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

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

doi:10.1107/S2056989019014105

research communications

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ISSN: 2056-9890

Volume 75| Part 11| November 2019| Pages 1763-1767

https://doi.org/10.1107/S2056989019014105

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

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

^aDepartment of Chemistry, Sri Siddhartha Academy of Higher Education, Tumkur 572 107, Karnataka, India, ^bDepartment of Chemistry, Vidya Vikas Institute of Engineering & Technology, Visvesvaraya Technological University, Alanahally, Mysuru 570 028, 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 J. Jasinsk, Keene State College, USA (Received 19 August 2019; accepted 16 October 2019; online 29 October 2019)

2-(4-Nitrophenyl)-2-oxoethyl picolinate, C₁₄H₁₀N₂O₅, was synthesized under mild conditions. The chemical and molecular structures were confirmed by single-crystal X-ray diffraction analysis. The molecules are linked by inversion into centrosymmetric dimers via weak intermolecular C—H⋯O interactions, forming R₂²(10) ring motifs, and further strengthened by weak π–π interactions. Hirshfeld surface analyses, the d_norm surfaces, electrostatic potential and two-dimensional fingerprint (FP) plots were used to verify the contributions of the different intermolecular interactions within the supramolecular structure. The shape-index surface shows that two sides of the molecules are involved with the same contacts in neighbouring molecules and curvedness plots show flat surface patches that are characteristic of planar stacking.

Keywords: crystal structure; $[R_{2}^{2}]$ (10) ring motif; intermoleculsr interactions; Hirshfeld surface analysis.

CCDC references: 1449658; 1449658

1. Chemical context

Derivatives of phenacyl bromide have found significant application in the identification of organic acids (Rather & Reid, 1919 ). In organic chemistry, phenacyl benzoate is a derivative of an acid, formed by reaction between an acid and phenacyl bromide. The syntheses of phenacyl esters have many advantages in organic chemistry because they are usually solids and provide a useful means of characterizing acids and phenols. Phenacyl esters are useful for the photoremoval of protecting groups for carboxylic acids in organic synthesis and biochemistry. These compounds can be photolysed under neutral and mild conditions (Sheehan et al., 1973 ; Ruzicka et al., 2002 ; Literák et al., 2006 ). They also find application in the field of synthetic chemistry, such as in the synthesis of oxazoles and imidazoles (Huang et al., 1996 ), as well as with benzoxazepine (Gandhi et al., 1995 ). In continuation of our work on the synthesis of these ester derivaties (Kumar et al., 2014 ), we report herein the crystal and molecular structures of 2-(4-nitrophenyl)-2-oxoethyl picolinate.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1, and bond lengths and angles are listed in Table 1. The compound is composed of two aromatic rings (4-nitrophenyl and pyridine) linked by C—C(=O)—O—C(=O) bonds forming a bridge. The unique molecular conformation of this compound is characterized by three torsion angles, viz. τ₁ (N2—C10—C9—O3), τ₂ (C7—C8—O1—C9) and τ₃ (O2—C7—C6—C1), whereby τ₁ [−6.1 (2)°] signifies the apparent coplanarity of the mean planes of the pyridine and adjacent carbonyl rings at the connecting bridge. The torsion angle value of τ₂ = −147.02 (11)° between the two carbonyl groups indicates a –anticlinal conformation. Likewise, owing to a substitution on the functional group, the title compound experiences steric repulsion between the substituent and adjacent carbonyl groups, which can influence the torsion angle [τ₃ = 2.4 (2)%] and resulting in a +synclinal conformation. The bond lengths and angles are normal and the molecular conformation is characterized by a dihedral angle of 31.58 (8)° between the mean planes of the two aromatic rings. The nitro group lies nearly in the plane of the phenyl ring, as indicated by the torsion angle values of −4.7 (2) and −5.1 (2)° for C4—C3—N1—O4 and C2—C3—N1—O5, respectively.

