Crystal structure and Hirshfeld surface analysis of (E)-4-{[2-(4-hy­droxy­benzo­yl)hydrazin-1-yl­idene]meth­yl}pyridin-1-ium nitrate

Naziri, M.A.; Şahin, E.; Hökelek, T.

doi:10.1107/S2056989018002141

research communications

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ISSN: 2056-9890

Volume 74| Part 3| March 2018| Pages 323-327

https://doi.org/10.1107/S2056989018002141

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Crystal structure and Hirshfeld surface analysis of (E)-4-{[2-(4-hydroxybenzoyl)hydrazin-1-ylidene]methyl}pyridin-1-ium nitrate

Mir Abolfazl Naziri,^a Ertan Şahin ^a and Tuncer Hökelek ^b ^*

^aDepartment of Inorganic Chemistry, Atatürk University, Erzurum, Turkey, and ^bDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 1 February 2018; accepted 5 February 2018; online 7 February 2018)

The asymmetric unit of the title aroyl hydrazone Schiff base salt, C₁₃H₁₂N₃O₂⁺·N O₃⁻, consists of one molecular cation in the keto tautomeric form, adopting an E configuration with respect to the azomethine bond, and one nitrate anion. The two units are linked via an N—H⋯O hydrogen bond. The molecule overall is non-planar, with the pyridinium and benzene rings being inclined to each other by 4.21 (4)°. In the crystal, cations and anions are linked via intermolecular O—H⋯O and bifurcated N—H⋯O hydrogen bonds, forming a two-dimensional network parallel to (101). These networks are further linked by C—H⋯O hydrogen bonds, forming slabs parallel to (101). The slabs are linked by offset π–π interactions, involving the benzene and pyridinium rings of adjacent slabs [intercentroid distance = 3.610 (2) Å], forming a three-dimensional structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯O/O⋯H (45.1%), H⋯H (19.3%), H⋯C/C⋯H (14.5%), H⋯N/N⋯H (7.9%) and C⋯C (6.0%) interactions.

Keywords: crystal structure; aroyl hydrazone; Schiff base; hydrogen bonding; π–π interactions; Hirshfeld surface.

CCDC reference: 1822116

1. Chemical context

Hydrazone Schiff bases and their coordination compounds have gained importance recently because of their application as models in biological, analytical and antimicrobial systems, and also due to their anticancer, antibacterial as well as antifungal activities (Ruben et al., 2003 ). Aroyl hydrazones are a class of versatile ligands, capable of generating various molecular architectures and coordination polyhedra (Ruben et al., 2003; Uppadine Gisselbrecht & Lehn, 2004 ; Uppadine & Lehn, 2004 ; Wood et al., 2004 ). Aroyl hydrazones are obtainable through hydrazide-ketone/aldehyde condensation, and they exhibit flexible metal-chelating capabilities through their keto–enol tautomerism and possible reversible deprotonation. The empty N,O-donor chelating pockets of aroyl hydrazones that are incorporated into frameworks can potentially make them amenable to post-synthetic metalation (Evans et al., 2014 ). The structure determination of the title aroyl hydrazone Schiff base salt was undertaken in order to compare the results obtained with those reported previously. In this context, we synthesized the title compound, (E)-4-{[2-(4-hydroxybenzoyl)hydrazin-1-ylidene]methyl}pyridin-1-ium nitrate, and report herein on its crystal and molecular structures along with the Hirshfeld surface analysis.

