Variable Unidentate Ligands in Cu(I)(XXY) and Cu(I)(XYZ) Complexes—Structural Aspects

This manuscript provides a structural analysis of over eighty copper(I) compounds mostly reported in the Cambridge Structural Database (CSD) version 5.45 in which unidentate ligands build up various inner coordinate spheres. These complexes crystallized in four crystal classes: trigonal (1 example),...

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Main Authors: Milan Melník, Veronika Mikušová, Peter Mikuš
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Inorganics
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Online Access:https://www.mdpi.com/2304-6740/13/6/182
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author Milan Melník
Veronika Mikušová
Peter Mikuš
author_facet Milan Melník
Veronika Mikušová
Peter Mikuš
author_sort Milan Melník
collection DOAJ
description This manuscript provides a structural analysis of over eighty copper(I) compounds mostly reported in the Cambridge Structural Database (CSD) version 5.45 in which unidentate ligands build up various inner coordinate spheres. These complexes crystallized in four crystal classes: trigonal (1 example), triclinic (10 examples), orthorhombic (13 examples), and monoclinic (58 examples). The analyzed complexes can be divided into two groups according to the type of coordinating ligands (L = X, Y, Z) incorporated into their structure: Cu(XXY) (more common) and Cu(XYZ). The structural data of L-Cu-L bond angles show that the angular distortion from the regular trigonal geometry grows with total mean values of deviation from 120.0°, in the order within the first group: 3.2°(Cu(IIP)) < 6.1°(Cu(ClClY)) < 6.5°(Cu(SSY)) < 8.2°(Cu(PPY)) < 8.9°(Cu(BrBrY)) < 16.9°(Cu(NNY)) < 19.8°(Cu(CCY)) < 25.5°(Cu(SeSeY)) and within the second group: 3.1°(Cu(SIP)) < 14.3°(Cu(SClP) < 15.5°(Cu(SBrP). The donor atoms are responsible for the distortion as follows: the soft donor atoms diminish the distortion while the borderline and the hard growing amplify the distortion. Given the importance of Cu(I) compounds in (bio)inorganic functional materials and catalysis, the correct interpretation of the geometry of Cu(I) complexes in terms of the coordination polyhedra is crucial for understanding the properties of the respective compounds.
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spelling doaj-art-14c6a976014345ca8cfab191ac3bb4e02025-08-20T03:27:29ZengMDPI AGInorganics2304-67402025-06-0113618210.3390/inorganics13060182Variable Unidentate Ligands in Cu(I)(XXY) and Cu(I)(XYZ) Complexes—Structural AspectsMilan Melník0Veronika Mikušová1Peter Mikuš2Department of Pharmaceutical Analysis and Nuclear Pharmacy, Faculty of Pharmacy, Comenius University Bratislava, Odbojárov 10, SK-832 32 Bratislava, SlovakiaDepartment of Galenic Pharmacy, Faculty of Pharmacy, Comenius University Bratislava, Odbojárov 10, SK-832 32 Bratislava, SlovakiaDepartment of Pharmaceutical Analysis and Nuclear Pharmacy, Faculty of Pharmacy, Comenius University Bratislava, Odbojárov 10, SK-832 32 Bratislava, SlovakiaThis manuscript provides a structural analysis of over eighty copper(I) compounds mostly reported in the Cambridge Structural Database (CSD) version 5.45 in which unidentate ligands build up various inner coordinate spheres. These complexes crystallized in four crystal classes: trigonal (1 example), triclinic (10 examples), orthorhombic (13 examples), and monoclinic (58 examples). The analyzed complexes can be divided into two groups according to the type of coordinating ligands (L = X, Y, Z) incorporated into their structure: Cu(XXY) (more common) and Cu(XYZ). The structural data of L-Cu-L bond angles show that the angular distortion from the regular trigonal geometry grows with total mean values of deviation from 120.0°, in the order within the first group: 3.2°(Cu(IIP)) < 6.1°(Cu(ClClY)) < 6.5°(Cu(SSY)) < 8.2°(Cu(PPY)) < 8.9°(Cu(BrBrY)) < 16.9°(Cu(NNY)) < 19.8°(Cu(CCY)) < 25.5°(Cu(SeSeY)) and within the second group: 3.1°(Cu(SIP)) < 14.3°(Cu(SClP) < 15.5°(Cu(SBrP). The donor atoms are responsible for the distortion as follows: the soft donor atoms diminish the distortion while the borderline and the hard growing amplify the distortion. Given the importance of Cu(I) compounds in (bio)inorganic functional materials and catalysis, the correct interpretation of the geometry of Cu(I) complexes in terms of the coordination polyhedra is crucial for understanding the properties of the respective compounds.https://www.mdpi.com/2304-6740/13/6/182Cu(I)(XXY)Cu(I)(XYZ)complexesunidentate ligandsstructural analysisdistortion
spellingShingle Milan Melník
Veronika Mikušová
Peter Mikuš
Variable Unidentate Ligands in Cu(I)(XXY) and Cu(I)(XYZ) Complexes—Structural Aspects
Inorganics
Cu(I)(XXY)
Cu(I)(XYZ)
complexes
unidentate ligands
structural analysis
distortion
title Variable Unidentate Ligands in Cu(I)(XXY) and Cu(I)(XYZ) Complexes—Structural Aspects
title_full Variable Unidentate Ligands in Cu(I)(XXY) and Cu(I)(XYZ) Complexes—Structural Aspects
title_fullStr Variable Unidentate Ligands in Cu(I)(XXY) and Cu(I)(XYZ) Complexes—Structural Aspects
title_full_unstemmed Variable Unidentate Ligands in Cu(I)(XXY) and Cu(I)(XYZ) Complexes—Structural Aspects
title_short Variable Unidentate Ligands in Cu(I)(XXY) and Cu(I)(XYZ) Complexes—Structural Aspects
title_sort variable unidentate ligands in cu i xxy and cu i xyz complexes structural aspects
topic Cu(I)(XXY)
Cu(I)(XYZ)
complexes
unidentate ligands
structural analysis
distortion
url https://www.mdpi.com/2304-6740/13/6/182
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