Table 1
Selected geometric parameters (Å, °)

O1—C8	1.4329 (17)	O5—N1	1.211 (2)
O1—C9	1.3374 (16)	N1—C3	1.4761 (19)
O2—C7	1.2021 (18)	N2—C10	1.3372 (18)
O3—C9	1.1969 (17)	N2—C11	1.339 (2)
O4—N1	1.205 (2)

C8—O1—C9	116.39 (10)	O2—C7—C8	121.71 (13)
O4—N1—O5	123.38 (16)	O1—C8—C7	108.11 (11)
O4—N1—C3	118.83 (14)	O1—C9—O3	123.96 (13)
O5—N1—C3	117.79 (15)	O1—C9—C10	111.08 (11)
C10—N2—C11	115.93 (13)	O3—C9—C10	124.96 (12)
N1—C3—C2	118.29 (14)	N2—C10—C9	114.56 (12)
N1—C3—C4	118.83 (13)	N2—C10—C14	124.07 (13)
O2—C7—C6	120.57 (13)	N2—C11—C12	123.99 (16)

Figure 1
The molecular structure of the title compound, indicating the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

There are no classical hydrogen bonds in the structure. However, the structure is consolidated by weak C—H⋯O intermolecular interactions. Specifically, singular weak intermolecular C8—H8B⋯O3(−x, −y, −z) interactions stabilize the supramolecular architecture by forming $[R_{2}^{2}]$ (10) ring motifs and chains along [011] (Fig. 2). The molecular structure is also stabilized by weak intermolecular C—O⋯Cg, N—O⋯Cg and Cg⋯Cg interactions. The hydrogen-bond geometry and lone pair-π interactions are listed in Table 2. The molecule also exhibits Cg⋯Cg interactions, i.e. Cg1⋯Cg1 [Cg1 is the centroid of the N2/C10/C14–C11 ring; Cg⋯Cg distance = 4.6293 (10) Å, α = 0°, β = 42.1°, the perpendicular distance of Cg1 on itself = 3.4332 (7) Å (symmetry code: x − 1, y, z)] and Cg2⋯Cg2 [Cg2 is the centroid of the pyridine ring;; Cg⋯Cg distance = 4.6292 (10) Å, α = 0°, β = 40.3°, γ = 40.3° and the perpendicular distance of Cg2 on itself = 3.5322 (6) Å (symmetry code: x + 1, y, z)]. These weak intermolecular interactions link the molecules to form a one-dimensional chain along the c axis and the molecules exhibit layered stacking (Fig. 3).

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the pyridine and nitrophenyl rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O3ⁱ	0.93	2.55	3.2283 (18)	130
C8—H8B⋯O3ⁱ	0.97	2.45	3.2681 (17)	141
C12—H12A⋯O5ⁱⁱ	0.93	2.52	3.396 (3)	157
C13—H13A⋯O2ⁱⁱⁱ	0.93	2.47	3.277 (2)	146
C9—O3⋯Cg1		3.35 (1)	3.4735 (16)	86 (1)
C7—O2⋯Cg2		3.58 (1)	3.8788 (15)	67 (1)
N1—O4⋯Cg2		3.76 (1)	3.5479 (16)	71 (1)
N1—O5⋯Cg2		3.68 (1)	3.5479 (16)	74 (1)
Symmetry codes: (i) -x, -y, -z; (ii) x+2, y, z-1; (iii) -x+2, -y+1, -z.

Figure 2
A view of two molecules of the title compound linked by inversion into centrosymmetric dimers by weak C8—H8B⋯O3 intermolecular interactions forming an $[R_{2}^{2}]$ (10) ring motif. [See Note 1]

Figure 3
The packing of molecules of the title compound in the ab plane, viewed along the c axis. Cyan dashed lines indicate weak intermolecular C—H⋯O interactions forming $[R_{2}^{2}]$ (10) ring motifs.

4. Hirshfeld surface analysis

Hirshfeld surfaces and fingerprint plots (McKinnon et al., 2007 ) were generated for the title compound based on the crystallographic information file (CIF) using CrystalExplorer (Wolff et al., 2012 ). Hirshfeld surfaces enable 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 (−0.196 to 1.128 a.u.) and shape-index (−1.0 to 1.0 a.u.), respectively. The calculated volume inside the Hirshfeld surface is 311.97 Å³ in the area of 305.78 Å³.