2. Structural commentary

The asymmetric unit of the title aroyl hydrazone Schiff base salt contains one molecular cation and one nitrate anion, which are linked via an N⁺—H ⋯ O hydrogen bond (Fig. 1, Table 1). The organic cation is in the keto tautomeric form, which can be verified from the C=O and C—NH bond lengths of the amide unit: O2=C7 is 1.228 (2) Å and N1—C7 is 1.359 (2) Å. Amide unit bond lengths for aroyl hydrazones are in the ranges 1.218–1.292 Å for C=O bonds and 1.313–1.365 Å for C–N bonds in the keto tautomeric form, and 1.284–1.314 Å for C=O bonds and 1.291–1.331 Å for C—N bonds in the enol tautomeric form (Hosseini-Monfared et al., 2013 ). The three bond angles around atom C7, viz. O2—C7—N1 [121.65 (15)°], O2—C7—C5 [122.00 (15)°] and N1—C7—C5 [116.35 (14)°], differ from 120°, probably in order to decrease the repulsion between the lone pairs present on atoms N1 and O2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2ⁱ	0.96 (2)	1.79 (2)	2.742 (2)	170 (2)
N1—H1B⋯O4ⁱⁱⁱ	0.84 (2)	2.25 (2)	3.057 (2)	161 (2)
N1—H1B⋯O5ⁱⁱⁱ	0.84 (2)	2.47 (2)	3.174 (3)	141 (2)
N3—H3A⋯O4	0.97 (2)	1.80 (2)	2.763 (2)	178 (2)
C1—H1⋯O2ⁱ	0.93	2.58	3.258 (2)	130
C8—H8⋯O4ⁱⁱⁱ	0.93	2.42	3.243 (2)	148
C10—H10⋯O1ⁱⁱ	0.93	2.48	3.375 (2)	162
C11—H11⋯O5^iv	0.93	2.42	3.104 (3)	130
C12—H12⋯O3^v	0.93	2.34	3.191 (2)	152
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) -x+1, -y+2, -z+1.

Figure 1
The molecular structure of the title aroyl hydrazone Schiff base salt, with the atom-numbering scheme. The N—H_Pym⋯O_N (Pym = pyridinium and N = nitrate) hydrogen bond (see Table 1

) is shown as a dashed line. Displacement ellipsoids are drawn at the 50% probability level.

The configuration at the N2=C8 [1.276 (2) Å] bond is E, where torsion angle N1—N2—C8—C9 is −177.58 (14)°. On the other hand, torsion angles N2—N1—C7—C5 and C8—N2—N1—C7 are −179.66 (13) and −178.09 (15)°, respectively, and the benzene (C1–C6) and pyridinium (N3/C9–C13) rings are oriented at a dihedral angle of 4.21 (4)°, probably due to the steric interactions between the hydrogen atoms (Table 2). Thus, the molecule is non-planar as a whole. The central C9—C8=N2—N1—C7=O2 moiety of the molecular cation adopts an extended double-bonded conformation and has a maximum deviation of 0.0331 (18) Å for atom C8, from the mean plane.

Table 2
Selected interatomic distances (Å)

O1⋯H10ⁱ	2.48	C7⋯H1Aⁱⁱ	2.72 (2)
O2⋯H1ⁱⁱ	2.58	H1⋯H1A	2.28
O2⋯H1Aⁱⁱ	1.79 (2)	H1B⋯O4ⁱⁱⁱ	2.25 (2)
O2⋯H4	2.52	H1B⋯O5ⁱⁱⁱ	2.47 (2)
O3⋯H3A	2.48 (2)	H1B⋯N4ⁱⁱⁱ	2.73 (2)
O3⋯H12	2.59	H6⋯O4ⁱⁱⁱ	2.71
O4⋯H3A	1.80 (2)	H6⋯O5ⁱⁱⁱ	2.75
N1⋯H6	2.59	H6⋯N4ⁱⁱⁱ	2.81
N2⋯H1Aⁱⁱ	2.56 (2)	H6⋯H1B	2.11
N2⋯H10	2.62	H8⋯O4ⁱⁱⁱ	2.42
N4⋯H3A	2.47 (2)	H8⋯H1B	2.12
C6⋯H1B	2.61 (2)	H8⋯H13	2.46
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

3. Supramolecular features

Hydrogen bonding and van der Waals contacts are the dominant interactions in the crystal packing. In the crystal, O—H_Hydr⋯O_Hydrz, N—H_Pym⋯O_N and bifurcated N—H_Hydrz⋯O_N (Hydr = hydroxy, Hydrz = hydrazide, Pym = pyridinium and N = nitrate) hydrogen bonds (Table 1) link the cations and anions into a two-dimensional network parallel to (101), as illustrated in Fig. 2. A series of C—H⋯O hydrogen bonds [C—H_Bnz⋯O_Hydrz, C—H_Pym⋯O_N, C—H_Pym⋯O_Hydr and C—H_Meth⋯O_N (Bnz = benzene and Meth = methine)] link adjacent layers, forming slabs parallel to (101); see Fig. 3. The slabs are linked by offset π–π interactions, forming a three-dimensional structure. The offset π–π interaction between the benzene (Cg1 is the centroid of atoms C1–C6) and pyridinium (Cg2 is the centroid of atoms N3/C9–C13) rings of adjacent slabs has an intercentroid Cg1⋯Cg2(−x + 2, −y + 1, −z + 1) distance of 3.610 (2) Å, while α is 4.2 (1)°, and the interplanar distances are 3.263 (7) and 3.366 (7) Å, with an offset distance of 1.303 Å.

