Synthesis, characterization and structural analysis of com­plexes from 2,2′:6′,2′′-terpyridine derivatives with transition metals

Fajardo, D.A.; Arteaga, D.; Ellena, J.; Santiago, P.H.O.; D'Vries, R.F.; Lenis, L.A.

doi:10.1107/S2053229624004224

crystallography in latin america

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 80| Part 6| June 2024| Pages 200-211

https://doi.org/10.1107/S2053229624004224

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Synthesis, characterization and structural analysis of complexes from 2,2′:6′,2′′-terpyridine derivatives with transition metals

Daniel A. Fajardo,^a Danny Arteaga,^a Javier Ellena,^b Pedro H. O. Santiago,^b Richard F. D'Vries ^a ^* and Luis Alberto Lenis ^a ^*

^aGrupo de Investigación Química de Productos Naturales (QPN), Facultad de Ciencias Naturales, Exactas y de la educación, Universidad del Cauca, Popayán 19003, Colombia, and ^bSão Carlos Institute of Physics, University of São Paulo, CEP 13.566-590, São Carlos, SP, Brazil
^*Correspondence e-mail: richard.dvries@unicauca.edu.co, albertolenis@unicauca.edu.co

Edited by M. Rosales-Hoz, Cinvestav, Mexico (Received 6 February 2024; accepted 7 May 2024; online 16 May 2024)

The synthesis and structural characterization of three families of coordination complexes synthesized from 4′-phenyl-2,2′:6′,2′′-terpyridine (8, Ph-TPY), 4′-(4-chlorophenyl)-2,2′:6′,2′′-terpyridine (9, ClPh-TPY) and 4′-(4-methoxyphenyl)-2,2′:6′,2′′-terpyridine (10, MeOPh-TPY) ligands with the divalent metals Co²⁺, Fe²⁺, Mn²⁺ and Ni²⁺ are reported. The compounds were synthesized from a 1:2 mixture of the metal and ligand, resulting in a series of complexes with the general formula [M(R-TPY)₂](ClO₄)₂ (where M = Co²⁺, Fe²⁺, Mn²⁺ and Ni²⁺, and R-TPY = Ph-TPY, ClPh-TPY and MeOPh-TPY). The general formula and structural and supramolecular features were determinated by single-crystal X-ray diffraction for bis(4′-phenyl-2,2′:6′,2′′-terpyridine)nickel(II) bis(perchlorate), [Ni(C₂₁H₁₅N₃)₂](ClO₄)₂ or [Ni(Ph-TPY)₂](ClO₄)₂, bis[4′-(4-methoxyphenyl)-2,2′:6′,2′′-terpyridine]manganese(II) bis(perchlorate), [Mn(C₂₂H₁₇N₃O)₂](ClO₄)₂ or [Mn(MeOPh-TPY)₂](ClO₄)₂, and bis(4′-phenyl-2,2′:6′,2′′-terpyridine)manganese(II) bis(perchlorate), [Mn(C₂₁H₁₅N₃)₂](ClO₄)₂ or [Mn(Ph-TPY)₂](ClO₄)₂. In all three cases, the complexes present distorted octahedral coordination polyhedra and the crystal packing is determined mainly by weak C—H⋯π interactions. All the compounds (except for the Ni derivatives, for which FT–IR, UV–Vis and thermal analysis are reported) were fully characterized by spectroscopic (FT–IR, UV–Vis and NMR spectroscopy) and thermal (TGA–DSC, thermogravimetric analysis–differential scanning calorimetry) methods.

Keywords: crystal structure; terpyridine; chelate complex; supramolecular analysis; pincer ligand; coordination chemistry.

CCDC references: 2331329; 2331330; 2331331

1. Introduction

Terpyridine derivatives, e.g. 2,2′:6′,2′′-terpyridines (2-TPY), have been the most important and recognized nitrogenous compounds since their discovery (Castro Agudelo et al., 2012 ; Morgan & Burstall, 1932 ) and have been of great interest in different areas of chemistry research, mainly in coordination chemistry, materials science and metal-based drug development (Panicker & Sivaramakrishna, 2022 ; Luo et al., 2007 ; Musiol et al., 2022 ; Gil-Moles & Concepción Gimeno, 2024 ). From the family of nitrogen-based ligands, terpyridines and their derivatives have been widely used as precursors for the synthesis of several transition-metal complexes with exciting chemical and physical properties (Winter & Schubert, 2020 ; Fu et al., 2023 ). The ability of TPY to chelate a variety of metal ions has turned it and its derivatives into valuable ligands for the synthesis of complexes with a variety of architectures, which allows them to display a range of important properties. They can be of value in the synthesis of compounds with photophysical and electrochemical properties, broad absorption spectrum and long excited-state lifetimes, characteristics which are of potential value in different applications (Kohle et al., 1997 ; Nazeeruddin et al., 1999 ; Romain et al., 2009 ; Momeni et al., 2024 ). Among the most important structural properties are the structural flexibility, tridentate planar–torsional shape and the high electronic conjugation of the three pyridine rings (Gibson & Spitzmesser, 2003 ), which makes them very interesting ligands for the construction of new materials (Liu et al., 2020 ). The appropriate spatial distribution of the three N atoms allows 2-TPY to act as a tridentate pincer ligand with the ability to coordinate with a wide range of metals (Husson & Knorr, 2012 ; Abhijnakrishna et al., 2023 ).

For these reasons, the synthesis of such nitrogen-based ligands has been widely studied and Kröhnke-type reaction methods are the most used (Sasaki, 2016 ; Tu et al., 2005 , 2007 ; Zych et al., 2017 ; Fajardo Perafan et al., 2023 ). Because the 2-TPY ligand has an excellent ability to form chelate-like coordination complexes, of the type [M(R-TPY)₂]X₂, with high stability, the synthesis of these complexes is straightforward to achieve. The complexes are generally synthesized by refluxing the metal salt and the ligand in a 1:2 ratio. Due to the size of the complex formed, it is necessary to exchange the anion (X = SO₄²⁻, PF₆⁻ and ClO₄⁻) to stabilize the charge of the complex cation formed and to enhance the formation of crystalline solids (Indumathy et al., 2007 ). The considerable thermal and chemical stability of these complexes (Jantunen et al., 2006 ) is associated with the strong retrodonation from the metal centre to the ligand (d–π*), as well as with the chelating effect (Schubert et al., 2006 ). The importance of obtaining these coordination complexes lies in their excellent chemical and physical properties that give them great biological applicability and high potential in medicinal chemistry (Clarke, 2003 ; Zou et al., 2016 ; Gil-Moles & Concepción Gimeno, 2024), ion sensors (Fermi et al., 2014 ), materials science (Saccone et al., 2016 ), supramolecular polymers (Zheng et al., 2014 ), coordination polymer (CP) synthesis (Momeni & Heydari, 2015 ; Young et al., 2017 ; Elahi et al., 2021 ), catalysis (Husson & Guyard, 2018 ; Liu et al., 2022 ), optics (Tan et al., 2015 ; Zhang et al., 2017 ) and the electronics field (Ozawa et al., 2015 ; Zych et al., 2017; Laschuk et al., 2020 ), all influenced by the electronic nature of the terpyridine ligands used (Aroua et al., 2017 ). Based on the above considerations, in the present investigation, we report the synthesis, spectroscopic, thermal and structural characterization of 12 transition-metal coordination complexes with the general formula [M(R-TPY)₂](ClO₄)₂. The three families of coordination complexes were obtained with good reaction yields from three 4-substituted terpyridine ligands (R-TPY = Ph-TPY, ClPh-TPY and MeOPh-TPY) and four divalent metal cations (M = Co²⁺, Fe²⁺, Mn²⁺ and Ni²⁺), using the perchlorate anion (ClO⁴⁻) as the counter-ion. On this occasion, it was possible to determine and study the structures and crystal packing of [Ni(Ph-TPY)₂](ClO₄)₂ (15d), [Mn(MeOPh-TPY)₂](ClO₄)₂ (17c) and [Mn(Ph-TPY)₂](ClO₄)₂ (15c) from single-crystal X-ray diffraction data.

2. Experimental

2.1. Materials and methods

All reagents and solvents for the synthesis were purchased from Sigma–Aldrich and were used as received without further purification. For all air-sensitive reactions, the synthetic procedures were conducted under an N₂ atmosphere, and the solvents employed were dried according to standard procedures. FT–IR spectra (KBr) were recorded using a Thermo Nicolet iS10 spectrophotometer. ¹H NMR (400 MHz) and ¹³C NMR (100 MHz) spectra were obtained on a Bruker Ultra Shield Avance II spectrometer at room temperature (298 K) using deuterated solvents, such as dimethyl sulfoxide (DMSO). The chemical shift values (δ) are reported in parts per million (ppm). Multiplicities are denoted as: s (singlet), d (doublet), t (triplet), q (quartet), dd (doublet of doublets) and m (multiplet). The UV–Vis measurements were recorded on a Thermo Genesys 6 spectrophotometer with diluted solutions prepared with anhydrous acetonitrile (ACN). Thermal analysis (TGA–DSC) was performed in a TA instrument (Discovery SDT 650) under the following conditions: temperature range 25–900 °C, nitrogen atmosphere (100 ml min⁻¹ flow) and heating rate 20 °C min⁻¹.

2.2. Synthesis

2.2.1. Synthesis of the R-TPY ligands

The R-TPY ligands were obtained following a Kröhnke-type reaction with some synthetic modification as reported by us in previous work (Fajardo Perafan et al., 2023). To a 100 ml round-bottomed flask containing 20 ml of EtOH were added 0.3961 g (6 mmol) of KOH and the resulting mixture stirred until complete dissolution was achieved. To this solution were added slowly 450 µl (4 mmol) of 2-acetylpyridine and the appropriate aromatic aldehyde (2 mmol). The resulting solution was stirred at room temperature for 2 h. After this time, an excess of 30% NH₄OH (aq, 5 ml) was added slowly to the mixture, which was stirred for 5 min at room temperature. The flask was connected to a reflux system within microwave irradiation equipment for synthesis and irradiated continuously for 12 min at 70 W with a non-variable temperature (50 °C). The reaction progress was followed by thin-layer chromatography (TLC). The reaction mixture was cooled to room temperature and quenched with cold deionized water (50 ml). The precipitate which formed was collected by vacuum filtration and washed several times with EtOH/H₂O. The solid was allowed to dry overnight at 70 °C and was then purified by recrystallization from EtOH. TLC was carried out using a mobile phase of an isobutyl alcohol–acetone–chloroform mixture (4:3:3 v/v/v) with the addition of two drops of dilute acetic acid.

Ph-TPY: yield: 68.97 ± 0.09%; m.p. 200.3–202.0 °C. FT–IR (KBr pellet, cm⁻¹): 3051.88, 2000.00–1700.00, 1600.75–1439.15, 146.17, 1392.42, 761.48. UV–Vis (ACN acidified, 200.0–800.0 nm): 277.5, 311.5. ¹H NMR (400 MHz, CDCl₃): δ 8.802 (s, 2H, H3′,5′), 8.771 (d, 2H, H3,3′′), 8.72 (d, 2H, H6,6′′), 7.959–7.910 (m, 4H, H4,4′′, HII,VI), 7.556–7.456 (m, 3H, HIII,IV,V), 7.395 (dd, 2H, H5,5′′). ¹³C NMR (100 MHz, CDCl₃): δ 155.88 (C2′,6′), 155.55 (C2,2′′), 150.47 (C4′), 148.78 (C6,6′′), 138.31 (CI), 137.32 (C4,4′′), 129.11 (CII,VI), 127.39 (CIII,IV,V), 123.94, (C5,5′′), 121.6 (C3,3′′), 119.2 (C3′,5′). MS (solid probe, EI): 309.10.

ClPh-TPY: yield: 57.26 ± 0.08%; m.p. 168.0–171.9 °C. FT–IR (KBr pellet, cm⁻¹): 3061.44, 3016.84, 2000.00–1700.00, 1606.03–1443.86, 1496.04, 1384.90, 1091.29, 786.47. UV–Vis (ACN acidified, 200.0–800.0 nm): 278.0, 311.0. ¹H NMR (400 MHz, CDCl₃): δ 8.753–8.744 (m, 4H, H3,3′,5′,3′′), 8.697 (d, 2H, H6,6′′), 7.939–7.859 (m, 4H, H4,4′′, HII,VI), 7.495 (d, 2H, HIII,V), 7.390 (dd, 2H, H5,5′′). ¹³C NMR (100 MHz, CDCl₃): δ 156.24 (C2′,6′), 155.74 (C2,2′′), 149.24 (C4′), 148.81 (C6,6′′), 137.4 (C4,4′′), 136.82 (CI), 135.3 (CIV), 129.23 (CII,VI), 128.65 (CIII,V), 123.96 (C5,5′′), 121.65 (C3,3′′), 118.83 (C3′,5′). MS (solid probe, EI): 343.25.

MeOPh-TPY: yield: 48.91 ± 0.08%; m.p. 167.1–168.9 °C. FT–IR (KBr pellet, cm⁻¹): 3050.59, 3013.18, 2963.42, 2935.19, 2841.78, 2000.00–1700.00, 1600.67–1438.82, 1467.72, 1391.55, 1265.04, 1040.60, 1187.15, 833.18, 790.65. UV–Vis (ACN acidified, 200.0–800.0 nm): 290.0, 315.0. ¹H NMR (400 MHz, CDCl₃): δ 8.795–8.76, (m, 4H, H3,3′,5′,3′′), 8.71 (d, 2H, H6,6′′), 7.940–7.913 (m, 4H, H4,4′′,II,VI), 7.396 (d, 2H, HIII,V), 7.055 (dd, 2H, H5,5′′), 3.90 (s, 3H, OCH₃). ¹³C NMR (100 MHz, CDCl₃): δ 160.57 (CIV), 156.15 (C2′,6′), 155.59 (C2,2′′), 149.81 (C4′), 148.88 (C6,6′′), 137.08 (C4,4′′), 130.63 (CI), 128.55 (CII,VI), 123.81 (C5,5′′), 121.48 (C3,3′′), 118.41 (C3′,5′), 114.35 (CIII,V), 55.38 (OCH₃). MS (solid probe, EI): 339.20.

2.2.2. Synthesis of [M(R-TPY)](ClO₄)₂

All the obtained compounds were synthesized following the same procedure: 2 mmol of R-TPY (R = Ph, –PhCl or –PhOMe) were added to 20 ml of hot MetOH until complete dissolution was achieved. 1 mmol of MCl₂ (M = Co²⁺, Fe²⁺, Mn²⁺ or Ni²⁺) was dissolved in 10 ml of deionized water. Both solutions are mixed in a 50 ml round-bottomed flask under constant stirring and refluxed for 2 h. After cooling, 10 ml of a 0.5 M aqueous NaClO₄ solution was added slowly with caution (CAUTION: perchlorate salts are considered toxic substances and sensitive explosives) and stirred for 30 min. The reaction mixture was cooled in ice and a solid precipitate formed which was filtered off under vacuum and washed with cold methanol. The solid obtained was dried overnight at 60 °C and purified by recrystallization from MetOH–ACN (2:1 v/v).

2.2.3. Coordination complex series A (15a–d)

[Co(Ph-TPY)₂](ClO₄)₂: yield: 90.41%. FT–IR (KBr pellet, cm⁻¹): 3060.98, 1615.94–1548.05, 1471.45, 1384.46, 1089.19, 764.90, 623.53, 473.53. UV–Vis (ACN, nm): 287.5, 325.0, 520.0. Solid colour: red. ¹H NMR (400 MHz, DMSO): δ 9.822 (s, 2H, H3′,5′), 9.226 (d, 2H, H3,3′′), 8.583 (d, 2H, H6,6′′), 7.595 (dd, 2H, H4,4′′), 7.661 (d, 2H, HII,VI), 7.270 (m, 3H, HIII,IV,V), 7.000 (dd, 2H, H5,5′′).

[Fe(Ph-TPY)₂](ClO₄)₂: yield: 88.58%. FT–IR (KBr pellet, cm⁻¹): 3063.84, 1616.66, 1467.58, 1384.23, 1121.02–1106.53, 765.88, 623.94, 479.18. UV–Vis (ACN, nm): 287.0, 324.0, 568.0. Solid colour: purple. ¹H NMR (400 MHz, DMSO): δ 9.688 (s, 2H, H3′,5′), 9.090 (d, 2H, H3,3′′), 8.572 (d, 2H, H6,6′′), 8.043 (dd, 2H, H4,4′′), 7.836 (dd, 2H, HII,VI), 7.312 (d, 2H, HIII,V), 7.212 (dd, 3H, IV), 7.043 (dd, 2H, H5,5′′). ¹³C NMR (100 MHz, DMSO): 163.23 (C2′6′), 159.89 (C2,2′′), 157.86 (C4′), 152.78 (C6,6′′), 142.23 (CI), 141.48 (CIV), 138.73 (C4,4′′), 130.72 (CII,VI), 129.47 (CIII, V), 127.63 (C5,5′′), 124.09 (C3,3′′), 120.86 (C3′,5′).

[Mn(Ph-TPY)₂](ClO₄)₂: yield: 80.45%. FT–IR (KBr pellet, cm⁻¹): 3060.70, 1614.39–1548.45, 1475.65, 1384.57, 1087.43, 767.45, 622.75, 477.13. UV–Vis (ACN, 200.0–800.0 nm): 289.5, 329.0. Solid colour: yellow. ¹H NMR (400 MHz, DMSO): δ 8.630 (s, 2H, H3′,5′), 8.335 (d, 2H, H3,3′′), 7.935 (d, 2H, H6,6′′), 7.466 (m, 4H, H4,4′′,II,VI), 7.130 (d, 2H, HIII,V), 6.091 (dd, 2H, HIV), 6.697 (dd, 2H, H5,5′′).

[Ni(Ph-TPY)₂](ClO₄)₂: yield: 57.78%. FT–IR (KBr pellet, cm⁻¹): 3061.40, 1615.17–1554.62, 1473.55, 1384.43, 1089.23, 765.47, 624.21, 470.65 cm⁻¹. UV–Vis (ACN, nm): 287.5, 328.0. Solid colour: green.

2.2.4. Coordination complex series B (16a–d)

[Co(ClPh-TPY)₂](ClO₄)₂: yield: 68.78%. FT–IR (KBr pellet, cm⁻¹): 3055.94, 1615.96–1547.88, 1492.49, 1384.53, 1089.63, 791.37, 620.20, 479.18. UV–Vis (ACN, 200.0–800.0 nm): 287.0, 324.0, 520.5. Solid colour: red. ¹H NMR (400 MHz, DMSO): δ 10.400 (s, 2H, H3′,5′), 8.742 (d, 2H, H3,3′′), 8.420 (d, 2H, H6,6′′), 7.630 (dd, 2H, H4,4′′), 7.543 (d, 2H, HII,VI), 7.250 (d, 2H, HIII,V), 6.940 (dd, 2H, H5,5′′). ¹³C NMR (100 MHz, DMSO): δ 163.10 (C2′6′), 154.00 (C2,2′′), 153.46 (C4′), 147.30 (C6,6′′), 141.15 (CI), 140.62 (CIV), 136.64 (C4,4′′), 129.49 (CII,VI), 127.58 (CIII, V), 121.82 (C5,5′′), 120.89 (C3,3′′), 120.26 (C3′,5′).

