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Communication

Homo-Chromophores in Cu(I)(XXX), (X3 = N3, C3, Cl3, S3, P3, Br3, or I3) Derivatives—Structural Aspects

by
Milan Melník
1,*,
Veronika Mikušová
2 and
Peter Mikuš
2,3,*
1
Department of Pharmaceutical Analysis and Nuclear Pharmacy, Faculty of Pharmacy, Comenius University Bratislava, Odbojárov 10, SK-832 32 Bratislava, Slovakia
2
Department of Galenic Pharmacy, Faculty of Pharmacy, Comenius University Bratislava, Odbojárov 10, SK-832 32 Bratislava, Slovakia
3
Toxicological and Antidoping Centre, Faculty of Pharmacy, Comenius University Bratislava, Odbojárov 10, SK-832 32 Bratislava, Slovakia
*
Authors to whom correspondence should be addressed.
Inorganics 2025, 13(2), 36; https://doi.org/10.3390/inorganics13020036
Submission received: 22 December 2024 / Revised: 20 January 2025 / Accepted: 23 January 2025 / Published: 25 January 2025
(This article belongs to the Special Issue Applications and Future Trends for Novel Copper Complexes)
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Abstract

:
The structural aspects of homo-chromophores in Cu(I)(XXX) complexes, where X3 = N3, C3, Cl3, S3, P3, Br3, or I3, are analyzed in this study. These copper(I) derivatives crystallize in five distinct crystal systems as follows: rhombohedral (1 example), trigonal (1 example), orthorhombic (4 examples), triclinic (5 examples), and monoclinic (15 examples). The angular distortion from regular trigonal geometry increases in the following order: Cu(ClClCl) < Cu(NNN) < Cu(PPP) < Cu(BrBrBr) < Cu(III) < Cu(CCC) < Cu(SSS). For Cu(I)(XX) complexes, the deviation from linear geometry increases in the order: Cu(SeSe) < Cu(SS) < Cu(OO) < Cu(ClCl) < Cu(NN) < Cu(CC) < Cu(PP) < Cu(BrBr). The structural parameters of Cu(I)(XXX) are examined, discussed, and compared with those of homonuclear Cu(I)(XX) complexes.

Graphical Abstract

1. Introduction

Over the past 50 years, systematic studies on the stereoselectivity of coordination compounds have garnered increasing attention. Stereoselectivity in these compounds is frequently closely related to the stereospecificity observed in biological systems, catalysis, and the stereochemical effects in various technical processes. Controlling the coordination environment in transition metal complexes remains a central goal in the design of molecules and materials across diverse areas of inorganic chemistry, including bioinorganic chemistry, catalysis, and supramolecular self-assembly. The development and synthesis of new ligands will continue to be a key focus in the field of inorganic chemistry [1,2].
Copper in the +2 oxidation state is by far the most common, although it can also exist in other oxidation states, such as +1, +3, and +4, with copper(I) being the most predominant among them. A thorough review of copper(I) structural chemistry, covering studies up to 1992, included nearly a thousand analyzed and classified structures [3].
It is widely recognized that Cu(I) complexes display unique intrinsic stereochemical preferences [4]. Copper(II), with its d9 configuration, typically adopts stereochemistries that are stabilized by ligand field effects, resulting from distinctly favorable d-orbital splitting. In contrast, copper(I), with its d10 configuration, has its stereochemistry primarily governed by static and charge effects. These differences in stereochemical preferences play a significant role in copper’s involvement in redox chemistry. Blue copper proteins illustrate this by selecting a donor ligand set and stereochemistry that balances the inherent preferences of copper(I) and copper(II) [5].
Heteroleptic copper complexes hold significant potential for noble metal-free photocatalysis and photochemistry. The activity of [Cu(NˆN)(PˆP)]+ complexes is the most important application in photo-catalyzed transformations, particularly proton and CO2 reduction together with other photochemical applications such as sensors, are presented [6].
Photocatalyzed and photosensitized chemical processes have garnered increasing interest recently, emerging as some of the most dynamic areas of chemical research, primarily due to their applications in fields such as medicine, chemical synthesis, materials science, and environmental chemistry. Photoactive copper(I) complexes are especially attractive among all homogeneous catalytic systems. Some review papers discussed this subject [7,8,9,10]. It is well known that copper(II) ion as a d9 system undergoes Jahn–Teller distortion and imposes a distortion in coordination geometries which facilitates the catalytic routes for different organic transformations [11,12,13,14]. Analogically, the degree of distortion in Cu(I) complexes could be related to their catalytic activity. According to our best knowledge, however, no systematic study has been published to compare catalytic activity (e.g., via turnover numbers) to the degree of distortion. Therefore, structural studies comparing the degree of distortion of Cu(I) complexes differently coordinated with ligands possessing various types of donor atoms are worthy of being carried out as a first step in subsequent structure–activity relationship studies.
In the group of Cu(I) complexes, our recent research has focused on the structures of trans-X-Cu(I)-X (where X = O, NL, CL, PL, SL, SeL, Cl, or Br) [15]. Another study examined over 100 coordinated Cu(I) complexes with compositions such as C-Cu-Y (Y = OL, CL, NL, SiL, BL, PL, Cl, Br, I, AlL, or SnL) and Se-Cu-Y (Y = Br, I) [16]. Coordination geometries for two coordination numbers of copper(I) can include two possibilities: linear and bent, with the deviation from linearity influenced by the ligand properties, following the trend: hard < borderline < soft.
Three-coordinate copper(I) complexes exhibit more structural diversity than two-coordinate complexes, and these three-coordinate complexes represent another significant category of copper(I) compounds in ongoing research. This paper aims to analyze the structural data of homo-monodentate copper(I) complexes of the form Cu(I)(XXX), where X = N3, C3, Cl3, S3, P3, Br3, or I3. These complexes are systematically analyzed and classified to aid in understanding the stereochemical interactions within the copper(I) coordination sphere.

2. Results and Discussion

Two main methods are typically used to prepare Cu(XXX) derivatives (where X = N, C, Cl, S, P, Br, or I). The first method involves reducing a copper(II) salt in the presence of a ligand, with sulfur (S) and phosphorus (P) donor molecules often acting both as ligands and reducing agents. The second, more widely used method involves directly reacting ligands with copper(I) salts in a non-aqueous solvent, like acetonitrile, under an inert atmosphere (typically dry nitrogen). It can be summarized from the compounds analyzed in Section 2.1, Section 2.2 and Section 2.3 that complexes possessing ligands with soft donor atoms (C, S, P, Se, I) to bound to central atom Cu(I) are prepared preferably employing the first synthetic approach while complexes possessing ligands with hard or borderline donor atoms (O, N, Cl, or Br) bound to central atom Cu(I) are prepared preferably employing the second synthetic approach.
There are almost 30 copper(I) complexes of the type Cu(XXX) (X3 = N3, C3, Cl3, S3, P3, Br3,or I3). The monodentate ligand builds up a homogeneous inner coordination sphere about copper(I) atoms with various degrees of angular distortion from regular trigonal geometry. There are seven types of derivatives. The properties of the ligands are determined by the properties of their donor atoms, which can be hard (O, N, Cl), soft (C, S, P, Se, I), or borderline (Br). Since Cu(I) is a soft central atom, it is a prerequisite for the formation of stronger bonds with soft donor atoms of ligands than with hard and borderline ones.

2.1. Cu(NNN), Cu(CCC) Derivatives

In two complexes, monoclinic [Cu(2-Mepy)3]ClO4 [17] and trigonal [Cu(C16H15N2)3]CF3SO3 0.5 (C6H6) [18] N-donor ligand create [Cu(NNN)]+. The mean Cu-N bond distance is 1.995 (±5)Å. Interestingly, angular distortion from regular trigonal geometry is observed even in the [Cu(2-Mepy)3]+ cation, where the trigonal plane consists of the same ligands, and the N-Cu-N bond angles are 113°, 118°, and 139°, respectively. This distortion is linked to the orientation of the picoline rings, two of which are nearly orthogonal to the coordination plane, while the third is coplanar with the Cu(N)3 unit, minimizing steric interactions between the methyl groups. On the other hand, the [Cu(C16H15N2)3]+, which also contains the same ligand, has regular trigonal geometry, (N-Cu-N) bond angles of 120° [18,19].
In monoclinic [Cu(C11H20N2)3](C8H31B2N2O3).0.5(C4H8O) [20], three monodentate ligands create angular distortion from regular trigonal geometry via C-donor atoms. The C-Cu-C bond angles are 112.4, 122.3, and 125.2°. The mean value of Cu-C bond distance is 1.987 (±3) Å.
The structure of [Cu(C11H20N2)3]+ is shown in Figure 1 and the structure of [Cu(C16H17)3]+ in Figure 2.

2.2. Cu(ClClCl), Cu(SSS) Derivatives

There are three copper(I) derivatives, orthorhombic (C6H14N2)2[CuCl3] [21], monoclinic [Cu(I)(C6H14N2)2][Cu(I)Cl3] [22], and triclinic (C2H8N)2[Cu(I)Cl3] [23] in which chloride ligands build up a homogeneous inner coordination sphere about each Cu(I) atom (CuCl3). The mean value of Cu-Cl bond distance is 2.165 (±12) Å and Cl-Cu-Cl bond angles are 120.0 (±1.5)°.
The copper(I) complexes in which S-donor ligands create an inner coordination sphere about copper(I) atoms (CuS3) are the most common ones. X-ray data show that based on S-Cu-S bond angles, the complexes can be categorized into three groups. The angular distortion from regular trigonal geometry grows with a deviation of S-Cu-S bond angles from 120°. The deviation is growing in the sequence: 120.0 (±0.5)° [Cu(etu)3]SO4 [24], [Cu(Et2tu)3].0.5SO4 [25]} < 120.0 (±3.4)° [Cu(tu)3](C8H5O4) [26], [Cu(Me3PS3]ClO4 [27]. (NEt4)2[Cu(PhS)3] [28], [Cu(C4H6N2S)3]NO3 [29] < 120.0 ± 20.4°[Cu(Me4tu)3]BF4 [24], [Cu(SHpy)3]NO3 [30], (PPh4)2[Cu(PhS)3] [31]. The total mean value of Cu-S bond distance is 2.253 (±21) Å. The structure of [Cu(PhS)3] [31] is shown in Figure 3, as an example. In the case of a halogenated complex (Figure 4), there is an ionic bond within the complex anion and two cation organic molecules.

2.3. Cu(PPP), Cu(BrBrBr), and Cu(III) Derivatives

In triclinic [Cu(Ph3P)3][VCO)6] [32] and monoclinic [Cu{PPh2BH2NMe3}3]BF4.1.69 CH2Cl2 [33], monodentate P-donor ligands build up a Cu(P)3 inner coordination sphere. X-ray data show that angular distortion from regular trigonal geometry especially occurs in the monoclinic complex. The Cu-P bond distances and P-Cu-P bond angles, triclinic vs. monoclinic are: 2.295 (±2) Å and 120.0 ±(2.6)° vs. 2.315 (±14) Å and 120.0 (±8.6)°, respectively. As an example, the structure of [Cu(PPh3)3]+ [32] is illustrated in Figure 5 [32]. In the case of halogenated complexes (Figure 6 and Figure 7), there is an ionic bond within the complex anion and two cation organic molecules.
There are three complexes: triclinic (C11H12N)2[CuBr3] [34], and two orthorhombic (PPh3Me)2[CuBr3] [35] and [Cu(II)(C6H8N2)4][Cu(I)Br3]H2O [36] in which three bromide atoms about each Cu(I) atom angular distortion from regular trigonal geometry. The mean Cu-Br bond distance is 2.355 (±12) Å and the mean value of the Br-Cu-Br bond angle is 120.0 (±2.8)°.
In six complexes, one is orthorhombic (Co(Cp2)2)[CuI3] [37], and the remaining five are monoclinic (PPh3Me)2[CuI3] [38], (C14H16N2)[CuI3] [39], (C20H20N4)[CuI3] [40], (C26H22NO4)[CuI3] [41], and (C9H10N3)2[CuI3] [42], where iodine serves as a ligand. In each complex, iodine builds up an angular distortion from regular trigonal geometry (CuI3). The total mean value of Cu-I bond distance is 2.550 (±15) Å and of I-Cu-I bond angles 120.0 (±3.6)°.

3. Materials and Methods

In this structural study, the Cambridge Crystallographic Database CSD version 5.45 (CCDC, Cambridge, UK) was used for the analysis of the structures. The program Diamond, Diamond Version 3.2k, serial no:1.3.2.20007208.2426 (Crystal Impact, Bonn, Germany) were used for creating the vizualizations of chemical structures.

4. Conclusions

This article has categorized homo-copper(I) compounds of the Cu(XXX) type. There are seven types: Cu(NNN), Cu(CCC), Cu(ClClCl), Cu(SSS), Cu(PPP), Cu(BrBrBr), and Cu(III). It is observed that copper(I) complex cations can be isolated in salts with larger inorganic anions, such as ClO4, CF3SO3, SO4, NO3, and BF4. Conversely, copper(I) complex anions can be isolated with larger organic cations, including C6H14N2, C8H3O4, C11H12N, C9H10N3, C14H16N2, C20H20N4, and C26H22NO4.
Copper(I) compounds are mostly colorless, although some exhibit color. This coloration can result from ligand absorptions or charge-transfer bands. The latter is most frequently observed with electron-withdrawing ligands, which stabilize the Cu(I) oxidation state and result in a reddish color. Furthermore, steric factors related to the ligands also play a crucial role in influencing the compound’s properties.
Recently, structural parameters of homo-two coordinate copper(I) compounds were analyzed [2]. The data are compared with the data of homo-three coordinate copper(I) compounds.
The total mean values of Cu-X bond distances along with the respective bond angles for CuX2 and CuX3 are given in Table 1.
As can be seen, the covalent radius of the donor atom as well as coordination number plays a significant role in the Cu-X bond distance. The Cu-X bond distance elongates with increasing both the covalent radius and coordination number. A relationship between the sum of covalent radii and the corresponding Cu-X bond distance can refer to the theoretical stability of such bond and, by that, the assumed stability of the given complex. This knowledge can be useful when comparing the assumed stability of the complexes within a given structural type.
There are two possible geometries for a coordination number of two: linear and bent. In CuX2 complexes, they deviate from 180°perfect linear growing in the order (X): Se < S < O < Cl < N < C < P < Br. In the CuX3 complexes, the angular distortion from regular trigonal geometry (120°) grows in the order of (X): Cl < N < P < Br < I < C = S. Generally, the (catalytic) activity of the complex increases with the degree of distortion [3] which underlines the importance of such theoretical knowledge when predicting the structure-activity relationship.
Concerning synthesis guidelines, there is a relationship between a type of donor atom of the ligand, i.e., soft (C, S, P, Se, I), borderline (Br), or hard (O, N, Cl), and its preferences to given central atom (soft/hard, e.g., Cu(I) soft) when binding; two synthetic approaches used for the creation of Cu(XXX) complexes with monodentate ligands having the following preferences: (i) the first method based on the reduction of a copper(II) salt in the presence of a ligand involves ligands with soft donor atoms, while (ii) the second method is based on directly reacting ligands with copper(I) salts involving ligands with hard and borderline donor atoms. A classification of homo-copper(I) compounds of the Cu(XXX) type is described, with seven types of compounds being distinguished. When taking into consideration the existing Cu(XXX) complexes with ligands possessing both soft and hard donor atoms (listed in Table 1), an existence or possibility of also preparing Cu(XXX) complexes with ligands possessing O, F, and Se donor atoms (i.e., hard or soft) cannot be rightfully excluded.

Author Contributions

Conceptualization, M.M. and P.M.; Methodology M.M. and P.M.; Writing—Original draft preparation, M.M. and P.M.; Data curation, M.M.; Writing—Review and editing, V.M.; supervision, M.M. and P.M.; funding acquisition, P.M. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the project VEGA 1/0514/22, VEGA 1/0146/23, and KEGA 041UK-4/2024.

Data Availability Statement

The original contributions presented in the study are included in the article, further inquiries can be directed to the corresponding authors.

Acknowledgments

This work was supported by the Faculty of Pharmacy, Comenius University Bratislava. Structural data used in this study for discussion and calculations were obtained from the Cambridge Crystallographic Database (CCDB) with an institutional license of the Slovak University of Technology in Bratislava.

Conflicts of Interest

The authors declare no conflicts of interest.

Abbreviations

2-Mepy2-methylpyridine
(C2H8N)2bis (dimethylammonium)
(C6H14N2)22+(*)bis (rac-cyclohexane-1,2-diamine)
C4H6N2S1-methylimidazoline-2(3H)-thione
C4H8Otetrahydrofuran
C6H14N22+1,4-diazoniabicyclo [2.2.2] octane
C6H8N2O21,3-dimethylimidazolium
C9H10N3[1-methyl-3-(pyridine-2-yl)-1H-imidazol-3-ium]
C11H12N1+2-ethylisoquinoline-2-ium
C11H20N2(4,5-dimethyl-1,3-bis(propan-2-yl)-imidazol-2-ylidene)
C14H16N24,4′-(ethene-1,2diyl)bis(1-methylpyridin-1-ium)
C16H15N2cinnamylidene-p-toluidine
C18H31B2N2O32-(2-t-butoxy-4,4,5,5 tetramethyl-1,3,2)5-dioxaborolan-2-yl)-1,3-dimethyl-2,3-dihydro-1H-1,3,2-benzoborate
C20H20N41,1′-(biphenyl-4,4′-diyl)bis(3-methyl-1H-imidazol-3-ium)
C26H22NO4(11,12-dimethoxy-14-phenyl-8,9-dihydro[1,3] dioxolo[4,5]isoquinolino [2,1-b] isoqunolin-7-ium)
Cpcyclopentadiene
Et2tudiethyl thiourea
etuethylene thiourea
Me4tutetramethyl thiourea
NEt4+tetraethylammonium
PhSthiophenyl
PPh2BH2NMe3(trimethylammonio(dihydrio)borato)diphenylphosphine
PPh3triphenylphosphine
PPh3Me+methyl triphenylphosphonium
PPh4+tetraphenyl phosphonium
tuthiourea

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Inorganics 13 00036 g001
Figure 1. Structure of [Cu(C11H20N2)3]+ [20].
Figure 1. Structure of [Cu(C11H20N2)3]+ [20].
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Figure 2. Structure of [Cu(C16H17)3]+ [17].
Figure 2. Structure of [Cu(C16H17)3]+ [17].
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Figure 3. Structure of [Cu(PhS)3] [31].
Figure 3. Structure of [Cu(PhS)3] [31].
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Figure 4. Structure of (C6H14N2)2[CuCl3]2- [21].
Figure 4. Structure of (C6H14N2)2[CuCl3]2- [21].
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Figure 5. Structure of [Cu(PPh3)3]+ [32].
Figure 5. Structure of [Cu(PPh3)3]+ [32].
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Figure 6. Structure of (C11H12N)1+2[CuBr3]2− [34].
Figure 6. Structure of (C11H12N)1+2[CuBr3]2− [34].
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Figure 7. Structure of (PPh3Me)1+2[CuI3]2− [34].
Figure 7. Structure of (PPh3Me)1+2[CuI3]2− [34].
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Table 1. The total mean values of structural data for homo-two and three coordinated Cu(I) compounds.
Table 1. The total mean values of structural data for homo-two and three coordinated Cu(I) compounds.
XCuX2CuX3
(cov. Radius)
(Å)		Cu-X
(Å)		(Cu-X)2
(°)		Cu-X
(Å)		(X-Cu-X)3
(°)
O (0.73)1.844176.5--
N (0.75)1.886174.51.990120.0 (±2.3)
C (0.77)1.900174.01.987 (±3)120.0 (±7.1)
Cl (0.99)2.104175.92.165 (±12)120.0 (±1.5)
S (1.02)2.137176.62.253 (±21)120.0 (±7.1)
P (1.06)2.236172.32.296 (±21)120.0 (±2.6)
Br (1.14)2.240169.72.355 (±12)120.0 (±2.8)
Se (1.16)2.268180--
I (1.33)--2.550 (±15)120.0 (±3.6)
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Melník, M.; Mikušová, V.; Mikuš, P. Homo-Chromophores in Cu(I)(XXX), (X3 = N3, C3, Cl3, S3, P3, Br3, or I3) Derivatives—Structural Aspects. Inorganics 2025, 13, 36. https://doi.org/10.3390/inorganics13020036

AMA Style

Melník M, Mikušová V, Mikuš P. Homo-Chromophores in Cu(I)(XXX), (X3 = N3, C3, Cl3, S3, P3, Br3, or I3) Derivatives—Structural Aspects. Inorganics. 2025; 13(2):36. https://doi.org/10.3390/inorganics13020036

Chicago/Turabian Style

Melník, Milan, Veronika Mikušová, and Peter Mikuš. 2025. "Homo-Chromophores in Cu(I)(XXX), (X3 = N3, C3, Cl3, S3, P3, Br3, or I3) Derivatives—Structural Aspects" Inorganics 13, no. 2: 36. https://doi.org/10.3390/inorganics13020036

APA Style

Melník, M., Mikušová, V., & Mikuš, P. (2025). Homo-Chromophores in Cu(I)(XXX), (X3 = N3, C3, Cl3, S3, P3, Br3, or I3) Derivatives—Structural Aspects. Inorganics, 13(2), 36. https://doi.org/10.3390/inorganics13020036

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