Crystal structure of bis­{3-(benzo[d][1,3]dioxol-5-yl)-5-[6-(1H-pyrazol-1-yl)pyridin-2-yl]-4H-1,2,4-triazol-4-ido}nickel(II) methanol disolvate

Znovjyak, K.; Shova, S.; Nikolian, V.; Khairulin, A.; Fritsky, I.O.; Malinkin, S.O.; Seredyuk, M.

doi:10.1107/S2056989025006851

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ISSN: 2056-9890

Volume 81| Part 9| September 2025| Pages 821-826

https://doi.org/10.1107/S2056989025006851

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Crystal structure of bis{3-(benzo[d][1,3]dioxol-5-yl)-5-[6-(1H-pyrazol-1-yl)pyridin-2-yl]-4H-1,2,4-triazol-4-ido}nickel(II) methanol disolvate

Kateryna Znovjyak,^a ^* Sergiu Shova,^b Vazghen Nikolian,^c Andrii Khairulin,^d Igor O. Fritsky,^a Sergey O. Malinkin ^a and Maksym Seredyuk ^a

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska Street 64, Kyiv, 01601, Ukraine, ^bDepartment of Inorganic Polymers, "Petru Poni" Institute of Macromolecular, Chemistry, Romanian Academy of Science, Aleea Grigore Ghica Voda 41-A, Iasi, 700487, Romania, ^cWimbleAI Inc., 548 Market Street, Unit 55559, San Francisco, California, USA, and ^dChemBioCenter, Kyiv National Taras Shevchenko University, Kyiv 02094, 61 Winston Churchill Street, Ukraine
^*Correspondence e-mail: [email protected]

Edited by C. Schulzke, Universität Greifswald, Germany (Received 21 July 2025; accepted 30 July 2025; online 12 August 2025)

The unit cell of the title compound, [Ni(C₁₇H₁₁N₆O₂)₂]·2CH₃OH, consists of a neutral complex and two methanol molecules. In the complex, the two tridentate 2-[3-(benzo[d][1,3]dioxol-5-yl)-1H-1,2,4-triazol-5-yl]-6-(1H-pyrazol-1-yl)pyridine ligands coordinate to the central Ni^II ion through nitrogen atoms of the pyrazole, pyridine and triazole groups, forming a pseudooctahedral coordination sphere. Neighbouring molecules are linked through weak C—H(pz)⋯π(ph) interactions into monoperiodic chains, which are further linked through weak C–H⋯H/N/C interactions into diperiodic layers. The intermolecular contacts were quantified using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing the relative contributions of the contacts to the crystal packing to be H⋯H 38.4%, C⋯H/H⋯C 25.3%, N⋯H/H⋯N 14.1%, and O⋯H/H⋯O 11.8%. The average Ni—N bond distance is 2.085 Å. Energy framework analysis at the HF/3–21 G theory level was performed to quantify the interaction energies in the crystal structure.

Keywords: crystal structure; nickel(II) complexes; neutral complexes; tridentate ligands.

CCDC reference: 2477384

1. Chemical context

A broad class of coordination compounds is represented by 3d-metal complexes based on tridentate bisazolepyridine ligands (Halcrow et al., 2019 ; Suryadevara et al., 2022 ), which find application in many fields, for example in catalysis (Xing et al., 2014 ; Wei et al., 2015 ) and molecular magnetism (Suryadevara et al., 2022). In the case of asymmetric ligand design, where one of the azole groups carries a hydrogen on a nitrogen heteroatom and acts as a Brønsted acid, deprotonation can produce neutral complexes (Seredyuk et al., 2014 ; Grunwald et al., 2023 ). The periphery of the molecule, i.e. ligand substituents, also plays an important role, determining the way the molecules interact with each other, influencing the intermolecular connectivity, interaction energy and the organization of the structure.

Encouraged by our results in spin-transition complexes of 3d-metals formed by N-heterocyclic ligands (Seredyuk et al., 2006 , 2007a ,b , 2024a ; Piñeiro-López et al., 2018 ), we report here a new neutral Ni^II complex based on the asymmetric deprotonated ligand 2-[3-(benzo[d][1,3]dioxol-5-yl)-1H-1,2,4-triazol-5-yl)-6-(1H-pyrazol-1-yl]pyridine, which continues our lasting project on the study of 3d-metal complexes of bisazolepyridines and related organic polydentate ligands.

2. Structural commentary

The complex has a conical structure with the nickel(II) residing on twofold rotation axis and half of the formula in the asymmetric unit. The phenyl ring of the benzodioxole moiety of the ligand is rotated by 18.6 (1)° relative to the almost planar pyrazole-pyridine-triazole (pz-py-trz) fragment. The independent methanol molecule forms an O—H⋯N hydrogen bond with the trz ring of the ligand molecule (Fig. 1). The central Ni ion of the complex has a distorted octahedral N₆ coordination environment formed by the nitrogen donor atoms of the two tridentate ligands. The average Ni—N bond length is 2.085 Å. Distortion indices were calculated to assess how much the coordination polyhedron deviates from ideal octahedral geometry. The average trigonal distortion parameters Σ = Σ₁¹²(|90 − φ_i|), where φ_i refers to the twelve cis angles N—Ni—N′ (Drew et al., 1995 ), and Θ = Σ₁²⁴(|60 − θ_i|), where θ_i is the angle generated by superposition of two opposite faces of an octahedron (Chang et al., 1990 ) are 117.2 and 391.6°, respectively. The values reveal a deviation of the coordination environment from an ideal octahedron (where Σ = Θ = 0), which is, however, in the expected range for bisazolepyridine and similar ligands (see below). The calculated continuous shape measure [CShM(O_h)] value relative to the ideal octahedral symmetry is 3.599 (Kershaw Cook et al., 2015 ). The volume of the [NiN₆] coordination polyhedron is 11.431 Å³.

Figure 1
The molecular structure in the asymmetric unit of the title compound and contact atoms with displacement ellipsoids drawn at the 50% probability level. The strong O—H⋯N (red) and weak C–H⋯N/C/O (cyan) hydrogen bonds are shown with the nearest neighbours. Symmetry codes: (i) 1 − x, 1 + y, $[{3\over 2}]$ − z; (ii) − $[{1\over 2}]$ + x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z; (iii) $[{1\over 2}]$ + x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z; (iv) − $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, 1 − z.

3. Supramolecular features

Owing to the small head-group and large planar substituent at the tail, adjacent complex molecules are interlocked and interact via a weak, off-centre, almost perpendicular (83.6°) C—H(pz)⋯π(ph) intermolecular contact between the pyrazole (pz) and phenyl (ph) groups with distances H2/C2⋯C_g(ph) = 2.68/3.580 (4) Å. The formed monoperiodic supramolecular chains extend along the b-axis direction with the stacking periodicity equal to 10.4956 (4) Å (= cell parameter b) (Fig. 2). Through weak intermolecular C—H(pz, py)⋯N/C interactions in the range 3.270 (4)–3.732 (5) Å (Table 1), neighbouring chains are joined into corrugated diperiodic layers in the ab plane. The layers stack without strong interlayer interactions below the van der Waals radii; however, the solvent molecules occupying voids between the layers participate in the bonding between separate layers. The methanol molecule forms a strong O—H⋯N hydrogen bond with the deprotonated trz group and weak C—H⋯O hydrogen bonds with the CH₂ group of the benzodioxole moiety belonging to a molecule in a neighbouring chain. A list of the considered hydrogen-bonding intermolecular interactions is provided in Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O3ⁱ	0.95	2.35	3.282 (5)	165
C5—H5⋯O3ⁱ	0.95	2.57	3.505 (4)	167
C7—H7⋯C1ⁱⁱ	0.95	2.68	3.605 (5)	163
C1—H1⋯N6ⁱⁱⁱ	0.95	2.33	3.270 (4)	170
C17—H17A⋯C18^iv	0.99	2.78	3.479 (7)	129
C17—H17A⋯O3^iv	0.99	2.68	3.550 (6)	147
O3—H3A⋯N5	0.82 (4)	1.94 (4)	2.752 (4)	173 (4)
Symmetry codes: (i) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Figure 2
(a) A fragment of monoperiodic supramolecular column formed by stacking of molecules along the b axis; (b) supramolecular diperiodic layers formed by stacking of the supramolecular columns in the ab plane (for a better representation, each column has a different colour); (c) stacking of the diperiodic layers along the b-axis direction with the methanol molecules in the voids.

A Hirshfeld surface analysis was performed and the associated two-dimensional fingerprint plots were generated using CrystalExplorer 21.5 (Spackman et al., 2021 ), with a standard resolution of the three-dimensional d_norm surfaces (Fig. 3a). The pale-red spots symbolize short contacts and negative d_norm values on the surface corresponding to the interactions described above. The electrostatic potential energy calculated using the HF/3-21G basis set is mapped on the Hirshfeld surface (Fig. 3b). The negative charge localizes on the trz-ph moieties of the molecules, while the pz-py moieties are relatively positively charged. The two-dimensional fingerprint plots, with their relative contributions to the Hirshfeld surface mapped over d_norm, are shown for the H⋯H, C⋯H/H⋯C, N⋯H/H⋯N and O⋯H/H⋯O contacts in Fig. 4. At 38.4%, the largest contribution to the overall crystal packing is from H⋯H interactions, which are located in the middle region of the fingerprint plot. C⋯H/H⋯C contacts contribute 25.3%, and O⋯H/H⋯O 11.8%, resulting in pairs of characteristic wings. The N⋯H/H⋯N contacts, represented by a pair of sharp spikes in the fingerprint plot, make a 14.1% contribution to the surface.

