Hydrothermal Syntheses and Single-Crystal Structures of Some Novel Guanidinium−Zinc−Phosphates

Abstract

The mild-condition hydrothermal syntheses and single-crystal structures of three new guanidinium zinc phosphates are reported. CN3H6·Zn2(HPO4)2H2PO4 and (CN3H6)2·Zn(HPO4)2 are built up from three-dimensional Zn/P/O frameworks encapsulating guanidinium cations in 12-ring channel systems. The latter material has the lowest nodal-framework-atom density per unit volume of any open-framework phase characterized so far. (CN3H6)6·Zn2(OH)(PO4)3·H2O is a one-dimensional phase with respect to Zn/P/O connectivity and has a unique triply bridged tetrahedral chain connectivity for simple phosphates. Crystal data: CN3H6·Zn2(HPO4)2H2PO4, M r = 478.78, monoclinic, space group P21 (No. 4), a = 5.1318(4) Å, b = 7.8411(7) Å, c = 16.510(1) Å, β = 90.110(7)°, V = 664.36(8) Å3, Z = 2, R = 2.43%, R w = 2.67% [2608 observed reflections with I > 3σ(I)]. (CN3H6)2·Zn(HPO4)2, M r = 377.50, orthorhombic, space group Pna21 (No. 33), a = 10.447(2) Å, b = 12.349(2) Å, c = 10.225(2) Å, V = 1319.2(5) Å3, Z = 4, R = 3.26%, R w = 3.32% [2252 observed reflections with I > 3σ(I)]. (CN3H6)6·Zn2(OH)(PO4)3·H2O, M r = 811.17, trigonal, space group R3̄ (No. 148), a = 20.016(7) Å, c = 13.955(6) Å, V = 4842(4) Å3, Z = 6, R = 5.31%, R w = 5.52% [630 observed reflections with I > 3σ(I)].

Open-Framework Inorganic Materials

“…This is not usually observed in aluminosilicates, nor in AlPOs unless the coordination of aluminum is increased to five or six. More recently, Harrison and Phillips [133,134] have described the synthesis of a series of zincophosphates prepared with the nitrogen-rich guanidinium cation; a molecule with trigonal planar geometry. Despite the small size of this organic species, the open frameworks of these compounds exhibits large pores bounded by 12-ring [134] or 18-ring channels.…”

“…More recently, Harrison and Phillips [133,134] have described the synthesis of a series of zincophosphates prepared with the nitrogen-rich guanidinium cation; a molecule with trigonal planar geometry. Despite the small size of this organic species, the open frameworks of these compounds exhibits large pores bounded by 12-ring [134] or 18-ring channels. [133] Although the Zn/P ratio is greater than 1, there is no Zn-O-Zn bonding in this structure; only terminal ZnÀOH 2 bonds occur, as was also observed in the zincophosphate templated by the DABCO molecule.…”

Hydrothermal Synthesis and Crystal Structure of Zn4(PO4)2(HPO4)2·0.5(C10H28N4)·2H2O, a New Layered Zinc Phosphate with 12-Ring Cavities

“…;(eq) is de"ned as one-third of the trace of the orthogonalized ; GH tensor. (10) 1.956(4) Zn(3)}O (11) 1.992(4) Zn(3)}O (8) 2.008(4) Zn(3)}OW1 2.022(5) Zn (3)}OW2 2.439(7) Zn(4)}O (12) 1.921 (5) Zn (4)}O (13) 1.948(4) Zn(4)}O (14) 1.931(4) Zn(4)}O (11) 2.011(4) P(1)}O (4) 1.512(5) P(1)}O (6) 1.514(5) P(1)}O (3) 1.533(5) P(1)}O (5) 1.583(5) P(2)}O (9) 1.534(5) P(2)}O(13)C3 1.550(5) P(2)}O (7) 1.538 (5) P (2)}O (10) 1.552(5) P(3)}O (2)C4 1.500(5) P(3)}O(12)C4 1.513(5) P(3)}O (8)C4 1.554(5) P(3)}O (11) 1.558(5) P(4)}O (16) 1.510 (5) P (4)}O (1)C5 1.521(4) P(4)}O (14) 1.532(5) P(4)}O (15) 1.589(5) O(10)}Zn(3)}O (8) 107.18 (19) O (10)}Zn (3)}O (11) 136.5(2) O(11)}Zn(3)}O (8) 109.67 (18) OW1}Zn (3 (8)}Zn (3) 127.8(3) Zn (3)}O (11)}Zn (4) 118.7(2) P(3)C1}O (8)}Zn (2) 112.4(2) P (3)}O (11)}Zn (3) 111.6(2) Zn(3)}O (8)}Zn (2) 113.7(2) P (3)}O (11)}Zn (4) 128.2(3) N(1)}C …”

Synthesis of Cobalt-Zinc Phosphates Templated by Polyamines

“…The feasibility of zinc and cobalt to tetrahedrally coordinate their phosphates makes them to be an important group of transition metal phosphates (Mandal & Natarajan, 2002;Harrison et al, 1991;Neeraj et al, 1999;Fan et al, 2000). Usually, these materials have been synthesized by employing hydrothermal or solvothermal conditions in the presence of organic amines as the structure-directing agents (SDA).…”