Na5(NH4)Mn3[B9P6O33(OH)3]·1.5H2O

Zhi-Sheng Lin; Ya-Xi Huang; Yurii Prots; Jing-Tai Zhao; Rüdiger Kniep

doi:10.1107/S1600536808037884

. 2008 Nov 22;64(Pt 12):i82–i83. doi: 10.1107/S1600536808037884

Na₅(NH₄)Mn₃[B₉P₆O₃₃(OH)₃]·1.5H₂O

Zhi-Sheng Lin ^a,^b,^c, Ya-Xi Huang ^b,^d, Yurii Prots ^b, Jing-Tai Zhao ^a, Rüdiger Kniep ^b,^*

PMCID: PMC2959984 PMID: 21581107

Abstract

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.

Related literature

Reviews on the preparation, crystal chemistry and applications of borophosphates are given in Kniep et al. (1998 ▶) and Ewald et al. (2007 ▶). For isostructural compounds, see Yang, Li et al. (2006 ▶) for Na₂Mn[B₃P₂O₁₁(OH)]·0.67H₂O; Yang, Yu et al. (2006 ▶) for Na₅(H₃O)Mn₃[B₉P₆O₃₃(OH)₃]·2H₂O; Liu et al. (2006 ▶) for Na₆Cu₃[B₉P₆O₃₃(OH)₃]·2H₂O.

Experimental

Crystal data

Na₅(NH₄)Mn₃[B₉P₆O₃₃(OH)₃]·1.5(H₂O)
M _r = 2373.94
Hexagonal,
a = 11.9331 (2) Å
c = 12.1290 (4) Å
V = 1495.76 (6) Å³
Z = 1
Mo Kα radiation
μ = 1.79 mm⁻¹
T = 295 K
0.08 × 0.04 × 0.04 mm

Data collection

Rigaku Mercury AFC7 CCD diffractometer
Absorption correction: multi-scan (Blessing, 1995 ▶) T _min = 0.779, T _max = 0.931
12243 measured reflections
2891 independent reflections
2784 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.099
S = 1.12
2891 reflections
191 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.81 e Å⁻³
Absolute structure: Flack (1983 ▶), 1374 Friedel pairs
Flack parameter: 0.43 (3)

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2004 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, ZSL_079. DOI: 10.1107/S1600536808037884/wm2204sup1.cif

e-64-00i82-sup1.cif^{(21.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037884/wm2204Isup2.hkl

e-64-00i82-Isup2.hkl^{(586.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O12—H1⋯O4ⁱ	0.86 (7)	2.11 (7)	2.959 (3)	167 (3)
O13⋯O10ⁱⁱ	–	–	2.8035 (11)	–
O13⋯Nⁱⁱⁱ	–	–	3.077 (16)	–
O14⋯O8^iv	–	–	3.284 (5)	–
O14⋯O6^iv	–	–	3.333 (3)	–
N⋯O13^v	–	–	2.988 (16)	–
N⋯O3^vi	–	–	2.991 (3)	–
N⋯O7^v	–	–	3.047 (3)	–

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

This project was supported by the doctoral joint project between the Chinese Academy of Sciences and the Max-Planck Society, the State ‘973’ project (grant No. 2007CB936704) and the Major Basic Research Programs of Shanghai (grant No. 07DJ14001).

supplementary crystallographic information

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). Up to now, only two manganese compounds containing borophosphate tubes, viz. Na₂Mn[B₃P₂O₁₁(OH)]^.0.67H₂O (Yang et al., 2006a) and Na₅(H₃O)Mn₃[B₉P₆O₃₃(OH)₃]^.2H₂O (Yang et al., 2006b) are listed in the literature. Here, we report on an ammonium substituted sodium manganese borophosphate, Na₅(NH₄)Mn₃[B₉P₆O₃₃(OH)₃]^.1.5H₂O.

The crystal structure of the title compound comprises tube-like borophosphate anions, _∞¹{[B₃P₂O₁₁(OH)]^4-}, which are built from 12-membered rings of alternating BO₄ and PO₄ tetrahedra, further interlinked by sharing common O-corners of neighbouring rings, and loop-branched by BO₂(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 NH₄⁺ 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. 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 2.8 to 3.35 Å between the ammonium N atom, water O atoms and framework O atoms indicate further hydrogen bonding interactions, but the corresponding H atoms were not located.

Experimental

Transparent, colourless single crystals of the title compound were synthesized hydrothermally from a mixture of H₃BO₃ (32.2 mmol), Mn(CH₃COO)₂^.4H₂O (3 mmol), (NH₄)₂HPO₄ (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 NH₄⁺ content was determined by elemental analysis and confirmed by IR spectroscopy.