Figure 3
(a) A projection of d_norm mapped on the Hirshfeld surface identifying contact points or areas for intermolecular interactions on the molecule. Red/blue and white areas represent regions where contacts are shorter/larger than the sum and close to the sum of the van der Waals radii, respectively. (b) Electrostatic potential for the title compound mapped on the Hirshfeld surface. Red/blue and white areas represent regions where the charge is negative/positive or close to zero.

Figure 4
(a) Decomposition of the two-dimensional fingerprint plot into specific interactions. (b) A projection of d_norm mapped on the Hirshfeld surfaces, showing the specific intermolecular interactions on the molecule.

The energy framework (Spackman et al., 2021), calculated using the wave function at the HF/3-21G theory level, including the electrostatic (E_ele), polarization (E_pol), dispersion (E_dis), repulsion (E_rep) forces, and the total energy diagrams (E_tot), is shown in Fig. 5. The cylindrical radii, adjusted to the same scale factor of 100, are proportional to the relative strength of the corresponding energies. The major contribution is due to dispersion forces (E_dis), reflecting dominating interactions in the crystal of the neutral molecules. The topology of the energy framework resembles the topology of the interactions within and between layers described above. The calculated value E_tot for the intrachain interaction is −50.5 kJ mol⁻¹, and for interchain interactions is down to −95.8 kJ mol⁻¹. The interlayer interactions are represented by an energy of −19.8 kJ mol⁻¹. The colour-coded interaction mappings within a radius of 3.8 Å of a central reference molecule together with full details of the various contributions to the total energy (E_ele, E_pol, E_dis, E_rep) are shown in the table in Fig. 5.

Figure 5
(a) The calculated energy frameworks, showing the total energy diagrams (E_tot), (b) decomposition of the energy framework into the part corresponding to the interactions within a supramolecular layer and (c) interlayer interactions. In the table, the corresponding colour-coded energy values E_tot are provided, including their E_ele, E_pol, E_dis, and E_rep components. Tube size is set at 100 scale.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, last update August 2024; Groom et al., 2016 ) reveals several similar neutral 3d M^II complexes with tridentate bisazolpyridine ligands with a deprotonable azole groups, for example, of Ni^II: YOCFAZ (Yuan et al., 2014 ), ZOCKOT (Xing et al., 2014), and ZOTVIP (Wei et al., 2015); of Fe^II: EGIDIL (Seredyuk et al., 2024b ), LUTGEO (Senthil Kumar et al., 2015 ), and XODCEB (Shiga et al., 2019 ). In addition, there are related complexes based on phenanthroline-benzimidazole (DOMQUT; Seredyuk et al., 2014), dipyridylpyrrol (NIRLOT; Grunwald et al., 2023). The values of the trigonal distortion and CShM(O_h) change in correspondence to the length of M—N distances, and for shorter distances they are systematically lower than for the longer distances. Table 2 collates some key structural parameters of the complexes and of the title compound.

Table 2
Computed distortion indices for the title compound and for similar complexes reported in the literature

CSD Refcode	Metal ion<	<M—N> (Å)	Σ (°)	Θ (°)	CShM(O_h)
Title compound	Ni	2.085	117.2	391.6	3.60
YOCFAZ	Ni	2.088^a	120.8^a	397.6^a	3.65^a
ZOCKOT	Ni	2.086	121.0	375.9	3.78
ZOTVIP	Ni	2.110	124.9	382.4	3.55
EGIDIL	Fe	1.955	89.8	314.6	2.25
EGIDIL02	Fe	2.167	146.8	492.8	5.28
LUTGEO	Fe	1.933	85.0	309.6	2.10
XODCEB	Fe	1.950	87.4	276.6	1.93
DOMQUT	Fe	1.991	88.5	320.0	2.48
DOMQUT02	Fe	2.183	139.6	486.9	5.31
NIRLOT	Fe	1.939	77.3	255.6	1.68
Note: (a) average value.

