Synthesis and Structural Characterization of Layered Calcium and Lanthanide Phosphonate Salts

Guang Cao; Vincent M. Lynch; J. Steven Swinnea; Thomas E. Mallouk

doi:10.1021/ic00336a016

Synthesis and Structural Characterization of Layered Calcium and Lanthanide Phosphonate Salts

Guang Cao, Vincent M. Lynch, J. Steven Swinnea, Thomas E. Mallouk

Chemistry

Research output: Contribution to journal › Article › peer-review

174 Scopus citations

Abstract

The crystal structures of two layered calcium phosphonate salts, Ca(O₃PCH₃)·H₂O and Ca(HO₃PC₆H₁₃)₂, were solved by single-crystal X-ray diffraction. Ca(O₃PCH₃)·H₂O is monoclinic, space group P2₁/c, with Z = 4, a = 8.8562 (13) Å, b = 6.6961 (10) Å, c = 8.1020 (10) Å, β; = 96.910 (11)°, and V = 476.97 (12) Å³. Ca atoms are coordinated by six oxygen atoms at a distance of ca. 2.4 Å, and by a seventh at 2.7 Å, making the coordination environment a distorted pentagonal bipyramid. In this salt, and in the structurally related M(O₃PC_nH_2n+1)·H₂O (n ≤ 5; M = Ca, Cd) series, the metal-phosphonate coordination is 5:5. Ca-(HO₃PC₆H₁₃)₂ is triclinic, space group P1, with Z = 2, a = 5.606 (2) Å, b = 7.343 (3) Å, c = 21.158 (7) Å, α = 97.31 (3)°, β = 96.98 (3)°, γ = 90.43 (4)°, and V = 857.2 (6) Å³. In this structure and the related Ca(HO₃PC_nH₂₊₁)₂ (6 < n < 18) series, the Ca atoms lie in approximately coplanar sheets and are coordinated by six oxygen atoms from different phosphonate groups lying above and below the plane. This structure is closely related to that of α-Zr(HPO₄)₂·H₂O and the tetravalent metal phosphonates M(O₃PR)₂ (M = Zr, Hf, Ti, Ce). Layered trivalent metal phosphonate salts MH(O₃PR)₂ (R = alkyl, phenyl; M = La, Sm, Ce) were also prepared. LaH(Ò₃PCH₃)₂ is triclinic with Z = 2, a = 5.398 (7) Å, b = 8.168 (18) Å, c = 10.162 (19) Å, α = 73.76 (16)°, β = 83.89 (13)°, γ = 73.50 (14)°, and V = 412.3 (13) Å³. The structure of the MH(O₃PR)₂ compounds appears to be closely related to that of the other 1:2 layered metal phosphonate salts Ca(HO₃PC_nH_2n+1)₂ and M(O₃PR)₂.

Original language	English (US)
Pages (from-to)	2112-2117
Number of pages	6
Journal	Inorganic chemistry
Volume	29
Issue number	11
DOIs	https://doi.org/10.1021/ic00336a016
State	Published - May 1 1990

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/ic00336a016

Cite this

@article{670ba52ee49d4899bbf03ed11eacd695,

title = "Synthesis and Structural Characterization of Layered Calcium and Lanthanide Phosphonate Salts",

abstract = "The crystal structures of two layered calcium phosphonate salts, Ca(O3PCH3)·H2O and Ca(HO3PC6H13)2, were solved by single-crystal X-ray diffraction. Ca(O3PCH3)·H2O is monoclinic, space group P21/c, with Z = 4, a = 8.8562 (13) {\AA}, b = 6.6961 (10) {\AA}, c = 8.1020 (10) {\AA}, β; = 96.910 (11)°, and V = 476.97 (12) {\AA}3. Ca atoms are coordinated by six oxygen atoms at a distance of ca. 2.4 {\AA}, and by a seventh at 2.7 {\AA}, making the coordination environment a distorted pentagonal bipyramid. In this salt, and in the structurally related M(O3PCnH2n+1)·H2O (n ≤ 5; M = Ca, Cd) series, the metal-phosphonate coordination is 5:5. Ca-(HO3PC6H13)2 is triclinic, space group P1, with Z = 2, a = 5.606 (2) {\AA}, b = 7.343 (3) {\AA}, c = 21.158 (7) {\AA}, α = 97.31 (3)°, β = 96.98 (3)°, γ = 90.43 (4)°, and V = 857.2 (6) {\AA}3. In this structure and the related Ca(HO3PCnH2+1)2 (6 < n < 18) series, the Ca atoms lie in approximately coplanar sheets and are coordinated by six oxygen atoms from different phosphonate groups lying above and below the plane. This structure is closely related to that of α-Zr(HPO4)2·H2O and the tetravalent metal phosphonates M(O3PR)2 (M = Zr, Hf, Ti, Ce). Layered trivalent metal phosphonate salts MH(O3PR)2 (R = alkyl, phenyl; M = La, Sm, Ce) were also prepared. LaH({\`O}3PCH3)2 is triclinic with Z = 2, a = 5.398 (7) {\AA}, b = 8.168 (18) {\AA}, c = 10.162 (19) {\AA}, α = 73.76 (16)°, β = 83.89 (13)°, γ = 73.50 (14)°, and V = 412.3 (13) {\AA}3. The structure of the MH(O3PR)2 compounds appears to be closely related to that of the other 1:2 layered metal phosphonate salts Ca(HO3PCnH2n+1)2 and M(O3PR)2.",

author = "Guang Cao and Lynch, \{Vincent M.\} and Swinnea, \{J. Steven\} and Mallouk, \{Thomas E.\}",

year = "1990",

month = may,

day = "1",

doi = "10.1021/ic00336a016",

language = "English (US)",

volume = "29",

pages = "2112--2117",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "11",

}

TY - JOUR

T1 - Synthesis and Structural Characterization of Layered Calcium and Lanthanide Phosphonate Salts

AU - Cao, Guang

AU - Lynch, Vincent M.

AU - Swinnea, J. Steven

AU - Mallouk, Thomas E.

PY - 1990/5/1

Y1 - 1990/5/1

N2 - The crystal structures of two layered calcium phosphonate salts, Ca(O3PCH3)·H2O and Ca(HO3PC6H13)2, were solved by single-crystal X-ray diffraction. Ca(O3PCH3)·H2O is monoclinic, space group P21/c, with Z = 4, a = 8.8562 (13) Å, b = 6.6961 (10) Å, c = 8.1020 (10) Å, β; = 96.910 (11)°, and V = 476.97 (12) Å3. Ca atoms are coordinated by six oxygen atoms at a distance of ca. 2.4 Å, and by a seventh at 2.7 Å, making the coordination environment a distorted pentagonal bipyramid. In this salt, and in the structurally related M(O3PCnH2n+1)·H2O (n ≤ 5; M = Ca, Cd) series, the metal-phosphonate coordination is 5:5. Ca-(HO3PC6H13)2 is triclinic, space group P1, with Z = 2, a = 5.606 (2) Å, b = 7.343 (3) Å, c = 21.158 (7) Å, α = 97.31 (3)°, β = 96.98 (3)°, γ = 90.43 (4)°, and V = 857.2 (6) Å3. In this structure and the related Ca(HO3PCnH2+1)2 (6 < n < 18) series, the Ca atoms lie in approximately coplanar sheets and are coordinated by six oxygen atoms from different phosphonate groups lying above and below the plane. This structure is closely related to that of α-Zr(HPO4)2·H2O and the tetravalent metal phosphonates M(O3PR)2 (M = Zr, Hf, Ti, Ce). Layered trivalent metal phosphonate salts MH(O3PR)2 (R = alkyl, phenyl; M = La, Sm, Ce) were also prepared. LaH(Ò3PCH3)2 is triclinic with Z = 2, a = 5.398 (7) Å, b = 8.168 (18) Å, c = 10.162 (19) Å, α = 73.76 (16)°, β = 83.89 (13)°, γ = 73.50 (14)°, and V = 412.3 (13) Å3. The structure of the MH(O3PR)2 compounds appears to be closely related to that of the other 1:2 layered metal phosphonate salts Ca(HO3PCnH2n+1)2 and M(O3PR)2.

AB - The crystal structures of two layered calcium phosphonate salts, Ca(O3PCH3)·H2O and Ca(HO3PC6H13)2, were solved by single-crystal X-ray diffraction. Ca(O3PCH3)·H2O is monoclinic, space group P21/c, with Z = 4, a = 8.8562 (13) Å, b = 6.6961 (10) Å, c = 8.1020 (10) Å, β; = 96.910 (11)°, and V = 476.97 (12) Å3. Ca atoms are coordinated by six oxygen atoms at a distance of ca. 2.4 Å, and by a seventh at 2.7 Å, making the coordination environment a distorted pentagonal bipyramid. In this salt, and in the structurally related M(O3PCnH2n+1)·H2O (n ≤ 5; M = Ca, Cd) series, the metal-phosphonate coordination is 5:5. Ca-(HO3PC6H13)2 is triclinic, space group P1, with Z = 2, a = 5.606 (2) Å, b = 7.343 (3) Å, c = 21.158 (7) Å, α = 97.31 (3)°, β = 96.98 (3)°, γ = 90.43 (4)°, and V = 857.2 (6) Å3. In this structure and the related Ca(HO3PCnH2+1)2 (6 < n < 18) series, the Ca atoms lie in approximately coplanar sheets and are coordinated by six oxygen atoms from different phosphonate groups lying above and below the plane. This structure is closely related to that of α-Zr(HPO4)2·H2O and the tetravalent metal phosphonates M(O3PR)2 (M = Zr, Hf, Ti, Ce). Layered trivalent metal phosphonate salts MH(O3PR)2 (R = alkyl, phenyl; M = La, Sm, Ce) were also prepared. LaH(Ò3PCH3)2 is triclinic with Z = 2, a = 5.398 (7) Å, b = 8.168 (18) Å, c = 10.162 (19) Å, α = 73.76 (16)°, β = 83.89 (13)°, γ = 73.50 (14)°, and V = 412.3 (13) Å3. The structure of the MH(O3PR)2 compounds appears to be closely related to that of the other 1:2 layered metal phosphonate salts Ca(HO3PCnH2n+1)2 and M(O3PR)2.

UR - https://www.scopus.com/pages/publications/0001472575

UR - https://www.scopus.com/inward/citedby.url?scp=0001472575&partnerID=8YFLogxK

U2 - 10.1021/ic00336a016

DO - 10.1021/ic00336a016

M3 - Article

AN - SCOPUS:0001472575

SN - 0020-1669

VL - 29

SP - 2112

EP - 2117

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 11

ER -

Synthesis and Structural Characterization of Layered Calcium and Lanthanide Phosphonate Salts

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this