Figure 2
Part of the crystal structure, viewed normal to (101). The O—H⋯O and N—H⋯O hydrogen bonds (see Table 1

) are shown as dashed lines, and C-bound H atoms have been omitted for clarity.

Figure 3
A view along the b axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1

), and only H atoms involved in these interactions have been included.

4. Hirshfeld surface analysis

In order to visualize the intermolecular interactions in the crystal of the title aroyl hydrazone Schiff base salt, a Hirshfeld surface (HS) analysis (Hirshfeld, 1977 ; Spackman & Jayatilaka, 2009 ) was carried out by using Crystal Explorer 17.5 (Turner et al., 2017 ). In the HS plotted over d_norm (Fig. 4), the white surfaces indicate contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (distinct contact) than the van der Waals radii, respectively (Venkatesan et al., 2016 ). The bright-red spots appearing near N—O4, N—O5 and hydrogen atoms H1A, H1B and H3A indicate their role as the respective donors and acceptors in the dominant O—H⋯O and N—H⋯O hydrogen bonds (Spackman et al., 2008 ; Jayatilaka et al., 2005 ). The shape-index of the HS is a tool to visualize the π–π stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π interactions. Fig. 5 clearly suggest that there are π–π interactions in (I). The overall two-dimensional fingerprint plot and those delineated into H⋯O/O⋯H, H⋯H, H⋯C/C⋯H, H⋯N/N⋯H, C⋯C, C⋯N/N⋯C, C⋯O/O⋯C, O⋯O, N⋯N and N⋯O/O⋯N contacts (McKinnon et al., 2007 ) are illustrated in Fig. 5 a–k, respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction is H⋯O/O⋯H contributing 45.1% to the overall crystal packing, which is reflected in Fig. 6b as pair of spikes with the tips at d_e + d_i ∼1.75 Å. The short H⋯O/O⋯H contacts are masked by strong O—H⋯O hydrogen bonding in this plot. In the fingerprint plot delineated into H⋯H contacts (Fig. 6c), the 19.3% contribution to the overall crystal packing is reflected as widely scattered points of high density due to the large hydrogen content of the molecule. The single spike in the centre at d_e = d_i = 1.2 Å in Fig. 5c is due to the short interatomic H ⋯ H contacts (Table 2). In the absence of C—H⋯π interactions in the crystal, the pair of characteristic wings resulting in the fingerprint plot delineated into H⋯C/C⋯H contacts with 14.5% contribution to the HS, Fig. 6d, and the pair of thin edges at d_e + d_i ∼1.93 Å result from short interatomic H⋯C/C⋯H contacts (Table 2). The H⋯N/N⋯H contacts in the structure with 7.9% contribution to the HS has a symmetrical distribution of points, Fig. 5e, with the tips at d_e + d_i ∼1.52 Å arising from the short interatomic H⋯N/N⋯H contacts listed in Table 2. The C⋯C contacts assigned to short interatomic C⋯C contacts with 6.0% contribution to the HS appear as an arrow-shaped distribution of points in Fig. 6f, with the vertex at d_e = d_i ∼1.65 Å. Finally, the C⋯N/N⋯C (Fig. 6g) and C⋯O/O⋯C (Fig. 6h) contacts in the structure with 3.4% and 1.9% contributions to the HS have nearly symmetrical distributions of points, with the scattered points of low densities.

Figure 4
View of the three-dimensional Hirshfeld surface of the title aroyl hydrazone Schiff base salt plotted over d_norm in the range −0.6521 to 1.7041 a.u.

