Further studies on dialkyltin 1,3-dithiole-2-thione-4,5-dithiolates, R2Sn(dmit). Crystal structures of orthorhombic- and monoclinic-Et2Sn(dmit), and Me2Sn(dmit)

G. M. Allan, Robert Alan Howie, Janet Mabel Scott Skakle, J. L. Wardell, S. M. S. V. Wardell

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

The crystal structures of orthorhombic and monoclinic diethyltin bis(1,3-dithiole-2-thione-4,5-dithiolate), [Et2Sn(dmit)], ortho-3 and mono-3, and dimethyltin bis(1,3-dithiole-2-thione-4,5-dithiolate) (4) have been determined. Transformation of solid ortho-3 to mono-3 occurs at 139-140 degreesC. Molecules of ortho-3, obtained by recrystallisation from aqueous acetone, and 4, are linked into chains as a result of intermolecular Sn-thione S(5) interactions: the tin centres are penta-coordinate with distorted trigonal bipyramidal geometries. The intermolecular, Sn-S(S) thione bonds {3.0083(15) Angstrom in ortho-3 at 150 K} [3.037(4) at 298 K], and 3.001(2) and 2.960(2) Angstrom in the two independent molecules of 4 at 150 KJ, are considerably longer than the primary intramolecular Sn bonds to the dithiolato S atoms [between 2.440(3) and 2.5235(15) Angstrom]. The two independent molecules of mono-3, obtained from aqueous methanol, have quite different arrangements: tin atoms in molecule A form two relatively weak intermolecular Sn-thione S bonds, 3.567(2) and 3.620(3) Angstrom, with the formation of sheets, while those in molecule B form one similar bond, Sn-S = 3.555(2) Angstrom to give chains, with a much longer contact, Sn . . .S = 3.927(2) Angstrom to another chain. The latter is only ca. 0.12 Angstrom less than the van der Waals radii sum for Sn and S. Sulfur-sulfur contacts, within the sum of the van der Waals radii of two S atoms, 3.60 Angstrom, in 3 and 4, not only reinforce the chains but also help to establish 3D networks. (C) 2001 Elsevier Science B.V. All rights reserved.

Original languageEnglish
Pages (from-to)189-200
Number of pages11
JournalJournal of Organometallic Chemistry
Volume627
DOIs
Publication statusPublished - 2001

Keywords

  • organotin
  • 1,3-dithiole-2-thione-4,5-dithiolate
  • crystal structures
  • polymorphism
  • X-RAY-DIFFRACTION
  • = ONIUM CATION
  • COMPLEXES
  • PSEUDOHALIDE
  • DITHIOLATE
  • HALIDE
  • TIN

Cite this

Further studies on dialkyltin 1,3-dithiole-2-thione-4,5-dithiolates, R2Sn(dmit). Crystal structures of orthorhombic- and monoclinic-Et2Sn(dmit), and Me2Sn(dmit). / Allan, G. M.; Howie, Robert Alan; Skakle, Janet Mabel Scott; Wardell, J. L.; Wardell, S. M. S. V.

In: Journal of Organometallic Chemistry, Vol. 627, 2001, p. 189-200.

Research output: Contribution to journalArticle

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title = "Further studies on dialkyltin 1,3-dithiole-2-thione-4,5-dithiolates, R2Sn(dmit). Crystal structures of orthorhombic- and monoclinic-Et2Sn(dmit), and Me2Sn(dmit)",
abstract = "The crystal structures of orthorhombic and monoclinic diethyltin bis(1,3-dithiole-2-thione-4,5-dithiolate), [Et2Sn(dmit)], ortho-3 and mono-3, and dimethyltin bis(1,3-dithiole-2-thione-4,5-dithiolate) (4) have been determined. Transformation of solid ortho-3 to mono-3 occurs at 139-140 degreesC. Molecules of ortho-3, obtained by recrystallisation from aqueous acetone, and 4, are linked into chains as a result of intermolecular Sn-thione S(5) interactions: the tin centres are penta-coordinate with distorted trigonal bipyramidal geometries. The intermolecular, Sn-S(S) thione bonds {3.0083(15) Angstrom in ortho-3 at 150 K} [3.037(4) at 298 K], and 3.001(2) and 2.960(2) Angstrom in the two independent molecules of 4 at 150 KJ, are considerably longer than the primary intramolecular Sn bonds to the dithiolato S atoms [between 2.440(3) and 2.5235(15) Angstrom]. The two independent molecules of mono-3, obtained from aqueous methanol, have quite different arrangements: tin atoms in molecule A form two relatively weak intermolecular Sn-thione S bonds, 3.567(2) and 3.620(3) Angstrom, with the formation of sheets, while those in molecule B form one similar bond, Sn-S = 3.555(2) Angstrom to give chains, with a much longer contact, Sn . . .S = 3.927(2) Angstrom to another chain. The latter is only ca. 0.12 Angstrom less than the van der Waals radii sum for Sn and S. Sulfur-sulfur contacts, within the sum of the van der Waals radii of two S atoms, 3.60 Angstrom, in 3 and 4, not only reinforce the chains but also help to establish 3D networks. (C) 2001 Elsevier Science B.V. All rights reserved.",
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T1 - Further studies on dialkyltin 1,3-dithiole-2-thione-4,5-dithiolates, R2Sn(dmit). Crystal structures of orthorhombic- and monoclinic-Et2Sn(dmit), and Me2Sn(dmit)

AU - Allan, G. M.

