Crystal structure and supra­molecular features of bis­{ethyl 2-[1-methyl-3-(pyridin-2-yl)-1H-1,2,4-triazol-5-yl]acetate}­tri­nitratolanthanum(III)

Halushchenko, V.; Korovin, O.; Rusakova, N.; Dyakonenko, V.; Khomenko, D.; Lampeka, R.; Smola, S.

doi:10.1107/S2056989025005419

research communications

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ISSN: 2056-9890

Volume 81| Part 7| July 2025| Pages 632-635

https://doi.org/10.1107/S2056989025005419

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Crystal structure and supramolecular features of bis{ethyl 2-[1-methyl-3-(pyridin-2-yl)-1H-1,2,4-triazol-5-yl]acetate}trinitratolanthanum(III)

Valeriia Halushchenko,^a Oleksandr Korovin,^a Natalya Rusakova,^a Viktoriya Dyakonenko,^b,^c Dmytro Khomenko,^d,^e Rostyslav Lampeka ^d and Serhii Smola ^a ^*

^aA. V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine, 86 Lyustdorfska doroga, Odessa, Ukraine, ^bSSI "Institute for Single Crystals", National Academy of Sciences of Ukraine, Nauky ave. 60, 61001 Kharkiv, Ukraine, ^cV. I. Vernadskii Institute of General and Inorganic Chemistry, National Academy of Sciences of Ukraine, Akad. Palladin Ave 32/34, Kyiv 03142, Ukraine, ^dDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64/13, 01601 Kyiv, Ukraine, and ^eEnamine Ltd. (www.enamine.net), Winston Churchill str. 78, 02094 Kyiv, Ukraine
^*Correspondence e-mail: [email protected]

Edited by L. Suescun, Universidad de la República, Uruguay (Received 10 April 2025; accepted 17 June 2025; online 24 June 2025)

The title lanthanum(III) complex, [La(Et-MPTA)₂(NO₃)₃] {where Et-MPTA is ethyl 2-[1-methyl-3-(pyridin-2-yl)-1H-1,2,4-triazol-5-yl]acetate} or [La(C₂₄H₂₈N₈O₄)(NO₃)₃], crystallizes in the monoclinic space group C2/c (No. 15). The lanthanum atom is twelve-coordinate, bonded to two oxygen atoms from carboxylate groups, four nitrogen atoms from two pyridinyl-1,2,4-triazole ligands, and six oxygen atoms of three NO₃⁻ anions. The coordination geometry around the lanthanum atom can be described as a distorted icosahedron. Supramolecular features include π-stacking interactions between pyridyl and triazole rings and weak intermolecular N—O⋯C interactions, which lead to the formation of layers parallel to the (101) plane.

Keywords: crystal structure; lanthanum(III) complex; pyridinyl-1,2,4-triazole; intermolecular interactions.

CCDC reference: 2465028

1. Chemical context

Triazole-based compounds have wide applications in various fields such as medicine, materials science, and pharmaceuticals (Morais et al., 2022 ). The variation of the substituents on the triazole ring allows the creation of a broad range of functional materials. Ligands containing the 1,2,4-triazole fragment coordinate through nitrogen donor centers, and complexes with 1,2,4-triazole ligands may exhibit photoluminescence (Matin et al., 2022 ; Schweinfurth et al., 2017 ). Rare-earth metal complexes with nitrogen-containing ligands have garnered significant interest due to their potential applications in various fields including catalysis, luminescence, and magnetic materials (Kainat et al., 2024 ; Kaczmarek et al., 2018 ; Zeybel & Köse, 2023 ).

The pyridinyl-1,2,4-triazole derivative used in this study, namely ethyl 2-[1-methyl-3-(pyridin-2-yl)-1H-1,2,4-triazol-5-yl]acetate, is a versatile ligand that can coordinate to metal ions in different modes, leading to diverse structural motifs. The investigation of the crystal structure of the lanthanum(III) complex with this ligand provides insights into lanthanide coordination chemistry and the supramolecular interactions that consolidate the crystal structure. Understanding these structural features is crucial for designing new lanthanide-based materials with tailored properties.