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 with shape-index and 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 of the title compound. 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⋯H, H⋯H, C⋯H/H⋯C, C⋯O/O⋯C and N⋯H/H⋯N contacts are illustrated in Fig. 6; the percentage contributions from the different interatomic contacts to the Hirshfeld surfaces are as follows: O—H 38.9%, H—H 21.7%, C—H12%, C—O 10.2% and N—H 8.2%, as shown in the two-dimensional fingerprint plots, respectively, in Fig. 6. The percentage contributions for the 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 interactions, and the individual types of interactions.

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 a number structures containing a moiety similar to the title compound, but with different substituents on the terminal phenyl rings. These include the following: 2-oxo-2-phenylethyl benzoate, 2-(4-bromophenyl)-2-oxoethyl 4-methoxybenzoate, 2-(4-bromophenyl)-2-oxoethyl 4-chlorobenzoate, 2-(4-bromophenyl)-2-oxoethyl 4-bromobenzoate, 2-(4-chlorophenyl)-2-oxoethyl 2-methoxybenzoate, 2-(4-bromophenyl)-2-oxoethyl 2-methoxybenzoate, 2-(4-chlorophenyl)-2-oxoethyl 2,4-difluoro-benzoate, 2-(4-chlorophenyl)-2-oxoethyl 2,4-difluorobenzoate, 2-(4-chlorophenyl)-2-oxoethyl benzoate, 2-(4-chlorophenyl)-2-oxoethyl 4-hydroxybenzoate, 2-(4-bromophenyl)-2-oxoethyl 2-methylbenzoate, 2-(4-chlorophenyl)-2-oxoethyl 4-methylbenzoate, 2-(4-bromophenyl)-2-oxoethyl 4-hydroxybenzoate, 2-(4-bromophenyl)-2-oxoethyl 4-methylbenzoate, 2-(2,4-dichlorophenyl)-2-oxoethyl 4-methoxybenzoate, 2-(4-fluorophenyl)-2-oxoethyl 4-methoxybenzoate and 2-(4-chlorophenyl)-2-oxoethyl 3,4-dimethoxybenzoate (Fun et al., 2011a ,b ,c ,d ,e ,f ,g ,h ,i ,j ,k ,l ,m ,n ,o ), 2-(4-fluorophenyl)-2-oxoethyl 2-methoxybenzoate (Isloor et al., 2012 ), 1-(4-bromophenyl)-2-(2-chlorophenoxy)ethanone (Shenvi et al., 2012 ) and 2,4-dichlorobenzyl 2-methoxybenzoate (Isloor et al., 2013 ). In these 19 compounds, the dihedral angles between the phenyl rings are in the range 3.2 (2)–85.92 (10)°. The difference may arise from the weak intermolecular interactions between adjacent molecules (Fig. 7).

Figure 7
Packing of the molecules when viewed down along the a axis. The dashed lines represent C—H⋯O hydrogen bonds.

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 nicotinic acid (0.079 g, 0.65 mmol) in dimethylformamide (5 ml) was stirred at room temperature for 5 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 [m.p. 407–410 K, determined with a Stuart Scientific (UK) apparatus].

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) = 1.2 or 1.5U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	C₁₄H₁₀N₂O₅
M_r	286.24
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	297
a, b, c (Å)	4.6292 (4), 10.6563 (9), 13.3592 (11)
α, β, γ (°)	99.136 (1), 93.426 (1), 100.556 (1)
V (Å³)	636.95 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.12
Crystal size (mm)	0.41 × 0.27 × 0.16

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.953, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	21701, 3496, 2571
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.690

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.136, 1.07
No. of reflections	3496
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.19
Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008 ), SHELXL2015 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC references: 1449658; 1449658

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989019014105/jj2216sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019014105/jj2216Isup2.hkl

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: SHELXL2015 (Sheldrick, 2015) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2015 (Sheldrick, 2015) and PLATON (Spek, 2009).

