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

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

doi:10.1107/S2056989019014336

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ISSN: 2056-9890

Volume 75| Part 11| November 2019| Pages 1792-1796

https://doi.org/10.1107/S2056989019014336

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

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 18 October 2019; accepted 21 October 2019; online 31 October 2019)

The title compound, C₁₅H₁₀ClNO₅, is relatively planar with the two aromatic rings being inclined to each other by 3.56 (11)°. The central —C(=O)—C–O—C(=O)— bridge is slightly twisted, with a C—C—O—C torsion angle of 164.95 (16)°. In the crystal, molecules are linked by C—H⋯O and C—H⋯Cl hydrogen bonds, forming layers parallel to the (101) plane. The layers are linked by a further C—H⋯O hydrogen bond, forming a three-dimensional supramolecular structure. There are a number of offset π–π interactions present between the layers [intercentroid distances vary from 3.8264 (15) to 3.9775 (14) Å]. Hirshfeld surface analyses, the d_norm surfaces, electrostatic potential and two-dimensional fingerprint 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 in the same contacts with neighbouring molecules, and the curvedness plot shows flat surface patches that are characteristic of planar stacking.

Keywords: crystal structure; supramolecular architecture; C—H⋯Cl hydrogen bonds; π–π interactions; Hirshfeld surface analysis.

CCDC references: 1449647; 1449647

1. Chemical context

Due to their numerous applications in various fields of chemistry, phenacyl benzoates are of great importance (Rather & Reid, 1919 ; Literák et al., 2006 ; Sheehan & Umezawa, 1973 ; Huang et al., 1996 ; Gandhi et al., 1995 ; Zhang et al., 2009 ). 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 structures of 2-(4-nitrophenyl)-2-oxoethyl chlorobenzoate (I). Its crystal and molecular structures are compared with those of 2-(4-nitrophenyl)-2-oxoethyl benzoate (II) (Sheshadri et al., 2019 ), published by us recently, and further details of uses and applications of such molecules are described therein.

2. Structural commentary

The molecular structure of the title compound, I, is shown in Fig. 1. The compound is composed of two aromatic rings (C1–C6 and C10–C15) linked by the –C7(=O2)—C8—O1—C9(=O3)– bridge. The bond lengths and angles in I are normal and similar to those reported for compound II. The two benzene rings are inclined to each other by 3.56 (11)°, indicating that they are almost coplanar, as in the structure of II. The nitro group (N1/O4/O5) lies almost in the plane of the benzene ring (C1–C6), with a dihedral angle between the two planes of 5.4 (4)°; the torsion angles C4—C3—N1—O4 and C2—C3—N1—O5 are −5.4 (3) and −5.1 (4)°, respectively. Atom Cl1 is displaced by 0.0749 (8) Å from the plane of benzene ring C10–C15.

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

The overall molecular conformation of I is characterized by three torsion angles, viz. τ₁ (C11—C10—C9—O3), τ₂ (C7—C8—O1—C9) and τ₃ (O2—C7—C6—C1). Torsion angle τ₁ at −12.5 (3)° signifies a certain noncoplanarity between the benzene ring (C10–C15) and the adjacent carbonyl group (C9=O3) as a result of steric repulsion between the substituent Cl1 and the adjacent carbonyl group C9=O3. This is also reflected in the torsion angle τ₂ of −164.95 (16)°, between the two carbonyl groups, C7=O2 and C9=O3, which have a –antiperiplanar conformation. Torsion angle τ₃, involving the benzene ring (C1–C6) and the adjacent carbonyl group (C7=O2), is −3.6 (3)° and indicates a –synperiplanar conformation. A comparison of the torsion angles in I and II, indicates that the insertion of the Cl atom in I has the most significant influence on torsion τ₂, which is −164.95 (16)° in I compared to 174.08 (9)° in II. Torsion angles τ₁ of −12.5 (3)° and τ₃ of −3.6 (3)° are slightly larger than the values observed in II, viz. 9.60 (16) and 1.88 (15)°, respectively. Hence, compound I has a less planar conformation than unsubstituted compound II.

