Ethyl 2-amino-1-(4-fluoro­phen­yl)-5-oxo-4,5-di­hydro-1H-pyrrole-3-carboxyl­ate: crystal structure and Hirshfeld surface analysis

Patel, U.H.; Jotaniya, C.; Shah, D.A.; Socha, B.

doi:10.1107/S2056989017011628

research communications

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ISSN: 2056-9890

Volume 73| Part 9| September 2017| Pages 1336-1340

https://doi.org/10.1107/S2056989017011628

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Ethyl 2-amino-1-(4-fluorophenyl)-5-oxo-4,5-dihydro-1H-pyrrole-3-carboxylate: crystal structure and Hirshfeld surface analysis

U. H. Patel,^a Chintan Jotaniya,^b ^* D. A. Shah ^c and Bhavesh Socha ^b

^aDepartment of Physics, V.V. Nagar, Anand, Gujarat, India, ^b103, X-Ray Lab, Department of Physics, V.V. Nagar, Anand, Gujarat, India, and ^cOrganic Synthesis Laboratory, M. G. Science Institute, Ahmedabad, Gujarat, India
^*Correspondence e-mail: chintan.jotaniya@gmail.com

Edited by P. Dastidar, Indian Association for the Cultivation of Science, India (Received 23 June 2017; accepted 8 August 2017; online 11 August 2017)

In the title molecule, C₁₂H₁₃FN₂O₃, the central pyrrole ring makes a dihedral angle of 9.2 (3)° with the ethoxy carbonyl moiety whereas the fluorophenyl ring is rotated by 67.6 (2)° from the pyrrole ring. Supramolecular aggregation is due to off-centric π–π stacking interactions involving screw-related pairs of molecules, which are further connected by N—H⋯O and C—H⋯O interactions, forming a sinusoidal pattern along the [001] direction on the bc plane. Three-dimensional Hirshfeld surface analysis and two-dimensional fingerprint plots confirm the contributions of these interactions.

Keywords: crystal structure; halogen-substituted pyrrole derivative; X-ray crystallography; Hirshfeld surface analysis; hydrogen bonding.

CCDC reference: 1555656

1. Chemical context

Pyrrole, an electron-rich five-membered unsaturated ring, and its derivatives are widely used as intermediates in the synthesis of organic compounds, medicines, pharmaceuticals, agrochemicals, perfumes etc. Its derivatives possess a broad spectrum of biological activities. Substitution by a halogen (Cl, Br, F, I) is known to increase the activities of drug molecules and this group of molecules interact with receptors via halogen bonding. Organofluorine compounds display a variety of pharmacological and agro-chemical properties. Specific halogen-bonding interactions are responsible for the supramolecular architecture in halogen-substituted heterocycles. Bearing in mind the importance of pyrrole and the role of halogens, we have synthesized a series of halogen-substituted pyrrole derivatives. Bromo and methoxy derivatives of the title molecule have been reported earlier (Patel et al., 2012 , 2013 ). As a continuation of these studies, the title molecule, with fluorine as one of the substituents, was synthesized and characterized crystallographically and by Hirshfeld surface analysis.

2. Structural commentary

In the title compound, Fig. 1, the F atom is displaced by 0.014 (3) Å from the phenyl ring, facilitating it in to take part in a number of intermolecular interactions. The heterocyclic five-membered pyrrole ring is essentially planar with a maximum displacement of 0.022 (4) Å for atom C3 from its mean plane. The fluorophenyl ring forms a dihedral angle of 67.6 (2)° whereas the mean plane of ethoxy carbonyl tail is inclined at 9.2 (3)° to the central pyrrole ring. The terminal ethoxy carbonyl chain adopts a zigzag extended conformation, as is usually observed in analogous derivatives, with the carbonyl oxygen atom O19 on the same side as the methyl carbon atom C17 [C17—O16—C15—O19 = 5.0 (7)°] and the ethoxy carbon atom C18 in a trans [C15—O16—C17—C18 = 144.6 (5)°] conformation with respect to the pyrrole ring. Bond lengths in the phenyl ring vary from 1.365 (6) to 1.385 (6) Å and the endocyclic angle varies from 118.0 (4) to 122.9 (4)° with an average value of 120.4 (4)°, which coincides exactly with the theoretical value 120° for sp² hybridization.

