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Cu81Sn22 is gamma-brass-like structured and crystallizes in the trigonal R3m space group. The structure is three-dimensional. there are twenty-eight inequivalent Cu sites. In the first Cu site, Cu is bonded in a 11-coordinate geometry to six Cu and five Sn atoms. There are a spread of Cu–Cu bond distances ranging from 2.55–2.69 Å. There are one shorter (2.61 Å) and four longer (2.90 Å) Cu–Sn bond lengths. In the second Cu site, Cu is bonded in a 11-coordinate geometry to six Cu and five Sn atoms. There are a spread of Cu–Cu bond distances ranging from 2.55–2.70 Å. There are one shorter (2.62 Å) and four longer (2.90 Å) Cu–Sn bond lengths. In the third Cu site, Cu is bonded in a distorted q6 geometry to twelve Cu atoms. There are a spread of Cu–Cu bond distances ranging from 2.46–2.55 Å. In the fourth Cu site, Cu is bonded in a distorted q6 geometry to twelve Cu atoms. There are a spread of Cu–Cu bond distances ranging from 2.46–2.55 Å. In the fifth Cu site, Cu is bonded in a 10-coordinate geometry to seven Cu and three Sn atoms. There are a spread of Cu–Cu bond distances ranging from 2.51–2.70 Å. There are one shorter (2.79 Å) and two longer (2.88 Å) Cu–Sn bond lengths. In the sixth Cu site, Cu is bonded in a 10-coordinate geometry to seven Cu and three Sn atoms. There are a spread of Cu–Cu bond distances ranging from 2.51–2.70 Å. There are one shorter (2.78 Å) and two longer (2.88 Å) Cu–Sn bond lengths. In the seventh Cu site, Cu is bonded in a 10-coordinate geometry to seven Cu and three Sn atoms. There are a spread of Cu–Cu bond distances ranging from 2.52–2.71 Å. There are one shorter (2.78 Å) and two longer (2.88 Å) Cu–Sn bond lengths. In the eighth Cu site, Cu is bonded in a 11-coordinate geometry to eight Cu and three Sn atoms. There are a spread of Cu–Cu bond distances ranging from 2.56–2.84 Å. There are one shorter (2.70 Å) and two longer (2.91 Å) Cu–Sn bond lengths. In the ninth Cu site, Cu is bonded in a 11-coordinate geometry to eight Cu and three Sn atoms. There are a spread of Cu–Cu bond distances ranging from 2.54–2.89 Å. There are one shorter (2.77 Å) and two longer (2.90 Å) Cu–Sn bond lengths. In the tenth Cu site, Cu is bonded in a 11-coordinate geometry to eight Cu and three Sn atoms. There are a spread of Cu–Cu bond distances ranging from 2.54–2.85 Å. There are a spread of Cu–Sn bond distances ranging from 2.74–2.92 Å. In the eleventh Cu site, Cu is bonded in a 12-coordinate geometry to nine Cu and three equivalent Sn atoms. All Cu–Cu bond lengths are 2.65 Å. All Cu–Sn bond lengths are 2.70 Å. In the twelfth Cu site, Cu is bonded in a 12-coordinate geometry to nine Cu and three Sn atoms. All Cu–Cu bond lengths are 2.66 Å. There are two shorter (2.69 Å) and one longer (2.70 Å) Cu–Sn bond lengths. In the thirteenth Cu site, Cu is bonded in a 12-coordinate geometry to nine Cu and three equivalent Sn atoms. There are three shorter (2.59 Å) and three longer (2.76 Å) Cu–Cu bond lengths. All Cu–Sn bond lengths are 2.70 Å. In the fourteenth Cu site, Cu is bonded in a 12-coordinate geometry to nine Cu and three Sn atoms. There are three shorter (2.59 Å) and two longer (2.77 Å) Cu–Cu bond lengths. All Cu–Sn bond lengths are 2.70 Å. In the fifteenth Cu site, Cu is bonded in a 10-coordinate geometry to six Cu and four