Crystal structure and Hirshfeld surface analysis of ethyl 6′-amino-2′-(chloro­meth­yl)-5′-cyano-2-oxo-1,2-di­hydro­spiro­[indoline-3,4′-pyran]-3′-carboxyl­ate

Naghiyev, F.N.; Grishina, M.M.; Khrustalev, V.N.; Akkurt, M.; Huseynova, A.T.; Akobirshoeva, A.A.; Mamedov, İ.G.

doi:10.1107/S2056989021006459

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 77| Part 7| July 2021| Pages 739-743

https://doi.org/10.1107/S2056989021006459

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Crystal structure and Hirshfeld surface analysis of ethyl 6′-amino-2′-(chloromethyl)-5′-cyano-2-oxo-1,2-dihydrospiro[indoline-3,4′-pyran]-3′-carboxylate

Farid N. Naghiyev,^a Maria M. Grishina,^b Victor N. Khrustalev,^b,^c Mehmet Akkurt,^d Afet T. Huseynova,^a Anzurat A. Akobirshoeva ^e ^* and İbrahim G. Mamedov ^a

^aDepartment of Chemistry, Baku State University, Z. Khalilov str. 23, Az, 1148 Baku, Azerbaijan, ^bPeoples' Friendship University of Russia (RUDN University), Miklukho-Maklay St. 6, Moscow, 117198, Russian Federation, ^cN. D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prosp. 47, Moscow, 119991, Russian Federation, ^dDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and ^eAcad Sci Republ Tadzhikistan, Kh Yu Yusufbekov Pamir Biol Inst, 1 Kholdorova St, Khorog 736002, Gbao, Tajikistan
^*Correspondence e-mail: anzurat2003@mail.ru

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 14 June 2021; accepted 21 June 2021; online 25 June 2021)

The molecular conformation of the title compound, C₁₇H₁₄ClN₃O₄, is stabilized by an intramolecular C—H⋯O contact, forming an S(6) ring motif. In the crystal, the molecules are connected by N—H⋯O hydrogen-bond pairs along the b-axis direction as dimers with R²₂(8) and R²₂(14) ring motifs and as ribbons formed by intermolecular C—H⋯N hydrogen bonds. There are weak van der Waals interactions between the ribbons. The most important contributions to the surface contacts are from H⋯H (34.9%), O⋯H/H⋯O (19.2%), C⋯H/H⋯C (11.9%), Cl⋯H/H⋯Cl (10.7%) and N⋯H/H⋯N (10.4%) interactions, as concluded from a Hirshfeld surface analysis.

Keywords: crystal structure; spirooxindole; dimers; hydrogen bond; Hirshfeld surface analysis.

CCDC reference: 2091350

1. Chemical context

Being the most significant tools in organic synthesis, carbon–carbon and carbon–heteroatom coupling reactions are important for the construction of fine chemicals such as pharmaceuticals, fragrances, antioxidants, etc. (Yadigarov et al., 2009 ; Khalilov et al., 2018a ,b ; Zubkov et al., 2018 ). These methods have found widespread application in the design of diverse heterocyclic ring systems, as well as spiro-heterocyclic compounds (Gurbanov et al., 2018 ; Maharramov et al., 2019 ; Mahmoudi et al., 2019 ; Mamedov et al., 2019 ; Yin et al., 2020 ). The spirooxindole moiety is a key bioactive fragment of various natural products (Fig. 1), series of derivatives already being used in medicinal practice (Zhou et al., 2020 ).

Figure 1
Natural products containing the spirooxindole motif.

In this work, in the framework of our ongoing structural studies (Akkurt et al., 2018 ; Naghiyev et al., 2020 , 2021 ), we report the crystal structure and Hirshfeld surface analysis of the title compound, ethyl 6′-amino-2′-(chloromethyl)-5′-cyano-2-oxo-1,2-dihydrospiro[indoline-3,4′-pyran]-3′-carboxylate.