2. Structural commentary

The title [La(Et-MPTA)₂(NO₃)₃] complex crystallizes in the monoclinic space group C2/c with the complex occupying a special position, at which the central lanthanum atom is located on a twofold axis. The coordination geometry around the lanthanum atom can be described as a distorted icosahedron (Fig. 1 inset), which is common for 12-coordinated Ln^III complexes (Jing et al., 1994 ; Jones et al., 1997 ; Chandrasekhar et al., 2009 ). The coordination polyhedron is formed by two oxygen atoms from the carboxylate groups, four nitrogen atoms from two pyridinyl-1,2,4-triazole of Et-MPTA ligands, and six oxygen atoms of three coordinated NO₃ anions (Fig. 1). The La—O bond lengths range from 2.648 (2) to 2.752 (2) Å, and the La—N bond lengths range from 2.735 (2) to 2.841 (2) Å (Table 1). These bond lengths are consistent with those reported for other lanthanum(III) complexes with nitrogen- and oxygen-donor ligands (Guillaumont, 2006 ; Mishra, 2008 ; Cotton et al., 2022 ). Three NO₃⁻ anions are coordinated to La^III ion via oxygen atoms in a terminal bidentate manner (de Bettencourt-Dias et al., 2012 ). One nitrate group is coordinated in a symmetric manner where the La—O6 bond length and its symmetry equivalent are both 2.648 (2) Å. Two other nitrate groups have asymmetric type of coordination with the La—O3 and La—O4 bond lengths equal to 2.658 (3) Å and 2.753 (3) Å, respectively.

Table 1
Selected bond lengths (Å)

La1—O1ⁱ	2.696 (2)	La1—O6ⁱ	2.648 (2)
La1—O1	2.696 (2)	La1—O6	2.648 (2)
La1—O3	2.658 (2)	La1—N1ⁱ	2.735 (2)
La1—O3ⁱ	2.658 (2)	La1—N1	2.735 (2)
La1—O4	2.752 (2)	La1—N4ⁱ	2.841 (2)
La1—O4ⁱ	2.752 (2)	La1—N4	2.841 (2)
Symmetry code: (i) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Figure 1
Molecular structure of the title compound. Hydrogen atoms and the disordered C11B, C12B atoms are omitted for clarity. Inset: icosahedral coordination environment around the La^III atom.

3. Supramolecular features

In the crystal, π-stacking interactions are observed between the pyridyl substituent and the triazole ring [C5⋯C7 = 3.283 (5) Å, Cg1⋯Cg2( $[{1\over 2}]$ − x, $[{3\over 2}]$ − y, 1 − z) = 3.809 (2) Å where Cg1 and Cg2 are the centroids of the N1–N3/C3/C5 and N4/C6–C10 rings, respectively] and an N6—O7⋯C1(x, −1 + y, z) weak intermolecular interaction [with an O⋯C distance of 2.913 (5) Å] is present, forming layers parallel to the ( $[\overline{1}]$ 01) plane (Fig. 2).

Figure 2
Crystal packing view of [La(Et-MPTA)₂(NO₃)₃] along the b axis.

The intermolecular interactions in the crystal structure of the title compound were analysed using the d_norm property (Fig. S1) mapped over the Hirshfeld surface (Spackman & Jayatilaka, 2009 ), which was calculated using the CrystalExplorer21 program (Spackman et al., 2021 ). The strongest contacts, which are visualized on the Hirshfeld surface are the N—O⋯C interactions. The lighter red spots correspond to π-interactions. The majority of the intermolecular interactions of the title compound are weak, and are represented in blue on the Hirshfeld surface.

For further exploration of the intermolecular interactions, two-dimensional fingerprint plots (McKinnon et al., 2007 ) were generated, as shown in Fig. S2. The major contributions to the crystal structure are from the H⋯H (39.9%) and H⋯O/O⋯H (37.9%) interactions. The H⋯C/C⋯H (6.9%), N⋯H/H⋯N (4.9%), N⋯C/C⋯N (3.5%), O⋯C/C⋯O (2.9%) and C⋯C (1.3%) interactions are less impactful in comparison.

4. Database survey

A search of the Cambridge Structural Database (CSD Version 5.46, updated November 2024; Groom et al., 2016 ) yielded twelve structures of lanthanide complexes with coordination number 12 and coordinated by three NO₃⁻ groups. Among them three structures with the La atom [refcodes AWAKER (Liu et al., 2021 ), MILWEJ (Liu et al., 2001 ), UBAMUI (Raja et al., 2016a )], six structures with the Ce atom [refcodes FOTXOC (Zhang & Liu, 2009 ), HIXWEQ (Christidis et al., 1999 ), HOZQOF (Lin et al., 2019 ), JORLIO (Nakase et al., 2018 ), USEBAX (Zhao et al., 2016 ), VAPDIC (Raja et al., 2016b )], and three structures with the Pr atom [refcodes KERPEF (Reddy et al., 2017 ), PICSON (Gueye et al., 2022 ), VIMWAR (Panayiotidou et al., 2013 )]. In the coordination polyhedrons of these structures, the Ln—O and Ln—N bond distances vary from 2.589–2.728 Å and 2.656–2.937 Å, respectively.

5. Synthesis and crystallization

Et-MPTA was synthesized according to a previously described procedure (Kharlova et al., 2019 ; Khomenko et al., 2016 ). For the synthesis of the La(Et-MPTA)₂(NO₃)₃ complex, 0.2 mmol (0.0866 g) of La(NO₃)₃·6H₂O and 0.4 mmol (0.0984 g) of the Et-MPTA ligand were dissolved separately in approximately 5 mL of methanol under heating. The methanolic solutions of La(NO₃)₃·6H₂O and the ligand were combined in a 25 mL beaker and heated for 1–2 h on a magnetic stirrer with constant non-turbulent stirring, avoiding boiling the reaction mixture. The solution was cooled to room temperature with the beaker kept open; the final volume was 6-7 mL. Over the next few hours, crystallization was observed. In order to study the structure, the crystals were used together with the mother liquor. For further analysis, the obtained crystals were separated from the solution, washed, and dried. The crystals are soluble in methanol, ethanol, and insoluble in water. IR (KBr), cm⁻¹: 3370 m, br (ν_OH stretching, adsorbed H₂O), 2963 w (ν_CH stretching, alkyl), 1740 s (ν_C=O stretching), 1605 m (ν_C=C, ν_C=N, stretching, aromatic), 1490 s (ν₄ stretching, NO₃), 1384 s (δ_C-H, scissoring CH₂), 1324 s (ν₁ stretching, NO₃), 1034 m (ν₃ stretching, NO₃), 1194 m (ν_C–O stretching, ether), 1034 w (ν_C-N stretching, ring, δ_C–H bending), 566 w (ν_La–O stretching), 434 w (ν_La–N stretching).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atoms were placed in calculated positions and refined using a riding model with U_iso(H) = nU_eq of the carrier atom (n = 1.5 for methyl groups and n = 1.2 for other hydrogen atoms). The C atoms of the ethyl group are disordered over two positions with an occupancy of 50%. Restraints were applied to the bond lengths in the disordered parts (O—C = 1.420 Å, C—C = 1.513 Å) within a standard deviation of 0.05 Å.

Table 2
Experimental details

Crystal data
Chemical formula	[La(NO₃)₃(C₁₂H₁₄N₄O₂)₂]
M_r	817.48
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	20.9094 (15), 9.0361 (5), 19.3753 (13)
β (°)	122.360 (8)
V (Å³)	3092.2 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.47
Crystal size (mm)	0.20 × 0.1 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.631, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	25399, 3551, 3079
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.062, 1.03
No. of reflections	3551
No. of parameters	244
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.84
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2019/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2465028

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025005419/oo2010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025005419/oo2010Isup2.hkl

Supporting Information Figure S1. DOI: https://doi.org/10.1107/S2056989025005419/oo2010sup4.tif

Supporting information Figure S2. DOI: https://doi.org/10.1107/S2056989025005419/oo2010sup5.tif

Supporting information file containing figures for Hirshfeld surface analysis. DOI: https://doi.org/10.1107/S2056989025005419/oo2010sup6.doc

checkCIF report

Computing details top

\ Bis{ethyl 2-[1-methyl-3-(pyridin-2-yl)-1H-1,2,4-triazol-5-yl]acetate}\ trinitratolanthanum(III) top

Crystal data top

[La(NO₃)₃(C₁₂H₁₄N₄O₂)₂]	F(000) = 1640
M_r = 817.48	D_x = 1.756 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.9094 (15) Å	Cell parameters from 6040 reflections
b = 9.0361 (5) Å	θ = 2.3–29.5°
c = 19.3753 (13) Å	µ = 1.47 mm⁻¹
β = 122.360 (8)°	T = 296 K
V = 3092.2 (4) Å³	Block, colourless
Z = 4	0.20 × 0.1 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	3079 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
φ and ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −27→27
T_min = 0.631, T_max = 0.746	k = −11→11
25399 measured reflections	l = −25→23
3551 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.062	w = 1/[σ²(F_o²) + (0.0207P)² + 5.1659P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3551 reflections	Δρ_max = 0.57 e Å⁻³
244 parameters	Δρ_min = −0.84 e Å⁻³
4 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	Occ. (<1)
La1	0.500000	0.70697 (3)	0.750000	0.02422 (8)
O1	0.49470 (11)	0.9461 (2)	0.83001 (13)	0.0342 (5)
O2	0.47068 (12)	1.1356 (3)	0.88686 (13)	0.0490 (6)
O3	0.41282 (12)	0.6737 (2)	0.81036 (13)	0.0420 (6)
O4	0.36568 (13)	0.5606 (3)	0.69543 (14)	0.0450 (6)
O5	0.30520 (15)	0.5608 (4)	0.75756 (18)	0.0757 (9)
O6	0.48997 (14)	0.4392 (2)	0.68942 (13)	0.0446 (6)
O7	0.500000	0.2329 (4)	0.750000	0.1035 (19)
N1	0.37318 (13)	0.8792 (3)	0.66653 (14)	0.0302 (6)
N2	0.30215 (14)	1.0757 (3)	0.62102 (17)	0.0396 (7)
N3	0.29540 (14)	1.0126 (3)	0.55397 (16)	0.0385 (6)
N4	0.40813 (13)	0.6946 (3)	0.57673 (14)	0.0306 (5)
N5	0.35979 (15)	0.5972 (3)	0.75405 (17)	0.0415 (7)
N6	0.500000	0.3676 (4)	0.750000	0.0504 (11)
C1	0.45126 (17)	1.0320 (3)	0.83070 (18)	0.0335 (7)
C2	0.36730 (18)	1.0331 (4)	0.7704 (2)	0.0453 (9)
H2A	0.343480	0.962493	0.787535	0.054*
H2B	0.347431	1.130488	0.769625	0.054*
C3	0.34823 (16)	0.9948 (3)	0.68711 (19)	0.0330 (7)
C4	0.2648 (2)	1.2166 (5)	0.6141 (3)	0.0697 (12)
H4A	0.300776	1.295679	0.631030	0.105*
H4B	0.244539	1.214648	0.648449	0.105*
H4C	0.224384	1.231862	0.558420	0.105*
C5	0.33897 (15)	0.8949 (3)	0.58451 (17)	0.0288 (6)
C6	0.35208 (15)	0.7916 (3)	0.53514 (17)	0.0312 (6)
C7	0.30868 (17)	0.7975 (4)	0.45033 (18)	0.0396 (7)
H7	0.269901	0.866415	0.423460	0.048*
C8	0.32411 (19)	0.6997 (4)	0.40704 (19)	0.0447 (8)
H8	0.296155	0.701751	0.350232	0.054*
C9	0.3815 (2)	0.5987 (4)	0.4488 (2)	0.0460 (9)
H9	0.392798	0.530563	0.420863	0.055*
C10	0.42195 (19)	0.6004 (4)	0.53292 (19)	0.0411 (8)
H10	0.461029	0.532385	0.560819	0.049*
C11A	0.5493 (3)	1.1248 (13)	0.9524 (5)	0.047 (3)	0.5
H11A	0.581712	1.165465	0.935363	0.057*	0.5
H11B	0.563293	1.022301	0.968023	0.057*	0.5
C11B	0.5489 (3)	1.1767 (13)	0.9403 (5)	0.053 (4)	0.5
H11C	0.554468	1.283395	0.940967	0.063*	0.5
H11D	0.579518	1.132313	0.921904	0.063*	0.5
C12A	0.5574 (5)	1.2123 (9)	1.0228 (5)	0.0440 (19)	0.5
H12A	0.541187	1.312379	1.005664	0.066*	0.5
H12B	0.609401	1.212011	1.067173	0.066*	0.5
H12C	0.526652	1.168387	1.040412	0.066*	0.5
C12B	0.5734 (5)	1.1211 (11)	1.0242 (6)	0.068 (3)	0.5
H12D	0.565756	1.016096	1.022133	0.102*	0.5
H12E	0.544112	1.168907	1.042468	0.102*	0.5
H12F	0.626122	1.142940	1.061360	0.102*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.02401 (12)	0.02188 (12)	0.02192 (12)	0.000	0.00906 (10)	0.000
O1	0.0289 (11)	0.0289 (11)	0.0396 (13)	0.0067 (9)	0.0150 (10)	0.0011 (9)
O2	0.0382 (13)	0.0619 (16)	0.0406 (14)	0.0085 (12)	0.0169 (12)	−0.0151 (12)
O3	0.0405 (13)	0.0439 (14)	0.0374 (13)	−0.0049 (10)	0.0180 (11)	−0.0037 (10)
O4	0.0427 (14)	0.0476 (15)	0.0392 (14)	−0.0067 (11)	0.0184 (12)	−0.0029 (11)
O5	0.0450 (16)	0.116 (3)	0.072 (2)	−0.0192 (16)	0.0356 (15)	0.0128 (18)
O6	0.0654 (16)	0.0292 (12)	0.0372 (13)	−0.0023 (11)	0.0261 (12)	0.0024 (10)
O7	0.228 (6)	0.024 (2)	0.098 (4)	0.000	0.113 (4)	0.000
N1	0.0252 (12)	0.0337 (14)	0.0289 (14)	0.0029 (11)	0.0126 (11)	0.0011 (11)
N2	0.0308 (14)	0.0368 (15)	0.0445 (17)	0.0100 (12)	0.0157 (13)	0.0054 (13)
N3	0.0347 (15)	0.0401 (16)	0.0342 (15)	0.0074 (12)	0.0141 (13)	0.0072 (12)
N4	0.0318 (13)	0.0277 (13)	0.0273 (12)	−0.0014 (11)	0.0126 (11)	0.0007 (11)
N5	0.0320 (15)	0.0463 (17)	0.0420 (17)	−0.0012 (13)	0.0170 (14)	0.0116 (14)
N6	0.081 (3)	0.022 (2)	0.057 (3)	0.000	0.042 (3)	0.000
C1	0.0336 (17)	0.0358 (17)	0.0283 (16)	0.0057 (14)	0.0146 (14)	0.0017 (14)
C2	0.0339 (18)	0.057 (2)	0.040 (2)	0.0081 (17)	0.0167 (16)	−0.0074 (17)
C3	0.0202 (15)	0.0351 (17)	0.0351 (18)	0.0018 (13)	0.0091 (14)	0.0015 (14)
C4	0.076 (3)	0.058 (3)	0.069 (3)	0.041 (2)	0.035 (2)	0.014 (2)
C5	0.0207 (14)	0.0300 (15)	0.0293 (16)	−0.0024 (12)	0.0092 (13)	0.0045 (13)
C6	0.0248 (14)	0.0337 (15)	0.0291 (15)	−0.0082 (14)	0.0104 (12)	0.0019 (15)
C7	0.0315 (16)	0.0482 (19)	0.0288 (16)	−0.0036 (16)	0.0092 (14)	0.0068 (16)
C8	0.0438 (19)	0.057 (2)	0.0254 (16)	−0.0148 (19)	0.0135 (15)	−0.0045 (17)
C9	0.054 (2)	0.049 (2)	0.0366 (19)	−0.0063 (18)	0.0252 (18)	−0.0093 (17)
C10	0.046 (2)	0.0388 (18)	0.0320 (18)	0.0020 (16)	0.0165 (16)	−0.0023 (15)
C11A	0.029 (5)	0.070 (9)	0.030 (5)	0.006 (4)	0.008 (4)	−0.021 (5)
C11B	0.049 (6)	0.045 (7)	0.058 (7)	−0.010 (4)	0.025 (5)	−0.011 (5)
C12A	0.050 (5)	0.045 (4)	0.038 (4)	−0.003 (4)	0.024 (4)	−0.014 (4)
C12B	0.057 (6)	0.082 (7)	0.053 (6)	−0.027 (6)	0.022 (5)	0.001 (6)

