing short O⋯H/H⋯O contacts by red dotted lines and intermolecular N—H⋯O and C—H⋯O interactions by black dashed lines and (c) d_norm showing short interatomic H⋯H, C⋯N/N⋯C and C⋯H/H⋯C contacts by sky-blue, black and red dashed lines, respectively.

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 d_e + d_i ∼ 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 d_e + d_i ∼ 2.3 Å distance correspond to short interatomic H⋯H contacts between methoxybenzene-H12 and methoxy-H17C atoms, Table 2.

Figure 6
(a) The full two-dimensional fingerprint plot for (I)

and those delineated into (b) H⋯H, (c) C⋯H/H⋯C, (d) O⋯H/H⋯O and (e) N⋯H/H⋯N contacts.

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 d_e + d_i = 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 asymmetric unit, 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 steric hindrance 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 refinement details are summarized in Table 4. The carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2–1.5U_eq(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 U_iso(H) set to 1.2U_eq(N).

Table 4
Experimental details

Crystal data
Chemical formula	C₂₃H₂₁N₃O₂
M_r	371.43
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	9.2879 (2), 21.9137 (3), 9.6740 (2)
β (°)	105.187 (2)
V (Å³)	1900.21 (6)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.68
Crystal size (mm)	0.31 × 0.29 × 0.16

Data collection
Diffractometer	Oxford Diffraction Xcaliber Eos Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011 )
T_min, T_max	0.904, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	25449, 3678, 3380
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.104, 1.03
No. of reflections	3678
No. of parameters	260
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.24
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1577439

Crystal structure: contains datablock . DOI: https://doi.org/10.1107/S2056989017014128/hb7709sup1.cif

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

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: 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).

1-{(E)-[(2E)-3-(4-Methoxyphenyl)-1-phenylprop-2-en-1-ylidene]amino}-3-phenylurea top

Crystal data top

C₂₃H₂₁N₃O₂	F(000) = 784
M_r = 371.43	D_x = 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

Data collection top

Oxford Diffraction Xcaliber Eos Gemini diffractometer	3678 independent reflections
Radiation source: fine-focus sealed tube	3380 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 16.1952 pixels mm^-1	θ_max = 71.4°, θ_min = 4.0°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −26→26
T_min = 0.904, T_max = 1.000	l = −11→11
25449 measured reflections

Refinement top

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(F_o²) + (0.0583P)² + 0.6586P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3678 reflections	Δρ_max = 0.22 e Å⁻³
260 parameters	Δρ_min = −0.24 e Å⁻³
2 restraints

Special details top

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) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

Percentage contributions of interatomic contacts to the Hirshfeld surface for (I) top

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

Summary of short interatomic contacts (Å) in (I) top

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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