Na5(NH4)Mn3[B9P6O33(OH)3]·1.5H2O

Lin, Z.-S.; Huang, Y.-X.; Prots, Y.; Zhao, J.-T.; Kniep, R.

doi:10.1107/S1600536808037884

inorganic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Pages i82-i83

doi:10.1107/S1600536808037884

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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 and Rüdiger Kniep ^b ^*

^aState Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, People's Republic of China, ^bMax-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Strasse 40, 01187 Dresden, Germany, ^cGraduate School of Chinese Academy of Sciences, Beijing, People's Republic of China, and ^dDepartment of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005, People's Republic of China
^*Correspondence e-mail: kniep@cpfs.mpg.de

(Received 6 November 2008; accepted 14 November 2008; online 22 November 2008)

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, P 6₃
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[F² > 2σ(F²)] = 0.040
wR(F²) = 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)

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)	–
Symmetry codes: (i) $[x-y+1, x, z+{\script{1\over 2}}]$ ; (ii) -x+y, -x, z; (iii) $[-x, -y, z+{\script{1\over 2}}]$ ; (iv) $[x-y, x, z+{\script{1\over 2}}]$ ; (v) x, y, z-1; (vi) x-1, y-1, z.

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. Borophosphate tubes in the crystal structure of Na₅(NH₄)Mn₃[B₉P₆O₃₃(OH)₃].1.5H₂O interconnected by MnO₆ coordination octahedra.
	Fig. 2. The overall framework of Na₅(NH₄)Mn₃[B₉P₆O₃₃(OH)₃].1.5H₂O viewed along [001], showing the resulting channel-system.

Pentasodium ammonium trimanganese(II) borophosphate sesquihydrate top

Crystal data top

Na₅(NH₄)Mn₃[B₉P₆O₃₃(OH)₃]·1.5(H₂O)	D_x = 2.635 Mg m⁻³
M_r = 2373.94	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6₃	Cell parameters from 7346 reflections
Hall symbol: P 6c	θ = 2.0–33.6°
a = 11.9331 (2) Å	µ = 1.79 mm⁻¹
c = 12.1290 (4) Å	T = 295 K
V = 1495.76 (6) Å³	Prism, colourless
Z = 1	0.08 × 0.04 × 0.04 mm
F(000) = 1164

Data collection top

Rigaku Mercury AFC7 CCD diffractometer	2891 independent reflections
Radiation source: fine-focus sealed tube	2784 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω–scans	θ_max = 30.0°, θ_min = 2.0°
Absorption correction: multi-scan (Blessing, 1995)	h = −16→12
T_min = 0.779, T_max = 0.931	k = −16→16
12243 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0419P)² + 2.5644P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
2891 reflections	Δρ_max = 0.66 e Å⁻³
191 parameters	Δρ_min = −0.81 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1374 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.43 (3)

Crystal data top

Na₅(NH₄)Mn₃[B₉P₆O₃₃(OH)₃]·1.5(H₂O)	Z = 1
M_r = 2373.94	Mo Kα radiation
Hexagonal, P6₃	µ = 1.79 mm⁻¹
a = 11.9331 (2) Å	T = 295 K
c = 12.1290 (4) Å	0.08 × 0.04 × 0.04 mm
V = 1495.76 (6) Å³

Data collection top

Rigaku Mercury AFC7 CCD diffractometer	2891 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	2784 reflections with I > 2σ(I)
T_min = 0.779, T_max = 0.931	R_int = 0.030
12243 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.099	Δρ_max = 0.66 e Å⁻³
S = 1.12	Δρ_min = −0.81 e Å⁻³
2891 reflections	Absolute structure: Flack (1983), 1374 Friedel pairs
191 parameters	Absolute structure parameter: 0.43 (3)
1 restraint

