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Bis{µ-(2,2′-bipyridine-1κ2N,N′)-(6,6′-dicarbonyl-1κ2O,O′:2κO′)bis(N,N-diethylthioureato-2κS)}(acetato-1κO)(µ-acetato-1κO:2-κO′)(methanol-2κO)thoriumnickel

by
Christelle Njiki Noufele
1,
Chien Thang Pham
2 and
Ulrich Abram
1,*
1
Institute of Chemistry and Biochemistry, Freie Universität Berlin, Fabeckstr. 34/36, D-14195 Berlin, Germany
2
Department of Inorganic Chemistry, VNU University of Science, Vietnam National University, Hanoi, 19 Le Thanh Tong, 10000 Hanoi, Vietnam
*
Author to whom correspondence should be addressed.
Molbank 2025, 2025(1), M1948; https://doi.org/10.3390/M1948
Submission received: 4 December 2024 / Revised: 26 December 2024 / Accepted: 3 January 2025 / Published: 6 January 2025
(This article belongs to the Section Structure Determination)
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Abstract

:
Reactions of 2,2′-bipyridine-6,6′-dicarbonyl-bis(N,N-diethylthiourea), H2Lbipy, with a mixture of thorium nitrate hydrate and nickel acetate hydrate in methanol with NEt3 as a supporting base yield brown single crystals of the bimetallic complex [ThNi(Lbipy)2(CH3COO)2(MeOH)]. Two 2,2′-bipyridine-centered bis(aroylthioureato) ligands connect the metal atoms in a way that the thorium atom is coordinated by two O,N,N,O donor atom sets, while the nickel atom establishes two S,O chelate rings in its equatorial coordination plane. The metal atoms are connected by a bridging acetato ligand, and their coordination spheres are completed by one methanol ligand (nickel) and a monodentate acetato ligand (thorium). A distorted octahedral coordination environment is established around the Ni2+ ion, while the Th4+ ion is in first approximation a 10-coordinate with a diffusely defined coordination polyhedron.

1. Introduction

Aroylthioureas are versatile ligands, which have found consideration in the coordination chemistry of many metal ions. Hundreds of their complexes with main-group and transition metal ions have been studied by X-ray diffraction [1,2,3,4,5]. Most of them represent simple bidentate S,O chelates with ligands of the type {L1}−. In recent years, however, several derivatives with more than one S,O chelating groups and/or additional donor atoms, e.g., in pyridine rings, have been developed. Some examples are shown in Figure 1. These new systems allow for the synthesis of multinuclear compounds with different arrangements of the metal ions [6,7,8,9,10,11,12,13,14,15]. Particularly, ligands of the type H2L3 allow for the designing of heterometallic complexes by the selective binding of different metal ions to the “soft” or “hard” donor atoms [16,17,18,19,20,21,22,23,24,25,26,27]. The selection of the individual coordination positions in such complexes strictly follow the classical concept of Pearson [28].
Actinide complexes with aroylthioureas are rare. There are only a few recent reports about uranyl complexes with ligands of the types {L2}2− and {L3}2−, in which the hard {UO2}2+ ions preferably use the central O,N,O donor atoms, and the peripheral sulfur atoms remain uncoordinated or bind to additional “soft” metal ions such as Ni2+, Co2+, Zn2+, and related ions [29,30,31]. The bipyridyl derivative H2Lbipy has found, hitherto, no consideration as a ligand in transition metal complexes. But there is a report about the structure of the uncoordinated compound together with that of the uranyl complex [UO2(Lbipy)], in which the ligand establishes an unusual S,N,N,N,S coordination in a distorted hexagonal plane [29]. Herein, we report about our attempts to prepare related products with Th4+ ions.