5. Synthesis and crystallization

The synthesis of the title compound is identical to that reported for a similar complex (Seredyuk et al., 2022 ). It was produced by using a layering technique in a standard test tube. The layering sequence was as follows: the bottom layer contained a solution of [Ni(L₂)](ClO₄)₂ prepared by dissolving L = 2-[3-(benzo[d][1,3]dioxol-5-yl)-1H-1,2,4-triazol-5-yl]-6-(1H-pyrazol-1-yl)pyridine (88 mg, 0.274 mmol) and Ni(ClO₄)₂·6H₂O (50 mg, 0.137 mmol) in boiling acetone (5 ml), to which chloroform (5 ml) was then added. The middle layer was a methanol–chloroform mixture (1:10) (10 ml), which was covered by a layer of methanol (10 ml) to which 100 µl of NEt₃ were added dropwise. The tube was sealed and violet plate-like single crystals appeared after 2 weeks (yield ca. 58%). Elemental analysis calculated for C₃₆H₃₀N₁₂NiO₆: C, 55.05; H, 3.85; N, 21.40. Found: C, 55.66; H, 3.48; N, 21.61.

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. The O-bound H atom was refined with U_iso(H) = 1.5U_eq(O); the hydrogen atom H3A was refined freely. All other H atoms were refined as riding [C—H = 0.95–0.99 Å with U_iso(H) = 1.2–1.5U_eq(C)]. An attempt to model a potential disorder in the oxalan moiety was unsuccessful as it did not improve the refinement. One reflection (002), which was obscured by the beamstop, was omitted as clear outlier.

Table 3
Experimental details

Crystal data
Chemical formula	[Ni(C₁₇H₁₁N₆O₂)₂]·2CH₄O
M_r	785.42
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	200
a, b, c (Å)	12.7636 (4), 10.4956 (4), 26.5411 (12)
V (Å³)	3555.5 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.61
Crystal size (mm)	0.3 × 0.25 × 0.04

Data collection
Diffractometer	Xcalibur, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2024 )
T_min, T_max	0.982, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12665, 3146, 2236
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.098, 1.04
No. of reflections	3146
No. of parameters	254
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.35
Computer programs: CrysAlis PRO (Rigaku OD, 2024), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2477384

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025006851/yz2071sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025006851/yz2071Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025006851/yz2071Isup3.cdx

checkCIF report

Computing details top

Bis{3-(benzo[d][1,3]dioxol-5-yl)-5-[6-(1H-pyrazol-1-yl)pyridin-2-yl]-4H-1,2,4-triazol-4-ido}nickel(II) methanol disolvate top

Crystal data top

[Ni(C₁₇H₁₁N₆O₂)₂]·2CH₄O	D_x = 1.467 Mg m⁻³
M_r = 785.42	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 2720 reflections
a = 12.7636 (4) Å	θ = 2.2–25.8°
b = 10.4956 (4) Å	µ = 0.61 mm⁻¹
c = 26.5411 (12) Å	T = 200 K
V = 3555.5 (2) Å³	Plate, clear light violet
Z = 4	0.3 × 0.25 × 0.04 mm
F(000) = 1624

Data collection top

Xcalibur, Eos diffractometer	3146 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2236 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
Detector resolution: 16.1593 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
ω scans	h = −10→15
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2024)	k = −12→9
T_min = 0.982, T_max = 1.000	l = −19→31
12665 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0254P)² + 2.476P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3146 reflections	Δρ_max = 0.31 e Å⁻³
254 parameters	Δρ_min = −0.35 e Å⁻³
0 restraints

