Crystal structure and Hirshfeld surface analysis of 2-azido-N-(4-fluoro­phen­yl)acetamide

Missioui, M.; Guerrab, W.; Alsubari, A.; Mague, J.T.; Ramli, Y.

doi:10.1107/S2056989022006764

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 78| Part 8| August 2022| Pages 855-859

https://doi.org/10.1107/S2056989022006764

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Crystal structure and Hirshfeld surface analysis of 2-azido-N-(4-fluorophenyl)acetamide

Mohcine Missioui,^a Walid Guerrab,^a Abdulsalam Alsubari,^b ^* Joel T. Mague ^c and Youssef Ramli ^a ‡

^aLaboratory of Medicinal Chemistry, Drug Sciences Research Center, Faculty of Medicine and Pharmacy, Mohammed V University in Rabat, Morocco, ^bLaboratory of Medicinal Chemistry, Faculty of Clinical Pharmacy, 21 September University, Yemen, and ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: alsubaripharmaco@21umas.edu.ye

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 6 June 2022; accepted 30 June 2022; online 29 July 2022)

The asymmetric unit of the title compound, C₈H₇FN₄O, consists of two independent molecules differing in the orientation of the azido group. Each molecule forms N—H⋯O hydrogen-bonded chains along along the c-axis direction with its symmetry-related counterparts and the chains are connected by C—F⋯π(ring), C=O⋯π(ring) and slipped π-stacking interactions. A Hirshfeld surface analysis of these interactions was performed.

Keywords: crystal structure; azide; acetamide; hydrogen bond; Hirshfeld surface.

CCDC reference: 2183049

1. Chemical context

Azides are a class of versatile organic compounds having the basic structure RN₃ where R can be an alkyl, acyl or aryl group. They have found valuable applications in medicinal chemistry (Contin et al., 2019 ) and molecular biology (Ahmed & Abdallah, 2019 ). On the other hand, amide bonds are a key structural unit in many physiologically active compounds and have ubiquitous presence in biopolymers such as proteins and glycoproteins (Cheng et al., 2016 ; Pattabiraman & Bode, 2011 ; Zheng et al., 2016 ). Acetamides are useful building blocks for the preparation of biologically active natural products, especially depsipeptide compounds. In particular, N-arylacetamides are significant intermediates for the synthesis of medicinal, agrochemical, and pharmaceutical compounds (Valeur & Bradley, 2009 ; Allen & Williams, 2011 ; Missioui et al., 2021 ; Missioui et al., 2022a ,b ). They have been identified as inhibitors of methionine aminopeptidase-2 and HIV protease, display potent antitumor activity, and play an important role in medicinal chemistry. As a result of the significance of this core, and in a continuation of our research efforts to synthesize N-arylacetamide-based heterocycles (Missioui et al., 2020 ; Al-Taifi et al., 2021 ; Guerrab et al., 2021 ; Missioui et al., 2022c ,d ), we report here the synthesis, molecular and crystal structures and a Hirshfeld surface analysis of the title compound.

2. Structural commentary

The asymmetric unit consists of two independent molecules differing moderately in conformation and connected by a weak C15=O2⋯Cg1 interaction [Cg1 is the centroid of the C1–C6 benzene ring; O2⋯Cg1 = 3.904 (2) Å, C15⋯Cg1 = 3.902 (2) Å, C15=O2⋯Cg1 = 80.88 (13)°] as shown in Fig. 1. The conformational difference is primarily in the orientation of the azide groups (Fig. 2). Thus the N3—N2—C8–C7 torsion angle between the planes defined by N1/C7/C8/O1 and C8/N2/N3/N4 is −106.1 (2)° while the corresponding dihedral angle in the other molecule is −175.4 (2)°. The dihedral angle between the plane defined by N1/C7/C8/O1 and that of the C1-C6 ring is 21.85 (13)° while the corresponding angle (N7—N6—C16—C15) in the other molecule is the same within experimental error. By comparison, in the p-tolyl analog (Missioui et al., 2022e ), which has three independent molecules in the asymmetric unit, the dihedral angles between the N/C/C/O and C/N/N/N planes are 7.6 (2), 86.34 (19) and 7.03 (19)° while those between the N/C/C/O and phenyl ring planes are 24.2 (2), 22.58 (10) and 15.38 (10)°.

