inorganic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Crystal structure of tris­­(hydroxyl­ammonium) orthophosphate

aDräger Safety AG & Co. KGaA, Revalstrasse 1, 23560 Lübeck, Germany, and bInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Str. 2, 24118 Kiel, Germany
*Correspondence e-mail: cnaether@ac.uni-kiel.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 1 October 2015; accepted 5 October 2015; online 10 October 2015)

The crystal structure of the title salt, ([H3NOH]+)3·[PO4]3−, consists of discrete hydroxyl­ammonium cations and ortho­phos­phate anions. The atoms of the cation occupy general positions, whereas the anion is located on a threefold rotation axis that runs through the phospho­rus atom and one of the phosphate O atoms. In the crystal structure, cations and anions are linked by inter­molecular O—H⋯O and N—H⋯O hydrogen bonds into a three-dimensional network. Altogether, one very strong O—H⋯O, two N—H⋯O hydrogen bonds of medium strength and two weaker bifurcated N—H⋯O inter­actions are observed.

1. Related literature

The structure determination of the title compound was undertaken as a part of a project on the synthesis and structural characterization of hydroxyl­ammonium salts with simple inorganic anions. For crystal structures of other hydroxyl­ammonium salts with perchlorate, chloride or sulfate anions, see: Dickens (1969[Dickens, B. (1969). Acta Cryst. B25, 1875-1882.]); Jerslev (1948[Jerslev, B. (1948). Acta Cryst. 1, 21-27.]); Shi et al. (1987[Shi, K.-L., Wang, R.-Q. & Mak, T. C. W. (1987). J. Mol. Struct. 160, 109-116.]); Mirceva & Golic (1995[Mirceva, A. & Golic, L. (1995). Acta Cryst. C51, 798-800.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • 3H4NO+·PO43−

  • Mr = 197.10

  • Trigonal, R 3c :H

  • a = 10.7072 (9) Å

  • c = 11.0283 (13) Å

  • V = 1094.9 (2) Å3

  • Z = 6

  • Mo Kα radiation

  • μ = 0.39 mm−1

  • T = 170 K

  • 0.15 × 0.12 × 0.11 mm

2.2. Data collection

  • Stoe IPDS-2 diffractometer

  • 5420 measured reflections

  • 647 independent reflections

  • 621 reflections with I > 2σ(I)

  • Rint = 0.047

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.034

  • wR(F2) = 0.090

  • S = 1.09

  • 647 reflections

  • 36 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.32 e Å−3

  • Absolute structure: Flack x determined using 287 quotients [(I+)−(I)]/[(I+)+(I)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.])

  • Absolute structure parameter: −0.06 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1O1⋯O3i 0.84 1.70 2.540 (3) 172
N1—H1N1⋯O2ii 0.91 1.90 2.785 (3) 163
N1—H2N1⋯O1iii 0.91 2.37 3.110 (4) 138
N1—H2N1⋯O3iv 0.91 2.20 2.884 (3) 132
N1—H3N1⋯O3 0.91 1.84 2.732 (3) 164
Symmetry codes: (i) [-y+{\script{4\over 3}}, x-y+{\script{2\over 3}}, z-{\script{1\over 3}}]; (ii) [-y+{\script{4\over 3}}, -x+{\script{2\over 3}}, z+{\script{1\over 6}}]; (iii) [x-{\script{1\over 3}}, x-y+{\script{1\over 3}}, z-{\script{1\over 6}}]; (iv) [-x+y+{\script{1\over 3}}, -x+{\script{2\over 3}}, z-{\script{1\over 3}}].

Data collection: X-AREA (Stoe, 2008[Stoe (2008). X-AREA. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Synthesis and crystallization top

The title compound tris­(hydroxyl­ammonium) orthophosphate was synthesized by the reaction of 29.4 g H3PO4 (0.30 mol) with 29.7 g NH2OH (0.90 mol) in aqueous solution under cooling. The resulting precipitate was filtered off, washed with mother liquor and dried in vacuum at 343 K for one day. The purity was checked by X-ray powder diffraction. Single crystals suitable for X-ray diffraction analysis were obtained by dissolving 0.5 g of the polycrystalline powder of tris­(hydroxyl­ammonium)­phosphate in 5 ml of water in a snap cap vial, allowing the solvent to evaporate slowly. After a few days colorless block-shaped crystals of the title compound were obtained.