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
Ni1	0.500000	0.69588 (5)	0.750000	0.02073 (17)
N3	0.34364 (17)	0.7067 (2)	0.76431 (9)	0.0210 (6)
N6	0.29635 (19)	0.4568 (2)	0.67333 (11)	0.0294 (7)
O3	0.6459 (2)	0.5655 (3)	0.61469 (11)	0.0479 (8)
N4	0.43894 (17)	0.5611 (2)	0.70073 (10)	0.0235 (6)
N2	0.38524 (18)	0.8644 (2)	0.81994 (10)	0.0268 (7)
N1	0.48769 (18)	0.8386 (2)	0.80741 (10)	0.0246 (6)
N5	0.47127 (18)	0.4777 (2)	0.66463 (10)	0.0262 (7)
C4	0.3065 (2)	0.7917 (3)	0.79625 (12)	0.0251 (8)
C10	0.3842 (2)	0.4172 (3)	0.64927 (13)	0.0263 (8)
C7	0.1705 (2)	0.6386 (3)	0.74627 (15)	0.0388 (10)
H7	0.123624	0.584348	0.728607	0.047*
C9	0.3345 (2)	0.5459 (3)	0.70425 (13)	0.0245 (8)
O2	0.2148 (3)	0.0879 (3)	0.54493 (14)	0.0921 (12)
C6	0.1333 (2)	0.7279 (4)	0.77975 (15)	0.0431 (11)
H6	0.059945	0.735043	0.785111	0.052*
C5	0.2007 (2)	0.8075 (3)	0.80573 (13)	0.0363 (9)
H5	0.175702	0.869689	0.828819	0.044*
C12	0.2941 (3)	0.2482 (3)	0.60018 (15)	0.0412 (10)
H12	0.234731	0.254816	0.621630	0.049*
C11	0.3833 (2)	0.3232 (3)	0.60829 (13)	0.0290 (8)
C8	0.2776 (2)	0.6292 (3)	0.73882 (12)	0.0250 (8)
C3	0.3786 (3)	0.9550 (3)	0.85594 (14)	0.0380 (10)
H3	0.316294	0.988162	0.870435	0.046*
O1	0.3599 (3)	0.0627 (3)	0.49288 (12)	0.0741 (10)
C16	0.4691 (3)	0.3094 (3)	0.57656 (13)	0.0363 (9)
H16	0.529763	0.359884	0.582264	0.044*
C14	0.3798 (3)	0.1522 (4)	0.52947 (15)	0.0462 (10)
C15	0.4686 (3)	0.2229 (3)	0.53634 (15)	0.0452 (10)
H15	0.527454	0.213721	0.514753	0.054*
C2	0.4785 (3)	0.9895 (3)	0.86743 (15)	0.0406 (10)
H2	0.499792	1.051567	0.891392	0.049*
C13	0.2950 (3)	0.1662 (4)	0.56088 (16)	0.0485 (11)
C1	0.5433 (2)	0.9155 (3)	0.83694 (13)	0.0287 (8)
H1	0.617703	0.919390	0.837224	0.034*
C18	0.6032 (4)	0.6536 (4)	0.58103 (17)	0.0741 (15)
H18A	0.570036	0.608158	0.552967	0.111*
H18B	0.658810	0.708858	0.568045	0.111*
H18C	0.550579	0.705408	0.598456	0.111*
C17	0.2564 (4)	0.0181 (5)	0.5035 (2)	0.0920 (18)
H17A	0.211247	0.029769	0.473482	0.110*
H17B	0.258379	−0.073876	0.511717	0.110*
H3A	0.597 (3)	0.534 (4)	0.6305 (15)	0.048 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0147 (3)	0.0252 (3)	0.0223 (3)	0.000	0.0005 (3)	0.000
N3	0.0162 (13)	0.0235 (14)	0.0234 (17)	0.0020 (11)	0.0026 (11)	−0.0039 (14)
N6	0.0246 (15)	0.0327 (17)	0.0310 (18)	−0.0006 (12)	−0.0024 (13)	−0.0107 (15)
O3	0.0357 (16)	0.058 (2)	0.050 (2)	0.0056 (13)	0.0075 (14)	0.0173 (17)
N4	0.0220 (15)	0.0247 (15)	0.0237 (17)	0.0005 (11)	0.0009 (12)	−0.0042 (14)
N2	0.0208 (15)	0.0291 (16)	0.0305 (18)	0.0003 (11)	0.0014 (12)	−0.0093 (15)
N1	0.0169 (14)	0.0303 (15)	0.0265 (16)	−0.0007 (11)	0.0048 (12)	0.0012 (13)
N5	0.0231 (15)	0.0283 (15)	0.0271 (18)	0.0007 (11)	−0.0004 (12)	−0.0063 (15)
C4	0.0186 (17)	0.0298 (19)	0.027 (2)	0.0004 (14)	−0.0004 (14)	−0.0028 (18)
C10	0.0264 (18)	0.0256 (19)	0.027 (2)	0.0039 (14)	−0.0006 (15)	0.0003 (18)
C7	0.0173 (18)	0.049 (2)	0.051 (3)	−0.0011 (14)	0.0014 (17)	−0.020 (2)
C9	0.0190 (18)	0.0267 (19)	0.028 (2)	−0.0011 (13)	0.0006 (14)	−0.0016 (18)
O2	0.104 (3)	0.091 (3)	0.082 (3)	−0.043 (2)	−0.005 (2)	−0.047 (2)
C6	0.0161 (18)	0.058 (3)	0.056 (3)	0.0009 (16)	0.0055 (17)	−0.019 (2)
C5	0.0253 (19)	0.046 (2)	0.038 (2)	0.0009 (16)	0.0043 (16)	−0.019 (2)
C12	0.044 (2)	0.041 (2)	0.039 (3)	−0.0047 (17)	−0.0009 (18)	−0.013 (2)
C11	0.0362 (19)	0.0242 (19)	0.027 (2)	0.0044 (14)	−0.0051 (16)	−0.0002 (18)
C8	0.0214 (17)	0.0274 (18)	0.026 (2)	−0.0009 (13)	−0.0020 (14)	−0.0039 (17)
C3	0.030 (2)	0.039 (2)	0.045 (3)	0.0021 (16)	0.0047 (17)	−0.018 (2)
O1	0.122 (3)	0.054 (2)	0.047 (2)	−0.0098 (19)	−0.0071 (19)	−0.0288 (19)
C16	0.045 (2)	0.032 (2)	0.031 (2)	0.0050 (16)	−0.0009 (17)	−0.003 (2)
C14	0.079 (3)	0.032 (2)	0.027 (2)	0.005 (2)	−0.008 (2)	−0.003 (2)
C15	0.064 (3)	0.040 (2)	0.032 (2)	0.0120 (19)	0.0068 (19)	0.000 (2)
C2	0.041 (2)	0.039 (2)	0.042 (3)	−0.0059 (17)	−0.0033 (18)	−0.017 (2)
C13	0.066 (3)	0.036 (2)	0.044 (3)	−0.0125 (19)	−0.013 (2)	−0.011 (2)
C1	0.0235 (17)	0.0300 (19)	0.033 (2)	−0.0098 (14)	−0.0064 (16)	−0.0005 (19)
C18	0.113 (4)	0.058 (3)	0.051 (3)	0.032 (3)	0.026 (3)	0.011 (3)
C17	0.143 (5)	0.065 (4)	0.069 (4)	−0.031 (4)	−0.016 (4)	−0.026 (3)

Geometric parameters (Å, º) top

Ni1—N3ⁱ	2.035 (2)	O2—C17	1.425 (5)
Ni1—N3	2.035 (2)	C6—H6	0.9500
Ni1—N4ⁱ	2.078 (3)	C6—C5	1.383 (4)
Ni1—N4	2.078 (3)	C5—H5	0.9500
Ni1—N1	2.143 (3)	C12—H12	0.9500
Ni1—N1ⁱ	2.143 (3)	C12—C11	1.401 (4)
N3—C4	1.319 (4)	C12—C13	1.353 (5)
N3—C8	1.353 (4)	C11—C16	1.389 (4)
N6—C10	1.356 (4)	C3—H3	0.9500
N6—C9	1.336 (4)	C3—C2	1.360 (4)
O3—C18	1.396 (5)	O1—C14	1.375 (4)
O3—H3A	0.82 (3)	O1—C17	1.430 (5)
N4—N5	1.362 (3)	C16—H16	0.9500
N4—C9	1.345 (3)	C16—C15	1.401 (5)
N2—N1	1.376 (3)	C14—C15	1.366 (5)
N2—C4	1.410 (4)	C14—C13	1.374 (5)
N2—C3	1.350 (4)	C15—H15	0.9500
N1—C1	1.330 (4)	C2—H2	0.9500
N5—C10	1.343 (4)	C2—C1	1.394 (5)
C4—C5	1.383 (4)	C1—H1	0.9500
C10—C11	1.468 (4)	C18—H18A	0.9800
C7—H7	0.9500	C18—H18B	0.9800
C7—C6	1.376 (5)	C18—H18C	0.9800
C7—C8	1.385 (4)	C17—H17A	0.9900
C9—C8	1.461 (4)	C17—H17B	0.9900
O2—C13	1.379 (4)

