Download citation
Download citation
link to html
The anionic component of the langbeinite-type title compound, ammonium oxonium dititanium(III,IV) tris­(phosphate), is an infinite three-dimensional [Ti2(PO4)3]2− network based on PO4 tetra­hedra corner-linked to TiO6 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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805021392/hb6237sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805021392/hb6237Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](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

Computing details top

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)3Dx = 2.827 Mg m3
Mr = 417.78Mo Kα radiation, λ = 0.71073 Å
Cubic, P213Cell parameters from 8307 reflections
Hall symbol: P 2ac 2ab 3θ = 3.4–28.1°
a = 9.9384 (4) ŵ = 2.20 mm1
V = 981.63 (4) Å3T = 295 K
Z = 4Block, black
F(000) = 8280.19 × 0.19 × 0.12 mm
Data collection top
Bruker APEX area-detector
diffractometer
816 independent reflections
Radiation source: fine-focus sealed tube815 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
φ and ω scansθmax = 28.4°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1313
Tmin = 0.666, Tmax = 0.778k = 1313
10934 measured reflectionsl = 1313
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022All 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 reflectionsΔρmax = 0.48 e Å3
68 parametersΔρmin = 0.45 e Å3
3 restraintsAbsolute structure: Flack (1983), 339 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (4)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ti10.08490 (5)0.08490 (5)0.08490 (5)0.0071 (2)
Ti20.35671 (5)0.35671 (5)0.35671 (5)0.0071 (2)
P10.04433 (7)0.26610 (7)0.37696 (7)0.0076 (2)
O10.0192 (2)0.1803 (2)0.2525 (2)0.015 (1)
O20.1946 (2)0.2620 (2)0.4174 (2)0.012 (1)
O30.0021 (2)0.4103 (2)0.3520 (2)0.014 (1)
O40.0365 (2)0.2042 (2)0.4940 (2)0.014 (1)
O50.2143 (3)0.2857 (3)0.7143 (3)0.035 (1)
N10.0733 (3)0.4267 (3)0.0733 (3)0.015 (1)
H10.038 (4)0.427 (5)0.152 (2)0.03 (1)*
H20.024 (1)0.476 (1)0.024 (1)0.05 (3)*
H30.219 (8)0.234 (6)0.645 (5)0.10 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti10.0071 (2)0.0071 (2)0.0071 (2)0.0000 (2)0.0000 (2)0.0000 (2)
Ti20.0071 (2)0.0071 (2)0.0071 (2)0.0000 (2)0.0000 (2)0.0000 (2)
P10.0076 (3)0.0080 (3)0.0070 (3)0.0001 (2)0.0006 (2)0.0002 (2)
O10.016 (1)0.017 (1)0.011 (1)0.001 (1)0.001 (1)0.004 (1)
O20.008 (1)0.013 (1)0.014 (1)0.001 (1)0.001 (1)0.002 (1)