[Fe(ClPh-TPY)₂](ClO₄)₂: yield: 71.37%. FT–IR (KBr pellet, cm⁻¹): 3055.95, 1615.96, 1492.26, 1384.51, 1087.82, 790.28, 621.86, 481.42. UV–Vis (ACN, nm): 287.0, 326.0, 568.0. Solid colour: purple. ¹H NMR (400 MHz, DMSO): δ 9.703 (s, 2H, H3′,5′), 8.617 (d, 2H, H3,3′′), 8.431 (d, 2H, H6,6′′), 7.637 (dd, 2H, H4,4′′), 7.544 (d, 2H, HII,VI), 7.265 (d, 2H, HIII,V), 6.941 (dd, 2H, H5,5′′). ¹³C NMR (100 MHz, DMSO): δ 163.11 (C2′6′), 159.96 (C2,2′′), 157.78 (C4′), 152.81 (C6,6′′), 141.16 (CI), 140.64 (CIV), 136.65 (C4,4′′), 129.50 (CII,VI), 127.59 (CIII, V), 121.83 (C5,5′′), 120.95 (C3,3′′), 120.27 (C3′,5′).

[Mn(ClPh-TPY)₂](ClO₄)₂: yield: 64.26%. FT–IR (KBr pellet, cm⁻¹): 3072.21, 1614.87–1546.09, 1476.35, 1384.50, 1090.59, 791.47, 622.45, 508.91. UV–Vis (ACN, nm): 290.0, 330.0. Solid colour: yellow. ¹H NMR (400 MHz, DMSO): δ 8.693 (s, 2H, H3′,5′), 8.635 (d, 2H, H3,3′′), 8.375 (d, 2H, H6,6′′), 7.981 (dd, 2H, H4,4′′), 7.584 (d, 2H, HII,VI), 7.204 (d, 2H, HIII,V), 6.840 (dd, 2H, H5,5′′).

[Ni(ClPh-TPY)₂](ClO₄)₂: yield: 64.98%. FT–IR (KBr pellet, cm⁻¹): 3072.56, 1614.12–1550.62, 1473.57, 1384.53, 1090.59, 792.26, 622.80, 505.93. UV–Vis (ACN, nm): 289.0, 326.0. Solid colour: green.

2.2.5. Coordination complex series C (17a–d)

[Co(MeOPh-TPY)₂](ClO₄)₂: yield: 72.81%. FT–IR (KBr pellet, cm⁻¹): 3073.62, 2931.48, 2840.23, 1601.74–1530.34, 1470.96, 1384.34, 1244.15, 1185.33, 1089.07, 832.42, 793.07, 622.92, 522.14. UV–Vis (ACN, nm): 284.5, 330.0, 522.0. Solid colour: red. ¹H NMR (400 MHz, DMSO): δ 9.752 (s, 2H, H3′,5′), 9.203 (d, 2H, H3,3′′), 8.614 (d, 2H, H6,6′′), 7.512 (dd, 2H, H4,4′′), 7.649 (d, 2H, HII,VI), 7.442 (d, 2H, HIII,V), 7.100 (dd, 2H, H5,5′′), 4.013 (s, 3H, OCH₃).

[Fe(MeOPh-TPY)₂](ClO₄)₂: yield: 88.36%. FT–IR (KBr pellet, cm⁻¹): 3073.09, 2934.42, 2843.17, 1603.13–1518.22, 1467.77, 1384.53, 1244.89, 1184.84, 1088.69, 831.57, 791.42, 623.09, 514.11. UV–Vis (ACN, nm): 285.0, 326.5, 570.0. Solid colour: purple. ¹H NMR (400 MHz, DMSO): δ 9.630 (s, 2H, H3′,5′), 9.069 (d, 2H, H3,3′′), 8.678 (d, 2H, H6,6′′), 7.528 (dd, 2H, H4,4′′), 7.378 (d, 2H, HII,VI), 7.280 (d, 2H, HIII,V), 7.169 (dd, 2H, H5,5′′), 3.851 (s, 3H, OCH₃). ¹³C NMR (100 MHz, DMSO): δ 161.47 (CIV), 160.45 (C2′6′), 157.98 (C2,2′′), 155.04 (C4′), 152.77 (C6,6′′), 138.63 (C4,4′′), 129.55 (CII,VI), 127.98 (CI), 123.96 (C5,5′′), 120.25 (C3,3′′), 117.28 (C3′,5′), 114.80 (CIII, V), 55.61 (OCH₃).

[Mn(MeOPh-TPY)₂](ClO₄)₂: yield: 92.08%. FT–IR (KBr pellet, cm⁻¹): 3058.05, 2937.37, 2837.29, 1601.50–1519.26, 1476.33, 1384.34, 1245.26, 1185.59, 1090.53, 832.71, 794.36, 622.99, 514.80. UV–Vis (ACN, nm): 288.0, 344.0. Solid colour: yellow. ¹H NMR (400 MHz, DMSO): δ 8.622 (m, 6H, H3′,5′,3,3′′,6,6′′), 7.862 (m, 2H, H4,4′′,II,VI), 7.458 (d, 2H, HIII,IV), 7.084 (dd, 2H, H5,5′′), 3.794 (s, 3H, OCH₃).

[Ni(MeOPh-TPY)₂](ClO₄)₂: yield: 81.02%. FT–IR (KBr pellet, cm⁻¹): 3072.77, 2937.37, 2837.29, 1602.82–1519.47, 1473.73, 1384.40, 1243.43, 1183.89, 1091.29, 831.89, 792.66, 622.84, 522.95. UV–Vis (ACN, nm): 282.5, 344.0. Solid colour: green.

2.3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. In all cases, non-H atoms were clearly resolved and full-matrix least-squares refinement with anisotropic displacement parameters was performed. In addition, the H atoms were stereochemically positioned and refined using the riding model. Mn compound 15c was refined using the SQUEEZE routine (Spek, 2015 ) in PLATON (Spek, 2020 ) to decrease the contribution of the disordered solvent (water molecule) in order to calculate the structure factors and improve the refinement values.

Table 1
Experimental details

Experiments were carried out at 100 K with Mo Kα radiation using a Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector. The absorption correction was Gaussian (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ). H-atom parameters were constrained.

	[Ni(Ph-TPY)₂](ClO₄)₂ (15d)	[Mn(MeOPh-TPY)₂](ClO₄)₂ (17c)	[Mn(Ph-TPY)₂](ClO₄)₂ (15c)
Crystal data
Chemical formula	[Ni(C₂₁H₁₅N₃)₂](ClO₄)₂	[Mn(C₂₂H₁₇N₃O)₂](ClO₄)₂	[Mn(C₂₁H₁₅N₃)₂](ClO₄)₂
M_r	876.33	932.61	872.56
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/c
a, b, c (Å)	9.3581 (2), 12.6255 (3), 31.4046 (8)	8.93282 (10), 12.32698 (13), 18.86081 (19)	9.51026 (18), 12.5149 (2), 31.2962 (6)
α, β, γ (°)	90, 97.038 (2), 90	89.8757 (8), 85.6122 (8), 83.5667 (9)	90, 96.8780 (18), 90
V (Å³)	3682.52 (15)	2057.68 (4)	3698.07 (12)
Z	4	2	4
μ (mm⁻¹)	0.74	0.52	0.57
Crystal size (mm)	0.10 × 0.08 × 0.06	0.15 × 0.10 × 0.08	0.30 × 0.11 × 0.03

Data collection
T_min, T_max	0.815, 1.000	0.662, 1.000	?, ?
No. of measured, independent and observed [I > 2σ(I)] reflections	52589, 9514, 7295	57826, 10630, 9347	63288, 9547, 8250
R_int	0.053	0.029	0.032
(sin θ/λ)_max (Å⁻¹)	0.676	0.676	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.094, 1.02	0.031, 0.083, 1.07	0.031, 0.084, 1.04
No. of reflections	9514	10630	9547
No. of parameters	560	570	560
No. of restraints	435	0	3
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.54	0.49, −0.42	0.43, −0.51
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ), SHELXT (Sheldrick, 2015a ), OLEX2 (Dolomanov et al., 2009 ), SHELXL2016 (Sheldrick, 2015b ), DIAMOND (Brandenburg et al., 2006 ), Mercury (Macrae et al., 2020 ) and PLATON (Spek, 2020).

3. Results and discussion

3.1. Synthesis

The synthetic approach to prepare the metal coordination complexes 15a–d, 16a–d and 17a–d was performed according to known synthetic procedures (see Fig. 1). The initial step was the preparation of organic terpyridine ligands 8–10 from 2-acetylpyridine and aromatic 4-substituted aldehydes following Kröhnke-type reaction methods (Wang & Hanan, 2005 ; Fajardo Perafan et al., 2023). These ligands are notable for the type of aromatic ring substituent: neutral (–H), electron-attracting (–Cl) and electron-donating (–OMe). The electronic properties of these substituents may be a key factor in the formation of the complexes, as will be discussed below (although the size of the cation may also have some influence). The experimental details of this synthesis were listed in the Experimental section, as well as in the supporting information (Scheme S1).

Figure 1
Synthesis route for the preparation of metal coordination complexes 15a–d, 16a–d and 17a–d.

The synthesis route for complexes 15a–d, 16a–d and 17a–d was by direct reaction between 2 molar equivalents of the terpyridine derivative (8, 9 or 10) and one molar equivalent of the metal salt (11, 12, 13 or 14) in methanol (MeOH) as reaction medium (Indumathy et al., 2007). Upon mixing the dissolved ligand with the metal salt solution, there was a noticeable change in the colouration of the mixture, i.e. red for complexes 15–17a, violet for 15–17b, yellow for 15–17c and green for 15–17d. At this point, the complexes formed in solution are [M(R-TPY)₂]Cl₂. To isolate them as crystalline solids, it was necessary to add sodium perchlorate (NaClO₄) in order to carry out an exchange of counter-ion, because ClO₄⁻ is a bulkier ion that favours the formation of crystalline packing. Thus, all the complexes formed were isolated as perchlorate salts, which importantly retain the colourations of the solutions from which they came. Additionally, from the reaction yield values of the obtained complexes, the influence of the substituent of each ligand on this value is highlighted. The complexes with the –OMe substituent (17a–d) were obtained in higher yield than those with the –Cl substituent (16a–d). This can be attributed to the first substituent being an electron donor, which generates a more negative electronic environment on the ligand and favours coordination. In contrast, the second substituent is an electron attractor, so, in this case, the ligand will have a more positive electron density, which translates into a lower coordination capacity. The structures of the compounds obtained in this research were confirmed by spectroscopic techniques, such as ¹H NMR, ¹³C NMR, FT–IR and mass spectrometry (MS), and the spectral data correlated with the structures. In addition, complexes [Ni(Ph-TPY)₂](ClO₄)₂ (15d), [Mn(MeOPh-TPY)₂](ClO₄)₂ (17c) and [Mn(Ph-TPY)₂](ClO₄)₂ (15c) were obtained as crystals suitable for single-crystal X-ray diffraction analysis. The solids obtained for the other compounds show crystals that eventually lose their crystallinity by desolvation and are thus not suitable for measurement by single-crystal diffraction.

3.2. Structural analysis

Displacement ellipsoid plots (50% probability level) for the asymmetric units of [Ni(Ph-TPY)₂](ClO₄)₂ (15d), [Mn(MeOPh-TPY)₂](ClO₄)₂ (17c) and [Mn(Ph-TPY)₂](ClO₄)₂ (15c) are presented in Fig. 2. The crystallographic and refinement data for the compounds are reported in Table 1.

Figure 2
Displacement ellipsoid diagrams drawn at the 50% probability level for (a) [Ni(Ph-TPY)₂](ClO₄)₂, (b) [Mn(MeOPh-TPY)₂](ClO₄)₂ and (c) [Mn(Ph-TPY)₂](ClO₄)₂. One perchlorate anion and the H atoms have been omitted for clarity.

[Ni(Ph-TPY)₂](ClO₄)₂ and [Mn(Ph-TPY)₂](ClO₄)₂ crystallize in the monoclinic space group P2₁/c. Both molecules present similar unit-cell parameters and crystal packing. On the other hand, [Mn(MeOPh-TPY)₂](ClO₄)₂ crystallizes in the triclinic space group P $[\overline{1}]$ . In all cases, the asymmetric unit is formed by one divalent cation, two R-TPY ligands (where R = –Ph or –OMe) and two perchlorate anions as counter-ions. Each R-TPY ligand is coordinated through three N atoms to the metal centre. The coordinated ligands are positioned perpendicular with respect to each other, forming a distorted octahedral polyhedron (MN₆) in a propeller-like arrangement (Fig. 3) (Carmona-Vargas et al., 2019 ). Table 2 shows the coordination M—N distances, where the shortest distances are between the N atoms of the central pyridine ring (N2 and N5). Substituent group influence is observed, making the M—N bond longer for the central ring of the electron-donating substituent (15c and 17c). The influence of the ionic radius on the bond distances can also be observed, being shorter for the Ni²⁺ complex (ionic radii, Ni = 0.69 Å and Mn = 0.83 Å; Shannon, 1976 ), suggesting a high-spin configuration for the Mn²⁺ complexes.

Table 2
Selected bond lengths (Å) for [Ni(Ph-TPY)₂](ClO₄)₂ (15d), [Mn(Ph-TPY)₂](ClO₄)₂ (17c) and [Mn(MeOPh-TPY)₂](ClO₄)₂ (15c)

	15d	17c	15c
M—N1	2.1263 (15)	2.2723 (12)	2.2664 (12)
M—N2	2.0014 (17)	2.2093 (14)	2.2080 (10)
M—N3	2.1175 (15)	2.2423 (12)	2.2738 (11)
M—N4	2.1313 (16)	2.2537 (12)	2.2375 (11)
M—N5	1.9956 (17)	2.1877 (11)	2.2002 (10)
M—N6	2.1147 (16)	2.2571 (12)	2.2970 (11)

Figure 3
Structural diagram in a polyhedral representation for (a) [Ni(Ph-TPY)₂](ClO₄)₂ and (b) [Mn(MeOPh-TPY)₂](ClO₄)₂.

In both cases, the coordinated ligands present a planarity distortion around the TPY core (see Table 3 and Fig. 3) by rotation around the C—C bond of TPY substituted with Ph and MeOPh, with values between 5.23 and 43.24° (see Table 3 and Fig. 3).

Table 3
Torsion and ring-to-ring angles (°) for [Ni(Ph-TPY)₂](ClO₄)₂ (15d), [Mn(Ph-TPY)₂](ClO₄)₂ (17c) and [Mn(MeOPh-TPY)₂](ClO₄)₂ (15c)

See Fig. 3 for ring definitions.

	15d	17c	15c
N1—C5—N3—C11	−8.59	−10.072	−3.66
N4—C26—N6—C32	−4.5	−3.412	−0.47
C17—C16—C8—C7	31.77	31.98	5.23
C30—C29—C37—C42	43.24	40.09	−27.63
Ring 1–Ring 2	7.28	8.496	1.49
Ring 3–Ring 4	14.39	14.38	16.63

[Ni(Ph-TPY)₂](ClO₄)₂ and [Mn(Ph-TPY)₂](ClO₄)₂ are isostructural and present similar packing. [Ni(Ph-TPY)₂](ClO₄)₂ is used to describe the observed interactions. The crystal packing is formed by C—H⋯π interactions between the substituted arene ring and the TPY core, with C18—H18⋯π, C21—H21⋯π and C34—H34⋯π distances of 3.487 (14), 3.668 (18) and 3.561 (10) Å, respectively (Fig. 4). Each perchlorate anion is surrounded by five complex molecules [Fig. 4(b)]. Therefore, C—H⋯O interactions are presented between the aromatic rings and the O atoms of the perchlorate anion, with distances ranging from 3.046 (18) to 3.480 (16) Å (Fig. 4). All H-atom contacts are summarized in the supporting information (Tables S21–S22).

Figure 4
(a) C—H⋯π interactions, (b) the perchlorate anion surrounded by five metal complexes and (c) a crystal packing representation for [Ni(Ph-TPY)₂](ClO₄)₂.

The packing of [Mn(MeOPh-TPY)₂](ClO₄)₂ is stabilized by C—H⋯O and π–π slipped-stacking interactions between the complex molecules along the [011] direction, with distances of 3.047 (14) and 3.803 (18) Å, respectively (Fig. 5). The chains are joined by C—H⋯O interactions between perchlorate O atoms and the aromatic rings of the ligand, with distances ranging from 3.109 (8) to 3.430 (10) Å (Fig. 5). All H-atom contacts are summarized in the supporting information (Table S23).

Figure 5
(a) C—H⋯O and π–π slipped-stacking interactions, (b) the perchlorate anion surrounded by five metal complexes and (c) a crystal packing representation for [Mn(MeOPh-TPY)₂](ClO₄)₂.

3.3. IR spectroscopy analysis

The FT–IR spectra of coordination complexes 15a–d, 16a–d and 17a–d are shown in Fig. 6. All the synthesized compounds present a similar IR profile. Compared with the spectra of the R-TPY free ligands (Fig. S1 in the supporting information), the bands are shifted to higher wavenumbers and the intensity of the C=N band (∼1450 cm⁻¹) increases, indicating the formation of the complexes. Additionally, bands due to in-plane and out-of-plane vibrations for ClO₄⁻ are observed around 1100 and 600 cm⁻¹, respectively. In addition, vibrations generated by the metal–ligand bonds are found above 500 cm⁻¹, which are higher than those found with the other ligands, indicating that M—N bonds require higher energy to vibrate, which is an indication of their higher structural stability (Nakamoto, 2008 ).

Figure 6
FT–IR (KBr) spectra of the metal coordination complexes: (a) 15a–d, (b) 16a–d and (c) 17a–d.

3.4. UV–Vis spectrophotometry

The electronic absorption spectra for coordination complexes 15a–d, 16a–d and 17a–d were recorded in acetonitrile solutions and are illustrated in Figs. 7 and 8; the corresponding data for the absorption bands and absorption maxima (λ_max) are summarized in the supporting information (Table S1). These complexes exhibit two types of transfer bands, namely, π–π* transitions originating from transfer bands of types CLCT (centred ligand charge transfer) and MLCT (metal-to-ligand charge transfer) due to 4d–π* transitions. The absorption bands at lower energies represent MLCT transitions, while the highest energy transitions correspond to CLCT transitions.

Figure 7
UV–Vis absorption spectra for (a) the Co coordination complexes and (b) the Fe coordination complexes in dilute solutions of acetonitrile.

Figure 8
UV–Vis absorption spectra and (a) the Mn coordination complexes and (b) the Ni coordination complexes in dilute solutions of acetonitrile.

In [M(Ph-TPY)₂](ClO₄)₂, [M(ClPh-TPY)₂](ClO₄)₂ and [M(MeOPh-TPY)₂](ClO₄)₂ (M = Co²⁺ and Fe²⁺), the bands around 287 and 325 nm are due to π–π* transitions within the aromatic residues of the ligand (pyridine and arene rings) and C=N bonds, respectively. The low-intensity bands observed around 520 nm in the Co complexes correspond to d–d transitions (Fig. 7) (Mughal et al., 2020 ). In the case of the Fe complexes, a medium-intensity band around 570 nm is associated with MLCT, i.e. Fe^II(dπ)–π*(ligand) (Mukherjee et al., 2018 ). It is now evident that both bands associated with the ligand in the three complexes are at longer wavelengths than in the ligands, so a bathochromic shift (lower energy) is being generated, which is expected due to the formation of the coordinate bonds between the metal cation and the N atoms of the ligand. In both cases, the complexes with the MeOPh-TPY ligand present a splitting of the band associated with the ligand and an increase in the intensity of the resultant band. This phenomenon may be due to MLCT as a result of the coordination of the metal with the N atom.

[M(Ph-TPY)₂](ClO₄)₂, [M(ClPh-TPY)₂](ClO₄)₂ and [M(MeOPh-TPY)₂](ClO₄)₂ (M = Mn²⁺ and Ni²⁺) present similar bands associated with π–π* transitions in aromatic rings and C=N bonds around 290 and 330 nm, respectively. In comparison with the free ligand, a higher bathochromic shift is observed. Similar to the Co and Fe complexes, the complexes with the MeOPh-TPY ligand present a splitting of the band and an increase in the intensity of the band at 344 nm, indicating increased LMCT. This behaviour may also be associated with the presence of an electron-donor group in the TPY system (Fig. 8).

3.5. NMR spectroscopy

¹H NMR and ¹³C NMR measurements for terpyridine ligands and the coordination complexes 15a–d, 16a–d and 17a–d were recorded in DMSO-d₆ solutions; all the spectra are illustrated in the supporting information (Figs. S3–S21) and the assignments of signals are given in the Experimental section (§2). NMR spectroscopy allows us to characterize each ligand and confirm the coordination of the 2-TPY ligands (8–10) with the metal cations (Co²⁺, Fe²⁺ and Mn²⁺, except for Ni²⁺). It is important to highlight that the complexes formed have an octahedral coordination sphere symmetry where the d orbitals split in T_2g e_g sets of orbitals. This behaviour gives rise to the generation of paramagnetic centres that can interfere with NMR measurements. This effect is strong in Ni²⁺ (d⁸ = T_2g⁶ e_g²) complexes, because the resolution of the signals was not possible. However, if we compare the signal type integration and the chemical shifts (δ) in the ¹H NMR and ¹³C NMR spectra of the ligands (Figs. S3–S8 and Tables S2–S7 in the supporting information) and the coordination complexes (Figs. S9–S21 and Tables S8–S20), it is evident that in all cases there are notable changes. For example, in the ¹H NMR spectra for the different ligands (Figs. S3, S5 and S7), a singlet signal is seen at 8.750–8.738 ppm due to the magnetically equivalent protons H3′ and H5′, while in the ¹H NMR spectra of the coordination complexes, this singlet signal has shifted to higher values of δ (low field) in the range 10.4–9.63 ppm. This behaviour suggests the formation of the proposed coordination complexes, which indicates the strong interactions generated between metal and ligand (Mughal et al., 2022 ). In general, the observed signals for the complexes are displaced to a low field due to an electron-deficient metal cation in the structure. It is also important to indicate that the signals associated with the ¹H and ¹³C atoms close to the pyridine N atom coordinated to the metal atoms present a higher deprotection and shift in their δ values compared with the free ligand. It is also possible to note that, in some spectra, low-intensity signals are observed due to a leaching process resulting from the decoordination of the ligands in solution.

3.6. Thermal stability

To determine the thermal stability of the complexes obtained, a TGA–DSC (thermogravimetric analysis–differential scanning calorimetry) study was performed in the temperature range 25–900 °C under an N₂ atmosphere (Fig. 9). In all cases, mass loss at low temperatures is associated with the presence of adsorbed solvent molecules. The thermal decomposition processes start at a relatively low temperature in the range 270–380 °C. The Mn compounds show an anomalous behaviour, with decomposition at temperatures below 100 °C, indicating low thermal stability, possibly due to the decomposition processes of the perchlorate anion. This decomposition process is more clearly observed in the DSC analysis. The peaks in the DSC profiles show the decomposition or explosion temperature for each complex, determined by the presence of the perchlorate anion in the structure (Singh et al., 2009 ).

Figure 9
TGA–DSC thermal analysis for the series of complexes 15a–d, 16a–d and 17a–d.

4. Conclusion

In this work, we have discussed the synthesis and spectroscopic and structural characterization of 12 transition-metal coordination complexes with the general formula [M(R-TPY)₂](ClO₄)₂. The new family of complexes were obtained from the efficient reaction of four divalent metal ions (M = Co²⁺, Fe²⁺, Mn²⁺ and Ni²⁺) with nitrogen-based ligands (R-TPY), where R (R = H, Cl and OCH₃) is the substituent at the 4′ position of the 2,2′:6′,2′′-terpyridine core. These substituents have a positive influence on the reaction yield of the complexes when R = OMe but a negative influence when R = Cl, probably due to the electron-donor or electron-acceptor nature, respectively. The TPY derivatives were prepared using the Kröhnke methodology assisted by microwave radiation. Crystals suitable for single-crystal X-ray diffraction were obtained for [Ni(Ph-TPY)₂](ClO₄)₂, [Mn(MeOPh-TPY)₂](ClO₄)₂ and [Mn(Ph-TPY)₂](ClO₄)₂ by slow evaporation of the solvent. In all cases, the complexes present distorted octahedral coordination polyhedra (MN₆) in a propeller-like arrangement. Due to the aromatic nature of the TPY structure, the crystal packing is formed mainly by weak C—H⋯π, C—H⋯O and π–π interactions. As it was impossible to obtain single crystals for all the synthesized complexes, they were characterized by spectroscopic techniques.

It is important to clarify that, due to the presence of metal centres with paramagnetic behaviour that interferes with the NMR measurements, as in the case for the Ni²⁺ complexes, it was not possible to characterize these complexes using this technique. This same effect causes some signals to widen and they cannot be identified clearly. Also, it is important to mention that the presence of unidentified low-intensity signals may be due to a leaching process or an excess of ligand in solution. All other spectroscopic, thermal and diffraction techniques confirm the formation of the complexes. The FT–IR and UV–Vis (λ) bands, and NMR signals (chemical shifts, δ) of the metal complexes are significantly shifted with respect to those of the precursor 2,2′:6′,2′′-terpyridine ligands, due to strong metal–ligand interactions. The absorption bands in the coordination complexes are shifted to longer wavelengths; these bathochromic shifts (red-shifted absorption) occur due to the formation of new covalent bonds between the terpyridine N atoms and the d-block transition-metal cation (M—N). A similar behaviour is observed in the FT–IR bands, where the perchlorate anion and metal–ligand (M—N) bands are also observed.

The thermal stability of the complexes is directly related to the presence of the perchlorate anion in the molecular structure causing low thermal stability. Different functional groups in the pendant ring of TPY allow the formation of different crystalline packings as a result of their nature. The introduction of these groups in TPY is important because they provide specific physicochemical properties that would enable the potential use of each molecule in different fields of application.

Supporting information

CCDC references: 2331329; 2331330; 2331331

Crystal structure: contains datablocks MnMeOTPY, MnPhTPY, NiPhTPY, global. DOI: https://doi.org/10.1107/S2053229624004224/zo3044sup1.cif

Structure factors: contains datablock NiPhTPY. DOI: https://doi.org/10.1107/S2053229624004224/zo3044NiPhTPYsup2.hkl

Structure factors: contains datablock MnMeOTPY. DOI: https://doi.org/10.1107/S2053229624004224/zo3044MnMeOTPYsup3.hkl

Structure factors: contains datablock MnPhTPY. DOI: https://doi.org/10.1107/S2053229624004224/zo3044MnPhTPYsup4.hkl

Additional schemes, figures and tables. DOI: https://doi.org/10.1107/S2053229624004224/zo3044sup5.pdf

Computing details top

Bis[4'-(4-methoxyphenyl)-2,2':6',2''-terpyridine]manganese(II) bis(perchlorate) (MnMeOTPY) top

Crystal data top

[Mn(C₂₂H₁₇N₃O)₂](ClO₄)₂	Z = 2
M_r = 932.61	F(000) = 958
Triclinic, P1	D_x = 1.505 Mg m⁻³
a = 8.93282 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.32698 (13) Å	Cell parameters from 44860 reflections
c = 18.86081 (19) Å	θ = 2.6–34.1°
α = 89.8757 (8)°	µ = 0.52 mm⁻¹
β = 85.6122 (8)°	T = 100 K
γ = 83.5667 (9)°	Block, light yellow
V = 2057.68 (4) Å³	0.15 × 0.10 × 0.08 mm

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	10630 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	9347 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.029
Detector resolution: 10.0000 pixels mm^-1	θ_max = 28.7°, θ_min = 2.5°
ω scans	h = −12→12
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2022)	k = −16→16
T_min = 0.662, T_max = 1.000	l = −25→25
57826 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0393P)² + 0.9933P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
10630 reflections	Δρ_max = 0.49 e Å⁻³
570 parameters	Δρ_min = −0.42 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Single crystals suitable for X-ray analysis were obtained by slow evaporation from acetonitrile using diethyl ether as antisolvent. Diffraction data for all the compounds were collected at room temperature on a Rigaku Synergy S diffractometer using photonjet microfocus source Mo Kα (λ = 0.71073 Å) radiation. The unit-cell parameters were determined using all reflections with CrysAlis PRO software (Agilent, 2014). Data integration and scaling were performed using CrysAlis PRO software (Agilent, 2014). The structures were solved and refined with SHELXT (Sheldrick, 2015a) and SHELXL (Sheldrick, 2015b) software, respectively, including in OLEX2 (Dolomanov et al., 2009). In all cases, non-H atoms were clearly resolved and full-matrix least-squares refinement with anisotropic displacement parameters was performed. In addition, the H atoms were stereochemically positioned and refined using the riding model (Sheldrick, 2008). The Mn compound [which one?] was refined using the SQUEEZE routine (Spek, 2015) in PLATON (Spek, 2020) to decrease the contribution of the disordered solvent (water molecule) to calculate the structure factors and improve the refinement values. Displacement ellipsoid plots for all structures were prepared with DIAMOND (Brandenburg et al., 2006). MERCURY were used for the preparation of artwork (Macrae et al., 2020). The CIF file of the complexes was deposited in the Cambridge Structural Data Base under the codes CCDC 2331329-2331331.

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

	x	y	z	U_iso*/U_eq
Mn1	0.84071 (2)	0.20014 (2)	0.74163 (2)	0.01322 (5)
Cl2	0.27866 (3)	0.73931 (2)	0.86546 (2)	0.01663 (7)
Cl1	0.44773 (4)	0.27267 (3)	0.51211 (2)	0.01862 (7)
O2	1.04363 (12)	0.38092 (8)	0.19702 (5)	0.0220 (2)
O1	0.61146 (13)	−0.26205 (9)	1.20844 (5)	0.0259 (2)
O8	0.13467 (11)	0.80637 (8)	0.87487 (5)	0.0219 (2)
O7	0.32762 (13)	0.73117 (9)	0.79090 (5)	0.0267 (2)
O9	0.26411 (13)	0.63223 (8)	0.89400 (6)	0.0276 (2)
O10	0.38971 (12)	0.78935 (9)	0.90230 (6)	0.0276 (2)
N4	0.71778 (12)	0.36568 (9)	0.72566 (6)	0.0156 (2)
N5	0.90456 (12)	0.25287 (8)	0.63304 (5)	0.0136 (2)
N1	0.94458 (12)	0.27627 (9)	0.83268 (6)	0.0147 (2)
N2	0.78219 (12)	0.11127 (8)	0.83983 (5)	0.01317 (19)
N6	1.01949 (12)	0.06923 (9)	0.69056 (6)	0.0147 (2)
O5	0.38629 (13)	0.17013 (9)	0.52369 (7)	0.0359 (3)
N3	0.68141 (12)	0.07699 (9)	0.71536 (5)	0.0147 (2)
O3	0.50570 (17)	0.27764 (11)	0.43929 (6)	0.0432 (3)
O6	0.33038 (15)	0.36195 (10)	0.52570 (7)	0.0391 (3)
O4	0.56453 (17)	0.27922 (11)	0.55862 (8)	0.0502 (4)
C11	0.64293 (14)	0.00707 (10)	0.76733 (6)	0.0135 (2)
C10	0.69668 (13)	0.02828 (10)	0.83820 (6)	0.0128 (2)
C6	0.83885 (13)	0.13535 (10)	0.90126 (6)	0.0131 (2)
C5	0.92485 (14)	0.23205 (10)	0.89801 (6)	0.0134 (2)
C7	0.81556 (14)	0.07495 (10)	0.96256 (6)	0.0138 (2)
H7	0.860232	0.092242	1.004630	0.017*
C27	0.83919 (14)	0.34763 (10)	0.60817 (6)	0.0133 (2)
C19	0.64295 (15)	−0.19800 (11)	1.15164 (7)	0.0171 (2)
C37	0.99495 (14)	0.33887 (10)	0.41620 (6)	0.0153 (2)
C12	0.56352 (14)	−0.08050 (10)	0.75412 (7)	0.0161 (2)
H12	0.535070	−0.127319	0.791654	0.019*
C4	0.97795 (15)	0.27649 (10)	0.95764 (7)	0.0168 (2)
H4	0.962878	0.244320	1.003077	0.020*
C16	0.69693 (14)	−0.07642 (10)	1.02729 (6)	0.0130 (2)
C9	0.66467 (14)	−0.03336 (10)	0.89824 (6)	0.0135 (2)
H9	0.601377	−0.090036	0.895816	0.016*
C26	0.72713 (14)	0.40883 (10)	0.65978 (6)	0.0138 (2)
C18	0.72148 (14)	−0.10719 (10)	1.15389 (6)	0.0157 (2)
H18	0.757195	−0.085778	1.197323	0.019*
C8	0.72601 (13)	−0.01167 (10)	0.96239 (6)	0.0126 (2)
C29	0.96743 (14)	0.31363 (10)	0.49237 (6)	0.0146 (2)
C17	0.74767 (14)	−0.04769 (10)	1.09233 (6)	0.0152 (2)
H17	0.801575	0.014272	1.094492	0.018*
C31	1.00055 (14)	0.18737 (10)	0.58924 (6)	0.0138 (2)
C13	0.52625 (15)	−0.09870 (11)	0.68529 (7)	0.0181 (2)
H13	0.473910	−0.159061	0.674975	0.022*
C25	0.63432 (15)	0.50116 (10)	0.64175 (7)	0.0174 (2)
H25	0.641606	0.529612	0.594921	0.021*
C40	1.03554 (15)	0.36605 (10)	0.26877 (6)	0.0163 (2)
C32	1.05891 (14)	0.08155 (10)	0.62066 (6)	0.0141 (2)
C15	0.64223 (15)	0.05958 (11)	0.64927 (7)	0.0180 (2)
H15	0.667643	0.109285	0.612925	0.022*
C28	0.87030 (14)	0.38170 (10)	0.53876 (6)	0.0151 (2)
H28	0.825980	0.450420	0.523158	0.018*
C39	0.90529 (15)	0.41530 (11)	0.30658 (7)	0.0182 (2)
H39	0.830398	0.458098	0.282286	0.022*
C2	1.07214 (15)	0.41551 (11)	0.88302 (7)	0.0193 (3)
H2	1.122655	0.479037	0.876440	0.023*
C30	1.03336 (14)	0.21484 (10)	0.51903 (7)	0.0155 (2)
H30	1.100492	0.166791	0.488934	0.019*
C38	0.88507 (15)	0.40186 (11)	0.37951 (7)	0.0176 (2)
H38	0.796116	0.435527	0.404955	0.021*
C33	1.14230 (15)	−0.00195 (11)	0.58015 (7)	0.0183 (2)
H33	1.171358	0.009268	0.531410	0.022*
C21	0.61682 (16)	−0.16794 (11)	1.02645 (7)	0.0185 (2)
H21	0.580120	−0.189282	0.983226	0.022*
C42	1.12654 (15)	0.29330 (11)	0.37761 (7)	0.0175 (2)
H42	1.203204	0.252366	0.401874	0.021*
C24	0.53044 (16)	0.55112 (11)	0.69369 (7)	0.0204 (3)
H24	0.464647	0.613768	0.682531	0.024*
C20	0.59031 (17)	−0.22761 (11)	1.08730 (7)	0.0215 (3)
H20	0.535822	−0.289320	1.085407	0.026*
C41	1.14771 (15)	0.30650 (11)	0.30466 (7)	0.0178 (2)
H41	1.238156	0.275115	0.279320	0.021*
C34	1.18242 (15)	−0.10165 (11)	0.61178 (7)	0.0196 (3)
H34	1.238636	−0.159698	0.584944	0.023*
C1	1.01489 (15)	0.36672 (10)	0.82639 (7)	0.0175 (2)
H1	1.026035	0.399002	0.780781	0.021*
C14	0.56647 (15)	−0.02757 (12)	0.63175 (7)	0.0195 (3)
H14	0.542599	−0.038407	0.584233	0.023*
C36	1.05989 (15)	−0.02783 (11)	0.72056 (7)	0.0173 (2)
H36	1.032639	−0.036698	0.769740	0.021*
C22	0.61991 (16)	0.41617 (11)	0.77528 (7)	0.0203 (3)
H22	0.616045	0.387219	0.822024	0.024*
C23	0.52374 (16)	0.50879 (11)	0.76177 (8)	0.0223 (3)
H23	0.454971	0.542401	0.798274	0.027*
C35	1.13919 (15)	−0.11532 (11)	0.68323 (7)	0.0192 (3)
H35	1.163471	−0.183154	0.705976	0.023*
C3	1.05346 (15)	0.36884 (11)	0.94953 (7)	0.0190 (3)
H3	1.092140	0.399852	0.989435	0.023*
C44	0.66597 (17)	−0.23664 (13)	1.27535 (7)	0.0239 (3)
H44A	0.776624	−0.242867	1.270677	0.036*
H44B	0.632577	−0.287756	1.311509	0.036*
H44C	0.625952	−0.161930	1.289560	0.036*
C43	1.16290 (18)	0.31801 (13)	0.15575 (7)	0.0268 (3)
H43A	1.151537	0.331365	0.105101	0.040*
H43B	1.158859	0.240288	0.165714	0.040*
H43C	1.260281	0.339129	0.168069	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.01649 (10)	0.01185 (9)	0.01116 (9)	−0.00133 (7)	−0.00057 (7)	0.00234 (6)
Cl2	0.02027 (15)	0.01290 (13)	0.01747 (14)	−0.00286 (11)	−0.00480 (11)	0.00059 (10)
Cl1	0.01966 (15)	0.01990 (15)	0.01669 (14)	−0.00161 (11)	−0.00475 (11)	0.00003 (11)
O2	0.0324 (5)	0.0215 (5)	0.0112 (4)	0.0017 (4)	−0.0022 (4)	0.0034 (3)
O1	0.0392 (6)	0.0274 (5)	0.0136 (4)	−0.0154 (5)	−0.0022 (4)	0.0073 (4)
O8	0.0209 (5)	0.0186 (5)	0.0260 (5)	−0.0003 (4)	−0.0035 (4)	−0.0028 (4)
O7	0.0361 (6)	0.0235 (5)	0.0181 (5)	0.0055 (4)	−0.0003 (4)	0.0000 (4)
O9	0.0326 (6)	0.0167 (5)	0.0349 (6)	−0.0062 (4)	−0.0066 (5)	0.0092 (4)
O10	0.0264 (5)	0.0257 (5)	0.0331 (6)	−0.0076 (4)	−0.0118 (4)	−0.0033 (4)
N4	0.0178 (5)	0.0138 (5)	0.0150 (5)	−0.0007 (4)	−0.0001 (4)	0.0015 (4)
N5	0.0144 (5)	0.0129 (5)	0.0134 (5)	−0.0009 (4)	−0.0019 (4)	0.0014 (4)
N1	0.0165 (5)	0.0127 (5)	0.0151 (5)	−0.0018 (4)	−0.0016 (4)	0.0022 (4)
N2	0.0144 (5)	0.0126 (5)	0.0125 (5)	−0.0011 (4)	−0.0009 (4)	0.0006 (4)
N6	0.0153 (5)	0.0140 (5)	0.0150 (5)	−0.0012 (4)	−0.0029 (4)	0.0024 (4)
O5	0.0305 (6)	0.0240 (6)	0.0554 (8)	−0.0103 (5)	−0.0075 (5)	−0.0013 (5)
N3	0.0154 (5)	0.0159 (5)	0.0128 (5)	−0.0004 (4)	−0.0025 (4)	0.0024 (4)
O3	0.0614 (9)	0.0381 (7)	0.0224 (6)	0.0185 (6)	0.0113 (5)	0.0058 (5)
O6	0.0411 (7)	0.0273 (6)	0.0439 (7)	0.0083 (5)	0.0111 (5)	−0.0045 (5)
O4	0.0582 (9)	0.0434 (8)	0.0599 (9)	−0.0259 (7)	−0.0461 (7)	0.0206 (6)
C11	0.0131 (5)	0.0139 (5)	0.0129 (5)	0.0005 (4)	−0.0012 (4)	0.0003 (4)
C10	0.0129 (5)	0.0123 (5)	0.0127 (5)	0.0007 (4)	−0.0006 (4)	−0.0001 (4)
C6	0.0135 (5)	0.0118 (5)	0.0138 (5)	−0.0004 (4)	−0.0006 (4)	−0.0001 (4)
C5	0.0138 (5)	0.0117 (5)	0.0142 (5)	−0.0003 (4)	−0.0003 (4)	0.0015 (4)
C7	0.0159 (6)	0.0139 (5)	0.0120 (5)	−0.0018 (4)	−0.0018 (4)	0.0003 (4)
C27	0.0143 (5)	0.0123 (5)	0.0135 (5)	−0.0016 (4)	−0.0019 (4)	0.0007 (4)
C19	0.0209 (6)	0.0172 (6)	0.0127 (5)	−0.0023 (5)	0.0012 (5)	0.0035 (4)
C37	0.0170 (6)	0.0164 (6)	0.0127 (5)	−0.0027 (5)	−0.0011 (4)	0.0023 (4)
C12	0.0165 (6)	0.0161 (6)	0.0157 (6)	−0.0019 (5)	−0.0013 (4)	0.0002 (4)
C4	0.0197 (6)	0.0160 (6)	0.0153 (6)	−0.0035 (5)	−0.0026 (5)	0.0018 (4)
C16	0.0143 (5)	0.0120 (5)	0.0123 (5)	−0.0003 (4)	0.0003 (4)	0.0020 (4)
C9	0.0146 (5)	0.0119 (5)	0.0143 (5)	−0.0020 (4)	−0.0010 (4)	0.0004 (4)
C26	0.0156 (6)	0.0120 (5)	0.0139 (5)	−0.0020 (4)	−0.0011 (4)	0.0004 (4)
C18	0.0175 (6)	0.0170 (6)	0.0125 (5)	−0.0013 (5)	−0.0014 (4)	0.0008 (4)
C8	0.0131 (5)	0.0116 (5)	0.0125 (5)	0.0011 (4)	0.0008 (4)	0.0009 (4)
C29	0.0148 (5)	0.0169 (6)	0.0125 (5)	−0.0029 (4)	−0.0009 (4)	0.0025 (4)
C17	0.0173 (6)	0.0140 (6)	0.0146 (6)	−0.0018 (4)	−0.0019 (4)	0.0011 (4)
C31	0.0139 (5)	0.0136 (5)	0.0137 (5)	−0.0010 (4)	−0.0017 (4)	0.0010 (4)
C13	0.0179 (6)	0.0180 (6)	0.0187 (6)	−0.0026 (5)	−0.0033 (5)	−0.0023 (5)
C25	0.0204 (6)	0.0144 (6)	0.0168 (6)	0.0009 (5)	−0.0015 (5)	0.0022 (4)
C40	0.0228 (6)	0.0148 (6)	0.0120 (5)	−0.0048 (5)	−0.0019 (5)	0.0027 (4)
C32	0.0132 (5)	0.0138 (5)	0.0153 (5)	−0.0009 (4)	−0.0029 (4)	0.0017 (4)
C15	0.0192 (6)	0.0213 (6)	0.0137 (6)	−0.0016 (5)	−0.0030 (5)	0.0028 (5)
C28	0.0175 (6)	0.0137 (5)	0.0142 (5)	−0.0009 (4)	−0.0019 (4)	0.0030 (4)
C39	0.0206 (6)	0.0164 (6)	0.0175 (6)	0.0001 (5)	−0.0047 (5)	0.0053 (5)
C2	0.0214 (6)	0.0137 (6)	0.0238 (6)	−0.0046 (5)	−0.0042 (5)	0.0033 (5)
C30	0.0148 (6)	0.0170 (6)	0.0143 (6)	0.0003 (4)	−0.0009 (4)	0.0009 (4)
C38	0.0192 (6)	0.0165 (6)	0.0163 (6)	0.0004 (5)	−0.0008 (5)	0.0025 (5)
C33	0.0190 (6)	0.0179 (6)	0.0171 (6)	0.0008 (5)	−0.0013 (5)	0.0006 (5)
C21	0.0240 (6)	0.0193 (6)	0.0134 (6)	−0.0069 (5)	−0.0027 (5)	0.0010 (5)
C42	0.0160 (6)	0.0208 (6)	0.0157 (6)	−0.0005 (5)	−0.0025 (4)	0.0033 (5)
C24	0.0208 (6)	0.0161 (6)	0.0228 (6)	0.0033 (5)	0.0004 (5)	0.0015 (5)
C20	0.0293 (7)	0.0203 (6)	0.0172 (6)	−0.0126 (5)	−0.0020 (5)	0.0027 (5)
C41	0.0182 (6)	0.0211 (6)	0.0137 (6)	−0.0015 (5)	0.0001 (4)	0.0013 (5)
C34	0.0178 (6)	0.0155 (6)	0.0249 (7)	0.0017 (5)	−0.0032 (5)	−0.0013 (5)
C1	0.0204 (6)	0.0143 (6)	0.0181 (6)	−0.0030 (5)	−0.0015 (5)	0.0042 (5)
C14	0.0198 (6)	0.0248 (7)	0.0142 (6)	−0.0014 (5)	−0.0046 (5)	−0.0010 (5)
C36	0.0171 (6)	0.0168 (6)	0.0184 (6)	−0.0024 (5)	−0.0032 (5)	0.0049 (5)
C22	0.0246 (7)	0.0186 (6)	0.0161 (6)	0.0001 (5)	0.0042 (5)	0.0030 (5)
C23	0.0236 (7)	0.0183 (6)	0.0226 (7)	0.0033 (5)	0.0060 (5)	0.0001 (5)
C35	0.0170 (6)	0.0147 (6)	0.0264 (7)	−0.0011 (5)	−0.0055 (5)	0.0045 (5)
C3	0.0219 (6)	0.0169 (6)	0.0196 (6)	−0.0049 (5)	−0.0063 (5)	0.0002 (5)
C44	0.0294 (7)	0.0297 (7)	0.0127 (6)	−0.0048 (6)	−0.0005 (5)	0.0042 (5)
C43	0.0310 (8)	0.0343 (8)	0.0137 (6)	0.0001 (6)	0.0017 (5)	0.0008 (5)

Geometric parameters (Å, º) top

Mn1—N4	2.2375 (11)	C9—C8	1.4042 (17)
Mn1—N5	2.2002 (10)	C26—C25	1.3886 (17)
Mn1—N1	2.2666 (11)	C18—H18	0.9500
Mn1—N2	2.2081 (10)	C18—C17	1.3906 (17)
Mn1—N6	2.2970 (11)	C29—C28	1.3951 (17)
Mn1—N3	2.2738 (11)	C29—C30	1.4017 (17)
Cl2—O8	1.4480 (10)	C17—H17	0.9500
Cl2—O7	1.4406 (10)	C31—C32	1.4886 (17)
Cl2—O9	1.4401 (10)	C31—C30	1.3838 (17)
Cl2—O10	1.4462 (10)	C13—H13	0.9500
Cl1—O5	1.4432 (12)	C13—C14	1.3888 (19)
Cl1—O3	1.4338 (12)	C25—H25	0.9500
Cl1—O6	1.4413 (12)	C25—C24	1.3911 (18)
Cl1—O4	1.4226 (12)	C40—C39	1.3956 (19)
O2—C40	1.3626 (15)	C40—C41	1.3920 (18)
O2—C43	1.4259 (17)	C32—C33	1.3939 (18)
O1—C19	1.3602 (15)	C15—H15	0.9500
O1—C44	1.4344 (17)	C15—C14	1.3856 (19)
N4—C26	1.3509 (16)	C28—H28	0.9500
N4—C22	1.3353 (17)	C39—H39	0.9500
N5—C27	1.3461 (15)	C39—C38	1.3856 (18)
N5—C31	1.3450 (16)	C2—H2	0.9500
N1—C5	1.3535 (15)	C2—C1	1.3855 (19)
N1—C1	1.3403 (16)	C2—C3	1.3852 (18)
N2—C10	1.3453 (16)	C30—H30	0.9500
N2—C6	1.3459 (15)	C38—H38	0.9500
N6—C32	1.3509 (16)	C33—H33	0.9500
N6—C36	1.3467 (16)	C33—C34	1.3877 (18)
N3—C11	1.3537 (15)	C21—H21	0.9500
N3—C15	1.3443 (16)	C21—C20	1.3812 (18)
C11—C10	1.4878 (16)	C42—H42	0.9500
C11—C12	1.3894 (17)	C42—C41	1.3863 (17)
C10—C9	1.3916 (16)	C24—H24	0.9500
C6—C5	1.4873 (17)	C24—C23	1.3846 (19)
C6—C7	1.3887 (16)	C20—H20	0.9500
C5—C4	1.3902 (17)	C41—H41	0.9500
C7—H7	0.9500	C34—H34	0.9500
C7—C8	1.4042 (17)	C34—C35	1.3882 (19)
C27—C26	1.4845 (17)	C1—H1	0.9500
C27—C28	1.3912 (16)	C14—H14	0.9500
C19—C18	1.3883 (18)	C36—H36	0.9500
C19—C20	1.3982 (18)	C36—C35	1.3844 (19)
C37—C29	1.4773 (16)	C22—H22	0.9500
C37—C38	1.4057 (17)	C22—C23	1.3853 (19)
C37—C42	1.3964 (18)	C23—H23	0.9500
C12—H12	0.9500	C35—H35	0.9500
C12—C13	1.3895 (17)	C3—H3	0.9500
C4—H4	0.9500	C44—H44A	0.9800
C4—C3	1.3892 (18)	C44—H44B	0.9800
C16—C8	1.4820 (16)	C44—H44C	0.9800
C16—C17	1.3995 (17)	C43—H43A	0.9800
C16—C21	1.4028 (17)	C43—H43B	0.9800
C9—H9	0.9500	C43—H43C	0.9800

N4—Mn1—N1	86.42 (4)	C28—C29—C30	117.88 (11)
N4—Mn1—N6	143.89 (4)	C30—C29—C37	119.53 (11)
N4—Mn1—N3	106.58 (4)	C16—C17—H17	119.0
N5—Mn1—N4	72.05 (4)	C18—C17—C16	121.92 (12)
N5—Mn1—N1	117.76 (4)	C18—C17—H17	119.0
N5—Mn1—N2	167.42 (4)	N5—C31—C32	114.98 (10)
N5—Mn1—N6	72.00 (4)	N5—C31—C30	121.56 (11)
N5—Mn1—N3	98.94 (4)	C30—C31—C32	123.34 (11)
N1—Mn1—N6	107.36 (4)	C12—C13—H13	120.4
N1—Mn1—N3	143.30 (4)	C14—C13—C12	119.18 (12)
N2—Mn1—N4	118.25 (4)	C14—C13—H13	120.4
N2—Mn1—N1	71.82 (4)	C26—C25—H25	120.7
N2—Mn1—N6	97.84 (4)	C26—C25—C24	118.64 (12)
N2—Mn1—N3	71.82 (4)	C24—C25—H25	120.7
N3—Mn1—N6	82.42 (4)	O2—C40—C39	116.01 (11)
O7—Cl2—O8	109.56 (6)	O2—C40—C41	124.01 (12)
O7—Cl2—O10	108.81 (7)	C41—C40—C39	119.98 (12)
O9—Cl2—O8	109.74 (6)	N6—C32—C31	115.67 (11)
O9—Cl2—O7	109.98 (7)	N6—C32—C33	121.80 (11)
O9—Cl2—O10	109.41 (7)	C33—C32—C31	122.45 (11)
O10—Cl2—O8	109.33 (6)	N3—C15—H15	118.5
O3—Cl1—O5	108.85 (8)	N3—C15—C14	122.99 (12)
O3—Cl1—O6	108.44 (7)	C14—C15—H15	118.5
O6—Cl1—O5	109.88 (8)	C27—C28—C29	119.13 (11)
O4—Cl1—O5	108.68 (8)	C27—C28—H28	120.4
O4—Cl1—O3	110.75 (10)	C29—C28—H28	120.4
O4—Cl1—O6	110.22 (9)	C40—C39—H39	120.0
C40—O2—C43	117.30 (11)	C38—C39—C40	120.08 (12)
C19—O1—C44	118.33 (11)	C38—C39—H39	120.0
C26—N4—Mn1	117.98 (8)	C1—C2—H2	121.0
C22—N4—Mn1	122.76 (9)	C3—C2—H2	121.0
C22—N4—C26	118.57 (11)	C3—C2—C1	117.97 (12)
C27—N5—Mn1	120.08 (8)	C29—C30—H30	120.0
C31—N5—Mn1	120.43 (8)	C31—C30—C29	119.93 (11)
C31—N5—C27	119.31 (10)	C31—C30—H30	120.0
C5—N1—Mn1	117.79 (8)	C37—C38—H38	119.7
C1—N1—Mn1	123.69 (8)	C39—C38—C37	120.61 (12)
C1—N1—C5	118.35 (11)	C39—C38—H38	119.7
C10—N2—Mn1	120.46 (8)	C32—C33—H33	120.4
C10—N2—C6	119.11 (10)	C34—C33—C32	119.28 (12)
C6—N2—Mn1	120.32 (8)	C34—C33—H33	120.4
C32—N6—Mn1	116.15 (8)	C16—C21—H21	119.4
C36—N6—Mn1	123.91 (9)	C20—C21—C16	121.23 (12)
C36—N6—C32	118.19 (11)	C20—C21—H21	119.4
C11—N3—Mn1	117.30 (8)	C37—C42—H42	119.3
C15—N3—Mn1	123.53 (9)	C41—C42—C37	121.41 (12)
C15—N3—C11	118.41 (11)	C41—C42—H42	119.3
N3—C11—C10	115.35 (11)	C25—C24—H24	120.3
N3—C11—C12	121.82 (11)	C23—C24—C25	119.45 (12)
C12—C11—C10	122.80 (11)	C23—C24—H24	120.3
N2—C10—C11	114.65 (10)	C19—C20—H20	119.7
N2—C10—C9	121.95 (11)	C21—C20—C19	120.58 (12)
C9—C10—C11	123.38 (11)	C21—C20—H20	119.7
N2—C6—C5	114.61 (10)	C40—C41—H41	120.2
N2—C6—C7	121.95 (11)	C42—C41—C40	119.56 (12)
C7—C6—C5	123.43 (11)	C42—C41—H41	120.2
N1—C5—C6	115.12 (11)	C33—C34—H34	120.5
N1—C5—C4	121.87 (11)	C33—C34—C35	119.02 (12)
C4—C5—C6	122.99 (11)	C35—C34—H34	120.5
C6—C7—H7	120.0	N1—C1—C2	123.33 (12)
C6—C7—C8	120.03 (11)	N1—C1—H1	118.3
C8—C7—H7	120.0	C2—C1—H1	118.3
N5—C27—C26	114.31 (10)	C13—C14—H14	120.8
N5—C27—C28	122.14 (11)	C15—C14—C13	118.43 (12)
C28—C27—C26	123.49 (11)	C15—C14—H14	120.8
O1—C19—C18	124.66 (12)	N6—C36—H36	118.4
O1—C19—C20	116.13 (12)	N6—C36—C35	123.19 (12)
C18—C19—C20	119.20 (11)	C35—C36—H36	118.4
C38—C37—C29	121.13 (11)	N4—C22—H22	118.5
C42—C37—C29	120.39 (11)	N4—C22—C23	123.05 (12)
C42—C37—C38	118.29 (11)	C23—C22—H22	118.5
C11—C12—H12	120.4	C24—C23—C22	118.28 (12)
C11—C12—C13	119.14 (12)	C24—C23—H23	120.9
C13—C12—H12	120.4	C22—C23—H23	120.9
C5—C4—H4	120.6	C34—C35—H35	120.8
C3—C4—C5	118.74 (12)	C36—C35—C34	118.49 (12)
C3—C4—H4	120.6	C36—C35—H35	120.8
C17—C16—C8	120.96 (11)	C4—C3—H3	120.1
C17—C16—C21	117.28 (11)	C2—C3—C4	119.72 (12)
C21—C16—C8	121.75 (11)	C2—C3—H3	120.1
C10—C9—H9	120.0	O1—C44—H44A	109.5
C10—C9—C8	119.92 (11)	O1—C44—H44B	109.5
C8—C9—H9	120.0	O1—C44—H44C	109.5
N4—C26—C27	114.89 (11)	H44A—C44—H44B	109.5
N4—C26—C25	121.96 (11)	H44A—C44—H44C	109.5
C25—C26—C27	123.11 (11)	H44B—C44—H44C	109.5
C19—C18—H18	120.1	O2—C43—H43A	109.5
C19—C18—C17	119.77 (12)	O2—C43—H43B	109.5
C17—C18—H18	120.1	O2—C43—H43C	109.5
C7—C8—C16	121.30 (11)	H43A—C43—H43B	109.5
C9—C8—C7	116.97 (11)	H43A—C43—H43C	109.5
C9—C8—C16	121.73 (11)	H43B—C43—H43C	109.5
C28—C29—C37	122.47 (11)

Mn1—N4—C26—C27	−9.44 (14)	C27—N5—C31—C30	−0.27 (18)
Mn1—N4—C26—C25	168.29 (10)	C27—C26—C25—C24	178.49 (12)
Mn1—N4—C22—C23	−168.08 (11)	C19—C18—C17—C16	0.04 (19)
Mn1—N5—C27—C26	0.53 (14)	C37—C29—C28—C27	174.07 (11)
Mn1—N5—C27—C28	−176.72 (9)	C37—C29—C30—C31	−175.90 (11)
Mn1—N5—C31—C32	−1.14 (14)	C37—C42—C41—C40	−0.2 (2)
Mn1—N5—C31—C30	174.88 (9)	C12—C11—C10—N2	174.79 (11)
Mn1—N1—C5—C6	1.48 (14)	C12—C11—C10—C9	−3.98 (19)
Mn1—N1—C5—C4	−176.77 (9)	C12—C13—C14—C15	−0.2 (2)
Mn1—N1—C1—C2	177.01 (10)	C16—C21—C20—C19	0.0 (2)
Mn1—N2—C10—C11	−2.43 (14)	C26—N4—C22—C23	2.2 (2)
Mn1—N2—C10—C9	176.36 (9)	C26—C27—C28—C29	−174.25 (11)
Mn1—N2—C6—C5	6.85 (14)	C26—C25—C24—C23	0.9 (2)
Mn1—N2—C6—C7	−174.19 (9)	C18—C19—C20—C21	0.5 (2)
Mn1—N6—C32—C31	9.74 (14)	C8—C16—C17—C18	179.92 (11)
Mn1—N6—C32—C33	−167.10 (10)	C8—C16—C21—C20	−179.95 (12)
Mn1—N6—C36—C35	164.11 (10)	C29—C37—C38—C39	−173.07 (12)
Mn1—N3—C11—C10	6.67 (13)	C29—C37—C42—C41	173.18 (12)
Mn1—N3—C11—C12	−171.06 (9)	C17—C16—C8—C7	5.23 (18)
Mn1—N3—C15—C14	168.71 (10)	C17—C16—C8—C9	−174.26 (12)
O2—C40—C39—C38	178.05 (12)	C17—C16—C21—C20	−0.5 (2)
O2—C40—C41—C42	−177.99 (12)	C31—N5—C27—C26	175.70 (11)
O1—C19—C18—C17	179.83 (12)	C31—N5—C27—C28	−1.55 (18)
O1—C19—C20—C21	−179.83 (13)	C31—C32—C33—C34	−174.73 (12)
N4—C26—C25—C24	1.0 (2)	C25—C24—C23—C22	−1.2 (2)
N4—C22—C23—C24	−0.4 (2)	C40—C39—C38—C37	0.1 (2)
N5—C27—C26—N4	5.83 (16)	C32—N6—C36—C35	−0.20 (19)
N5—C27—C26—C25	−171.86 (12)	C32—C31—C30—C29	176.52 (12)
N5—C27—C28—C29	2.75 (19)	C32—C33—C34—C35	−0.4 (2)
N5—C31—C32—N6	−5.90 (16)	C15—N3—C11—C10	177.08 (11)
N5—C31—C32—C33	170.91 (12)	C15—N3—C11—C12	−0.65 (18)
N5—C31—C30—C29	0.84 (19)	C28—C27—C26—N4	−176.96 (12)
N1—C5—C4—C3	−0.08 (19)	C28—C27—C26—C25	5.3 (2)
N2—C10—C9—C8	−1.93 (18)	C28—C29—C30—C31	0.36 (19)
N2—C6—C5—N1	−5.27 (16)	C39—C40—C41—C42	2.3 (2)
N2—C6—C5—C4	172.95 (11)	C30—C29—C28—C27	−2.07 (18)
N2—C6—C7—C8	−2.40 (18)	C30—C31—C32—N6	178.16 (12)
N6—C32—C33—C34	1.90 (19)	C30—C31—C32—C33	−5.02 (19)
N6—C36—C35—C34	1.6 (2)	C38—C37—C29—C28	−27.63 (19)
N3—C11—C10—N2	−2.91 (16)	C38—C37—C29—C30	148.45 (13)
N3—C11—C10—C9	178.31 (11)	C38—C37—C42—C41	−1.9 (2)
N3—C11—C12—C13	1.86 (19)	C33—C34—C35—C36	−1.2 (2)
N3—C15—C14—C13	1.5 (2)	C21—C16—C8—C7	−175.33 (12)
C11—N3—C15—C14	−1.06 (19)	C21—C16—C8—C9	5.17 (18)
C11—C10—C9—C8	176.75 (11)	C21—C16—C17—C18	0.46 (19)
C11—C12—C13—C14	−1.37 (19)	C42—C37—C29—C28	157.44 (13)
C10—N2—C6—C5	−176.95 (10)	C42—C37—C29—C30	−26.48 (18)
C10—N2—C6—C7	2.01 (18)	C42—C37—C38—C39	2.0 (2)
C10—C11—C12—C13	−175.70 (11)	C20—C19—C18—C17	−0.5 (2)
C10—C9—C8—C7	1.49 (17)	C41—C40—C39—C38	−2.2 (2)
C10—C9—C8—C16	−178.99 (11)	C1—N1—C5—C6	176.91 (11)
C6—N2—C10—C11	−178.63 (10)	C1—N1—C5—C4	−1.34 (18)
C6—N2—C10—C9	0.16 (18)	C1—C2—C3—C4	−0.6 (2)
C6—C5—C4—C3	−178.19 (12)	C36—N6—C32—C31	175.27 (11)
C6—C7—C8—C16	−178.95 (11)	C36—N6—C32—C33	−1.57 (18)
C6—C7—C8—C9	0.58 (17)	C22—N4—C26—C27	179.77 (11)
C5—N1—C1—C2	1.87 (19)	C22—N4—C26—C25	−2.51 (19)
C5—C6—C7—C8	176.47 (11)	C3—C2—C1—N1	−0.9 (2)
C5—C4—C3—C2	1.0 (2)	C44—O1—C19—C18	−1.7 (2)
C7—C6—C5—N1	175.78 (11)	C44—O1—C19—C20	178.59 (13)
C7—C6—C5—C4	−5.99 (19)	C43—O2—C40—C39	−170.34 (12)
C27—N5—C31—C32	−176.28 (11)	C43—O2—C40—C41	9.96 (19)

Bis(4'-phenyl-2,2':6',2''-terpyridine)manganese(II) bis(perchlorate) (MnPhTPY) top

Crystal data top

[Mn(C₂₁H₁₅N₃)₂](ClO₄)₂	F(000) = 1788
M_r = 872.56	D_x = 1.567 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.51026 (18) Å	Cell parameters from 38088 reflections
b = 12.5149 (2) Å	θ = 2.6–34.1°
c = 31.2962 (6) Å	µ = 0.57 mm⁻¹
β = 96.8780 (18)°	T = 100 K
V = 3698.07 (12) Å³	Block, yellow
Z = 4	0.30 × 0.11 × 0.03 mm

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	9547 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	8250 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.032
Detector resolution: 10.0000 pixels mm^-1	θ_max = 28.7°, θ_min = 2.6°
ω scans	h = −13→14
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2022)	k = −19→19
	l = −48→45
63288 measured reflections

Refinement top

Refinement on F²	3 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0383P)² + 2.5012P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.002
9547 reflections	Δρ_max = 0.43 e Å⁻³
560 parameters	Δρ_min = −0.51 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mn1	0.55217 (2)	0.66511 (2)	0.61483 (2)	0.01214 (6)
Cl2	0.03899 (4)	0.78696 (3)	0.51551 (2)	0.01592 (7)
Cl1	0.76703 (4)	0.90467 (3)	0.74675 (2)	0.02234 (8)
O8	0.03068 (13)	0.67290 (8)	0.50689 (4)	0.0236 (2)
O7	−0.02540 (12)	0.80943 (9)	0.55382 (3)	0.0241 (2)
O5	0.18577 (11)	0.81940 (9)	0.52167 (3)	0.0213 (2)
N5	0.60249 (12)	0.63127 (9)	0.68354 (3)	0.0132 (2)
O6	−0.03368 (13)	0.84378 (9)	0.47935 (4)	0.0276 (3)
N6	0.36831 (12)	0.72376 (9)	0.64782 (4)	0.0139 (2)
N2	0.48224 (12)	0.67389 (9)	0.54501 (4)	0.0123 (2)
N4	0.77714 (12)	0.60523 (9)	0.62545 (4)	0.0138 (2)
N1	0.43169 (12)	0.51278 (9)	0.59496 (4)	0.0141 (2)
N3	0.63622 (12)	0.81781 (9)	0.59029 (4)	0.0137 (2)
O1	0.65906 (16)	0.85930 (12)	0.71679 (4)	0.0420 (4)
C10	0.51562 (14)	0.75998 (10)	0.52251 (4)	0.0123 (2)
C11	0.60971 (14)	0.83862 (10)	0.54766 (4)	0.0129 (2)
C7	0.33460 (14)	0.60963 (11)	0.48354 (4)	0.0142 (2)
H7	0.273413	0.555629	0.470614	0.017*
C9	0.46060 (14)	0.77417 (11)	0.47975 (4)	0.0139 (2)
H9	0.487664	0.834390	0.464158	0.017*
C27	0.50548 (15)	0.65035 (11)	0.71035 (4)	0.0150 (3)
O3	0.7117 (8)	0.9230 (7)	0.78654 (16)	0.0558 (17)	0.63 (3)
C32	0.83040 (15)	0.58016 (10)	0.66632 (4)	0.0134 (2)
C37	0.69504 (15)	0.56670 (11)	0.81747 (4)	0.0140 (2)
C5	0.36273 (14)	0.50937 (10)	0.55456 (4)	0.0130 (2)
C39	0.85716 (15)	0.58695 (11)	0.88276 (4)	0.0165 (3)
H39	0.946484	0.609258	0.896764	0.020*
C29	0.66243 (15)	0.58427 (11)	0.77054 (4)	0.0144 (3)
C38	0.82713 (15)	0.59734 (11)	0.83840 (4)	0.0159 (3)
H38	0.896841	0.625481	0.822166	0.019*
C28	0.53130 (15)	0.62540 (12)	0.75376 (4)	0.0175 (3)
H28	0.459662	0.636353	0.772015	0.021*
C31	0.72924 (14)	0.59099 (10)	0.69895 (4)	0.0128 (2)
C22	0.25461 (15)	0.77547 (11)	0.62823 (4)	0.0160 (3)
H22	0.249169	0.788010	0.598135	0.019*
C30	0.76353 (15)	0.56662 (11)	0.74226 (4)	0.0149 (3)
H30	0.854065	0.538437	0.752509	0.018*
C16	0.29350 (15)	0.71704 (10)	0.41567 (4)	0.0141 (2)
C33	0.97100 (15)	0.55131 (11)	0.67687 (5)	0.0174 (3)
H33	1.006288	0.534072	0.705735	0.021*
C26	0.37499 (15)	0.70548 (11)	0.69054 (4)	0.0156 (3)
C1	0.40786 (15)	0.43499 (11)	0.62260 (4)	0.0170 (3)
H1	0.456432	0.437461	0.650936	0.020*
C15	0.71934 (15)	0.88546 (11)	0.61525 (4)	0.0170 (3)
H15	0.737822	0.870942	0.645190	0.020*
C23	0.14478 (15)	0.81139 (11)	0.64994 (5)	0.0177 (3)
H23	0.065895	0.847533	0.634981	0.021*
C40	0.75682 (16)	0.54398 (11)	0.90670 (4)	0.0170 (3)
H40	0.777778	0.535894	0.936980	0.020*
C6	0.39392 (14)	0.59966 (10)	0.52607 (4)	0.0127 (2)
C12	0.66710 (15)	0.92730 (11)	0.52940 (4)	0.0162 (3)
H12	0.647298	0.940444	0.499385	0.019*
C42	0.59376 (15)	0.52416 (11)	0.84167 (4)	0.0162 (3)
H42	0.503634	0.503029	0.827872	0.019*
C36	0.86477 (16)	0.60294 (11)	0.59492 (4)	0.0166 (3)
H36	0.828109	0.621775	0.566335	0.020*
C35	1.00601 (16)	0.57446 (11)	0.60306 (5)	0.0183 (3)
H35	1.064774	0.573173	0.580567	0.022*
C8	0.36532 (14)	0.69952 (11)	0.45980 (4)	0.0136 (2)
C14	0.77917 (16)	0.97545 (11)	0.59913 (5)	0.0186 (3)
H14	0.836793	1.022020	0.617733	0.022*
C24	0.15228 (16)	0.79362 (12)	0.69374 (5)	0.0213 (3)
H24	0.079328	0.818195	0.709534	0.026*
C34	1.05955 (16)	0.54793 (12)	0.64472 (5)	0.0193 (3)
H34	1.155959	0.527595	0.651278	0.023*
C17	0.15410 (16)	0.68177 (11)	0.40447 (4)	0.0167 (3)
H17	0.105846	0.645968	0.425177	0.020*
O2	0.8790 (7)	0.8296 (7)	0.7535 (3)	0.068 (2)	0.63 (3)
C18	0.08613 (16)	0.69891 (12)	0.36322 (5)	0.0185 (3)
H18	−0.007989	0.674014	0.355797	0.022*
C41	0.62557 (16)	0.51291 (12)	0.88606 (4)	0.0179 (3)
H41	0.556852	0.483697	0.902399	0.021*
C21	0.36073 (16)	0.77218 (12)	0.38509 (4)	0.0196 (3)
H21	0.454548	0.797856	0.392359	0.023*
C25	0.26879 (16)	0.73902 (13)	0.71425 (5)	0.0217 (3)
H25	0.275578	0.724815	0.744243	0.026*
C4	0.26772 (15)	0.42783 (11)	0.54152 (4)	0.0170 (3)
H4	0.219498	0.427119	0.513126	0.020*
C13	0.75362 (16)	0.99655 (11)	0.55536 (5)	0.0187 (3)
H13	0.794524	1.057186	0.543389	0.022*
C19	0.15471 (17)	0.75212 (13)	0.33278 (5)	0.0217 (3)
H19	0.108514	0.762657	0.304466	0.026*
C2	0.31509 (16)	0.35074 (11)	0.61163 (5)	0.0188 (3)
H2	0.300879	0.296708	0.632004	0.023*
O4	0.8043 (11)	1.0058 (4)	0.7301 (3)	0.0469 (14)	0.63 (3)
C20	0.29110 (18)	0.78976 (14)	0.34403 (5)	0.0248 (3)
H20	0.337486	0.827917	0.323519	0.030*
C3	0.24407 (16)	0.34735 (11)	0.57048 (5)	0.0188 (3)
H3	0.179972	0.290843	0.562074	0.023*
O3A	0.7150 (9)	0.9475 (18)	0.7823 (4)	0.071 (4)	0.37 (3)
O2A	0.8771 (11)	0.8339 (10)	0.7614 (4)	0.060 (3)	0.37 (3)
O4A	0.852 (2)	0.9827 (19)	0.7260 (5)	0.064 (4)	0.37 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.01269 (10)	0.01436 (10)	0.00917 (9)	−0.00060 (7)	0.00045 (7)	0.00137 (7)
Cl2	0.01597 (16)	0.01960 (16)	0.01186 (14)	0.00072 (11)	0.00028 (11)	0.00258 (11)
Cl1	0.02685 (19)	0.02322 (17)	0.01604 (16)	−0.00158 (14)	−0.00119 (13)	−0.00172 (13)
O8	0.0293 (6)	0.0202 (5)	0.0213 (5)	−0.0026 (4)	0.0025 (4)	0.0004 (4)
O7	0.0227 (6)	0.0319 (6)	0.0189 (5)	0.0048 (5)	0.0079 (4)	0.0014 (4)
O5	0.0160 (5)	0.0282 (6)	0.0198 (5)	−0.0017 (4)	0.0025 (4)	−0.0006 (4)
N5	0.0133 (5)	0.0149 (5)	0.0113 (5)	0.0008 (4)	0.0009 (4)	0.0003 (4)
O6	0.0316 (7)	0.0293 (6)	0.0191 (5)	−0.0003 (5)	−0.0084 (5)	0.0089 (4)
N6	0.0141 (6)	0.0151 (5)	0.0122 (5)	−0.0002 (4)	0.0005 (4)	0.0023 (4)
N2	0.0116 (5)	0.0133 (5)	0.0121 (5)	0.0004 (4)	0.0013 (4)	0.0000 (4)
N4	0.0151 (6)	0.0143 (5)	0.0123 (5)	−0.0001 (4)	0.0025 (4)	0.0001 (4)
N1	0.0145 (6)	0.0144 (5)	0.0134 (5)	0.0000 (4)	0.0013 (4)	0.0015 (4)
N3	0.0136 (5)	0.0148 (5)	0.0126 (5)	−0.0001 (4)	0.0011 (4)	0.0001 (4)
O1	0.0525 (9)	0.0480 (8)	0.0220 (6)	−0.0249 (7)	−0.0098 (6)	−0.0014 (5)
C10	0.0114 (6)	0.0126 (6)	0.0133 (6)	0.0013 (4)	0.0032 (5)	0.0004 (4)
C11	0.0112 (6)	0.0146 (6)	0.0129 (6)	0.0019 (5)	0.0012 (5)	−0.0002 (5)
C7	0.0141 (6)	0.0144 (6)	0.0135 (6)	0.0009 (5)	−0.0003 (5)	−0.0013 (5)
C9	0.0143 (6)	0.0147 (6)	0.0129 (6)	0.0010 (5)	0.0020 (5)	0.0017 (5)
C27	0.0136 (6)	0.0189 (6)	0.0124 (6)	0.0019 (5)	0.0012 (5)	0.0012 (5)
O3	0.074 (4)	0.079 (3)	0.0167 (19)	−0.008 (2)	0.0153 (17)	−0.009 (2)
C32	0.0156 (6)	0.0123 (6)	0.0126 (6)	0.0001 (5)	0.0022 (5)	0.0000 (5)
C37	0.0157 (6)	0.0150 (6)	0.0110 (6)	0.0026 (5)	0.0003 (5)	0.0006 (5)
C5	0.0130 (6)	0.0135 (6)	0.0127 (6)	0.0015 (5)	0.0020 (5)	−0.0003 (4)
C39	0.0155 (7)	0.0190 (6)	0.0144 (6)	0.0013 (5)	−0.0011 (5)	−0.0025 (5)
C29	0.0164 (7)	0.0157 (6)	0.0104 (6)	0.0000 (5)	−0.0009 (5)	0.0005 (5)
C38	0.0155 (7)	0.0188 (6)	0.0134 (6)	−0.0004 (5)	0.0021 (5)	−0.0002 (5)
C28	0.0166 (7)	0.0237 (7)	0.0126 (6)	0.0040 (5)	0.0037 (5)	0.0021 (5)
C31	0.0129 (6)	0.0128 (6)	0.0126 (6)	0.0003 (5)	0.0011 (5)	−0.0004 (4)
C22	0.0171 (7)	0.0157 (6)	0.0145 (6)	−0.0007 (5)	−0.0011 (5)	0.0031 (5)
C30	0.0141 (6)	0.0170 (6)	0.0132 (6)	0.0015 (5)	−0.0003 (5)	0.0008 (5)
C16	0.0169 (7)	0.0140 (6)	0.0113 (6)	0.0029 (5)	0.0010 (5)	−0.0010 (5)
C33	0.0161 (7)	0.0187 (6)	0.0173 (6)	0.0022 (5)	0.0014 (5)	0.0023 (5)
C26	0.0138 (6)	0.0187 (6)	0.0140 (6)	0.0024 (5)	0.0001 (5)	0.0026 (5)
C1	0.0186 (7)	0.0173 (6)	0.0147 (6)	−0.0003 (5)	0.0007 (5)	0.0029 (5)
C15	0.0158 (7)	0.0198 (7)	0.0150 (6)	−0.0005 (5)	0.0004 (5)	−0.0014 (5)
C23	0.0141 (7)	0.0176 (6)	0.0203 (7)	0.0012 (5)	−0.0022 (5)	0.0021 (5)
C40	0.0218 (7)	0.0186 (6)	0.0103 (6)	0.0031 (5)	0.0004 (5)	0.0000 (5)
C6	0.0123 (6)	0.0124 (6)	0.0136 (6)	0.0016 (5)	0.0024 (5)	0.0003 (4)
C12	0.0161 (7)	0.0172 (6)	0.0154 (6)	0.0000 (5)	0.0023 (5)	0.0024 (5)
C42	0.0146 (7)	0.0196 (6)	0.0141 (6)	0.0009 (5)	−0.0002 (5)	0.0012 (5)
C36	0.0203 (7)	0.0164 (6)	0.0138 (6)	−0.0006 (5)	0.0042 (5)	0.0005 (5)
C35	0.0194 (7)	0.0169 (6)	0.0200 (7)	0.0003 (5)	0.0084 (5)	0.0008 (5)
C8	0.0139 (6)	0.0155 (6)	0.0116 (6)	0.0031 (5)	0.0024 (5)	−0.0002 (5)
C14	0.0156 (7)	0.0185 (7)	0.0211 (7)	−0.0025 (5)	0.0002 (5)	−0.0031 (5)
C24	0.0167 (7)	0.0264 (7)	0.0210 (7)	0.0056 (6)	0.0032 (6)	−0.0001 (6)
C34	0.0144 (7)	0.0194 (7)	0.0246 (7)	0.0030 (5)	0.0046 (6)	0.0018 (5)
C17	0.0186 (7)	0.0155 (6)	0.0157 (6)	0.0003 (5)	0.0009 (5)	0.0018 (5)
O2	0.043 (3)	0.069 (4)	0.098 (4)	0.025 (3)	0.038 (3)	0.011 (3)
C18	0.0179 (7)	0.0194 (7)	0.0173 (6)	0.0014 (5)	−0.0015 (5)	−0.0014 (5)
C41	0.0188 (7)	0.0206 (7)	0.0146 (6)	0.0002 (5)	0.0037 (5)	0.0028 (5)
C21	0.0180 (7)	0.0266 (7)	0.0143 (6)	−0.0010 (6)	0.0025 (5)	0.0005 (5)
C25	0.0196 (7)	0.0321 (8)	0.0136 (6)	0.0071 (6)	0.0033 (5)	0.0029 (6)
C4	0.0180 (7)	0.0173 (6)	0.0151 (6)	−0.0017 (5)	0.0002 (5)	−0.0006 (5)
C13	0.0175 (7)	0.0158 (6)	0.0232 (7)	−0.0024 (5)	0.0035 (6)	0.0019 (5)
C19	0.0231 (8)	0.0296 (8)	0.0116 (6)	0.0027 (6)	−0.0011 (5)	0.0003 (5)
C2	0.0198 (7)	0.0168 (6)	0.0201 (7)	−0.0013 (5)	0.0040 (5)	0.0045 (5)
O4	0.053 (3)	0.0302 (18)	0.052 (2)	−0.0182 (17)	−0.014 (2)	0.0109 (14)
C20	0.0255 (8)	0.0369 (9)	0.0124 (6)	−0.0022 (6)	0.0043 (6)	0.0035 (6)
C3	0.0176 (7)	0.0160 (6)	0.0229 (7)	−0.0035 (5)	0.0027 (6)	0.0001 (5)
O3A	0.021 (3)	0.112 (8)	0.076 (7)	0.016 (3)	−0.005 (3)	−0.078 (6)
O2A	0.054 (6)	0.055 (5)	0.059 (4)	0.032 (4)	−0.041 (5)	−0.016 (3)
O4A	0.061 (7)	0.081 (8)	0.044 (4)	−0.047 (6)	−0.019 (4)	0.030 (5)

Geometric parameters (Å, º) top

Mn1—N5	2.1876 (11)	C38—H38	0.9500
Mn1—N2	2.2091 (11)	C28—H28	0.9500
Mn1—N3	2.2423 (12)	C31—C30	1.3894 (18)
Mn1—N4	2.2537 (12)	C22—C23	1.387 (2)
Mn1—N6	2.2571 (12)	C22—H22	0.9500
Mn1—N1	2.2723 (12)	C30—H30	0.9500
Cl2—O7	1.4378 (11)	C16—C21	1.396 (2)
Cl2—O6	1.4412 (11)	C16—C17	1.401 (2)
Cl2—O5	1.4443 (11)	C16—C8	1.4819 (18)
Cl2—O8	1.4530 (11)	C33—C34	1.388 (2)
Cl1—O3A	1.381 (8)	C33—H33	0.9500
Cl1—O2A	1.406 (8)	C26—C25	1.388 (2)
Cl1—O2	1.417 (6)	C1—C2	1.391 (2)
Cl1—O1	1.4231 (13)	C1—H1	0.9500
Cl1—O3	1.427 (5)	C15—C14	1.384 (2)
Cl1—O4	1.429 (6)	C15—H15	0.9500
Cl1—O4A	1.466 (9)	C23—C24	1.382 (2)
N5—C27	1.3408 (18)	C23—H23	0.9500
N5—C31	1.3418 (17)	C40—C41	1.391 (2)
N6—C22	1.3437 (18)	C40—H40	0.9500
N6—C26	1.3504 (17)	C12—C13	1.389 (2)
N2—C6	1.3419 (17)	C12—H12	0.9500
N2—C10	1.3459 (17)	C42—C41	1.3929 (19)
N4—C36	1.3415 (18)	C42—H42	0.9500
N4—C32	1.3547 (17)	C36—C35	1.384 (2)
N1—C1	1.3397 (18)	C36—H36	0.9500
N1—C5	1.3532 (17)	C35—C34	1.382 (2)
N3—C15	1.3431 (18)	C35—H35	0.9500
N3—C11	1.3530 (17)	C14—C13	1.388 (2)
C10—C9	1.3885 (18)	C14—H14	0.9500
C10—C11	1.4901 (18)	C24—C25	1.391 (2)
C11—C12	1.3896 (19)	C24—H24	0.9500
C7—C6	1.3877 (18)	C34—H34	0.9500
C7—C8	1.3982 (19)	C17—C18	1.3896 (19)
C7—H7	0.9500	C17—H17	0.9500
C9—C8	1.3958 (19)	C18—C19	1.387 (2)
C9—H9	0.9500	C18—H18	0.9500
C27—C28	1.3870 (18)	C41—H41	0.9500
C27—C26	1.4887 (19)	C21—C20	1.391 (2)
C32—C33	1.3862 (19)	C21—H21	0.9500
C32—C31	1.4909 (18)	C25—H25	0.9500
C37—C38	1.3991 (19)	C4—C3	1.391 (2)
C37—C42	1.400 (2)	C4—H4	0.9500
C37—C29	1.4807 (18)	C13—H13	0.9500
C5—C4	1.3914 (19)	C19—C20	1.385 (2)
C5—C6	1.4911 (18)	C19—H19	0.9500
C39—C38	1.3895 (19)	C2—C3	1.381 (2)
C39—C40	1.390 (2)	C2—H2	0.9500
C39—H39	0.9500	C20—H20	0.9500
C29—C28	1.3925 (19)	C3—H3	0.9500
C29—C30	1.4003 (19)

N5—Mn1—N2	170.51 (4)	C30—C31—C32	123.57 (12)
N5—Mn1—N3	117.17 (4)	N6—C22—C23	122.99 (13)
N2—Mn1—N3	72.32 (4)	N6—C22—H22	118.5
N5—Mn1—N4	72.45 (4)	C23—C22—H22	118.5
N2—Mn1—N4	109.30 (4)	C31—C30—C29	118.90 (12)
N3—Mn1—N4	87.87 (4)	C31—C30—H30	120.5
N5—Mn1—N6	72.76 (4)	C29—C30—H30	120.5
N2—Mn1—N6	106.16 (4)	C21—C16—C17	118.78 (13)
N3—Mn1—N6	101.95 (4)	C21—C16—C8	120.96 (13)
N4—Mn1—N6	144.53 (4)	C17—C16—C8	120.21 (12)
N5—Mn1—N1	98.65 (4)	C32—C33—C34	119.13 (13)
N2—Mn1—N1	71.87 (4)	C32—C33—H33	120.4
N3—Mn1—N1	144.10 (4)	C34—C33—H33	120.4
N4—Mn1—N1	101.55 (4)	N6—C26—C25	121.81 (13)
N6—Mn1—N1	90.29 (4)	N6—C26—C27	115.39 (12)
O7—Cl2—O6	110.25 (7)	C25—C26—C27	122.77 (12)
O7—Cl2—O5	109.58 (7)	N1—C1—C2	122.87 (13)
O6—Cl2—O5	109.33 (7)	N1—C1—H1	118.6
O7—Cl2—O8	109.14 (7)	C2—C1—H1	118.6
O6—Cl2—O8	109.18 (7)	N3—C15—C14	122.69 (13)
O5—Cl2—O8	109.34 (7)	N3—C15—H15	118.7
O3A—Cl1—O2A	107.8 (7)	C14—C15—H15	118.7
O3A—Cl1—O1	112.7 (5)	C24—C23—C22	118.76 (13)
O2A—Cl1—O1	114.5 (5)	C24—C23—H23	120.6
O2—Cl1—O1	107.6 (4)	C22—C23—H23	120.6
O2—Cl1—O3	109.0 (4)	C39—C40—C41	119.58 (13)
O1—Cl1—O3	109.1 (3)	C39—C40—H40	120.2
O2—Cl1—O4	115.2 (5)	C41—C40—H40	120.2
O1—Cl1—O4	107.7 (3)	N2—C6—C7	121.51 (12)
O3—Cl1—O4	108.0 (4)	N2—C6—C5	114.79 (11)
O3A—Cl1—O4A	111.6 (8)	C7—C6—C5	123.68 (12)
O2A—Cl1—O4A	97.9 (10)	C13—C12—C11	119.48 (13)
O1—Cl1—O4A	111.4 (5)	C13—C12—H12	120.3
C27—N5—C31	119.85 (11)	C11—C12—H12	120.3
C27—N5—Mn1	119.65 (9)	C41—C42—C37	119.78 (13)
C31—N5—Mn1	120.50 (9)	C41—C42—H42	120.1
C22—N6—C26	118.25 (12)	C37—C42—H42	120.1
C22—N6—Mn1	124.96 (9)	N4—C36—C35	123.12 (13)
C26—N6—Mn1	116.79 (9)	N4—C36—H36	118.4
C6—N2—C10	119.83 (11)	C35—C36—H36	118.4
C6—N2—Mn1	120.06 (9)	C34—C35—C36	118.40 (13)
C10—N2—Mn1	119.70 (9)	C34—C35—H35	120.8
C36—N4—C32	118.27 (12)	C36—C35—H35	120.8
C36—N4—Mn1	124.18 (9)	C9—C8—C7	117.82 (12)
C32—N4—Mn1	117.22 (9)	C9—C8—C16	121.33 (12)
C1—N1—C5	118.68 (12)	C7—C8—C16	120.79 (12)
C1—N1—Mn1	123.48 (9)	C15—C14—C13	118.92 (13)
C5—N1—Mn1	117.01 (9)	C15—C14—H14	120.5
C15—N3—C11	118.64 (12)	C13—C14—H14	120.5
C15—N3—Mn1	123.18 (9)	C23—C24—C25	118.70 (14)
C11—N3—Mn1	118.02 (9)	C23—C24—H24	120.7
N2—C10—C9	121.43 (12)	C25—C24—H24	120.7
N2—C10—C11	114.62 (11)	C35—C34—C33	119.31 (14)
C9—C10—C11	123.91 (12)	C35—C34—H34	120.3
N3—C11—C12	121.56 (12)	C33—C34—H34	120.3
N3—C11—C10	115.03 (11)	C18—C17—C16	120.31 (13)
C12—C11—C10	123.42 (12)	C18—C17—H17	119.8
C6—C7—C8	119.68 (12)	C16—C17—H17	119.8
C6—C7—H7	120.2	C19—C18—C17	120.49 (14)
C8—C7—H7	120.2	C19—C18—H18	119.8
C10—C9—C8	119.67 (12)	C17—C18—H18	119.8
C10—C9—H9	120.2	C40—C41—C42	120.72 (13)
C8—C9—H9	120.2	C40—C41—H41	119.6
N5—C27—C28	121.24 (13)	C42—C41—H41	119.6
N5—C27—C26	115.07 (12)	C20—C21—C16	120.36 (14)
C28—C27—C26	123.59 (13)	C20—C21—H21	119.8
N4—C32—C33	121.75 (12)	C16—C21—H21	119.8
N4—C32—C31	115.25 (12)	C26—C25—C24	119.49 (13)
C33—C32—C31	122.93 (12)	C26—C25—H25	120.3
C38—C37—C42	119.23 (12)	C24—C25—H25	120.3
C38—C37—C29	119.57 (12)	C3—C4—C5	119.33 (13)
C42—C37—C29	121.15 (12)	C3—C4—H4	120.3
N1—C5—C4	121.48 (12)	C5—C4—H4	120.3
N1—C5—C6	115.21 (12)	C14—C13—C12	118.70 (13)
C4—C5—C6	123.30 (12)	C14—C13—H13	120.6
C38—C39—C40	120.17 (13)	C12—C13—H13	120.6
C38—C39—H39	119.9	C20—C19—C18	119.45 (13)
C40—C39—H39	119.9	C20—C19—H19	120.3
C28—C29—C30	118.14 (12)	C18—C19—H19	120.3
C28—C29—C37	120.05 (12)	C3—C2—C1	118.56 (13)
C30—C29—C37	121.70 (12)	C3—C2—H2	120.7
C39—C38—C37	120.52 (13)	C1—C2—H2	120.7
C39—C38—H38	119.7	C19—C20—C21	120.58 (14)
C37—C38—H38	119.7	C19—C20—H20	119.7
C27—C28—C29	119.88 (13)	C21—C20—H20	119.7
C27—C28—H28	120.1	C2—C3—C4	119.08 (13)
C29—C28—H28	120.1	C2—C3—H3	120.5
N5—C31—C30	121.94 (12)	C4—C3—H3	120.5
N5—C31—C32	114.42 (11)

C6—N2—C10—C9	−0.04 (19)	C28—C27—C26—N6	179.68 (13)
Mn1—N2—C10—C9	−172.69 (10)	N5—C27—C26—C25	−174.73 (14)
C6—N2—C10—C11	177.57 (12)	C28—C27—C26—C25	1.5 (2)
Mn1—N2—C10—C11	4.92 (15)	C5—N1—C1—C2	−0.1 (2)
C15—N3—C11—C12	0.5 (2)	Mn1—N1—C1—C2	169.18 (11)
Mn1—N3—C11—C12	−175.00 (10)	C11—N3—C15—C14	−0.1 (2)
C15—N3—C11—C10	−179.51 (12)	Mn1—N3—C15—C14	175.09 (11)
Mn1—N3—C11—C10	5.02 (15)	N6—C22—C23—C24	0.2 (2)
N2—C10—C11—N3	−6.41 (17)	C38—C39—C40—C41	−0.9 (2)
C9—C10—C11—N3	171.12 (12)	C10—N2—C6—C7	−0.4 (2)
N2—C10—C11—C12	173.61 (13)	Mn1—N2—C6—C7	172.17 (10)
C9—C10—C11—C12	−8.9 (2)	C10—N2—C6—C5	−178.75 (11)
N2—C10—C9—C8	1.9 (2)	Mn1—N2—C6—C5	−6.13 (15)
C11—C10—C9—C8	−175.48 (12)	C8—C7—C6—N2	−0.9 (2)
C31—N5—C27—C28	−2.5 (2)	C8—C7—C6—C5	177.22 (12)
Mn1—N5—C27—C28	177.06 (11)	N1—C5—C6—N2	−2.35 (17)
C31—N5—C27—C26	173.85 (12)	C4—C5—C6—N2	176.36 (13)
Mn1—N5—C27—C26	−6.57 (16)	N1—C5—C6—C7	179.39 (12)
C36—N4—C32—C33	−0.84 (19)	C4—C5—C6—C7	−1.9 (2)
Mn1—N4—C32—C33	−174.46 (10)	N3—C11—C12—C13	−0.1 (2)
C36—N4—C32—C31	176.34 (12)	C10—C11—C12—C13	179.88 (13)
Mn1—N4—C32—C31	2.72 (15)	C38—C37—C42—C41	0.0 (2)
C1—N1—C5—C4	0.5 (2)	C29—C37—C42—C41	−177.20 (13)
Mn1—N1—C5—C4	−169.42 (10)	C32—N4—C36—C35	1.1 (2)
C1—N1—C5—C6	179.25 (12)	Mn1—N4—C36—C35	174.29 (10)
Mn1—N1—C5—C6	9.31 (15)	N4—C36—C35—C34	−0.5 (2)
C38—C37—C29—C28	−136.00 (14)	C10—C9—C8—C7	−3.2 (2)
C42—C37—C29—C28	41.19 (19)	C10—C9—C8—C16	173.95 (12)
C38—C37—C29—C30	40.11 (19)	C6—C7—C8—C9	2.7 (2)
C42—C37—C29—C30	−142.71 (14)	C6—C7—C8—C16	−174.43 (12)
C40—C39—C38—C37	1.2 (2)	C21—C16—C8—C9	32.5 (2)
C42—C37—C38—C39	−0.8 (2)	C17—C16—C8—C9	−145.05 (14)
C29—C37—C38—C39	176.49 (13)	C21—C16—C8—C7	−150.48 (14)
N5—C27—C28—C29	3.0 (2)	C17—C16—C8—C7	31.98 (19)
C26—C27—C28—C29	−173.07 (13)	N3—C15—C14—C13	−0.6 (2)
C30—C29—C28—C27	−1.8 (2)	C22—C23—C24—C25	−0.9 (2)
C37—C29—C28—C27	174.48 (13)	C36—C35—C34—C33	−0.4 (2)
C27—N5—C31—C30	0.9 (2)	C32—C33—C34—C35	0.7 (2)
Mn1—N5—C31—C30	−178.69 (10)	C21—C16—C17—C18	1.9 (2)
C27—N5—C31—C32	−176.25 (12)	C8—C16—C17—C18	179.45 (13)
Mn1—N5—C31—C32	4.17 (15)	C16—C17—C18—C19	−0.7 (2)
N4—C32—C31—N5	−4.42 (17)	C39—C40—C41—C42	0.1 (2)
C33—C32—C31—N5	172.73 (13)	C37—C42—C41—C40	0.3 (2)
N4—C32—C31—C30	178.50 (12)	C17—C16—C21—C20	−1.2 (2)
C33—C32—C31—C30	−4.4 (2)	C8—C16—C21—C20	−178.81 (14)
C26—N6—C22—C23	0.5 (2)	N6—C26—C25—C24	−0.4 (2)
Mn1—N6—C22—C23	−179.10 (10)	C27—C26—C25—C24	177.60 (14)
N5—C31—C30—C29	0.3 (2)	C23—C24—C25—C26	1.0 (2)
C32—C31—C30—C29	177.14 (12)	N1—C5—C4—C3	−0.7 (2)
C28—C29—C30—C31	0.2 (2)	C6—C5—C4—C3	−179.30 (13)
C37—C29—C30—C31	−175.98 (12)	C15—C14—C13—C12	0.9 (2)
N4—C32—C33—C34	−0.1 (2)	C11—C12—C13—C14	−0.6 (2)
C31—C32—C33—C34	−177.02 (13)	C17—C18—C19—C20	−1.1 (2)
C22—N6—C26—C25	−0.3 (2)	N1—C1—C2—C3	−0.2 (2)
Mn1—N6—C26—C25	179.27 (12)	C18—C19—C20—C21	1.7 (2)
C22—N6—C26—C27	−178.49 (12)	C16—C21—C20—C19	−0.5 (2)
Mn1—N6—C26—C27	1.11 (16)	C1—C2—C3—C4	0.1 (2)
N5—C27—C26—N6	3.41 (18)	C5—C4—C3—C2	0.4 (2)

Bis(4'-phenyl-2,2':6',2''-terpyridine)nickel(II) bis(perchlorate) (NiPhTPY) top

Crystal data top

[Ni(C₂₁H₁₅N₃)₂](ClO₄)₂	F(000) = 1800
M_r = 876.33	D_x = 1.581 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.3581 (2) Å	Cell parameters from 24227 reflections
b = 12.6255 (3) Å	θ = 2.5–33.3°
c = 31.4046 (8) Å	µ = 0.74 mm⁻¹
β = 97.038 (2)°	T = 100 K
V = 3682.52 (15) Å³	Block, light orange
Z = 4	0.10 × 0.08 × 0.06 mm

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	9514 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	7295 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.053
Detector resolution: 10.0000 pixels mm^-1	θ_max = 28.7°, θ_min = 2.5°
ω scans	h = −12→12
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2022)	k = −16→17
T_min = 0.815, T_max = 1.000	l = −41→42
52589 measured reflections

Refinement top

Refinement on F²	435 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0352P)² + 3.3821P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
9514 reflections	Δρ_max = 0.64 e Å⁻³
560 parameters	Δρ_min = −0.54 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.45313 (2)	0.67165 (2)	0.38521 (2)	0.01333 (7)
Cl2	0.97887 (5)	0.78974 (4)	0.49141 (2)	0.02213 (11)
Cl1	0.21363 (5)	0.92269 (4)	0.24853 (2)	0.02422 (11)
O8	0.97982 (18)	0.67651 (12)	0.50010 (5)	0.0281 (3)
N2	0.51734 (16)	0.68107 (12)	0.44827 (5)	0.0141 (3)
N5	0.39922 (17)	0.65160 (12)	0.32226 (5)	0.0149 (3)
N3	0.36801 (16)	0.81949 (12)	0.40160 (5)	0.0150 (3)
N4	0.63665 (17)	0.73271 (12)	0.35939 (5)	0.0153 (3)
O7	1.03924 (17)	0.80845 (13)	0.45232 (5)	0.0300 (4)
O5	0.83213 (17)	0.82817 (13)	0.48676 (5)	0.0305 (4)
N1	0.56197 (16)	0.52504 (12)	0.39778 (5)	0.0150 (3)
N6	0.24101 (17)	0.61193 (12)	0.38221 (5)	0.0148 (3)
O6	1.0601 (2)	0.84318 (14)	0.52657 (6)	0.0431 (5)
O1	0.3281 (2)	0.86989 (15)	0.27412 (6)	0.0432 (5)
C11	0.39025 (19)	0.84361 (14)	0.44381 (6)	0.0150 (4)
C10	0.48180 (19)	0.76651 (14)	0.47042 (6)	0.0139 (4)
C6	0.60250 (19)	0.60519 (14)	0.46752 (6)	0.0144 (4)
C9	0.5328 (2)	0.77833 (14)	0.51354 (6)	0.0158 (4)
H9	0.505366	0.838169	0.528984	0.019*
C31	0.27142 (19)	0.60874 (14)	0.30761 (6)	0.0151 (4)
C7	0.6573 (2)	0.61277 (14)	0.51031 (6)	0.0160 (4)
H7	0.716632	0.557990	0.523523	0.019*
C32	0.1769 (2)	0.59386 (14)	0.34180 (6)	0.0150 (4)
C33	0.0324 (2)	0.56748 (15)	0.33329 (7)	0.0182 (4)
H33	−0.010507	0.555517	0.304683	0.022*
C22	0.7524 (2)	0.78050 (14)	0.38051 (7)	0.0168 (4)
H22	0.758400	0.787381	0.410801	0.020*
C15	0.2843 (2)	0.88344 (15)	0.37516 (7)	0.0182 (4)
H15	0.268385	0.866400	0.345495	0.022*
C26	0.6302 (2)	0.72212 (15)	0.31626 (6)	0.0175 (4)
C4	0.7234 (2)	0.43312 (15)	0.45043 (7)	0.0189 (4)
H4	0.771109	0.428984	0.478880	0.023*
C28	0.4712 (2)	0.64245 (16)	0.25252 (6)	0.0187 (4)
H28	0.543636	0.651977	0.234154	0.022*
C27	0.4976 (2)	0.67007 (15)	0.29544 (6)	0.0167 (4)
C12	0.3292 (2)	0.93257 (15)	0.46021 (7)	0.0179 (4)
H12	0.346711	0.948280	0.489981	0.022*
C1	0.5830 (2)	0.44934 (15)	0.36943 (7)	0.0185 (4)
H1	0.533945	0.454587	0.341178	0.022*
C5	0.63146 (19)	0.51687 (14)	0.43826 (6)	0.0156 (4)
C37	0.3043 (2)	0.57916 (14)	0.18980 (6)	0.0163 (4)
C16	0.6910 (2)	0.71515 (14)	0.57908 (6)	0.0157 (4)
C35	0.0159 (2)	0.57788 (15)	0.40844 (7)	0.0196 (4)
H35	−0.037684	0.572543	0.432174	0.024*
C8	0.6249 (2)	0.70170 (14)	0.53421 (6)	0.0156 (4)
C29	0.3376 (2)	0.60056 (15)	0.23647 (6)	0.0173 (4)
C36	0.1606 (2)	0.60499 (15)	0.41440 (6)	0.0172 (4)
H36	0.204585	0.619275	0.442713	0.021*
C30	0.2357 (2)	0.58350 (15)	0.26470 (6)	0.0173 (4)
H30	0.143624	0.555153	0.254680	0.021*
C34	−0.0484 (2)	0.55889 (15)	0.36731 (7)	0.0207 (4)
H34	−0.147292	0.540038	0.362293	0.025*
C23	0.8639 (2)	0.82028 (15)	0.35977 (7)	0.0188 (4)
H23	0.944400	0.853616	0.375677	0.023*
C41	0.1443 (2)	0.59859 (15)	0.12386 (6)	0.0184 (4)
H41	0.055045	0.621815	0.109131	0.022*
C38	0.4062 (2)	0.53171 (15)	0.16699 (7)	0.0184 (4)
H38	0.495769	0.508838	0.181598	0.022*
C17	0.8301 (2)	0.67636 (15)	0.59224 (6)	0.0179 (4)
H17	0.881722	0.641089	0.572203	0.021*
C39	0.3764 (2)	0.51794 (15)	0.12283 (7)	0.0192 (4)
H39	0.445643	0.485270	0.107395	0.023*
C40	0.2459 (2)	0.55169 (15)	0.10117 (7)	0.0194 (4)
H40	0.226335	0.542719	0.070986	0.023*
C13	0.2422 (2)	0.99840 (15)	0.43267 (7)	0.0212 (4)
H13	0.198772	1.059359	0.443304	0.025*
C42	0.1725 (2)	0.61162 (15)	0.16785 (7)	0.0185 (4)
H42	0.101948	0.642816	0.183223	0.022*
C14	0.2201 (2)	0.97352 (15)	0.38943 (7)	0.0203 (4)
H14	0.161769	1.017505	0.369838	0.024*
C18	0.8925 (2)	0.68926 (15)	0.63440 (7)	0.0207 (4)
H18	0.986327	0.662215	0.643073	0.025*
C25	0.7372 (2)	0.76024 (17)	0.29377 (7)	0.0219 (4)
H25	0.729760	0.752056	0.263507	0.026*
C2	0.6733 (2)	0.36346 (16)	0.37950 (7)	0.0217 (4)
H2	0.685611	0.311102	0.358536	0.026*
C21	0.6194 (2)	0.76877 (16)	0.60888 (7)	0.0202 (4)
H21	0.526164	0.796943	0.600356	0.024*
C24	0.8561 (2)	0.81078 (16)	0.31587 (7)	0.0217 (4)
H24	0.930358	0.838190	0.300956	0.026*
C19	0.8188 (2)	0.74132 (16)	0.66385 (7)	0.0227 (4)
H19	0.861245	0.749420	0.692732	0.027*
C20	0.6825 (2)	0.78154 (17)	0.65077 (7)	0.0247 (4)
H20	0.631991	0.818131	0.670745	0.030*
C3	0.7451 (2)	0.35530 (15)	0.42056 (7)	0.0216 (4)
H3	0.808152	0.297560	0.428217	0.026*
O3	0.2592 (13)	0.9531 (12)	0.2092 (3)	0.060 (3)	0.54 (2)
O4	0.1845 (15)	1.0198 (6)	0.2704 (2)	0.061 (2)	0.54 (2)
O2	0.0905 (8)	0.8607 (9)	0.2423 (3)	0.087 (3)	0.54 (2)
O3A	0.2646 (12)	0.9837 (15)	0.2166 (5)	0.062 (4)	0.46 (2)
O4A	0.1294 (12)	0.9826 (13)	0.2744 (2)	0.053 (3)	0.46 (2)
O2A	0.1196 (17)	0.8454 (6)	0.2258 (6)	0.085 (5)	0.46 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01241 (11)	0.01601 (12)	0.01128 (12)	−0.00111 (9)	0.00028 (9)	−0.00063 (9)
Cl2	0.0235 (2)	0.0274 (2)	0.0151 (2)	−0.00382 (18)	0.00064 (19)	−0.00390 (18)
Cl1	0.0238 (2)	0.0324 (3)	0.0158 (2)	0.00260 (19)	−0.00016 (19)	0.0049 (2)
O8	0.0349 (9)	0.0294 (8)	0.0202 (8)	−0.0002 (7)	0.0036 (7)	−0.0005 (6)
N2	0.0116 (7)	0.0155 (7)	0.0149 (8)	−0.0020 (6)	0.0009 (6)	−0.0005 (6)
N5	0.0146 (7)	0.0167 (7)	0.0132 (8)	−0.0023 (6)	0.0006 (6)	0.0001 (6)
N3	0.0131 (7)	0.0170 (7)	0.0147 (8)	−0.0021 (6)	0.0003 (6)	0.0011 (6)
N4	0.0140 (7)	0.0178 (7)	0.0137 (8)	−0.0005 (6)	−0.0002 (6)	−0.0006 (6)
O7	0.0284 (8)	0.0374 (9)	0.0254 (9)	−0.0042 (7)	0.0081 (7)	0.0011 (7)
O5	0.0242 (8)	0.0382 (9)	0.0303 (9)	0.0025 (7)	0.0078 (7)	−0.0003 (7)
N1	0.0131 (7)	0.0169 (7)	0.0149 (8)	−0.0022 (6)	0.0013 (6)	−0.0014 (6)
N6	0.0151 (7)	0.0163 (7)	0.0127 (8)	−0.0003 (6)	0.0008 (6)	0.0001 (6)
O6	0.0548 (12)	0.0402 (10)	0.0284 (10)	−0.0048 (8)	−0.0185 (9)	−0.0116 (8)
O1	0.0499 (11)	0.0502 (11)	0.0260 (10)	0.0235 (9)	−0.0090 (8)	0.0041 (8)
C11	0.0128 (8)	0.0157 (8)	0.0163 (10)	−0.0030 (6)	0.0011 (7)	0.0013 (7)
C10	0.0113 (8)	0.0160 (8)	0.0144 (9)	−0.0016 (6)	0.0022 (7)	0.0007 (7)
C6	0.0141 (8)	0.0145 (8)	0.0146 (9)	−0.0007 (6)	0.0023 (7)	0.0012 (7)
C9	0.0172 (9)	0.0152 (8)	0.0152 (10)	−0.0008 (7)	0.0029 (7)	−0.0007 (7)
C31	0.0136 (8)	0.0169 (9)	0.0143 (10)	−0.0013 (7)	0.0005 (7)	0.0004 (7)
C7	0.0147 (8)	0.0161 (9)	0.0166 (10)	−0.0004 (7)	−0.0002 (7)	0.0025 (7)
C32	0.0147 (8)	0.0143 (8)	0.0159 (10)	−0.0011 (6)	0.0011 (7)	−0.0003 (7)
C33	0.0159 (9)	0.0197 (9)	0.0188 (10)	−0.0015 (7)	0.0004 (8)	−0.0039 (7)
C22	0.0163 (9)	0.0180 (9)	0.0156 (10)	0.0001 (7)	−0.0004 (7)	−0.0017 (7)
C15	0.0165 (9)	0.0212 (9)	0.0159 (10)	−0.0017 (7)	−0.0017 (7)	0.0033 (7)
C26	0.0161 (9)	0.0216 (9)	0.0148 (10)	−0.0039 (7)	0.0012 (7)	−0.0017 (7)
C4	0.0176 (9)	0.0197 (9)	0.0192 (10)	0.0001 (7)	0.0015 (8)	0.0023 (7)
C28	0.0168 (9)	0.0253 (10)	0.0143 (10)	−0.0026 (7)	0.0037 (8)	0.0006 (7)
C27	0.0147 (8)	0.0191 (9)	0.0162 (10)	−0.0027 (7)	0.0015 (7)	0.0009 (7)
C12	0.0181 (9)	0.0187 (9)	0.0168 (10)	−0.0014 (7)	0.0016 (8)	−0.0015 (7)
C1	0.0164 (9)	0.0208 (9)	0.0184 (10)	−0.0019 (7)	0.0020 (8)	−0.0037 (8)
C5	0.0139 (8)	0.0164 (8)	0.0168 (10)	−0.0024 (7)	0.0031 (7)	−0.0002 (7)
C37	0.0186 (9)	0.0169 (8)	0.0128 (9)	−0.0038 (7)	−0.0006 (7)	−0.0002 (7)
C16	0.0186 (9)	0.0151 (8)	0.0129 (9)	−0.0030 (7)	0.0005 (7)	0.0027 (7)
C35	0.0188 (9)	0.0204 (9)	0.0210 (11)	−0.0020 (7)	0.0083 (8)	−0.0023 (8)
C8	0.0148 (8)	0.0175 (9)	0.0147 (10)	−0.0030 (7)	0.0018 (7)	0.0010 (7)
C29	0.0180 (9)	0.0191 (9)	0.0142 (10)	−0.0009 (7)	−0.0001 (7)	−0.0005 (7)
C36	0.0190 (9)	0.0172 (9)	0.0155 (10)	−0.0002 (7)	0.0019 (7)	−0.0006 (7)
C30	0.0149 (9)	0.0196 (9)	0.0166 (10)	−0.0024 (7)	−0.0010 (7)	−0.0005 (7)
C34	0.0150 (9)	0.0210 (9)	0.0265 (11)	−0.0038 (7)	0.0044 (8)	−0.0046 (8)
C23	0.0136 (9)	0.0192 (9)	0.0229 (11)	−0.0021 (7)	−0.0005 (8)	−0.0013 (8)
C41	0.0174 (9)	0.0199 (9)	0.0168 (10)	−0.0010 (7)	−0.0024 (8)	0.0024 (7)
C38	0.0167 (9)	0.0199 (9)	0.0177 (10)	−0.0012 (7)	−0.0016 (8)	−0.0001 (7)
C17	0.0195 (9)	0.0184 (9)	0.0160 (10)	−0.0001 (7)	0.0027 (8)	−0.0004 (7)
C39	0.0201 (9)	0.0204 (9)	0.0171 (10)	−0.0003 (7)	0.0017 (8)	−0.0016 (7)
C40	0.0230 (10)	0.0205 (9)	0.0141 (10)	−0.0030 (7)	−0.0006 (8)	0.0010 (7)
C13	0.0184 (9)	0.0171 (9)	0.0283 (12)	0.0018 (7)	0.0033 (8)	0.0004 (8)
C42	0.0174 (9)	0.0195 (9)	0.0189 (10)	−0.0006 (7)	0.0033 (8)	−0.0009 (7)
C14	0.0173 (9)	0.0195 (9)	0.0233 (11)	0.0012 (7)	−0.0006 (8)	0.0058 (8)
C18	0.0202 (9)	0.0223 (10)	0.0184 (10)	−0.0002 (7)	−0.0020 (8)	0.0014 (8)
C25	0.0185 (9)	0.0324 (11)	0.0154 (10)	−0.0045 (8)	0.0039 (8)	−0.0011 (8)
C2	0.0210 (10)	0.0193 (9)	0.0250 (11)	−0.0001 (7)	0.0042 (8)	−0.0060 (8)
C21	0.0201 (10)	0.0240 (10)	0.0165 (10)	0.0006 (8)	0.0024 (8)	0.0022 (8)
C24	0.0169 (9)	0.0259 (10)	0.0230 (11)	−0.0052 (8)	0.0057 (8)	−0.0001 (8)
C19	0.0273 (11)	0.0276 (10)	0.0125 (10)	−0.0028 (8)	−0.0012 (8)	0.0019 (8)
C20	0.0273 (11)	0.0318 (11)	0.0158 (10)	0.0019 (9)	0.0063 (9)	−0.0012 (8)
C3	0.0200 (10)	0.0170 (9)	0.0278 (12)	0.0024 (7)	0.0037 (8)	−0.0016 (8)
O3	0.057 (5)	0.106 (8)	0.022 (3)	0.038 (4)	0.017 (2)	0.031 (3)
O4	0.077 (5)	0.050 (3)	0.060 (3)	0.026 (3)	0.029 (3)	−0.004 (2)
O2	0.053 (3)	0.144 (7)	0.067 (5)	−0.057 (4)	0.019 (4)	−0.004 (4)
O3A	0.018 (3)	0.095 (8)	0.075 (8)	0.002 (4)	0.016 (4)	0.060 (6)
O4A	0.040 (4)	0.091 (7)	0.030 (3)	0.034 (4)	0.011 (3)	0.003 (3)
O2A	0.107 (8)	0.049 (4)	0.081 (8)	−0.029 (4)	−0.069 (6)	0.012 (4)

Geometric parameters (Å, º) top

Ni1—N2	2.0014 (16)	C4—C3	1.390 (3)
Ni1—N5	1.9956 (16)	C28—H28	0.9500
Ni1—N3	2.1174 (16)	C28—C27	1.385 (3)
Ni1—N4	2.1313 (16)	C28—C29	1.394 (3)
Ni1—N1	2.1263 (16)	C12—H12	0.9500
Ni1—N6	2.1148 (16)	C12—C13	1.389 (3)
Cl2—O8	1.4552 (16)	C1—H1	0.9500
Cl2—O7	1.4325 (17)	C1—C2	1.387 (3)
Cl2—O5	1.4468 (16)	C37—C29	1.485 (3)
Cl2—O6	1.4306 (17)	C37—C38	1.396 (3)
Cl1—O1	1.4239 (17)	C37—C42	1.398 (3)
Cl1—O3	1.407 (8)	C16—C8	1.478 (3)
Cl1—O4	1.447 (5)	C16—C17	1.404 (3)
Cl1—O2	1.387 (8)	C16—C21	1.392 (3)
Cl1—O3A	1.394 (9)	C35—H35	0.9500
Cl1—O4A	1.417 (6)	C35—C36	1.388 (3)
Cl1—O2A	1.443 (7)	C35—C34	1.377 (3)
N2—C10	1.347 (2)	C29—C30	1.396 (3)
N2—C6	1.342 (2)	C36—H36	0.9500
N5—C31	1.342 (2)	C30—H30	0.9500
N5—C27	1.342 (2)	C34—H34	0.9500
N3—C11	1.351 (2)	C23—H23	0.9500
N3—C15	1.340 (2)	C23—C24	1.377 (3)
N4—C22	1.342 (2)	C41—H41	0.9500
N4—C26	1.355 (3)	C41—C40	1.389 (3)
N1—C1	1.337 (2)	C41—C42	1.384 (3)
N1—C5	1.359 (3)	C38—H38	0.9500
N6—C32	1.355 (2)	C38—C39	1.391 (3)
N6—C36	1.335 (2)	C17—H17	0.9500
C11—C10	1.485 (3)	C17—C18	1.390 (3)
C11—C12	1.388 (3)	C39—H39	0.9500
C10—C9	1.387 (3)	C39—C40	1.390 (3)
C6—C7	1.382 (3)	C40—H40	0.9500
C6—C5	1.491 (3)	C13—H13	0.9500
C9—H9	0.9500	C13—C14	1.385 (3)
C9—C8	1.401 (3)	C42—H42	0.9500
C31—C32	1.485 (3)	C14—H14	0.9500
C31—C30	1.385 (3)	C18—H18	0.9500
C7—H7	0.9500	C18—C19	1.385 (3)
C7—C8	1.404 (3)	C25—H25	0.9500
C32—C33	1.387 (3)	C25—C24	1.392 (3)
C33—H33	0.9500	C2—H2	0.9500
C33—C34	1.386 (3)	C2—C3	1.383 (3)
C22—H22	0.9500	C21—H21	0.9500
C22—C23	1.389 (3)	C21—C20	1.384 (3)
C15—H15	0.9500	C24—H24	0.9500
C15—C14	1.386 (3)	C19—H19	0.9500
C26—C27	1.484 (3)	C19—C20	1.388 (3)
C26—C25	1.381 (3)	C20—H20	0.9500
C4—H4	0.9500	C3—H3	0.9500
C4—C5	1.387 (3)

N2—Ni1—N3	77.49 (6)	C29—C28—H28	120.2
N2—Ni1—N4	101.35 (6)	N5—C27—C26	113.66 (17)
N2—Ni1—N1	77.82 (6)	N5—C27—C28	120.86 (17)
N2—Ni1—N6	103.39 (6)	C28—C27—C26	125.48 (17)
N5—Ni1—N2	175.27 (6)	C11—C12—H12	120.3
N5—Ni1—N3	107.20 (6)	C11—C12—C13	119.32 (19)
N5—Ni1—N4	77.68 (6)	C13—C12—H12	120.3
N5—Ni1—N1	97.51 (6)	N1—C1—H1	118.6
N5—Ni1—N6	77.80 (6)	N1—C1—C2	122.82 (19)
N3—Ni1—N4	96.80 (6)	C2—C1—H1	118.6
N3—Ni1—N1	155.25 (6)	N1—C5—C6	114.67 (16)
N1—Ni1—N4	89.75 (6)	N1—C5—C4	121.68 (18)
N6—Ni1—N3	86.91 (6)	C4—C5—C6	123.63 (18)
N6—Ni1—N4	155.20 (6)	C38—C37—C29	120.70 (17)
N6—Ni1—N1	97.09 (6)	C38—C37—C42	119.30 (18)
O7—Cl2—O8	109.18 (10)	C42—C37—C29	119.91 (17)
O7—Cl2—O5	109.10 (10)	C17—C16—C8	120.36 (17)
O5—Cl2—O8	109.41 (10)	C21—C16—C8	121.14 (17)
O6—Cl2—O8	109.16 (10)	C21—C16—C17	118.48 (18)
O6—Cl2—O7	110.83 (11)	C36—C35—H35	120.8
O6—Cl2—O5	109.14 (11)	C34—C35—H35	120.8
O1—Cl1—O4	107.5 (4)	C34—C35—C36	118.44 (19)
O1—Cl1—O2A	109.5 (4)	C9—C8—C7	117.73 (18)
O3—Cl1—O1	109.5 (5)	C9—C8—C16	121.64 (17)
O3—Cl1—O4	106.3 (6)	C7—C8—C16	120.59 (17)
O2—Cl1—O1	111.7 (4)	C28—C29—C37	119.75 (17)
O2—Cl1—O3	111.5 (6)	C28—C29—C30	118.76 (18)
O2—Cl1—O4	110.1 (5)	C30—C29—C37	121.44 (17)
O3A—Cl1—O1	111.4 (5)	N6—C36—C35	123.06 (19)
O3A—Cl1—O4A	112.3 (7)	N6—C36—H36	118.5
O3A—Cl1—O2A	105.0 (7)	C35—C36—H36	118.5
O4A—Cl1—O1	111.1 (3)	C31—C30—C29	118.68 (17)
O4A—Cl1—O2A	107.2 (6)	C31—C30—H30	120.7
C10—N2—Ni1	119.70 (13)	C29—C30—H30	120.7
C6—N2—Ni1	119.55 (12)	C33—C34—H34	120.2
C6—N2—C10	120.63 (16)	C35—C34—C33	119.51 (18)
C31—N5—Ni1	119.83 (13)	C35—C34—H34	120.2
C31—N5—C27	120.40 (17)	C22—C23—H23	120.4
C27—N5—Ni1	119.35 (13)	C24—C23—C22	119.15 (18)
C11—N3—Ni1	114.82 (12)	C24—C23—H23	120.4
C15—N3—Ni1	126.11 (13)	C40—C41—H41	119.9
C15—N3—C11	118.69 (16)	C42—C41—H41	119.9
C22—N4—Ni1	127.86 (13)	C42—C41—C40	120.24 (18)
C22—N4—C26	118.20 (16)	C37—C38—H38	120.0
C26—N4—Ni1	113.93 (12)	C39—C38—C37	119.92 (18)
C1—N1—Ni1	127.21 (14)	C39—C38—H38	120.0
C1—N1—C5	118.43 (16)	C16—C17—H17	119.8
C5—N1—Ni1	113.78 (12)	C18—C17—C16	120.40 (19)
C32—N6—Ni1	114.04 (12)	C18—C17—H17	119.8
C36—N6—Ni1	127.06 (13)	C38—C39—H39	119.8
C36—N6—C32	118.18 (16)	C40—C39—C38	120.42 (18)
N3—C11—C10	114.42 (16)	C40—C39—H39	119.8
N3—C11—C12	121.72 (17)	C41—C40—C39	119.69 (19)
C12—C11—C10	123.85 (18)	C41—C40—H40	120.2
N2—C10—C11	113.33 (16)	C39—C40—H40	120.2
N2—C10—C9	120.86 (17)	C12—C13—H13	120.6
C9—C10—C11	125.77 (16)	C14—C13—C12	118.75 (18)
N2—C6—C7	121.19 (17)	C14—C13—H13	120.6
N2—C6—C5	113.53 (16)	C37—C42—H42	119.8
C7—C6—C5	125.28 (17)	C41—C42—C37	120.41 (18)
C10—C9—H9	120.1	C41—C42—H42	119.8
C10—C9—C8	119.76 (17)	C15—C14—H14	120.5
C8—C9—H9	120.1	C13—C14—C15	118.98 (18)
N5—C31—C32	112.85 (16)	C13—C14—H14	120.5
N5—C31—C30	121.69 (17)	C17—C18—H18	119.8
C30—C31—C32	125.46 (17)	C19—C18—C17	120.38 (19)
C6—C7—H7	120.1	C19—C18—H18	119.8
C6—C7—C8	119.77 (17)	C26—C25—H25	120.3
C8—C7—H7	120.1	C26—C25—C24	119.34 (19)
N6—C32—C31	114.91 (16)	C24—C25—H25	120.3
N6—C32—C33	122.05 (18)	C1—C2—H2	120.5
C33—C32—C31	123.00 (18)	C3—C2—C1	118.93 (19)
C32—C33—H33	120.6	C3—C2—H2	120.5
C34—C33—C32	118.75 (19)	C16—C21—H21	119.6
C34—C33—H33	120.6	C20—C21—C16	120.78 (19)
N4—C22—H22	118.7	C20—C21—H21	119.6
N4—C22—C23	122.51 (19)	C23—C24—C25	118.72 (18)
C23—C22—H22	118.7	C23—C24—H24	120.6
N3—C15—H15	118.7	C25—C24—H24	120.6
N3—C15—C14	122.54 (19)	C18—C19—H19	120.3
C14—C15—H15	118.7	C18—C19—C20	119.4 (2)
N4—C26—C27	114.62 (16)	C20—C19—H19	120.3
N4—C26—C25	122.07 (18)	C21—C20—C19	120.5 (2)
C25—C26—C27	123.28 (18)	C21—C20—H20	119.7
C5—C4—H4	120.3	C19—C20—H20	119.7
C5—C4—C3	119.32 (19)	C4—C3—H3	120.6
C3—C4—H4	120.3	C2—C3—C4	118.81 (18)
C27—C28—H28	120.2	C2—C3—H3	120.6
C27—C28—C29	119.52 (18)

Ni1—N2—C10—C11	2.4 (2)	C22—N4—C26—C25	−1.0 (3)
Ni1—N2—C10—C9	−175.73 (13)	C22—C23—C24—C25	−0.8 (3)
Ni1—N2—C6—C7	175.37 (13)	C15—N3—C11—C10	178.71 (16)
Ni1—N2—C6—C5	−3.7 (2)	C15—N3—C11—C12	−0.2 (3)
Ni1—N5—C31—C32	7.4 (2)	C26—N4—C22—C23	0.9 (3)
Ni1—N5—C31—C30	−173.34 (14)	C26—C25—C24—C23	0.6 (3)
Ni1—N5—C27—C26	−10.1 (2)	C28—C29—C30—C31	−0.1 (3)
Ni1—N5—C27—C28	170.51 (14)	C27—N5—C31—C32	179.84 (16)
Ni1—N3—C11—C10	5.28 (19)	C27—N5—C31—C30	−0.9 (3)
Ni1—N3—C11—C12	−173.62 (14)	C27—C26—C25—C24	178.11 (19)
Ni1—N3—C15—C14	172.82 (14)	C27—C28—C29—C37	174.92 (17)
Ni1—N4—C22—C23	−177.83 (14)	C27—C28—C29—C30	−2.6 (3)
Ni1—N4—C26—C27	−0.2 (2)	C12—C11—C10—N2	173.82 (17)
Ni1—N4—C26—C25	177.81 (16)	C12—C11—C10—C9	−8.1 (3)
Ni1—N1—C1—C2	170.22 (14)	C12—C13—C14—C15	0.5 (3)
Ni1—N1—C5—C6	7.63 (19)	C1—N1—C5—C6	179.54 (16)
Ni1—N1—C5—C4	−171.35 (14)	C1—N1—C5—C4	0.6 (3)
Ni1—N6—C32—C31	5.90 (19)	C1—C2—C3—C4	0.5 (3)
Ni1—N6—C32—C33	−171.75 (14)	C5—N1—C1—C2	−0.5 (3)
Ni1—N6—C36—C35	171.14 (14)	C5—C6—C7—C8	178.28 (17)
N2—C10—C9—C8	1.3 (3)	C5—C4—C3—C2	−0.4 (3)
N2—C6—C7—C8	−0.6 (3)	C37—C29—C30—C31	−177.60 (17)
N2—C6—C5—N1	−3.0 (2)	C37—C38—C39—C40	0.4 (3)
N2—C6—C5—C4	175.97 (17)	C16—C17—C18—C19	−0.5 (3)
N5—C31—C32—N6	−8.5 (2)	C16—C21—C20—C19	0.2 (3)
N5—C31—C32—C33	169.08 (17)	C8—C16—C17—C18	179.80 (17)
N5—C31—C30—C29	1.9 (3)	C8—C16—C21—C20	−179.63 (18)
N3—C11—C10—N2	−5.1 (2)	C29—C28—C27—N5	3.7 (3)
N3—C11—C10—C9	172.98 (17)	C29—C28—C27—C26	−175.53 (18)
N3—C11—C12—C13	0.4 (3)	C29—C37—C38—C39	−176.21 (17)
N3—C15—C14—C13	−0.4 (3)	C29—C37—C42—C41	175.59 (17)
N4—C22—C23—C24	0.1 (3)	C36—N6—C32—C31	176.85 (16)
N4—C26—C27—N5	6.3 (2)	C36—N6—C32—C33	−0.8 (3)
N4—C26—C27—C28	−174.36 (18)	C36—C35—C34—C33	−0.1 (3)
N4—C26—C25—C24	0.3 (3)	C30—C31—C32—N6	172.21 (18)
N1—C1—C2—C3	0.0 (3)	C30—C31—C32—C33	−10.2 (3)
N6—C32—C33—C34	−0.3 (3)	C34—C35—C36—N6	−1.1 (3)
C11—N3—C15—C14	0.2 (3)	C38—C37—C29—C28	43.2 (3)
C11—C10—C9—C8	−176.58 (17)	C38—C37—C29—C30	−139.3 (2)
C11—C12—C13—C14	−0.5 (3)	C38—C37—C42—C41	−1.1 (3)
C10—N2—C6—C7	−0.7 (3)	C38—C39—C40—C41	−0.6 (3)
C10—N2—C6—C5	−179.68 (15)	C17—C16—C8—C9	−145.75 (19)
C10—C11—C12—C13	−178.43 (17)	C17—C16—C8—C7	31.7 (3)
C10—C9—C8—C7	−2.5 (3)	C17—C16—C21—C20	−1.4 (3)
C10—C9—C8—C16	175.05 (17)	C17—C18—C19—C20	−0.7 (3)
C6—N2—C10—C11	178.45 (16)	C40—C41—C42—C37	0.9 (3)
C6—N2—C10—C9	0.3 (3)	C42—C37—C29—C28	−133.4 (2)
C6—C7—C8—C9	2.2 (3)	C42—C37—C29—C30	44.0 (3)
C6—C7—C8—C16	−175.42 (17)	C42—C37—C38—C39	0.5 (3)
C31—N5—C27—C26	177.36 (16)	C42—C41—C40—C39	−0.1 (3)
C31—N5—C27—C28	−2.0 (3)	C18—C19—C20—C21	0.8 (3)
C31—C32—C33—C34	−177.79 (17)	C25—C26—C27—N5	−171.62 (19)
C7—C6—C5—N1	178.03 (17)	C25—C26—C27—C28	7.7 (3)
C7—C6—C5—C4	−3.0 (3)	C21—C16—C8—C9	32.4 (3)
C32—N6—C36—C35	1.5 (3)	C21—C16—C8—C7	−150.07 (19)
C32—C31—C30—C29	−178.91 (18)	C21—C16—C17—C18	1.6 (3)
C32—C33—C34—C35	0.8 (3)	C3—C4—C5—N1	−0.1 (3)
C22—N4—C26—C27	−179.02 (16)	C3—C4—C5—C6	−179.01 (18)

Selected bond lengths (Å) for complexes [Ni(Ph-TPY)₂](ClO₄)₂ (15d), [Mn(Ph-TPY)₂](ClO₄)₂ (17c) and [Mn(MeOPh-TPY)₂](ClO₄)₂ (15c) top

	15d	17c	15c
M—N1	2.1263 (15)	2.2723 (12)	2.2664 (12)
M—N2	2.0014 (17)	2.2093 (14)	2.2080 (10)
M—N3	2.1175 (15)	2.2423 (12)	2.2738 (11)
M—N4	2.1313 (16)	2.2537 (12)	2.2375 (11)
M—N5	1.9956 (17)	2.1877 (11)	2.2002 (10)
M—N6	2.1147 (16)	2.2571 (12)	2.2970 (11)

Torsion angles (°) and ring-to-ring angle (°) parameters for complexes [Ni(Ph-TPY)₂](ClO₄)₂ (15d), [Mn(Ph-TPY)₂](ClO₄)₂ (17c) and [Mn(MeOPh-TPY)₂](ClO₄)₂ (15c) top

	15d	17c	15c
N1—C5—N3—C11	-8.59	-10.072	-3.66
N4—C26—N6—C32	-4.5	-3.412	-0.47
C17—C16—C8—C7	31.77	31.98	5.23
C30—C29—C37—C42	43.24	40.09	-27.63
Ring 1–Ring 2	7.28	8.496	1.49
Ring 3–Ring 4	14.39	14.38	16.63

Acknowledgements

The authors would like to thank the Quimica de Productos Naturales (QPN) research group from the chemistry department at Universidad del Cauca. The results described in this article are part of the research project with ID-5407, financed by Universidad del Cauc. JE is grateful to the Brazilian agencies FAPESP and CNPq. The research group (QPN) from the Universidad del Cauca (Popayán, Colombia) would like to thank Acta Crystallographica Section C: Structural Chemistry for the invitation to participate in this special collection (Crystallography in Latin America: a vibrant community). All the authors declare no competing financial interest.

Funding information

Funding for this research was provided by: Universidad del Cauca (award No. 501100005682); Fundação de Amparo à Pesquisa do Estado de São Paulo (process No. 2017/15850-0 to J. Ellena); Conselho Nacional de Desenvolvimento Científico e Tecnológico (process No. 312505/2021-3 to J. Ellena).

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crystallography in latin america\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Synthesis, characterization and structural analysis of com­plexes from 2,2′:6′,2′′-terpyridine derivatives with transition metals

1. Introduction

2. Experimental

2.1. Materials and methods

2.2. Synthesis

2.2.1. Synthesis of the R-TPY ligands

2.2.2. Synthesis of [M(R-TPY)](ClO4)2

2.2.3. Coordination com­plex series A (15a–d)

2.2.4. Coordination com­plex series B (16a–d)

2.2.5. Coordination com­plex series C (17a–d)

2.3. Refinement

3. Results and discussion

3.1. Synthesis

3.2. Structural analysis

3.3. IR spectroscopy analysis

3.4. UV–Vis spectrophotometry

3.5. NMR spectroscopy

3.6. Thermal stability

4. Conclusion

Supporting information

Acknowledgements

Funding information

References

crystallography in latin america

Synthesis, characterization and structural analysis of complexes from 2,2′:6′,2′′-terpyridine derivatives with transition metals

2.2.2. Synthesis of [M(R-TPY)](ClO₄)₂

2.2.3. Coordination complex series A (15a–d)

2.2.4. Coordination complex series B (16a–d)

2.2.5. Coordination complex series C (17a–d)