N3ⁱ—Ni1—N3	173.57 (14)	C4—C5—H5	121.8
N3—Ni1—N4	77.75 (10)	C6—C5—C4	116.3 (3)
N3—Ni1—N4ⁱ	106.77 (10)	C6—C5—H5	121.8
N3ⁱ—Ni1—N4	106.77 (9)	C11—C12—H12	121.0
N3ⁱ—Ni1—N4ⁱ	77.75 (9)	C13—C12—H12	121.0
N3—Ni1—N1	75.88 (9)	C13—C12—C11	118.0 (4)
N3—Ni1—N1ⁱ	99.53 (9)	C12—C11—C10	119.8 (3)
N3ⁱ—Ni1—N1ⁱ	75.88 (9)	C16—C11—C10	120.9 (3)
N3ⁱ—Ni1—N1	99.53 (9)	C16—C11—C12	119.3 (3)
N4—Ni1—N4ⁱ	94.21 (14)	N3—C8—C7	120.0 (3)
N4—Ni1—N1	153.63 (9)	N3—C8—C9	111.4 (3)
N4ⁱ—Ni1—N1ⁱ	153.63 (9)	C7—C8—C9	128.6 (3)
N4—Ni1—N1ⁱ	93.21 (10)	N2—C3—H3	126.6
N4ⁱ—Ni1—N1	93.21 (10)	N2—C3—C2	106.7 (3)
N1—Ni1—N1ⁱ	91.26 (14)	C2—C3—H3	126.6
C4—N3—Ni1	120.7 (2)	C14—O1—C17	104.8 (3)
C4—N3—C8	120.3 (3)	C11—C16—H16	119.2
C8—N3—Ni1	118.9 (2)	C11—C16—C15	121.7 (3)
C9—N6—C10	101.7 (2)	C15—C16—H16	119.2
C18—O3—H3A	107 (3)	C15—C14—O1	128.2 (4)
N5—N4—Ni1	140.06 (18)	C15—C14—C13	121.0 (4)
C9—N4—Ni1	114.1 (2)	C13—C14—O1	110.9 (4)
C9—N4—N5	105.8 (2)	C16—C15—H15	121.4
N1—N2—C4	117.6 (2)	C14—C15—C16	117.2 (4)
C3—N2—N1	111.6 (2)	C14—C15—H15	121.4
C3—N2—C4	130.7 (3)	C3—C2—H2	126.9
N2—N1—Ni1	112.28 (18)	C3—C2—C1	106.1 (3)
C1—N1—Ni1	143.5 (2)	C1—C2—H2	126.9
C1—N1—N2	104.2 (3)	C12—C13—O2	127.6 (4)
C10—N5—N4	105.5 (2)	C12—C13—C14	122.8 (4)
N3—C4—N2	113.3 (2)	C14—C13—O2	109.6 (4)
N3—C4—C5	123.3 (3)	N1—C1—C2	111.3 (3)
C5—C4—N2	123.3 (3)	N1—C1—H1	124.4
N6—C10—C11	123.3 (3)	C2—C1—H1	124.4
N5—C10—N6	113.3 (3)	O3—C18—H18A	109.5
N5—C10—C11	123.3 (3)	O3—C18—H18B	109.5
C6—C7—H7	120.6	O3—C18—H18C	109.5
C6—C7—C8	118.8 (3)	H18A—C18—H18B	109.5
C8—C7—H7	120.6	H18A—C18—H18C	109.5
N6—C9—N4	113.7 (3)	H18B—C18—H18C	109.5
N6—C9—C8	128.6 (3)	O2—C17—O1	109.1 (4)
N4—C9—C8	117.7 (3)	O2—C17—H17A	109.9
C13—O2—C17	105.5 (4)	O2—C17—H17B	109.9
C7—C6—H6	119.4	O1—C17—H17A	109.9
C7—C6—C5	121.2 (3)	O1—C17—H17B	109.9
C5—C6—H6	119.4	H17A—C17—H17B	108.3

Ni1—N3—C4—N2	−3.3 (4)	C10—C11—C16—C15	−178.1 (3)
Ni1—N3—C4—C5	176.9 (3)	C7—C6—C5—C4	−0.2 (6)
Ni1—N3—C8—C7	−177.2 (3)	C9—N6—C10—N5	0.3 (4)
Ni1—N3—C8—C9	0.9 (3)	C9—N6—C10—C11	−176.1 (3)
Ni1—N4—N5—C10	178.3 (3)	C9—N4—N5—C10	−0.6 (3)
Ni1—N4—C9—N6	−178.4 (2)	C6—C7—C8—N3	0.2 (5)
Ni1—N4—C9—C8	3.8 (4)	C6—C7—C8—C9	−177.5 (3)
Ni1—N1—C1—C2	179.5 (3)	C12—C11—C16—C15	0.4 (5)
N3—C4—C5—C6	0.3 (5)	C11—C12—C13—O2	−177.2 (4)
N6—C10—C11—C12	−15.0 (5)	C11—C12—C13—C14	1.1 (6)
N6—C10—C11—C16	163.5 (3)	C11—C16—C15—C14	0.0 (5)
N6—C9—C8—N3	179.5 (3)	C8—N3—C4—N2	179.7 (3)
N6—C9—C8—C7	−2.6 (6)	C8—N3—C4—C5	−0.1 (5)
N4—N5—C10—N6	0.2 (4)	C8—C7—C6—C5	0.0 (6)
N4—N5—C10—C11	176.5 (3)	C3—N2—N1—Ni1	−179.7 (2)
N4—C9—C8—N3	−3.1 (4)	C3—N2—N1—C1	0.3 (3)
N4—C9—C8—C7	174.8 (3)	C3—N2—C4—N3	−176.7 (3)
N2—N1—C1—C2	−0.4 (4)	C3—N2—C4—C5	3.1 (6)
N2—C4—C5—C6	−179.5 (3)	C3—C2—C1—N1	0.4 (4)
N2—C3—C2—C1	−0.2 (4)	O1—C14—C15—C16	179.4 (3)
N1—N2—C4—N3	−0.2 (4)	O1—C14—C13—O2	−1.6 (5)
N1—N2—C4—C5	179.6 (3)	O1—C14—C13—C12	179.9 (4)
N1—N2—C3—C2	−0.1 (4)	C14—O1—C17—O2	3.1 (5)
N5—N4—C9—N6	0.8 (4)	C15—C14—C13—O2	177.9 (4)
N5—N4—C9—C8	−176.9 (3)	C15—C14—C13—C12	−0.7 (6)
N5—C10—C11—C12	169.0 (3)	C13—O2—C17—O1	−4.1 (5)
N5—C10—C11—C16	−12.5 (5)	C13—C12—C11—C10	177.6 (3)
C4—N3—C8—C7	−0.1 (5)	C13—C12—C11—C16	−1.0 (5)
C4—N3—C8—C9	177.9 (3)	C13—C14—C15—C16	0.1 (6)
C4—N2—N1—Ni1	3.2 (3)	C17—O2—C13—C12	−178.1 (4)
C4—N2—N1—C1	−176.8 (3)	C17—O2—C13—C14	3.4 (5)
C4—N2—C3—C2	176.6 (3)	C17—O1—C14—C15	179.6 (4)
C10—N6—C9—N4	−0.7 (4)	C17—O1—C14—C13	−1.0 (5)
C10—N6—C9—C8	176.8 (3)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3ⁱⁱ	0.95	2.35	3.282 (5)	165
C5—H5···O3ⁱⁱ	0.95	2.57	3.505 (4)	167
C7—H7···C1ⁱⁱⁱ	0.95	2.68	3.605 (5)	163
C1—H1···N6^iv	0.95	2.33	3.270 (4)	170
C17—H17A···C18^v	0.99	2.78	3.479 (7)	129
C17—H17A···O3^v	0.99	2.68	3.550 (6)	147
O3—H3A···N5	0.82 (4)	1.94 (4)	2.752 (4)	173 (4)

