Crystal structure and Hirshfeld surface analysis of dimethyl 5-[2-(2,4,6-trioxo-1,3-diazinan-5-yl­idene)hydrazin-1-yl]benzene-1,3-di­carboxyl­ate 0.224-hydrate

Atioğlu, Z.; Akkurt, M.; Mammadova, G.Z.; Huseynov, F.E.; Hajiyeva, S.R.; Shamilov, N.T.; Bhattarai, A.

doi:10.1107/S2056989021006563

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 77| Part 7| July 2021| Pages 759-764

https://doi.org/10.1107/S2056989021006563

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Crystal structure and Hirshfeld surface analysis of dimethyl 5-[2-(2,4,6-trioxo-1,3-diazinan-5-ylidene)hydrazin-1-yl]benzene-1,3-dicarboxylate 0.224-hydrate

Zeliha Atioğlu,^a Mehmet Akkurt,^b Gunay Z. Mammadova,^c Fatali E. Huseynov,^d Sevinj R. Hajiyeva,^c Nazim T. Shamilov ^c and Ajaya Bhattarai ^e ^*

^aDepartment of Aircraft Electrics and Electronics, School of Applied Sciences, Cappadocia University, Mustafapaşa, 50420 Ürgüp, Nevşehir, Turkey, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cDepartment of Chemistry, Baku State University, Z. Khalilov str. 23, AZ, 1148 Baku, Azerbaijan, ^dDepartment of Ecology and Soil Sciences, Baku State University, Z. Khalilov str. 23, AZ, 1148 Baku, Azerbaijan, and ^eDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal
^*Correspondence e-mail: bkajaya@yahoo.com

Edited by A. V. Yatsenko, Moscow State University, Russia (Received 11 June 2021; accepted 22 June 2021; online 30 June 2021)

In the crystal, the whole molecule of the title compound, C₁₄H₁₂N₄O₇·0.224H₂O, is nearly planar with a maximum deviation from the least-squares plane of 0.352 (1) Å. The molecular conformation is stabilized by an intramolecular N—H⋯O hydrogen bond, generating an S(6) ring motif. In the crystal, molecules are linked by centrosymmetric pairs of N—H⋯O hydrogen bonds, forming ribbons along the c-axis direction. These ribbons connected by van der Waals contacts, forming sheets parallel to the ac plane. There are also intermolecular van der Waals contacts and and C—H⋯π interactions between the sheets. A Hirshfeld surface analysis indicates that the most prevalent interactions are O⋯H/H⋯O (41.2%), H⋯H (19.2%), C⋯H/H⋯C (12.2%) and C⋯O/ O⋯C (8.4%).

Keywords: crystal structure; 1,3-diazinane ring; hydrogen bonds; Hirshfeld surface analysis.

CCDC reference: 2091530

1. Chemical context

Arylhydrazones, besides their biological significance (Viswanathan et al., 2019 ), can also be used as precursors in the synthesis of coordination compounds (Gurbanov et al., 2017 , 2018a ,b ; Ma et al., 2017a ,b ) and as building blocks in the construction of supramolecular structures owing to their hydrogen-bond donor and acceptor capabilities (Mahmoudi et al., 2016 , 2017a ,b ,c , 2018a ,b ; 2019 ). All the reported hydrazone ligands are stabilized in the hydrazone form by intramolecular resonance-assisted hydrogen bonding (RAHB) between the hydrazone =N—NH— fragment and the carbonyl group, giving a six-membered ring (Gurbanov et al., 2020a ; Kopylovich et al., 2011a ,b ; Mizar et al., 2012 ). The use of multifunctional ligands in coordination chemistry is a common way to increase the water solubility of metal complexes, which is important for catalytic applications in aqueous medium (Ma et al., 2020 , 2021 ; Mahmudov et al., 2013 ; Sutradhar et al., 2015 , 2016 ). Moreover, non-covalent interactions such as hydrogen, halogen and chalcogen bonds as well as π-interactions or their cooperation are able to contribute to synthesis and catalysis and improve the properties of materials (Gurbanov et al., 2020b ; Karmakar et al., 2017 ; Khalilov et al., 2018a ,b ; Mac Leod et al., 2012 ; Shikhaliyev et al., 2019 ; Shixaliyev et al., 2014 ). For that, the main skeleton of the hydrazone ligand should be decorated by non-covalent bond donor centre(s). In a continuation of our work in this area, we have prepared a new hydrazone ligand, dimethyl 5-{2-[2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene] hydrazineyl}isophthalate, which provides the centres for coordination and intermolecular non-covalent interactions.

