DOI: 10.1002/anie.200500214. {Sn[Zn4Sn4S17]}6−: A Robust Open Framework Based on Metal‐Linked Penta‐Supertetrahedral [Zn4Sn4S17]10− Clusters with Ion‐Exchange Properties

{Sn[Zn4Sn4S17]}6−: A Robust Open Framework Based on Metal‐Linked Penta‐Supertetrahedral [Zn4Sn4S17]10− Clusters with Ion‐Exchange Properties

10.1002/anie.200500214

Crossref journal-article

Wiley

Angewandte Chemie International Edition (311)

Authors 5

Manolis J. Manos (first)
Ratnasabapathy G. Iyer (additional)
Eric Quarez (additional)
J. H. Liao (additional)
Mercouri G. Kanatzidis (additional)

References 48 Referenced 190

10.1126/science.258.5089.1769
10.1021/ja00109a012
10.1021/cm00058a024
10.1021/cm9506060
10.1002/(SICI)1521-3757(19980202)110:3<354::AID-ANGE354>3.0.CO;2-R
10.1002/(SICI)1521-3773(19980216)37:3<342::AID-ANIE342>3.0.CO;2-P
10.1021/ja9713486
10.1002/chem.200306041
10.1002/ange.200460386
10.1002/anie.200460386
10.1038/nature02159
10.1021/ja030103s
P. Feng X. Bu N. Zheng Acc. Chem. Res.2005 (ASAP article);
10.1126/science.283.5405.1145
10.1021/ja010413f
10.1002/ange.200250748
10.1002/anie.200250748
10.1021/ic034600l
10.1002/zaac.200400154
10.1002/1521-3757(20021115)114:22<4444::AID-ANGE4444>3.0.CO;2-9
10.1002/1521-3773(20021115)41:22<4269::AID-ANIE4269>3.0.CO;2-8
10.1021/ja029601b
10.1002/zaac.200300235
10.1039/b402686a
10.1002/chem.200400521
K6Sn[Zn4Sn4S17] (1): A mixture of Sn (0.5 mmol) Zn (0.4 mmol) K2S (1 mmol) and S (8 mmol) was sealed under vacuum (≈10−4torr) in a 9‐mm silica tube heated (≈40 °C h−1) to 400 °C for 96 h and then cooled to 25 °C at a rate of 6 °C h−1. The excess flux was removed withN N‐dimethylformamide (DMF) to reveal a mixture of pale yellow polyhedral crystals of1and orange crystals of K2Sn2S5. In some preparations the product contained a small quantity of S8 which could be removed by washing with CS2. Treating the mixture of1and K2Sn2S5with aqueous K2CO3(pH 9–10) completely dissolved the ternary phase and pure compound1was obtained (yield ≈30–60 %). EDS analysis on several crystals of1gave an average composition of K5.6Sn5.2Zn4S17.2.
10.1002/9780470166444.ch2
K5CsSn[Zn4Sn4S17] (2) and K5RbSn[Zn4Sn4S17] (3): A mixture of Sn (0.5 mmol) Zn (0.4 mmol) K2S (0.9 mmol) Cs2S or Rb2S (0.1 mmol) and S (8 mmol) was sealed under vacuum (≈10−4torr) in a 9‐mm silica tube heated (≈40 °C h−1) to 400 °C for 96 h and then cooled to room temperature at a rate of 6 °C h−1. The excess flux was removed with DMF to reveal a mixture of pale yellow polyhedral crystals of2or3(yield 30–50 % based on Sn) and orange crystals of K2Sn2S5. The ternary phase was removed by washing with K2CO3. EDS analysis on several crystals of2and3gave compositions of K5.1CsSn5.1Zn4.6S17.6and K4.6RbSn5Zn4.7S16.8 respectively.
Crystal data: K6Sn5Zn4S17 space groupI$\bar 4$m2(No. 119) a=13.7425(7) c=9.7272(5) Å V=1837.04(16) Z=2 R1(F)=0.0452 wR2(F2)=0.0878; K5CsSn5Zn4S17 space groupI$\bar 4$m2 a=13.7684(11) c=9.5630(9) Å V=1812.8(5) Z=2 R1(F)=0.0669 wR2(F2)=0.1277; K5RbSn5Zn4S17 space groupI$\bar 4$m2 a=13.7687(10) c=9.7767(6) Å V=1853.4(2) Z=2 R1(F)=0.0553 wR2(F2)=0.0762. Further details on the investigation of the crystal structure may be obtained from the Fachinformationszentrum Karlsruhe 76344 Eggenstein‐Leopoldshafen Germany (fax: (+49) 7247‐808‐666; e‐mail: crysdata@fiz‐karlsruhe.de) on quoting the depository numbers CSD‐415015 CSD‐415016 and CSD‐415018 (for the compounds K6Sn5Zn4S17 K5CsSn5Zn4S17 and K5RbSn5Zn4S17 respectively).
10.1021/ja00081a067
10.1021/cm00042a021
10.1039/a706279f
10.1515/znb-1997-0604 / Z. Naturforsch. B by Loose b)A. (1997)
10.1016/S0144-2449(97)00047-X
The split‐occupancy sites and possible rattling of these ions inside the cages explains the much higher thermal‐displacement parameters of K3 and K2 relative to that of K1.
Reactions aiming to form K6Sn[M4Sn4S17] analogues (M=Hg2+ Cd2+ Co2+ Fe2+) or the Se analogue of1led to other quaternary and ternary phases. However compounds with Sn atoms partially replaced by Ge or Zn atoms partially replaced by other divalent atoms (such as Hg2+or Cd2+) have been isolated and these results will be published elsewhere. Efforts to prepare K6Ge[Zn4Ge4S17] resulted instead in K10Zn4Ge4S17.[4]
Interestingly the material exhibits selectivity against Li and Na ions. In water these have a strongly held hydration sphere that prevents the large hydrated ions from entering the structure. Preliminary ion‐exchange experiments of compound1with CsCl at room temperature showed that only one K+ion can be exchanged by one Cs+ion. Crystallographic analysis of the exchanged material showed that only the K3 ions were exchanged with Cs ions.
A typical ion‐exchange experimental route for the preparation of compound4is as follows: An excess of solid RbI (0.2 mmol) was added to a suspension of compound1(0.01 mmol) in water (20 mL). The mixture was stirred for ≈12 h. Then the yellowish‐white crystalline material was isolated by filtration washed several times with water acetone and ether (in this order) and dried in air.
Rb5KSn5Zn4S17(ion‐exchanged) space groupI$\bar 4$m2 a=13.8354(10) c=9.8893(9) Å V=1893.0(3) Z=2 R1(F)=0.0793 wR2(F2)=0.1519. Further details on the crystal structure investigations may be obtained from the Fachinformationszentrum Karlsruhe 76344 Eggenstein‐Leopoldshafen Germany (fax: (+49) 7247‐808‐666; e‐mail: crysdata@fiz‐karlsruhe.de) on quoting the depository number CSD‐415017.
10.1063/1.1680242
T. Kerr M. Armatas P. N. Trikalitis O. Palchik M. G. Kanatzidis unpublished results.

