The anionic component of the langbeinite-type title compound, ammonium oxonium dititanium(III,IV) tris(phosphate), is an infinite three-dimensional [Ti
2(PO
4)
3]
2− network based on PO
4 tetrahedra corner-linked to TiO
6 octahedra; the charge-balancing ammonium and oxonium cations occupy the cavities in the network and interact by way of N—H
O and O—H
O hydrogen bonds. The two independent Ti atoms, the ammonium N atom and the oxonium O atom lie on special positions of site symmetry 3.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (P-O) = 0.002 Å
- R factor = 0.022
- wR factor = 0.065
- Data-to-parameter ratio = 12.0
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT731_ALERT_1_B Bond Calc 0.86(5), Rep 0.860(10) ...... 5.00 su-Rat
O5 -H3 1.555 1.555
PLAT735_ALERT_1_B D-H Calc 0.86(5), Rep 0.860(10) ...... 5.00 su-Rat
O5 -H3 1.555 1.555
Alert level C
CELLV02_ALERT_1_C The supplied cell volume s.u. differs from that
calculated from the cell parameter s.u.'s by > 2
Calculated cell volume su = 6.84
Cell volume su given = 4.00
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
PLAT313_ALERT_2_C Oxygen with three covalent bonds (rare) ........ O5
PLAT731_ALERT_1_C Bond Calc 0.86(3), Rep 0.860(10) ...... 3.00 su-Rat
N1 -H1 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.86(3), Rep 0.860(10) ...... 3.00 su-Rat
N1 -H1 1.555 1.555
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 28.40
From the CIF: _reflns_number_total 816
Count of symmetry unique reflns 478
Completeness (_total/calc) 170.71%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 338
Fraction of Friedel pairs measured 0.707
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
2 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
ammonium oxonium dititanium(III,IV) tris(phosphate)
top
Crystal data top
(NH4)(H3O)Ti2(PO4)3 | Dx = 2.827 Mg m−3 |
Mr = 417.78 | Mo Kα radiation, λ = 0.71073 Å |
Cubic, P213 | Cell parameters from 8307 reflections |
Hall symbol: P 2ac 2ab 3 | θ = 3.4–28.1° |
a = 9.9384 (4) Å | µ = 2.20 mm−1 |
V = 981.63 (4) Å3 | T = 295 K |
Z = 4 | Block, black |
F(000) = 828 | 0.19 × 0.19 × 0.12 mm |
Data collection top
Bruker APEX area-detector diffractometer | 816 independent reflections |
Radiation source: fine-focus sealed tube | 815 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
φ and ω scans | θmax = 28.4°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.666, Tmax = 0.778 | k = −13→13 |
10934 measured reflections | l = −13→13 |
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)] = 0.022 | All H-atom parameters refined |
wR(F2) = 0.065 | w = 1/[σ2(Fo2) + (0.0438P)2 + 1.2965P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
816 reflections | Δρmax = 0.48 e Å−3 |
68 parameters | Δρmin = −0.45 e Å−3 |
3 restraints | Absolute structure: Flack (1983), 339 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (4) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ti1 | 0.08490 (5) | 0.08490 (5) | 0.08490 (5) | 0.0071 (2) | |
Ti2 | 0.35671 (5) | 0.35671 (5) | 0.35671 (5) | 0.0071 (2) | |
P1 | 0.04433 (7) | 0.26610 (7) | 0.37696 (7) | 0.0076 (2) | |
O1 | 0.0192 (2) | 0.1803 (2) | 0.2525 (2) | 0.015 (1) | |
O2 | 0.1946 (2) | 0.2620 (2) | 0.4174 (2) | 0.012 (1) | |
O3 | −0.0021 (2) | 0.4103 (2) | 0.3520 (2) | 0.014 (1) | |
O4 | −0.0365 (2) | 0.2042 (2) | 0.4940 (2) | 0.014 (1) | |
O5 | 0.2143 (3) | 0.2857 (3) | 0.7143 (3) | 0.035 (1) | |
N1 | −0.0733 (3) | 0.4267 (3) | 0.0733 (3) | 0.015 (1) | |
H1 | −0.038 (4) | 0.427 (5) | 0.152 (2) | 0.03 (1)* | |
H2 | −0.024 (1) | 0.476 (1) | 0.024 (1) | 0.05 (3)* | |