Figure 5
Hirshfeld surface of the title aroyl hydrazone Schiff base salt plotted over shape-index.

Figure 6
The full two-dimensional fingerprint plots for the title aroyl hydrazone Schiff base salt, showing (a) all interactions, and delineated into (b) H⋯O/O⋯H, (c) H⋯H, (d) H⋯C/C⋯H, (e) H⋯N/N⋯H, (f) C⋯C, (g) C⋯N/N⋯C, (h) C⋯O/O⋯C, (i) O⋯O, (j) N⋯N and (k) N⋯O/O⋯N interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts.

The Hirshfeld surface representations with the function d_norm plotted onto the surface are shown for the H⋯O/O⋯H, H⋯H, H⋯C/C⋯H, H⋯N/N⋯H, C⋯C and C⋯N/N⋯C interactions in Fig. 7a–f, respectively.

Figure 7
The Hirshfeld surface representations with the function d_norm plotted onto the surface for (a) H⋯O/O⋯H, (b) H⋯H, (c) H⋯C/C⋯H, (d) H⋯N/N⋯H, (e) C⋯C and (f) C⋯N/N⋯C interactions.

The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯O/O⋯H, H⋯H and H⋯C/C⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ).

5. Synthesis and crystallization

The title compound was prepared by the reaction of Cd(NO₃)₂·4H₂O (0.15 g, 0.5 mmol) and 4-[(4-hydroxybenzoyl)hydrazonemethyl]pyridin (0.12 g, 0.5 mmol) in ethanol by using a branched-tube method (Shaabani et al., 2017 ). After two months, the formation of yellow-coloured crystals was observed. They were filtered off and washed several times with hot ethanol for purification (yield: 0.20 g, 74%, m.p. 613 K). Analysis calculated for C₁₃H₁₂N₄O₅: C, 51.32; H, 3.98; N, 17.41. Found: C, 51.08; H, 4.14; N, 17.09. Characteristic IR bands (cm⁻¹): 3526 m, ν(OH); 1375 m, ν(N—O); 1644 s, ν(C=N); 1501 s, ν(N=O); 1105 s, ν(NN).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms of the OH and NH groups were located in a difference-Fourier map and refined freely. The C-bound H atoms were positioned geometrically with C—H = 0.93 Å, and refined as riding with U_iso(H) = 1.2U_eq(C). The highest residual electron density was found 2.48 Å from atom H1.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₃H₁₂N₃O₂⁺·NO₃⁻
M_r	304.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	8.335 (3), 13.929 (5), 12.184 (4)
β (°)	95.902 (10)
V (Å³)	1407.1 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.15 × 0.14 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.945, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	44410, 3499, 2508
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.149, 1.04
No. of reflections	3499
No. of parameters	211
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.25
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2015 ).

Supporting information

CCDC reference: 1822116

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018002141/su5422sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018002141/su5422Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018002141/su5422Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2015).

(E)-4-{[2-(4-Hydroxybenzoyl)hydrazin-1-ylidene]methyl}pyridin-1-ium nitrate top

Crystal data top

C₁₃H₁₂N₃O₂⁺·NO₃⁻	F(000) = 632
M_r = 304.27	D_x = 1.436 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9700 reflections
a = 8.335 (3) Å	θ = 3.1–27.5°
b = 13.929 (5) Å	µ = 0.11 mm⁻¹
c = 12.184 (4) Å	T = 296 K
β = 95.902 (10)°	Block, colourless
V = 1407.1 (8) Å³	0.15 × 0.14 × 0.12 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3499 independent reflections
Radiation source: fine-focus sealed tube	2508 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
φ and ω scans	θ_max = 28.4°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −11→10
T_min = 0.945, T_max = 0.976	k = −18→18
44410 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0782P)² + 0.4149P] where P = (F_o² + 2F_c²)/3
3499 reflections	(Δ/σ)_max < 0.001
211 parameters	Δρ_max = 0.75 e Å⁻³
0 restraints	Δρ_min = −0.25 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.

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.