O30.013 (1)0.010 (1)0.018 (1)0.004 (1)0.002 (1)0.003 (1)
O40.015 (1)0.016 (1)0.013 (1)0.000 (1)0.006 (1)0.004 (1)
O50.035 (1)0.035 (1)0.035 (1)0.002 (1)0.002 (1)0.002 (1)
N10.015 (1)0.015 (1)0.015 (1)0.001 (1)0.001 (1)0.001 (1)
Geometric parameters (Å, º) top
Ti1—O12.025 (2)Ti2—O4viii1.922 (2)
Ti1—O1i2.025 (2)P1—O11.523 (2)
Ti1—O1ii2.025 (2)P1—O21.547 (2)
Ti1—O3iii2.020 (2)P1—O31.526 (2)
Ti1—O3iv2.020 (2)P1—O41.542 (2)
Ti1—O3v2.020 (2)O3—Ti1ix2.020 (2)
Ti2—O21.961 (2)O4—Ti2x1.922 (2)
Ti2—O2i1.961 (2)O5—H30.86 (1)
Ti2—O2ii1.961 (2)N1—H10.86 (1)
Ti2—O4vi1.922 (2)N1—H20.85 (1)
Ti2—O4vii1.922 (2)
O1—Ti1—O1i91.8 (1)O2i—Ti2—O4vi175.0 (1)
O1—Ti1—O1ii91.8 (1)O2i—Ti2—O4vii93.7 (1)
O1—Ti1—O3iii90.9 (1)O2i—Ti2—O4viii86.7 (1)
O1—Ti1—O3iv85.0 (1)O2ii—Ti2—O4vi86.7 (1)
O1—Ti1—O3v175.9 (1)O2ii—Ti2—O4vii175.0 (1)
O1i—Ti1—O1ii91.8 (1)O2ii—Ti2—O4viii93.7 (1)
O1i—Ti1—O3iii175.9 (1)O4vi—Ti2—O4vii89.5 (1)
O1i—Ti1—O3iv90.9 (1)O4vi—Ti2—O4viii89.5 (1)
O1i—Ti1—O3v85.0 (1)O4viii—Ti2—O4vii89.5 (1)
O1ii—Ti1—O3iii85.0 (1)O1—P1—O3110.1 (1)
O1ii—Ti1—O3iv175.9 (1)O1—P1—O4107.7 (1)
O1ii—Ti1—O3v90.9 (1)O3—P1—O4109.9 (1)
O3iii—Ti1—O3iv92.5 (1)O1—P1—O2110.8 (1)
O3iii—Ti1—O3v92.5 (1)O3—P1—O2111.0 (1)
O3iv—Ti1—O3v92.5 (1)O4—P1—O2107.3 (1)
O2—Ti2—O2i90.4 (1)P1—O1—Ti1151.3 (1)
O2—Ti2—O2ii90.4 (1)P1—O2—Ti2134.5 (1)
O2—Ti2—O4vi93.7 (1)P1—O3—Ti1ix151.6 (1)
O2—Ti2—O4vii86.7 (1)P1—O4—Ti2x174.7 (2)
O2—Ti2—O4viii175.0 (1)H1—N1—H2107 (3)
O2i—Ti2—O2ii90.4 (1)
O3—P1—O1—Ti1103.0 (3)O4—P1—O2—Ti2160.9 (2)
O4—P1—O1—Ti1137.2 (3)O4vi—Ti2—O2—P1167.9 (2)
O2—P1—O1—Ti120.2 (3)O4vii—Ti2—O2—P178.7 (2)
O3iv—Ti1—O1—P1141.6 (3)O2ii—Ti2—O2—P1105.4 (1)
O3iii—Ti1—O1—P1126.0 (3)O2i—Ti2—O2—P115.1 (2)
O1i—Ti1—O1—P150.8 (2)O1—P1—O3—Ti1ix144.4 (3)
O1ii—Ti1—O1—P141.0 (3)O4—P1—O3—Ti1ix26.0 (3)
O1—P1—O2—Ti281.8 (2)O2—P1—O3—Ti1ix92.5 (3)
O3—P1—O2—Ti240.9 (2)
Symmetry codes: (i) y, z, x; (ii) z, x, y; (iii) x, y1/2, z+1/2; (iv) y1/2, z+1/2, x; (v) z+1/2, x, y1/2; (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) x1/2, y+1/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H3···O20.86 (1)2.30 (5)2.966 (4)135 (6)
N1—H1···O30.86 (1)2.03 (1)2.864 (3)165 (4)
N1—H2···O4i0.85 (1)2.35 (1)3.039 (4)138 (1)
N1—H2···O4ix0.85 (1)2.35 (1)3.039 (4)138 (1)
N1—H2···O4xi0.85 (1)2.35 (1)3.039 (4)138 (1)
Symmetry codes: (i) y, z, x; (ix) x, y+1/2, z+1/2; (xi) z1/2, x+1/2, y.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds