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

Znovjyak, K.; Fritsky, I.O.; Sliva, T.Y.; Amirkhanov, V.M.; Malinkin, S.O.; Shova, S.; Seredyuk, M.

doi:10.1107/S2056989022009744

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ISSN: 2056-9890

Volume 78| Part 11| November 2022| Pages 1107-1112

https://doi.org/10.1107/S2056989022009744

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

Kateryna Znovjyak,^a Igor O. Fritsky,^a Tatiana Y. Sliva,^a Vladimir M. Amirkhanov,^a Sergey O. Malinkin,^a Sergiu Shova ^b and Maksym Seredyuk ^a ^*

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska Street 64, Kyiv, 01601, Ukraine, and ^bDepartment of Inorganic Polymers, "Petru Poni", Institute of Macromolecular Chemistry, Romanian Academy of Science, Aleea Grigore Ghica Voda 41-A, Iasi 700487, Romania
^*Correspondence e-mail: mlseredyuk@gmail.com

Edited by C. Schulzke, Universität Greifswald, Germany (Received 31 August 2022; accepted 4 October 2022; online 11 October 2022)

As a result of the high symmetry of the Aea2 structure, the asymmetric unit of the title compound, [Fe^II(C₁₈H₁₅N₆)₂]·2MeOH, consists of half of a charge-neutral complex molecule and a discrete methanol molecule. The planar anionic tridentate ligand 2-[5-(3,4-dimethylphenyl)-4H-1,2,4-triazol-3-ato]-6-(1H-pyrazol-1-yl)pyridine coordinates the Fe^II ion meridionally through the N atoms of the pyrazole, pyridine and triazole groups, forming a pseudo-octahedral coordination sphere of the central ion. The average Fe—N bond distance is 1.955 Å, indicating a low-spin state of the Fe^II ion. Neighbouring cone-shaped molecules, nested into each other, are linked through double weak C—H(pz)⋯π(ph') interactions into mono-periodic columns, which are further linked through weak C—H⋯N′/C′ interactions into di-periodic layers. No interactions shorter than the sum of the van der Waals radii of the neighbouring layers are observed. Energy framework analysis at the B3LYP/6–31 G(d,p) theory level, performed to quantify the intermolecular interaction energies, reproduces the weak interlayer interactions in contrast to the strong interaction within the layers. Intermolecular contacts were quantified using Hirshfeld surface analysis and two-dimensional fingerprint plots, showing the relative contributions of the contacts to the crystal packing to be H⋯H 48.5%, H⋯C/C⋯H 28.9%, H⋯N/N⋯H 16.2% and C⋯C 2.4%.

Keywords: crystal structure; spin-crossover; spin transition; energy frameworks.

CCDC reference: 2211089

1. Chemical context

Bisazolepyridines are a broad class of meridional tridentate ligands used to synthesize charged Fe^II compounds capable of switching between a spin state with the t_2g⁴e_g² configuration (high-spin, total spin S = 2) and a spin state with the t_2g⁶e_g⁰ configuration (low-spin, total spin S = 0) due to temperature variation, light irradiation or external pressure (Halcrow, 2014 ; Halcrow et al., 2019 ). In the case of asymmetric ligand design, where one of the azole groups carries a hydrogen on the nitrogen heteroatom, it was shown that deprotonation can produce neutral complex species that can be high-spin (Schäfer et al., 2013 ), low-spin (Shiga et al., 2019 ) or exhibit temperature-induced transitions between the spin states of the central atom (Seredyuk et al., 2014 ), depending on the ligand field strength. The substituents of ligands can also play an important role in behaviour of the solid samples, determining the way molecules interact with each other and, therefore, influencing the spin state adopted by the central atom. As we have recently shown, the dynamic rearrangement of the substituent groups can lead to an abnormally large hysteresis of the thermal high-spin transition due to the supramolecular mechanism of blocking the deformation of the complex molecule by the methoxy group (Seredyuk et al., 2022 ).

In a continuation of our interest in 3d-metal complexes formed by polydentate ligands (Bartual-Murgui et al., 2017 ; Bonhommeau et al., 2012 ; Valverde-Muñoz et al., 2020 ), we report here the structural characterization of a new electroneutral complex [Fe^IIL₂]⁰ based on an asymmetric mono-deprotonated ligand with two methyl substituents on the phenyl group, L = 2-[5-(3,4-dimethylphenyl)-4H-1,2,4-triazol-3-ato]-6-(1H-pyrazol-1-yl)pyridine.