2. Structural commentary

In the title compound (Fig. 2), the 2,3-dihydro-1H-indole ring system (N1/C1/C4/C12–C17) is nearly planar [maximum deviation = 0.039 (1) Å for C1], while the 4H-pyran ring (O1/C2–C6) adopts a flattened-boat conformation [puckering parameters (Cremer & Pople, 1975 ): Q_T = 0.1091 (13) Å, θ = 77.0 (6) ° and φ = 139.6 (7) °]. The planes of the 2,3-dihydro-1H-indole ring system and the 4H-pyran ring are approximately perpendicular to each other, subtending a dihedral angle of 84.52 (5)°. The C5—C6—C11—Cl1, C6—C5—C8—O2, C6—C5—C8—O3, C5—C8—O3—C9 and C8—O3—C9—C10 torsion angles are −103.28 (13), −29.78 (18), 150.69 (11), 178.03 (10) and −169.29 (12)°, respectively. An intramolecular C11—H11B⋯O2 contact stabilizes the molecular conformation of the title compound (Fig. 2, Table 1), generating an S(6) ring motif (Bernstein et al., 1995 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4ⁱ	0.853 (17)	1.981 (17)	2.8292 (14)	173.0 (17)
N2—H2B⋯O4ⁱⁱ	0.887 (18)	2.095 (18)	2.9636 (15)	166.0 (17)
C11—H11B⋯O2	0.99	2.15	2.9039 (17)	131
C13—H13⋯N7ⁱⁱⁱ	0.95	2.56	3.333 (2)	138
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 2
The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids at the 50% probability level.

3. Supramolecular features

In the crystal, the molecules are joined by N—H⋯O hydrogen-bond pairs along the b-axis direction as dimers with $[R_{2}^{2}]$ (8) and $[R_{2}^{2}]$ (14) ring motifs and by intermolecular C—H⋯N hydrogen bonds as ribbons (Table 1; Figs. 3 and 4). Between the ribbons are only weak van der Waals contacts (Table 2). There are no C—H⋯π or π–π interactions in the crystal structure.

Table 2
Summary of short interatomic contacts (Å) in the title compound

Contact	Distance	Symmetry operation
O3⋯H15	2.88	−1 + x, y, z
H9A⋯Cl1	3.06	−x, 1 − y, 2 − z
H2B⋯O4	2.095	−x, 1 − y, 1 − z
H16⋯H11B	2.37	1 − x, 1 − y, 2 − z
H1⋯O4	1.981	−x, −y, 1 − z
H16⋯H2A	2.49	1 − x, 1 − y, 1 − z
H13⋯N7	2.56	1 − x, −y, 1 − z
H10A⋯H11A	2.49	x, − 1 + y, z
H10A⋯C14	2.93	1 − x, −y, 2 − z

Figure 3
A view of the intermolecular N—H⋯O and C—H⋯N hydrogen bonds in the crystal packing of the title compound down the a axis.

Figure 4
A view of the intermolecular N—H⋯O and C—H⋯N hydrogen bonds in the crystal packing of the title compound down the b axis.

4. Hirshfeld surface analysis

A Hirshfeld surface analysis was performed to investigate the intermolecular interactions (Tables 1 and 2) quantitatively and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) were generated with CrystalExplorer17 (Turner et al., 2017 ). The Hirshfeld surface plotted over d_norm in the range −0.6053 to 1.4079 a.u. is shown in Fig. 5. The red spots on the Hirshfeld surface represent N—H⋯O contacts. The Hirshfeld surface mapped over electrostatic potential (Spackman et al., 2008 ) is shown in Fig. 6. The positive electrostatic potential (blue region) over the surface indicates hydrogen-donor potential, whereas the hydrogen-bond acceptors are represented by negative electrostatic potential (red region).

Figure 5
Hirshfeld surface of the title compound mapped with d_norm in the range −0.6053 to 1.4079 a.u.

Figure 6
View of the three-dimensional Hirshfeld surface of the title compound plotted over electrostatic potential energy in the range −0.0500 to 0.0500 a.u. using the STO-3 G basis set at the Hartree–Fock level of theory. Hydrogen-bond donors and acceptors are shown as blue and red regions around the atoms, corresponding to positive and negative potentials, respectively.

Fig. 7 shows the full two-dimensional fingerprint plot and those delineated into the major contacts: the H⋯H (34.9%; Fig. 7b) interactions are the major factor in the crystal packing with O⋯H/H⋯O (19.2%; Fig. 7c), C⋯H/H⋯C (11.9%; Fig. 7d), Cl⋯H/H⋯Cl (10.7%; Fig. 7e) and N⋯H/H⋯N (10.4%; Fig. 7f) interactions representing the next highest contributions. Other weak interactions (contribution percentages) are O⋯N/N⋯O (2.3%), O⋯C/C⋯O (2.1%), N⋯C/C⋯N (2.1%), Cl⋯N/N⋯Cl (1.7%), Cl⋯O/O⋯Cl (1.4%), C⋯C (1.0%), N⋯N (0.7%), O⋯O (0.6%), Cl⋯C/C⋯Cl (0.6%) and Cl⋯Cl (0.3%).

