Synthesis, crystal structure and Hirshfeld surface analysis of [Cu(NO3)2{8-methyl­phenanthridin-6(5H)-one}4]

Gurbanov, A.V.; Hökelek, T.; Woldemariam, M.M.

doi:10.1107/S2056989025009892

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 81| Part 12| December 2025| Pages 1140-1143

https://doi.org/10.1107/S2056989025009892

Open

access

Synthesis, crystal structure and Hirshfeld surface analysis of [Cu(NO₃)₂{8-methylphenanthridin-6(5H)-one}₄]

Atash V. Gurbanov,^a Tuncer Hökelek ^b and Menberu Mengesha Woldemariam ^c ^*

^aExcellence Center, Baku State University, Z. Khalilov Str. 33, AZ1148, Baku, Azerbaijan, ^bHacettepe University, Department of Physics, 06800 Beytepe-Ankara, Türkiye, and ^cDepartment of Physics, Jimma University, Jimma, Ethiopia
^*Correspondence e-mail: [email protected]

Edited by F. F. Ferreira, Universidade Federal do ABC, Brazil (Received 15 October 2025; accepted 6 November 2025; online 11 November 2025)

The asymmetric unit of the title compound, tetrakis[8-methylphenanthridin-6(5H)-one-κO]bis(nitrato-κO)copper(II), [Cu(NO₃)₂(C₁₄H₁₁NO)₄], contains one Cu^II cation located on a centre of symmetry, two 8-methylphenanthridin-6(5H)-one (MPHNT) ligands and one nitrate anion, where the Cu^II atom is in a slightly distorted octahedral environment. Intramolecular N—H⋯O hydrogen bonds are observed. In the crystal, C—H⋯O hydrogen bonds link the molecules, enclosing S(6), S(9) and R⁴₄(18) ring motifs. In addition π–π interactions with centroid-to-centroid distances of 3.808 (2) Å and also a series of C—H⋯π(ring) interactions help to consolidate the packing in a three-dimensional architecture within the crystal. A Hirshfeld surface analysis revealed that the most important contributions for the crystal packing are from H⋯H (41.1%), H⋯C/C⋯H (29.9%), H⋯O/O⋯H (14.8%) and C⋯C (10.0%) interactions.

Keywords: copper complexes; N-containing compounds; crystal structure; non-covalent interactions.

CCDC reference: 2501014

1. Chemical context

N-containing organic compounds are a widely used and versatile class of ligands in coordination chemistry due to the nitrogen atom's strong σ-donor characteristics, which stabilize various metal oxidation states (Gurbanov et al., 2023 ; Mahmudov et al., 2021 , 2023 ; Kretschmer, 2020 ; Peris, 2018 ). These ligands are employed in diverse applications, including molecular recognition, homogenous catalysis, crystal engineering, material science, organic synthesis and medicinal chemistry (Gadzhieva et al., 2005 ; Maharramov et al., 2011 ; Gurbanov et al., 2022 ). Alteration of the metal centre as well as substituents at the N-ligands dictate the sensing and analytical properties, catalytic activity, and supramolecular arrangements of the corresponding metal complexes (Aliyeva et al., 2024 ; Gurbanov et al., 2018 ; Huseynov et al., 2018 ). In particular, the coordination chemistry of copper with N-ligands is extremely rich due to its oxidation states Cu⁰, Cu^I, Cu^II and Cu^III allowing it to act through one- or two-electron processes in organic transformations (Allen et al., 2013 ). We have synthesized a new copper(II) complex with an 8-methylphenanthridin-6(5H)-one ligand, which is consolidated through intra- and intermolecular non-covalent interactions. Herein, we report its synthesis and molecular and crystal structures together with the results of a Hirshfeld surface analysis.

2. Structural commentary

The asymmetric unit of the title compound, C₅₆H₄₄CuN₆O₁₀, (I) contains one Cu^II cation located on a crystallographic inversion centre, two 8-methylphenanthridin-6(5H)-one (MPHNT) and one nitrate anion (Fig. 1). The Cu^II atom is in a slightly distorted octahedral environment and is coordinated by four symmetry-related MPHNT O atoms (O1, O2 and O1′, O2′) in the basal plane at distances of 1.953 (2) and 1.942 (2) Å in a square-planar arrangement and by two symmetry-related O atoms (O5 and O5′>) at distances of 2.520 (3) Å in the axial positions (Table 1) [symmetry code: (′) $[{1\over 2}]$ − x, $[{1\over 2}]$ − y, −z + 1]. The phenanthridin ring systems [(A (N1/C1–C13) and (B (N2/C15–C27)] are essentially planar with r.m.s. deviations of 0.03 (4) and 0.03 (6) Å, respectively (Fig. 1). Atoms O1, O2, C14 and C28 are −0.006 (3), 0.182 (3), 0.046 (6) and 0.100 (6) Å away from the best least-squares planes of the corresponding ring systems. The ring systems are oriented at a dihedral angle of A/B = 68.97 (6)°. Intramolecular N—H⋯O hydrogen bonds (Table 2) occur between N atoms of MPHNT and O atoms of nitrate anions (Fig. 1).