Geometric parameters (Å, º) top

La1—O1ⁱ	2.696 (2)	C1—C2	1.500 (4)
La1—O1	2.696 (2)	C2—H2A	0.9700
La1—O3	2.658 (2)	C2—H2B	0.9700
La1—O3ⁱ	2.658 (2)	C2—C3	1.482 (4)
La1—O4	2.752 (2)	C4—H4A	0.9600
La1—O4ⁱ	2.752 (2)	C4—H4B	0.9600
La1—O6ⁱ	2.648 (2)	C4—H4C	0.9600
La1—O6	2.648 (2)	C5—C6	1.464 (4)
La1—N1ⁱ	2.735 (2)	C6—C7	1.389 (4)
La1—N1	2.735 (2)	C7—H7	0.9300
La1—N4ⁱ	2.841 (2)	C7—C8	1.370 (5)
La1—N4	2.841 (2)	C8—H8	0.9300
O1—C1	1.200 (3)	C8—C9	1.375 (5)
O2—C1	1.323 (4)	C9—H9	0.9300
O2—C11A	1.446 (5)	C9—C10	1.377 (4)
O2—C11B	1.440 (5)	C10—H10	0.9300
O3—N5	1.266 (3)	C11A—H11A	0.9700
O4—N5	1.251 (3)	C11A—H11B	0.9700
O5—N5	1.224 (3)	C11A—C12A	1.506 (5)
O6—N6	1.256 (3)	C11B—H11C	0.9700
O7—N6	1.217 (5)	C11B—H11D	0.9700
N1—C3	1.321 (4)	C11B—C12B	1.505 (5)
N1—C5	1.357 (3)	C12A—H12A	0.9600
N2—N3	1.355 (4)	C12A—H12B	0.9600
N2—C3	1.335 (4)	C12A—H12C	0.9600
N2—C4	1.462 (4)	C12B—H12D	0.9600
N3—C5	1.317 (4)	C12B—H12E	0.9600
N4—C6	1.334 (4)	C12B—H12F	0.9600
N4—C10	1.339 (4)

O1—La1—O1ⁱ	73.45 (9)	C3—N2—N3	109.9 (3)
O1ⁱ—La1—O4	120.78 (6)	C3—N2—C4	129.8 (3)
O1ⁱ—La1—O4ⁱ	104.97 (7)	C5—N3—N2	102.5 (2)
O1—La1—O4	104.97 (7)	C6—N4—La1	120.53 (19)
O1—La1—O4ⁱ	120.78 (6)	C6—N4—C10	116.9 (3)
O1ⁱ—La1—N1	61.91 (7)	C10—N4—La1	122.4 (2)
O1ⁱ—La1—N1ⁱ	63.81 (7)	O4—N5—O3	117.4 (3)
O1—La1—N1ⁱ	61.91 (7)	O5—N5—O3	120.8 (3)
O1—La1—N1	63.81 (7)	O5—N5—O4	121.8 (3)
O1ⁱ—La1—N4ⁱ	120.07 (7)	O6—N6—La1	58.98 (18)
O1—La1—N4	120.07 (7)	O6ⁱ—N6—La1	58.98 (18)
O1ⁱ—La1—N4	64.01 (7)	O6ⁱ—N6—O6	118.0 (4)
O1—La1—N4ⁱ	64.01 (7)	O7—N6—La1	180.0
O3—La1—O1	65.72 (6)	O7—N6—O6	121.02 (18)
O3ⁱ—La1—O1ⁱ	65.72 (6)	O7—N6—O6ⁱ	121.02 (18)
O3ⁱ—La1—O1	126.35 (6)	O1—C1—O2	124.4 (3)
O3—La1—O1ⁱ	126.35 (6)	O1—C1—C2	124.9 (3)
O3—La1—O3ⁱ	167.00 (9)	O2—C1—C2	110.6 (3)
O3ⁱ—La1—O4	125.16 (7)	C1—C2—H2A	109.3
O3ⁱ—La1—O4ⁱ	46.80 (7)	C1—C2—H2B	109.3
O3—La1—O4	46.80 (7)	H2A—C2—H2B	108.0
O3—La1—O4ⁱ	125.16 (7)	C3—C2—C1	111.5 (3)
O3—La1—N1ⁱ	118.72 (7)	C3—C2—H2A	109.3
O3ⁱ—La1—N1ⁱ	69.40 (7)	C3—C2—H2B	109.3
O3ⁱ—La1—N1	118.72 (7)	N1—C3—N2	110.0 (3)
O3—La1—N1	69.40 (7)	N1—C3—C2	126.4 (3)
O3—La1—N4ⁱ	70.42 (7)	N2—C3—C2	123.5 (3)
O3—La1—N4	109.05 (7)	N2—C4—H4A	109.5
O3ⁱ—La1—N4ⁱ	109.05 (7)	N2—C4—H4B	109.5
O3ⁱ—La1—N4	70.41 (7)	N2—C4—H4C	109.5
O4—La1—O4ⁱ	122.58 (10)	H4A—C4—H4B	109.5
O4—La1—N4	67.77 (7)	H4A—C4—H4C	109.5
O4ⁱ—La1—N4ⁱ	67.76 (7)	H4B—C4—H4C	109.5
O4—La1—N4ⁱ	109.92 (7)	N1—C5—C6	122.2 (3)
O4ⁱ—La1—N4	109.92 (7)	N3—C5—N1	114.5 (3)
O6—La1—O1ⁱ	119.69 (7)	N3—C5—C6	123.2 (3)
O6ⁱ—La1—O1ⁱ	165.76 (6)	N4—C6—C5	115.8 (2)
O6—La1—O1	165.77 (6)	N4—C6—C7	123.1 (3)
O6ⁱ—La1—O1	119.70 (7)	C7—C6—C5	121.1 (3)
O6—La1—O3	100.45 (7)	C6—C7—H7	120.6
O6ⁱ—La1—O3ⁱ	100.45 (7)	C8—C7—C6	118.7 (3)
O6ⁱ—La1—O3	67.16 (7)	C8—C7—H7	120.6
O6—La1—O3ⁱ	67.16 (7)	C7—C8—H8	120.5
O6—La1—O4	64.43 (7)	C7—C8—C9	119.0 (3)
O6—La1—O4ⁱ	63.50 (7)	C9—C8—H8	120.5
O6ⁱ—La1—O4	63.50 (7)	C8—C9—H9	120.7
O6ⁱ—La1—O4ⁱ	64.43 (7)	C8—C9—C10	118.6 (3)
O6ⁱ—La1—O6	47.95 (9)	C10—C9—H9	120.7
O6ⁱ—La1—N1	127.14 (7)	N4—C10—C9	123.6 (3)
O6—La1—N1	115.86 (7)	N4—C10—H10	118.2
O6ⁱ—La1—N1ⁱ	115.86 (7)	C9—C10—H10	118.2
O6—La1—N1ⁱ	127.14 (7)	O2—C11A—H11A	110.4
O6ⁱ—La1—N4	109.33 (7)	O2—C11A—H11B	110.4
O6ⁱ—La1—N4ⁱ	66.26 (7)	O2—C11A—C12A	106.5 (6)
O6—La1—N4	66.25 (7)	H11A—C11A—H11B	108.6
O6—La1—N4ⁱ	109.33 (7)	C12A—C11A—H11A	110.4
N1—La1—O4ⁱ	165.39 (7)	C12A—C11A—H11B	110.4
N1ⁱ—La1—O4ⁱ	65.10 (7)	O2—C11B—H11C	110.4
N1—La1—O4	65.11 (7)	O2—C11B—H11D	110.4
N1ⁱ—La1—O4	165.39 (7)	O2—C11B—C12B	106.8 (7)
N1—La1—N1ⁱ	110.63 (10)	H11C—C11B—H11D	108.6
N1ⁱ—La1—N4	123.34 (7)	C12B—C11B—H11C	110.4
N1—La1—N4ⁱ	123.34 (7)	C12B—C11B—H11D	110.4
N1—La1—N4	59.67 (7)	C11A—C12A—H12A	109.5
N1ⁱ—La1—N4ⁱ	59.67 (7)	C11A—C12A—H12B	109.5
N4—La1—N4ⁱ	175.51 (10)	C11A—C12A—H12C	109.5
C1—O1—La1	142.1 (2)	H12A—C12A—H12B	109.5
C1—O2—C11A	112.3 (4)	H12A—C12A—H12C	109.5
C1—O2—C11B	120.3 (6)	H12B—C12A—H12C	109.5
N5—O3—La1	99.98 (17)	C11B—C12B—H12D	109.5
N5—O4—La1	95.78 (17)	C11B—C12B—H12E	109.5
N6—O6—La1	97.0 (2)	C11B—C12B—H12F	109.5
C3—N1—La1	133.32 (19)	H12D—C12B—H12E	109.5
C3—N1—C5	103.0 (2)	H12D—C12B—H12F	109.5
C5—N1—La1	119.27 (18)	H12E—C12B—H12F	109.5
N3—N2—C4	120.2 (3)

La1—O1—C1—O2	174.4 (2)	N4—C6—C7—C8	−0.3 (5)
La1—O1—C1—C2	−2.8 (5)	C1—O2—C11A—C12A	−162.2 (7)
La1—O3—N5—O4	2.3 (3)	C1—O2—C11B—C12B	−110.0 (8)
La1—O3—N5—O5	−177.9 (3)	C1—C2—C3—N1	50.7 (4)
La1—O4—N5—O3	−2.2 (3)	C1—C2—C3—N2	−129.2 (3)
La1—O4—N5—O5	178.0 (3)	C3—N1—C5—N3	0.4 (3)
La1—O6—N6—O6ⁱ	−0.003 (3)	C3—N1—C5—C6	178.3 (3)
La1—O6—N6—O7	180.000 (2)	C3—N2—N3—C5	−0.1 (3)
La1—N1—C3—N2	154.6 (2)	C4—N2—N3—C5	176.8 (3)
La1—N1—C3—C2	−25.3 (5)	C4—N2—C3—N1	−176.1 (3)
La1—N1—C5—N3	−159.02 (19)	C4—N2—C3—C2	3.8 (5)
La1—N1—C5—C6	18.9 (3)	C5—N1—C3—N2	−0.5 (3)
La1—N4—C6—C5	−3.8 (3)	C5—N1—C3—C2	179.6 (3)
La1—N4—C6—C7	175.5 (2)	C5—C6—C7—C8	178.9 (3)
La1—N4—C10—C9	−175.5 (3)	C6—N4—C10—C9	−0.4 (5)
O1—C1—C2—C3	−37.0 (5)	C6—C7—C8—C9	0.5 (5)
O2—C1—C2—C3	145.4 (3)	C7—C8—C9—C10	−0.6 (5)
N1—C5—C6—N4	−9.9 (4)	C8—C9—C10—N4	0.6 (5)
N1—C5—C6—C7	170.8 (3)	C10—N4—C6—C5	−179.0 (3)
N2—N3—C5—N1	−0.2 (3)	C10—N4—C6—C7	0.2 (4)
N2—N3—C5—C6	−178.1 (3)	C11A—O2—C1—O1	−5.7 (7)
N3—N2—C3—N1	0.4 (3)	C11A—O2—C1—C2	171.9 (6)
N3—N2—C3—C2	−179.7 (3)	C11B—O2—C1—O1	15.8 (6)
N3—C5—C6—N4	167.8 (3)	C11B—O2—C1—C2	−166.6 (5)
N3—C5—C6—C7	−11.4 (4)

Symmetry code: (i) −x+1, y, −z+3/2.

Acknowledgements

The authors are grateful to the National Academy of Sciences of Ukraine for funding the research (project 0125U000387) and the Center for collective use of scientific equipment "Single-crystal diffractometric system SMART APEX II CCD" of the V. I. Vernadsky Institute of General and Inorganic Chemistry of the National Academy of Sciences of Ukraine.

Funding information

Funding for this research was provided by: National Academy of Sciences of Ukraine (grant No. 0125U000387).

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