2. Structural commentary

The asymmetric unit of the title structure contains one title molecule and a water molecule, which partially occupies a small cavity with an occupancy factor of 0.224 (5). The title molecule (Fig. 1) is nearly planar with the largest deviation from the least-squares plane being 0.352 (1) Å for the methylcarboxylate atom O6. The 1,3-diazinane ring makes a dihedral angle of 9.96 (5)° with the benzene ring. The planar molecular conformation is stabilized by an intramolecular N—H⋯O contact (Table 1), generating an S(6) ring motif (Bernstein et al., 1995 ).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C5–C10 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.86	2.03	2.8800 (13)	174
N2—H2N⋯O3ⁱⁱ	0.90	2.01	2.8931 (15)	168
N4—H4N⋯O3	0.86	2.02	2.6571 (15)	131
C6—H6⋯Ow1	0.95	2.14	3.061 (6)	163
C12—H12B⋯O1ⁱⁱⁱ	0.98	2.39	3.2743 (17)	149
C14—H14B⋯O4^iv	0.98	2.53	3.4754 (16)	163
C12—H12C⋯Cg2^v	0.98	2.73	3.4717 (15)	133
Symmetry codes: (i) $[-x+1, y, -z+{\script{5\over 2}}]$ ; (ii) $[-x+1, y, -z+{\script{3\over 2}}]$ ; (iii) ; (iv) x, y, z+1; (v) $[x, -y+1, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

In the crystal, the molecules are linked by pairs of N—H⋯O hydrogen bonds into ribbons along the c-axis direction (Table 1). These ribbons are connected by van der Waals interactions, forming sheets parallel to the ac plane. There are also other van der Waals contacts and C—H⋯π interactions between the sheets (Table 2), consolidating the crystal packing (Figs. 2–4 ).

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

Contact	Distance	Symmetry operation
O1⋯*Ow1	3.129	x, y, 1 + z
O1⋯H12B	2.39	x, y, 1 + z
O1⋯H4N	2.59	x, 1 − y, $[{1\over 2}]$ + z
H12A⋯O1	2.67	$[{1\over 2}]$ − x, $[{1\over 2}]$ − y, 1 − z
H1N⋯O2	2.03	1 − x, y, $[{5\over 2}]$ − z
O2⋯*Ow1	2.662	1 − x, y, $[{3\over 2}]$ − z
N2⋯O2	3.226	1 − x, 1 − y, 2 − z
O2⋯H14C	2.64	$[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z
H2N⋯O3	2.01	1 − x, y, $[{3\over 2}]$ − z
H4N⋯O1	2.59	x, 1 − y, − $[{1\over 2}]$ + z
H12B⋯O1	2.39	x, y, − 1 + z
H8⋯O6	2.66	−x, y, $[{1\over 2}]$ − z
H14A⋯O6	2.67	−x, 1 − y, 1 − z
H14C⋯O2	2.64	− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z
C1⋯*Ow1	3.297	x, 1 − y, $[{1\over 2}]$ + z
H6⋯*Ow1	2.14	x, y, z
H12B⋯C12	3.10	$[{1\over 2}]$ − x, $[{1\over 2}]$ − y, −z
H14B⋯C14	2.93	−x, y, $[{3\over 2}]$ − z
H12A⋯*Ow1	2.70	$[{1\over 2}]$ − x, $[{1\over 2}]$ − y, −z
*Ow1 indicates the oxygen atom of the water molecule with an occupancy of 0.224 (5).

Figure 2
A view down the a axis showing the intermolecular contacts forming the layered structure.

Figure 3
A view of intermolecular hydrogen bonds forming the ribbons along the c-axis direction.

Figure 4
A view of the projection on the ab plane showing the contacts between layers.

4. Hirshfeld surface analysis

The Hirshfeld surface for the title molecule was performed and its associated two-dimensional fingerprint plots were prepared using Crystal Explorer 17 (Turner et al., 2017 ) to further investigate the intermolecular interactions in the title structure. The oxygen atom of the water molecule with partial occupancy was not taken into account. The Hirshfeld surface mapped over d_norm with corresponding colours representing intermolecular interactions is shown in Fig. 5. The red spots on the surface correspond to the N—H⋯O and C—H⋯O interactions (Tables 1 and 2). The Hirshfeld surface mapped over electrostatic potential (Spackman et al., 2009 ) is shown in Fig. 6. The blue regions indicate positive electrostatic potential (hydrogen-bond donors), while the red regions indicate negative electrostatic potential (hydrogen-bond acceptors). The two-dimensional fingerprint plots (McKinnon et al., 2007 ) are shown in Fig. 7. O⋯H/H.·O contacts make the largest contribution (41.2%; Fig. 7b) to the Hirshfeld surface. The other large contributions to the Hirshfeld surface are from H⋯H (19.2%; Fig. 7c), C⋯H/H⋯C (12.2%; Fig. 7d) and C⋯O/O⋯C (8.4%; Fig. 7e) interactions. All contributions to the Hirshfeld surface are listed in Table 3. These interactions play a crucial role in the overall cohesion of the crystal packing.

Table 3
Percentage contributions of interatomic contacts to the Hirshfeld surface for the title compound

Contact	Percentage contribution
O⋯H/H⋯O	41.2
H⋯H	19.2
C⋯H/H⋯C	12.2
C⋯O/O⋯C	8.4
O⋯O	5.6
N⋯O/O⋯N	4.7
C⋯N/N⋯C	3.2
C⋯C	2.8
N⋯H/H⋯N	2.7

Figure 5
A view of the Hirshfeld surface mapped over d_norm, with interactions to neighbouring molecules shown as green dashed lines.

