Two New Tetramethylammonium Zinc Phosphates: N(CH3)4·Zn(HPO4)(H2PO4), an Open Framework Phase Built up from a Low-Density 12-Ring Topology, and N(CH3)4·Zn(H2PO4)3, a Molecular Cluster

Transformations of low-dimensional zinc phosphates to complex open-framework structures. Part 1: zero-dimensional to one-, two- and three-dimensional structures

“…A framework with the formula Zn(PO 4 ) 3 would result in a net negative charge of 27, which is balanced by the protonation of the amine and some of the oxygen atoms. Bond valence sum values 11 clearly indicate that P(1)-O (7), P(2)-O (10), P(3)-O (11) and P(3)-O (12) with distances of 1.596(3), 1.580(4), 1.539(4) and 1.563(3) A ˚are P-OH linkages in agreement with the proton positions found in the difference Fourier maps.…”

“…2552( 1) 2064( 1) 1789( 1) 22(1) P( 3) 1665( 1) 13( 1) 2370( 1) 23( 1) O( 1) 410( 2) 1573( 2) 1471( 2) 26( 1) O( 2) 1517( 3) 314( 2) 360( 2) 34( 1) O( 3) 1133( 3) 2401( 2) 1891( 2) 26( 1) O( 4) 2762( 2) 2259( 2) 863( 2) 27( 1) O( 5) 2975( 2) 2853( 2) 2339( 2) 27( 1) O( 6) 1486( 2) 2468( 2) 3166( 2) 23( 1) O( 7) 2307( 3) 755( 2) 2427( 2) 26( 1) O( 8) 2527( 3) 2105( 2) 2567( 2) 31( 1) O( 9) 21640( 3) 1667( 2) 1562( 2) 34( 1) O (10) 240...…”

“…, 5 and to [N(CH 3 ) 4 ]Zn(H 2 PO 4 ) 3 , reported earlier. 10 The Zn atoms in II are tetrahedrally coordinated with respect to the oxygen atoms with average Zn-O bond distances of 1. 4).…”

“…10b). The amine molecule is connected to the Zn center via the Zn-N bond and 10 with two PO 2 (OH) 2 groups would be more reactive than I and II, and would possibly result in many interesting structures. Among the higher dimensional phosphates obtained, IV and VI have three-dimensional structures, while III and VII have layered structures.…”

“…Both the monomers, I and II, along with [N(CH 3 ) 4 ][Zn(H 2 PO 4 ) 3 ] 10have the same configuration for the 4-membered ring, made with Zn and PO 2 (OH) 2 units, but the terminal moieties create the subtle differences between the two. While in the zinc phosphate, [N(CH 3 ) 4 ][Zn(H 2 PO 4 ) 3 ],10 the terminal hanging units from the Zn center are made up of PO 2 (OH) 2 units, in I they are PO 3 (OH) and PO 2 (OH) 2 units, and in II it is PO 3 (OH) units only. It has been postulated that the facile formation of higher dimensional structures from a lower dimensional one occurs via the deprotonation of the terminal -OH groups.…”