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

	x	y	z	U_iso*/U_eq
O1	1.15687 (19)	0.08055 (9)	0.24127 (12)	0.0576 (4)
H1A	1.207 (3)	0.1109 (18)	0.183 (2)	0.080 (8)*
O2	0.82328 (18)	0.32288 (9)	0.59284 (11)	0.0549 (4)
O3	0.3316 (2)	0.99298 (10)	0.57667 (11)	0.0619 (4)
O4	0.37385 (19)	0.95570 (10)	0.74819 (11)	0.0595 (4)
O5	0.22205 (19)	1.07556 (11)	0.69841 (15)	0.0730 (5)
N1	0.81569 (17)	0.43407 (10)	0.45738 (12)	0.0392 (3)
H1B	0.830 (3)	0.4512 (15)	0.3928 (19)	0.055 (6)*
N2	0.74051 (16)	0.49881 (10)	0.51883 (11)	0.0368 (3)
N3	0.50122 (17)	0.80177 (10)	0.64341 (12)	0.0408 (3)
H3A	0.456 (3)	0.8548 (17)	0.6811 (19)	0.069 (7)*
N4	0.30832 (18)	1.00915 (10)	0.67253 (13)	0.0438 (4)
C1	1.08209 (19)	0.24460 (12)	0.27240 (13)	0.0367 (4)
H1	1.1286	0.2655	0.2104	0.044*
C2	1.0865 (2)	0.14803 (12)	0.30031 (14)	0.0386 (4)
C3	1.0173 (2)	0.11743 (13)	0.39341 (15)	0.0452 (4)
H3	1.0208	0.0528	0.4129	0.054*
C4	0.9439 (2)	0.18265 (12)	0.45671 (14)	0.0410 (4)
H4	0.8980	0.1616	0.5189	0.049*
C5	0.93716 (18)	0.27990 (11)	0.42900 (13)	0.0334 (3)
C6	1.00883 (18)	0.30970 (12)	0.33645 (13)	0.0353 (4)
H6	1.0073	0.3744	0.3176	0.042*
C7	0.85500 (18)	0.34613 (11)	0.50025 (13)	0.0352 (3)
C8	0.7030 (2)	0.57893 (12)	0.47233 (14)	0.0417 (4)
H8	0.7236	0.5893	0.3997	0.050*
C9	0.62801 (18)	0.65447 (11)	0.53250 (13)	0.0347 (3)
C10	0.56331 (19)	0.63741 (12)	0.63168 (14)	0.0377 (4)
H10	0.5629	0.5758	0.6610	0.045*
C11	0.5004 (2)	0.71264 (12)	0.68521 (15)	0.0402 (4)
H11	0.4565	0.7019	0.7513	0.048*
C12	0.5620 (2)	0.82024 (12)	0.54903 (15)	0.0441 (4)
H12	0.5613	0.8827	0.5221	0.053*
C13	0.6257 (2)	0.74791 (12)	0.49147 (14)	0.0401 (4)
H13	0.6673	0.7610	0.4251	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0805 (10)	0.0412 (7)	0.0580 (9)	−0.0054 (6)	0.0395 (8)	−0.0132 (6)
O2	0.0797 (10)	0.0457 (7)	0.0451 (7)	0.0120 (6)	0.0345 (7)	0.0058 (6)
O3	0.0884 (11)	0.0562 (9)	0.0452 (8)	0.0093 (7)	0.0264 (7)	0.0067 (6)
O4	0.0837 (10)	0.0566 (8)	0.0401 (7)	0.0142 (7)	0.0156 (7)	−0.0006 (6)
O5	0.0723 (10)	0.0593 (9)	0.0875 (12)	0.0217 (8)	0.0090 (9)	−0.0260 (8)
N1	0.0496 (8)	0.0387 (8)	0.0316 (7)	0.0066 (6)	0.0145 (6)	−0.0011 (6)
N2	0.0385 (7)	0.0374 (7)	0.0360 (7)	0.0026 (5)	0.0107 (6)	−0.0047 (6)
N3	0.0446 (8)	0.0330 (7)	0.0466 (8)	0.0026 (6)	0.0132 (6)	−0.0013 (6)
N4	0.0502 (8)	0.0359 (7)	0.0473 (9)	−0.0017 (6)	0.0142 (7)	−0.0056 (6)
C1	0.0379 (8)	0.0441 (9)	0.0296 (8)	−0.0016 (7)	0.0103 (6)	−0.0001 (7)
C2	0.0416 (8)	0.0398 (9)	0.0364 (8)	−0.0050 (7)	0.0134 (7)	−0.0096 (7)
C3	0.0586 (11)	0.0329 (9)	0.0479 (10)	−0.0051 (7)	0.0236 (8)	−0.0023 (7)
C4	0.0500 (9)	0.0389 (9)	0.0373 (9)	−0.0059 (7)	0.0198 (7)	−0.0004 (7)
C5	0.0327 (7)	0.0369 (8)	0.0315 (8)	−0.0005 (6)	0.0080 (6)	−0.0027 (6)
C6	0.0355 (8)	0.0375 (8)	0.0340 (8)	0.0018 (6)	0.0085 (6)	0.0034 (6)
C7	0.0359 (8)	0.0368 (8)	0.0343 (8)	−0.0011 (6)	0.0104 (6)	−0.0018 (6)
C8	0.0496 (9)	0.0437 (9)	0.0333 (8)	0.0058 (8)	0.0110 (7)	−0.0005 (7)
C9	0.0346 (8)	0.0363 (8)	0.0334 (8)	0.0004 (6)	0.0046 (6)	−0.0009 (6)
C10	0.0421 (8)	0.0314 (8)	0.0412 (9)	−0.0028 (6)	0.0113 (7)	0.0022 (7)
C11	0.0434 (9)	0.0373 (9)	0.0422 (9)	−0.0030 (7)	0.0154 (7)	0.0006 (7)
C12	0.0522 (10)	0.0350 (9)	0.0464 (10)	0.0042 (7)	0.0106 (8)	0.0088 (7)
C13	0.0449 (9)	0.0425 (9)	0.0342 (8)	0.0030 (7)	0.0096 (7)	0.0070 (7)