Table 1
Selected geometric parameters (Å, °)

Cu1—O2	1.942 (2)	Cu1—O5	2.520 (3)
Cu1—O1	1.953 (2)

O2ⁱⁱ—Cu1—O1	90.74 (11)	O1—Cu1—O5	90.79 (11)
O2—Cu1—O1	89.26 (11)	O2—Cu1—O5	94.21 (11)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Table 2
Hydrogen-bond geometry (Å, °)

Cg1, Cg3, Cg4 and Cg5 are the centroids of the (N1/C1/C2/C7/C8/C13), (C2–C7), (C8–C13) and (C16–C21) rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O5	0.90	1.97	2.852 (4)	165
N2—H2N⋯O5	0.90	2.07	2.806 (4)	139
C4—H4A⋯O4ⁱⁱⁱ	0.93	2.60	3.433 (6)	150
C9—H9A⋯O1ⁱ	0.93	2.60	3.514 (5)	169
C12—H12A⋯O3ⁱⁱ	0.93	2.57	3.455 (6)	158
C14—H14C⋯Cg5^vi	0.96	2.92	3.768 (6)	147
C20—H20A⋯Cg3^vii	0.93	2.86	3.644 (5)	143
C23—H23A⋯Cg1^vii	0.93	2.89	3.726 (5)	151
C24—H24A⋯Cg4^vii	0.93	2.77	3.557 (5)	143
C28—H28C⋯Cg3^viii	0.96	2.88	3.716 (6)	146
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) ; (vi) $[x, -y-1, z-{\script{1\over 2}}]$ ; (vii) ; (viii) $[x, -y, z-{\script{1\over 2}}]$ .

Figure 1
The asymmetric unit of the title compound with the atom-numbering scheme and 50% probability ellipsoids. Intramolecular N—H⋯O hydrogen bonds are shown as dashed lines.

3. Supramolecular features

In the crystal, C—H⋯O hydrogen bonds (Table 2) link the molecules, enclosing S(6), S(9) and R₄⁴(18) ring motifs (Etter et al., 1990 ) (Fig. 2). In addition, π–π interactions between (N2/C15/C16/C21/C22/C27) and (C22–C27) rings with centroid–to–centroid distances of 3.808 (2) Å [where α = 0.8 (2)° and slippage = 1.592 Å] and a series of the C—H⋯π(ring) interactions (Table 2) help to consolidate the packing in a three-dimensional architecture within the crystal.

Figure 2
The partial packing diagram of the title compound. Intramolecular N—H⋯O and intermolecular C—H⋯O hydrogen bonds are shown as dashed lines. H atoms not involved in these interactions been omitted for clarity.

4. Hirshfeld surface analysis

To visualize the intermolecular interactions in the title compound, a Hirshfeld surface (HS) analysis was carried out using Crystal Explorer 17.5 (Spackman et al., 2021 ). In the HS plotted over d_norm (Fig. 3), the contact distances equal, shorter and longer than the sum of van der Waals radii are shown by the white, red and blue colours, respectively. According to the two-dimensional fingerprint plots, H⋯H, H⋯C/C⋯H, H⋯O/O⋯H and C⋯C contacts make the most important contributions to the HS (Fig. 4).

Figure 3
View of the three-dimensional Hirshfeld surface plotted over d_norm.

Figure 4
The full two-dimensional fingerprint plots, showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯C/C⋯H, (d) H⋯O/O⋯H, (e) C⋯C, (f) H⋯N/N⋯H, (g) C⋯N/N⋯C, (h) O⋯O, (i) O⋯Cu/Cu⋯O and (j) 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.

