Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046193/wm2143sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046193/wm2143Isup2.hkl |
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.
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.
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.
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).
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).
(NH4)[B3PO6(OH)3]·0.5H2O | Z = 2 |
Mr = 237.48 | F(000) = 240 |
Triclinic, P1 | Dx = 1.808 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.3665 (2) Å | Cell parameters from 2516 reflections |
b = 9.3680 (4) Å | θ = 5–55° |
c = 10.8267 (8) Å | µ = 0.35 mm−1 |
α = 81.532 (9)° | T = 296 K |
β = 85.369 (9)° | Rod, colourless |
γ = 83.641 (8)° | 0.35 × 0.20 × 0.20 mm |
V = 434.41 (4) Å3 |
Bruker SMART CCD diffractometer | 1996 independent reflections |
Radiation source: fine-focus sealed tube | 1788 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scans | θmax = 27.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −5→5 |
Tmin = 0.887, Tmax = 0.993 | k = −12→12 |
6501 measured reflections | l = −14→13 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | All H-atom parameters refined |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0522P)2 + 0.3672P] where P = (Fo2 + 2Fc2)/3 |
1996 reflections | (Δ/σ)max = 0.001 |
157 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
(NH4)[B3PO6(OH)3]·0.5H2O | γ = 83.641 (8)° |
Mr = 237.48 | V = 434.41 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.3665 (2) Å | Mo Kα radiation |
b = 9.3680 (4) Å | µ = 0.35 mm−1 |
c = 10.8267 (8) Å | T = 296 K |
α = 81.532 (9)° | 0.35 × 0.20 × 0.20 mm |
β = 85.369 (9)° |
Bruker SMART CCD diffractometer | 1996 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1788 reflections with I > 2σ(I) |
Tmin = 0.887, Tmax = 0.993 | Rint = 0.024 |
6501 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.099 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.41 e Å−3 |
1996 reflections | Δρmin = −0.48 e Å−3 |
157 parameters |
x | y | z | Uiso*/Ueq | ||
P1 | 0.38071 (10) | 0.32784 (5) | 0.87493 (4) | 0.01661 (15) | |
B1 | −0.0816 (4) | 0.2710 (2) | 0.73583 (18) | 0.0161 (4) | |
B2 | 1.2037 (5) | 0.2978 (2) | 0.52774 (19) | 0.0215 (4) | |
B3 | 0.2114 (5) | 0.0630 (2) | 0.6493 (2) | 0.0223 (4) | |
O1 | 0.5814 (3) | 0.29141 (15) | 0.75672 (12) | 0.0209 (3) | |
O2 | 0.4119 (3) | 0.48339 (14) | 0.89765 (12) | 0.0231 (3) | |
O3 | 0.0456 (3) | 0.33077 (15) | 0.83671 (12) | 0.0229 (3) | |
O4 | 0.4403 (3) | 0.21875 (15) | 0.98843 (13) | 0.0263 (3) | |
O5 | 0.0212 (3) | 0.11655 (13) | 0.73935 (12) | 0.0213 (3) | |
O6 | 1.0000 (3) | 0.35280 (13) | 0.61382 (12) | 0.0202 (3) | |
O7 | 0.6934 (4) | 0.62278 (16) | 0.57923 (14) | 0.0333 (4) | |
