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Acta Cryst. (2007). E63, i185    [ doi:10.1107/S1600536807046193 ]

(NH4)[B3PO6(OH)3]·0.5H2O

W. Liu and J. Zhao

Abstract top

The title compound, ammonium catena-[monoboro-monodihydrogendiborate-monohydrogenphosphate] hemihydrate, was obtained under solvothermal conditions using glycol as the solvent. The crystal structure is constructed of one-dimensional infinite borophosphate chains, which are interconnected by ammonium ions and water molecules via a complex hydrogen-bond network to form a three-dimensional structure. The water molecules of crystallization are disordered over inversion centres, and their H atoms were not located.

Comment top

In the asymmetic unit of the title compound three crystallographically distinct boron atoms are present. Two of them are coordinated by three O-atoms to form nearly triagonal planar BO3 units, which are interconnected with one BO4 tetrahedron to form a 6-membered borate ring. The slightly distorted PO4 tetrahedron bridges the borate rings by sharing common vertices with the BO4 groups, leading to an infinite borophosphate chain (Fig.1) extending parallel to the a axis (Fig. 2). According to the latest review on the crystal chemistry of borophosphates (Ewald et al., 2007), the functional building units (FBU) are of the type 2Δ2□:<2Δ□>□, forming cB zweier-single chains.

A complex hydrogen-bond network (Fig. 2) consolidates the borophosphate chains into a three-dimensional structure. The OH groups of parallel chains interact with the intermediate NH4 cations via N—H···O hydrogen bonds and with terminal framework O atoms via O—H···O hydrogen bonds. The latter type of hydrogen bonds is also observed for the water molecules which are located on inversion centres.

In comparison to (NH4)[B3PO6(OH)3].0.5H2O, the structures of the related compounds Li[B3PO6(OH)3] (Hauf & Kniep, 1997) and (NH4)2[B3PO7(OH)2] (Hauf & Kniep, 1996) comprise similar borophosphate chains. However, Li[B3PO6(OH)3] comprises cB single-chains with a different periodicity in which the rings alternate with P2/4 units, and (NH4)2[B3PO7(OH)2] is made up of borophosphae chains where the PO3OH group is replaced by PO4, resulting in a different stacking of the chains and thus a different hydrogen bonding scheme.

Related literature top

The related compounds Li[B3PO6(OH)3] (Hauf & Kniep, 1997) and (NH4)2[B3PO7(OH)2] (Hauf & Kniep, 1996) comprise similar borophosphate chains, but show a different periodicity of the rings and a replacement of PO3OH by PO4 for the latter. A review on the crystal chemical classification of borophosphates was published recently (Ewald et al., 2007).

Experimental top

The title compound was prepared under solvothermal conditons. 1.04 g of (NH4)2B4O7 (SCR, >99.5%), 0.9 g NH4H2PO4 (SCR, >99.5%) and 5 ml of glycol (SCR, >99%) were placed in a Teflon-lined stainless steel autoclave and heated to 403 K for 5 d, followed by cooling to room temperature. Colourless rod-shaped crystals were obtained.

