Crystal structure and Hirshfeld surface analysis of 2-(4-nitro­phen­yl)-2-oxoethyl benzoate

Sheshadri, S.N.; Chidan Kumar, C.S.; Naveen, S.; Veeraiah, M.K.; Raghava Reddy, K.; Warad, I.

doi:10.1107/S2056989019013975

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ISSN: 2056-9890

Volume 75| Part 11| November 2019| Pages 1719-1723

https://doi.org/10.1107/S2056989019013975

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Crystal structure and Hirshfeld surface analysis of 2-(4-nitrophenyl)-2-oxoethyl benzoate

S. N. Sheshadri,^a C. S. Chidan Kumar,^b S. Naveen,^c ^* M. K. Veeraiah,^d Kakarla Raghava Reddy ^e and Ismail Warad ^f ^*

^aDepartment of Chemistry, GSSS Institute of Engineering and Technology for Women, Mysuru 570 016, Karnataka, India, ^bDepartment of Engineering Chemistry, Vidya Vikas Institute of Engineering & Technology, Visvesvaraya Technological University, Alanahally, Mysuru 570 028, Karnataka, India, ^cDepartment of Physics, School of Engineering and Technology, Jain University, Bangalore 562 112, India, ^dDepartment of Chemistry, Sri Siddhartha Institute of Technology, Tumkur 572 105, Karnataka, India, ^eSchool of Chemical & Biomolecular Engineering, The University of Sydney, Sydney, NSW, Australia, and ^fDepartment of Chemistry, Science College, An-Najah National University, PO Box 7, Nablus, West Bank, Palestinian Territories
^*Correspondence e-mail: s.naveen@jainuniversity.ac.in, khalil.i@najah.edu

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 9 October 2019; accepted 14 October 2019; online 22 October 2019)

The title compound, C₁₅H₁₁NO₅, is relatively planar, with the planes of the two aromatic rings being inclined to each other by 3.09 (5)°. In the crystal, molecules are linked by a pair of C—H⋯O hydrogen bonds, forming inversion dimers, which enclose an R₂²(16) ring motif. The dimers are linked by a further pair of C—H⋯O hydrogen-bonds forming ribbons enclosing R₄⁴(26) ring motifs. The ribbons are linked by offset π–π interactions [centroid–centroid distances = 3.6754 (6)–3.7519 (6) Å] to form layers parallel to the ac plane. Through Hirshfeld surface analyses, the d_norm surfaces, electrostatic potential and two-dimensional fingerprint (FP) plots were examined to verify the contributions of the different intermolecular contacts within the supramolecular structure. The shape-index surface shows that two sides of the molecule are involved with the same contacts in neighbouring molecules, and the curvedness plot shows flat surface patches that are characteristic of planar stacking.

Keywords: crystal structure; $[R_{2}^{2}]$ (16) ring motif; C-H⋯O hydrogen bonds; offset π–π interactions; Hirshfeld surface analysis.

