Crystal structures of two copper(I)–6,6′-dimethyl-2,2′-bipyridyl (dmbpy) compounds, [Cu(dmbpy)2]2[MF6]·xH2O (M = Zr, Hf; x = 1.134, 0.671)

• Published in: Acta crystallographica. Section E, Crystallographic communications Vol. 77; no. Pt 8; pp. 819 - 823
• Main Authors: Wang, Yiran, Nisbet, Matthew L., Poeppelmeier, Kenneth R.
• Format: Journal Article
• Language: English
• Published: International Union of Crystallography 01-08-2021
• Subjects: crystal structures; cui complex; d0 early transition metals; hydrothermal synthesis; Research Communications
• ISSN: 2056-9890; 2056-9890
• DOI: 10.1107/S2056989021007295

The syntheses and crystal structures of two bimetallic mol­ecular compounds, namely, bis­(6,6′-dimethyl-2,2′-bi­pyridine)­copper(I) hexa­fluorido­zirconate(IV) 1.134-hydrate, [Cu(dmbpy)
2
]
2
[ZrF
6
]·1.134H
2
O (dmbpy = 6,6′-dimethyl-2,2′-bipyridyl, C
12
H
12
N
2
), (I), and bis­(6,6′-dimethyl-2,2′-bi­pyridine)­copper(I) hexa­fluorido­hafnate(IV) 0.671-hydrate, [Cu(dmbpy)
2
]
2
[HfF
6
]·0.671H
2
O, (II), are reported. Apart from a slight site occupancy difference for the water mol­ecule of crystallization, compounds (I) and (II) are isostructural, featuring isolated tetra­hedral cations of copper(I) ions coordinated by two dmbpy ligands and centrosymmetric, octa­hedral anions of fluorinated early transition metals.
The syntheses and crystal structures of two bimetallic mol­ecular compounds, namely, bis[bis­(6,6′-dimethyl-2,2′-bi­pyridine)­copper(I)] hexa­fluorido­zir­con­ate(IV) 1.134-hydrate, [Cu(dmbpy)
2
]
2
[ZrF
6
]·1.134H
2
O (dmbpy = 6,6′-di­methyl-2,2′-bipyri­dyl, C
12
H
12
N
2
), (I), and bis[bis­(6,6′-dimethyl-2,2′-bi­pyr­idine)­copper(I)] hexa­fluorido­hafnate(IV) 0.671-hydrate, [Cu(dmbpy)
2
]
2
[HfF
6
]·0.671H
2
O, (II), are reported. Apart from a slight site occupany difference for the water mol­ecule of crystallization, compounds (I) and (II) are isostructural, featuring isolated tetra­hedral cations of copper(I) ions coordinated by two dmbpy ligands and centrosymmetric, octa­hedral anions of fluorinated early transition metals. The tetra­hedral environments of the copper complexes are distorted owing to the steric effects of the dmbpy ligands. The extended structures are built up through Coulombic inter­actions between cations and anions and π–π stacking inter­actions between heterochiral Δ- and Λ-[Cu(dmbpy)
2
]
+
complexes. A comparison between the title compounds and other [Cu(dmbpy)
2
]
+
compounds with monovalent and bivalent anions reveals a significant influence of the cation-to-anion ratio on the resulting crystal packing architectures, providing insights for future crystal design of distorted tetra­hedral copper compounds.