5. Synthesis and crystallization

832 mg (4.0 mmol) of 8-methylphenanthridin-6(5H)-one were dissolved in 100 mL of ethanol and 233 mg (1.0 mmol) of Cu(NO₃)₂·2.5H₂O were added with stirring. The mixture was stirred for 5 min and left standing for slow solvent evaporation. Brown crystals started to form in the reaction mixture after 2 d at room temperature. After 3 d they were filtered off and dried in air. Yield: 55% (based on Cu). Analysis calculated for C₅₆H₄₄CuN₆O₁₀ (M = 1024.55): C, 65.65; H, 4.33; N, 8.20. Found: C 65.62; H, 4.30; N, 8.17%. IR, cm⁻¹: 3212 ν(N—H) and 1648 ν(C=O).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The N- and C-bound H-atom positions were calculated geometrically at distances of 0.90 (for NH), 0.93 (for aromatic CH) and 0.96 Å (for CH₃) and refined using a riding model by applying the constraint of U_iso(H) = k × U_eq(C,N), where k = 1.5 for methyl H atoms and k = 1.2 for the other H atoms.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu(NO₃)₂(C₁₄H₁₁NO)₄]
M_r	1024.51
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	22.279 (2), 11.9230 (11), 18.1267 (16)
β (°)	102.444 (4)
V (Å³)	4701.9 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.54
Crystal size (mm)	0.26 × 0.21 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.861, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	31022, 4623, 2755
R_int	0.087
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.184, 1.02
No. of reflections	4623
No. of parameters	333
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.28
Computer programs: APEX4 and SAINT (Bruker, 2016 ), SHELXT2019/1 (Sheldrick, 2015a ), SHELXL2019/1 (Sheldrick, 2015b ), ORTEP-3 for Windows and WinGX publication routines (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2501014

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989025009892/ee2022sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025009892/ee2022Isup2.hkl

checkCIF report

Computing details top

Tetrakis[8-methylphenanthridin-6(5H)-one-κO]bis(nitrato-κO)copper(II) top

Crystal data top

[Cu(NO₃)₂(C₁₄H₁₁NO)₄]	F(000) = 2124
M_r = 1024.51	D_x = 1.447 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.279 (2) Å	Cell parameters from 3386 reflections
b = 11.9230 (11) Å	θ = 3.2–20.3°
c = 18.1267 (16) Å	µ = 0.54 mm⁻¹
β = 102.444 (4)°	T = 296 K
V = 4701.9 (8) Å³	Prism, brown
Z = 4	0.26 × 0.21 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	2755 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.087
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 26.0°, θ_min = 3.2°
T_min = 0.861, T_max = 0.934	h = −27→27
31022 measured reflections	k = −14→14
4623 independent reflections	l = −22→22

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)] = 0.060	Hydrogen site location: mixed
wR(F²) = 0.184	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0967P)² + 2.2853P] where P = (F_o² + 2F_c²)/3
4623 reflections	(Δ/σ)_max < 0.001
333 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.28 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
Cu1	0.250000	0.250000	0.500000	0.0399 (2)
O1	0.23229 (12)	0.2038 (2)	0.39416 (14)	0.0487 (7)
O2	0.23037 (12)	0.4036 (2)	0.46793 (15)	0.0490 (7)
O3	0.42140 (18)	0.2859 (4)	0.6104 (2)	0.0918 (12)
O4	0.41796 (16)	0.1304 (3)	0.5488 (2)	0.0909 (12)
O5	0.36260 (13)	0.2693 (2)	0.49965 (16)	0.0557 (8)
N1	0.31896 (15)	0.1148 (3)	0.38002 (19)	0.0510 (9)
H1N	0.339116	0.157220	0.418564	0.061*
N2	0.32132 (17)	0.4913 (3)	0.5025 (2)	0.0593 (10)
H2N	0.335582	0.427329	0.526291	0.071*
N3	0.40159 (17)	0.2283 (3)	0.5554 (2)	0.0583 (10)
C1	0.25888 (18)	0.1347 (3)	0.3591 (2)	0.0440 (9)
C2	0.35192 (18)	0.0411 (3)	0.3432 (2)	0.0470 (10)
C3	0.4148 (2)	0.0288 (4)	0.3704 (3)	0.0627 (12)
H3A	0.434875	0.069264	0.412391	0.075*
C4	0.4475 (2)	−0.0448 (4)	0.3342 (3)	0.0687 (13)
H4A	0.489718	−0.052775	0.351440	0.082*
C5	0.4174 (2)	−0.1058 (4)	0.2727 (3)	0.0694 (13)
H5A	0.439192	−0.155812	0.249106	0.083*
C6	0.3553 (2)	−0.0929 (4)	0.2464 (3)	0.0593 (12)
H6A	0.335682	−0.134016	0.204511	0.071*
C7	0.32065 (18)	−0.0194 (3)	0.2808 (2)	0.0475 (10)
C8	0.25515 (18)	−0.0035 (3)	0.2560 (2)	0.0437 (9)
C9	0.2184 (2)	−0.0650 (4)	0.1974 (2)	0.0587 (12)
H9A	0.236506	−0.119799	0.172896	0.070*
C10	0.1568 (2)	−0.0466 (4)	0.1753 (2)	0.0590 (11)
H10A	0.134131	−0.087837	0.135259	0.071*
C11	0.1266 (2)	0.0326 (4)	0.2113 (2)	0.0556 (11)
C12	0.16139 (19)	0.0903 (3)	0.2707 (2)	0.0499 (10)
H12A	0.142317	0.141936	0.296581	0.060*
C13	0.22473 (18)	0.0737 (3)	0.2935 (2)	0.0443 (9)
C14	0.0588 (2)	0.0528 (5)	0.1853 (3)	0.0811 (15)
H14A	0.044342	0.095921	0.222726	0.122*
H14B	0.037661	−0.017822	0.178320	0.122*
H14C	0.051105	0.093187	0.138434	0.122*
C15	0.2617 (2)	0.4901 (3)	0.4683 (2)	0.0508 (10)
C16	0.3621 (2)	0.5793 (4)	0.4979 (2)	0.0570 (11)
C17	0.4239 (2)	0.5659 (4)	0.5316 (3)	0.0736 (14)
H17A	0.437657	0.500156	0.557358	0.088*
C18	0.4649 (3)	0.6521 (5)	0.5264 (3)	0.0861 (16)
H18A	0.506435	0.644243	0.548237	0.103*
C19	0.4429 (3)	0.7502 (5)	0.4883 (3)	0.0865 (16)
H19A	0.469955	0.808523	0.484932	0.104*
C20	0.3808 (3)	0.7613 (4)	0.4551 (3)	0.0711 (14)
H20A	0.367097	0.827183	0.429407	0.085*
C21	0.3388 (2)	0.6769 (4)	0.4592 (2)	0.0592 (11)
C22	0.2743 (2)	0.6844 (3)	0.4257 (2)	0.0551 (11)
C23	0.2475 (3)	0.7787 (4)	0.3877 (3)	0.0724 (14)
H23A	0.271265	0.842018	0.384730	0.087*
C24	0.1844 (3)	0.7790 (4)	0.3534 (3)	0.0712 (14)
H24A	0.167386	0.842725	0.327463	0.085*
C25	0.1475 (2)	0.6888 (4)	0.3572 (3)	0.0652 (13)
C26	0.1735 (2)	0.5943 (4)	0.3975 (2)	0.0576 (11)
H26A	0.148801	0.532905	0.401998	0.069*
C27	0.2356 (2)	0.5913 (3)	0.4307 (2)	0.0525 (10)
C28	0.0813 (2)	0.6927 (5)	0.3189 (3)	0.0905 (17)
H28A	0.068979	0.769309	0.308519	0.136*
H28B	0.057088	0.659934	0.351196	0.136*
H28C	0.075071	0.651528	0.272393	0.136*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0504 (4)	0.0317 (3)	0.0358 (4)	−0.0007 (3)	0.0054 (3)	0.0007 (3)
O1	0.0540 (17)	0.0476 (14)	0.0409 (15)	0.0093 (14)	0.0027 (13)	−0.0027 (13)
O2	0.0569 (17)	0.0347 (14)	0.0542 (16)	−0.0018 (13)	0.0092 (14)	0.0065 (12)
O3	0.081 (3)	0.127 (3)	0.060 (2)	−0.011 (2)	−0.0015 (19)	−0.025 (2)
O4	0.068 (2)	0.073 (2)	0.122 (3)	0.0179 (19)	−0.002 (2)	0.013 (2)
O5	0.0504 (18)	0.0598 (18)	0.0530 (17)	0.0034 (14)	0.0028 (14)	0.0067 (13)
N1	0.048 (2)	0.053 (2)	0.049 (2)	−0.0009 (16)	0.0032 (17)	−0.0049 (16)
N2	0.064 (3)	0.0394 (19)	0.070 (2)	−0.0005 (17)	0.004 (2)	0.0080 (17)
N3	0.043 (2)	0.070 (3)	0.061 (2)	−0.0010 (19)	0.0082 (19)	0.0013 (19)
C1	0.050 (3)	0.039 (2)	0.041 (2)	0.0074 (18)	0.0065 (19)	0.0061 (17)
C2	0.046 (2)	0.048 (2)	0.048 (2)	0.0030 (19)	0.012 (2)	0.0027 (18)
C3	0.056 (3)	0.066 (3)	0.064 (3)	0.000 (2)	0.007 (2)	0.001 (2)
C4	0.051 (3)	0.072 (3)	0.085 (4)	0.009 (2)	0.018 (3)	0.008 (3)
C5	0.067 (3)	0.065 (3)	0.081 (3)	0.006 (3)	0.027 (3)	−0.004 (3)
C6	0.061 (3)	0.055 (3)	0.065 (3)	0.004 (2)	0.020 (2)	−0.009 (2)
C7	0.049 (3)	0.049 (2)	0.046 (2)	0.0028 (19)	0.012 (2)	0.0031 (18)
C8	0.052 (2)	0.040 (2)	0.040 (2)	−0.0011 (18)	0.0122 (18)	−0.0007 (16)
C9	0.069 (3)	0.064 (3)	0.044 (2)	−0.001 (2)	0.014 (2)	−0.009 (2)
C10	0.062 (3)	0.067 (3)	0.045 (2)	−0.011 (2)	0.005 (2)	−0.011 (2)
C11	0.053 (3)	0.067 (3)	0.044 (2)	−0.002 (2)	0.003 (2)	0.001 (2)
C12	0.056 (3)	0.053 (2)	0.042 (2)	0.001 (2)	0.014 (2)	−0.0004 (18)
C13	0.047 (2)	0.046 (2)	0.038 (2)	0.0000 (18)	0.0057 (18)	0.0031 (17)
C14	0.055 (3)	0.109 (4)	0.073 (3)	0.002 (3)	0.001 (3)	−0.010 (3)
C15	0.060 (3)	0.045 (2)	0.047 (2)	−0.001 (2)	0.009 (2)	0.0006 (19)
C16	0.067 (3)	0.052 (3)	0.052 (3)	−0.005 (2)	0.013 (2)	0.002 (2)
C17	0.067 (3)	0.069 (3)	0.079 (4)	−0.009 (3)	0.002 (3)	0.008 (3)
C18	0.074 (4)	0.088 (4)	0.091 (4)	−0.011 (3)	0.006 (3)	−0.002 (3)
C19	0.084 (4)	0.080 (4)	0.093 (4)	−0.013 (3)	0.013 (3)	0.010 (3)
C20	0.077 (4)	0.062 (3)	0.077 (3)	−0.004 (3)	0.023 (3)	0.021 (2)
C21	0.068 (3)	0.058 (3)	0.051 (2)	−0.002 (2)	0.011 (2)	−0.001 (2)
C22	0.067 (3)	0.048 (3)	0.051 (2)	0.005 (2)	0.012 (2)	0.0020 (19)
C23	0.080 (4)	0.064 (3)	0.077 (3)	0.004 (3)	0.025 (3)	0.025 (3)
C24	0.076 (4)	0.062 (3)	0.077 (3)	0.021 (3)	0.020 (3)	0.029 (3)
C25	0.077 (3)	0.062 (3)	0.054 (3)	0.012 (3)	0.008 (2)	−0.004 (2)
C26	0.064 (3)	0.049 (2)	0.059 (3)	0.003 (2)	0.012 (2)	−0.001 (2)
C27	0.062 (3)	0.049 (2)	0.045 (2)	0.003 (2)	0.010 (2)	0.0021 (19)
C28	0.074 (4)	0.101 (4)	0.087 (4)	0.029 (3)	−0.004 (3)	−0.003 (3)

Geometric parameters (Å, º) top

Cu1—O2ⁱ	1.942 (2)	C10—H10A	0.9300
Cu1—O2	1.942 (2)	C11—C12	1.369 (6)
Cu1—O1	1.953 (2)	C11—C14	1.502 (6)
Cu1—O5	2.520 (3)	C12—C13	1.396 (5)
Cu1—O1ⁱ	1.953 (2)	C12—H12A	0.9300
O1—C1	1.264 (4)	C14—H14A	0.9600
O2—C15	1.245 (5)	C14—H14B	0.9600
O3—N3	1.212 (5)	C14—H14C	0.9600
O4—N3	1.237 (5)	C15—C27	1.446 (6)
O5—N3	1.279 (5)	C16—C17	1.390 (6)
N1—C1	1.331 (5)	C16—C21	1.400 (6)
N1—C2	1.403 (5)	C17—C18	1.391 (7)
N1—H1N	0.9000	C17—H17A	0.9300
N2—C15	1.339 (5)	C18—C19	1.393 (7)
N2—C16	1.401 (5)	C18—H18A	0.9300
N2—H2N	0.9001	C19—C20	1.392 (8)
C1—C13	1.460 (5)	C19—H19A	0.9300
C2—C3	1.389 (6)	C20—C21	1.388 (6)
C2—C7	1.394 (6)	C20—H20A	0.9300
C3—C4	1.392 (6)	C21—C22	1.437 (6)
C3—H3A	0.9300	C22—C23	1.385 (6)
C4—C5	1.377 (7)	C22—C27	1.420 (6)
C4—H4A	0.9300	C23—C24	1.409 (7)
C5—C6	1.371 (6)	C23—H23A	0.9300
C5—H5A	0.9300	C24—C25	1.364 (7)
C6—C7	1.401 (6)	C24—H24A	0.9300
C6—H6A	0.9300	C25—C26	1.398 (6)
C7—C8	1.444 (5)	C25—C28	1.490 (7)
C8—C9	1.401 (5)	C26—C27	1.385 (6)
C8—C13	1.403 (5)	C26—H26A	0.9300
C9—C10	1.362 (6)	C28—H28A	0.9600
C9—H9A	0.9300	C28—H28B	0.9600
C10—C11	1.399 (6)	C28—H28C	0.9600

