Abstract
The compound Re
2
Cl
5
(C
4
H
10
S
2
)
2
crystallizes in the monoclinic system with a unit cell of dimensions
a
= 8.023 ± 0.008 Å,
b
= 14.355 ± 0.005 Å,
c
= 8.423 ± 0.006 Å,
β
= 105.5 ±0-1° occupied by two formula units. The space group is P2
1
/
m
. The structure, which has been refined to a discrepancy index of 0.064, consists of binuclear units with a staggered rotational configuration. This result together with magnetic data suggests that the compound is best formulated as a zwitterion, Cl(C
4
H
10
S
2
)
2
Re
+
(II) ≡ Re¯(III) Cl
4
, with the single unpaired electron occupying a singly degenerate orbital localized on the rhenium atom which has a formal oxidation state of III. The metal-metal bond then has an order of 3. This bonding may be compared with the Re-Re bonding in the octachlorodirhenium (III) anions and other related structures.
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