2. Structural commentary

The asymmetric unit comprises half of the molecule and a discrete MeOH molecule forming a hydrogen bond O26—H26⋯N12 with the triazole (trz) ring (Fig. 1). The Fe^II ion has a pseudo-octahedral coordination environment composed of the nitrogen donor atoms of the pyrazole (pz), pyridine (py) and trz heterocycles with an average Fe—N distance of 1.957 Å (V[FeN₆] = 9.654 Å³) being typical for low-spin complexes with an N₆ coordination environment (Gütlich & Goodwin, 2004 ). The pz, py, trz and phenyl rings, together with the two methyl substituents of one ligand, all lie essentially in the same plane.

Figure 1
The molecular structure of half the title compound as refined in the asymmetric unit with displacement ellipsoids drawn at the 50% probability level. The O—H⋯N hydrogen bond is indicated by the dashed line. This and the next figure were generated with the program Mercury (Macrae et al., 2020

The average trigonal distortion parameters, Σ = Σ₁¹²(|90 − φ_i|), with φ_i being the N—Fe—N′ angle (Drew et al., 1995 ), and Θ = Σ₁²⁴(|60 − θ_i|), with θ_i being the angle generated by superposition of two opposite faces of the octahedron (Chang et al., 1990 ), are 92.8 and 295.0°, respectively. The values reveal a deviation of the coordination environment from an ideal octahedron which is, however, in the expected range for complexes with similar bisazolepyridine ligands (see below). The calculated continuous shape measure (CShM) value relative to the ideal O_h symmetry is 2.18 (Kershaw Cook et al., 2015 ).

3. Supramolecular features

As a result of the tapered shape, neighbouring complex molecules are embedded in each other and interact through two weak intermolecular C—H(pz)⋯π(ph') contacts between the pyrazole (pz) and phenyl (ph) groups, respectively [distance C2)(pz)⋯C_g(ph') is 3.392 Å, angle between planes of the rings is 73.77°]. The formed mono-periodic supramolecular columns protrude along the c-axis with a stacking periodicity equal to 10.6511 (7) Å (= cell parameter c) (Fig. 2a). Weak intermolecular hydrogen-bonding interactions C—H(pz, py)⋯N/C(pz, trz)/O(MeOH) in the range 2.257–2.893 Å (Table 1), link neighbouring columns into corrugated di-periodic layers in the bc plane (Fig. 2b,c). The layers stack along the b-axis direction without any strong or weak interlayer interactions shorter than the sum of the van der Waals radii (Fig. 2c). The voids between the layers are occupied by methanol molecules, which participate in the strong hydrogen bonding mentioned above, and weak hydrogen bonding with the aromatic substituents within the layers (a complete list of intermolecular interactions is given in Table 1).

Table 1
Hydrogen bonding (Å) of the title compound

Hydrogen bond	Length	Symmetry operation of the contact atom
C7⋯H—C21(pz)	2.827	1 − x, 1 − y, 1 + z
C6⋯H—C21(pz)	2.777	1 − x, 1 − y, 1 + z
C5⋯H—C21(pz)	2.756	1 − x, 1 − y, 1 + z
C4⋯H—C21(pz)	2.802	1 − x, 1 − y, 1 + z
C3⋯H—C21(pz)	2.893	1 − x, 1 − y, 1 + z
N9⋯H—C15(py)	2.475	$[{1\over 2}]$ + x, 1 − y, $[{1\over 2}]$ + z
N9⋯H—C20(pz)	2.522	$[{1\over 2}]$ + x, 1 − y, $[{1\over 2}]$ + z
H7⋯C20(pz)	2.641	$[{1\over 2}]$ + x, 1 − y, $[{1\over 2}]$ + z
N12⋯H—O26	2.017	x, y, z
H17⋯O26	2.329	x, y, z
O26⋯H—C22(pz)	2.257	− $[{1\over 2}]$ + x, 1 − y, $[{1\over 2}]$ + z

Figure 2
(a) A fragment of the mono-periodic supramolecular columns formed by stacking of molecules along the c axis. (b) Di-periodic supramolecular layers formed by stacking of the supramolecular columns. For a better representation, each column has a different colour. Red dashed lines represent weak hydrogen bonds. (c) Stacking of the di-periodic layers along the c axis. Blue shaded areas correspond to the interlayer space without intermolecular interactions shorter than the sum of the van der Waals radii. The methanol molecules are not shown for clarity.