Figure 6
The Hirshfeld surface of the title compound plotted over electrostatic potential energy in the range from −0.0500 to 0.0500 a.u. using the STO-3G 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.

Figure 7
The two-dimensional fingerprint plots of the title compound, showing (a) all interactions, and delineated into (b) O⋯H/H⋯O, (c) H⋯H, (d) C⋯H/H⋯C and (e) C⋯O/O⋯C, 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 search of Cambridge Crystallographic Database (CSD, version 5.40, update of September 2019; Groom et al., 2016 ) was undertaken for structures containing the 5-(2-methylhydrazinylidene)-1,3-diazinane moiety. The first three structures are free bases are: 2-{2-[(1H-imidazol-5-yl)methylidene]-1-methylhydrazinyl}pyridine (QUGVEW; Bocian et al., 2020 ), 2-{2-[(1H-imidazol-2-yl)methylidene]-1-methylhydrazinyl}-1H-benzimidazole monohydrate (QUGVIA; Bocian et al., 2020) and 2-{1-methyl-2-[(1-methyl-1H-imidazol-2-yl)methylidene]hydrazinyl}-1H-benzimidazole hydrate unknown solvate (QUGVOG; Bocian et al., 2020). The other two are triflate salts are: 5-{[2-(1H-benzimidazol-2-yl)-2-methylhydrazinylidene]methyl}-1H-imidazol-3-ium trifluoromethanesulfonate monohydrate (QUGVUM; Bocian et al., 2020) and (2-{2-[(1H-imidazol-3-ium-2-yl)methylene]-1-methylhydrazineyl}pyridin-1-ium) bis(trifluoromethanesulfonate) (QUGWAT; Bocian et al., 2020).

In the structures of QUGVEW, QUGVIA, QUGVOG, QUGVUM and QUGWAT, the most important contribution to the stabilization of the crystal packing is provided by π–π interactions, especially between cations in the structures of salts, while the characteristics of the crystal architecture are influenced by directional interactions, especially relatively strong hydrogen bonds. In one of the structures (QUGWAT), an interesting example of a non-typical F⋯O interaction was found whose length, 2.859 (2) Å, is one of the shortest ever reported.

6. Synthesis and crystallization

Diazotization: 2.09 g (10 mmol) of dimethyl 5-aminoisophthalate were dissolved in 50 mL of water, the solution was cooled on an ice bath to 273 K and 0.69 g (10 mmol) of NaNO₂ were added; 2.00 mL of HCl were then added in 0.5 mL portions over 1 h. The temperature of the mixture should not exceed 278 K.

Azocoupling: NaOH (0.40 g, 10 mmol) was added to a mixture of 10 mmol (1.28 g) of barbituric acid with 25.00 mL of water. The solution was cooled on an ice bath and a suspension of 3,5-bis(methoxycarbonyl)benzenediazonium chloride, prepared according to the procedure described above, was added in two equal portions under vigorous stirring for 1 h. The formed precipitate of the title compound was filtered off, recrystallized from methanol and dried in air. Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

The title compound: Yield, 68% (based on barbituric acid), yellow powder soluble in DMSO, methanol, ethanol and DMF. Analysis calculated for C₁₄H₁₂N₄O₇ (M_r = 348.27): C, 48.28; H, 3.47; N, 16.09; found: C, 48.25 H, 3.41; N, 16.03%. ESI–MS: m/z: 349.2 [M_r + H]⁺. IR (KBr): 3160, 3090 and 2846 ν(NH), 1745 and 1663 ν(C=O), 1610 ν(C=O⋯H) cm^{−1. 1}H NMR (300.130 MHz) in DMSO-d₆, internal TMS, δ (ppm): 8.20–8.36 (3H, Ar—H), 11.32 (s, 1H, N—H), 11.54 (s, 1H, N—H), 14.08 (s, 1H, N—H). ¹³C{¹H} NMR (75.468 MHz, DMSO-d₆). δ: 55.6 (2OCH₃), 119.54 (2Ar—H), 121.8 (Ar-H), 127.4 (2C—COOCH₃), 133.25 (C=N), 142.87 (C—NHN=), 150.24 (C=O), 160.32 (C=O), 161.90 (C=O⋯H) and 166.56 (2COOCH₃).

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 4. The H atoms of the NH groups were located by difference Fourier synthesis and their coordinates were fixed. All C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 and 0.98 Å, and with U_iso(H) = 1.2 or 1.5U_eq(C). There is a small cavity in the crystal, which is only partially occupied by a water molecule, with an occupancy of 0.224 (5), and its hydrogen atoms could not be located.