Sn atoms. There are one shorter (2.64 Å) and two longer (2.86 Å) Cu–Cu bond lengths. There are a spread of Cu–Sn bond distances ranging from 2.57–2.87 Å. In the sixteenth Cu site, Cu is bonded in a 11-coordinate geometry to seven Cu and four Sn atoms. There are a spread of Cu–Cu bond distances ranging from 2.61–2.88 Å. There are a spread of Cu–Sn bond distances ranging from 2.60–2.85 Å. In the seventeenth Cu site, Cu is bonded in a 11-coordinate geometry to seven Cu and four Sn atoms. There are a spread of Cu–Cu bond distances ranging from 2.62–2.88 Å. There are a spread of Cu–Sn bond distances ranging from 2.62–2.85 Å. In the eighteenth Cu site, Cu is bonded in a distorted q6 geometry to nine Cu and three equivalent Sn atoms. All Cu–Cu bond lengths are 2.59 Å. All Cu–Sn bond lengths are 2.64 Å. In the nineteenth Cu site, Cu is bonded in a 12-coordinate geometry to nine Cu and three Sn atoms. All Cu–Cu bond lengths are 2.61 Å. All Cu–Sn bond lengths are 2.65 Å. In the twentieth Cu site, Cu is bonded in a distorted q6 geometry to nine Cu and three equivalent Sn atoms. All Cu–Cu bond lengths are 2.60 Å. All Cu–Sn bond lengths are 2.83 Å. In the twenty-first Cu site, Cu is bonded in a distorted q6 geometry to nine Cu and three Sn atoms. Both Cu–Cu bond lengths are 2.60 Å. There are two shorter (2.82 Å) and one longer (2.84 Å) Cu–Sn bond lengths. In the twenty-second Cu site, Cu is bonded to nine Cu and three equivalent Sn atoms to form face-sharing CuCu9Sn3 cuboctahedra. All Cu–Sn bond lengths are 2.78 Å. In the twenty-third Cu site, Cu is bonded to nine Cu and three Sn atoms to form face-sharing CuCu9Sn3 cuboctahedra. All Cu–Sn bond lengths are 2.78 Å. In the twenty-fourth Cu site, Cu is bonded in a 2-coordinate geometry to eleven Cu and two equivalent Sn atoms. The Cu–Cu bond length is 2.68 Å. Both Cu–Sn bond lengths are 2.56 Å. In the twenty-fifth Cu site, Cu is bonded in a 2-coordinate geometry to eleven Cu and two Sn atoms. The Cu–Cu bond length is 2.69 Å. Both Cu–Sn bond lengths are 2.57 Å. In the twenty-sixth Cu site, Cu is bonded in a 12-coordinate geometry to eight Cu and four Sn atoms. The Cu–Cu bond length is 2.68 Å. There are a spread of Cu–Sn bond distances ranging from 2.72–2.82 Å. In the twenty-seventh Cu site, Cu is bonded in a 9-coordinate geometry to nine Cu and four Sn atoms. Both Cu–Cu bond lengths are 2.63 Å. There are two shorter (2.80 Å) and two longer (2.81 Å) Cu–Sn bond lengths. In the twenty-eighth Cu site, Cu is bonded in a 11-coordinate geometry to eight Cu and three Sn atoms. Both Cu–Cu bond lengths are 2.93 Å. There are two shorter (2.68 Å) and one longer (2.72 Å) Cu–Sn bond lengths. There are seven inequivalent Sn sites. In the first Sn site, Sn is bonded in a 11-coordinate geometry to eleven Cu atoms. In the second Sn site, Sn is bonded in a 11-coordinate geometry to eleven Cu atoms. In the third Sn site, Sn is bonded in a 1-coordinate geometry to thirteen Cu atoms. In the fourth Sn site, Sn is bonded in a 1-coordinate geometry to thirteen Cu atoms. In the fifth Sn site, Sn is bonded in a 12-coordinate geometry to twelve Cu atoms. In the sixth Sn site, Sn is bonded in a 11-coordinate geometry to eleven Cu atoms. In the seventh Sn site, Sn is bonded in a 11-coordinate geometry to eleven Cu atoms.

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