Figure 1
ORTEP view of the title molecule with the atom-labelling scheme and displacement ellipsoids drawn at the 50% probability level.

The intramolecular N6—H61⋯O19 hydrogen bond involving the carbonyl oxygen atom O19 leads to the formation of a pseudo-six-membered ring with an S(6) graph-set motif.

3. Supramolecular features

In the crystal, two pairs of screw-related molecules are held together by off-centric π–π stacking interactions involving the pyrrole ring and the phenyl ring of a screw-related molecule (−x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z) [centroid–centroid distance = 4.179 (2) Å, slippage = 2.036 Å, dihedral angle between planes = 5.9 (2)°], forming chains along [010]. The structure contains infinite zigzag chains of screw-related molecules, forming a sinusoidal patterns along [001] on the bc plane as shown in Fig. 2.

Figure 2
View of the packing showing π–π stacking interactions and N—H⋯O and C—H⋯O hydrogen bonds (dashed lines) in the bc plane.

The molecular packing features N—H⋯O interactions, which lead to the formation of chains alon [001], and π–π stacking interactions, which link the molecules along [010]. In addition, C—H1⋯O interactions stack the molecules along [100] (Fig. 2, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H61⋯O19	0.86	2.2400	2.806 (4)	123
N6—H62⋯O7ⁱ	0.86	2.2100	2.970 (4)	147
C13—H13⋯O7ⁱⁱ	0.93	2.6000	3.320 (5)	135
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x-1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

4. Analysis of the Hirshfeld Surfaces

Crystal Explorer 3.1 (Wolff et al., 2012 ) was used to generate Hirshfeld surfaces mapped over d_norm, d_e and electrostatic potential for the title compound. The electrostatic potentials were calculated using TONTO (Spackman et al., 2008 ; Jayatilaka et al., 2005 ) as integrated in Crystal Explorer and are mapped on Hirshfeld surfaces using the STO-3G basis set at the Hartree–Fock level of theory over a range ±0.10 au as shown in Fig. 3. The positive electrostatic potential (blue region) over the surface indicates a hydrogen-bond donor, whereas the hydrogen-bond acceptors are represented by negative electrostatic potential (red region). The contact distances d_i and d_e from the Hirshfeld surface to the nearest atom inside and outside, respectively, enables the analysis of the intermolecular interactions through the mapping of d_norm.

Figure 3
View of the Hirshfeld surface mapped over the calculated electrostatic potential for the title compound. The red and blue regions represent negative and positive electrostatic potentials, respectively.

A view of the Hirshfeld surface mapped over d_norm, shape-index and curvedness for the title compound are shown in Fig. 4. Hirshfeld surfaces marked with red regions in d_norm near atoms O7, O19, N6, H62 and H10 reveal the active participation of the respective atoms in intermolecular interactions. The occurrence of N—H⋯O and C—H⋯O interactions is confirmed by analysis of the Hirshfeld surface. N6—H62⋯O19 interactions are shown on the Hirshfeld surface marked with bright-red dotted lines in Fig. 5. Yellow dotted lines mapped on the d_norm Hirshfeld surface in Fig. 6 reveal the presence of C13—H13⋯O7 and C17—H172⋯O19 interactions.

Figure 4
View of the Hirshfeld surface mapped over (a) d_norm, (b) shape-index and (c) curvedness.

Figure 5
d_norm mapped on the Hirshfeld surface for visualizing the N—H⋯O intermolecular interactions of the title compound. Red dotted lines represent hydrogen bonds.

Figure 6
d_norm mapped on the Hirshfeld surface for visualizing the C—H⋯O intermolecular interactions (yellow dotted lines) of the title compound.