Table 4
Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₄O₇·0.224H₂O
M_r	351.86
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	24.2097 (11), 12.6311 (6), 10.4022 (5)
β (°)	113.133 (2)
V (Å³)	2925.2 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.13
Crystal size (mm)	0.34 × 0.32 × 0.27

Data collection
Diffractometer	Bruker APEXII CCD
No. of measured, independent and observed [I > 2σ(I)] reflections	34832, 2944, 2699
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.102, 1.04
No. of reflections	2944
No. of parameters	241
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.21
Computer programs: APEX2 and SAINT (Bruker, 2007 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2091530

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021006563/yk2153sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021006563/yk2153Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021006563/yk2153Isup3.cml

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: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

Dimethyl 5-[2-(2,4,6-trioxo-1,3-diazinan-5-ylidene)hydrazin-1-yl]benzene-1,3-dicarboxylate 0.224-hydrate top

Crystal data top

C₁₄H₁₂N₄O₇·0.224H₂O	F(000) = 1454
M_r = 351.86	D_x = 1.598 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.2097 (11) Å	Cell parameters from 9840 reflections
b = 12.6311 (6) Å	θ = 3.2–26.4°
c = 10.4022 (5) Å	µ = 0.13 mm⁻¹
β = 113.133 (2)°	T = 150 K
V = 2925.2 (2) Å³	Block, orange
Z = 8	0.34 × 0.32 × 0.27 mm

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.017
φ and ω scans	θ_max = 26.4°, θ_min = 3.2°
34832 measured reflections	h = −30→30
2944 independent reflections	k = −15→15
2699 reflections with I > 2σ(I)	l = −13→13

Refinement top

Refinement on F²	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0586P)² + 2.1077P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2944 reflections	Δρ_max = 0.29 e Å⁻³
241 parameters	Δρ_min = −0.21 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	Occ. (<1)
C1	0.37057 (5)	0.39423 (9)	0.82909 (12)	0.0190 (2)
C2	0.37833 (5)	0.39902 (9)	0.97648 (12)	0.0207 (2)
C3	0.48693 (5)	0.37742 (9)	1.04270 (12)	0.0208 (2)
C4	0.42279 (5)	0.38365 (8)	0.79361 (12)	0.0186 (2)
C5	0.24165 (5)	0.38344 (8)	0.50833 (12)	0.0192 (2)
C6	0.23130 (5)	0.37794 (9)	0.36716 (12)	0.0204 (2)
H6	0.263906	0.380695	0.338172	0.025*
C7	0.17254 (5)	0.36834 (9)	0.26874 (11)	0.0197 (2)
C8	0.12459 (5)	0.36539 (9)	0.31079 (12)	0.0201 (2)
H8	0.084612	0.358679	0.243355	0.024*
C9	0.13569 (5)	0.37237 (9)	0.45277 (12)	0.0200 (2)
C10	0.19423 (5)	0.38111 (9)	0.55282 (12)	0.0203 (2)
H10	0.201704	0.385399	0.649417	0.024*
C11	0.15859 (5)	0.35937 (9)	0.11562 (12)	0.0211 (2)
C12	0.19700 (5)	0.35182 (11)	−0.05977 (12)	0.0264 (3)
H12A	0.177183	0.284238	−0.096410	0.040*
H12B	0.235389	0.355077	−0.070599	0.040*
H12C	0.171209	0.410245	−0.111573	0.040*
C13	0.08236 (5)	0.37078 (10)	0.49220 (12)	0.0231 (3)
C14	0.04671 (6)	0.39831 (12)	0.66992 (14)	0.0307 (3)
H14A	0.022390	0.461429	0.630597	0.046*
H14B	0.062181	0.401216	0.772194	0.046*
H14C	0.021864	0.334851	0.636695	0.046*
N1	0.43716 (4)	0.38898 (8)	1.07229 (10)	0.0215 (2)
H1N	0.445330	0.388946	1.160377	0.026 (4)*
N2	0.47752 (4)	0.37483 (8)	0.90340 (10)	0.0209 (2)
H2N	0.510968	0.367522	0.886519	0.032 (4)*
N3	0.31416 (4)	0.39456 (7)	0.73771 (10)	0.0197 (2)
N4	0.30173 (4)	0.38952 (8)	0.60489 (10)	0.0202 (2)
H4N	0.329280	0.391432	0.572748	0.041 (5)*
O1	0.33809 (4)	0.41106 (8)	1.01707 (9)	0.0285 (2)
O2	0.53768 (4)	0.37191 (8)	1.13392 (9)	0.0279 (2)
O3	0.41946 (4)	0.38163 (7)	0.67172 (8)	0.0229 (2)
O4	0.10827 (4)	0.35077 (8)	0.02776 (9)	0.0310 (2)
O5	0.20773 (4)	0.36060 (7)	0.08791 (8)	0.0250 (2)
O6	0.03258 (4)	0.35068 (10)	0.41153 (10)	0.0431 (3)
O7	0.09668 (4)	0.39450 (8)	0.62583 (9)	0.0292 (2)
OW1	0.3463 (2)	0.3484 (4)	0.3151 (6)	0.0466 (19)	0.224 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0158 (5)	0.0212 (5)	0.0187 (5)	−0.0008 (4)	0.0054 (4)	−0.0001 (4)
C2	0.0184 (5)	0.0233 (6)	0.0203 (6)	−0.0022 (4)	0.0074 (5)	−0.0026 (4)
C3	0.0192 (5)	0.0237 (6)	0.0179 (5)	0.0009 (4)	0.0054 (4)	−0.0003 (4)
C4	0.0166 (5)	0.0198 (5)	0.0175 (5)	−0.0002 (4)	0.0047 (4)	0.0010 (4)
C5	0.0157 (5)	0.0195 (5)	0.0193 (5)	−0.0003 (4)	0.0034 (4)	0.0016 (4)
C6	0.0188 (5)	0.0220 (5)	0.0209 (6)	0.0006 (4)	0.0081 (4)	0.0018 (4)
C7	0.0203 (5)	0.0198 (5)	0.0177 (6)	0.0005 (4)	0.0061 (4)	0.0010 (4)
C8	0.0171 (5)	0.0211 (5)	0.0189 (5)	−0.0002 (4)	0.0034 (4)	0.0003 (4)
C9	0.0173 (5)	0.0223 (5)	0.0193 (5)	−0.0007 (4)	0.0061 (4)	0.0006 (4)
C10	0.0197 (5)	0.0229 (5)	0.0172 (5)	−0.0006 (4)	0.0061 (4)	0.0006 (4)
C11	0.0210 (5)	0.0222 (5)	0.0192 (5)	0.0008 (4)	0.0070 (4)	0.0011 (4)
C12	0.0253 (6)	0.0365 (7)	0.0180 (6)	0.0003 (5)	0.0092 (5)	0.0008 (5)
C13	0.0185 (6)	0.0295 (6)	0.0192 (5)	−0.0006 (4)	0.0053 (4)	0.0002 (4)
C14	0.0221 (6)	0.0462 (8)	0.0262 (6)	−0.0023 (5)	0.0121 (5)	−0.0036 (5)
N1	0.0184 (5)	0.0310 (5)	0.0141 (5)	−0.0001 (4)	0.0054 (4)	−0.0023 (4)
N2	0.0149 (5)	0.0304 (5)	0.0167 (5)	0.0025 (4)	0.0056 (4)	0.0005 (4)
N3	0.0174 (5)	0.0219 (5)	0.0181 (5)	−0.0007 (3)	0.0053 (4)	−0.0001 (3)
N4	0.0153 (5)	0.0270 (5)	0.0176 (5)	−0.0005 (3)	0.0055 (4)	0.0017 (4)
O1	0.0192 (4)	0.0439 (5)	0.0244 (4)	−0.0026 (4)	0.0108 (3)	−0.0066 (4)
O2	0.0190 (4)	0.0441 (5)	0.0169 (4)	0.0043 (4)	0.0032 (3)	−0.0004 (3)
O3	0.0178 (4)	0.0344 (5)	0.0161 (4)	−0.0001 (3)	0.0062 (3)	0.0014 (3)
O4	0.0211 (4)	0.0510 (6)	0.0187 (4)	−0.0024 (4)	0.0056 (3)	−0.0028 (4)
O5	0.0204 (4)	0.0370 (5)	0.0172 (4)	0.0008 (3)	0.0071 (3)	0.0015 (3)
O6	0.0175 (4)	0.0853 (8)	0.0252 (5)	−0.0085 (5)	0.0069 (4)	−0.0130 (5)
O7	0.0190 (4)	0.0498 (6)	0.0193 (4)	−0.0038 (4)	0.0080 (3)	−0.0038 (4)
OW1	0.031 (3)	0.056 (3)	0.058 (3)	0.001 (2)	0.024 (2)	0.004 (2)

Geometric parameters (Å, º) top

C1—N3	1.3223 (15)	C9—C10	1.3945 (16)
C1—C4	1.4557 (16)	C9—C13	1.5006 (16)
C1—C2	1.4708 (15)	C10—H10	0.9500
C2—O1	1.2140 (14)	C11—O4	1.2068 (14)
C2—N1	1.3864 (14)	C11—O5	1.3298 (14)
C3—O2	1.2242 (14)	C12—O5	1.4581 (14)
C3—N1	1.3638 (15)	C12—H12A	0.9800
C3—N2	1.3759 (15)	C12—H12B	0.9800
C4—O3	1.2387 (14)	C12—H12C	0.9800
C4—N2	1.3724 (14)	C13—O6	1.1944 (15)
C5—C6	1.3909 (16)	C13—O7	1.3280 (15)
C5—C10	1.3968 (16)	C14—O7	1.4533 (14)
C5—N4	1.4080 (14)	C14—H14A	0.9800
C6—C7	1.3936 (16)	C14—H14B	0.9800
C6—H6	0.9500	C14—H14C	0.9800
C7—C8	1.3926 (16)	N1—H1N	0.8580
C7—C11	1.4970 (15)	N2—H2N	0.8982
C8—C9	1.3963 (16)	N3—N4	1.2950 (14)
C8—H8	0.9500	N4—H4N	0.8557