Refinement top

H atoms bonded to N and to framework-O atoms were located in a difference map and were refined with N—H = 0.90–0.94 and O—H = 0.79–0.82 Å. The O atom (Ow) of the water molecule is situated on an inversion centre. It was not possible to locate the corresponding H atoms, which points to a disorder due to the formation of various hydrogen bonds.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. View of a part of the infinite borophospate chains, with atom labels and 50% probability displacement ellipsoids. H atoms are displayed as spheres of arbitrary radius. [Symmetry code: (i) −x, −y, −z.]
[Figure 2] Fig. 2. The packing of the title compound, as viewed down the a axis, showing the hydrogen bonding scheme (dashed lines). Colour code: B yellow; P pink; O red; N blue; H white.
ammonium catena-[monoboro-mono-dihydrogendiborate-monohydrogenphosphate] hemihydrate top
Crystal data top
(NH4)[B3PO6(OH)3]·0.5H2OZ = 2
Mr = 237.48F000 = 240
Triclinic, P1Dx = 1.808 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 4.3665 (2) ÅCell parameters from 2516 reflections
b = 9.3680 (4) Åθ = 5–55º
c = 10.8267 (8) ŵ = 0.35 mm−1
α = 81.532 (9)ºT = 296 (2) K
β = 85.369 (9)ºRod, colourless
γ = 83.641 (8)º0.35 × 0.20 × 0.20 mm
V = 434.41 (4) Å3
Data collection top
Bruker SMART CCD
diffractometer		1996 independent reflections
Radiation source: fine-focus sealed tube1788 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.024
T = 296(2) Kθmax = 27.5º
ω scansθmin = 2.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −5→5
Tmin = 0.887, Tmax = 0.993k = −12→12
6501 measured reflectionsl = −14→13
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038All H-atom parameters refined
wR(F2) = 0.099  w = 1/[σ2(Fo2) + (0.0522P)2 + 0.3672P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
1996 reflectionsΔρmax = 0.41 e Å−3
157 parametersΔρmin = −0.48 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(NH4)[B3PO6(OH)3]·0.5H2Oγ = 83.641 (8)º
Mr = 237.48V = 434.41 (4) Å3
Triclinic, P1Z = 2
a = 4.3665 (2) ÅMo Kα
b = 9.3680 (4) ŵ = 0.35 mm−1
c = 10.8267 (8) ÅT = 296 (2) K
α = 81.532 (9)º0.35 × 0.20 × 0.20 mm
β = 85.369 (9)º
Data collection top
Bruker SMART CCD
diffractometer		1996 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		1788 reflections with I > 2σ(I)
Tmin = 0.887, Tmax = 0.993Rint = 0.024
6501 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038157 parameters
wR(F2) = 0.099All H-atom parameters refined
S = 1.06Δρmax = 0.41 e Å−3
1996 reflectionsΔρmin = −0.48 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.38071 (10)0.32784 (5)0.87493 (4)0.01661 (15)
B1−0.0816 (4)0.2710 (2)0.73583 (18)0.0161 (4)
B21.2037 (5)0.2978 (2)0.52774 (19)0.0215 (4)
B30.2114 (5)0.0630 (2)0.6493 (2)0.0223 (4)
O10.5814 (3)0.29141 (15)0.75672 (12)0.0209 (3)
O20.4119 (3)0.48339 (14)0.89765 (12)0.0231 (3)
O30.0456 (3)0.33077 (15)0.83671 (12)0.0229 (3)
O40.4403 (3)0.21875 (15)0.98843 (13)0.0263 (3)
O50.0212 (3)0.11655 (13)0.73935 (12)0.0213 (3)
O61.0000 (3)0.35280 (13)0.61382 (12)0.0202 (3)
O70.6934 (4)0.62278 (16)0.57923 (14)0.0333 (4)
O80.6974 (4)0.08201 (16)1.33756 (16)0.0391 (4)
O90.3100 (3)0.15115 (14)0.54252 (12)0.0255 (3)
N1−0.0636 (5)0.6964 (2)0.8055 (2)0.0339 (4)
Ow0.00000.00001.00000.0738 (10)
H1−0.195 (7)0.730 (3)0.866 (3)0.044 (8)*
H20.768 (8)0.539 (4)0.580 (3)0.060 (10)*
H30.073 (8)0.620 (4)0.842 (3)0.055 (9)*
H40.603 (8)0.104 (4)1.399 (3)0.055 (9)*
H50.026 (8)0.774 (4)0.762 (3)0.058 (9)*
H6−0.167 (9)0.665 (4)0.745 (4)0.070 (11)*
H70.4445 (1)0.4834 (1)0.9712 (1)0.048 (1)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0144 (2)0.0187 (2)0.0176 (2)−0.00196 (16)0.00014 (17)−0.00570 (17)
B10.0148 (8)0.0170 (9)0.0166 (9)−0.0014 (7)0.0017 (7)−0.0044 (7)
B20.0244 (10)0.0182 (9)0.0200 (10)0.0017 (8)0.0036 (8)−0.0024 (7)