The two-dimensional fingerprint plots (Rohl et al., 2008 ) for the title molecule are shown in Fig. 7. The inter atomic H⋯H contacts appear as scattered points over the larger part of the plot along with one distinct spike with the highest contribution within the Hirshfeld surface of 44.9% (Fig. 7b), followed by 20.8% for O⋯H/H⋯O contacts, which appear as pairs of adjacent spikes having almost same length. The contributions of H⋯F/F⋯H and C⋯H/H⋯C contacts are 12.8 and 10.4%, respectively. The contribution of C⋯C contacts, i.e. 3.0%, shows the π–π stacking interactions in the compound have a relatively smaller contribution. Apart from these, C⋯O/O⋯C, C⋯N/N⋯C, O⋯F/F⋯O, O⋯N/N⋯O and C⋯F/F⋯C contacts are found, as summarized in Table 2.

Table 2
Summary of various contacts and their percentage contributions to the Hirshfeld surface

Type of contact	Contribution
H⋯H	44.9
O⋯H/H⋯O	20.8
H⋯F/F⋯H	12.8
C⋯H/H⋯C	10.4
C⋯C	3.4
C⋯O/O⋯C	3.0
C⋯N/N⋯C	1.8
O⋯F/F⋯O	1.0
O⋯N/N⋯O	0.6
C⋯F/F⋯C	0.5

Figure 7
The two-dimensional fingerprint plots for the title compound, showing contributions from different contacts, (a) all, (b) H⋯H, (c) O⋯H/H⋯O, (d) H⋯F/F⋯H, (e) C⋯H/H⋯C and (f) C⋯C, respectively.

5. Database survey

Two analogous structures, 2-amino-1(4-bromophenyl)-5-oxo-4,5-dihydro-1H-pyrrole-3-carboxylic acid ethyl ester (Patel et al., 2012) and 2-amino-1-(4-methoxyphenyl)-5-oxo-4,5-dihydro-1H-pyrrole-3-carboxylic acid ethyl ester (Patel et al., 2013), in which the fluorophenyl ring of the title compound is replaced by a bromo or methoxyphenyl ring, are reported in the Cambridge Structural Database (Groom et al., 2016 ).

6. Synthesis and crystallization

In a 50 ml flat-bottom flask, a mixture of dry toluene (15 ml), potassium hydroxide (0.012 mol, 0.672 g) and 18-crown-6 (0.0005 mol, 0.132 g) were prepared. Ethyl cyanoacetate (0.006 mol, 0.6787 g) was then added to this stirred mixture, followed by the portionwise addition of N-(4-fluorophenyl)-2-chloroacetamide (0.005 mol, 1.2425 g) after 5 min. The stirring was continued until the chloroacetamide derivative had been consumed (20 min), monitored TLC (hexane:ethyl acetate 7:3). On completion of the reaction, water (25 ml) was added to the reaction mixture and stirring continued for a further 5 min. This was then taken into a separating funnel and the aqueous phase was neutralized with glacial acetic acid (pH = 7). The phases were separated and the aqueous phase extracted with toluene (10 ml). The combined organic layers were dried over magnesium sulfate and the toluene removed in vacuo to obtain a solid product. The crude product was crystallized from ethanol to obtain 1.42 g (87% yield) of 2-amino-1-(4-fluorophenyl)-oxo-4,5-dihydro-1H-pyrrole-3-carboxylic acid ethyl ester, m.p. 783.24 K. It is more or less soluble in different solvents such as benzene, ethanol, DMF, DMSO, CH₂CL₂, CHCl₃, ethyl acetate but diffraction quality crystal could be grown by the slow evaporation method at room temperature from ethyl acetate only after repeated trials.

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. Carbon-bound H atoms were placed in their calculated positions (C—H = 0.93–0.97 Å) and are included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	C₁₃H₁₃FN₂O₃
M_r	264.25
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	273
a, b, c (Å)	5.5357 (16), 8.548 (2), 27.026 (7)
V (Å³)	1278.9 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.7 × 0.3 × 0.2

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007 )
T_min, T_max	0.962, 0.979
No. of measured, independent and observed [I > 2Σ(I)] reflections	7696, 2975, 2322
R_int	0.032

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.148, 1.18
No. of reflections	2975
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.24
Computer programs: APEX2 and SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1555656

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989017011628/ds2246sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017011628/ds2246Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Ethyl 2-amino-1-(4-fluorophenyl)-5-oxo-4,5-dihydro-1H-pyrrole-3-carboxylate: top

Crystal data top

C₁₃H₁₃FN₂O₃	D_x = 1.372 Mg m⁻³
M_r = 264.25	Melting point: 783.39 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7696 reflections
a = 5.5357 (16) Å	θ = 1.5–28.2°
b = 8.548 (2) Å	µ = 0.11 mm⁻¹
c = 27.026 (7) Å	T = 273 K
V = 1278.9 (6) Å³	Transparent, colourless
Z = 4	0.7 × 0.3 × 0.2 mm
F(000) = 552

Data collection top

Bruker SMART APEX CCD diffractometer	2975 independent reflections
Radiation source: SEALED TUBE	2322 reflections with I > 2Σ(I)
Graphite monochromator	R_int = 0.032
ω–2θ scan	θ_max = 28.2°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −7→6
T_min = 0.962, T_max = 0.979	k = −10→11
7696 measured reflections	l = −34→32

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.075	H-atom parameters constrained
wR(F²) = 0.148	Weighting scheme based on measured s.u.'s
S = 1.18	(Δ/σ)_max = 0.006
2975 reflections	Δρ_max = 0.23 e Å⁻³
173 parameters	Δρ_min = −0.24 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

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

	x	y	z	U_iso*/U_eq
F14	0.0103 (6)	0.1908 (3)	0.41628 (9)	0.0777 (11)
O7	−0.3466 (5)	0.3868 (3)	0.20473 (10)	0.0501 (9)
O16	0.0782 (6)	0.1173 (4)	0.04855 (10)	0.0675 (11)
O19	0.3634 (6)	0.0024 (4)	0.09592 (11)	0.0665 (11)
N1	−0.0226 (5)	0.2174 (3)	0.21258 (11)	0.0380 (9)
N6	0.3131 (6)	0.0484 (3)	0.19821 (11)	0.0449 (10)
C2	−0.1947 (7)	0.3016 (4)	0.18607 (14)	0.0402 (11)
C3	−0.1510 (8)	0.2676 (4)	0.13223 (14)	0.0457 (12)
C4	0.0711 (7)	0.1663 (4)	0.13244 (13)	0.0403 (11)
C5	0.1342 (6)	0.1388 (4)	0.18000 (13)	0.0351 (11)
C8	−0.0114 (6)	0.2105 (4)	0.26584 (12)	0.0345 (11)
C9	0.1786 (7)	0.2794 (4)	0.29063 (14)	0.0420 (12)
C10	0.1843 (8)	0.2732 (5)	0.34181 (15)	0.0503 (12)
C11	0.0017 (8)	0.1985 (5)	0.36617 (14)	0.0490 (14)
C12	−0.1879 (8)	0.1282 (5)	0.34218 (15)	0.0527 (16)
C13	−0.1941 (7)	0.1362 (4)	0.29129 (14)	0.0437 (12)
C15	0.1869 (8)	0.0873 (5)	0.09193 (14)	0.0473 (12)
C17	0.1672 (12)	0.0330 (8)	0.00528 (17)	0.094 (2)
C18	−0.0234 (14)	−0.0020 (10)	−0.0268 (2)	0.134 (4)
H9	0.30124	0.32939	0.27321	0.0506*
H10	0.31042	0.31912	0.35929	0.0606*
H12	−0.30851	0.07676	0.35975	0.0630*
H13	−0.32196	0.09126	0.27406	0.0526*
H31	−0.12308	0.36342	0.11386	0.0551*
H32	−0.28713	0.21277	0.11777	0.0551*
H61	0.40656	−0.00181	0.17837	0.0539*
H62	0.33375	0.04110	0.22967	0.0539*
H171	0.28599	0.09643	−0.01185	0.1126*
H172	0.24516	−0.06313	0.01573	0.1126*
H181	0.03741	−0.05787	−0.05497	0.2012*
H182	−0.09846	0.09335	−0.03758	0.2012*
H183	−0.14019	−0.06545	−0.00986	0.2012*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F14	0.087 (2)	0.109 (2)	0.0371 (14)	0.006 (2)	−0.0004 (14)	0.0091 (13)
O7	0.0503 (16)	0.0487 (14)	0.0512 (16)	0.0128 (15)	−0.0068 (14)	−0.0092 (12)
O16	0.071 (2)	0.098 (2)	0.0334 (15)	0.011 (2)	−0.0043 (14)	−0.0106 (16)
O19	0.064 (2)	0.084 (2)	0.0516 (18)	0.017 (2)	0.0054 (15)	−0.0114 (16)
N1	0.0386 (17)	0.0400 (15)	0.0355 (17)	0.0025 (15)	−0.0067 (14)	0.0008 (13)
N6	0.0452 (19)	0.0525 (18)	0.0371 (17)	0.0057 (17)	0.0003 (15)	−0.0050 (14)
C2	0.046 (2)	0.0337 (18)	0.041 (2)	0.0002 (19)	−0.0057 (19)	−0.0048 (16)
C3	0.050 (2)	0.043 (2)	0.044 (2)	−0.001 (2)	−0.012 (2)	−0.0030 (17)
C4	0.042 (2)	0.0419 (19)	0.037 (2)	0.0004 (17)	−0.0040 (17)	−0.0021 (17)
C5	0.0337 (19)	0.0340 (17)	0.0377 (19)	−0.0045 (16)	−0.0009 (16)	−0.0005 (15)
C8	0.034 (2)	0.0346 (17)	0.0349 (19)	0.0072 (17)	0.0009 (16)	−0.0007 (14)
C9	0.042 (2)	0.043 (2)	0.041 (2)	−0.008 (2)	−0.0008 (18)	0.0053 (16)
C10	0.045 (2)	0.057 (2)	0.049 (2)	0.000 (2)	−0.012 (2)	−0.0007 (19)
C11	0.057 (3)	0.059 (2)	0.031 (2)	0.010 (2)	0.000 (2)	0.0080 (18)
C12	0.045 (2)	0.062 (3)	0.051 (3)	−0.001 (2)	0.011 (2)	0.011 (2)
C13	0.036 (2)	0.045 (2)	0.050 (2)	−0.0025 (19)	−0.0008 (18)	−0.0012 (18)
C15	0.048 (2)	0.052 (2)	0.042 (2)	−0.006 (2)	−0.0012 (19)	−0.0025 (18)
C17	0.091 (4)	0.146 (5)	0.045 (3)	0.017 (5)	0.002 (3)	−0.025 (3)
C18	0.108 (6)	0.205 (8)	0.090 (4)	0.009 (6)	−0.017 (4)	−0.078 (5)

Geometric parameters (Å, º) top

F14—C11	1.357 (5)	C9—C10	1.385 (6)
O7—C2	1.221 (5)	C10—C11	1.365 (6)
O16—C15	1.343 (5)	C11—C12	1.372 (6)
O16—C17	1.459 (6)	C12—C13	1.378 (6)
O19—C15	1.222 (6)	C17—C18	1.398 (9)
N1—C2	1.393 (5)	C3—H31	0.9700
N1—C5	1.407 (4)	C3—H32	0.9700
N1—C8	1.442 (4)	C9—H9	0.9300
N6—C5	1.349 (5)	C10—H10	0.9300
C2—C3	1.503 (5)	C12—H12	0.9300
C3—C4	1.504 (6)	C13—H13	0.9300
C4—C5	1.353 (5)	C17—H171	0.9700
C4—C15	1.437 (5)	C17—H172	0.9700
N6—H61	0.8600	C18—H181	0.9600
N6—H62	0.8600	C18—H182	0.9600
C8—C13	1.378 (5)	C18—H183	0.9600
C8—C9	1.379 (5)

C15—O16—C17	117.0 (4)	O16—C15—C4	112.1 (4)
C2—N1—C5	110.3 (3)	O19—C15—C4	124.7 (4)
C2—N1—C8	124.4 (3)	O16—C17—C18	110.4 (5)
C5—N1—C8	125.4 (3)	C2—C3—H31	111.00
O7—C2—N1	124.5 (3)	C2—C3—H32	111.00
O7—C2—C3	128.7 (4)	C4—C3—H31	111.00
N1—C2—C3	106.7 (3)	C4—C3—H32	111.00
C2—C3—C4	103.8 (3)	H31—C3—H32	109.00
C3—C4—C5	108.4 (3)	C8—C9—H9	120.00
C3—C4—C15	129.2 (3)	C10—C9—H9	120.00
C5—C4—C15	121.8 (3)	C9—C10—H10	121.00
N1—C5—N6	119.9 (3)	C11—C10—H10	121.00
N1—C5—C4	110.6 (3)	C11—C12—H12	121.00
N6—C5—C4	129.5 (3)	C13—C12—H12	121.00
C5—N6—H62	120.00	C8—C13—H13	120.00
H61—N6—H62	120.00	C12—C13—H13	120.00
C5—N6—H61	120.00	O16—C17—H171	110.00
C9—C8—C13	120.9 (3)	O16—C17—H172	110.00
N1—C8—C13	119.1 (3)	C18—C17—H171	110.00
N1—C8—C9	120.0 (3)	C18—C17—H172	110.00
C8—C9—C10	119.1 (4)	H171—C17—H172	108.00
C9—C10—C11	118.9 (4)	C17—C18—H181	109.00
F14—C11—C10	118.6 (4)	C17—C18—H182	109.00
F14—C11—C12	118.5 (4)	C17—C18—H183	109.00
C10—C11—C12	122.9 (4)	H181—C18—H182	109.00
C11—C12—C13	118.0 (4)	H181—C18—H183	109.00
C8—C13—C12	120.2 (4)	H182—C18—H183	109.00
O16—C15—O19	123.3 (4)

C17—O16—C15—O19	5.0 (7)	C3—C4—C5—N6	176.4 (3)
C17—O16—C15—C4	−174.9 (4)	C15—C4—C5—N1	−173.6 (3)
C15—O16—C17—C18	144.6 (5)	C15—C4—C5—N6	4.7 (6)
C5—N1—C2—O7	−176.3 (3)	C3—C4—C15—O16	2.6 (6)
C8—N1—C2—O7	4.7 (5)	C3—C4—C5—N1	−1.9 (4)
C5—N1—C2—C3	2.9 (4)	C3—C4—C15—O19	−177.3 (4)
C5—N1—C8—C9	69.1 (4)	C5—C4—C15—O16	172.5 (4)
C2—N1—C8—C13	67.1 (4)	C5—C4—C15—O19	−7.4 (7)
C5—N1—C8—C13	−111.7 (4)	N1—C8—C9—C10	179.2 (3)
C2—N1—C5—N6	−179.2 (3)	C13—C8—C9—C10	0.0 (5)
C8—N1—C5—N6	−0.2 (5)	N1—C8—C13—C12	−179.9 (3)
C2—N1—C5—C4	−0.7 (4)	C9—C8—C13—C12	−0.7 (5)
C8—N1—C5—C4	178.3 (3)	C8—C9—C10—C11	0.2 (6)
C2—N1—C8—C9	−112.1 (4)	C9—C10—C11—C12	0.3 (7)
C8—N1—C2—C3	−176.1 (3)	C9—C10—C11—F14	179.0 (4)
O7—C2—C3—C4	175.4 (4)	F14—C11—C12—C13	−179.7 (4)
N1—C2—C3—C4	−3.8 (4)	C10—C11—C12—C13	−1.0 (7)
C2—C3—C4—C5	3.5 (4)	C11—C12—C13—C8	1.2 (6)
C2—C3—C4—C15	174.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H61···O19	0.86	2.2400	2.806 (4)	123
N6—H62···O7ⁱ	0.86	2.2100	2.970 (4)	147
C13—H13···O7ⁱⁱ	0.93	2.6000	3.320 (5)	135
C17—H172···O19	0.97	2.3300	2.692 (6)	101

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

Summary of various contacts and their percentage contributions to the Hirshfeld surface top

Type of contact	Contribution
H···H	44.9
O···H/H···O	20.8
H···F/F···H	12.8
C···H/H···C	10.4
C···C	3.4
C···O/O···C	3.0
C···N/N···C	1.8
O···F/F···O	1.0
O···N/N···O	0.6
C···F/F···C	0.5

Acknowledgements

The authors are thankful to the Department of Physics, SPU, for providing the financial support to carry out the work and also to CSMCRI, Bhavnagar, for the data collection.

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