Figure 1
The asymmetric unit with labeling scheme and 50% probability ellipsoids. The C15=O2⋯Cg1 interaction is depicted by a dashed line.

Figure 2
Overlay of the two molecules in the asymmetric unit. The yellow molecule contains O1 while the red one contains O2.

3. Supramolecular features

In the crystal, the molecule containing O1 is linked into chains extending along the c-axis direction by N1—H1⋯O1ⁱ hydrogen bonds [symmetry code: (i) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ], while N5—H5A⋯O2ⁱ hydrogen bonds form parallel chains for the second independent molecule (Table 1 and Fig. 3). The chains are linked by C4—F1⋯Cg1ⁱⁱ and C12—F2⋯Cg2ⁱⁱⁱ [Cg2 is the centroid of the C9–C14 benzene ring; symmetry codes: (ii) −x + 1, −y + 1, −z + 1; (iii) −x + 2, −y + 1, −z + 2] interactions as well as by the C15=O2⋯Cg1 interaction noted above and weak, slipped π-stacking between centrosymmetrically related C1–C6 benzene rings [centroid–centroid = 3.8661 (13) Å, slippage = 1.6 Å] (Table 1 and Fig. 4). For the related p-tolyl analog (Missioui et al., 2022e) each independent molecule forms chains with its symmetry-related counterparts through N—H⋯O hydrogen bonds. There do not appear to be significant intermolecular interactions between the chains although it is possible that very weak C=O⋯π(ring) interactions exist.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.17	2.921 (2)	146
N5—H5A⋯O2ⁱ	0.86	2.13	2.885 (2)	146
C4—F1⋯Cg1ⁱⁱ	1.35 (1)	3.76 (1)	3.563 (2)	72 (1)
C12—F2⋯Cg2ⁱⁱⁱ	1.36 (1)	3.98 (1)	3.942 (2)	79 (1)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) ; (iii) .

Figure 3
Perspective view of the chain structure with N—H⋯O hydrogen bonds and C15=O2⋯Cg1 interactions depicted, respectively, by violet and light-blue dashed lines. Non-interacting hydrogen atoms are omitted for clarity.

Figure 4
Packing viewed along the c-axis direction showing the linking of chains via C—F⋯π(ring) (green dashed lines) and C15=O2⋯Cg1 (light-blue dashed lines) and slipped π-stacking (orange dashed lines) interactions. N—H⋯O hydrogen bonds and non-interacting hydrogen atoms are omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (CSD, version 5.43, updated to March 2022; Groom et al., 2016 ) with the search fragment A gave eleven hits of which three contained the 2-azidoacetamide unit while 30 hits resulted from a search with fragment B, of which six contained the 2-azidoacetamide unit.

In the first group, the aromatic ring has a –CO₂Et group in the 2-position (ARAPIU: Yassine et al., 2016a ), the second has ⁱPrS– groups in the 2- and 3-positions (CEMRUJ: Okamura et al., 2013 ) and the last has a –CO₂ⁿBu group in the 2-position (OVIBAY: Yassine et al., 2016b ). The six relevant structures in the second group include ones with an unsubstituted phenyl group (ASEDIO: Guerrab et al., 2021) and those with the 4-position containing –NO₂ (QAGNOF: Missioui et al., 2020), HC≡C– (DAPYOM: Madhusudhanan et al., 2021 ), MeO– (TARHIH: Missioui et al., 2021) and 2-acetoxymethyl-3,4,5-triacetoxy-tetrahydro-2H-pyran-6-yl-O– (BEBPIJ: Cecioni et al., 2012 ). The sixth has Cl at the 4-position and a 2-chlorobenzoyl substituent in the 2-position (VIFVOX: Cortes Eduardo et al., 2012 ). In ARAPIU and OVIBAY, the amide hydrogens form intramolecular N—H⋯O hydrogen bonds with the carboxyl oxygen while in CEMRUJ an intramolecular interaction of the amide hydrogen with the sulfur atom in the 2-position is postulated. Thus, none of these structures show the formation of chains as seen in the present case nor do any have more than one molecule in the asymmetric unit. Among the others, ASEDIO has two independent molecules in the asymmetric unit and it also, like QAGNOF and BEBPIJ, forms chains through N—H⋯O hydrogen bonds. In ASEDIO, the chains are connected by π-interactions between the terminal two nitrogens of the azide group and a phenyl ring, while in QAGNOF the chains are connected by C—H⋯O and C—H⋯N hydrogen bonds. The remaining structures in the first group all contain the —N=N—C fragment while the remainder of the second group all contain triazoles as the N₃-containing fragment and are not considered relevant to the present structure.

5. Hirshfeld surface analysis

A Hirshfeld surface analysis was performed with CrystalExplorer 21.5 (Spackman et al., 2021 ) with the details of the pictorial output described in a recent publication (Tan et al., 2019 ). Fig. 5a and 5c, respectively, show the d_norm surfaces of the molecule containing O1 and that containing O2 plotted over the range −0.4316 to 1.3253 in arbitrary units while Fig. 5b and 5d show the corresponding shape-index functions. In both, two adjacent molecules that are part of the hydrogen-bonded chains are included with the N—H⋯O and C—H⋯O interactions shown by dashed lines. The pattern of orange and blue triangles indicative of a π-interaction is clearly evident in the lower part of Fig. 5b and corresponds to the C4—F1⋯Cg1 interaction. This is less clear in Fig. 5d but the data in Table 1 clearly support a similar interaction for this molecule. Fig. 6 presents fingerprint plots for the molecule containing O1 with Fig. 6a showing all intermolecular interactions and Fig. 6b–6f those delineated into N⋯H/H⋯N (34.3%), H⋯H (13.5%), O⋯H/H⋯O (12.2%), C⋯H/H⋯C (11.9%) and F⋯H/H⋯F (9.7%), respectively. The two spikes in Fig. 6d primarily represent the N—H⋯O hydrogen bonds but their breadth at longer values of d_i + d_e than at the tips indicate the contributions from C—H⋯O hydrogen bonds. Fig. 7 shows the fingerprint plots for the molecule containing O2 with Fig. 7a showing all intermolecular interactions and Fig. 7b–7f those delineated into N⋯H/H⋯N (28.8%), H⋯H (18.2%), C⋯H/H⋯C (12.6%), F⋯H/H⋯F (12.6%) and O⋯H/H⋯O (11.6%), respectively. Although the ordering of interactions based on their percentage of the total is not the same as in the other molecule, the percentages are not greatly different between the two and the corresponding plots are very similar type by type.

Figure 5
The (a) d_norm and (b) shape-index surfaces for the molecule containing O1, and the (c) d_norm and (d) shape-index surfaces for the molecule containing O2 together with the two closest molecules of each type.

Figure 6
Fingerprint plots for the molecule containing O1 showing intermolecular interactions. (a) all; (b) N⋯H/H⋯N; (c) H⋯H; (d) O⋯H/H⋯O; (e) C⋯H/H⋯C; (f) F⋯H/H⋯F.

Figure 7
Fingerprint plots for the molecule containing O2 showing intermolecular interactions. (a) all; (b) N⋯H/H⋯N; (c) H⋯H; (d) C⋯H/H⋯C; (e) F⋯H/H⋯F; (f) O⋯H/H⋯O.

6. Synthesis and crystallization

2-Chloro-N-(4-fluorophenyl)acetamide (0.011 mol), and sodium azide (0.015 mol) were dissolved in a mixture of ethanol/water (70:30) and refluxed for 24 h at 353 K. After completion of the reaction (monitored by thin-layer chromatography, TLC), the 2-azido-N-(4-fluorophenyl)acetamide that precipitated was filtered off and washed with cold water. A portion of the product was dissolved in hot ethanol, the solution was filtered, and the filtrate was left undisturbed for 7 days to form colorless, thick plate-like crystals.

