(4-Nitro­phen­yl)methyl 2,3-di­hydro-1H-pyrrole-1-carboxyl­ate: crystal structure and Hirshfeld analysis

Zukerman-Schpector, J.; Soto-Monsalve, M.; De Almeida Santos, R.H.; Garcia, A.L.L.; Correia, C.R.D.; Jotani, M.M.; Tiekink, E.R.T.

doi:10.1107/S2056989018002451

research communications

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ISSN: 2056-9890

Volume 74| Part 3| March 2018| Pages 371-375

https://doi.org/10.1107/S2056989018002451

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(4-Nitrophenyl)methyl 2,3-dihydro-1H-pyrrole-1-carboxylate: crystal structure and Hirshfeld analysis

Julio Zukerman-Schpector,^a ^* Monica Soto-Monsalve,^b Regina H. De Almeida Santos,^b Ariel L. L. Garcia,^c Carlos Roque D. Correia,^c Mukesh M. Jotani ^d and Edward R. T. Tiekink ^e ‡

^aLaboratório de Cristalografia, Esterodinâmica e Modelagem Molecular, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, ^bInstituto de Química de São Carlos, Universidade de São Paulo, São Carlos, SP, Brazil, ^cInstituto de Química, Universidade Estadual de Campinas, UNICAMP, CP 6154, CEP. 13084-971, Campinas, São Paulo, Brazil, ^dDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380 001, India, and ^eCentre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
^*Correspondence e-mail: julio@power.ufscar.br

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 7 February 2018; accepted 10 February 2018; online 23 February 2018)

In the title compound, C₁₂H₁₂N₂O₄, the dihydropyrrole ring is almost planar (r.m.s. deviation = 0.0049 Å) and is nearly coplanar with the adjacent C₂O₂ residue [dihedral angle = 4.56 (9)°], which links to the 4-nitrobenzene substituent [dihedral angle = 4.58 (8)°]. The molecule is concave, with the outer rings lying to the same side of the central C₂O₂ residue and being inclined to each other [dihedral angle = 8.30 (7)°]. In the crystal, supramolecular layers parallel to (10-5) are sustained by nitrobenzene-C—H⋯O(carbonyl) and pyrrole-C—H⋯O(nitro) interactions. The layers are connected into a three-dimensional architecture by π(pyrrole)–π(nitrobenzene) stacking [inter-centroid separation = 3.7414 (10) Å] and nitro-O⋯π(pyrrole) interactions.

Keywords: crystal structure; dihydropyrrole; ester; nitro-O⋯π interactions; Hirshfeld surface analysis.

CCDC reference: 1823263

1. Chemical context

Many hydroxylated prolines and homoprolines have the ability to inhibit glycosides and glycosyltransferases, key enzymes in biosynthesis and the processing of glycoproteins and glycolipids (Rule et al., 1985 ; Fleet & Son, 1988 ; Wong, 1997 ). Glycoproteins are macromolecules involved in the recognition (cell–cell interactions and host–pathogen) and control of mechanisms associated with biological structures. Thus, compounds that are capable of inhibiting the biosynthetic pathway of glycoproteins have broad chemotherapeutic potential in the treatment of metabolic diseases such as diabetes, obesity, cancer, tuberculosis and viral infections among others (Kordik & Reitz, 1999 ; Nishimura, 2003 ; Cheng & Josse, 2004 ). Some hydroxylated prolines are of interest in this context owing to their ability to inhibit glycosidases and because they are found as substructures of natural bioactive compounds. For example, (2S,3R,4S)-3,4-dihydroxyproline (II), see scheme, is found as a component of the repeating decapeptide sequence of the Mefp1 adhesive protein (Mytilus edulis foot protein 1), produced by the marine mussel, Mytilus edulis (Taylor et al., 1994 ; Taylor & Weir, 2000 ). This protein is responsible for the fixation of mussels to rocks. As a part of a study into the development of new and flexible methodologies for the efficient synthesis of several natural and synthetic products with important pharmacological properties, using the Heck–Matsuda arylation reaction as a crucial step, (II) was prepared from the title compound, (I), for the purpose of evaluating the best protecting group for use in future syntheses of greater complexity (Garcia, 2008 ). During the Heck–Matsuda reaction, it was found that the protective group of the nitrogen atom in (I) exerted some influence on the reaction time, but did not influence the yield of the expected intermediate when compared to the Heck–Matsuda reaction applied to the enecarbamate, ethyl 2,3-dihydro-1H-pyrrole-1-carboxylate (Garcia, 2008). It is noted that the first synthesis of (I) was actually reported nearly 50 years ago (Heine & Mente, 1971 ). Herein, the crystal and molecular structures of (I) are described along with an analysis of the calculated Hirshfeld surfaces.