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

Crystal data top

C₁₄H₁₀N₂O₅	Z = 2
M_r = 286.24	F(000) = 296
Triclinic, P1	D_x = 1.492 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.6292 (4) Å	Cell parameters from 2571 reflections
b = 10.6563 (9) Å	θ = 1.6–29.4°
c = 13.3592 (11) Å	µ = 0.12 mm⁻¹
α = 99.136 (1)°	T = 297 K
β = 93.426 (1)°	Rectangle, white
γ = 100.556 (1)°	0.41 × 0.27 × 0.16 mm
V = 636.95 (9) Å³

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	3496 independent reflections
Radiation source: fine-focus sealed tube	2571 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 18.4 pixels mm^-1	θ_max = 29.4°, θ_min = 1.6°
φ and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −14→14
T_min = 0.953, T_max = 0.981	l = −18→18
21701 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0588P)² + 0.1188P] where P = (F_o² + 2F_c²)/3
3496 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.18 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	0.5089 (2)	0.21852 (9)	0.04455 (7)	0.0528 (3)
O2	0.3481 (3)	0.40340 (11)	0.16679 (10)	0.0824 (5)
O3	0.2932 (2)	0.05168 (10)	−0.07629 (8)	0.0578 (3)
O4	−0.6315 (3)	0.13249 (15)	0.50999 (11)	0.0961 (6)
O5	−0.5484 (4)	0.33778 (16)	0.55148 (12)	0.1149 (7)
N1	−0.5128 (3)	0.23923 (15)	0.49895 (10)	0.0653 (5)
N2	0.7107 (3)	0.12934 (12)	−0.20395 (9)	0.0563 (4)
C1	−0.0180 (4)	0.38578 (14)	0.32225 (12)	0.0581 (5)
C2	−0.2018 (4)	0.37345 (15)	0.39938 (12)	0.0614 (5)
C3	−0.3152 (3)	0.25177 (14)	0.41686 (10)	0.0493 (4)
C4	−0.2565 (3)	0.14168 (14)	0.36073 (11)	0.0547 (4)
C5	−0.0737 (3)	0.15511 (13)	0.28293 (11)	0.0512 (4)
C6	0.0465 (3)	0.27660 (12)	0.26370 (9)	0.0426 (3)
C7	0.2433 (3)	0.29607 (13)	0.17993 (10)	0.0466 (4)
C8	0.2962 (3)	0.17779 (13)	0.11235 (10)	0.0491 (4)
C9	0.4795 (3)	0.14691 (12)	−0.04857 (10)	0.0435 (4)
C10	0.7087 (3)	0.20214 (12)	−0.11282 (10)	0.0442 (4)
C11	0.9099 (4)	0.17721 (17)	−0.26372 (13)	0.0659 (6)
C12	1.1060 (4)	0.29307 (18)	−0.23613 (14)	0.0707 (6)
