TY - JOUR
T1 - Synthesis and structure of a lead(II)-citrate
T2 - {Na(H2O) 3}[Pb5(C6H5O7) 3(C6H6O7)(H2O) 3]·9.5H2O
AU - Chu, Christopher
AU - Darling, Kari
AU - Netusil, Ross
AU - Doyle, Robert P.
AU - Zubieta, Jon
N1 - Funding Information:
This work was supported in part by grants from the National Science Foundation , CHE-0907787 (JZ), the Office of the Dean of Arts and Sciences (RPD), and the National Science Foundation REU Program (RN) .
Copyright:
Copyright 2011 Elsevier B.V., All rights reserved.
PY - 2011/11/30
Y1 - 2011/11/30
N2 - The reaction of lead(II) nitrate with trisodium citrate Na 3(C6H5O7) in a 1:22.5 ratio at pH 4.8 provides crystals of {Na(H2O)3}[Pb5(H 2O)3(C6H5O7) 3(C6H6O7)]·9.5H2O (1). The structure of 1 is two-dimensional and exhibits five distinct Pb(II) sites and four different modes of citrate bonding. The five lead sites all display hemidirected coordination geometries, that is, irregular distribution of neighboring oxygen atoms resulting in obvious gaps in the coordination spheres. Consequently, the lead coordination geometries exhibit proximal bonding to a number of oxygen donors, as well as distal interactions with nearest neighbors. The coordination numbers vary from 8 to 10, with '5+3', '5+4', '6+4' and '7+3' coordination modes where the first number refers to the proximal ligands and the second to the distal set. The four crystallographically distinct citrate groups include three with deprotonated carboxylate groups (C6H 5O7)3- and one with a single protonated carboxyl group (C6H6O7)2. The citrate ligands bridge 3, 5, 7 and 7 lead sites. Three of the citrate groups exhibit tridentate chelation coordination to a lead site through two carboxylate oxygen donors and the hydroxyl groups. One citrate group projects an uncoordinated -OH group and a pendant protonated carboxyl group into the interlamellar domain. This latter carboxyl group coordinates to a sodium cation, which exhibits five coordinate geometry defined by three aqua ligands and the carbonyl oxygen of the -CO2H groups in the basal plane and a citrate -OH donor in the apical position.
AB - The reaction of lead(II) nitrate with trisodium citrate Na 3(C6H5O7) in a 1:22.5 ratio at pH 4.8 provides crystals of {Na(H2O)3}[Pb5(H 2O)3(C6H5O7) 3(C6H6O7)]·9.5H2O (1). The structure of 1 is two-dimensional and exhibits five distinct Pb(II) sites and four different modes of citrate bonding. The five lead sites all display hemidirected coordination geometries, that is, irregular distribution of neighboring oxygen atoms resulting in obvious gaps in the coordination spheres. Consequently, the lead coordination geometries exhibit proximal bonding to a number of oxygen donors, as well as distal interactions with nearest neighbors. The coordination numbers vary from 8 to 10, with '5+3', '5+4', '6+4' and '7+3' coordination modes where the first number refers to the proximal ligands and the second to the distal set. The four crystallographically distinct citrate groups include three with deprotonated carboxylate groups (C6H 5O7)3- and one with a single protonated carboxyl group (C6H6O7)2. The citrate ligands bridge 3, 5, 7 and 7 lead sites. Three of the citrate groups exhibit tridentate chelation coordination to a lead site through two carboxylate oxygen donors and the hydroxyl groups. One citrate group projects an uncoordinated -OH group and a pendant protonated carboxyl group into the interlamellar domain. This latter carboxyl group coordinates to a sodium cation, which exhibits five coordinate geometry defined by three aqua ligands and the carbonyl oxygen of the -CO2H groups in the basal plane and a citrate -OH donor in the apical position.
KW - 2-D structure
KW - Citrate complexes
KW - Hydrothermal synthesis
KW - Pb(II) citrate structure
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U2 - 10.1016/j.ica.2011.08.054
DO - 10.1016/j.ica.2011.08.054
M3 - Article
AN - SCOPUS:80055007409
SN - 0020-1693
VL - 378
SP - 186
EP - 193
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 1
ER -