3. Supramolecular features

The crystal structure of the title compound, is stabilized by intermolecular hydrogen bonds of the types C—H⋯O and C—H⋯Cl (Table 1). Molecules are linked by the C2—H2⋯O3ⁱ, C14—H14⋯O4ⁱ and C13—H13⋯Cl1ⁱⁱⁱ hydrogen bonds to form layers lying parallel to the (101) plane; see Fig. 2 and Table 1. The layers are linked by C8—H8A⋯O3ⁱⁱ hydrogen bonds and offset π–π interactions (see Table 2), forming a supramolecular three-dimensional structure (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O3ⁱ	0.93	2.54	3.258 (2)	135
C8—H8A⋯O3ⁱⁱ	0.97	2.59	3.553 (3)	171
C13—H13⋯Cl1ⁱⁱⁱ	0.93	2.82	3.670 (3)	153
C14—H14⋯O4ⁱ	0.93	2.50	3.211 (4)	134
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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

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

Cg(I)	Cg(J)	Cg(I)⋯Cg(J) (Å)	α (°)	β (°)	γ (°)	CgI_Perp (Å)	CgJ_Perp (Å)	Offset (Å)
Cg1	Cg1^iv	3.9775 (14)	0.02 (10)	31.8	31.8	3.3791 (9)	3.3791 (9)	2.098
Cg1	Cg2^v	3.8801 (14)	3.56 (11)	30.1	29.1	3.3895 (9)	3.3559 (10)	1.948
Cg2	Cg2^vi	3.8264 (15)	0.00 (11)	24.8	24.8	3.4722 (10)	3.4722 (10)	1.608
Symmetry codes: (iv) −x + 1, −y + 1, −z; (v) −x + 1, −y + 1, −z + 1; (vi) −x, −y + 1, −z + 1.

Figure 2
A view normal to the (101) plane of the crystal packing of compound I. The hydrogen bonds are shown as dashed lines (Table 1

; symmetry codes as in Table 1

), and, for clarity, only the H atoms involved in hydrogen bonding have been included.

Figure 3
The crystal packing of compound I, viewed along the b axis, showing the layered stacking. For clarity, only the H atoms involved in hydrogen bonding have been included, and the hydrogen bonds are shown as dashed lines (Table 1

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 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 strength of the interactions. Fig. 4(a) shows the Hirshfeld surface mapped over d_norm (−0.154 to 1.305) and for Fig. 4(b) the electrostatic potential. The Hirshfeld surface illustrated in Fig. 4(a) reflects the involvement of different atoms with the intermolecular interactions through the appearance of blue and red patches, which correspond to the regions of positive and negative electrostatic potential shown in Fig. 4(b). The shape-index surface (Fig. 5a) clearly shows that the two sides of the molecule are involved in contacts with neighbouring molecules and the curvedness plot (Fig. 5b) shows flat surface patches characteristic of planar stacking.

Figure 4
A view of the Hirshfeld surface of compound I, mapped over d_norm.

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

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 Cl⋯H/H⋯Cl contacts are illustrated in Fig. 6. The percentage contributions from the different interatomic contacts to the Hirshfeld surfaces are as follows: O⋯H (34.8%), H⋯H (18.8%), C⋯H (14.7%) and Cl⋯H (10.1%), shown in the two-dimensional fingerprint plots, respectively, in Fig. 6. The percentage contributions for other intermolecular contacts are less than 5% in the Hirshfeld surface mapping.

Figure 6
The two-dimensional fingerprint plots of compound I, 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. In these structures, the two aromatic rings are inclined to each other by dihedral angles varying from ca 0 to 90°. There were seven structures with a nitro substituent on one of the aromatic rings. 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 only 3.56 (11)° in the title compound. In the crystal structure of the recently published compound 2-(4-nitrophenyl)-2-oxoethyl benzoate (II) (Sheshadri et al., 2019), this dihedral angle is 3.09 (5)°.

6. Synthesis and crystallization

The title compound, was synthesized as per the procedure reported earlier by 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 2-chlorobenzoic acid (0.156 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, washed with water and recrystallized from ethanol to give colourless block-like crystals (m.p. 386–390 K).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. C-bound H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	C₁₅H₁₀ClNO₅
M_r	319.69
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	12.6646 (18), 12.4099 (18), 9.0902 (13)
β (°)	99.947 (2)
V (Å³)	1407.2 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.30
Crystal size (mm)	0.55 × 0.26 × 0.19

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.796, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	36449, 4122, 2586
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.141, 1.06
No. of reflections	4122
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.44
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: 1449647; 1449647

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989019014336/su5521sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019014336/su5521Isup2.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: 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 2-chlorobenzoate top