N3—C1—C4	124.93 (10)	O4—C11—O5	124.04 (10)
N3—C1—C2	114.97 (10)	O4—C11—C7	123.45 (10)
C4—C1—C2	120.00 (10)	O5—C11—C7	112.50 (9)
O1—C2—N1	119.97 (10)	O5—C12—H12A	109.5
O1—C2—C1	125.19 (10)	O5—C12—H12B	109.5
N1—C2—C1	114.84 (9)	H12A—C12—H12B	109.5
O2—C3—N1	122.53 (10)	O5—C12—H12C	109.5
O2—C3—N2	121.04 (10)	H12A—C12—H12C	109.5
N1—C3—N2	116.41 (10)	H12B—C12—H12C	109.5
O3—C4—N2	120.22 (10)	O6—C13—O7	124.04 (11)
O3—C4—C1	123.21 (10)	O6—C13—C9	123.36 (11)
N2—C4—C1	116.56 (10)	O7—C13—C9	112.60 (9)
C6—C5—C10	121.20 (10)	O7—C14—H14A	109.5
C6—C5—N4	117.59 (10)	O7—C14—H14B	109.5
C10—C5—N4	121.20 (10)	H14A—C14—H14B	109.5
C5—C6—C7	119.25 (10)	O7—C14—H14C	109.5
C5—C6—H6	120.4	H14A—C14—H14C	109.5
C7—C6—H6	120.4	H14B—C14—H14C	109.5
C8—C7—C6	120.52 (10)	C3—N1—C2	126.63 (9)
C8—C7—C11	117.69 (10)	C3—N1—H1N	112.8
C6—C7—C11	121.79 (10)	C2—N1—H1N	120.6
C7—C8—C9	119.52 (10)	C4—N2—C3	125.51 (10)
C7—C8—H8	120.2	C4—N2—H2N	119.7
C9—C8—H8	120.2	C3—N2—H2N	114.8
C10—C9—C8	120.75 (11)	N4—N3—C1	120.55 (10)
C10—C9—C13	121.89 (10)	N3—N4—C5	120.38 (9)
C8—C9—C13	117.35 (10)	N3—N4—H4N	121.7
C9—C10—C5	118.75 (10)	C5—N4—H4N	117.9
C9—C10—H10	120.6	C11—O5—C12	115.04 (9)
C5—C10—H10	120.6	C13—O7—C14	115.50 (9)

N3—C1—C2—O1	−5.85 (17)	C6—C7—C11—O5	0.66 (15)
C4—C1—C2—O1	177.58 (11)	C10—C9—C13—O6	−170.65 (13)
N3—C1—C2—N1	174.41 (9)	C8—C9—C13—O6	9.75 (18)
C4—C1—C2—N1	−2.17 (15)	C10—C9—C13—O7	9.60 (16)
N3—C1—C4—O3	5.51 (18)	C8—C9—C13—O7	−170.00 (10)
C2—C1—C4—O3	−178.27 (10)	O2—C3—N1—C2	177.97 (11)
N3—C1—C4—N2	−173.94 (10)	N2—C3—N1—C2	−0.46 (17)
C2—C1—C4—N2	2.27 (15)	O1—C2—N1—C3	−178.47 (11)
C10—C5—C6—C7	−0.97 (16)	C1—C2—N1—C3	1.29 (17)
N4—C5—C6—C7	177.91 (10)	O3—C4—N2—C3	179.07 (11)
C5—C6—C7—C8	0.67 (16)	C1—C4—N2—C3	−1.46 (16)
C5—C6—C7—C11	−178.47 (10)	O2—C3—N2—C4	−177.92 (11)
C6—C7—C8—C9	0.14 (16)	N1—C3—N2—C4	0.53 (17)
C11—C7—C8—C9	179.32 (10)	C4—C1—N3—N4	−2.91 (17)
C7—C8—C9—C10	−0.68 (16)	C2—C1—N3—N4	−179.30 (9)
C7—C8—C9—C13	178.92 (10)	C1—N3—N4—C5	176.15 (10)
C8—C9—C10—C5	0.40 (16)	C6—C5—N4—N3	−179.84 (10)
C13—C9—C10—C5	−179.18 (10)	C10—C5—N4—N3	−0.97 (16)
C6—C5—C10—C9	0.43 (16)	O4—C11—O5—C12	0.65 (16)
N4—C5—C10—C9	−178.40 (10)	C7—C11—O5—C12	179.85 (9)
C8—C7—C11—O4	0.70 (17)	O6—C13—O7—C14	−1.96 (19)
C6—C7—C11—O4	179.87 (11)	C9—C13—O7—C14	177.79 (10)
C8—C7—C11—O5	−178.51 (10)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C5–C10 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.86	2.03	2.8800 (13)	174
N2—H2N···O3ⁱⁱ	0.90	2.01	2.8931 (15)	168
N4—H4N···O3	0.86	2.02	2.6571 (15)	131
N4—H4N···O1ⁱⁱⁱ	0.86	2.59	2.9302 (14)	105
C6—H6···Ow1	0.95	2.14	3.061 (6)	163
C12—H12B···O1^iv	0.98	2.39	3.2743 (17)	149
C14—H14B···O4^v	0.98	2.53	3.4754 (16)	163
C12—H12C···Cg2ⁱⁱⁱ	0.98	2.73	3.4717 (15)	133

Symmetry codes: (i) −x+1, y, −z+5/2; (ii) −x+1, y, −z+3/2; (iii) x, −y+1, z−1/2; (iv) x, y, z−1; (v) x, y, z+1.