C13	1.1009 (4)	0.36515 (16)	−0.14264 (14)	0.0675 (5)
C14	0.8961 (3)	0.31902 (13)	−0.07891 (12)	0.0536 (4)
H1A	0.06280	0.46770	0.30960	0.0700*
H2A	−0.24750	0.44630	0.43860	0.0740*
H4A	−0.33680	0.06020	0.37440	0.0660*
H5A	−0.03160	0.08170	0.24340	0.0610*
H8A	0.36960	0.12060	0.15300	0.0590*
H8B	0.11330	0.13120	0.07380	0.0590*
H11A	0.91590	0.12910	−0.32780	0.0790*
H12A	1.24020	0.32180	−0.28060	0.0850*
H13A	1.23200	0.44370	−0.12200	0.0810*
H14A	0.88590	0.36610	−0.01480	0.0640*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0520 (5)	0.0536 (5)	0.0472 (5)	−0.0055 (4)	0.0231 (4)	0.0038 (4)
O2	0.1022 (9)	0.0475 (6)	0.0962 (9)	−0.0035 (6)	0.0567 (8)	0.0123 (6)
O3	0.0560 (6)	0.0544 (6)	0.0562 (6)	−0.0052 (4)	0.0168 (4)	0.0034 (4)
O4	0.1105 (11)	0.0952 (10)	0.0910 (10)	0.0128 (8)	0.0615 (9)	0.0306 (8)
O5	0.1705 (16)	0.0994 (11)	0.0930 (10)	0.0483 (11)	0.0884 (11)	0.0174 (9)
N1	0.0719 (8)	0.0818 (10)	0.0506 (7)	0.0243 (7)	0.0280 (6)	0.0176 (7)
N2	0.0651 (7)	0.0588 (7)	0.0479 (6)	0.0142 (6)	0.0207 (5)	0.0096 (5)
C1	0.0717 (9)	0.0420 (7)	0.0613 (9)	0.0079 (6)	0.0242 (7)	0.0080 (6)
C2	0.0757 (10)	0.0527 (8)	0.0587 (9)	0.0193 (7)	0.0263 (7)	0.0035 (7)
C3	0.0501 (7)	0.0608 (8)	0.0394 (6)	0.0129 (6)	0.0150 (5)	0.0098 (6)
C4	0.0638 (8)	0.0489 (7)	0.0510 (7)	0.0032 (6)	0.0225 (6)	0.0102 (6)
C5	0.0617 (8)	0.0416 (7)	0.0489 (7)	0.0045 (6)	0.0223 (6)	0.0035 (5)
C6	0.0424 (6)	0.0427 (6)	0.0412 (6)	0.0037 (5)	0.0103 (5)	0.0057 (5)
C7	0.0451 (6)	0.0453 (7)	0.0479 (7)	0.0010 (5)	0.0143 (5)	0.0089 (5)
C8	0.0500 (7)	0.0483 (7)	0.0478 (7)	0.0002 (5)	0.0222 (5)	0.0087 (5)
C9	0.0437 (6)	0.0432 (6)	0.0456 (7)	0.0082 (5)	0.0143 (5)	0.0102 (5)
C10	0.0461 (6)	0.0452 (6)	0.0455 (7)	0.0116 (5)	0.0175 (5)	0.0126 (5)
C11	0.0812 (11)	0.0742 (10)	0.0521 (8)	0.0272 (9)	0.0313 (8)	0.0170 (7)
C12	0.0771 (10)	0.0764 (11)	0.0763 (11)	0.0270 (9)	0.0479 (9)	0.0368 (9)
C13	0.0670 (9)	0.0548 (8)	0.0852 (11)	0.0043 (7)	0.0367 (8)	0.0236 (8)
C14	0.0573 (8)	0.0468 (7)	0.0581 (8)	0.0057 (6)	0.0256 (6)	0.0107 (6)