Crystal data top

C₁₅H₁₀ClNO₅	F(000) = 656
M_r = 319.69	D_x = 1.509 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6264 reflections
a = 12.6646 (18) Å	θ = 2.3–27.5°
b = 12.4099 (18) Å	µ = 0.30 mm⁻¹
c = 9.0902 (13) Å	T = 294 K
β = 99.947 (2)°	Block, colourless
V = 1407.2 (3) Å³	0.55 × 0.26 × 0.19 mm
Z = 4

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	4122 independent reflections
Radiation source: Rotating Anode	2586 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
Detector resolution: 18.4 pixels mm^-1	θ_max = 30.1°, θ_min = 1.6°
φ and ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −17→17
T_min = 0.796, T_max = 0.946	l = −12→12
36449 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	H-atom parameters constrained
wR(F²) = 0.141	W = 1/[Σ²(FO²) + (0.0456P)² + 0.8032P] WHERE P = (FO² + 2FC²)/3
S = 1.06	(Δ/σ)_max < 0.001
4122 reflections	Δρ_max = 0.26 e Å⁻³
199 parameters	Δρ_min = −0.44 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
Cl1	0.13276 (6)	0.19871 (4)	0.64688 (9)	0.0704 (3)
O1	0.32241 (12)	0.43016 (11)	0.42430 (17)	0.0451 (5)
O2	0.44530 (13)	0.57459 (11)	0.32308 (19)	0.0553 (6)
O3	0.31616 (15)	0.26717 (12)	0.5238 (2)	0.0662 (7)
O4	0.8091 (3)	0.28826 (18)	−0.0648 (4)	0.1349 (15)
O5	0.8233 (2)	0.45298 (17)	−0.1127 (3)	0.1031 (10)
N1	0.78442 (18)	0.38048 (17)	−0.0532 (3)	0.0632 (8)
C1	0.60280 (16)	0.53537 (15)	0.1467 (2)	0.0378 (6)
C2	0.68013 (17)	0.51241 (15)	0.0615 (2)	0.0407 (6)
C3	0.70239 (17)	0.40590 (16)	0.0379 (2)	0.0432 (7)
C4	0.65143 (19)	0.32166 (16)	0.0961 (3)	0.0493 (7)
C5	0.57408 (18)	0.34589 (15)	0.1802 (3)	0.0458 (7)
C6	0.54870 (15)	0.45265 (14)	0.2066 (2)	0.0356 (6)
C7	0.46407 (16)	0.48220 (15)	0.2957 (2)	0.0367 (6)
C8	0.40417 (18)	0.38936 (16)	0.3492 (2)	0.0429 (6)
C9	0.28099 (17)	0.35666 (15)	0.5069 (2)	0.0394 (6)
C10	0.19286 (15)	0.40267 (15)	0.5758 (2)	0.0365 (6)
C11	0.12673 (17)	0.33809 (16)	0.6478 (2)	0.0414 (6)
C12	0.05046 (19)	0.3840 (2)	0.7205 (3)	0.0548 (8)
C13	0.0388 (2)	0.4942 (2)	0.7222 (3)	0.0604 (9)
C14	0.10067 (19)	0.55891 (18)	0.6499 (3)	0.0544 (8)