Figure 7
The two-dimensional fingerprint plots of the title compound, showing (a) all interactions, and those delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) C⋯H/H⋯C, (e) Cl⋯H/H⋯Cl and (f) N⋯H/H⋯N interactions [d_e and d_i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (internal) the surface, respectively].

5. Database survey

A survey of the Cambridge Structural Database (CSD version 5.41, update of March 2020; Groom et al., 2016 ) using 2-amino-6-(chloromethyl)-4H-pyran-3-carbonitrile as the main skeleton revealed the presence of three structures, ethyl 6-amino-2-(chloromethyl)-5-cyano-4-(o-tolyl)-4H-pyran-3-carboxylate (CSD refcode HIRNUS; Athimoolam et al., 2007 ), 2-amino-6-chloromethyl-3-cyano-5-ethoxycarbonyl-4-(2-furyl)-4H-pyran (JEGWEX; Lokaj et al., 1990 ) and ethyl 6′-amino-2′-(chloromethyl)-5′-cyano-2-oxo-1,2-dihydrospiro[indole-3,4′-pyran]-3′-carboxylate (WIMBEC; Magerramov et al., 2018 ).

In the crystal of HIRNUS, the six-membered pyran ring adopts a near-boat conformation. The crystal structure features two intramolecular C—H⋯O interactions and the crystal packing is stabilized by intermolecular N—H⋯O hydrogen bonds. These lead to two primary motifs, viz. R²₂(12) and C(8). Combination of these primary motifs leads to a secondary $[R_{2}^{2}]$ (20) ring motif.

In the crystal of JEGWEX, a potential precursor for fluoroquinoline synthesis, the pyran ring is nearly planar, with the most outlying atoms displaced from the best-plane fit through all non-H atoms by 0.163 (2) and 0.118 (2) Å. The molecules are arranged in layers oriented parallel to the (011) plane. In addition, the molecules are linked by a weak C—H⋯O hydrogen bond, which gives rise to chains with base vector [111].

In WIMBEC, the pyran ring exhibits a near-boat conformation with puckering parameters Q_T = 0.085 (7) Å, θ = 84 (5)° and φ = 154 (5)°. In the crystal, molecules are linked as dimers by pairs of N—H⋯O hydrogen bonds, forming ribbons along the b-axis direction. These ribbons are connected by weak van der Waals interactions, stabilizing the molecular packing.

6. Synthesis and crystallization

The title compound was synthesized using previously reported procedures (Luo et al., 2015 ; Magerramov et al., 2018), and colourless needles were obtained upon recrystallization from methanol solution.

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. The H atoms of the NH and NH₂ groups were located in a difference map, and their positional parameters were allowed to freely refine [N1—H1 = 0.853 (17), N2—H2A = 0.843 (19) and N2—H2B = 0.889 (18) Å], but their isotropic displacement parameters were constrained to take a value of 1.2U_eq(N). All H atoms bound to C atoms were positioned geometrically and refined as riding with C—H = 0.95 (aromatic), 0.99 (methylene) and 0.98 Å (methyl), with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for the others. Four reflections, 0 0 1, 0 1 0, 1 0 0 and 1 2 0, affected by the incident beam-stop and owing to poor agreement between observed and calculated intensities, and five outliers, $[\overline{1}]$ $[\overline{3}]$ 3, 3 1 1, $[\overline{1}]$ 1 4, $[\overline{1}]$ $[\overline{6}]$ 9 and 4 $[\overline{11}]$ 2, were omitted in the final cycles of refinement.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₇H₁₄ClN₃O₄
M_r	359.76
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	8.0218 (2), 10.2278 (3), 10.6714 (3)
α, β, γ (°)	98.8503 (7), 108.0048 (7), 96.3852 (6)
V (Å³)	810.92 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.26
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Bruker D8 QUEST PHOTON-III CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.903, 0.949
No. of measured, independent and observed [I > 2σ(I)] reflections	18865, 5899, 4685
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.758

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.106, 1.03
No. of reflections	5899
No. of parameters	236
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.63
Computer programs: APEX3 (Bruker, 2018 ), SAINT (Bruker, 2013 ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2091350

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021006459/vm2250sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021006459/vm2250Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021006459/vm2250Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

Ethyl 6'-amino-2'-(chloromethyl)-5'-cyano-2-oxo-1,2-dihydrospiro[indoline-3,4'-pyran]-3'-carboxylate top

Crystal data top

C₁₇H₁₄ClN₃O₄	Z = 2
M_r = 359.76	F(000) = 372
Triclinic, P1	D_x = 1.473 Mg m⁻³
a = 8.0218 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.2278 (3) Å	Cell parameters from 6340 reflections
c = 10.6714 (3) Å	θ = 2.6–32.5°
α = 98.8503 (7)°	µ = 0.26 mm⁻¹
β = 108.0048 (7)°	T = 100 K
γ = 96.3852 (6)°	Prism, colourless
V = 810.92 (4) Å³	0.25 × 0.20 × 0.15 mm

Data collection top

Bruker D8 QUEST PHOTON-III CCD diffractometer	4685 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.039
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 32.6°, θ_min = 2.6°
T_min = 0.903, T_max = 0.949	h = −12→12
18865 measured reflections	k = −15→15
5899 independent reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: mixed
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0366P)² + 0.4187P] where P = (F_o² + 2F_c²)/3
5899 reflections	(Δ/σ)_max = 0.001
236 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq
Cl1	−0.00786 (5)	0.62296 (4)	0.86942 (4)	0.03426 (11)
O1	0.20564 (12)	0.57639 (8)	0.66693 (9)	0.01580 (17)
O2	0.34827 (14)	0.39501 (10)	1.01602 (9)	0.0221 (2)
O3	0.24269 (13)	0.20082 (9)	0.86649 (9)	0.01705 (17)
O4	−0.01410 (11)	0.18103 (8)	0.54781 (9)	0.01560 (17)
N1	0.22730 (14)	0.07160 (10)	0.58525 (11)	0.01426 (19)
H1	0.171 (2)	−0.0075 (17)	0.5472 (17)	0.017*
N2	0.20156 (16)	0.58493 (11)	0.45919 (12)	0.0189 (2)
H2A	0.198 (2)	0.5484 (18)	0.3819 (19)	0.023*
H2B	0.158 (2)	0.6601 (18)	0.4714 (18)	0.023*
C1	0.14677 (15)	0.18025 (11)	0.59191 (11)	0.0124 (2)
C2	0.23180 (15)	0.51172 (11)	0.55510 (12)	0.0137 (2)
C3	0.28549 (15)	0.38996 (11)	0.54920 (12)	0.0131 (2)
C4	0.29313 (15)	0.30748 (11)	0.65670 (11)	0.01141 (19)
C5	0.27019 (15)	0.39250 (11)	0.77759 (11)	0.01218 (19)
C6	0.23527 (15)	0.51749 (12)	0.77729 (12)	0.0138 (2)
C7	0.32238 (18)	0.33266 (13)	0.43295 (13)	0.0182 (2)
N7	0.3547 (2)	0.28501 (14)	0.33968 (13)	0.0300 (3)
C8	0.29278 (15)	0.33459 (12)	0.90096 (12)	0.0139 (2)
C9	0.2632 (2)	0.12998 (14)	0.97758 (14)	0.0231 (3)