2. Structural commentary

The molecular structure of (I), Fig. 1, is a 1-methylene-4-nitrobenzene ester derived from dihydropyrrole-1-carboxylic acid. In (I), the dihydropyrrole ring is almost planar with the r.m.s. deviation of the five fitted atoms being 0.0049 Å, and the maximum deviation of any of the constituent atoms being 0.0065 (11) Å for atom C2. The adjacent C₂O₂ residue (O1,O2,C5,C6) is essentially co-planar, with the dihedral angle between the two planes being 4.56 (9)°. The planarity extends to the 4-nitrobenzene ring, with the dihedral angle between the C₂O₂ and C₆ planes being 4.58 (8)°. However, the molecule is not planar but rather is curved as the outer rings lie to the same side of the central C₂O₂ residue; the dihedral angle = 8.30 (7)°. To a first approximation, the nitro group is co-planar with the benzene ring to which is connected, as seen in the value of the O4—N2—C10—C9 torsion angle of 173.50 (15)°.

Figure 1
The molecular structure of (I)

, showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.

3. Supramolecular features

The molecular packing of (I) features a variety of directional interactions, Table 1. Thus, nitrobenzene-C12—H⋯O1(carbonyl) interactions occur over a centre of inversion and lead to 14-membered {⋯HC₃OCO}₂ synthons. The dimeric aggregates are connected into a supramolecular layer via pyrrole-C4—H⋯O3(nitro) interactions. The layers lie parallel to (10 $[\overline{5}]$ ), Fig. 2a. Two types of interactions connect layers into a three-dimensional architecture.Thus, π(N1,C1–C4)–π(C7–C12)ⁱ stacking interactions occur between pyrrole and nitrobenzene rings: inter-centroid separation = 3.7414 (10) Å and angle of inclination = 7.99 (9)° for symmetry code: (i): $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z. The other interactions between layers are of the type nitro-O4⋯π(N1,C1–C4), Table 1. These interactions are well known in consolidating the packing of nitro-containing compounds (Huang et al., 2008 ). A view of the unit-cell contents is shown in Fig. 2b.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1/C1–C4 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O3ⁱ	0.93	2.40	3.227 (2)	149
C12—H12⋯O1ⁱⁱ	0.93	2.47	3.318 (2)	152
N2—O4⋯Cg1ⁱⁱⁱ	1.22 (1)	3.42 (1)	3.6327 (16)	90 (1)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z+1; (iii) -x+1, -y+1, -z+1.

Figure 2
Molecular packing in (I)

: (a) view of the supramolecular layer parallel to (10 $[\overline{5}]$ ) plane and (b) view of the unit-cell contents shown in projection down the b axis. The C—H⋯O, N—O⋯π and π–π contacts are shown as orange, blue and purple dashed lines, respectively.

4. Hirshfeld surface analysis

The Hirshfeld surface calculations for (I) were performed as per a recent study (Zukerman-Schpector et al., 2017 ) and serve to provide additional information on the molecular packing.