4. Hirshfeld surface and 2D fingerprint plots

Hirshfeld surface analysis was performed and the associated two-dimensional fingerprint plots were generated using Crystal Explorer (Spackman et al., 2021 ), with a standard resolution of the three-dimensional d_norm surfaces plotted over a fixed colour scale of −0.6122 (red) to 1.3609 (blue) a.u. (Fig. 3). The pale-red spots symbolize short contacts and negative d_norm values on the surface correspond to the interactions described above. The overall two-dimensional fingerprint plot is illustrated in Fig. 4. The Hirshfeld surfaces mapped over d_norm are shown for the H⋯H, H⋯C/C⋯H, H⋯N/N⋯H and C⋯C contacts, and the two-dimensional fingerprint plots, associated with their relative contributions to the Hirshfeld surface. At 48.5%, the largest contribution to the overall crystal packing is from H⋯H interactions, which are located mostly in the central region of the fingerprint plot. H⋯C/C⋯H contacts contribute 28.9%, resulting in a pair of characteristic wings. The H⋯N/N⋯H contacts, represented by a pair of sharp spikes in the fingerprint plot, make a 16.2% contribution to the Hirshfeld surface. Finally, C⋯C contacts, which account for a contribution of 2.4%, are mostly distributed in the middle part of the plot.

Figure 3
A projection of d_norm mapped on the Hirshfeld surface, showing the intermolecular interactions within the molecule. Red areas represent regions where contacts are shorter than the sum of the van der Waals radii, blue areas represent regions where contacts are longer than the sum of van der Waals radii, and white areas are regions where contacts are close to the sum of van der Waals radii. This and the next two figures were generated with the program Crystal Explorer (Spackman et al., 2021

Figure 4
(a) The overall two-dimensional fingerprint plot and those decomposed into specified interactions. (b) Hirshfeld surface representations with the function d_norm plotted onto the surface for the different interactions.

5. Energy frameworks

The energy frameworks, calculated using the wave function at the B3LYP/6-31G(d,p) theory level, including the electrostatic potential forces (E_ele), the dispersion forces (E_dis) and the total energy diagrams (E_tot), are shown in Fig. 5 (Spackman et al., 2021). The cylindrical radii, adjusted to the same scale factor of 100, are proportional to the relative strength of the corresponding energies. The major contribution to the intermolecular interactions comes from dispersion forces (E_dis), reflecting the dominant interactions in the network of the electroneutral molecules. The topology of the energy framework resembles the topology of the intermolecular interactions within and between the supramolecular layers described above. Because of the high lattice symmetry, there are only two different attractive interactions between the molecules within the layers, equal to −58.5 and −90.6 kJ mol⁻¹. As for the interlayer interactions, the absence of supramolecular bonding leads to very weak interactions in the range −7.4 to +2.5 kJ mol⁻¹, i.e. from weakly attracting to weakly repulsive. The colour-coded interaction mappings within a radius of 3.8 Å of a central reference molecule for the title compound together with full details of the various contributions to the total energy (E_tot) are given in the supporting information

Figure 5
The calculated energy frameworks, showing (a) the electrostatic potential forces (E_ele), (b) the dispersion forces (E_dis) and (c) the total energy diagrams (E_tot). Tube size is set at 100 scale.

6. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, last update February 2021; Groom et al., 2016 ) reveals several similar neutral Fe^II complexes with a deprotonated azole group, for example, those based on pyrazole-pyridine-benzimidazole, XODCEB (Shiga et al., 2019), phenathroline-tetrazole, QIDJET (Zhang et al., 2007 ), and phenanthroline-benzimidazole, DOMQUT (Seredyuk et al., 2014). We also included in the comparison data for three polymorphs, in different spin states, of a complex structurally similar to the title compound, but carrying a methoxy group on the phenyl substituent (EJQOA, BEJQUG, BEJQUG01, BEJRAN, BEJRER; Seredyuk et al., 2022) (see schematic structures of all complexes in the supporting information. The Fe—N distances of these complexes in the low-spin state are 1.946–1.991 Å, while in the high-spin state they are in the range 2.138–2.184 Å. The values of the trigonal distortion and CShM(O_h) change correspondingly, and in the low-spin state they are systematically lower than in the high-spin state. The respective structural parameters of the title compound and related complexes are given in Table 2.

Table 2
Computed distortion indices (Å, °) for the title compound and similar literature complexes

CSD code	Spin state	<Fe—N>	Σ	Θ	CShM(O_h)
Title compound	Low-spin	1.957	92.8	295.0	2.18
XODCEB^a	Low-spin	1.950	87.4	276.6	1.92
QIDJET01^b	Low-spin	1.970	90.3	341.3	2.47
QIDJET^b	High-spin	2.184	145.5	553.3	5.88
DOMQIH^c	Low-spin	1.962	83.8	280.7	2.02
DOMQUT^c	Low-spin	1.991	88.5	320.0	2.48
DOMQUT02^c	High-spin	2.183	139.6	486.9	5.31
EJQOA^d	Low-spin	1.946	87.5	308.9	2.16
BEJQUG^d	Low-spin	1.952	97.9	309.9	2.37
BEJQUG01^d	High-spin	2.138	118.0	375.9	3.34
BEJRAN^d	Low-spin	1.946	107.7	384.5	3.20
BEJRER^d	High-spin	2.139	147.8	507.2	4.92
Notes: (a) Shiga et al. (2019); (b) Zhang et al. (2007); (c) Seredyuk et al. (2014); (d) Seredyuk et al. (2022).

