Sb⋯Sb and Bi⋯Bi interactions in Cs8M4(P2Se6)5 (M= Sb, Bi)

Timothy J. McCarthy, Tim Hogan, Carl R. Kannewurf, Mercouri G Kanatzidis

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Abstract

Cs8M4(P2Se6)5 (M = Sb, Bi) were synthesized by reacting Bi (Sb) with a molten mixture of Cs2Se/P4Se10/Se at 460°C. The structure features weak M⋯M interactions and a [P2Se6]4- ligand in three unique bonding modes. The [M4(P2Se6)5]n 8n- layers are composed of [M4(P2-Se6)4] zigzag chains that are linked via [P2Se6]4- ligands to form a staircase layered framework. The layers are interdigitated to form tunnels along the b direction. Cs+ ions are found in the tunnels and within the layers. The dark red crystals of Cs8Sb4(P2Se6)5 (I) (75% yield) and the black crystals of the isostructural Cs8Bi4(P2Se6)5 (II) (90% yield) are stable in air and water. Compound I crystallizes in the monoclinic space group P21/n (No. 14) with a = 15.489(3) Å, b = 11.505(2) Å, c = 17.772(3) Å, β = 95.59(2)°, V = 3152 Å3, Z = 2, and dc = 4.455g/cm3, with Fo2 > 3σ(Fσ2)=3544, number of variables = 236, and 2θmax = 50°. The final R/Rw = 3.2/4.9. Compound II is X-ray isomorphous with a = 15.752(4) Å, b = 11.523(2) Å, c = 17.916(2) Å, β = 95.20(2)°, V = 3241 Å3, Z = 2, and dc=4.694 g/cm3, with Fo2 > 3σ(Fσ2) = 2598, number of variables = 236, and 2θmax = 50°. The final R/Rw = 5.4/6.7. The optical band gaps of I and II were determined by optical spectroscopy to be 1.58 and 1.44 eV, respectively. Both compounds melt congruently at 532 (I) and 497°C (II).

Original languageEnglish
Pages (from-to)1072-1079
Number of pages8
JournalChemistry of Materials
Volume6
Issue number7
Publication statusPublished - 1994

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Tunnels
Ligands
Crystals
Optical band gaps
Molten materials
Ions
X rays
Water
Air
Optical spectroscopy
Direction compound

ASJC Scopus subject areas

  • Materials Chemistry
  • Materials Science(all)

Cite this

McCarthy, T. J., Hogan, T., Kannewurf, C. R., & Kanatzidis, M. G. (1994). Sb⋯Sb and Bi⋯Bi interactions in Cs8M4(P2Se6)5 (M= Sb, Bi). Chemistry of Materials, 6(7), 1072-1079.

Sb⋯Sb and Bi⋯Bi interactions in Cs8M4(P2Se6)5 (M= Sb, Bi). / McCarthy, Timothy J.; Hogan, Tim; Kannewurf, Carl R.; Kanatzidis, Mercouri G.

In: Chemistry of Materials, Vol. 6, No. 7, 1994, p. 1072-1079.

Research output: Contribution to journalArticle

McCarthy, TJ, Hogan, T, Kannewurf, CR & Kanatzidis, MG 1994, 'Sb⋯Sb and Bi⋯Bi interactions in Cs8M4(P2Se6)5 (M= Sb, Bi)', Chemistry of Materials, vol. 6, no. 7, pp. 1072-1079.
McCarthy, Timothy J. ; Hogan, Tim ; Kannewurf, Carl R. ; Kanatzidis, Mercouri G. / Sb⋯Sb and Bi⋯Bi interactions in Cs8M4(P2Se6)5 (M= Sb, Bi). In: Chemistry of Materials. 1994 ; Vol. 6, No. 7. pp. 1072-1079.
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title = "Sb⋯Sb and Bi⋯Bi interactions in Cs8M4(P2Se6)5 (M= Sb, Bi)",
abstract = "Cs8M4(P2Se6)5 (M = Sb, Bi) were synthesized by reacting Bi (Sb) with a molten mixture of Cs2Se/P4Se10/Se at 460°C. The structure features weak M⋯M interactions and a [P2Se6]4- ligand in three unique bonding modes. The [M4(P2Se6)5]n 8n- layers are composed of [M4(P2-Se6)4] zigzag chains that are linked via [P2Se6]4- ligands to form a staircase layered framework. The layers are interdigitated to form tunnels along the b direction. Cs+ ions are found in the tunnels and within the layers. The dark red crystals of Cs8Sb4(P2Se6)5 (I) (75{\%} yield) and the black crystals of the isostructural Cs8Bi4(P2Se6)5 (II) (90{\%} yield) are stable in air and water. Compound I crystallizes in the monoclinic space group P21/n (No. 14) with a = 15.489(3) {\AA}, b = 11.505(2) {\AA}, c = 17.772(3) {\AA}, β = 95.59(2)°, V = 3152 {\AA}3, Z = 2, and dc = 4.455g/cm3, with Fo2 > 3σ(Fσ2)=3544, number of variables = 236, and 2θmax = 50°. The final R/Rw = 3.2/4.9. Compound II is X-ray isomorphous with a = 15.752(4) {\AA}, b = 11.523(2) {\AA}, c = 17.916(2) {\AA}, β = 95.20(2)°, V = 3241 {\AA}3, Z = 2, and dc=4.694 g/cm3, with Fo2 > 3σ(Fσ2) = 2598, number of variables = 236, and 2θmax = 50°. The final R/Rw = 5.4/6.7. The optical band gaps of I and II were determined by optical spectroscopy to be 1.58 and 1.44 eV, respectively. Both compounds melt congruently at 532 (I) and 497°C (II).",
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AU - McCarthy, Timothy J.