O8 | 0.6974 (4) | 0.08201 (16) | 1.33756 (16) | 0.0391 (4) | |
O9 | 0.3100 (3) | 0.15115 (14) | 0.54252 (12) | 0.0255 (3) | |
N1 | −0.0636 (5) | 0.6964 (2) | 0.8055 (2) | 0.0339 (4) | |
Ow | 0.0000 | 0.0000 | 1.0000 | 0.0738 (10) | |
H1 | −0.195 (7) | 0.730 (3) | 0.866 (3) | 0.044 (8)* | |
H2 | 0.768 (8) | 0.539 (4) | 0.580 (3) | 0.060 (10)* | |
H3 | 0.073 (8) | 0.620 (4) | 0.842 (3) | 0.055 (9)* | |
H4 | 0.603 (8) | 0.104 (4) | 1.399 (3) | 0.055 (9)* | |
H5 | 0.026 (8) | 0.774 (4) | 0.762 (3) | 0.058 (9)* | |
H6 | −0.167 (9) | 0.665 (4) | 0.745 (4) | 0.070 (11)* | |
H7 | 0.4445 (1) | 0.4834 (1) | 0.9712 (1) | 0.048 (1)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0144 (2) | 0.0187 (2) | 0.0176 (2) | −0.00196 (16) | 0.00014 (17) | −0.00570 (17) |
B1 | 0.0148 (8) | 0.0170 (9) | 0.0166 (9) | −0.0014 (7) | 0.0017 (7) | −0.0044 (7) |
B2 | 0.0244 (10) | 0.0182 (9) | 0.0200 (10) | 0.0017 (8) | 0.0036 (8) | −0.0024 (7) |
B3 | 0.0268 (10) | 0.0168 (9) | 0.0218 (10) | −0.0010 (8) | 0.0045 (8) | −0.0021 (8) |
O1 | 0.0134 (6) | 0.0309 (7) | 0.0207 (6) | −0.0026 (5) | 0.0003 (5) | −0.0117 (5) |
O2 | 0.0285 (7) | 0.0187 (6) | 0.0242 (7) | −0.0022 (5) | −0.0054 (5) | −0.0083 (5) |
O3 | 0.0131 (6) | 0.0341 (7) | 0.0244 (7) | −0.0020 (5) | 0.0004 (5) | −0.0151 (6) |
O4 | 0.0267 (7) | 0.0255 (7) | 0.0247 (7) | −0.0015 (5) | −0.0008 (6) | 0.0014 (5) |
O5 | 0.0254 (7) | 0.0164 (6) | 0.0203 (6) | −0.0004 (5) | 0.0068 (5) | −0.0021 (5) |
O6 | 0.0238 (6) | 0.0157 (6) | 0.0190 (6) | 0.0021 (5) | 0.0039 (5) | −0.0012 (5) |
O7 | 0.0507 (10) | 0.0181 (7) | 0.0247 (7) | 0.0054 (6) | 0.0147 (7) | 0.0020 (6) |
O8 | 0.0572 (11) | 0.0165 (7) | 0.0360 (9) | 0.0054 (7) | 0.0233 (8) | 0.0003 (6) |
O9 | 0.0356 (8) | 0.0159 (6) | 0.0216 (7) | 0.0024 (5) | 0.0110 (6) | −0.0019 (5) |
N1 | 0.0409 (11) | 0.0272 (9) | 0.0313 (10) | −0.0006 (8) | 0.0034 (9) | −0.0018 (8) |
Ow | 0.104 (3) | 0.061 (2) | 0.0554 (19) | −0.0294 (19) | −0.0163 (19) | 0.0156 (15) |
P1—O4 | 1.4984 (14) | B3—O9 | 1.386 (3) |
P1—O2 | 1.5354 (13) | O1—B1iii | 1.466 (2) |
P1—O3 | 1.5487 (13) | O2—H7 | 0.8202 (13) |
P1—O1 | 1.5503 (13) | O6—B1iii | 1.465 (2) |
B1—O5 | 1.462 (2) | O7—B2ii | 1.354 (3) |
B1—O6i | 1.465 (2) | O7—H2 | 0.81 (4) |
B1—O1i | 1.466 (2) | O8—B3iv | 1.363 (2) |
B1—O3 | 1.470 (2) | O8—H4 | 0.79 (4) |
B2—O6 | 1.353 (2) | O9—B2i | 1.391 (2) |
B2—O7ii | 1.354 (3) | N1—H1 | 0.90 (3) |
B2—O9iii | 1.391 (2) | N1—H3 | 0.94 (3) |
B3—O5 | 1.347 (2) | N1—H5 | 0.92 (4) |
B3—O8iv | 1.363 (2) | N1—H6 | 0.92 (4) |
O4—P1—O2 | 112.48 (8) | O5—B3—O9 | 121.62 (17) |
O4—P1—O3 | 111.15 (8) | O8iv—B3—O9 | 119.41 (17) |
O2—P1—O3 | 105.07 (8) | B1iii—O1—P1 | 129.61 (11) |
O4—P1—O1 | 113.18 (8) | P1—O2—H7 | 109.52 (12) |
O2—P1—O1 | 110.67 (8) | B1—O3—P1 | 131.73 (11) |
O3—P1—O1 | 103.64 (7) | B3—O5—B1 | 123.09 (15) |
O5—B1—O6i | 111.34 (14) | B2—O6—B1iii | 123.07 (14) |
O5—B1—O1i | 109.82 (14) | B2ii—O7—H2 | 109 (2) |
O6i—B1—O1i | 107.39 (14) | B3iv—O8—H4 | 111 (2) |
O5—B1—O3 | 110.95 (14) | B3—O9—B2i | 118.75 (15) |
O6i—B1—O3 | 110.65 (14) | H1—N1—H3 | 109 (3) |
O1i—B1—O3 | 106.51 (13) | H1—N1—H5 | 108 (3) |
O6—B2—O7ii | 123.54 (17) | H3—N1—H5 | 116 (3) |
O6—B2—O9iii | 120.76 (17) | H1—N1—H6 | 112 (3) |
O7ii—B2—O9iii | 115.63 (16) | H3—N1—H6 | 110 (3) |
O5—B3—O8iv | 118.96 (18) | H5—N1—H6 | 103 (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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4v | 0.90 (3) | 1.93 (3) | 2.821 (3) | 172 (3) |
N1—H3···O2 | 0.94 (3) | 1.92 (4) | 2.849 (3) | 169 (3) |
N1—H5···O8vi | 0.92 (4) | 2.04 (4) | 2.942 (3) | 168 (3) |
N1—H6···O7i | 0.92 (4) | 2.05 (4) | 2.946 (3) | 164 (3) |
O7—H2···O6 | 0.81 (4) | 1.92 (4) | 2.7170 (19) | 166 (3) |
O8—H4···O9vii | 0.79 (4) | 2.00 (4) | 2.789 (2) | 171 (3) |
O2—H7···O2vi | 0.8201 (13) | 1.6804 (13) | 2.476 (2) | 163.02 (5) |
Ow···O5 | 2.869 (3) | |||
Ow···O4 | 2.944 (2) |
Symmetry codes: (i) x−1, y, z; (v) −x, −y+1, −z+2; (vi) −x+1, −y+1, −z+2; (vii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | (NH4)[B3PO6(OH)3]·0.5H2O |
Mr | 237.48 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 4.3665 (2), 9.3680 (4), 10.8267 (8) |
α, β, γ (°) | 81.532 (9), 85.369 (9), 83.641 (8) |
V (Å3) | 434.41 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.35 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.887, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6501, 1996, 1788 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.099, 1.06 |
No. of reflections | 1996 |
No. of parameters | 157 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.41, −0.48 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
P1—O4 | 1.4984 (14) | B1—O3 | 1.470 (2) |
P1—O2 | 1.5354 (13) | B2—O6 | 1.353 (2) |
P1—O3 | 1.5487 (13) | B2—O7ii | 1.354 (3) |
P1—O1 | 1.5503 (13) | B2—O9iii | 1.391 (2) |
B1—O5 | 1.462 (2) | B3—O5 | 1.347 (2) |
B1—O6i | 1.465 (2) | B3—O8iv | 1.363 (2) |
B1—O1i | 1.466 (2) | B3—O9 | 1.386 (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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4v | 0.90 (3) | 1.93 (3) | 2.821 (3) | 172 (3) |
N1—H3···O2 | 0.94 (3) | 1.92 (4) | 2.849 (3) | 169 (3) |
N1—H5···O8vi | 0.92 (4) | 2.04 (4) | 2.942 (3) | 168 (3) |
N1—H6···O7i | 0.92 (4) | 2.05 (4) | 2.946 (3) | 164 (3) |
O7—H2···O6 | 0.81 (4) | 1.92 (4) | 2.7170 (19) | 166 (3) |
O8—H4···O9vii | 0.79 (4) | 2.00 (4) | 2.789 (2) | 171 (3) |
O2—H7···O2vi | 0.8201 (13) | 1.6804 (13) | 2.476 (2) | 163.02 (5) |
Ow···O5 | . | . | 2.869 (3) | . |
Ow···O4 | . | . | 2.944 (2) | . |
Symmetry codes: (i) x−1, y, z; (v) −x, −y+1, −z+2; (vi) −x+1, −y+1, −z+2; (vii) x, y, z+1. |
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.