7. Synthesis and crystallization

The ligand L was synthesized by the Suzuki cross-coupling reaction from the commercially available precursors (Enamine Ltd.) according to the method described in the literature (Seredyuk et al., 2022). The synthesis of the title compound was performed with a layering technique in a standard test tube. The layering sequence was as follows: the bottom layer contained a solution of [Fe(L₂)](BF₄)₂ prepared by dissolving L = 2-[(3,4-dimethylphenyl)-4H-1,2,4-triazol-3-yl)]-6-(1H-pyrazol-1-yl)pyridine (100 mg, 0.316 mmol) and Fe(BF₄)₂·6H₂O (53 mg, 0.158 mmol) in boiling acetone, 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 was added dropwise. The tube was sealed, and black plate-like single crystals appeared within 3-4 weeks (yield ca 75%). Elemental analysis calculated for C₃₈H₃₈FeN₁₂O₂: C, 60.80; H, 5.10; N, 22.39. Found: C, 60.50; H, 5.31; N, 22.71.

8. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were placed in calculated positions using idealized geometries, with C—H = 0.98 Å for methyl groups and 0.95 Å for aromatic H atoms, and refined using a riding model with U_iso(H) = 1.2–1.5U_eq(C); the hydrogen atom H26 was refined freely. Two OMIT commands were used to exclude beamstop-affected data.

Table 3
Experimental details

Crystal data
Chemical formula	[Fe(C₁₈H₁₅N₆)₂]·2CH₄O
M_r	750.65
Crystal system, space group	Orthorhombic, Aea2
Temperature (K)	180
a, b, c (Å)	12.6854 (10), 26.315 (2), 10.6511 (7)
V (Å³)	3555.5 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.48
Crystal size (mm)	0.3 × 0.24 × 0.04

Data collection
Diffractometer	Xcalibur, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.824, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6911, 3047, 2211
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.100, 1.00
No. of reflections	3047
No. of parameters	247
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.84, −0.50
Absolute structure	Flack x determined using 703 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 ).
Absolute structure parameter	−0.02 (3)
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2211089

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022009744/yz2021sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022009744/yz2021Isup2.hkl

Supporting data for energy framework analysis and schematic structures of related complexes. DOI: https://doi.org/10.1107/S2056989022009744/yz2021sup4.doc

Supporting information file. DOI: https://doi.org/10.1107/S2056989022009744/yz2021Isup5.cdx

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2022); cell refinement: CrysAlis PRO (Rigaku OD, 2022); data reduction: CrysAlis PRO (Rigaku OD, 2022); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

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

Crystal data top

[Fe(C₁₈H₁₅N₆)₂]·2CH₄O	D_x = 1.402 Mg m⁻³
M_r = 750.65	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Aea2	Cell parameters from 1363 reflections
a = 12.6854 (10) Å	θ = 2.6–22.8°
b = 26.315 (2) Å	µ = 0.48 mm⁻¹
c = 10.6511 (7) Å	T = 180 K
V = 3555.5 (5) Å³	Plate, clear dark red
Z = 4	0.3 × 0.24 × 0.04 mm
F(000) = 1568

Data collection top

Xcalibur, Eos diffractometer	3047 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2211 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.071
Detector resolution: 16.1593 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
ω scans	h = −12→15
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	k = −25→31
T_min = 0.824, T_max = 1.000	l = −12→12
6911 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.061	w = 1/[σ²(F_o²) + (0.0192P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.100	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 0.84 e Å⁻³
3047 reflections	Δρ_min = −0.50 e Å⁻³
247 parameters	Absolute structure: Flack x determined using 703 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
1 restraint	Absolute structure parameter: −0.02 (3)
Primary atom site location: dual