H3 | 0.219 (8) | 0.234 (6) | 0.645 (5) | 0.10 (3)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ti1 | 0.0071 (2) | 0.0071 (2) | 0.0071 (2) | 0.0000 (2) | 0.0000 (2) | 0.0000 (2) |
Ti2 | 0.0071 (2) | 0.0071 (2) | 0.0071 (2) | 0.0000 (2) | 0.0000 (2) | 0.0000 (2) |
P1 | 0.0076 (3) | 0.0080 (3) | 0.0070 (3) | 0.0001 (2) | 0.0006 (2) | −0.0002 (2) |
O1 | 0.016 (1) | 0.017 (1) | 0.011 (1) | −0.001 (1) | 0.001 (1) | −0.004 (1) |
O2 | 0.008 (1) | 0.013 (1) | 0.014 (1) | −0.001 (1) | −0.001 (1) | 0.002 (1) |
O3 | 0.013 (1) | 0.010 (1) | 0.018 (1) | 0.004 (1) | 0.002 (1) | 0.003 (1) |
O4 | 0.015 (1) | 0.016 (1) | 0.013 (1) | 0.000 (1) | 0.006 (1) | 0.004 (1) |
O5 | 0.035 (1) | 0.035 (1) | 0.035 (1) | −0.002 (1) | 0.002 (1) | −0.002 (1) |
N1 | 0.015 (1) | 0.015 (1) | 0.015 (1) | −0.001 (1) | 0.001 (1) | 0.001 (1) |
Geometric parameters (Å, º) top
Ti1—O1 | 2.025 (2) | Ti2—O4viii | 1.922 (2) |
Ti1—O1i | 2.025 (2) | P1—O1 | 1.523 (2) |
Ti1—O1ii | 2.025 (2) | P1—O2 | 1.547 (2) |
Ti1—O3iii | 2.020 (2) | P1—O3 | 1.526 (2) |
Ti1—O3iv | 2.020 (2) | P1—O4 | 1.542 (2) |
Ti1—O3v | 2.020 (2) | O3—Ti1ix | 2.020 (2) |
Ti2—O2 | 1.961 (2) | O4—Ti2x | 1.922 (2) |
Ti2—O2i | 1.961 (2) | O5—H3 | 0.86 (1) |
Ti2—O2ii | 1.961 (2) | N1—H1 | 0.86 (1) |
Ti2—O4vi | 1.922 (2) | N1—H2 | 0.85 (1) |
Ti2—O4vii | 1.922 (2) | | |
| | | |
O1—Ti1—O1i | 91.8 (1) | O2i—Ti2—O4vi | 175.0 (1) |
O1—Ti1—O1ii | 91.8 (1) | O2i—Ti2—O4vii | 93.7 (1) |
O1—Ti1—O3iii | 90.9 (1) | O2i—Ti2—O4viii | 86.7 (1) |
O1—Ti1—O3iv | 85.0 (1) | O2ii—Ti2—O4vi | 86.7 (1) |
O1—Ti1—O3v | 175.9 (1) | O2ii—Ti2—O4vii | 175.0 (1) |
O1i—Ti1—O1ii | 91.8 (1) | O2ii—Ti2—O4viii | 93.7 (1) |
O1i—Ti1—O3iii | 175.9 (1) | O4vi—Ti2—O4vii | 89.5 (1) |
O1i—Ti1—O3iv | 90.9 (1) | O4vi—Ti2—O4viii | 89.5 (1) |
O1i—Ti1—O3v | 85.0 (1) | O4viii—Ti2—O4vii | 89.5 (1) |
O1ii—Ti1—O3iii | 85.0 (1) | O1—P1—O3 | 110.1 (1) |
O1ii—Ti1—O3iv | 175.9 (1) | O1—P1—O4 | 107.7 (1) |
O1ii—Ti1—O3v | 90.9 (1) | O3—P1—O4 | 109.9 (1) |
O3iii—Ti1—O3iv | 92.5 (1) | O1—P1—O2 | 110.8 (1) |
O3iii—Ti1—O3v | 92.5 (1) | O3—P1—O2 | 111.0 (1) |
O3iv—Ti1—O3v | 92.5 (1) | O4—P1—O2 | 107.3 (1) |
O2—Ti2—O2i | 90.4 (1) | P1—O1—Ti1 | 151.3 (1) |
O2—Ti2—O2ii | 90.4 (1) | P1—O2—Ti2 | 134.5 (1) |
O2—Ti2—O4vi | 93.7 (1) | P1—O3—Ti1ix | 151.6 (1) |
O2—Ti2—O4vii | 86.7 (1) | P1—O4—Ti2x | 174.7 (2) |
O2—Ti2—O4viii | 175.0 (1) | H1—N1—H2 | 107 (3) |
O2i—Ti2—O2ii | 90.4 (1) | | |
| | | |
O3—P1—O1—Ti1 | 103.0 (3) | O4—P1—O2—Ti2 | −160.9 (2) |
O4—P1—O1—Ti1 | −137.2 (3) | O4vi—Ti2—O2—P1 | 167.9 (2) |
O2—P1—O1—Ti1 | −20.2 (3) | O4vii—Ti2—O2—P1 | 78.7 (2) |
O3iv—Ti1—O1—P1 | −141.6 (3) | O2ii—Ti2—O2—P1 | −105.4 (1) |
O3iii—Ti1—O1—P1 | 126.0 (3) | O2i—Ti2—O2—P1 | −15.1 (2) |
O1i—Ti1—O1—P1 | −50.8 (2) | O1—P1—O3—Ti1ix | 144.4 (3) |
O1ii—Ti1—O1—P1 | 41.0 (3) | O4—P1—O3—Ti1ix | 26.0 (3) |
O1—P1—O2—Ti2 | 81.8 (2) | O2—P1—O3—Ti1ix | −92.5 (3) |
O3—P1—O2—Ti2 | −40.9 (2) | | |
Symmetry codes: (i) y, z, x; (ii) z, x, y; (iii) −x, y−1/2, −z+1/2; (iv) y−1/2, −z+1/2, −x; (v) −z+1/2, −x, y−1/2; (vi) x+1/2, −y+1/2, −z+1; (vii) −y+1/2, −z+1, x+1/2; (viii) −z+1, x+1/2, −y+1/2; (ix) −x, y+1/2, −z+1/2; (x) x−1/2, −y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H3···O2 | 0.86 (1) | 2.30 (5) | 2.966 (4) | 135 (6) |
N1—H1···O3 | 0.86 (1) | 2.03 (1) | 2.864 (3) | 165 (4) |
N1—H2···O4i | 0.85 (1) | 2.35 (1) | 3.039 (4) | 138 (1) |
N1—H2···O4ix | 0.85 (1) | 2.35 (1) | 3.039 (4) | 138 (1) |
N1—H2···O4xi | 0.85 (1) | 2.35 (1) | 3.039 (4) | 138 (1) |
Symmetry codes: (i) y, z, x; (ix) −x, y+1/2, −z+1/2; (xi) z−1/2, −x+1/2, −y. |