In addition to the bright-red spots on the Hirshfeld surface mapped over d_norm in Fig. 3 near the pyrrole-H4, nitrobenzene-H12, and the nitro-O3 and carbonyl-O1 atoms, representing the respective donors and acceptors of intermolecular C—H⋯O interactions (labelled `1' and `2'), the diminutive red spots appearing near the pyrrole-H3 and nitro-O4 atoms in Fig. 3 (labelled `3') also indicate the influence of comparatively weak C—H⋯O contacts in the crystal (Table 2). The nitrobenzene-C9 and C11 atoms form inter-layer short C⋯H/H⋯C and C⋯C contacts (Table 2) with the pyrrole-H1B and ester-C5 atoms, respectively, Fig. 4a. The other short interatomic C⋯H/H⋯C contacts between the nitrobenzene-H11 and pyrrole-C2 and C3 atoms (Table 2) are intra-layer, Fig. 4a. The building up of the three-dimensional architecture through π–π-stacking interactions and nitro-N—O⋯π(pyrrole) contacts is highlighted in Fig. 4b, showing the Hirshfeld surface mapped over the electrostatic potential.

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

Contact	Distance	Symmetry operation
O4⋯H3	2.47	x, −1 + y, z
C5⋯C11	3.37	$[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
C2⋯H11	2.81	x, −1 + y, z
C3⋯H11	2.91	x, − 1 + y, z
C9⋯H1B	2.92	$[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z

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

mapped over d_norm in the range −0.225 to +1.393 au, showing intermolecular C—H⋯O contacts as black dashed lines.

Figure 4
Views of Hirshfeld surfaces for (I)

mapped: (a) over d_norm in the range −0.225 to + 1.393 au, highlighting inter- and intra-layer C⋯C and C⋯H/H⋯C contacts as black and sky-blue dashed lines, respectively, and (b) over the electrostatic potential in the range ±0.077 au (the red and blue regions represent negative and positive electrostatic potentials, respectively), showing intermolecular N—O⋯π and π–π contacts as black dotted lines.

The overall two-dimensional fingerprint plot and those delineated into H⋯H, O⋯H/H⋯O and C⋯H/H⋯C contacts (McKinnon et al., 2007 ) are illustrated in Fig. 5a–d, respectively, and the percentage contribution from the identified interatomic contacts to the Hirshfeld surface are summarized in Table 3. The comparatively low, i.e. 39.0%, contribution from H⋯H contacts to the overall surface is due to the involvement of many hydrogen atoms in directional intermolecular interactions, e.g. C—H⋯O, π (Tables 1 and 2). Hence, the interatomic H⋯H contacts have a reduced influence in the crystal as their interatomic separations are equal to or greater than sum of their van der Waals radii (Fig. 5b). Conversely, the relatively significant contribution of 33.8% from O⋯H/H⋯O contacts to the Hirshfeld surface is consistent with this observation. The fingerprint plot delineated into O⋯H/H⋯O contacts (Fig. 5c) features a pair of green aligned points within the pair of spikes with their tips at d_e + d_i ∼2.3 Å superimposed upon a distribution blue points characterizing intermolecular C—H⋯O interactions. The short interatomic C⋯H/H⋯C contacts in the inter- and intra-layer regions are represented by the two pairs of short forceps-like spikes at d_e + d_i ∼2.8 and 2.9 Å, respectively, in Fig. 5d. The small but discernible contributions from interatomic C⋯C and C⋯N/N⋯C contacts (Table 3) result from short inter-layer contacts and π–π stacking interactions. The presence of the N—O⋯π contact in the structure is also evident from the contribution of C⋯O/O⋯C and N⋯O/O⋯N contacts to the Hirshfeld surface as summarized in Table 3. The small contributions from the other remaining interatomic contacts (Table 3) have a negligible influence on the packing.

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

Contact	Percentage contribution
H⋯H	39.0
O⋯H/H⋯O	33.8
C⋯H/H⋯C	15.2
C⋯O/O⋯C	3.7
C⋯C	2.4
C⋯N/N⋯C	1.7
O⋯O	1.4
N⋯H/H⋯N	1.0
N⋯O/O⋯N	0.9
N⋯N	0.9

Figure 5
(a) The full two-dimensional fingerprint plot for (I)

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

5. Database survey

Dihydropyrrole rings as found in (I) have rarely been characterized crystallographically and only one structure is deposited in the Cambridge Structural Database (Groom et al., 2016 ), namely the adduct, ZnI₂(4,5-dihydro-3H-pyrrole)₂ (refcode WAZXAW; Freer et al., 1993 ). Here, despite having sp²-carbon centres as in (I), the rings are planar with one lying on a crystallographic mirror plane and the other disposed across a mirror plane (r.m.s. deviation = 0.007 Å), implying disorder in the latter.

6. Synthesis and crystallization

A solution of (4-nitrophenyl)methyl 2-hydroxypyrrolidine-1-carboxylate (2.85 g, 10.704 mmol) in toluene (100 ml) was cooled to 273 K in an ice/water bath. Under an atmosphere of nitrogen, 2,4-lutidine (6.2 ml, 53.634 mmol) was added to this solution. The solution was stirred for 15 min at 273 K. A trifluoroacetic anhydride (TFAA) solution (13.2 ml of a 0.8 M solution, 10.56 mmol) in dry toluene was then added. The bath was removed and the solution stirred for 2 h at room temperature. Subsequently, the flask was immersed for 20 min in an oil bath preheated to 393–403 K with a reflux condenser. The solution was concentrated in a rotary evaporator and the residue was purified by flash column chromatography on silica gel, using a mixture of EtOAc/n-hexane (1:4) as the eluent. The yield of (I) was 2.103 g (80% based on TFAA). Irregular yellow crystals of (I) were obtained from the slow evaporation of its CH₂Cl₂ solution.

Spectroscopic characterization. ¹H NMR (300 MHz, Py-d₅, solution comprises rotamers): δ 8.21 (apparent d, J = 7.3 Hz, 2H, H3′ and H5′), 7.54 (d, J = 8.1 Hz, 2H, H2′ and H6′), 6.80 and 6.68 (2 × m, 1H, H2), 5.35 (s, 2H, CH₂), 5.03 (m, 1H, H3), 3.71 (apparent t, J = 9.5 Hz, 2H, H5a,5b), 2.46 (apparent quint., J = 9.5 Hz, 2H, H4a,4b). ¹³C NMR (75 MHz, Py-d₅, solution comprises rotamers): δ = 152.3 (CO₂R), 151.5 (CO₂R), 147.8 (C4′), 144.9 (C1′), 129.8 (C2), 129.2 (C2), 128.4 (C2′ and C6′), 128.3 (C2′ and C6′), 123.9 (C3′ and C5′), 109.4 (C3), 65.8 (CH₂), 65.6 (CH₂), 45.8 (C5), 45.4 (C5), 30.1 (C4), 29.0 (C4). ESI–MS (m/z) calculated for C₁₂H₁₂N₂O₄ 248.07971, found 248.07876.

7. Refinement details

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 = 0.93–0.97 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2U_eq(C).

Table 4
Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂O₄
M_r	248.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	290
a, b, c (Å)	9.0385 (3), 12.2518 (4), 10.5452 (3)
β (°)	96.102 (1)
V (Å³)	1161.14 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.52 × 0.22 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1995 )
T_min, T_max	0.724, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	23727, 2394, 2013
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.117, 1.09
No. of reflections	2394
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.18
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SIR2014 (Burla et al., 2015 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ), MarvinSketch (ChemAxon, 2010 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1823263

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018002451/hb7736sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018002451/hb7736Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018002451/hb7736Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: MarvinSketch (ChemAxon, 2010) and publCIF (Westrip, 2010).

(4-Nitrophenyl)methyl 2,3-dihydro-1H-pyrrole-1-carboxylate top

Crystal data top

C₁₂H₁₂N₂O₄	F(000) = 520
M_r = 248.24	D_x = 1.420 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.0385 (3) Å	Cell parameters from 9984 reflections
b = 12.2518 (4) Å	θ = 2.6–26.5°
c = 10.5452 (3) Å	µ = 0.11 mm⁻¹
β = 96.102 (1)°	T = 290 K
V = 1161.14 (6) Å³	Irregular, yellow
Z = 4	0.52 × 0.22 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	2013 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.023
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	θ_max = 26.5°, θ_min = 2.6°
T_min = 0.724, T_max = 0.745	h = −9→11
23727 measured reflections	k = −15→15
2394 independent reflections	l = −13→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0501P)² + 0.3399P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2394 reflections	Δρ_max = 0.16 e Å⁻³
163 parameters	Δρ_min = −0.18 e Å⁻³

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	0.95640 (13)	0.32527 (10)	0.51064 (14)	0.0665 (4)
O2	0.73098 (11)	0.38092 (8)	0.41873 (11)	0.0489 (3)
O3	0.20267 (15)	0.75353 (13)	0.19648 (17)	0.0896 (5)
O4	0.34938 (16)	0.88645 (10)	0.24771 (15)	0.0720 (4)
N1	0.77129 (13)	0.20438 (10)	0.45899 (13)	0.0468 (3)
N2	0.32222 (15)	0.78902 (12)	0.24108 (13)	0.0532 (3)
C1	0.86033 (17)	0.10688 (13)	0.49447 (17)	0.0514 (4)
H1A	0.8888	0.1046	0.5858	0.062*
H1B	0.9495	0.1052	0.4508	0.062*
C2	0.75720 (19)	0.01184 (14)	0.45210 (19)	0.0581 (4)
H2A	0.7987	−0.0322	0.3881	0.070*
H2B	0.7401	−0.0342	0.5239	0.070*
C3	0.61637 (18)	0.06612 (14)	0.39787 (18)	0.0558 (4)
H3	0.5308	0.0292	0.3652	0.067*
C4	0.62960 (16)	0.17304 (13)	0.40258 (16)	0.0505 (4)
H4	0.5549	0.2216	0.3725	0.061*
C5	0.83046 (16)	0.30513 (12)	0.46670 (15)	0.0443 (3)
C6	0.78181 (17)	0.49186 (12)	0.42996 (17)	0.0490 (4)
H6A	0.8665	0.5019	0.3819	0.059*
H6B	0.8127	0.5089	0.5186	0.059*
C7	0.65706 (15)	0.56621 (11)	0.37923 (13)	0.0400 (3)
C8	0.51427 (16)	0.52938 (12)	0.33957 (14)	0.0442 (3)
H8	0.4927	0.4553	0.3436	0.053*
C9	0.40373 (17)	0.60201 (12)	0.29406 (15)	0.0445 (3)
H9	0.3082	0.5774	0.2672	0.053*
C10	0.43818 (16)	0.71143 (12)	0.28935 (13)	0.0414 (3)
C11	0.57881 (17)	0.75032 (12)	0.32932 (16)	0.0481 (4)
H11	0.5996	0.8246	0.3262	0.058*
C12	0.68753 (17)	0.67727 (12)	0.37385 (16)	0.0478 (4)
H12	0.7828	0.7025	0.4007	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0418 (6)	0.0487 (7)	0.1027 (10)	−0.0039 (5)	−0.0220 (6)	0.0065 (6)
O2	0.0409 (6)	0.0331 (5)	0.0694 (7)	0.0014 (4)	−0.0086 (5)	0.0017 (4)
O3	0.0510 (8)	0.0752 (10)	0.1334 (14)	0.0052 (7)	−0.0338 (8)	0.0061 (9)
O4	0.0699 (9)	0.0433 (7)	0.0990 (10)	0.0135 (6)	−0.0083 (7)	0.0061 (6)
N1	0.0352 (6)	0.0369 (6)	0.0660 (8)	0.0025 (5)	−0.0052 (5)	0.0040 (6)
N2	0.0467 (8)	0.0498 (8)	0.0610 (8)	0.0086 (6)	−0.0039 (6)	0.0025 (6)
C1	0.0442 (8)	0.0408 (8)	0.0681 (10)	0.0078 (6)	0.0017 (7)	0.0066 (7)
C2	0.0561 (10)	0.0417 (8)	0.0766 (11)	0.0010 (7)	0.0070 (8)	0.0059 (8)
C3	0.0440 (8)	0.0476 (9)	0.0752 (11)	−0.0077 (7)	0.0032 (8)	−0.0010 (8)
C4	0.0342 (8)	0.0459 (8)	0.0696 (10)	−0.0006 (6)	−0.0026 (7)	0.0024 (7)
C5	0.0363 (7)	0.0403 (8)	0.0545 (8)	0.0023 (6)	−0.0034 (6)	0.0027 (6)
C6	0.0432 (8)	0.0352 (7)	0.0660 (10)	−0.0034 (6)	−0.0066 (7)	0.0011 (7)
C7	0.0387 (7)	0.0369 (7)	0.0435 (7)	0.0005 (6)	−0.0006 (6)	−0.0008 (6)
C8	0.0447 (8)	0.0347 (7)	0.0519 (8)	−0.0042 (6)	−0.0009 (6)	0.0008 (6)
C9	0.0367 (7)	0.0434 (8)	0.0516 (8)	−0.0046 (6)	−0.0028 (6)	−0.0015 (6)
C10	0.0391 (7)	0.0406 (8)	0.0434 (7)	0.0050 (6)	−0.0007 (6)	−0.0006 (6)
C11	0.0461 (8)	0.0325 (7)	0.0640 (9)	−0.0023 (6)	−0.0019 (7)	−0.0013 (6)
C12	0.0370 (8)	0.0392 (8)	0.0647 (9)	−0.0040 (6)	−0.0056 (7)	−0.0029 (7)

Geometric parameters (Å, º) top

O1—C5	1.2080 (18)	C3—H3	0.9300
O2—C5	1.3527 (17)	C4—H4	0.9300
O2—C6	1.4356 (17)	C6—C7	1.503 (2)
O3—N2	1.2123 (18)	C6—H6A	0.9700
O4—N2	1.2193 (18)	C6—H6B	0.9700
N1—C5	1.3442 (19)	C7—C8	1.389 (2)
N1—C4	1.4070 (18)	C7—C12	1.391 (2)
N1—C1	1.4665 (18)	C8—C9	1.385 (2)
N2—C10	1.4656 (19)	C8—H8	0.9300
C1—C2	1.528 (2)	C9—C10	1.378 (2)
C1—H1A	0.9700	C9—H9	0.9300
C1—H1B	0.9700	C10—C11	1.381 (2)
C2—C3	1.495 (2)	C11—C12	1.374 (2)
C2—H2A	0.9700	C11—H11	0.9300
C2—H2B	0.9700	C12—H12	0.9300
C3—C4	1.316 (2)

C5—O2—C6	115.15 (11)	O1—C5—O2	124.40 (14)
C5—N1—C4	127.92 (13)	N1—C5—O2	111.31 (12)
C5—N1—C1	121.91 (12)	O2—C6—C7	108.85 (12)
C4—N1—C1	109.61 (12)	O2—C6—H6A	109.9
O3—N2—O4	122.62 (15)	C7—C6—H6A	109.9
O3—N2—C10	118.50 (14)	O2—C6—H6B	109.9
O4—N2—C10	118.88 (14)	C7—C6—H6B	109.9
N1—C1—C2	104.18 (12)	H6A—C6—H6B	108.3
N1—C1—H1A	110.9	C8—C7—C12	119.16 (13)
C2—C1—H1A	110.9	C8—C7—C6	123.24 (13)
N1—C1—H1B	110.9	C12—C7—C6	117.59 (12)
C2—C1—H1B	110.9	C9—C8—C7	120.57 (14)
H1A—C1—H1B	108.9	C9—C8—H8	119.7
C3—C2—C1	103.94 (13)	C7—C8—H8	119.7
C3—C2—H2A	111.0	C10—C9—C8	118.68 (13)
C1—C2—H2A	111.0	C10—C9—H9	120.7
C3—C2—H2B	111.0	C8—C9—H9	120.7
C1—C2—H2B	111.0	C9—C10—C11	121.93 (14)
H2A—C2—H2B	109.0	C9—C10—N2	119.17 (13)
C4—C3—C2	110.99 (14)	C11—C10—N2	118.90 (13)
C4—C3—H3	124.5	C12—C11—C10	118.75 (14)
C2—C3—H3	124.5	C12—C11—H11	120.6
C3—C4—N1	111.26 (14)	C10—C11—H11	120.6
C3—C4—H4	124.4	C11—C12—C7	120.90 (13)
N1—C4—H4	124.4	C11—C12—H12	119.5
O1—C5—N1	124.29 (13)	C7—C12—H12	119.5

C5—N1—C1—C2	−171.59 (15)	O2—C6—C7—C12	−175.74 (14)
C4—N1—C1—C2	0.51 (18)	C12—C7—C8—C9	0.6 (2)
N1—C1—C2—C3	−0.98 (18)	C6—C7—C8—C9	179.78 (14)
C1—C2—C3—C4	1.2 (2)	C7—C8—C9—C10	−0.2 (2)
C2—C3—C4—N1	−0.9 (2)	C8—C9—C10—C11	−0.4 (2)
C5—N1—C4—C3	171.74 (16)	C8—C9—C10—N2	179.85 (13)
C1—N1—C4—C3	0.2 (2)	O3—N2—C10—C9	−6.2 (2)
C4—N1—C5—O1	−175.78 (17)	O4—N2—C10—C9	173.50 (15)
C1—N1—C5—O1	−5.2 (3)	O3—N2—C10—C11	174.03 (17)
C4—N1—C5—O2	4.1 (2)	O4—N2—C10—C11	−6.2 (2)
C1—N1—C5—O2	174.65 (14)	C9—C10—C11—C12	0.6 (2)
C6—O2—C5—O1	−3.7 (2)	N2—C10—C11—C12	−179.62 (14)
C6—O2—C5—N1	176.46 (13)	C10—C11—C12—C7	−0.2 (2)
C5—O2—C6—C7	−176.99 (13)	C8—C7—C12—C11	−0.4 (2)
O2—C6—C7—C8	5.1 (2)	C6—C7—C12—C11	−179.60 (15)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N1/C1–C4 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O3ⁱ	0.93	2.40	3.227 (2)	149
C12—H12···O1ⁱⁱ	0.93	2.47	3.318 (2)	152
N2—O4···Cg1ⁱⁱⁱ	1.22 (1)	3.42 (1)	3.6327 (16)	90 (1)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1.

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

Contact	Distance	Symmetry operation
O4···H3	2.47	x, -1 + y, z
C5···C11	3.37	3/2 - x, -1/2 + y, 1/2 - z
C2···H11	2.81	x, -1 + y, z
C3···H11	2.91	x, - 1 + y, z
C9···H1B	2.92	3/2 - x, 1/2 + y, 1/2 - z

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

Contact	Percentage contribution
H···H	39.0
O···H/H···O	33.8
C···H/H···C	15.2
C···O/O···C	3.7
C···C	2.4
C···N/N···C	1.7
O···O	1.4
N···H/H···N	1.0
N···O/O···N	0.9
N···N	0.9

Footnotes

‡Additional correspondence author, e-mail: edwardt@sunway.edu.my.

Funding information

The Brazilian agencies Coordination for the Improvement of Higher Education Personnel, CAPES and National Council for Scientific and Technological Development, CNPq, for a fellowship to JZ-S (305626/2013–2) are acknowledged for support.

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