O5···N2	2.806 (4)	C9···C15ⁱⁱ	3.197 (5)
O5···N1	2.852 (4)	C9···C27ⁱⁱ	3.308 (6)
H9A···O1ⁱⁱ	2.60	C6···H9A	2.71
O1···H12A	2.48	C7···H23A^iv	2.90
O2···H26A	2.48	C9···H6A	2.72
O3···H12Aⁱ	2.58	C20···H23A	2.68
O4···H3A	2.68	C23···H20A	2.67
O4···H1N	2.64	H1N···H3A	2.40
O4···H26Aⁱ	2.72	H2N···H17A	2.39
O4···H4Aⁱⁱⁱ	2.60	H6A···H9A	2.17
O5···H1N	1.97	H12A···H14A	2.37
O5···H2N	2.07	H14A···H14A^v	2.39
N3···H1N	2.71	H20A···H23A	2.12
C6···C26ⁱⁱ	3.388 (7)	H24A···H28A	2.32

O2ⁱ—Cu1—O2	180.0	C12—C13—C8	120.8 (4)
O2ⁱ—Cu1—O1	90.74 (11)	C12—C13—C1	119.1 (4)
O2—Cu1—O1	89.26 (11)	C8—C13—C1	120.0 (4)
O2ⁱ—Cu1—O1ⁱ	89.26 (11)	C11—C14—H14A	109.5
O2—Cu1—O1ⁱ	90.74 (11)	C11—C14—H14B	109.5
O1—Cu1—O1ⁱ	180.00 (5)	H14A—C14—H14B	109.5
O1—Cu1—O5	90.79 (11)	C11—C14—H14C	109.5
O2—Cu1—O5	94.21 (11)	H14A—C14—H14C	109.5
C1—O1—Cu1	131.4 (2)	H14B—C14—H14C	109.5
C15—O2—Cu1	133.6 (3)	O2—C15—N2	120.7 (4)
C1—N1—C2	124.9 (4)	O2—C15—C27	121.4 (4)
C1—N1—H1N	115.1	N2—C15—C27	117.9 (4)
C2—N1—H1N	119.8	C17—C16—C21	122.8 (4)
C15—N2—C16	124.8 (4)	C17—C16—N2	118.7 (4)
C15—N2—H2N	115.1	C21—C16—N2	118.5 (4)
C16—N2—H2N	119.8	C16—C17—C18	119.2 (5)
O3—N3—O4	123.5 (4)	C16—C17—H17A	120.4
O3—N3—O5	119.9 (4)	C18—C17—H17A	120.4
O4—N3—O5	116.6 (4)	C17—C18—C19	119.3 (6)
O1—C1—N1	121.6 (4)	C17—C18—H18A	120.4
O1—C1—C13	121.1 (4)	C19—C18—H18A	120.4
N1—C1—C13	117.3 (3)	C20—C19—C18	120.3 (5)
C3—C2—C7	121.5 (4)	C20—C19—H19A	119.9
C3—C2—N1	119.2 (4)	C18—C19—H19A	119.9
C7—C2—N1	119.2 (4)	C21—C20—C19	121.9 (5)
C2—C3—C4	119.3 (4)	C21—C20—H20A	119.1
C2—C3—H3A	120.4	C19—C20—H20A	119.1
C4—C3—H3A	120.4	C20—C21—C16	116.6 (5)
C5—C4—C3	120.1 (5)	C20—C21—C22	123.9 (4)
C5—C4—H4A	120.0	C16—C21—C22	119.5 (4)
C3—C4—H4A	120.0	C23—C22—C27	117.6 (4)
C6—C5—C4	120.1 (4)	C23—C22—C21	123.0 (4)
C6—C5—H5A	120.0	C27—C22—C21	119.4 (4)
C4—C5—H5A	120.0	C22—C23—C24	120.2 (5)
C5—C6—C7	121.8 (4)	C22—C23—H23A	119.9
C5—C6—H6A	119.1	C24—C23—H23A	119.9
C7—C6—H6A	119.1	C25—C24—C23	122.0 (4)
C2—C7—C6	117.2 (4)	C25—C24—H24A	119.0
C2—C7—C8	118.7 (4)	C23—C24—H24A	119.0
C6—C7—C8	124.1 (4)	C24—C25—C26	118.4 (5)
C9—C8—C13	116.5 (4)	C24—C25—C28	119.9 (5)
C9—C8—C7	123.7 (4)	C26—C25—C28	121.7 (5)
C13—C8—C7	119.8 (4)	C27—C26—C25	120.7 (4)
C10—C9—C8	121.8 (4)	C27—C26—H26A	119.7
C10—C9—H9A	119.1	C25—C26—H26A	119.7
C8—C9—H9A	119.1	C26—C27—C22	121.0 (4)
C9—C10—C11	121.7 (4)	C26—C27—C15	119.3 (4)
C9—C10—H10A	119.1	C22—C27—C15	119.6 (4)
C11—C10—H10A	119.1	C25—C28—H28A	109.5
C12—C11—C10	117.4 (4)	C25—C28—H28B	109.5
C12—C11—C14	121.7 (4)	H28A—C28—H28B	109.5
C10—C11—C14	120.9 (4)	C25—C28—H28C	109.5
C11—C12—C13	121.7 (4)	H28A—C28—H28C	109.5
C11—C12—H12A	119.1	H28B—C28—H28C	109.5
C13—C12—H12A	119.1

Cu1—O1—C1—N1	−29.9 (5)	Cu1—O2—C15—N2	−7.3 (6)
Cu1—O1—C1—C13	150.4 (3)	Cu1—O2—C15—C27	171.2 (3)
C2—N1—C1—O1	−178.8 (3)	C16—N2—C15—O2	171.4 (4)
C2—N1—C1—C13	0.9 (5)	C16—N2—C15—C27	−7.1 (6)
C1—N1—C2—C3	179.3 (4)	C15—N2—C16—C17	−175.2 (4)
C1—N1—C2—C7	−1.6 (6)	C15—N2—C16—C21	4.6 (6)
C7—C2—C3—C4	0.6 (6)	C21—C16—C17—C18	−0.7 (8)
N1—C2—C3—C4	179.7 (4)	N2—C16—C17—C18	179.1 (5)
C2—C3—C4—C5	−1.0 (7)	C16—C17—C18—C19	0.7 (8)
C3—C4—C5—C6	1.1 (7)	C17—C18—C19—C20	−0.6 (9)
C4—C5—C6—C7	−0.7 (7)	C18—C19—C20—C21	0.6 (9)
C3—C2—C7—C6	−0.2 (6)	C19—C20—C21—C16	−0.6 (7)
N1—C2—C7—C6	−179.3 (3)	C19—C20—C21—C22	−179.8 (5)
C3—C2—C7—C8	179.3 (4)	C17—C16—C21—C20	0.7 (7)
N1—C2—C7—C8	0.2 (5)	N2—C16—C21—C20	−179.1 (4)
C5—C6—C7—C2	0.3 (6)	C17—C16—C21—C22	179.9 (4)
C5—C6—C7—C8	−179.2 (4)	N2—C16—C21—C22	0.1 (6)
C2—C7—C8—C9	−175.5 (4)	C20—C21—C22—C23	−1.9 (7)
C6—C7—C8—C9	4.0 (6)	C16—C21—C22—C23	178.9 (4)
C2—C7—C8—C13	1.6 (5)	C20—C21—C22—C27	177.5 (4)
C6—C7—C8—C13	−178.9 (4)	C16—C21—C22—C27	−1.7 (6)
C13—C8—C9—C10	3.4 (6)	C27—C22—C23—C24	−2.0 (7)
C7—C8—C9—C10	−179.4 (4)	C21—C22—C23—C24	177.4 (5)
C8—C9—C10—C11	−1.7 (7)	C22—C23—C24—C25	1.0 (8)
C9—C10—C11—C12	−1.0 (6)	C23—C24—C25—C26	1.1 (8)
C9—C10—C11—C14	179.1 (5)	C23—C24—C25—C28	−179.0 (5)
C10—C11—C12—C13	1.9 (6)	C24—C25—C26—C27	−2.0 (7)
C14—C11—C12—C13	−178.3 (4)	C28—C25—C26—C27	178.1 (4)
C11—C12—C13—C8	−0.1 (6)	C25—C26—C27—C22	0.9 (6)
C11—C12—C13—C1	−177.7 (4)	C25—C26—C27—C15	−176.6 (4)
C9—C8—C13—C12	−2.5 (5)	C23—C22—C27—C26	1.1 (6)
C7—C8—C13—C12	−179.8 (4)	C21—C22—C27—C26	−178.4 (4)
C9—C8—C13—C1	175.1 (4)	C23—C22—C27—C15	178.6 (4)
C7—C8—C13—C1	−2.2 (5)	C21—C22—C27—C15	−0.9 (6)
O1—C1—C13—C12	−1.7 (5)	O2—C15—C27—C26	4.1 (6)
N1—C1—C13—C12	178.6 (3)	N2—C15—C27—C26	−177.4 (4)
O1—C1—C13—C8	−179.3 (3)	O2—C15—C27—C22	−173.5 (4)
N1—C1—C13—C8	1.0 (5)	N2—C15—C27—C22	5.1 (6)

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

Hydrogen-bond geometry (Å, º) top

Cg1, Cg3, Cg4 and Cg5 are the centroids of the (N1/C1/C2/C7/C8/C13), (C2–C7), (C8–C13) and (C16–C21) rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O5	0.90	1.97	2.852 (4)	165
N2—H2N···O5	0.90	2.07	2.806 (4)	139
C4—H4A···O4ⁱⁱⁱ	0.93	2.60	3.433 (6)	150
C9—H9A···O1ⁱⁱ	0.93	2.60	3.514 (5)	169
C12—H12A···O3ⁱ	0.93	2.57	3.455 (6)	158
C14—H14C···Cg5^vi	0.96	2.92	3.768 (6)	147
C20—H20A···Cg3^vii	0.93	2.86	3.644 (5)	143
C23—H23A···Cg1^vii	0.93	2.89	3.726 (5)	151
C24—H24A···Cg4^vii	0.93	2.77	3.557 (5)	143
C28—H28C···Cg3^viii	0.96	2.88	3.716 (6)	146

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

Acknowledgements

The authors' contributions are as follows. Conceptualization, AVG, TH and MMW; synthesis and X-ray analysis AVG; Hirshfeld surface analysis, TH; funding acquisition, AVG; writing (review and editing of the manuscript), AVG and TH; supervision, TH.

Funding information

This work has been supported by the Baku State University. TH is also grateful to Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004).

References

Aliyeva, V. A., Gurbanov, A. V., Huseynov, F. E., Hajiyeva, S. R., Conceição, N. R., Nunes, A. V. M., Pombeiro, A. J. L. & Mahmudov, K. T. (2024). Polyhedron 255, 116955. Web of Science CrossRef Google Scholar
Allen, S. E., Walvoord, R. R., Padilla-Salinas, R. & Kozlowski, M. C. (2013). Chem. Rev. 113, 6234–6458. Web of Science CrossRef CAS PubMed Google Scholar
Bruker (2016). APEX4 and SAINT. Bruker AXS, Madison, Wisconsin, USA. Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef ICSD CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gadzhieva, S. R., Guseinov, F. E. & Chyragov, F. M. (2005). J. Anal. Chem. 60, 819–821. Web of Science CrossRef CAS Google Scholar
Gurbanov, A. V., Gomila, R. M., Frontera, A., Shikhaliyev, N. Q., Zeynalli, N. R., Mahmudov, K. T. & Pombeiro, A. J. L. (2023). Cryst. Growth Des. 23, 7647–7652. Web of Science CSD CrossRef CAS Google Scholar
Gurbanov, A. V., Huseynov, F. E., Mahmoudi, G., Maharramov, A. M., Guedes da Silva, F. C., Mahmudov, K. T. & Pombeiro, A. J. L. (2018). Inorg. Chim. Acta 469, 197–201. Web of Science CSD CrossRef CAS Google Scholar
Gurbanov, A. V., Kuznetsov, M. L., Resnati, G., Mahmudov, K. T. & Pombeiro, A. J. L. (2022). Cryst. Growth Des. 22, 3932–3940. Web of Science CSD CrossRef CAS Google Scholar
Huseynov, F. E., Shamilov, N. T., Mahmudov, K. T., Maharramov, A. M., Guedes da Silva, M. F. C. & Pombeiro, A. J. L. (2018). J. Organomet. Chem. 867, 102–105. Web of Science 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
Kretschmer, R. (2020). Chem. A Eur. J. 26, 2099–2119. Web of Science CrossRef CAS Google Scholar
Maharramov, A. M., Gadzhieva, S. R., Bahmanova, F. N., Gamidov, S. Z. & Chyragov, F. M. (2011). J. Anal. Chem. 66, 480–483. Google Scholar
Mahmudov, K. T., Huseynov, F. E., Aliyeva, V. A., Guedes da Silva, M. F. C. & Pombeiro, A. J. L. (2021). Chem. A Eur. J. 27, 14370–14389. Web of Science CrossRef CAS Google Scholar
Mahmudov, K. T. & Pombeiro, A. J. L. (2023). Chem. Eur. J. 29, e202203861. Web of Science CrossRef PubMed Google Scholar
Peris, E. (2018). Chem. Rev. 118, 9988–10031. Web of Science CrossRef CAS PubMed 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, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.