2. Results

No solid products could be isolated from attempted reactions of Th(NO3)·4 H2O with the bipyridine-centered proligand H2Lbipy irrespective of the solvents used. However, a potential hydrolysis of the ligand and the formation of 2,2′-bipyridine-6,6′-dicarboxylate cannot be excluded in aqueous solvents under the influence of a base. Similar reactions were observed for reactions of the pyridine-centered ligand H2L3 with uranyl compounds such as acetate, nitrate, or (NBu4)2[UO2Cl4] [29].
More promising was the reaction with a mixture of thorium nitrate and nickel acetate. A light-green precipitate was obtained after the addition of Ni(CH3COO)2·4 H2O to a mixture of Th(NO3)4·6 H2O, H2Lbipy, and triethylamine in methanol and slight heating to 50 °C (Scheme 1). The solid is soluble in polar organic solvents such as CHCl3 or CH2Cl2, and yellow crystals of the composition [ThNi(Lbipy)2(CH3COO)2(MeOH)] were obtained after slow evaporation of the CH2Cl2/MeOH mixture at room temperature.
The IR spectrum of the crystals shows a broad band at 3443 cm−1, which corresponds to O-H vibrations. The absence of NH vibrations suggests the deprotonation of the organic ligands. Two carbonyl bands are observed at 1591 and 1568 cm−1. They indicate the presence of different carbonyl units in the molecule and, consequently, at least two different bonding situations of the organic ligand in the product. The observed stretching frequencies correspond to a strong bathochromic shift of the carbonyl stretches of {Lbipy}2− with regard to the value of 1707 cm−1 in the uncoordinated ligand [29]. This is a strong hint for chelate formation including the oxygen atoms and a considerable degree of electron delocalization within the chelate rings. Such strong shifts are typical for S,O chelate-bonded aroylthioureato ligands [1,2,3,5,6,7,8,9,10,11,12,13,14,15,16,17] but were also observed for complexes of doubly deprotonated {L2}2− and {L3}2− ligands, in which only the central O,N,O units were used for complex formation [29,30,31].
The conclusions derived from the spectroscopic data are confirmed by a single-crystal X-ray study on the obtained yellow crystals. [ThNi(Lbipy)2(CH3COO)2(MeOH)]·2 CH2Cl2 crystallizes in the monclinic space group C2/c. The neutral complex is composed of two doubly deprotonated {Lbipy}2− ligands, one Th4+ ion, one Ni2+ ion, two acetato ligands, and one coordinated molecule of MeOH. The {Lbipy}2− ligands coordinate tetradentate to the thorium ions via their central O,N,N,O donor atoms. The Ni2+ ion is six-coordinate by two chelating S,O units forming the equatorial plane of the coordination sphere, one methanol ligand, and one oxygen atom of a bridging acetato ligand. An ellipsoid representation of the resulting bonding situation is illustrated in Figure 2, and selected bond lengths and angles are summarized in Table 1.
There are only a few structural studies on bipyridine complexes of thorium, and most of them are related to organometallic compounds, which contain 2,2′-bipyridine co-ligands [32,33,34,35,36,37,38,39,40,41,42,43,44,45]. The Th–N bond lengths found in these compounds appear in a relatively large range between 2.325 and 2.821 Å, and the values found for the title compound of the present communication belong to the upper part of this range. The reason for this finding is most probably the fact that the bipyridine chelate rings in [ThNi(Lbipy)2(CH3COO)2(MeOH)] are a part of the larger O,N,N,O chelating system, which may cause steric restraints. Thus, a comparison with compounds having such additional donor atoms seems to be more appropriate. There are only three examples of such thorium complexes: [Th(TMBiPDA)2(H2O)2]4+ (TMBiPDA = N,N,N’,N’-tetramethyl-2,2′-bipyridine-6,6′-dicarboxamide) with averaged Th–N bonds of 2.681 Å [43], [Th(EtPhFBiPDA)(NO3)4]. (EtPhFBiPDA = N,N’-diethyl-N,N’-(2-F-phenyl)-2,2′-bipyridine-6,6′-dicarboxamide) with averaged Th–N bonds of 2.688 Å [44], and [Th(EttolBiPDA)(NO3)4]. (EttolBiPDA = N,N’-diethyl-N,N’-tolyl-2,2′-bipyridine-6,6′-dicarboxamide) with averaged Th–N bonds of 2.676 Å [45]. The Th–O bonds in [ThNi(Lbipy)2(CH3COO)2(MeOH)] involving the bridging oxygen atoms O5 and O45 are clearly longer than the Th–O15 and Th–O55 bonds due to restraints caused by the rigid skeleton of the organic ligand, while the corresponding C–O bonds of the aroylthioureato ligands are not significantly influenced and reflect a marked double-bond character.
The Ni2+ ion has a distorted octahedral coordination sphere which consists of an almost planar basal plane formed by two S,O chelates in cis-arrangement, which is similar to the square-planar coordination sphere of the bis-chelate [Ni(Et2btu)2] (HEt2btu = N,N-diethylbenzoylthiourea, see ligands of type HL1 in Figure 1) [46,47]. In [ThNi(Lbipy)2(CH3COO)2(MeOH)], the axial positions of Ni2+ are occupied by one oxygen atom of the bridging acetato ligand and one molecule of methanol. The extension of the square planar coordination sphere of nickel(II) aroylthioureato complexes by, e.g., solvent molecules and the formation of octahedral, paramagnetic Ni(II) complexes is not without precedence and has been described for pyridine adducts before [7,48,49].
Under the assumption of (at least weak) coordinative bonds between the thorium ion and the bridging oxygen atoms O5 and O45 with Th–O distances of 2.529(4) and 2.508 Å, the thorium atom has the coordination number ten. Frequently, sphenocoronas or bicapped square antiprisms are common polyhedra for the description of ten-coordinate metal centers with two tetradentate and two monodentate ligands [50]. They also play an important role in the description of the coordination polyhedron of the thorium atom in the present compound, but none of them gives a fully satisfactory result. A closer inspection by means of the SHAPE algorithm [50,51,52,53,54,55] shows that in addition to the sphenocorona (3.68789) and bicapped square antiprism (4.30835), significant contributions of a staggered dodecahedron (4.49391), a tetradecahedron (4.89319), a metabidiminished icosahedron (6.30995), a pentagonal antiprism (7.18142), a hexadecahedron (7.55529), and a bicapped cube (8.84040) also play a role. The values in parenthesis describe the continuous SHAPE measures derived for these idealized polyhedra. They can be read in a way that the lower their numerical value is, the higher is the contribution of the idealized polyhedron to the geometry of the compound under study. Figure 3 contains a graphical representation of the coordination polyhedron of [ThNi(Lbipy)2(CH3COO)2(MeOH)] together with some polyhedra with relevant contributions. More details and the values for the less relevant polyhedra are provided as Supporting Material.
In conclusion, it can be stated that the dipyridine derivative H2Lbipy is a suitable ligand for the formation of bimetallic complexes containing a mixture of “hard” and “soft” metal ions. The synthetic concept is simple and can most probably be extended to mixtures of other actinides or lanthanides with middle- or late-transition metal ions.

3. Materials and Methods

3.1. General Considerations

IR spectra were measured as KBr pellets on a Shimadzu IR Affinity-1 (Shimadzu, Kyoto, Japan). UV/vis spectra were measured and recorded on a SPECORD 40 instrument (Analytic Jena, Jena, Germany). The intensities for the X-ray determinations were collected on a Bruker APEX 2 instrument (BRUKER, Billerica, MA, USA) with Mo/Kα radiation. Absorption correction was carried out by SADABS [56]. Structure solution and refinement were performed with the SHELX programs [57,58] included in OLEX2, version 1.5 [59]. Hydrogen atoms were calculated for idealized positions and treated with the ‘riding model’ option of SHELXL. The solvent mask option of OLEX2 was applied to treat diffuse electron density due to disordered solvent molecules. Details are given in the Supplementary Materials. The representation of molecular structure was realized using the program MERCURY, version 2024, 2.0 [60].

3.2. Radiation Precautions

All synthetic work with thorium was performed in a laboratory approved for the handling of radioactive material. All personnel working on this project were permanently monitored for potential contaminations.

3.3. Synthesis of [ThNi(Lbipy)2(CH3COO)2(MeOH)]

H2Lbipy (39.5 mg, 0.1 mmol) was added to a stirred solution of Th(NO3)4∙6 H2O (25 mg, 0.05 mmol) in MeOH (2 mL). After 15 min, 3 drops of NEt3 were added, and the reaction mixture was stirred at room temperature for 1 h. Then, a solution of Ni(CH3COO)2∙4 H2O (25 mg, 0.1 mmol) in MeOH (1 mL) was added. A brownish solid precipitated within a few minutes. It was filtered off, washed with MeOH, and dried under vacuum conditions. Single crystals for X-ray diffraction were obtained by slow evaporation of a CH2Cl2/MeOH 1:1 (v/v) solution at room temperature. Yield: 38% (53.2 mg). Elemental analysis: Calcd. for C50H68Cl2N12O11S4ThNi ([Ni{Th(Lbipy)2(OAc)2(MeOH)}]·CH2Cl2·2 H2O): C, 42.6; H, 4.5; N, 12.2; S, 9.3%. Found: C, 42.3; H, 4.4; N, 12.1; S, 9.2%. IR (KBr, cm−1): 3443 (s), 3075 (w), 2970 (m), 2932 (m), 2872 (w), 1591 (vs), 1568 (vs), 1516 (m), 1460 (m), 1422 (s), 1383 (vs), 1315 (m), 1278 (m), 1248 (m), 1204 (w), 1090 (m), 1010 (w), 893 (m), 847 (s), 818 (s), 760 (m), 641 (m), 509 (w).

Supplementary Materials

Table S1: Crystallographic data of [ThNi(Lbipy)2(CH3COO)2(MeOH)] x 2 CH2Cl2 and data collection parameters; Figure S1: Ellipsoid representation of the structure of [ThNi(Lbipy)2(CH3COO)2(MeOH)] × 2 CH2Cl2 (1.5 equivalents of diffuse CH2Cl2 have been removed by a solvent mask, see Table S1). The thermal ellipsoids are set at a 30% probability level. Hydrogen atoms bonding to carbon atoms are omitted for clarity. The Figure also illustrates the positional disorders in some of the NEt2 groups and an acetate ligand; Table S2: Bond lengths (Å) in [ThNi(Lbipy)2(CH3COO)2(MeOH)] × 2 CH2Cl2; Table S3: Bond angles (°) in [ThNi(Lbipy)2(CH3COO)2(MeOH)] × 2 CH2Cl2; Figure S2: IR spectrum (KBr) of [ThNi(Lbipy)2(CH3COO)2(MeOH)] × 2 CH2Cl2; Figure S3: IR spectrum (KBr) of H2Lbipy; Table S4: Continuous SHAPE measures (CShM) for [ThNi(Lbipy)2(CH3COO)2(MeOH)] considering all idealized polyhedra for complexes with coordination number ten.

Author Contributions

Conceptualization, C.N.N. and U.A.; methodology, C.N.N. and C.T.P.; validation, C.N.N., C.T.P., and U.A.; formal analysis, C.N.N. and C.T.P.; investigation, C.N.N., C.T.P., and U.A.; resources, U.A.; data curation, C.N.N. and U.A.; writing—original draft preparation, U.A.; writing—review and editing, C.N.N., C.T.P., and U.A; visualization, U.A.; supervision, U.A.; project administration, U.A.; funding acquisition, C.N.N. and U.A. All authors have read and agreed to the published version of this manuscript.

Funding

This research was funded by the Rosa-Luxemburg-Foundation (PhD scholarship to C.N.N.) and German Academic Exchange Service (scholarship to C.T.P.).

Data Availability Statement

Data are contained within this article and the Supplementary Materials.

Acknowledgments

We would like to acknowledge the assistance of the Core Facility BioSupraMol supported by the DFG.

Conflicts of Interest

The authors declare no conflicts of interest.

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Molbank 2025 m1948 g001
Figure 1. Aroylthioureas as potential chelating ligands.
Figure 1. Aroylthioureas as potential chelating ligands.
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Molbank 2025 m1948 sch001
Scheme 1. Reactions of H2Lbipy with thorium nitrate (and nickel acetate).
Scheme 1. Reactions of H2Lbipy with thorium nitrate (and nickel acetate).
Molbank 2025 m1948 sch001
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Figure 2. Representation of the molecular structure of [ThNi(Lbipy)2(CH3COO)2(MeOH)]. Thermal ellipsoids represent 30% probability. For color code, see atomic labeling scheme.
Figure 2. Representation of the molecular structure of [ThNi(Lbipy)2(CH3COO)2(MeOH)]. Thermal ellipsoids represent 30% probability. For color code, see atomic labeling scheme.
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Figure 3. (a) Representation of the coordination polyhedron of the Th4+ ion in [ThNi(Lbipy)2(CH3COO)2(MeOH)] and (b) idealized polyhedra with significant contributions to the coordination sphere of [ThNi(Lbipy)2(CH3COO)2(MeOH)] together with their continuous SHAPE measures in parentheses [50,51,52]. The atomic labeling scheme and the color code correspond to the values used in Figure 2.
Figure 3. (a) Representation of the coordination polyhedron of the Th4+ ion in [ThNi(Lbipy)2(CH3COO)2(MeOH)] and (b) idealized polyhedra with significant contributions to the coordination sphere of [ThNi(Lbipy)2(CH3COO)2(MeOH)] together with their continuous SHAPE measures in parentheses [50,51,52]. The atomic labeling scheme and the color code correspond to the values used in Figure 2.
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Table 1. Selected bond lengths (Å) and angles in [ThNi(Lbipy)2(CH3COO)2(MeOH)].
Table 1. Selected bond lengths (Å) and angles in [ThNi(Lbipy)2(CH3COO)2(MeOH)].
Th–O52.529(4)Th–N262.715(5)Th–N362.703(5)Th–O152.354(4)Th–O812.433(4)
Th–O452.508(4)Th–N662.728(5)Th–N762.684(5)Th–O552.388(4)Th–O862.322(5)
Ni–O52.053(4)Ni–O452.062(5)Ni–S12.386(2)Ni–S412.337(2)Ni–O822.051(5)
Ni–O892.111(5)S1–C21.716(8)C2–N31.371(9)C2–N61.32(1)N3–C41.292(9)
C4–O51.289(8)C14–O151.290(7)C14–N131.290(7)N13–C121.396(9)C12–S111.675(7)
C12–N161.339(9)S41–C421.703(7)C42–N431.371(9)C42–N461.34(1)N43-C441.288(9)
C44–O451.296(8)S51–C521.686(8)C52–N531.39(1)C52–N561.33(1)N53–C541.294(9)
C54–O551.291(8)O82–C831.245(8)C83–O821.245(8)O86–C871.252(9)C87–O851.227(9)
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Noufele, C.N.; Pham, C.T.; Abram, U. Bis{µ-(2,2′-bipyridine-1κ2N,N′)-(6,6′-dicarbonyl-1κ2O,O′:2κO′)bis(N,N-diethylthioureato-2κS)}(acetato-1κO)(µ-acetato-1κO:2-κO′)(methanol-2κO)thoriumnickel. Molbank 2025, 2025, M1948. https://doi.org/10.3390/M1948

AMA Style

Noufele CN, Pham CT, Abram U. Bis{µ-(2,2′-bipyridine-1κ2N,N′)-(6,6′-dicarbonyl-1κ2O,O′:2κO′)bis(N,N-diethylthioureato-2κS)}(acetato-1κO)(µ-acetato-1κO:2-κO′)(methanol-2κO)thoriumnickel. Molbank. 2025; 2025(1):M1948. https://doi.org/10.3390/M1948

Chicago/Turabian Style

Noufele, Christelle Njiki, Chien Thang Pham, and Ulrich Abram. 2025. "Bis{µ-(2,2′-bipyridine-1κ2N,N′)-(6,6′-dicarbonyl-1κ2O,O′:2κO′)bis(N,N-diethylthioureato-2κS)}(acetato-1κO)(µ-acetato-1κO:2-κO′)(methanol-2κO)thoriumnickel" Molbank 2025, no. 1: M1948. https://doi.org/10.3390/M1948

APA Style

Noufele, C. N., Pham, C. T., & Abram, U. (2025). Bis{µ-(2,2′-bipyridine-1κ2N,N′)-(6,6′-dicarbonyl-1κ2O,O′:2κO′)bis(N,N-diethylthioureato-2κS)}(acetato-1κO)(µ-acetato-1κO:2-κO′)(methanol-2κO)thoriumnickel. Molbank, 2025(1), M1948. https://doi.org/10.3390/M1948

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