Na5(NH4)Mn3[B9P6O33(OH)3]·1.5H2O

The overall hexagonal framework of the title compound, pentasodium ammonium trimanganese(II) borophosphate sesquihydrate, consists of tube-like borophosphate anions, ∞ 1{[B3P2O11(OH)]4−}, made up of corner-sharing PO4 and BO4 tetrahedra and BO2(OH) triangles, forming ten-membered ring windows. The tubes are interconnected via distorted MnO6 octahedra, establishing a three-dimensional open-framework structure with two different types of ring-channels (12- and six-membered) that run along [001]. The 12-membered ring channels are occupied by NH4 + ions and water molecules. The ten-membered ring windows in the walls of the tubes are occupied by Na+ ions. The remaining Na+ ions and the water molecules, one of which is half-occupied, reside within the six-membered ring channels. The structural setup is consolidated by an O—H⋯O hydrogen bond between the OH group and an opposite O atom of the framework. Donor–acceptor distances ranging from 2.80 to 3.35 Å between the ammonium N atom, water O atoms and framework O atoms indicate further hydrogen-bonding interactions.

The overall hexagonal framework of the title compound, pentasodium ammonium trimanganese(II) borophosphate sesquihydrate, consists of tube-like borophosphate anions, 1 1 {[B 3 P 2 O 11 (OH)] 4À }, made up of corner-sharing PO 4 and BO 4 tetrahedra and BO 2 (OH) triangles, forming ten-membered ring windows. The tubes are interconnected via distorted MnO 6 octahedra, establishing a three-dimensional openframework structure with two different types of ring-channels (12-and six-membered) that run along [001]. The 12membered ring channels are occupied by NH 4 + ions and water molecules. The ten-membered ring windows in the walls of the tubes are occupied by Na + ions. The remaining Na + ions and the water molecules, one of which is half-occupied, reside within the six-membered ring channels. The structural setup is consolidated by an O-HÁ Á ÁO hydrogen bond between the OH group and an opposite O atom of the framework. Donoracceptor distances ranging from 2.80 to 3.35 Å between the ammonium N atom, water O atoms and framework O atoms indicate further hydrogen-bonding interactions.

Comment
In the past several years, borophosphates have attracted extensive attention due to their rich structural chemistry and potential applications as catalysts (Kniep et al., 1998;Ewald et al., 2007). Although a large variety of borophosphate anions has been reported, tube-like borophosphate anions are particularly rare (Liu et al., 2006;Yang et al., 2006a;Yang et al., 2006b of neighbouring rings, and loop-branched by BO 2 (OH) triangles resulting in 10-membered ring windows on the walls of the tubes (Fig. 1). The manganese atoms are in a distorted octahedral coordination, surrounded by four oxygen atoms from phosphate tetrahedra (O1, O2, O5, O6) and two oxygen atoms from borate tetrahedra (O10, O11). The Mn-coordination octahedra interconnect the neighboring borophosphate tubes to form a three-dimensional framework with two different types of channels (Fig. 2), namely 6-and 12-membered ring channels. The 12-membered ring channels are occupied by NH 4 + ions and water molecules; the 10-membered ring windows in the walls of the tubes are occupied by Na + ions. The remaining Na + ions and water molecules reside in the 6-membered ring channels. 4H 2 O (3 mmol), (NH 4 ) 2 HPO 4 (6.4 mmol), NaF (5 mmol), and water (133.4 mmol). The educt mixture was transferred into a Teflon-lined stainless steel autoclave (internal volume 25 ml) and kept at 513 K for five days.
The autoclave was cooled down to ambient temperature by removing out of the oven. The reaction products were washed with hot distilled water (333 K) until the boric acid was completely removed. Finally, the solids were dried in air at 333 K.
Hexagonal prismatic crystals were selected for single-crystal diffraction. The NH 4 + content was determined by elemental analysis and confirmed by IR spectroscopy.

Refinement
The measured crystal was racemically twinned with an approximate twin fraction of 2:3. The hydrogen position bonded to O12 was found in a difference Fourier map and was refined freely. The hydrogen positions of the ammonium N atom and of the uncoordinated water atoms at O13 and O14 were not localized. The occupancy of O13 was refined to 0.50 (2). In the last refinement cycle this value was fixed to 0.50. Fig. 1