Refinement top

The N–H and O–H hydrogen atoms were located in a difference map but in the final refinement they were positioned with idealized geometry allowed to rotate but not to tip. H atoms were refined with Uiso(H) = 1.5Ueq(N,O) using a riding model with O—H = 0.82 Å and N—H = 0.99 Å, respectively.

Related literature top

The structure determination of the title compound was undertaken as a part of a project on the synthesis and structural characterization of hydroxylammonium salts with simple inorganic anions. For crystal structures of other hydroxylammonium salts with perchlorate, chloride or sulfate anions, see: Dickens (1969); Jerslev (1948); Shi et al. (1987); Mirceva & Golic (1995).

Structure description top

The structure determination of the title compound was undertaken as a part of a project on the synthesis and structural characterization of hydroxylammonium salts with simple inorganic anions. For crystal structures of other hydroxylammonium salts with perchlorate, chloride or sulfate anions, see: Dickens (1969); Jerslev (1948); Shi et al. (1987); Mirceva & Golic (1995).

Synthesis and crystallization top

The title compound tris­(hydroxyl­ammonium) orthophosphate was synthesized by the reaction of 29.4 g H3PO4 (0.30 mol) with 29.7 g NH2OH (0.90 mol) in aqueous solution under cooling. The resulting precipitate was filtered off, washed with mother liquor and dried in vacuum at 343 K for one day. The purity was checked by X-ray powder diffraction. Single crystals suitable for X-ray diffraction analysis were obtained by dissolving 0.5 g of the polycrystalline powder of tris­(hydroxyl­ammonium)­phosphate in 5 ml of water in a snap cap vial, allowing the solvent to evaporate slowly. After a few days colorless block-shaped crystals of the title compound were obtained.

Refinement details top

The N–H and O–H hydrogen atoms were located in a difference map but in the final refinement they were positioned with idealized geometry allowed to rotate but not to tip. H atoms were refined with Uiso(H) = 1.5Ueq(N,O) using a riding model with O—H = 0.82 Å and N—H = 0.99 Å, respectively.

Computing details top

Data collection: X-AREA (Stoe, 2008); cell refinement: X-AREA (Stoe, 2008); data reduction: X-AREA (Stoe, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. View of the molecular components of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: i) = -x+y, -x+1, z, ii) = -y+1, x-y, z.]
[Figure 2] Fig. 2. Crystal structure of the title compound in a view along the crystallographic c axis. Intermolecular hydrogen bonding is shown as dashed lines. For clarity, only parts of the hydrogen bonding interactions are shown.
Tris(hydroxylammonium) orthophosphate top
Crystal data top
3H4NO+·PO43Dx = 1.793 Mg m3
Mr = 197.10Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c:HCell parameters from 5420 reflections
a = 10.7072 (9) Åθ = 7.6–59.2°
c = 11.0283 (13) ŵ = 0.39 mm1
V = 1094.9 (2) Å3T = 170 K
Z = 6Block, colorless
F(000) = 6240.15 × 0.12 × 0.11 mm
Data collection top
Stoe IPDS-2
diffractometer
Rint = 0.047
ω scansθmax = 29.0°, θmin = 3.8°
5420 measured reflectionsh = 1414
647 independent reflectionsk = 1414
621 reflections with I > 2σ(I)l = 1515
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.034 w = 1/[σ2(Fo2) + (0.0636P)2 + 0.3897P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.090(Δ/σ)max < 0.001
S = 1.09Δρmax = 0.24 e Å3
647 reflectionsΔρmin = 0.32 e Å3
36 parametersAbsolute structure: Flack x determined using 287 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraintAbsolute structure parameter: 0.06 (9)
Crystal data top
3H4NO+·PO43Z = 6
Mr = 197.10Mo Kα radiation
Trigonal, R3c:Hµ = 0.39 mm1
a = 10.7072 (9) ÅT = 170 K
c = 11.0283 (13) Å0.15 × 0.12 × 0.11 mm
V = 1094.9 (2) Å3
Data collection top
Stoe IPDS-2
diffractometer
621 reflections with I > 2σ(I)
5420 measured reflectionsRint = 0.047
647 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.090Δρmax = 0.24 e Å3
S = 1.09Δρmin = 0.32 e Å3
647 reflectionsAbsolute structure: Flack x determined using 287 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
36 parametersAbsolute structure parameter: 0.06 (9)
1 restraint
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.6408 (2)0.5792 (2)0.5089 (3)0.0230 (5)
H1O10.68270.55670.45620.035*
N10.5202 (3)0.4522 (2)0.5550 (2)0.0203 (5)
H1N10.55150.40320.60160.030*
H2N10.46680.39550.49220.030*
H3N10.46490.47670.60080.030*
P10.33330.66670.64509 (11)0.0166 (3)
O20.33330.66670.5059 (3)0.0223 (8)
O30.3977 (2)0.5747 (2)0.69256 (18)0.0202 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0240 (11)0.0183 (9)0.0246 (9)0.0089 (8)0.0057 (9)0.0017 (8)
N10.0201 (11)0.0179 (12)0.0219 (12)0.0087 (10)0.0025 (10)0.0006 (10)
P10.0171 (3)0.0171 (3)0.0157 (5)0.00855 (17)0.0000.000
O20.0233 (11)0.0233 (11)0.0205 (18)0.0116 (6)0.0000.000
O30.0207 (10)0.0200 (9)0.0200 (10)0.0103 (8)0.0003 (9)0.0002 (8)
Geometric parameters (Å, º) top
O1—N11.421 (3)P1—O21.535 (4)
O1—H1O10.8400P1—O3i1.548 (2)
N1—H1N10.9100P1—O3ii1.548 (2)
N1—H2N10.9100P1—O31.548 (2)
N1—H3N10.9100
N1—O1—H1O1109.5O2—P1—O3i109.77 (9)
O1—N1—H1N1109.5O2—P1—O3ii109.77 (9)
O1—N1—H2N1109.5O3i—P1—O3ii109.17 (9)
H1N1—N1—H2N1109.5O2—P1—O3109.77 (9)
O1—N1—H3N1109.5O3i—P1—O3109.17 (9)
H1N1—N1—H3N1109.5O3ii—P1—O3109.17 (9)
H2N1—N1—H3N1109.5
Symmetry codes: (i) y+1, xy+1, z; (ii) x+y, x+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···O3iii0.841.702.540 (3)172
N1—H1N1···O2iv0.911.902.785 (3)163
N1—H2N1···O1v0.912.373.110 (4)138
N1—H2N1···O3vi0.912.202.884 (3)132
N1—H3N1···O30.911.842.732 (3)164
Symmetry codes: (iii) y+4/3, xy+2/3, z1/3; (iv) y+4/3, x+2/3, z+1/6; (v) x1/3, xy+1/3, z1/6; (vi) x+y+1/3, x+2/3, z1/3.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···O3i0.841.702.540 (3)172.3
N1—H1N1···O2ii0.911.902.785 (3)163.3
N1—H2N1···O1iii0.912.373.110 (4)137.9
N1—H2N1···O3iv0.912.202.884 (3)131.5
N1—H3N1···O30.911.842.732 (3)164.4
Symmetry codes: (i) y+4/3, xy+2/3, z1/3; (ii) y+4/3, x+2/3, z+1/6; (iii) x1/3, xy+1/3, z1/6; (iv) x+y+1/3, x+2/3, z1/3.
 

Acknowledgements

We gratefully acknowledge financial support by the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

References

First citationBrandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationDickens, B. (1969). Acta Cryst. B25, 1875–1882.  CrossRef IUCr Journals Web of Science Google Scholar
First citationJerslev, B. (1948). Acta Cryst. 1, 21–27.  CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationMirceva, A. & Golic, L. (1995). Acta Cryst. C51, 798–800.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationParsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationShi, K.-L., Wang, R.-Q. & Mak, T. C. W. (1987). J. Mol. Struct. 160, 109–116.  CrossRef CAS Web of Science Google Scholar
First citationStoe (2008). X-AREA. Stoe & Cie, Darmstadt, Germany.  Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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