B30.0268 (10)0.0168 (9)0.0218 (10)−0.0010 (8)0.0045 (8)−0.0021 (8)
O10.0134 (6)0.0309 (7)0.0207 (6)−0.0026 (5)0.0003 (5)−0.0117 (5)
O20.0285 (7)0.0187 (6)0.0242 (7)−0.0022 (5)−0.0054 (5)−0.0083 (5)
O30.0131 (6)0.0341 (7)0.0244 (7)−0.0020 (5)0.0004 (5)−0.0151 (6)
O40.0267 (7)0.0255 (7)0.0247 (7)−0.0015 (5)−0.0008 (6)0.0014 (5)
O50.0254 (7)0.0164 (6)0.0203 (6)−0.0004 (5)0.0068 (5)−0.0021 (5)
O60.0238 (6)0.0157 (6)0.0190 (6)0.0021 (5)0.0039 (5)−0.0012 (5)
O70.0507 (10)0.0181 (7)0.0247 (7)0.0054 (6)0.0147 (7)0.0020 (6)
O80.0572 (11)0.0165 (7)0.0360 (9)0.0054 (7)0.0233 (8)0.0003 (6)
O90.0356 (8)0.0159 (6)0.0216 (7)0.0024 (5)0.0110 (6)−0.0019 (5)
N10.0409 (11)0.0272 (9)0.0313 (10)−0.0006 (8)0.0034 (9)−0.0018 (8)
Ow0.104 (3)0.061 (2)0.0554 (19)−0.0294 (19)−0.0163 (19)0.0156 (15)
Geometric parameters (Å, °) top
P1—O41.4984 (14)B3—O91.386 (3)
P1—O21.5354 (13)O1—B1iii1.466 (2)
P1—O31.5487 (13)O2—H70.8202 (13)
P1—O11.5503 (13)O6—B1iii1.465 (2)
B1—O51.462 (2)O7—B2ii1.354 (3)
B1—O6i1.465 (2)O7—H20.81 (4)
B1—O1i1.466 (2)O8—B3iv1.363 (2)
B1—O31.470 (2)O8—H40.79 (4)
B2—O61.353 (2)O9—B2i1.391 (2)
B2—O7ii1.354 (3)N1—H10.90 (3)
B2—O9iii1.391 (2)N1—H30.94 (3)
B3—O51.347 (2)N1—H50.92 (4)
B3—O8iv1.363 (2)N1—H60.92 (4)
O4—P1—O2112.48 (8)O5—B3—O9121.62 (17)
O4—P1—O3111.15 (8)O8iv—B3—O9119.41 (17)
O2—P1—O3105.07 (8)B1iii—O1—P1129.61 (11)
O4—P1—O1113.18 (8)P1—O2—H7109.52 (12)
O2—P1—O1110.67 (8)B1—O3—P1131.73 (11)
O3—P1—O1103.64 (7)B3—O5—B1123.09 (15)
O5—B1—O6i111.34 (14)B2—O6—B1iii123.07 (14)
O5—B1—O1i109.82 (14)B2ii—O7—H2109 (2)
O6i—B1—O1i107.39 (14)B3iv—O8—H4111 (2)
O5—B1—O3110.95 (14)B3—O9—B2i118.75 (15)
O6i—B1—O3110.65 (14)H1—N1—H3109 (3)
O1i—B1—O3106.51 (13)H1—N1—H5108 (3)
O6—B2—O7ii123.54 (17)H3—N1—H5116 (3)
O6—B2—O9iii120.76 (17)H1—N1—H6112 (3)
O7ii—B2—O9iii115.63 (16)H3—N1—H6110 (3)
O5—B3—O8iv118.96 (18)H5—N1—H6103 (3)
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z+1; (iii) x+1, y, z; (iv) −x+1, −y, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O4v0.90 (3)1.93 (3)2.821 (3)172 (3)
N1—H3···O20.94 (3)1.92 (4)2.849 (3)169 (3)
N1—H5···O8vi0.92 (4)2.04 (4)2.942 (3)168 (3)
N1—H6···O7i0.92 (4)2.05 (4)2.946 (3)164 (3)
O7—H2···O60.81 (4)1.92 (4)2.7170 (19)166 (3)
O8—H4···O9vii0.79 (4)2.00 (4)2.789 (2)171 (3)
O2—H7···O2vi0.8201 (13)1.6804 (13)2.476 (2)163.02 (5)
Ow—···.O5..2.869 (3).
Ow—···.O4..2.944 (2).
Symmetry codes: (v) −x, −y+1, −z+2; (vi) −x+1, −y+1, −z+2; (i) x−1, y, z; (vii) x, y, z+1.
Selected geometric parameters (Å) top
P1—O41.4984 (14)B1—O31.470 (2)
P1—O21.5354 (13)B2—O61.353 (2)
P1—O31.5487 (13)B2—O7ii1.354 (3)
P1—O11.5503 (13)B2—O9iii1.391 (2)
B1—O51.462 (2)B3—O51.347 (2)
B1—O6i1.465 (2)B3—O8iv1.363 (2)
B1—O1i1.466 (2)B3—O91.386 (3)
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z+1; (iii) x+1, y, z; (iv) −x+1, −y, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O4v0.90 (3)1.93 (3)2.821 (3)172 (3)
N1—H3···O20.94 (3)1.92 (4)2.849 (3)169 (3)
N1—H5···O8vi0.92 (4)2.04 (4)2.942 (3)168 (3)
N1—H6···O7i0.92 (4)2.05 (4)2.946 (3)164 (3)
O7—H2···O60.81 (4)1.92 (4)2.7170 (19)166 (3)
O8—H4···O9vii0.79 (4)2.00 (4)2.789 (2)171 (3)
O2—H7···O2vi0.8201 (13)1.6804 (13)2.476 (2)163.02 (5)
Ow—···.O5..2.869 (3).
Ow—···.O4..2.944 (2).
Symmetry codes: (v) −x, −y+1, −z+2; (vi) −x+1, −y+1, −z+2; (i) x−1, y, z; (vii) x, y, z+1.
Acknowledgements top

This work was supported by the opening project of the State Key Laboratory of High Performance Ceramics and Superfine Microstructure (SKL200706SIC).

references
References top

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Ewald, B., Huang, Y. X. & Kniep, R. (2007). Z. Anorg. Allg. Chem. 633, 1517–1540.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Hauf, C. & Kniep, R. (1996). Z. Kristallogr. 211, 705–706.

Hauf, C. & Kniep, R. (1997). Z. Kristallogr. 212, 313–314.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.