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
Fe1	0.500000	0.500000	0.32399 (13)	0.0198 (3)
N13	0.3533 (4)	0.48261 (19)	0.3181 (6)	0.0170 (12)
N23	0.4520 (4)	0.5467 (2)	0.1903 (5)	0.0202 (15)
N19	0.3481 (4)	0.5393 (2)	0.1587 (4)	0.0219 (15)
N10	0.4953 (5)	0.4455 (3)	0.4514 (5)	0.0211 (15)
O26	0.1937 (5)	0.3536 (3)	0.6135 (7)	0.074 (3)
H26	0.255 (9)	0.359 (4)	0.602 (8)	0.10 (4)*
N12	0.3978 (4)	0.3867 (2)	0.5544 (4)	0.0214 (15)
N9	0.5624 (4)	0.4206 (2)	0.5293 (5)	0.0205 (15)
C14	0.2907 (5)	0.5053 (3)	0.2340 (6)	0.0189 (17)
C16	0.1439 (5)	0.4588 (3)	0.3039 (6)	0.0266 (18)
H16	0.070880	0.450760	0.300859	0.032*
C11	0.3991 (6)	0.4244 (3)	0.4689 (6)	0.0187 (17)
C18	0.3142 (5)	0.4458 (3)	0.3926 (6)	0.0208 (17)
C17	0.2084 (5)	0.4332 (3)	0.3877 (6)	0.0232 (18)
H17	0.180469	0.407444	0.440732	0.028*
C2	0.5444 (6)	0.3525 (3)	0.6874 (6)	0.0221 (17)
C15	0.1835 (5)	0.4957 (3)	0.2245 (5)	0.0231 (17)
H15	0.139860	0.513428	0.166841	0.028*
C20	0.3249 (6)	0.5650 (3)	0.0514 (6)	0.028 (2)
H20	0.258538	0.565681	0.010235	0.034*
C7	0.6517 (6)	0.3493 (3)	0.7117 (6)	0.031 (2)
H7	0.698294	0.368889	0.661329	0.037*
C21	0.4130 (6)	0.5893 (3)	0.0140 (7)	0.031 (2)
H21	0.420863	0.610314	−0.057996	0.038*
C6	0.6947 (6)	0.3191 (3)	0.8056 (7)	0.0300 (19)
C5	0.6260 (7)	0.2904 (3)	0.8814 (7)	0.036 (2)
C4	0.5194 (7)	0.2928 (3)	0.8593 (6)	0.040 (2)
H4	0.473076	0.273418	0.910428	0.048*
C22	0.4901 (6)	0.5776 (3)	0.1021 (7)	0.0274 (19)
H22	0.560432	0.589870	0.099718	0.033*
C24	0.8132 (5)	0.3196 (3)	0.8284 (8)	0.048 (2)
H24A	0.846198	0.345213	0.774413	0.072*
H24B	0.842489	0.286043	0.808838	0.072*
H24C	0.827202	0.327787	0.916573	0.072*
C8	0.5027 (5)	0.3860 (3)	0.5907 (6)	0.0205 (17)
C3	0.4769 (6)	0.3232 (3)	0.7632 (6)	0.035 (2)
H3	0.402940	0.323876	0.749434	0.042*
C27	0.1677 (7)	0.3185 (4)	0.7045 (8)	0.060 (3)
H27A	0.208643	0.287319	0.691455	0.089*
H27B	0.092312	0.310638	0.699199	0.089*
H27C	0.183692	0.332462	0.787647	0.089*
C25	0.6686 (7)	0.2584 (3)	0.9889 (7)	0.057 (3)
H25A	0.722244	0.234986	0.956909	0.085*
H25B	0.610868	0.238992	1.026777	0.085*
H25C	0.700073	0.280733	1.052319	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0140 (7)	0.0239 (8)	0.0216 (6)	−0.0013 (8)	0.000	0.000
N13	0.010 (3)	0.020 (3)	0.022 (3)	0.000 (3)	−0.003 (3)	0.002 (3)
N23	0.014 (3)	0.028 (4)	0.019 (3)	−0.003 (3)	0.000 (3)	−0.002 (3)
N19	0.016 (3)	0.024 (4)	0.025 (3)	−0.002 (3)	−0.002 (3)	0.002 (3)
N10	0.019 (3)	0.026 (4)	0.018 (3)	0.001 (3)	−0.003 (3)	0.002 (3)
O26	0.024 (4)	0.082 (6)	0.115 (6)	0.009 (4)	0.018 (4)	0.066 (5)
N12	0.013 (3)	0.025 (4)	0.026 (3)	0.000 (3)	−0.004 (3)	0.001 (3)
N9	0.020 (4)	0.024 (4)	0.018 (3)	0.000 (3)	−0.003 (3)	0.004 (3)
C14	0.012 (4)	0.024 (5)	0.021 (4)	−0.007 (4)	0.003 (3)	−0.003 (3)
C16	0.013 (4)	0.034 (5)	0.032 (5)	−0.005 (4)	0.003 (3)	0.000 (4)
C11	0.022 (4)	0.019 (5)	0.015 (4)	−0.001 (4)	−0.004 (3)	−0.002 (3)
C18	0.014 (4)	0.028 (5)	0.020 (3)	−0.002 (4)	0.002 (3)	−0.004 (3)
C17	0.012 (4)	0.032 (5)	0.025 (4)	−0.009 (4)	−0.002 (3)	0.000 (4)
C2	0.025 (4)	0.024 (5)	0.017 (4)	−0.002 (4)	−0.005 (3)	−0.001 (3)
C15	0.015 (4)	0.027 (5)	0.028 (4)	0.001 (4)	−0.007 (3)	0.004 (4)
C20	0.027 (5)	0.036 (5)	0.022 (4)	0.014 (4)	0.001 (3)	0.004 (4)
C7	0.032 (5)	0.032 (5)	0.027 (5)	0.010 (4)	0.003 (4)	0.001 (4)
C21	0.024 (5)	0.035 (6)	0.035 (5)	0.006 (5)	0.004 (4)	0.017 (4)
C6	0.038 (5)	0.024 (4)	0.028 (4)	0.013 (4)	−0.013 (4)	−0.007 (4)
C5	0.051 (6)	0.028 (5)	0.030 (4)	0.006 (5)	−0.019 (4)	0.001 (4)
C4	0.056 (6)	0.033 (5)	0.031 (6)	−0.017 (5)	−0.006 (4)	0.013 (4)
C22	0.025 (5)	0.029 (5)	0.029 (4)	−0.010 (4)	0.006 (4)	0.006 (4)
C24	0.040 (5)	0.060 (6)	0.045 (4)	0.020 (5)	−0.008 (5)	0.012 (6)
C8	0.017 (4)	0.024 (5)	0.021 (4)	0.002 (4)	0.002 (3)	−0.005 (3)
C3	0.029 (5)	0.044 (6)	0.031 (4)	−0.009 (4)	−0.011 (4)	0.001 (4)
C27	0.043 (6)	0.056 (7)	0.080 (6)	0.008 (6)	0.020 (5)	0.025 (6)
C25	0.080 (8)	0.044 (7)	0.047 (5)	0.002 (6)	−0.024 (5)	0.012 (4)