H9A	0.1751	0.1491	1.0225	0.028*
H9B	0.3840	0.1588	1.0446	0.028*
C10	0.2340 (3)	−0.01675 (15)	0.91875 (16)	0.0317 (3)
H10A	0.2419	−0.0684	0.9899	0.048*
H10B	0.3251	−0.0348	0.8779	0.048*
H10C	0.1160	−0.0431	0.8500	0.048*
C11	0.21988 (17)	0.61386 (13)	0.89102 (13)	0.0187 (2)
H11A	0.2843	0.7039	0.8960	0.022*
H11B	0.2752	0.5848	0.9765	0.022*
C12	0.41277 (15)	0.10561 (12)	0.64735 (12)	0.0137 (2)
C13	0.53735 (17)	0.02074 (13)	0.66518 (13)	0.0181 (2)
H13	0.5037	−0.0737	0.6349	0.022*
C14	0.71502 (17)	0.08061 (14)	0.72987 (13)	0.0201 (2)
H14	0.8044	0.0255	0.7431	0.024*
C15	0.76464 (16)	0.21894 (14)	0.77546 (13)	0.0188 (2)
H15	0.8866	0.2568	0.8189	0.023*
C16	0.63576 (16)	0.30242 (12)	0.75758 (12)	0.0150 (2)
H16	0.6684	0.3968	0.7893	0.018*
C17	0.45955 (15)	0.24390 (12)	0.69254 (11)	0.0126 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01877 (16)	0.0398 (2)	0.0354 (2)	0.00475 (13)	0.00875 (14)	−0.01772 (16)
O1	0.0210 (4)	0.0116 (4)	0.0157 (4)	0.0066 (3)	0.0060 (3)	0.0028 (3)
O2	0.0293 (5)	0.0206 (4)	0.0140 (4)	−0.0004 (4)	0.0064 (4)	0.0013 (3)
O3	0.0244 (4)	0.0127 (4)	0.0150 (4)	0.0044 (3)	0.0067 (3)	0.0042 (3)
O4	0.0128 (4)	0.0121 (4)	0.0196 (4)	0.0027 (3)	0.0029 (3)	0.0014 (3)
N1	0.0146 (4)	0.0092 (4)	0.0171 (5)	0.0030 (3)	0.0032 (4)	0.0006 (3)
N2	0.0264 (6)	0.0154 (5)	0.0196 (5)	0.0099 (4)	0.0099 (4)	0.0080 (4)
C1	0.0139 (5)	0.0103 (5)	0.0128 (5)	0.0022 (4)	0.0041 (4)	0.0020 (4)
C2	0.0137 (5)	0.0124 (5)	0.0157 (5)	0.0032 (4)	0.0052 (4)	0.0033 (4)
C3	0.0152 (5)	0.0114 (5)	0.0137 (5)	0.0037 (4)	0.0055 (4)	0.0030 (4)
C4	0.0125 (5)	0.0091 (4)	0.0129 (5)	0.0029 (4)	0.0044 (4)	0.0021 (4)
C5	0.0114 (5)	0.0124 (5)	0.0121 (5)	0.0021 (4)	0.0037 (4)	0.0009 (4)
C6	0.0136 (5)	0.0130 (5)	0.0135 (5)	0.0029 (4)	0.0032 (4)	0.0010 (4)
C7	0.0233 (6)	0.0174 (5)	0.0178 (6)	0.0101 (5)	0.0079 (5)	0.0079 (4)
N7	0.0461 (8)	0.0317 (6)	0.0223 (6)	0.0239 (6)	0.0170 (6)	0.0113 (5)
C8	0.0127 (5)	0.0144 (5)	0.0156 (5)	0.0028 (4)	0.0059 (4)	0.0029 (4)
C9	0.0362 (7)	0.0196 (6)	0.0195 (6)	0.0091 (5)	0.0134 (5)	0.0097 (5)
C10	0.0528 (10)	0.0182 (6)	0.0293 (7)	0.0106 (6)	0.0163 (7)	0.0111 (6)
C11	0.0182 (5)	0.0175 (5)	0.0169 (5)	0.0065 (4)	0.0029 (4)	−0.0032 (4)
C12	0.0142 (5)	0.0137 (5)	0.0136 (5)	0.0047 (4)	0.0045 (4)	0.0027 (4)
C13	0.0220 (6)	0.0171 (5)	0.0173 (6)	0.0106 (4)	0.0071 (5)	0.0035 (4)
C14	0.0194 (6)	0.0270 (6)	0.0171 (6)	0.0131 (5)	0.0066 (5)	0.0056 (5)
C15	0.0130 (5)	0.0288 (6)	0.0157 (5)	0.0065 (4)	0.0049 (4)	0.0049 (5)
C16	0.0145 (5)	0.0185 (5)	0.0128 (5)	0.0030 (4)	0.0056 (4)	0.0033 (4)
C17	0.0136 (5)	0.0144 (5)	0.0111 (5)	0.0041 (4)	0.0050 (4)	0.0027 (4)