Yield 69%, m.p. 358–360K, FT–IR (ATR, υ, cm⁻¹) 3254 υ (N—H amide), 1027 υ (N—C amide), 1660 υ (C=O amide), 3073 υ(C—H_arom), 1175 υ(C—N), 2961 υ(C—H, CH₂), 2109 υ (N₃), ¹H NMR (DMSO–d₆) δ ppm: 4.02 (2H, s, CH₂), 6.93–7.11 (4H, m, J = 1.3 Hz, H_arom), 10.05 (1H, s, NH), ¹³C NMR (DMSO–d₆) δ ppm: 51.18 (CH₂), 131.47 (C_arom—N), 113.90–120.86 (C_arom); 165.71 (C=O); HRMS (ESI–MS) (m/z) calculated for C₈H₇FN₄O 194.18; found 194.1165.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms attached to carbon were placed in calculated positions (C—H = 0.95–0.99 Å) while those attached to nitrogen were placed in locations derived from a difference map and their parameters adjusted to give N—H = 0.91 Å. All were included as riding contributions with isotropic displacement parameters 1.2–1.5 times those of the attached atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₇FN₄O
M_r	194.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.8398 (7), 19.0207 (11), 9.3307 (5)
β (°)	112.378 (2)
V (Å³)	1778.93 (18)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	1.00
Crystal size (mm)	0.47 × 0.25 × 0.15

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.75, 0.87
No. of measured, independent and observed [I > 2σ(I)] reflections	12623, 3224, 2545
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.162, 1.06
No. of reflections	3224
No. of parameters	254
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.24
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SHELXT/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ), and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 2183049

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989022006764/vm2266sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022006764/vm2266Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989022006764/vm2266Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

2-Azido-N-(4-fluorophenyl)acetamide top

Crystal data top

C₈H₇FN₄O	F(000) = 800
M_r = 194.18	D_x = 1.450 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 10.8398 (7) Å	Cell parameters from 8481 reflections
b = 19.0207 (11) Å	θ = 2.3–68.3°
c = 9.3307 (5) Å	µ = 1.00 mm⁻¹
β = 112.378 (2)°	T = 296 K
V = 1778.93 (18) Å³	Thick plate, colourless
Z = 8	0.47 × 0.25 × 0.15 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	3224 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2545 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.034
Detector resolution: 10.4167 pixels mm^-1	θ_max = 68.5°, θ_min = 4.4°
ω scans	h = −12→11
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −22→22
T_min = 0.75, T_max = 0.87	l = −11→11
12623 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.162	w = 1/[σ²(F_o²) + (0.0828P)² + 0.4718P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3224 reflections	Δρ_max = 0.45 e Å⁻³
254 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL 2018/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: dual	Extinction coefficient: 0.0033 (5)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) 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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) while those attached to nitrogen were placed in locations derived from a difference map and their parameters adjusted to give N—H = 0.91 Å. All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms.

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

	x	y	z	U_iso*/U_eq
F1	0.75450 (16)	0.51934 (8)	0.5506 (2)	0.1053 (6)
O1	0.37628 (16)	0.27865 (8)	0.11857 (16)	0.0704 (5)
N1	0.38854 (15)	0.30447 (8)	0.36111 (17)	0.0528 (4)
H1	0.357573	0.292390	0.429765	0.063*
N2	0.23792 (19)	0.15768 (11)	0.1118 (2)	0.0780 (6)
N3	0.1406 (2)	0.15796 (10)	−0.0097 (2)	0.0673 (5)
N4	0.0587 (3)	0.15058 (17)	−0.1238 (3)	0.1192 (11)
C1	0.48107 (18)	0.36020 (10)	0.4020 (2)	0.0494 (4)
C2	0.5065 (2)	0.40201 (11)	0.2943 (2)	0.0614 (5)
H2	0.461604	0.394037	0.188729	0.074*
C3	0.5994 (2)	0.45573 (12)	0.3457 (3)	0.0725 (6)
H3	0.617810	0.483972	0.274916	0.087*
C4	0.6637 (2)	0.46685 (11)	0.5015 (3)	0.0702 (6)
C5	0.6383 (2)	0.42787 (12)	0.6092 (3)	0.0675 (6)
H5	0.681609	0.437309	0.714400	0.081*
C6	0.54707 (19)	0.37419 (11)	0.5590 (2)	0.0569 (5)
H6	0.529166	0.346752	0.631306	0.068*
C7	0.34277 (18)	0.26790 (10)	0.2280 (2)	0.0517 (5)
C8	0.2417 (2)	0.21221 (12)	0.2228 (3)	0.0655 (6)
H8A	0.265262	0.191575	0.324847	0.079*
H8B	0.154166	0.233482	0.193244	0.079*
F2	1.2344 (2)	0.51818 (12)	0.9845 (3)	0.1438 (9)
O2	0.86230 (17)	0.27797 (9)	0.55142 (18)	0.0760 (5)
N5	0.87105 (16)	0.30220 (9)	0.79296 (17)	0.0546 (4)
H5A	0.839332	0.289670	0.860681	0.065*
N6	0.6704 (2)	0.18385 (13)	0.4918 (2)	0.0899 (7)
N7	0.5847 (2)	0.14001 (11)	0.4654 (2)	0.0670 (5)
N8	0.5019 (2)	0.10061 (15)	0.4215 (3)	0.0952 (8)
C9	0.96341 (19)	0.35814 (10)	0.8354 (2)	0.0536 (5)
C10	0.9881 (2)	0.40031 (12)	0.7283 (3)	0.0644 (5)
H10	0.943298	0.392439	0.622692	0.077*
C11	1.0801 (3)	0.45421 (14)	0.7798 (4)	0.0827 (7)
H11	1.098105	0.482845	0.709361	0.099*
C12	1.1445 (3)	0.46493 (15)	0.9364 (4)	0.0907 (8)
C13	1.1195 (3)	0.42528 (16)	1.0435 (3)	0.0904 (8)
H13	1.162906	0.434404	1.148769	0.108*
C14	1.0292 (2)	0.37163 (13)	0.9929 (3)	0.0713 (6)
H14	1.011492	0.343792	1.064795	0.086*
C15	0.82697 (19)	0.26628 (10)	0.6592 (2)	0.0539 (5)
C16	0.7313 (2)	0.20775 (12)	0.6530 (2)	0.0636 (5)
H16A	0.778421	0.169287	0.719587	0.076*
H16B	0.662987	0.224593	0.687969	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0904 (10)	0.0706 (9)	0.1334 (15)	−0.0264 (8)	0.0185 (10)	0.0103 (9)
O1	0.0994 (11)	0.0750 (10)	0.0495 (8)	−0.0053 (8)	0.0428 (8)	−0.0079 (7)
N1	0.0596 (9)	0.0653 (10)	0.0411 (8)	−0.0057 (7)	0.0275 (7)	−0.0050 (7)
N2	0.0694 (11)	0.0849 (14)	0.0739 (13)	0.0008 (10)	0.0208 (10)	−0.0273 (10)
N3	0.0781 (12)	0.0777 (12)	0.0517 (11)	0.0052 (9)	0.0310 (10)	−0.0057 (8)
N4	0.1118 (19)	0.160 (3)	0.0615 (14)	0.0438 (19)	0.0055 (14)	−0.0281 (15)
C1	0.0507 (10)	0.0542 (10)	0.0484 (9)	0.0043 (8)	0.0247 (8)	−0.0003 (8)
C2	0.0684 (12)	0.0663 (13)	0.0534 (11)	0.0030 (10)	0.0276 (9)	0.0079 (9)
C3	0.0763 (14)	0.0614 (13)	0.0873 (16)	0.0025 (11)	0.0396 (13)	0.0198 (11)
C4	0.0589 (12)	0.0535 (12)	0.0897 (17)	−0.0022 (9)	0.0186 (11)	0.0052 (11)
C5	0.0646 (12)	0.0637 (13)	0.0652 (13)	−0.0030 (10)	0.0146 (10)	−0.0036 (10)
C6	0.0621 (11)	0.0621 (12)	0.0484 (10)	−0.0026 (9)	0.0231 (9)	−0.0008 (8)
C7	0.0568 (10)	0.0593 (11)	0.0429 (9)	0.0079 (8)	0.0234 (8)	−0.0033 (8)
C8	0.0651 (12)	0.0739 (13)	0.0620 (12)	−0.0080 (10)	0.0292 (10)	−0.0187 (10)
F2	0.1302 (15)	0.1254 (16)	0.174 (2)	−0.0711 (13)	0.0557 (15)	−0.0489 (15)
O2	0.1083 (13)	0.0784 (10)	0.0623 (9)	−0.0201 (9)	0.0561 (9)	−0.0135 (7)
N5	0.0633 (10)	0.0632 (10)	0.0437 (8)	−0.0014 (7)	0.0276 (7)	0.0018 (7)
N6	0.1168 (17)	0.1021 (17)	0.0610 (12)	−0.0385 (14)	0.0453 (12)	−0.0225 (11)
N7	0.0765 (12)	0.0788 (12)	0.0501 (9)	−0.0018 (11)	0.0292 (9)	−0.0103 (9)
N8	0.0906 (15)	0.123 (2)	0.0712 (13)	−0.0231 (15)	0.0300 (12)	−0.0307 (13)
C9	0.0530 (10)	0.0571 (11)	0.0538 (10)	0.0049 (8)	0.0239 (8)	−0.0017 (8)
C10	0.0691 (13)	0.0655 (13)	0.0654 (13)	−0.0018 (10)	0.0334 (10)	0.0007 (10)
C11	0.0871 (17)	0.0708 (15)	0.106 (2)	−0.0101 (13)	0.0538 (16)	−0.0003 (14)
C12	0.0779 (16)	0.0806 (18)	0.112 (2)	−0.0217 (13)	0.0351 (16)	−0.0251 (16)
C13	0.0863 (17)	0.096 (2)	0.0774 (17)	−0.0134 (15)	0.0181 (14)	−0.0200 (15)
C14	0.0750 (14)	0.0762 (15)	0.0578 (12)	−0.0036 (11)	0.0201 (10)	−0.0046 (11)
C15	0.0615 (11)	0.0580 (11)	0.0472 (10)	0.0029 (8)	0.0262 (9)	0.0004 (8)
C16	0.0717 (13)	0.0722 (13)	0.0502 (11)	−0.0077 (10)	0.0270 (9)	−0.0008 (9)

Geometric parameters (Å, º) top

F1—C4	1.353 (3)	F2—C12	1.358 (3)
O1—C7	1.224 (2)	O2—C15	1.225 (2)
N1—C7	1.343 (2)	N5—C15	1.341 (2)
N1—C1	1.409 (2)	N5—C9	1.411 (3)
N1—H1	0.8600	N5—H5A	0.8600
N2—N3	1.220 (3)	N6—N7	1.202 (3)
N2—C8	1.455 (3)	N6—C16	1.465 (3)
N3—N4	1.105 (3)	N7—N8	1.120 (3)
C1—C2	1.389 (3)	C9—C10	1.385 (3)
C1—C6	1.390 (3)	C9—C14	1.391 (3)
C2—C3	1.386 (3)	C10—C11	1.382 (3)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.368 (4)	C11—C12	1.374 (4)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.359 (3)	C12—C13	1.358 (4)
C5—C6	1.374 (3)	C13—C14	1.368 (4)
C5—H5	0.9300	C13—H13	0.9300
C6—H6	0.9300	C14—H14	0.9300
C7—C8	1.511 (3)	C15—C16	1.508 (3)
C8—H8A	0.9700	C16—H16A	0.9700
C8—H8B	0.9700	C16—H16B	0.9700

C7—N1—C1	127.90 (16)	C15—N5—C9	127.53 (16)
C7—N1—H1	116.0	C15—N5—H5A	116.2
C1—N1—H1	116.0	C9—N5—H5A	116.2
N3—N2—C8	116.02 (19)	N7—N6—C16	115.87 (19)
N4—N3—N2	171.2 (3)	N8—N7—N6	171.2 (2)
C2—C1—C6	119.27 (18)	C10—C9—C14	119.6 (2)
C2—C1—N1	123.51 (17)	C10—C9—N5	123.08 (18)
C6—C1—N1	117.20 (17)	C14—C9—N5	117.35 (18)
C3—C2—C1	119.3 (2)	C11—C10—C9	119.4 (2)
C3—C2—H2	120.3	C11—C10—H10	120.3
C1—C2—H2	120.3	C9—C10—H10	120.3
C4—C3—C2	119.4 (2)	C12—C11—C10	119.1 (3)
C4—C3—H3	120.3	C12—C11—H11	120.4
C2—C3—H3	120.3	C10—C11—H11	120.4
F1—C4—C5	118.5 (2)	C13—C12—F2	119.4 (3)
F1—C4—C3	119.0 (2)	C13—C12—C11	122.5 (2)
C5—C4—C3	122.4 (2)	F2—C12—C11	118.2 (3)
C4—C5—C6	118.4 (2)	C12—C13—C14	118.5 (3)
C4—C5—H5	120.8	C12—C13—H13	120.7
C6—C5—H5	120.8	C14—C13—H13	120.7
C5—C6—C1	121.11 (19)	C13—C14—C9	120.9 (2)
C5—C6—H6	119.4	C13—C14—H14	119.6
C1—C6—H6	119.4	C9—C14—H14	119.6
O1—C7—N1	124.23 (19)	O2—C15—N5	124.02 (19)
O1—C7—C8	122.15 (17)	O2—C15—C16	121.86 (18)
N1—C7—C8	113.61 (16)	N5—C15—C16	114.10 (16)
N2—C8—C7	110.25 (17)	N6—C16—C15	107.63 (17)
N2—C8—H8A	109.6	N6—C16—H16A	110.2
C7—C8—H8A	109.6	C15—C16—H16A	110.2
N2—C8—H8B	109.6	N6—C16—H16B	110.2
C7—C8—H8B	109.6	C15—C16—H16B	110.2
H8A—C8—H8B	108.1	H16A—C16—H16B	108.5

C7—N1—C1—C2	22.8 (3)	C15—N5—C9—C10	23.2 (3)
C7—N1—C1—C6	−158.76 (19)	C15—N5—C9—C14	−158.3 (2)
C6—C1—C2—C3	1.5 (3)	C14—C9—C10—C11	1.4 (3)
N1—C1—C2—C3	179.95 (18)	N5—C9—C10—C11	179.8 (2)
C1—C2—C3—C4	−0.4 (3)	C9—C10—C11—C12	−0.3 (4)
C2—C3—C4—F1	179.9 (2)	C10—C11—C12—C13	−1.2 (5)
C2—C3—C4—C5	−1.3 (4)	C10—C11—C12—F2	180.0 (2)
F1—C4—C5—C6	−179.38 (19)	F2—C12—C13—C14	−179.6 (3)
C3—C4—C5—C6	1.8 (4)	C11—C12—C13—C14	1.6 (5)
C4—C5—C6—C1	−0.6 (3)	C12—C13—C14—C9	−0.5 (4)
C2—C1—C6—C5	−1.0 (3)	C10—C9—C14—C13	−1.0 (4)
N1—C1—C6—C5	−179.57 (18)	N5—C9—C14—C13	−179.5 (2)
C1—N1—C7—O1	−0.3 (3)	C9—N5—C15—O2	−0.3 (3)
C1—N1—C7—C8	−178.95 (18)	C9—N5—C15—C16	178.13 (18)
N3—N2—C8—C7	−106.1 (2)	N7—N6—C16—C15	−175.4 (2)
O1—C7—C8—N2	24.7 (3)	O2—C15—C16—N6	−13.6 (3)
N1—C7—C8—N2	−156.63 (18)	N5—C15—C16—N6	168.00 (19)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.17	2.921 (2)	146
N5—H5A···O2ⁱ	0.86	2.13	2.885 (2)	146
C4—F1···Cg1ⁱⁱ	1.35 (1)	3.76 (1)	3.563 (2)	72 (1)
C12—F2···Cg2ⁱⁱⁱ	1.36 (1)	3.98 (1)	3.942 (2)	79 (1)

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

Footnotes

‡Additional correspondence author, e-mail: y.ramli@um5r.ac.ma.

Acknowledgements

Author contributions are as follows. Conceptualization, YR; methodology, MM and AA; investigation, WG, MM; writing (original draft), JMT and YR; writing (review and editing of the manuscript), YR; formal analysis, AA and YR; supervision, YR; crystal-structure determination and validation, JTM.

Funding information

The support of NSF–MRI grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

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