C15	0.17715 (17)	0.51397 (16)	0.5769 (3)	0.0443 (7)
H1	0.58650	0.60680	0.16450	0.0450*
H2	0.71620	0.56730	0.02110	0.0490*
H4	0.66890	0.25050	0.07900	0.0590*
H5	0.53830	0.29040	0.21980	0.0550*
H8A	0.37220	0.34550	0.26490	0.0510*
H8B	0.45330	0.34460	0.41680	0.0510*
H12	0.00710	0.34040	0.76810	0.0660*
H13	−0.01150	0.52480	0.77300	0.0720*
H14	0.09130	0.63320	0.64990	0.0650*
H15	0.21870	0.55860	0.52770	0.0530*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0741 (4)	0.0363 (3)	0.1119 (6)	−0.0032 (3)	0.0471 (4)	0.0109 (3)
O1	0.0529 (9)	0.0353 (7)	0.0540 (9)	0.0031 (6)	0.0285 (7)	0.0035 (6)
O2	0.0648 (11)	0.0323 (7)	0.0754 (11)	−0.0003 (7)	0.0311 (9)	−0.0077 (7)
O3	0.0755 (12)	0.0382 (8)	0.0983 (14)	0.0158 (8)	0.0524 (11)	0.0190 (8)
O4	0.165 (3)	0.0587 (13)	0.222 (3)	0.0172 (14)	0.149 (3)	−0.0060 (16)
O5	0.1241 (19)	0.0699 (13)	0.144 (2)	−0.0058 (13)	0.1036 (18)	0.0043 (13)
N1	0.0670 (14)	0.0509 (11)	0.0825 (16)	−0.0031 (10)	0.0433 (12)	−0.0073 (11)
C1	0.0436 (11)	0.0268 (8)	0.0437 (11)	−0.0021 (7)	0.0095 (9)	−0.0019 (8)
C2	0.0446 (11)	0.0342 (9)	0.0456 (12)	−0.0058 (8)	0.0141 (9)	0.0031 (8)
C3	0.0444 (12)	0.0394 (10)	0.0504 (13)	−0.0019 (9)	0.0214 (10)	−0.0037 (9)
C4	0.0588 (14)	0.0296 (9)	0.0659 (15)	−0.0004 (9)	0.0284 (12)	−0.0048 (9)
C5	0.0554 (13)	0.0288 (9)	0.0591 (14)	−0.0051 (9)	0.0268 (11)	−0.0009 (9)
C6	0.0393 (10)	0.0295 (8)	0.0392 (11)	−0.0031 (7)	0.0106 (9)	−0.0026 (8)
C7	0.0412 (11)	0.0320 (9)	0.0383 (11)	−0.0015 (8)	0.0105 (9)	−0.0013 (8)
C8	0.0517 (12)	0.0341 (9)	0.0486 (12)	0.0005 (8)	0.0250 (10)	−0.0021 (8)
C9	0.0428 (11)	0.0322 (9)	0.0458 (12)	−0.0011 (8)	0.0149 (9)	0.0010 (8)
C10	0.0355 (10)	0.0339 (9)	0.0410 (11)	0.0012 (7)	0.0089 (9)	0.0032 (8)
C11	0.0409 (11)	0.0368 (9)	0.0491 (12)	−0.0001 (8)	0.0149 (9)	0.0046 (9)
C12	0.0500 (13)	0.0566 (13)	0.0644 (16)	0.0006 (11)	0.0288 (12)	0.0066 (12)
C13	0.0540 (14)	0.0560 (14)	0.0790 (18)	0.0104 (11)	0.0336 (14)	−0.0026 (13)
C14	0.0537 (14)	0.0369 (11)	0.0762 (17)	0.0096 (9)	0.0214 (13)	−0.0022 (10)
C15	0.0456 (12)	0.0343 (10)	0.0553 (13)	0.0018 (8)	0.0150 (10)	0.0030 (9)

Geometric parameters (Å, º) top

Cl1—C11	1.732 (2)	C10—C11	1.401 (3)
O1—C8	1.428 (3)	C10—C15	1.396 (3)
O1—C9	1.344 (2)	C11—C12	1.384 (3)
O2—C7	1.206 (2)	C12—C13	1.376 (4)
O3—C9	1.197 (2)	C13—C14	1.367 (4)
O4—N1	1.196 (3)	C14—C15	1.383 (3)
O5—N1	1.199 (3)	C1—H1	0.9300
N1—C3	1.470 (3)	C2—H2	0.9300
C1—C2	1.379 (3)	C4—H4	0.9300
C1—C6	1.396 (3)	C5—H5	0.9300
C2—C3	1.376 (3)	C8—H8A	0.9700
C3—C4	1.381 (3)	C8—H8B	0.9700
C4—C5	1.376 (3)	C12—H12	0.9300
C5—C6	1.394 (3)	C13—H13	0.9300
C6—C7	1.496 (3)	C14—H14	0.9300
C7—C8	1.506 (3)	C15—H15	0.9300
C9—C10	1.485 (3)

C8—O1—C9	114.31 (15)	C10—C11—C12	120.71 (19)
O4—N1—O5	123.0 (3)	C11—C12—C13	120.0 (2)
O4—N1—C3	118.4 (3)	C12—C13—C14	120.5 (2)
O5—N1—C3	118.6 (2)	C13—C14—C15	120.1 (2)
C2—C1—C6	120.74 (17)	C10—C15—C14	121.0 (2)
C1—C2—C3	118.07 (18)	C2—C1—H1	120.00
N1—C3—C2	118.53 (18)	C6—C1—H1	120.00
N1—C3—C4	118.41 (19)	C1—C2—H2	121.00
C2—C3—C4	123.1 (2)	C3—C2—H2	121.00
C3—C4—C5	118.17 (19)	C3—C4—H4	121.00
C4—C5—C6	120.72 (19)	C5—C4—H4	121.00
C1—C6—C5	119.24 (18)	C4—C5—H5	120.00
C1—C6—C7	118.47 (16)	C6—C5—H5	120.00
C5—C6—C7	122.29 (18)	O1—C8—H8A	110.00
O2—C7—C6	122.01 (18)	O1—C8—H8B	110.00
O2—C7—C8	122.19 (19)	C7—C8—H8A	110.00
C6—C7—C8	115.80 (16)	C7—C8—H8B	110.00
O1—C8—C7	109.30 (16)	H8A—C8—H8B	108.00
O1—C9—O3	121.9 (2)	C11—C12—H12	120.00
O1—C9—C10	111.65 (16)	C13—C12—H12	120.00
O3—C9—C10	126.36 (19)	C12—C13—H13	120.00
C9—C10—C11	122.06 (17)	C14—C13—H13	120.00
C9—C10—C15	120.13 (18)	C13—C14—H14	120.00
C11—C10—C15	117.74 (18)	C15—C14—H14	120.00
Cl1—C11—C10	122.61 (16)	C10—C15—H15	120.00
Cl1—C11—C12	116.66 (17)	C14—C15—H15	119.00

C9—O1—C8—C7	−164.95 (16)	C5—C6—C7—O2	177.1 (2)
C8—O1—C9—O3	5.3 (3)	C5—C6—C7—C8	−2.8 (3)
C8—O1—C9—C10	−177.15 (15)	O2—C7—C8—O1	3.6 (3)
O4—N1—C3—C2	174.8 (3)	C6—C7—C8—O1	−176.59 (15)
O4—N1—C3—C4	−5.1 (4)	O1—C9—C10—C11	170.13 (17)
O5—N1—C3—C2	−5.4 (3)	O1—C9—C10—C15	−13.2 (3)
O5—N1—C3—C4	174.7 (3)	O3—C9—C10—C11	−12.5 (3)
C6—C1—C2—C3	−0.2 (3)	O3—C9—C10—C15	164.3 (2)
C2—C1—C6—C5	0.4 (3)	C9—C10—C11—Cl1	−6.6 (3)
C2—C1—C6—C7	−178.83 (17)	C9—C10—C11—C12	175.2 (2)
C1—C2—C3—N1	179.79 (19)	C15—C10—C11—Cl1	176.60 (17)
C1—C2—C3—C4	−0.4 (3)	C15—C10—C11—C12	−1.6 (3)
N1—C3—C4—C5	−179.5 (2)	C9—C10—C15—C14	−175.3 (2)
C2—C3—C4—C5	0.7 (4)	C11—C10—C15—C14	1.6 (3)
C3—C4—C5—C6	−0.5 (4)	Cl1—C11—C12—C13	−178.1 (2)
C4—C5—C6—C1	0.0 (3)	C10—C11—C12—C13	0.2 (3)
C4—C5—C6—C7	179.2 (2)	C11—C12—C13—C14	1.3 (4)
C1—C6—C7—O2	−3.7 (3)	C12—C13—C14—C15	−1.3 (4)
C1—C6—C7—C8	176.42 (17)	C13—C14—C15—C10	−0.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3ⁱ	0.93	2.54	3.258 (2)	135
C8—H8A···O3ⁱⁱ	0.97	2.59	3.553 (3)	171
C13—H13···Cl1ⁱⁱⁱ	0.93	2.82	3.670 (3)	153
C14—H14···O4ⁱ	0.93	2.50	3.211 (4)	134

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x, y+1/2, −z+3/2.

Table 2. π–π contacts (Å, °) in the crystal of compound I. top

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

Cg(I)	Cg(J)	Cg(I)···Cg(J) (Å)	α (°)	β (°)	γ (°)	CgI_Perp (Å)	CgJ_Perp (Å)	Offset (Å)
Cg1	Cg1^iv	3.9775 (14)	0.02 (10)	31.8	31.8	3.3791 (9)	3.3791 (9)	2.098
Cg1	Cg2^v	3.8801 (14)	3.56 (11)	30.1	29.1	3.3895 (9)	3.3559 (10)	1.948
Cg2	Cg2^vi	3.8264 (15)	0.00 (11)	24.8	24.8	3.4722 (10)	3.4722 (10)	1.608

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

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.

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Volume 75| Part 11| November 2019| Pages 1792-1796

https://doi.org/10.1107/S2056989019014336

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Hirshfeld surface analysis and two-dimensional fingerprint plots

5. Database survey

6. Synthesis and crystallization

7. Refinement

Supporting information

Acknowledgements

References

research communications

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

3. Supramolecular features