Geometric parameters (Å, º) top

Cl1—C11	1.7842 (13)	C6—C11	1.4871 (17)
O1—C2	1.3595 (15)	C7—N7	1.1550 (18)
O1—C6	1.3725 (14)	C9—C10	1.497 (2)
O2—C8	1.2063 (15)	C9—H9A	0.9900
O3—C8	1.3417 (14)	C9—H9B	0.9900
O3—C9	1.4586 (15)	C10—H10A	0.9800
O4—C1	1.2308 (14)	C10—H10B	0.9800
N1—C1	1.3495 (14)	C10—H10C	0.9800
N1—C12	1.4064 (15)	C11—H11A	0.9900
N1—H1	0.853 (17)	C11—H11B	0.9900
N2—C2	1.3379 (15)	C12—C13	1.3837 (16)
N2—H2A	0.843 (19)	C12—C17	1.3907 (16)
N2—H2B	0.889 (18)	C13—C14	1.3966 (19)
C1—C4	1.5592 (16)	C13—H13	0.9500
C2—C3	1.3610 (15)	C14—C15	1.393 (2)
C3—C7	1.4183 (17)	C14—H14	0.9500
C3—C4	1.5156 (16)	C15—C16	1.3995 (17)
C4—C5	1.5138 (16)	C15—H15	0.9500
C4—C17	1.5183 (16)	C16—C17	1.3840 (16)
C5—C6	1.3390 (16)	C16—H16	0.9500
C5—C8	1.4944 (16)

C2—O1—C6	119.01 (9)	C10—C9—H9A	110.3
C8—O3—C9	115.95 (10)	O3—C9—H9B	110.3
C1—N1—C12	111.77 (10)	C10—C9—H9B	110.3
C1—N1—H1	123.4 (11)	H9A—C9—H9B	108.6
C12—N1—H1	124.8 (11)	C9—C10—H10A	109.5
C2—N2—H2A	118.0 (12)	C9—C10—H10B	109.5
C2—N2—H2B	119.3 (11)	H10A—C10—H10B	109.5
H2A—N2—H2B	120.6 (16)	C9—C10—H10C	109.5
O4—C1—N1	126.32 (11)	H10A—C10—H10C	109.5
O4—C1—C4	125.13 (10)	H10B—C10—H10C	109.5
N1—C1—C4	108.42 (9)	C6—C11—Cl1	110.59 (9)
N2—C2—O1	110.94 (10)	C6—C11—H11A	109.5
N2—C2—C3	127.13 (11)	Cl1—C11—H11A	109.5
O1—C2—C3	121.91 (10)	C6—C11—H11B	109.5
C2—C3—C7	118.87 (11)	Cl1—C11—H11B	109.5
C2—C3—C4	122.67 (10)	H11A—C11—H11B	108.1
C7—C3—C4	118.26 (10)	C13—C12—C17	122.36 (11)
C5—C4—C3	109.52 (9)	C13—C12—N1	128.15 (11)
C5—C4—C17	112.86 (9)	C17—C12—N1	109.49 (10)
C3—C4—C17	112.55 (9)	C12—C13—C14	116.79 (12)
C5—C4—C1	113.49 (9)	C12—C13—H13	121.6
C3—C4—C1	107.25 (9)	C14—C13—H13	121.6
C17—C4—C1	100.85 (9)	C15—C14—C13	121.72 (11)
C6—C5—C8	120.03 (10)	C15—C14—H14	119.1
C6—C5—C4	121.88 (10)	C13—C14—H14	119.1
C8—C5—C4	118.07 (9)	C14—C15—C16	120.36 (12)
C5—C6—O1	123.81 (11)	C14—C15—H15	119.8
C5—C6—C11	127.27 (11)	C16—C15—H15	119.8
O1—C6—C11	108.91 (10)	C17—C16—C15	118.24 (11)
N7—C7—C3	178.80 (14)	C17—C16—H16	120.9
O2—C8—O3	123.11 (11)	C15—C16—H16	120.9
O2—C8—C5	127.00 (11)	C16—C17—C12	120.53 (11)
O3—C8—C5	109.89 (10)	C16—C17—C4	130.24 (11)
O3—C9—C10	106.89 (11)	C12—C17—C4	109.23 (10)
O3—C9—H9A	110.3