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

Contact	Distance	Symmetry operation
O1···*Ow1	3.129	x, y, 1 + z
O1···H12B	2.39	x, y, 1 + z
O1···H4N	2.59	x, 1 - y, 1/2 + z
H12A···O1	2.67	1/2 - x, 1/2 - y, 1 - z
H1N···O2	2.03	1 - x, y, 5/2 - z
O2···*Ow1	2.662	1 - x, y, 3/2 - z
N2···O2	3.226	1 - x, 1 - y, 2 - z
O2···H14C	2.64	1/2 + x, 1/2 - y, 1/2 + z
H2N···O3	2.01	1 - x, y, 3/2 - z
H4N···O1	2.59	x, 1 - y, - 1/2 + z
H12B···O1	2.39	x, y, - 1 + z
H8···O6	2.66	-x, y, 1/2 - z
H14A···O6	2.67	-x, 1 - y, 1 - z
H14C···O2	2.64	-1/2 + x, 1/2 - y, - 1/2 + z
C1···*Ow1	3.297	x, 1 - y, 1/2 + z
H6···*Ow1	2.14	x, y, z
H12B···C12	3.10	1/2 - x, 1/2 - y, -z
H14B···C14	2.93	-x, y, 3/2 - z
H12A···*Ow1	2.70	1/2 - x, 1/2 - y, -z

*Ow1 indicates the oxygen atom of the water molecule with an occupancy of 0.224 (5).

Percentage contributions of interatomic contacts to the Hirshfeld surface for the title compound top

Contact	Percentage contribution
O···H/H···O	41.2
H···H	19.2
C···H/H···C	12.2
C···O/O···C	8.4
O···O	5.6
N···O/O···N	4.7
C···N/N···C	3.2
C···C	2.8
N···H/H···N	2.7

Acknowledgements

The authors' contributions are as follows. Conceptualization, ZA, MA, GZM, FEH, SRH, NTS, and AB; methodology, SRH, and NTS; investigation, ZA, and GZM; writing (original draft), FEH, MA and AB; writing (review and editing of the manuscript), MA and AB; crystal-structure determination, GZM; visualization, ZA, and MA; funding acquisition, GZM, FEH, SRH, and NTS; resources, ZA, MA and AB; supervision, MA and AB.

Funding information

This work was supported by Baku State University.