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AU - Kanatzidis, Mercouri G

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N2 - Cs8M4(P2Se6)5 (M = Sb, Bi) were synthesized by reacting Bi (Sb) with a molten mixture of Cs2Se/P4Se10/Se at 460°C. The structure features weak M⋯M interactions and a [P2Se6]4- ligand in three unique bonding modes. The [M4(P2Se6)5]n 8n- layers are composed of [M4(P2-Se6)4] zigzag chains that are linked via [P2Se6]4- ligands to form a staircase layered framework. The layers are interdigitated to form tunnels along the b direction. Cs+ ions are found in the tunnels and within the layers. The dark red crystals of Cs8Sb4(P2Se6)5 (I) (75% yield) and the black crystals of the isostructural Cs8Bi4(P2Se6)5 (II) (90% yield) are stable in air and water. Compound I crystallizes in the monoclinic space group P21/n (No. 14) with a = 15.489(3) Å, b = 11.505(2) Å, c = 17.772(3) Å, β = 95.59(2)°, V = 3152 Å3, Z = 2, and dc = 4.455g/cm3, with Fo2 > 3σ(Fσ2)=3544, number of variables = 236, and 2θmax = 50°. The final R/Rw = 3.2/4.9. Compound II is X-ray isomorphous with a = 15.752(4) Å, b = 11.523(2) Å, c = 17.916(2) Å, β = 95.20(2)°, V = 3241 Å3, Z = 2, and dc=4.694 g/cm3, with Fo2 > 3σ(Fσ2) = 2598, number of variables = 236, and 2θmax = 50°. The final R/Rw = 5.4/6.7. The optical band gaps of I and II were determined by optical spectroscopy to be 1.58 and 1.44 eV, respectively. Both compounds melt congruently at 532 (I) and 497°C (II).

AB - Cs8M4(P2Se6)5 (M = Sb, Bi) were synthesized by reacting Bi (Sb) with a molten mixture of Cs2Se/P4Se10/Se at 460°C. The structure features weak M⋯M interactions and a [P2Se6]4- ligand in three unique bonding modes. The [M4(P2Se6)5]n 8n- layers are composed of [M4(P2-Se6)4] zigzag chains that are linked via [P2Se6]4- ligands to form a staircase layered framework. The layers are interdigitated to form tunnels along the b direction. Cs+ ions are found in the tunnels and within the layers. The dark red crystals of Cs8Sb4(P2Se6)5 (I) (75% yield) and the black crystals of the isostructural Cs8Bi4(P2Se6)5 (II) (90% yield) are stable in air and water. Compound I crystallizes in the monoclinic space group P21/n (No. 14) with a = 15.489(3) Å, b = 11.505(2) Å, c = 17.772(3) Å, β = 95.59(2)°, V = 3152 Å3, Z = 2, and dc = 4.455g/cm3, with Fo2 > 3σ(Fσ2)=3544, number of variables = 236, and 2θmax = 50°. The final R/Rw = 3.2/4.9. Compound II is X-ray isomorphous with a = 15.752(4) Å, b = 11.523(2) Å, c = 17.916(2) Å, β = 95.20(2)°, V = 3241 Å3, Z = 2, and dc=4.694 g/cm3, with Fo2 > 3σ(Fσ2) = 2598, number of variables = 236, and 2θmax = 50°. The final R/Rw = 5.4/6.7. The optical band gaps of I and II were determined by optical spectroscopy to be 1.58 and 1.44 eV, respectively. Both compounds melt congruently at 532 (I) and 497°C (II).

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