CCDC references: 1449646; 1449646

1. Chemical context

Photoreleasable protecting groups have been of long-standing interest for their diverse applications in various multistep syntheses (Ruzicka et al., 2002 ; Literák et al., 2006 ). The reaction between an acid and a phenacyl bromide yields the keto ester derivative. As a protecting group, the ester derivatives are well known as protecting groups for carboxylic acids in chemical synthesis (Rather & Reid, 1919 ; Literák et al., 2006). They can easily be cleaved under completely neutral or mild conditions (Sheehan & Umezawa, 1973 ) and are therefore used for the identification of organic acids. Versatile applications of these compounds are seen in the field of synthetic chemistry, such as in the synthesis of oxazoles and imidazoles (Huang et al., 1996 ), as well as benzoxazepine (Gandhi et al., 1995 ), and they are also useful in peptide synthesis. Studies reveal an inhibitory activity against two isozymes of 11b-hydroxysteroid dehydrogenases (11b-HSD1 and 11b-HSD2), which catalyze the interconversion of active cortisol and inactive cortisone (Zhang et al., 2009 ). Researchers have reported the synthesis and photolysis studies of a number of phenacyl esters. The commercial importance of phenacyl benzoates arose due to their applications in various fields of chemistry. In continuation of our work on such molecules (Kumar et al., 2014 ; Chidan Kumar et al., 2014 ), we report herein on the crystal and molecular structure of 2-(4-nitrophenyl)-2-oxoethyl benzoate.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The compound is composed of two aromatic rings linked by a C—C(=O)—O—C(=O) bridge. The unique molecular conformation of this compound is characterized by three torsion angles, viz. τ₁ (C11—C10—C9—O3), τ₂ (C7—C8—O1—C9) and τ₃ (O2—C7—C8—O1), whereby the τ₁ value of 9.60 (16)° signifies the apparent coplanarity between the mean planes of the phenyl ring and the adjacent carbonyl groups of the connecting bridge. The τ₂ value of 174.08 (9)° between the two carbonyl groups indicates an antiperiplanar conformation. Likewise, owing to a substitution on the functional group, the title compound experiences steric repulsion between the substituent and adjacent carbonyl groups, influencing the torsion angle [τ₃ = 1.88 (15)°], and it adopts a +synperiplanar conformation. The bond lengths and angles are normal and the molecular conformation is characterized by a dihedral angle of 3.09 (5)° between the mean planes of the two aromatic rings indicating that they are coplanar. The nitro group lies almost in the plane of the phenyl ring, as indicated by the torsion angle values of 7.80 (15) and 8.46 (15)° for C4—C3—N1—O4 and C2—C3—N1—O5, respectively.

Figure 1
The molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystal, there are no classical hydrogen bonds present. However, the structure is stabilized by weak intermolecular C—H⋯O interactions. Specifically, a pair of intermolecular C5—H5⋯O3ⁱ interactions stabilize the supramolecular architecture by forming inversion dimers with an $[R_{2}^{2}]$ (16) ring motif (Table 1 and Fig. 2). The dimers are linked by a further pair of C—H⋯O hydrogen bonds, forming ribbons that enclose R₄⁴(26) ring motifs (Table 1 and Fig. 2). The ribbons are linked by a series of offset π–π interactions (Table 2), forming layers that stack up the b-axis direction (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O3ⁱ	0.95	2.47	3.3967 (14)	164
C13—H13⋯O5ⁱⁱ	0.95	2.54	3.2361 (14)	130
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x-1, y, z-2.

Table 2
π–π contacts (Å, °) in the crystal of the title compound

Cg1 and Cg2 are the centroids of rings C1–C6 and C10–C15, respectively.

Cg(I)	Cg(J)	Cg(I)⋯Cg(J) (Å)	α (°)	β (°)	γ (°)	CgI_Perp (Å)	CgJ_Perp (Å)	offset (Å)
Cg1	Cg2ⁱⁱⁱ	3.6754 (6)	3.09 (5)	22.5	21.5	3.4199 (4)	3.3948 (4)	1.408
Cg1	Cg2^iv	3.7519 (6)	3.09 (5)	27.9	25.1	3.3975 (4)	3.3171 (4)	1.753
Cg2	Cg1^v	3.7519 (6)	3.09 (5)	25.1	27.9	3.3171 (4)	3.3975 (4)	1.592
Cg2	Cg1^vi	3.6754 (6)	3.09 (5)	21.5	22.5	3.3948 (4)	3.4200 (4)	1.346
Symmetry codes: (iii) x, y, z + 1; (iv) x + 1, y, z + 1; (v) x − 1, y, z − 1; (vi) x, y, z − 1.

Figure 2
A partial view of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (Table 1

) and only H atoms H5 and H13 have been included.

Figure 3
The crystal packing of the title compound, viewed along the c axis. The hydrogen bonds are shown as dashed lines (Table 1

) and only H atoms H5 and H13 have been included.

4. Hirshfeld surface analysis and two-dimensional fingerprint plots

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) were performed and created with CrystalExplorer17 (Turner et al., 2017 ). Hirshfeld surface analysis enables the visualization of intermolecular interactions by different colours and colour intensity, representing short or long contacts and indicating the relative strengths of the interactions. Figs. 4 and 5 show the Hirshfeld surfaces mapped over d_norm (−0.195 to 1.091 a.u.) and shape-index (−1.0 to 1.0 a.u.), respectively.

Figure 4
A view of the three-dimensional Hirshfeld surface of the title compound mapped over d_norm.

Figure 5
Hirshfeld surface of the title compound, mapped over (a) the shape-index and (b) the curvedness.

In Fig. 4, the dark spots near the C and O atoms result from C—H⋯O interactions, which play a significant role in the molecular packing. The Hirshfeld surfaces illustrated in Fig. 4 also reflect the involvement of different atoms in the intermolecular interactions through the appearance of blue and red regions around the participating atoms, which correspond to positive and negative electrostatic potential, respectively. The shape-index surface clearly shows that the two sides of the molecules are involved in the same contacts with neighbouring molecules and the curvedness plots show flat surface patches characteristic of planar stacking.

The overall two-dimensional fingerprint plot for the title compound and those delineated into O—H/H—O, H—H, C—H/H—C and C—C contacts are illustrated in Fig. 6. The percentage contributions from the different interatomic contacts to the Hirshfeld surfaces are O⋯H = 35.9%, H⋯H = 29.7%, C⋯H = 14.7% and C⋯C = 10.3%, and are shown in the two-dimensional fingerprint plots in Fig. 6. The percentage contributions of other intermolecular contacts are less than 5% in the Hirshfeld surface mapping.

Figure 6
Two-dimensional fingerprint plots of the title compound, showing the percentage contributions of all contacts and of individual atom-atom contacts.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.40, last update May 2019; Groom et al., 2016 ) using 2-oxo-2-phenylethyl benzoate as the main skeleton revealed the presence of 62 structures with different substituents on the terminal phenyl rings (see supplementary information file S1). In these structures, the two aromatic rings are inclined to each other by dihedral angles varying from ca 0 to 90°. There are seven structures with a nitro substituent on one of the aromatic rings (see supplementary information file S2). However, there is only one compound with the same skeleton as the title compound, i.e. 2-(biphenyl-4-yl)-2-oxoethyl 4-nitrobenzoate (CSD refcode CISSAB; Kwong et al., 2017 ). Here, the two aromatic rings are inclined to each other by ca 70.96°, compared to an inclination of only 3.09 (5)° in the title compound.

6. Synthesis and crystallization

The title compound was synthesized as per the procedure of Kumar et al. (2014). A mixture of 2-bromo-1-(4-nitrophenyl)ethanone (0.2 g, 0.5 mmol), potassium carbonate (0.087 g, 0.63 mmol) and benzoic acid (0.079 g, 0.65 mmol) in dimethylformamide (5 ml) was stirred at room temperature for 2 h. After completion of the reaction, the reaction mixture was poured into ice-cold water. The solid product obtained was filtered off, washed with water and recrystallized from ethanol to give colourless needle-like crystals (m.p. 386–390 K).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms on C atoms were positioned geometrically (C—H = 0.95–0.99 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	C₁₅H₁₁NO₅
M_r	285.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.3371 (4), 21.0051 (11), 8.3069 (4)
β (°)	102.711 (1)
V (Å³)	1248.86 (11)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.12
Crystal size (mm)	0.37 × 0.19 × 0.11

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.959, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	14140, 3496, 3133
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.708

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.120, 1.06
No. of reflections	3696
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.30
Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008 ), Mercury (Macrae et al., 2008 ), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1449646; 1449646

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989019013975/su5520sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019013975/su5520Isup2.hkl

CSD search file S1. DOI: https://doi.org/10.1107/S2056989019013975/su5520sup3.pdf

CSD search file S2. DOI: https://doi.org/10.1107/S2056989019013975/su5520sup4.pdf

Supporting information file. DOI: https://doi.org/10.1107/S2056989019013975/su5520Isup5.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

2-(4-Nitrophenyl)-2-oxoethyl benzoate top

Crystal data top

C₁₅H₁₁NO₅	F(000) = 592
M_r = 285.25	D_x = 1.517 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3133 reflections
a = 7.3371 (4) Å	θ = 1.9–30.2°
b = 21.0051 (11) Å	µ = 0.12 mm⁻¹
c = 8.3069 (4) Å	T = 100 K
β = 102.711 (1)°	Needle, colourless
V = 1248.86 (11) Å³	0.37 × 0.19 × 0.11 mm
Z = 4

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	3496 independent reflections
Radiation source: Rotating Anode	3133 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 18.4 pixels mm^-1	θ_max = 30.2°, θ_min = 1.9°
φ and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −29→29
T_min = 0.959, T_max = 0.988	l = −11→11
14140 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0687P)² + 0.3119P] where P = (F_o² + 2F_c²)/3
3696 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2sigma(F²) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.14827 (11)	0.38115 (4)	0.37625 (9)	0.0160 (2)
O2	0.34743 (16)	0.30646 (4)	0.58368 (11)	0.0357 (3)
O3	−0.02999 (13)	0.46698 (4)	0.29186 (10)	0.0227 (3)
O4	0.55675 (12)	0.44140 (4)	1.40112 (10)	0.0228 (2)
O5	0.70482 (14)	0.35199 (5)	1.40652 (11)	0.0292 (3)
N1	0.59732 (13)	0.39281 (5)	1.33492 (11)	0.0167 (2)
C1	0.47223 (14)	0.31711 (5)	0.92088 (13)	0.0142 (3)
C2	0.54458 (14)	0.32506 (5)	1.08833 (13)	0.0142 (3)
C3	0.51595 (14)	0.38305 (5)	1.15843 (12)	0.0129 (2)
C4	0.41568 (14)	0.43237 (5)	1.06970 (13)	0.0137 (2)
C5	0.34479 (14)	0.42390 (5)	0.90160 (12)	0.0128 (2)
C6	0.37472 (13)	0.36653 (5)	0.82655 (12)	0.0123 (2)
C7	0.30848 (15)	0.35532 (5)	0.64525 (13)	0.0152 (3)
C8	0.19380 (15)	0.40611 (5)	0.54070 (12)	0.0144 (3)
C9	0.03139 (14)	0.41587 (5)	0.26299 (12)	0.0132 (2)
C10	−0.01390 (13)	0.38341 (5)	0.09985 (12)	0.0122 (2)
C11	−0.11222 (14)	0.41756 (5)	−0.03566 (13)	0.0140 (3)
C12	−0.16055 (14)	0.38880 (5)	−0.18959 (13)	0.0159 (3)
C13	−0.11199 (15)	0.32571 (5)	−0.20797 (13)	0.0168 (3)
C14	−0.01248 (15)	0.29164 (5)	−0.07323 (13)	0.0162 (3)
C15	0.03811 (14)	0.32043 (5)	0.08058 (13)	0.0138 (3)
H1	0.48900	0.27770	0.86970	0.0170*
H2	0.61170	0.29180	1.15300	0.0170*
H4	0.39580	0.47110	1.12250	0.0160*
H5	0.27610	0.45710	0.83790	0.0150*
H8A	0.07880	0.41510	0.58050	0.0170*
H8B	0.26650	0.44600	0.54450	0.0170*
H11	−0.14620	0.46060	−0.02260	0.0170*
H12	−0.22660	0.41220	−0.28210	0.0190*
H13	−0.14680	0.30570	−0.31290	0.0200*
H14	0.02090	0.24860	−0.08660	0.0190*
H15	0.10770	0.29740	0.17220	0.0170*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0200 (4)	0.0170 (4)	0.0090 (3)	0.0052 (3)	−0.0008 (3)	−0.0008 (3)
O2	0.0581 (7)	0.0226 (4)	0.0179 (4)	0.0205 (4)	−0.0097 (4)	−0.0078 (3)
O3	0.0325 (5)	0.0174 (4)	0.0160 (4)	0.0090 (3)	0.0003 (3)	−0.0014 (3)
O4	0.0256 (4)	0.0266 (4)	0.0150 (4)	0.0018 (3)	0.0018 (3)	−0.0064 (3)
O5	0.0366 (5)	0.0313 (5)	0.0149 (4)	0.0113 (4)	−0.0048 (4)	0.0036 (3)
N1	0.0159 (4)	0.0219 (4)	0.0115 (4)	0.0000 (3)	0.0015 (3)	0.0007 (3)
C1	0.0155 (5)	0.0123 (4)	0.0142 (5)	−0.0001 (3)	0.0017 (4)	0.0004 (3)
C2	0.0142 (5)	0.0138 (4)	0.0137 (5)	0.0008 (3)	0.0012 (4)	0.0032 (3)
C3	0.0120 (4)	0.0171 (4)	0.0093 (4)	−0.0018 (3)	0.0015 (3)	0.0007 (3)
C4	0.0142 (4)	0.0138 (4)	0.0128 (4)	0.0007 (3)	0.0026 (4)	−0.0012 (3)
C5	0.0130 (4)	0.0128 (4)	0.0119 (4)	0.0016 (3)	0.0010 (3)	0.0007 (3)
C6	0.0117 (4)	0.0126 (4)	0.0119 (4)	−0.0012 (3)	0.0012 (3)	−0.0005 (3)
C7	0.0171 (5)	0.0145 (4)	0.0120 (4)	0.0007 (4)	−0.0012 (4)	−0.0007 (3)
C8	0.0184 (5)	0.0149 (4)	0.0089 (4)	0.0024 (4)	0.0010 (4)	−0.0004 (3)
C9	0.0139 (4)	0.0142 (4)	0.0112 (4)	−0.0001 (3)	0.0020 (4)	0.0019 (3)
C10	0.0115 (4)	0.0144 (4)	0.0106 (4)	−0.0010 (3)	0.0021 (3)	0.0002 (3)
C11	0.0136 (4)	0.0151 (4)	0.0129 (5)	0.0012 (3)	0.0022 (4)	0.0021 (3)
C12	0.0142 (5)	0.0207 (5)	0.0118 (5)	−0.0004 (4)	0.0007 (4)	0.0030 (4)
C13	0.0180 (5)	0.0209 (5)	0.0109 (4)	−0.0024 (4)	0.0022 (4)	−0.0011 (4)
C14	0.0203 (5)	0.0156 (5)	0.0128 (5)	0.0002 (4)	0.0041 (4)	−0.0012 (4)
C15	0.0157 (5)	0.0142 (4)	0.0113 (4)	0.0004 (3)	0.0027 (4)	0.0015 (3)

Geometric parameters (Å, º) top

O1—C8	1.4324 (12)	C10—C15	1.3958 (15)
O1—C9	1.3407 (13)	C11—C12	1.3879 (15)
O2—C7	1.2087 (14)	C12—C13	1.3894 (15)
O3—C9	1.2085 (14)	C13—C14	1.3923 (15)
O4—N1	1.2267 (13)	C14—C15	1.3883 (15)
O5—N1	1.2266 (14)	C1—H1	0.9500
N1—C3	1.4706 (13)	C2—H2	0.9500
C1—C2	1.3855 (15)	C4—H4	0.9500
C1—C6	1.3988 (15)	C5—H5	0.9500
C2—C3	1.3859 (15)	C8—H8A	0.9900
C3—C4	1.3853 (15)	C8—H8B	0.9900
C4—C5	1.3901 (14)	C11—H11	0.9500
C5—C6	1.3962 (15)	C12—H12	0.9500
C6—C7	1.4959 (14)	C13—H13	0.9500
C7—C8	1.5096 (15)	C14—H14	0.9500
C9—C10	1.4878 (14)	C15—H15	0.9500
C10—C11	1.3945 (14)

C8—O1—C9	116.69 (8)	C12—C13—C14	120.25 (10)
O4—N1—O5	123.90 (9)	C13—C14—C15	120.18 (10)
O4—N1—C3	118.53 (9)	C10—C15—C14	119.60 (10)
O5—N1—C3	117.56 (9)	C2—C1—H1	120.00
C2—C1—C6	120.58 (10)	C6—C1—H1	120.00
C1—C2—C3	117.89 (10)	C1—C2—H2	121.00
N1—C3—C2	118.40 (9)	C3—C2—H2	121.00
N1—C3—C4	118.54 (9)	C3—C4—H4	121.00
C2—C3—C4	123.06 (9)	C5—C4—H4	121.00
C3—C4—C5	118.44 (10)	C4—C5—H5	120.00
C4—C5—C6	119.88 (9)	C6—C5—H5	120.00
C1—C6—C5	120.11 (9)	O1—C8—H8A	111.00
C1—C6—C7	117.39 (9)	O1—C8—H8B	111.00
C5—C6—C7	122.50 (9)	C7—C8—H8A	111.00
O2—C7—C6	120.33 (10)	C7—C8—H8B	111.00
O2—C7—C8	120.69 (10)	H8A—C8—H8B	109.00
C6—C7—C8	118.98 (9)	C10—C11—H11	120.00
O1—C8—C7	105.87 (8)	C12—C11—H11	120.00
O1—C9—O3	123.56 (9)	C11—C12—H12	120.00
O1—C9—C10	111.72 (9)	C13—C12—H12	120.00
O3—C9—C10	124.72 (9)	C12—C13—H13	120.00
C9—C10—C11	118.15 (9)	C14—C13—H13	120.00
C9—C10—C15	121.80 (9)	C13—C14—H14	120.00
C11—C10—C15	120.06 (9)	C15—C14—H14	120.00
C10—C11—C12	120.11 (10)	C10—C15—H15	120.00
C11—C12—C13	119.78 (10)	C14—C15—H15	120.00

C9—O1—C8—C7	174.08 (9)	C1—C6—C7—C8	176.74 (10)
C8—O1—C9—O3	2.69 (15)	C5—C6—C7—O2	175.36 (11)
C8—O1—C9—C10	−176.70 (9)	C5—C6—C7—C8	−4.18 (15)
O4—N1—C3—C2	−172.74 (10)	O2—C7—C8—O1	1.88 (15)
O4—N1—C3—C4	7.80 (15)	C6—C7—C8—O1	−178.58 (9)
O5—N1—C3—C2	8.46 (15)	O1—C9—C10—C11	−171.02 (9)
O5—N1—C3—C4	−171.00 (10)	O1—C9—C10—C15	9.44 (14)
C6—C1—C2—C3	0.43 (16)	O3—C9—C10—C11	9.60 (16)
C2—C1—C6—C5	−1.83 (16)	O3—C9—C10—C15	−169.95 (11)
C2—C1—C6—C7	177.27 (10)	C9—C10—C11—C12	−178.79 (10)
C1—C2—C3—N1	−178.03 (9)	C15—C10—C11—C12	0.77 (15)
C1—C2—C3—C4	1.41 (16)	C9—C10—C15—C14	178.01 (10)
N1—C3—C4—C5	177.65 (9)	C11—C10—C15—C14	−1.52 (15)
C2—C3—C4—C5	−1.79 (16)	C10—C11—C12—C13	0.53 (16)
C3—C4—C5—C6	0.33 (15)	C11—C12—C13—C14	−1.06 (16)
C4—C5—C6—C1	1.43 (15)	C12—C13—C14—C15	0.30 (17)
C4—C5—C6—C7	−177.62 (10)	C13—C14—C15—C10	0.99 (16)
C1—C6—C7—O2	−3.72 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3ⁱ	0.95	2.47	3.3967 (14)	164
C13—H13···O5ⁱⁱ	0.95	2.54	3.2361 (14)	130

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

π–π contacts (Å, °) in the crystal of the title compound. top

Cg 1 and Cg2 are the centroids of rings C1–C6 and C10–C15, respectively.

Cg(I)	Cg(J)	Cg(I)···Cg(J) (Å)	α (°)	β (°)	γ (°)	CgI_Perp (Å)	CgJ_Perp (Å)	offset (Å)
Cg1	Cg2ⁱⁱⁱ	3.6754 (6)	3.09 (5)	22.5	21.5	3.4199 (4)	3.3948 (4)	1.408
Cg1	Cg2^iv	3.7519 (6)	3.09 (5)	27.9	25.1	3.3975 (4)	3.3171 (4)	1.753
Cg2	Cg1^v	3.7519 (6)	3.09 (5)	25.1	27.9	3.3171 (4)	3.3975 (4)	1.592
Cg2	Cg1^vi	3.6754 (6)	3.09 (5)	21.5	22.5	3.3948 (4)	3.4200 (4)	1.346

Symmetry codes: (iii) x, y, z + 1; (iv) x + 1, y, z + 1; (v) x - 1, y, z - 1; (vi) x, y, z - 1.

Acknowledgements

CSCK extends his appreciation to Vidya Vikas Research & Development Centre for facilities and encouragement. NS thanks Jain University for sanctioning research grants under a minor project.

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