Dates

Type	When
Created	20 years, 3 months ago (May 11, 2005, 6:47 a.m.)
Deposited	1 year, 10 months ago (Oct. 10, 2023, 10:24 p.m.)
Indexed	1 month ago (July 24, 2025, 6:53 a.m.)
Issued	20 years, 2 months ago (May 30, 2005)
Published	20 years, 2 months ago (May 30, 2005)
Published Online	20 years, 2 months ago (May 30, 2005)
Published Print	20 years, 2 months ago (June 6, 2005)

Funders 0

None

BibTeX

@article{Manos_2005, title={{Sn[Zn4Sn4S17]}6−: A Robust Open Framework Based on Metal‐Linked Penta‐Supertetrahedral [Zn4Sn4S17]10− Clusters with Ion‐Exchange Properties}, volume={44}, ISSN={1521-3773}, url={http://dx.doi.org/10.1002/anie.200500214}, DOI={10.1002/anie.200500214}, number={23}, journal={Angewandte Chemie International Edition}, publisher={Wiley}, author={Manos, Manolis J. and Iyer, Ratnasabapathy G. and Quarez, Eric and Liao, J. H. and Kanatzidis, Mercouri G.}, year={2005}, month=may, pages={3552–3555} }

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    "date-parts": [
      [
        2005,
        5,
        30
      ]
    ]
  }
}