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mn2	0.50444 (6)	0.50073 (7)	0.04544 (11)	0.01330 (12)
P1	0.62139 (9)	0.81051 (9)	0.00965 (7)	0.0111 (2)
P2	0.37924 (9)	0.19394 (10)	0.08857 (7)	0.0120 (2)
B1	0.2928 (4)	0.2502 (4)	0.6961 (4)	0.0118 (7)
B2	0.2992 (4)	0.2504 (5)	0.8974 (4)	0.0151 (8)
B3	0.4938 (3)	0.4004 (3)	0.7921 (5)	0.0159 (6)
O1	0.5750 (3)	0.6785 (3)	0.9591 (3)	0.0169 (6)
O2	0.7011 (3)	0.9084 (3)	0.9177 (2)	0.0162 (6)
O3	0.7199 (3)	0.8385 (3)	0.1043 (2)	0.0150 (6)
O4	0.5126 (3)	0.8296 (3)	0.0515 (3)	0.0177 (5)
O5	0.2925 (3)	0.0953 (3)	0.1789 (2)	0.0152 (5)
O6	0.4181 (3)	0.3245 (3)	0.1360 (3)	0.0179 (6)
O7	0.2859 (3)	0.1639 (3)	0.9886 (3)	0.0182 (6)
O8	0.6857 (3)	0.5090 (3)	0.0545 (3)	0.0175 (6)
O9	0.5731 (3)	0.6364 (3)	0.1961 (3)	0.0147 (5)
O10	0.26579 (18)	0.17981 (18)	0.7974 (3)	0.0132 (3)
O11	0.4355 (3)	0.3637 (3)	0.8933 (3)	0.0157 (6)
O12	0.6273 (2)	0.4785 (2)	0.7907 (3)	0.0235 (5)
H1	0.648 (7)	0.498 (7)	0.723 (6)	0.07 (2)*
Na1	0.71486 (14)	0.73129 (14)	0.8014 (2)	0.0273 (3)
Na2	0.3333	0.6667	0.9533 (3)	0.0251 (6)
N	0.0000	0.0000	0.0452 (12)	0.0243 (10)
Na3	0.6667	0.3333	0.9477 (3)	0.0248 (6)
O13	0.0000	0.0000	0.8007 (19)	0.041 (2)*	0.50
O14	0.3333	0.6667	0.7692 (9)	0.090 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn2	0.0140 (2)	0.01171 (19)	0.0136 (2)	0.00596 (15)	−0.00045 (17)	0.00050 (14)
P1	0.0127 (4)	0.0114 (4)	0.0093 (4)	0.0061 (3)	0.0005 (3)	0.0014 (3)
P2	0.0128 (4)	0.0126 (4)	0.0103 (4)	0.0061 (4)	−0.0003 (4)	0.0009 (3)
B1	0.0110 (17)	0.0120 (17)	0.0113 (18)	0.0050 (14)	0.0000 (15)	0.0011 (15)
B2	0.018 (2)	0.0153 (18)	0.014 (2)	0.0096 (16)	0.0016 (16)	0.0004 (16)
B3	0.0135 (13)	0.0121 (12)	0.0206 (17)	0.0054 (10)	0.0010 (19)	0.0038 (19)
O1	0.0212 (13)	0.0161 (12)	0.0113 (14)	0.0079 (11)	0.0016 (11)	0.0013 (10)
O2	0.0210 (14)	0.0136 (12)	0.0125 (12)	0.0076 (11)	0.0022 (11)	0.0018 (10)
O3	0.0168 (13)	0.0148 (12)	0.0128 (14)	0.0075 (10)	−0.0020 (11)	0.0041 (10)
O4	0.0158 (12)	0.0161 (12)	0.0214 (14)	0.0081 (11)	0.0002 (11)	−0.0001 (11)
O5	0.0188 (13)	0.0134 (12)	0.0129 (12)	0.0078 (10)	0.0019 (11)	0.0022 (10)
O6	0.0211 (13)	0.0129 (12)	0.0184 (15)	0.0074 (11)	0.0021 (12)	0.0014 (11)
O7	0.0179 (14)	0.0180 (13)	0.0150 (15)	0.0061 (11)	−0.0019 (12)	0.0034 (11)
O8	0.0124 (11)	0.0162 (12)	0.0229 (14)	0.0064 (10)	0.0007 (11)	−0.0036 (11)
O9	0.0159 (12)	0.0160 (12)	0.0086 (12)	0.0053 (10)	0.0001 (11)	−0.0001 (11)
O10	0.0151 (8)	0.0132 (8)	0.0117 (8)	0.0074 (7)	−0.0023 (13)	−0.0018 (13)
O11	0.0146 (12)	0.0156 (12)	0.0142 (14)	0.0055 (10)	−0.0013 (11)	−0.0007 (11)
O12	0.0143 (10)	0.0297 (12)	0.0193 (13)	0.0055 (9)	−0.0020 (14)	0.0008 (15)
Na1	0.0289 (7)	0.0381 (7)	0.0212 (7)	0.0215 (6)	−0.0001 (10)	−0.0012 (11)
Na2	0.0238 (8)	0.0238 (8)	0.0278 (15)	0.0119 (4)	0.000	0.000
N	0.0161 (12)	0.0161 (12)	0.041 (3)	0.0081 (6)	0.000	0.000
Na3	0.0241 (8)	0.0241 (8)	0.0261 (14)	0.0121 (4)	0.000	0.000