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

Computed distortion indices for the title compound and for similar complexes reported in the literature top

CSD Refcode	Metal ion<	<M—N> (Å)	Σ (°)	Θ (°)	CShM(O_h)
Title compound	Ni	2.085	117.2	391.6	3.60
YOCFAZ	Ni	2.088^a	120.8^a	397.6^a	3.65^a
ZOCKOT	Ni	2.086	121.0	375.9	3.78
ZOTVIP	Ni	2.110	124.9	382.4	3.55
EGIDIL	Fe	1.955	89.8	314.6	2.25
EGIDIL02	Fe	2.167	146.8	492.8	5.28
LUTGEO	Fe	1.933	85.0	309.6	2.10
XODCEB	Fe	1.950	87.4	276.6	1.93
DOMQUT	Fe	1.991	88.5	320.0	2.48
DOMQUT02	Fe	2.183	139.6	486.9	5.31
NIRLOT	Fe	1.939	77.3	255.6	1.68

Note: (a) averaged value.

Hydrogen-bond geometry (Å, °). top

*D–H···A*	*D–H*	*H···A*	*D···A*	*D–H···A*
C3–H···O3ⁱⁱ	0.95	2.36	3.282 (5)	165
C5–H···O3ⁱⁱ	0.95	2.57	3.505 (4)	167
C7–H···C1ⁱⁱⁱ	0.95	2.68	3.605 (5)	163
N6···H–C1ⁱⁱⁱ	0.95	2.33	3.270 (4)	170
C17–H···C18^iv	0.99	2.78	3.479 (7)	129
C17–H···O3^iv	0.99	2.68	3.550 (6)	147
O3–H···N6	0.82	1.94	2.753 (4)	172

Symmetry codes: (i) 1-x,1+y,1.5-z; (ii) -1/2+x,1/2+y,1.5-z; (iii) -1/2+x,-1/2+y,1.5-z; (iv) -1/2+x,1/2-y,1-z

Acknowledgements

The authors are grateful to the FAIRE programme provided by the Cambridge Crystallographic Data Centre (CCDC) for the opportunity to use the Cambridge Structural Database (CSD) and associated software. Author contributions are as follows: Conceptualization, KZ and MS; methodology, KZ; formal analysis, AK; synthesis, SOM; single-crystal measurements, SS; writing (original draft), KZ; writing (review and editing of the manuscript), VN, MS; visualization and calculations, KZ, IOF; funding acquisition, MS and KZ.

Funding information

Funding for this research was provided by grant No. 24BF037-03 from the Ministry of Education and Science of Ukraine. This work was supported by the European Union's HORIZON-MSCA-2023-SE-01 programme under grant agreement No. 101183082 – PacemCAT.

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