References

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
Bocian, A., Gorczyński, A., Marcinkowski, D., Dutkiewicz, G., Patroniak, V. & Kubicki, M. (2020). Acta Cryst. C76, 367–374. CrossRef IUCr Journals Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. 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., Kuznetsov, M. L., Demukhamedova, S. D., Alieva, I. N., Godjaev, N. M., Zubkov, F. I., Mahmudov, K. T. & Pombeiro, A. J. L. (2020a). CrystEngComm, 22, 628–633. CrossRef CAS Google Scholar
Gurbanov, A. V., Kuznetsov, M. L., Mahmudov, K. T., Pombeiro, A. J. L. & Resnati, G. (2020b). Chem. Eur. J. 26, 14833–14837. CrossRef CAS PubMed Google Scholar
Gurbanov, A. V., Maharramov, A. M., Zubkov, F. I., Saifutdinov, A. M. & Guseinov, F. I. (2018a). Aust. J. Chem. 71, 190–194. Web of Science CrossRef CAS Google Scholar
Gurbanov, A. V., Mahmoudi, G., Guedes da Silva, M. F. C., Zubkov, F. I., Mahmudov, K. T. & Pombeiro, A. J. L. (2018b). Inorg. Chim. Acta, 471, 130–136. Web of Science CSD CrossRef CAS Google Scholar
Gurbanov, A. V., Mahmudov, K. T., Sutradhar, M., Guedes da Silva, F. C., Mahmudov, T. A., Guseinov, F. I., Zubkov, F. I., Maharramov, A. M. & Pombeiro, A. J. L. (2017). J. Organomet. Chem. 834, 22–27. Web of Science CSD CrossRef CAS Google Scholar
Karmakar, A., Rúbio, G. M. D. M., Paul, A., Guedes da Silva, M. F. C., Mahmudov, K. T., Guseinov, F. I., Carabineiro, S. A. C. & Pombeiro, A. J. L. (2017). Dalton Trans. 46, 8649–8657. Web of Science CSD CrossRef CAS PubMed 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
Kopylovich, M. N., Mahmudov, K. T., Haukka, M., Luzyanin, K. V. & Pombeiro, A. J. L. (2011a). Inorg. Chim. Acta, 374, 175–180. Web of Science CSD CrossRef CAS Google Scholar
Kopylovich, M. N., Mahmudov, K. T., Mizar, A. & Pombeiro, A. J. L. (2011b). Chem. Commun. 47, 7248–7250. Web of Science CrossRef CAS Google Scholar
Ma, Z., Gurbanov, A. V., Maharramov, A. M., Guseinov, F. I., Kopylovich, M. N., Zubkov, F. I., Mahmudov, K. T. & Pombeiro, A. J. L. (2017a). J. Mol. Catal. A Chem. 426, 526–533. Web of Science CSD CrossRef CAS Google Scholar
Ma, Z., Gurbanov, A. V., Sutradhar, M., Kopylovich, M. N., Mahmudov, K. T., Maharramov, A. M., Guseinov, F. I., Zubkov, F. I. & Pombeiro, A. J. L. (2017b). Mol. Catal. 428, 17–23. Web of Science CSD CrossRef CAS Google Scholar
Ma, Z., Mahmudov, K. T., Aliyeva, V. A., Gurbanov, A. V., Guedes da Silva, M. F. C. & Pombeiro, A. J. L. (2021). Coord. Chem. Rev. 437, 213859. Web of Science CrossRef Google Scholar
Ma, Z., Mahmudov, K. T., Aliyeva, V. A., Gurbanov, A. V. & Pombeiro, A. J. L. (2020). Coord. Chem. Rev. 423, 213482. Web of Science CrossRef Google Scholar
Mac Leod, T. C. O., Kopylovich, M. N., Guedes da Silva, M. F. C., Mahmudov, K. T. & Pombeiro, A. J. L. (2012). Appl. Catal. Gen. 439–440, 15–23. CrossRef CAS Google Scholar
Mahmoudi, G., Bauzá, A., Gurbanov, A. V., Zubkov, F. I., Maniukiewicz, W., Rodríguez-Diéguez, A., López-Torres, E. & Frontera, A. (2016). CrystEngComm, 18, 9056–9066. Web of Science CSD CrossRef CAS Google Scholar
Mahmoudi, G., Dey, L., Chowdhury, H., Bauzá, A., Ghosh, B. K., Kirillov, A. M., Seth, S. K., Gurbanov, A. V. & Frontera, A. (2017a). Inorg. Chim. Acta, 461, 192–205. CrossRef CAS Google Scholar
Mahmoudi, G., Gurbanov, A. V., Rodríguez-Hermida, S., Carballo, R., Amini, M., Bacchi, A., Mitoraj, M. P., Sagan, F., Kukułka, M. & Safin, D. A. (2017b). Inorg. Chem. 56, 9698–9709. Web of Science CSD CrossRef CAS PubMed 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
Mahmoudi, G., Seth, S. K., Bauzá, A., Zubkov, F. I., Gurbanov, A. V., White, J., Stilinović, V., Doert, T. & Frontera, A. (2018a). CrystEngComm, 20, 2812–2821. CrossRef CAS Google Scholar
Mahmoudi, G., Zangrando, E., Mitoraj, M. P., Gurbanov, A. V., Zubkov, F. I., Moosavifar, M., Konyaeva, I. A., Kirillov, A. M. & Safin, D. A. (2018b). New J. Chem. 42, 4959–4971. Web of Science CSD CrossRef CAS Google Scholar
Mahmoudi, G., Zaręba, J. K., Gurbanov, A. V., Bauzá, A., Zubkov, F. I., Kubicki, M., Stilinović, V., Kinzhybalo, V. & Frontera, A. (2017c). Eur. J. Inorg. Chem. pp. 4763–4772. CrossRef Google Scholar
Mahmudov, K. T., Kopylovich, M. N., Haukka, M., Mahmudova, G. S., Esmaeila, E. F., Chyragov, F. M. & Pombeiro, A. J. L. (2013). J. Mol. Struct. 1048, 108–112. 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
Mizar, A., Guedes da Silva, M. F. C., Kopylovich, M. N., Mukherjee, S., Mahmudov, K. T. & Pombeiro, A. J. L. (2012). Eur. J. Inorg. Chem. pp. 2305–2313. Web of Science CSD CrossRef 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
Shikhaliyev, N. Q., Kuznetsov, M. L., Maharramov, A. M., Gurbanov, A. V., Ahmadova, N. E., Nenajdenko, V. G., Mahmudov, K. T. & Pombeiro, A. J. L. (2019). CrystEngComm, 21, 5032–5038. CrossRef CAS Google Scholar
Shixaliyev, N. Q., Gurbanov, A. V., Maharramov, A. M., Mahmudov, K. T., Kopylovich, M. N., Martins, L. M. D. R. S., Muzalevskiy, V. M., Nenajdenko, V. G. & Pombeiro, A. J. L. (2014). New J. Chem. 38, 4807–4815. Web of Science CSD CrossRef CAS Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Sutradhar, M., Alegria, E. C. B. A., Mahmudov, K. T., Guedes da Silva, M. F. C. & Pombeiro, A. J. L. (2016). RSC Adv. 6, 8079–8088. Web of Science CSD CrossRef CAS Google Scholar
Sutradhar, M., Martins, L. M. D. R. S., Guedes da Silva, M. F. C., Mahmudov, K. T., Liu, C.-M. & Pombeiro, A. J. L. (2015). Eur. J. Inorg. Chem. pp. 3959–3969. Web of Science CSD CrossRef Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). Crystal Explorer 17. The University of Western Australia. Google Scholar
Viswanathan, A., Kute, D., Musa, A., Mani, S. K., Sipilä, V., Emmert-Streib, F., Zubkov, F. I., Gurbanov, A. V., Yli-Harja, O. & Kandhavelu, M. (2019). Eur. J. Med. Chem. 166, 291–303. Web of Science CrossRef CAS PubMed Google Scholar

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