Geometric parameters (Å, º) top

Mn2—O8	2.118 (3)	O5—B1^ix	1.475 (5)
Mn2—O1ⁱ	2.126 (3)	O5—Na1^iv	2.584 (3)
Mn2—O6	2.127 (3)	O6—Na1^iv	2.434 (4)
Mn2—O4ⁱⁱ	2.162 (3)	O7—P2^vii	1.562 (3)
Mn2—O9	2.303 (3)	O8—P2^x	1.505 (3)
Mn2—O11ⁱ	2.326 (4)	O8—Na3ⁱ	2.376 (3)
Mn2—Na3ⁱ	3.6069 (13)	O9—B3^iv	1.354 (6)
Mn2—Na2ⁱ	3.6582 (12)	O9—B1^iv	1.493 (5)
P1—O1ⁱ	1.513 (3)	O10—Na1ⁱⁱⁱ	2.360 (2)
P1—O4	1.514 (3)	O11—Mn2^vii	2.326 (4)
P1—O2ⁱ	1.550 (3)	O12—Na1	2.656 (3)
P1—O3	1.555 (3)	O12—Na3	2.768 (4)
P1—Na2ⁱ	3.0544 (12)	O12—H1	0.86 (8)
P1—Na1ⁱ	3.094 (3)	Na1—O10^x	2.360 (2)
P2—O6	1.500 (3)	Na1—O6^vi	2.434 (4)
P2—O8ⁱⁱⁱ	1.505 (3)	Na1—O5^vi	2.584 (3)
P2—O5	1.562 (3)	Na1—P1^vii	3.094 (3)
P2—O7ⁱ	1.562 (3)	Na1—P2^vi	3.118 (3)
P2—Na1^iv	3.118 (3)	Na1—H1	2.66 (8)
P2—Na3ⁱ	3.4270 (19)	Na2—O14	2.232 (11)
B1—O10	1.430 (5)	Na2—O4^xi	2.370 (3)
B1—O5^v	1.475 (5)	Na2—O4^vii	2.370 (3)
B1—O3^vi	1.491 (5)	Na2—O4^xii	2.370 (3)
B1—O9^vi	1.493 (5)	Na2—O1^viii	2.817 (3)
B2—O10	1.416 (6)	Na2—O1ⁱⁱ	2.817 (3)
B2—O7	1.466 (6)	Na2—P1^xi	3.0544 (12)
B2—O2ⁱⁱ	1.494 (5)	Na2—P1^vii	3.0544 (12)
B2—O11	1.509 (5)	Na2—P1^xii	3.0544 (12)
B3—O9^vi	1.354 (6)	Na2—Mn2^xi	3.6582 (12)
B3—O11	1.371 (6)	Na2—Mn2^xii	3.6582 (12)
B3—O12	1.386 (4)	Na3—O8^xiii	2.376 (3)
O1—P1^vii	1.513 (3)	Na3—O8^xiv	2.376 (3)
O1—Mn2^vii	2.126 (3)	Na3—O8^vii	2.376 (3)
O1—Na1	2.407 (4)	Na3—O12ⁱⁱⁱ	2.768 (4)
O1—Na2	2.817 (3)	Na3—O12^x	2.768 (4)
O2—B2^viii	1.494 (5)	Na3—P2^xiv	3.4270 (19)
O2—P1^vii	1.550 (3)	Na3—P2^xiii	3.4270 (19)
O2—Na1	2.614 (4)	Na3—P2^vii	3.4270 (19)
O3—B1^iv	1.491 (5)	Na3—Mn2^xiii	3.6069 (13)
O4—Mn2^viii	2.162 (3)	Na3—Mn2^xiv	3.6069 (13)
O4—Na2ⁱ	2.370 (3)	Na3—Mn2^vii	3.6069 (13)

O8—Mn2—O1ⁱ	95.34 (12)	B3^iv—O9—Mn2	120.6 (2)
O8—Mn2—O6	89.88 (12)	B1^iv—O9—Mn2	118.7 (2)
O1ⁱ—Mn2—O6	174.49 (15)	B2—O10—B1	118.2 (2)
O8—Mn2—O4ⁱⁱ	174.93 (18)	B2—O10—Na1ⁱⁱⁱ	115.7 (3)
O1ⁱ—Mn2—O4ⁱⁱ	88.22 (11)	B1—O10—Na1ⁱⁱⁱ	119.3 (3)
O6—Mn2—O4ⁱⁱ	86.46 (12)	B3—O11—B2	117.6 (3)
O8—Mn2—O9	86.00 (12)	B3—O11—Mn2^vii	122.7 (2)
O1ⁱ—Mn2—O9	82.24 (11)	B2—O11—Mn2^vii	116.6 (3)
O6—Mn2—O9	96.39 (14)	B3—O12—Na1	115.5 (2)
O4ⁱⁱ—Mn2—O9	90.91 (12)	B3—O12—Na3	94.0 (3)
O8—Mn2—O11ⁱ	93.89 (12)	Na1—O12—Na3	125.72 (15)
O1ⁱ—Mn2—O11ⁱ	97.79 (14)	B3—O12—H1	106 (5)
O6—Mn2—O11ⁱ	83.59 (12)	Na1—O12—H1	81 (5)
O4ⁱⁱ—Mn2—O11ⁱ	89.20 (12)	Na3—O12—H1	135 (5)
O9—Mn2—O11ⁱ	179.89 (14)	O10^x—Na1—O1	125.56 (16)
O1ⁱ—P1—O4	113.43 (17)	O10^x—Na1—O6^vi	120.09 (16)
O1ⁱ—P1—O2ⁱ	105.09 (17)	O1—Na1—O6^vi	108.15 (9)
O4—P1—O2ⁱ	112.12 (18)	O10^x—Na1—O5^vi	114.43 (12)
O1ⁱ—P1—O3	111.51 (18)	O1—Na1—O5^vi	111.70 (11)
O4—P1—O3	109.4 (2)	O6^vi—Na1—O5^vi	57.80 (11)
O2ⁱ—P1—O3	104.87 (18)	O10^x—Na1—O2	117.98 (12)
O6—P2—O8ⁱⁱⁱ	114.34 (17)	O1—Na1—O2	57.76 (11)
O6—P2—O5	104.92 (18)	O6^vi—Na1—O2	111.69 (11)
O8ⁱⁱⁱ—P2—O5	112.87 (17)	O5^vi—Na1—O2	67.76 (7)
O6—P2—O7ⁱ	110.57 (19)	O10^x—Na1—O12	80.64 (8)
O8ⁱⁱⁱ—P2—O7ⁱ	109.5 (2)	O1—Na1—O12	85.06 (12)
O5—P2—O7ⁱ	104.11 (17)	O6^vi—Na1—O12	79.46 (12)
O10—B1—O5^v	109.7 (3)	O5^vi—Na1—O12	136.89 (14)
O10—B1—O3^vi	108.1 (3)	O2—Na1—O12	142.78 (14)
O5^v—B1—O3^vi	108.4 (3)	O14—Na2—O4^xi	120.17 (10)
O10—B1—O9^vi	110.9 (3)	O14—Na2—O4^vii	120.17 (10)
O5^v—B1—O9^vi	110.6 (3)	O4^xi—Na2—O4^vii	96.95 (13)
O3^vi—B1—O9^vi	109.0 (3)	O14—Na2—O4^xii	120.17 (10)
O10—B2—O7	109.1 (4)	O4^xi—Na2—O4^xii	96.95 (13)
O10—B2—O2ⁱⁱ	109.2 (3)	O4^vii—Na2—O4^xii	96.95 (13)
O7—B2—O2ⁱⁱ	107.9 (3)	O14—Na2—O1^viii	91.45 (9)
O10—B2—O11	111.2 (3)	O4^xi—Na2—O1^viii	57.64 (10)
O7—B2—O11	110.1 (4)	O4^vii—Na2—O1^viii	69.66 (9)
O2ⁱⁱ—B2—O11	109.2 (4)	O4^xii—Na2—O1^viii	147.64 (16)
O9^vi—B3—O11	123.0 (3)	O14—Na2—O1ⁱⁱ	91.45 (9)
O9^vi—B3—O12	120.0 (5)	O4^xi—Na2—O1ⁱⁱ	69.66 (10)
O11—B3—O12	117.0 (5)	O4^vii—Na2—O1ⁱⁱ	147.64 (16)
P1^vii—O1—Mn2^vii	126.55 (19)	O4^xii—Na2—O1ⁱⁱ	57.64 (10)
P1^vii—O1—Na1	101.82 (16)	O1^viii—Na2—O1ⁱⁱ	119.937 (9)
Mn2^vii—O1—Na1	121.96 (15)	O14—Na2—O1	91.45 (9)
P1^vii—O1—Na2	83.98 (13)	O4^xi—Na2—O1	147.64 (16)
Mn2^vii—O1—Na2	94.45 (11)	O4^vii—Na2—O1	57.64 (10)
Na1—O1—Na2	123.48 (15)	O4^xii—Na2—O1	69.66 (9)
B2^viii—O2—P1^vii	135.3 (3)	O1^viii—Na2—O1	119.937 (9)
B2^viii—O2—Na1	132.2 (3)	O1ⁱⁱ—Na2—O1	119.937 (8)
P1^vii—O2—Na1	92.40 (14)	O8^xiii—Na3—O8^xiv	93.15 (13)
B1^iv—O3—P1	127.0 (3)	O8^xiii—Na3—O8^vii	93.15 (13)
P1—O4—Mn2^viii	127.87 (17)	O8^xiv—Na3—O8^vii	93.15 (13)
P1—O4—Na2ⁱ	101.43 (16)	O8^xiii—Na3—O12ⁱⁱⁱ	120.52 (9)
Mn2^viii—O4—Na2ⁱ	107.56 (13)	O8^xiv—Na3—O12ⁱⁱⁱ	78.10 (11)
B1^ix—O5—P2	131.9 (3)	O8^vii—Na3—O12ⁱⁱⁱ	145.34 (9)
B1^ix—O5—Na1^iv	133.0 (2)	O8^xiii—Na3—O12^x	78.10 (10)
P2—O5—Na1^iv	94.29 (14)	O8^xiv—Na3—O12^x	145.34 (9)
P2—O6—Mn2	125.0 (2)	O8^vii—Na3—O12^x	120.52 (9)
P2—O6—Na1^iv	102.20 (17)	O12ⁱⁱⁱ—Na3—O12^x	77.89 (13)
Mn2—O6—Na1^iv	128.53 (15)	O8^xiii—Na3—O12	145.34 (9)
B2—O7—P2^vii	127.6 (3)	O8^xiv—Na3—O12	120.52 (9)
P2^x—O8—Mn2	128.59 (17)	O8^vii—Na3—O12	78.10 (10)
P2^x—O8—Na3ⁱ	122.40 (16)	O12ⁱⁱⁱ—Na3—O12	77.89 (13)
Mn2—O8—Na3ⁱ	106.59 (13)	O12^x—Na3—O12	77.89 (13)
B3^iv—O9—B1^iv	119.0 (3)

Symmetry codes: (i) x, y, z−1; (ii) −x+y, −x+1, z; (iii) −y+1, x−y, z; (iv) −x+1, −y+1, z−1/2; (v) x−y, x, z+1/2; (vi) −x+1, −y+1, z+1/2; (vii) x, y, z+1; (viii) −y+1, x−y+1, z; (ix) y, −x+y, z−1/2; (x) −x+y+1, −x+1, z; (xi) −y+1, x−y+1, z+1; (xii) −x+y, −x+1, z+1; (xiii) −x+y+1, −x+1, z+1; (xiv) −y+1, x−y, z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H1···O4^xv	0.86 (7)	2.11 (7)	2.959 (3)	167 (3)
O13···O10^xvi			2.8035 (11)
O13···N^xvii			3.077 (16)
O14···O8^v			3.284 (5)
O14···O6^v			3.333 (3)
N···O13ⁱ			2.988 (16)
N···O3^xviii			2.991 (3)
N···O7ⁱ			3.047 (3)

Symmetry codes: (i) x, y, z−1; (v) x−y, x, z+1/2; (xv) x−y+1, x, z+1/2; (xvi) −x+y, −x, z; (xvii) −x, −y, z+1/2; (xviii) x−1, y−1, z.

Experimental details

Crystal data
Chemical formula	Na₅(NH₄)Mn₃[B₉P₆O₃₃(OH)₃]·1.5(H₂O)
M_r	2373.94
Crystal system, space group	Hexagonal, P6₃
Temperature (K)	295
a, c (Å)	11.9331 (2), 12.1290 (4)
V (Å³)	1495.76 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.79
Crystal size (mm)	0.08 × 0.04 × 0.04

Data collection
Diffractometer	Rigaku Mercury AFC7 CCD diffractometer
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.779, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	12243, 2891, 2784
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.099, 1.12
No. of reflections	2891
No. of parameters	191
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.81
Absolute structure	Flack (1983), 1374 Friedel pairs
Absolute structure parameter	0.43 (3)

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2004).

Hydrogen-bond geometry (Å, º) top

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)	.

Symmetry codes: (i) x−y+1, x, z+1/2; (ii) −x+y, −x, z; (iii) −x, −y, z+1/2; (iv) x−y, x, z+1/2; (v) x, y, z−1; (vi) x−1, y−1, z.

Acknowledgements

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).

References

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