AU - Howie, Robert Alan

AU - Skakle, Janet Mabel Scott

AU - Wardell, J. L.

AU - Wardell, S. M. S. V.

PY - 2001

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N2 - The crystal structures of orthorhombic and monoclinic diethyltin bis(1,3-dithiole-2-thione-4,5-dithiolate), [Et2Sn(dmit)], ortho-3 and mono-3, and dimethyltin bis(1,3-dithiole-2-thione-4,5-dithiolate) (4) have been determined. Transformation of solid ortho-3 to mono-3 occurs at 139-140 degreesC. Molecules of ortho-3, obtained by recrystallisation from aqueous acetone, and 4, are linked into chains as a result of intermolecular Sn-thione S(5) interactions: the tin centres are penta-coordinate with distorted trigonal bipyramidal geometries. The intermolecular, Sn-S(S) thione bonds {3.0083(15) Angstrom in ortho-3 at 150 K} [3.037(4) at 298 K], and 3.001(2) and 2.960(2) Angstrom in the two independent molecules of 4 at 150 KJ, are considerably longer than the primary intramolecular Sn bonds to the dithiolato S atoms [between 2.440(3) and 2.5235(15) Angstrom]. The two independent molecules of mono-3, obtained from aqueous methanol, have quite different arrangements: tin atoms in molecule A form two relatively weak intermolecular Sn-thione S bonds, 3.567(2) and 3.620(3) Angstrom, with the formation of sheets, while those in molecule B form one similar bond, Sn-S = 3.555(2) Angstrom to give chains, with a much longer contact, Sn . . .S = 3.927(2) Angstrom to another chain. The latter is only ca. 0.12 Angstrom less than the van der Waals radii sum for Sn and S. Sulfur-sulfur contacts, within the sum of the van der Waals radii of two S atoms, 3.60 Angstrom, in 3 and 4, not only reinforce the chains but also help to establish 3D networks. (C) 2001 Elsevier Science B.V. All rights reserved.

AB - The crystal structures of orthorhombic and monoclinic diethyltin bis(1,3-dithiole-2-thione-4,5-dithiolate), [Et2Sn(dmit)], ortho-3 and mono-3, and dimethyltin bis(1,3-dithiole-2-thione-4,5-dithiolate) (4) have been determined. Transformation of solid ortho-3 to mono-3 occurs at 139-140 degreesC. Molecules of ortho-3, obtained by recrystallisation from aqueous acetone, and 4, are linked into chains as a result of intermolecular Sn-thione S(5) interactions: the tin centres are penta-coordinate with distorted trigonal bipyramidal geometries. The intermolecular, Sn-S(S) thione bonds {3.0083(15) Angstrom in ortho-3 at 150 K} [3.037(4) at 298 K], and 3.001(2) and 2.960(2) Angstrom in the two independent molecules of 4 at 150 KJ, are considerably longer than the primary intramolecular Sn bonds to the dithiolato S atoms [between 2.440(3) and 2.5235(15) Angstrom]. The two independent molecules of mono-3, obtained from aqueous methanol, have quite different arrangements: tin atoms in molecule A form two relatively weak intermolecular Sn-thione S bonds, 3.567(2) and 3.620(3) Angstrom, with the formation of sheets, while those in molecule B form one similar bond, Sn-S = 3.555(2) Angstrom to give chains, with a much longer contact, Sn . . .S = 3.927(2) Angstrom to another chain. The latter is only ca. 0.12 Angstrom less than the van der Waals radii sum for Sn and S. Sulfur-sulfur contacts, within the sum of the van der Waals radii of two S atoms, 3.60 Angstrom, in 3 and 4, not only reinforce the chains but also help to establish 3D networks. (C) 2001 Elsevier Science B.V. All rights reserved.

KW - organotin

KW - 1,3-dithiole-2-thione-4,5-dithiolate

KW - crystal structures

KW - polymorphism

KW - X-RAY-DIFFRACTION

KW - = ONIUM CATION

KW - COMPLEXES

KW - PSEUDOHALIDE

KW - DITHIOLATE

KW - HALIDE

KW - TIN

U2 - 10.1016/S0022-328X(01)00735-5

DO - 10.1016/S0022-328X(01)00735-5

M3 - Article

VL - 627

SP - 189

EP - 200

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -