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Eu6Sb6S17 is isotypic with Sr6Sb6S17 and can be regarded as consisting of two isolated [Sb3S7]5- anions and an S32- polysulfide anion that are joined together by Eu2+ cations. There are six crystallographically unique Eu2+ cations bound by sulfide and polysulfide anions in seven-, eight- and nine-coordinate environments. Each of the [Sb3S7]5- anions consists of a trinuclear assembly of corner-sharing SbS3 units. The [Sb3S7]5- anions are connected by long (3.1 Å) Sb-S inter­actions, forming one-dimensional ribbons running down the a axis and packed with opposing directions of polarity. The bent S32- anions stack in columns parallel to the a axis, oriented in opposing directions with respect to one another. The overall structure is three-dimensional and has channels running down the a axis to house the stereochemically active lone pair of electrons on the Sb3+ centers. The presence of Eu2+ is supported by both magnetic measurements and bond-valence calculations.
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