C12—N1—C1—O4	−179.07 (12)	C2—O1—C6—C5	−7.59 (17)
C12—N1—C1—C4	4.71 (13)	C2—O1—C6—C11	173.03 (10)
C6—O1—C2—N2	−178.30 (10)	C9—O3—C8—O2	−1.51 (17)
C6—O1—C2—C3	0.39 (17)	C9—O3—C8—C5	178.03 (10)
N2—C2—C3—C7	2.90 (19)	C6—C5—C8—O2	−29.78 (18)
O1—C2—C3—C7	−175.56 (11)	C4—C5—C8—O2	148.52 (12)
N2—C2—C3—C4	−171.94 (12)	C6—C5—C8—O3	150.69 (11)
O1—C2—C3—C4	9.61 (18)	C4—C5—C8—O3	−31.00 (14)
C2—C3—C4—C5	−11.44 (15)	C8—O3—C9—C10	−169.29 (12)
C7—C3—C4—C5	173.69 (10)	C5—C6—C11—Cl1	−103.28 (13)
C2—C3—C4—C17	−137.85 (12)	O1—C6—C11—Cl1	76.07 (11)
C7—C3—C4—C17	47.28 (14)	C1—N1—C12—C13	176.98 (12)
C2—C3—C4—C1	112.13 (12)	C1—N1—C12—C17	−2.67 (14)
C7—C3—C4—C1	−62.74 (13)	C17—C12—C13—C14	−0.81 (18)
O4—C1—C4—C5	58.07 (15)	N1—C12—C13—C14	179.59 (12)
N1—C1—C4—C5	−125.66 (10)	C12—C13—C14—C15	0.58 (19)
O4—C1—C4—C3	−63.02 (15)	C13—C14—C15—C16	0.2 (2)
N1—C1—C4—C3	113.24 (10)	C14—C15—C16—C17	−0.69 (18)
O4—C1—C4—C17	179.05 (11)	C15—C16—C17—C12	0.48 (17)
N1—C1—C4—C17	−4.69 (12)	C15—C16—C17—C4	−178.77 (11)
C3—C4—C5—C6	4.62 (15)	C13—C12—C17—C16	0.29 (18)
C17—C4—C5—C6	130.85 (11)	N1—C12—C17—C16	179.96 (10)
C1—C4—C5—C6	−115.19 (12)	C13—C12—C17—C4	179.68 (11)
C3—C4—C5—C8	−173.65 (9)	N1—C12—C17—C4	−0.65 (13)
C17—C4—C5—C8	−47.42 (13)	C5—C4—C17—C16	−56.14 (16)
C1—C4—C5—C8	66.54 (13)	C3—C4—C17—C16	68.46 (15)
C8—C5—C6—O1	−177.31 (10)	C1—C4—C17—C16	−177.56 (12)
C4—C5—C6—O1	4.46 (18)	C5—C4—C17—C12	124.55 (10)
C8—C5—C6—C11	1.96 (18)	C3—C4—C17—C12	−110.86 (11)
C4—C5—C6—C11	−176.28 (11)	C1—C4—C17—C12	3.13 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.853 (17)	1.981 (17)	2.8292 (14)	173.0 (17)
N2—H2B···O4ⁱⁱ	0.887 (18)	2.095 (18)	2.9636 (15)	166.0 (17)
C11—H11B···O2	0.99	2.15	2.9039 (17)	131
C13—H13···N7ⁱⁱⁱ	0.95	2.56	3.333 (2)	138

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

Summary of short interatomic contacts (Å) in the title compound top

Contact	Distance	Symmetry operation
O3···H15	2.88	-1 + x, y, z
H9A···Cl1	3.06	-x, 1 - y, 2 - z
H2B···O4	2.095	-x, 1 - y, 1 - z
H16···H11B	2.37	1 - x, 1 - y, 2 - z
H1···O4	1.981	-x, -y, 1 - z
H16···H2A	2.49	1 - x, 1 - y, 1 - z
H13···N7	2.56	1 - x, -y, 1 - z
H10A···H11A	2.49	x, - 1 + y, z
H10A···C14	2.93	1 - x, -y, 2 - z

Acknowledgements

The authors' contributions are as follows. Conceptualization, FNN and IGM; methodology, FNN and IGM; investigation, VNK, FNN, MMG and AAA; writing (original draft), MA and IGM; writing (review and editing of the manuscript), MA and IGM; visualization, MA, FNN and IGM; funding acquisition, VNK and FNN; resources, ATH, AAA and FNN; supervision, IGM and MA.;

Funding information

This work was supported by Baku State University and the RUDN University Strategic Academic Leadership Program.