Geometric parameters (Å, º) top

O1—C2	1.354 (2)	C4—C3	1.376 (2)
O1—H1A	0.96 (3)	C4—H4	0.9300
O2—C7	1.228 (2)	C5—C4	1.396 (2)
O3—N4	1.224 (2)	C5—C6	1.393 (2)
O4—N4	1.264 (2)	C5—C7	1.482 (2)
N1—C7	1.359 (2)	C6—C1	1.379 (2)
N1—H1B	0.84 (2)	C6—H6	0.9300
N2—N1	1.3649 (19)	C8—H8	0.9300
N2—C8	1.276 (2)	C9—C8	1.459 (2)
N3—C11	1.342 (2)	C9—C10	1.393 (2)
N3—C12	1.329 (2)	C9—C13	1.394 (2)
N3—H3A	0.97 (2)	C10—C11	1.367 (2)
N4—O5	1.2325 (19)	C10—H10	0.9300
C1—H1	0.9300	C11—H11	0.9300
C2—C1	1.387 (2)	C12—H12	0.9300
C2—C3	1.391 (2)	C13—C12	1.366 (2)
C3—H3	0.9300	C13—H13	0.9300

O1···H10ⁱ	2.48	C7···H1Aⁱⁱ	2.72 (2)
O2···H1ⁱⁱ	2.58	H1···H1A	2.28
O2···H1Aⁱⁱ	1.79 (2)	H1B···O4ⁱⁱⁱ	2.25 (2)
O2···H4	2.52	H1B···O5ⁱⁱⁱ	2.47 (2)
O3···H3A	2.48 (2)	H1B···N4ⁱⁱⁱ	2.73 (2)
O3···H12	2.59	H6···O4ⁱⁱⁱ	2.71
O4···H3A	1.80 (2)	H6···O5ⁱⁱⁱ	2.75
N1···H6	2.59	H6···N4ⁱⁱⁱ	2.81
N2···H1Aⁱⁱ	2.56 (2)	H6···H1B	2.11
N2···H10	2.62	H8···O4ⁱⁱⁱ	2.42
N4···H3A	2.47 (2)	H8···H1B	2.12
C6···H1B	2.61 (2)	H8···H13	2.46

C2—O1—H1A	109.6 (15)	C6—C5—C7	123.46 (15)
N2—N1—H1B	116.3 (15)	C1—C6—C5	120.92 (15)
C7—N1—N2	119.41 (14)	C1—C6—H6	119.5
C7—N1—H1B	124.2 (15)	C5—C6—H6	119.5
C8—N2—N1	116.08 (14)	O2—C7—N1	121.65 (15)
C11—N3—H3A	120.6 (14)	O2—C7—C5	122.00 (15)
C12—N3—C11	121.66 (15)	N1—C7—C5	116.35 (14)
C12—N3—H3A	117.7 (14)	N2—C8—C9	120.38 (15)
O3—N4—O4	119.23 (15)	N2—C8—H8	119.8
O3—N4—O5	122.40 (17)	C9—C8—H8	119.8
O5—N4—O4	118.37 (16)	C10—C9—C8	122.46 (15)
C2—C1—H1	120.0	C10—C9—C13	118.54 (14)
C6—C1—C2	120.06 (14)	C13—C9—C8	118.96 (15)
C6—C1—H1	120.0	C9—C10—H10	120.5
O1—C2—C1	123.03 (15)	C11—C10—C9	119.00 (15)
O1—C2—C3	117.33 (16)	C11—C10—H10	120.5
C1—C2—C3	119.64 (15)	N3—C11—C10	120.71 (16)
C2—C3—H3	120.0	N3—C11—H11	119.6
C4—C3—C2	120.02 (16)	C10—C11—H11	119.6
C4—C3—H3	120.0	N3—C12—C13	120.30 (16)
C3—C4—C5	120.96 (15)	N3—C12—H12	119.9
C3—C4—H4	119.5	C13—C12—H12	119.9
C5—C4—H4	119.5	C9—C13—H13	120.1
C4—C5—C7	118.16 (14)	C12—C13—C9	119.79 (15)
C6—C5—C4	118.38 (14)	C12—C13—H13	120.1

N2—N1—C7—O2	0.7 (2)	C7—C5—C6—C1	−179.26 (15)
N2—N1—C7—C5	−179.66 (13)	C4—C5—C7—O2	15.3 (2)
C8—N2—N1—C7	−178.09 (15)	C4—C5—C7—N1	−164.34 (15)
N1—N2—C8—C9	−177.58 (14)	C6—C5—C7—O2	−164.23 (16)
C12—N3—C11—C10	0.3 (3)	C6—C5—C7—N1	16.1 (2)
C11—N3—C12—C13	0.1 (3)	C5—C6—C1—C2	−0.6 (2)
O1—C2—C1—C6	−179.76 (15)	C10—C9—C8—N2	−13.9 (3)
C3—C2—C1—C6	−0.3 (3)	C13—C9—C8—N2	163.87 (16)
O1—C2—C3—C4	−179.94 (17)	C8—C9—C10—C11	177.61 (16)
C1—C2—C3—C4	0.6 (3)	C13—C9—C10—C11	−0.1 (2)
C5—C4—C3—C2	0.0 (3)	C8—C9—C13—C12	−177.27 (16)
C6—C5—C4—C3	−0.9 (3)	C10—C9—C13—C12	0.6 (2)
C7—C5—C4—C3	179.50 (16)	C9—C10—C11—N3	−0.3 (3)
C4—C5—C6—C1	1.2 (2)	C9—C13—C12—N3	−0.6 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱ	0.96 (2)	1.79 (2)	2.742 (2)	170 (2)
N1—H1B···O4ⁱⁱⁱ	0.84 (2)	2.25 (2)	3.057 (2)	161 (2)
N1—H1B···O5ⁱⁱⁱ	0.84 (2)	2.47 (2)	3.174 (3)	141 (2)
N3—H3A···O4	0.97 (2)	1.80 (2)	2.763 (2)	178 (2)
C1—H1···O2ⁱ	0.93	2.58	3.258 (2)	130
C8—H8···O4ⁱⁱⁱ	0.93	2.42	3.243 (2)	148
C10—H10···O1ⁱⁱ	0.93	2.48	3.375 (2)	162
C11—H11···O5^iv	0.93	2.42	3.104 (3)	130
C12—H12···O3^v	0.93	2.34	3.191 (2)	152

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

Acknowledgements

The authors acknowledge the Scientific and Technological Research Application and Research Center, Sinop University, Turkey, for use of the Bruker D8 QUEST diffractometer.

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