Geometric parameters (Å, º) top

Fe1—N13	1.917 (5)	C2—C8	1.455 (9)
Fe1—N13ⁱ	1.917 (5)	C2—C3	1.407 (9)
Fe1—N23ⁱ	1.977 (6)	C15—H15	0.9500
Fe1—N23	1.977 (6)	C20—H20	0.9500
Fe1—N10ⁱ	1.974 (6)	C20—C21	1.349 (9)
Fe1—N10	1.974 (6)	C7—H7	0.9500
N13—C14	1.338 (8)	C7—C6	1.389 (9)
N13—C18	1.348 (8)	C21—H21	0.9500
N23—N19	1.375 (7)	C21—C22	1.389 (9)
N23—C22	1.333 (9)	C6—C5	1.409 (10)
N19—C14	1.403 (8)	C6—C24	1.522 (9)
N19—C20	1.360 (8)	C5—C4	1.373 (10)
N10—N9	1.358 (8)	C5—C25	1.520 (10)
N10—C11	1.355 (9)	C4—H4	0.9500
O26—H26	0.79 (11)	C4—C3	1.406 (9)
O26—C27	1.380 (9)	C22—H22	0.9500
N12—C11	1.345 (8)	C24—H24A	0.9800
N12—C8	1.386 (8)	C24—H24B	0.9800
N9—C8	1.352 (8)	C24—H24C	0.9800
C14—C15	1.387 (8)	C3—H3	0.9500
C16—H16	0.9500	C27—H27A	0.9800
C16—C17	1.386 (9)	C27—H27B	0.9800
C16—C15	1.383 (9)	C27—H27C	0.9800
C11—C18	1.463 (9)	C25—H25A	0.9800
C18—C17	1.384 (8)	C25—H25B	0.9800
C17—H17	0.9500	C25—H25C	0.9800
C2—C7	1.388 (9)