References

Akkurt, M., Duruskari, G. S., Toze, F. A. A., Khalilov, A. N. & Huseynova, A. T. (2018). Acta Cryst. E74, 1168–1172. Web of Science CSD CrossRef IUCr Journals Google Scholar
Athimoolam, S., Devi, N. S., Bahadur, S. A., Kannan, R. S. & Perumal, S. (2007). Acta Cryst. E63, o4680–o4681. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2013). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2018). APEX3. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals 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
Gurbanov, A. V., Mahmoudi, G., Guedes da Silva, M. F. C., Zubkov, F. I., Mahmudov, K. T. & Pombeiro, A. J. L. (2018). Inorg. Chim. Acta, 471, 130–136. Web of Science CSD CrossRef CAS Google Scholar
Khalilov, A. N., Asgarova, A. R., Gurbanov, A. V., Maharramov, A. M., Nagiyev, F. N. & Brito, I. (2018a). Z. Kristallogr. New Cryst. Struct. 233, 1019–1020. Web of Science CSD CrossRef CAS Google Scholar
Khalilov, A. N., Asgarova, A. R., Gurbanov, A. V., Nagiyev, F. N. & Brito, I. (2018b). Z. Kristallogr. New Cryst. Struct. 233, 947–948. Web of Science CSD CrossRef CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Lokaj, J., Kettmann, V., Pavelčík, F., Ilavský, D. & Marchalín, Š. (1990). Acta Cryst. C46, 788–791. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Luo, N.-H., Zheng, D.-G., Xie, G.-H., Yang, Y.-C. & Yang, L.-S. (2015). Huaxue Shiji, 37, 742–746. CAS Google Scholar
Magerramov, A. M., Naghiyev, F. N., Mamedova, G. Z., Asadov, Kh. A. & Mamedov, I. G. (2018). Russ. J. Org. Chem. 54, 1731–1734. CSD CrossRef CAS Google Scholar
Maharramov, A. M., Duruskari, G. S., Mammadova, G. Z., Khalilov, A. N., Aslanova, J. M., Cisterna, J., Cárdenas, A. & Brito, I. (2019). J. Chil. Chem. Soc. 64, 4441–4447. Web of Science CSD CrossRef CAS Google Scholar
Mahmoudi, G., Khandar, A. A., Afkhami, F. A., Miroslaw, B., Gurbanov, A. V., Zubkov, F. I., Kennedy, A., Franconetti, A. & Frontera, A. (2019). CrystEngComm, 21, 108–117. Web of Science CSD CrossRef CAS Google Scholar
Mamedov, I. G., Khrustalev, V. N., Dorovatovskii, P. V., Naghiev, F. N. & Maharramov, A. M. (2019). Mendeleev Commun. 29, 232–233. Web of Science CSD CrossRef CAS Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
Naghiyev, F. N., Cisterna, J., Khalilov, A. N., Maharramov, A. M., Askerov, R. K., Asadov, K. A., Mamedov, I. G., Salmanli, K. S., Cárdenas, A. & Brito, I. (2020). Molecules, 25, 2235–2248. Web of Science CSD CrossRef CAS Google Scholar
Naghiyev, F. N., Grishina, M. M., Khrustalev, V. N., Khalilov, A. N., Akkurt, M., Akobirshoeva, A. A. & Mamedov, İ. G. (2021). Acta Cryst. E77, 195–199. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm, 10, 377–388. CAS Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. https://hirshfeldsurface.net Google Scholar
Yadigarov, R. R., Khalilov, A. N., Mamedov, I. G., Nagiev, F. N., Magerramov, A. M. & Allakhverdiev, M. A. (2009). Russ. J. Org. Chem. 45, 1856–1858. Web of Science CrossRef CAS Google Scholar
Yin, J., Khalilov, A. N., Muthupandi, P., Ladd, R. & Birman, V. B. (2020). J. Am. Chem. Soc. 142, 60–63. Web of Science CSD CrossRef CAS PubMed Google Scholar
Zhou, L.-M., Qu, R.-Y. & Yang, G.-F. (2020). Exp. Opin. Drug. Discov. 15, 603–625. CrossRef CAS Google Scholar
Zubkov, F. I., Mertsalov, D. F., Zaytsev, V. P., Varlamov, A. V., Gurbanov, A. V., Dorovatovskii, P. V., Timofeeva, T. V., Khrustalev, V. N. & Mahmudov, K. T. (2018). J. Mol. Liq. 249, 949–952. Web of Science CSD CrossRef CAS Google Scholar

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