Geometric parameters (Å, º) top

O1—C8	1.4329 (17)	C7—C8	1.4973 (19)
O1—C9	1.3374 (16)	C9—C10	1.4998 (19)
O2—C7	1.2021 (18)	C10—C14	1.3737 (19)
O3—C9	1.1969 (17)	C11—C12	1.375 (3)
O4—N1	1.205 (2)	C12—C13	1.362 (3)
O5—N1	1.211 (2)	C13—C14	1.387 (2)
N1—C3	1.4761 (19)	C1—H1A	0.9300
N2—C10	1.3372 (18)	C2—H2A	0.9300
N2—C11	1.339 (2)	C4—H4A	0.9300
C1—C2	1.382 (2)	C5—H5A	0.9300
C1—C6	1.386 (2)	C8—H8A	0.9700
C2—C3	1.369 (2)	C8—H8B	0.9700
C3—C4	1.369 (2)	C11—H11A	0.9300
C4—C5	1.387 (2)	C12—H12A	0.9300
C5—C6	1.3822 (19)	C13—H13A	0.9300
C6—C7	1.5006 (19)	C14—H14A	0.9300

C8—O1—C9	116.39 (10)	N2—C11—C12	123.99 (16)
O4—N1—O5	123.38 (16)	C11—C12—C13	119.00 (17)
O4—N1—C3	118.83 (14)	C12—C13—C14	118.62 (16)
O5—N1—C3	117.79 (15)	C10—C14—C13	118.39 (14)
C10—N2—C11	115.93 (13)	C2—C1—H1A	120.00
C2—C1—C6	120.27 (14)	C6—C1—H1A	120.00
C1—C2—C3	118.56 (14)	C1—C2—H2A	121.00
N1—C3—C2	118.29 (14)	C3—C2—H2A	121.00
N1—C3—C4	118.83 (13)	C3—C4—H4A	121.00
C2—C3—C4	122.88 (14)	C5—C4—H4A	121.00
C3—C4—C5	118.09 (13)	C4—C5—H5A	120.00
C4—C5—C6	120.56 (13)	C6—C5—H5A	120.00
C1—C6—C5	119.64 (13)	O1—C8—H8A	110.00
C1—C6—C7	117.81 (12)	O1—C8—H8B	110.00
C5—C6—C7	122.54 (12)	C7—C8—H8A	110.00
O2—C7—C6	120.57 (13)	C7—C8—H8B	110.00
O2—C7—C8	121.71 (13)	H8A—C8—H8B	108.00
C6—C7—C8	117.70 (12)	N2—C11—H11A	118.00
O1—C8—C7	108.11 (11)	C12—C11—H11A	118.00
O1—C9—O3	123.96 (13)	C11—C12—H12A	120.00
O1—C9—C10	111.08 (11)	C13—C12—H12A	121.00
O3—C9—C10	124.96 (12)	C12—C13—H13A	121.00
N2—C10—C9	114.56 (12)	C14—C13—H13A	121.00
N2—C10—C14	124.07 (13)	C10—C14—H14A	121.00
C9—C10—C14	121.36 (12)	C13—C14—H14A	121.00

C9—O1—C8—C7	−147.02 (11)	C4—C5—C6—C1	−0.5 (2)
C8—O1—C9—O3	−1.63 (19)	C4—C5—C6—C7	−179.49 (13)
C8—O1—C9—C10	178.12 (11)	C1—C6—C7—O2	2.4 (2)
O4—N1—C3—C2	174.45 (15)	C1—C6—C7—C8	−175.97 (13)
O4—N1—C3—C4	−4.7 (2)	C5—C6—C7—O2	−178.60 (14)
O5—N1—C3—C2	−5.1 (2)	C5—C6—C7—C8	3.1 (2)
O5—N1—C3—C4	175.83 (15)	O2—C7—C8—O1	6.80 (19)
C11—N2—C10—C9	178.95 (13)	C6—C7—C8—O1	−174.90 (11)
C11—N2—C10—C14	−0.4 (2)	O1—C9—C10—N2	174.17 (12)
C10—N2—C11—C12	0.4 (3)	O1—C9—C10—C14	−6.46 (18)
C6—C1—C2—C3	0.6 (3)	O3—C9—C10—N2	−6.1 (2)
C2—C1—C6—C5	−0.1 (2)	O3—C9—C10—C14	173.28 (14)
C2—C1—C6—C7	178.99 (15)	N2—C10—C14—C13	0.0 (2)
C1—C2—C3—N1	−179.64 (15)	C9—C10—C14—C13	−179.32 (14)
C1—C2—C3—C4	−0.6 (2)	N2—C11—C12—C13	−0.1 (3)
N1—C3—C4—C5	179.10 (13)	C11—C12—C13—C14	−0.4 (3)
C2—C3—C4—C5	0.0 (2)	C12—C13—C14—C10	0.4 (2)
C3—C4—C5—C6	0.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O3ⁱ	0.93	2.55	3.2283 (18)	130
C8—H8B···O3ⁱ	0.97	2.45	3.2681 (17)	141
C12—H12A···O5ⁱⁱ	0.93	2.52	3.396 (3)	157
C13—H13A···O2ⁱⁱⁱ	0.93	2.47	3.277 (2)	146
C9—O3···Cg1		3.35 (1)	3.4735 (16)	86 (1)
C7—O2···Cg2		3.58 (1)	3.8788 (15)	67 (1)
N1—O4···Cg2		3.76 (1)	3.5479 (16)	71 (1)
N1—O5···Cg2		3.68 (1)	3.5479 (16)	74 (1)

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

Acknowledgements

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

References

Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fun, H.-K., Arshad, S., Garudachari, B., Isloor, A. M. & Satyanarayan, M. N. (2011a). Acta Cryst. E67, o1582–o1583. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Arshad, S., Garudachari, B., Isloor, A. M. & Satyanarayan, M. N. (2011b). Acta Cryst. E67, o1599. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Asik, S. I. J., Garudachari, B., Isloor, A. M. & Satyanarayan, M. N. (2011c). Acta Cryst. E67, o1687. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Chia, T. S., Shenvi, S., Isloor, A. M. & Garudachari, B. (2011d). Acta Cryst. E67, o3379. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Loh, W.-S., Garudachari, B., Isloor, A. M. & Satyanarayana, M. N. (2011e). Acta Cryst. E67, o2854. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Loh, W.-S., Garudachari, B., Isloor, A. M. & Satyanarayana, M. N. (2011f). Acta Cryst. E67, o3030. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Loh, W.-S., Garudachari, B., Isloor, A. M. & Satyanarayan, M. N. (2011g). Acta Cryst. E67, o1529. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Loh, W.-S., Garudachari, B., Isloor, A. M. & Satyanarayan, M. N. (2011h). Acta Cryst. E67, o3456. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Ooi, C. W., Garudachari, B., Isloor, A. M. & Satyanarayan, M. N. (2011i). Acta Cryst. E67, o3119. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Quah, C. K., Garudachari, B., Isloor, A. M. & Satyanarayan, M. N. (2011j). Acta Cryst. E67, o1724. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Quah, C. K., Vijesh, A. M., Isloor, A. M. & Arulmoli, T. (2011k). Acta Cryst. E67, o3351. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Shahani, T., Garudachari, B., Isloor, A. M. & Satyanarayan, M. N. (2011l). Acta Cryst. E67, o3154. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Shahani, T., Garudachari, B., Isloor, A. M. & Satyganarayan, M. N. (2011m). Acta Cryst. E67, o1802. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Shahani, T., Garudachari, G., Isloor, A. M. & Shivananda, K. N. (2011n). Acta Cryst. E67, o2682. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Yeap, C. S., Garudachari, B., Isloor, A. M. & Satyanarayan, M. N. (2011o). Acta Cryst. E67, o1723. CrossRef IUCr Journals Google Scholar
Gandhi, S. S., Bell, K. L. & Gibson, M. S. (1995). Tetrahedron, 51, 13301–13308. CrossRef CAS Web of Science Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Huang, W., Pei, J., Chen, B., Pei, W. & Ye, X. (1996). Tetrahedron, 52, 10131–10136. CrossRef CAS Google Scholar
Isloor, A. M., Garudachari, B., Gerber, T., Hosten, E. & Betz, R. (2013). Acta Cryst. E69, o509. CrossRef IUCr Journals Google Scholar
Isloor, A. M., Garudachari, B., Satyanarayan, M. N., Gerber, T., Hosten, E. & Betz, R. (2012). Acta Cryst. E68, o513. CrossRef IUCr Journals Google Scholar
Kumar, C. S. C., Chia, T. S., Ooi, C. W., Quah, C. K., Chandraju, S. & Fun, H. K. (2014). Z. Kristallogr. Cryst. Mater. 229, 328–342. CSD CrossRef Google Scholar
Literák, J., Dostálová, A. & Klán, P. (2006). J. Org. Chem. 71, 713–723. PubMed Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
Rather, J. B. & Reid, E. (1919). J. Am. Chem. Soc. 41, 75–83. CrossRef CAS Google Scholar
Ruzicka, R., Zabadal, M. & Klán, P. (2002). Synth. Commun. 32, 2581–2590. CrossRef CAS Google Scholar
Sheehan, J. C. & Umezawa, K. (1973). J. Org. Chem. 38, 3771–3774. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shenvi, S. S., Isloor, A. M., Gerber, T., Hosten, E. & Betz, R. (2012). Acta Cryst. E68, o3478. CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wolff, S. K., Grimwood, D. J., McKinnon, J. J., Turner, M. J., Jayatilaka, D. & Spackman, M. A. (2012). CrystalExplorer. University of Western Australia. Google Scholar

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