N13—Fe1—N13ⁱ	176.2 (4)	C14—C15—H15	121.9
N13—Fe1—N23	80.0 (3)	C16—C15—C14	116.2 (6)
N13—Fe1—N23ⁱ	97.3 (2)	C16—C15—H15	121.9
N13ⁱ—Fe1—N23	97.3 (2)	N19—C20—H20	126.1
N13ⁱ—Fe1—N23ⁱ	80.0 (3)	C21—C20—N19	107.8 (7)
N13—Fe1—N10	79.6 (3)	C21—C20—H20	126.1
N13—Fe1—N10ⁱ	103.0 (2)	C2—C7—H7	118.2
N13ⁱ—Fe1—N10ⁱ	79.6 (3)	C6—C7—C2	123.7 (7)
N13ⁱ—Fe1—N10	103.0 (2)	C6—C7—H7	118.2
N23ⁱ—Fe1—N23	87.9 (3)	C20—C21—H21	127.0
N10ⁱ—Fe1—N23	93.0 (2)	C20—C21—C22	106.1 (7)
N10—Fe1—N23ⁱ	93.0 (2)	C22—C21—H21	127.0
N10ⁱ—Fe1—N23ⁱ	159.5 (2)	C7—C6—C5	118.4 (7)
N10—Fe1—N23	159.5 (2)	C7—C6—C24	119.9 (7)
N10—Fe1—N10ⁱ	93.2 (4)	C5—C6—C24	121.6 (7)
C14—N13—Fe1	119.4 (5)	C6—C5—C25	120.6 (7)
C14—N13—C18	119.8 (6)	C4—C5—C6	119.1 (7)
C18—N13—Fe1	120.6 (5)	C4—C5—C25	120.3 (8)
N19—N23—Fe1	112.5 (4)	C5—C4—H4	119.1
C22—N23—Fe1	140.8 (5)	C5—C4—C3	121.9 (7)
C22—N23—N19	105.2 (6)	C3—C4—H4	119.1
N23—N19—C14	116.6 (5)	N23—C22—C21	110.9 (7)
C20—N19—N23	110.0 (6)	N23—C22—H22	124.5
C20—N19—C14	133.2 (6)	C21—C22—H22	124.5
N9—N10—Fe1	138.8 (5)	C6—C24—H24A	109.5
C11—N10—Fe1	114.9 (5)	C6—C24—H24B	109.5
C11—N10—N9	106.3 (6)	C6—C24—H24C	109.5
C27—O26—H26	117 (7)	H24A—C24—H24B	109.5
C11—N12—C8	100.8 (6)	H24A—C24—H24C	109.5
C8—N9—N10	105.7 (5)	H24B—C24—H24C	109.5
N13—C14—N19	111.0 (6)	N12—C8—C2	123.7 (6)
N13—C14—C15	123.3 (6)	N9—C8—N12	113.2 (6)
C15—C14—N19	125.7 (6)	N9—C8—C2	123.1 (6)
C17—C16—H16	119.3	C2—C3—C4	119.8 (7)
C15—C16—H16	119.3	C2—C3—H3	120.1
C15—C16—C17	121.4 (7)	C4—C3—H3	120.1
N10—C11—C18	115.4 (6)	O26—C27—H27A	109.5
N12—C11—N10	114.0 (6)	O26—C27—H27B	109.5
N12—C11—C18	130.6 (7)	O26—C27—H27C	109.5
N13—C18—C11	109.5 (6)	H27A—C27—H27B	109.5
N13—C18—C17	120.5 (6)	H27A—C27—H27C	109.5
C17—C18—C11	130.0 (7)	H27B—C27—H27C	109.5
C16—C17—H17	120.6	C5—C25—H25A	109.5
C18—C17—C16	118.7 (7)	C5—C25—H25B	109.5
C18—C17—H17	120.6	C5—C25—H25C	109.5
C7—C2—C8	121.7 (6)	H25A—C25—H25B	109.5
C7—C2—C3	117.2 (7)	H25A—C25—H25C	109.5
C3—C2—C8	121.1 (6)	H25B—C25—H25C	109.5

Fe1—N13—C14—N19	1.3 (8)	C11—N12—C8—C2	177.6 (6)
Fe1—N13—C14—C15	−178.9 (5)	C11—C18—C17—C16	−178.4 (6)
Fe1—N13—C18—C11	−0.5 (8)	C18—N13—C14—N19	−174.9 (6)
Fe1—N13—C18—C17	−179.7 (5)	C18—N13—C14—C15	4.9 (10)
Fe1—N23—N19—C14	7.5 (7)	C17—C16—C15—C14	0.0 (10)
Fe1—N23—N19—C20	−168.3 (4)	C2—C7—C6—C5	−0.6 (11)
Fe1—N23—C22—C21	163.0 (6)	C2—C7—C6—C24	−177.8 (7)
Fe1—N10—N9—C8	−178.8 (5)	C15—C16—C17—C18	1.1 (11)
Fe1—N10—C11—N12	178.9 (5)	C20—N19—C14—N13	168.7 (7)
Fe1—N10—C11—C18	−1.0 (8)	C20—N19—C14—C15	−11.1 (12)
N13—C14—C15—C16	−3.1 (10)	C20—C21—C22—N23	0.6 (9)
N13—C18—C17—C16	0.7 (11)	C7—C2—C8—N12	173.2 (6)
N23—N19—C14—N13	−5.8 (8)	C7—C2—C8—N9	−8.5 (11)
N23—N19—C14—C15	174.4 (6)	C7—C2—C3—C4	0.6 (11)
N23—N19—C20—C21	−0.4 (8)	C7—C6—C5—C4	0.5 (11)
N19—N23—C22—C21	−0.8 (8)	C7—C6—C5—C25	−177.4 (7)
N19—C14—C15—C16	176.7 (6)	C6—C5—C4—C3	0.0 (12)
N19—C20—C21—C22	−0.1 (9)	C5—C4—C3—C2	−0.6 (11)
N10—N9—C8—N12	0.9 (8)	C22—N23—N19—C14	176.5 (6)
N10—N9—C8—C2	−177.5 (6)	C22—N23—N19—C20	0.8 (8)
N10—C11—C18—N13	1.0 (8)	C24—C6—C5—C4	177.7 (7)
N10—C11—C18—C17	−179.9 (7)	C24—C6—C5—C25	−0.3 (12)
N12—C11—C18—N13	−178.9 (7)	C8—N12—C11—N10	0.4 (7)
N12—C11—C18—C17	0.2 (13)	C8—N12—C11—C18	−179.8 (7)
N9—N10—C11—N12	0.2 (8)	C8—C2—C7—C6	177.9 (6)
N9—N10—C11—C18	−179.7 (6)	C8—C2—C3—C4	−177.3 (6)
C14—N13—C18—C11	175.7 (6)	C3—C2—C7—C6	0.0 (11)
C14—N13—C18—C17	−3.6 (10)	C3—C2—C8—N12	−8.9 (11)
C14—N19—C20—C21	−175.2 (7)	C3—C2—C8—N9	169.3 (7)
C11—N10—N9—C8	−0.6 (7)	C25—C5—C4—C3	178.0 (7)
C11—N12—C8—N9	−0.8 (7)

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen bonding (Å) of the title compound top

Hydrogen bond	Length	Symmetry operation of the contact atom
C7···H—C21(pz)	2.827	1 - x, 1 - y, 1 + z
C6···H—C21(pz)	2.777	1 - x, 1 - y, 1 + z
C5···H—C21(pz)	2.756	1 - x, 1 - y, 1 + z
C4···H—C21(pz)	2.802	1 - x, 1 - y, 1 + z
C3···H—C21(pz)	2.893	1 - x, 1 - y, 1 + z
N9···H—C15(py)	2.475	1/2 + x, 1 - y, 1/2 + z
N9···H—C20(pz)	2.522	1/2 + x, 1 - y, 1/2 + z
H7···C20(pz)	2.641	1/2 + x, 1 - y, 1/2 + z
N12···H—O26	2.017	x, y, z
H17···O26	2.329	x, y, z
O26···H—C22(pz)	2.257	-1/2 + x, 1 - y, 1/2 + z

Computed distortion indices (Å, °) for the title compound and similar literature complexes top

CSD code	Spin state	<Fe—N>	Σ	Θ	CShM(O_h)
Title compound	Low-spin	1.957	92.8	295.0	2.18
XODCEB^a	Low-spin	1.950	87.4	276.6	1.92
QIDJET01^b	Low-spin	1.970	90.3	341.3	2.47
QIDJET^b	High-spin	2.184	145.5	553.3	5.88
DOMQIH^c	Low-spin	1.962	83.8	280.7	2.02
DOMQUT^c	Low-spin	1.991	88.5	320.0	2.48
DOMQUT02^c	High-spin	2.183	139.6	486.9	5.31
EJQOA^d	Low-spin	1.946	87.5	308.9	2.16
BEJQUG^d	Low-spin	1.952	97.9	309.9	2.37
BEJQUG01^d	High-spin	2.138	118.0	375.9	3.34
BEJRAN^d	Low-spin	1.946	107.7	384.5	3.20
BEJRER^d	High-spin	2.139	147.8	507.2	4.92

Notes: (a) Shiga et al. (2019); (b) Zhang et al. (2007); (c) Seredyuk et al. (2014); (d) Seredyuk et al. (2014).

Acknowledgements

Author contributions are as follows: Conceptualization, KZ and MS; methodology, KZ; formal analysis, IOF; synthesis, SOM; single-crystal measurements, SS; writing (original draft), MS; writing (review and editing of the manuscript), TYS, MS; visualization and calculations, VMA; funding acquisition, KZ, MS.

Funding information

Funding for this research was provided by a grant from the Ministry of Education and Science of Ukraine for perspective development of a scientific direction `Mathematical sciences and natural sciences' at Taras Shevchenko National University of Kyiv.

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