The crystal structure of monoclinic thallium(III) hydrogendiphosphate, TlHP2O7, has been solved from laboratory X-ray powder diffraction data and refined by the Rietveld method. All atoms occupy general positions. The TlIII ions have a distorted octahedral coordination environment of O atoms from four diphosphate groups. Adjacent TlO6 octahedra form edge-shared Tl2O10 dimers which share corners with PO4 tetrahedra to build a three-dimensional polymeric structure.
Supporting information
Key indicators
- Powder X-ray study
- T = 295 K
- Mean (P-O) = 0.015 Å
- R factor = 0.076
- wR factor = 0.106
- Data-to-parameter ratio = 19.9
checkCIF/PLATON results
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2 ALERT level C = Check and explain
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Data collection: local program; cell refinement: FULLPROF (Rodríguez-Carvajal, 2001); data reduction: local program; program(s) used to solve structure: EXPO (Altomare et al., 1999); program(s) used to refine structure: FULLPROF; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: FULLPROF and PLATON (Spek, 2003).
thallium(III) hydrogen diphosphate
top
Crystal data top
TlHP2O7 | Z = 4 |
Mr = 379.33 | F(000) = 672 |
Monoclinic, P21/n | Dx = 4.527 Mg m−3 |
Hall symbol: -P 2yn | Cu Kα radiation, λ = 1.54180 Å |
a = 8.78516 (15) Å | T = 295 K |
b = 9.09283 (17) Å | Particle morphology: plate-like |
c = 7.24420 (12) Å | colourless |
β = 105.8725 (9)° | flat sheet, 30 × 30 mm |
V = 556.62 (2) Å3 | Specimen preparation: Prepared at 295 K |
Data collection top
HZG-4A (Carl Zeiss, Jena) diffractometer | Data collection mode: reflection |
Radiation source: fine-focus sealed X-ray tube, BSV-29 | Scan method: step |
Specimen mounting: packed powder pellet | 2θmin = 12.0°, 2θmax = 137.0°, 2θstep = 0.02° |
Refinement top
Refinement on Inet | Profile function: A pseudo-Voigt profile function was used.
The value of the η-parameter is 0.62. |
Least-squares matrix: full with fixed elements per cycle | 52 parameters |
Rp = 0.076 | 8 restraints |
Rwp = 0.106 | 0 constraints |
Rexp = 0.135 | H-atom parameters constrained |
RBragg = 0.055 | Weighting scheme based on measured s.u.'s |
R(F2) = 0.035 | (Δ/σ)max = 0.03 |
6251 data points | Background function: A polynomial background function was used.
Five polynomial coefficients were refined. |
Excluded region(s): none | Preferred orientation correction: A Marsh–Dollase correction of intensities (Marsh, 1932; Dollase,
1986)
for the (101) preferred orientation of plate-like grains was applied.
The refined values of coefficients are G1 = 0.668(6), G2 = 0.316(19). |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All su's are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Tl | 0.4945 (2) | 0.29669 (18) | 0.5376 (2) | 0.0060 (4)* | |
P1 | 0.7278 (8) | −0.0021 (9) | 0.6794 (10) | 0.0047 (19)* | |
P2 | 0.7351 (9) | 0.1374 (8) | 0.3049 (10) | 0.0047 (19)* | |
O1 | 0.5857 (18) | 0.084 (2) | 0.664 (3) | 0.0060 (19)* | |
O2 | 0.692 (2) | −0.1578 (13) | 0.662 (3) | 0.0060 (19)* | |
O3 | 0.8646 (15) | 0.011 (3) | 0.8528 (18) | 0.0060 (19)* | |
O4 | 0.8009 (19) | 0.042 (2) | 0.4989 (18) | 0.0060 (19)* | |
O5 | 0.662 (2) | 0.2699 (15) | 0.354 (3) | 0.0060 (19)* | |
O6 | 0.626 (2) | 0.038 (2) | 0.142 (2) | 0.0060 (19)* | |
H6 | 0.67616 | −0.03768 | 0.12077 | 0.050* | |
O7 | 0.8863 (17) | 0.187 (2) | 0.271 (3) | 0.0060 (19)* | |
Geometric parameters (Å, º) top
Tl—O1 | 2.195 (19) | P1—O3 | 1.487 (15) |
Tl—O5 | 2.250 (19) | P1—O4 | 1.656 (16) |
Tl—O3i | 2.33 (2) | P2—O4 | 1.618 (16) |
Tl—O2ii | 2.253 (18) | P2—O5 | 1.455 (17) |
Tl—O3iii | 2.31 (2) | P2—O6 | 1.584 (18) |
Tl—O7iv | 2.160 (19) | P2—O7 | 1.486 (18) |
P1—O1 | 1.452 (19) | O6—H6 | 0.8500 |
P1—O2 | 1.448 (15) | | |
| | | |
O1—Tl—O5 | 85.9 (6) | O2—P1—O3 | 105.0 (14) |
O1—Tl—O3i | 119.7 (7) | O2—P1—O4 | 106.9 (11) |
O1—Tl—O2ii | 83.8 (6) | O3—P1—O4 | 104.4 (9) |
O1—Tl—O3iii | 167.6 (7) | O4—P2—O5 | 108.0 (11) |
O1—Tl—O7iv | 85.6 (7) | O4—P2—O6 | 109.9 (10) |
O3i—Tl—O5 | 85.4 (5) | O4—P2—O7 | 100.6 (11) |
O2ii—Tl—O5 | 92.2 (7) | O5—P2—O6 | 115.9 (11) |
O3iii—Tl—O5 | 92.2 (5) | O5—P2—O7 | 105.3 (11) |
O5—Tl—O7iv | 165.7 (7) | O6—P2—O7 | 115.9 (11) |
O2ii—Tl—O3i | 156.0 (6) | Tl—O1—P1 | 135.7 (12) |
O3i—Tl—O3iii | 72.3 (7) | Tlii—O2—P1 | 135.0 (12) |
O3i—Tl—O7iv | 89.0 (6) | Tlv—O3—P1 | 116.9 (14) |
O2ii—Tl—O3iii | 84.0 (6) | Tlvi—O3—P1 | 135.1 (15) |
O2ii—Tl—O7iv | 98.2 (7) | Tlv—O3—Tlvi | 107.7 (5) |
O3iii—Tl—O7iv | 98.5 (6) | P1—O4—P2 | 133.8 (12) |
O1—P1—O2 | 111.0 (11) | Tl—O5—P2 | 129.7 (10) |
O1—P1—O3 | 120.1 (12) | Tlvii—O7—P2 | 139.1 (13) |
O1—P1—O4 | 108.7 (11) | P2—O6—H6 | 111.00 |
| | | |
O5—Tl—O1—P1 | 21.4 (18) | O4—P1—O2—Tlii | −72.4 (17) |
O3i—Tl—O1—P1 | −60.9 (19) | O1—P1—O3—Tlv | 143.0 (10) |
O2ii—Tl—O1—P1 | 114.1 (18) | O1—P1—O3—Tlvi | −43.8 (17) |
O7iv—Tl—O1—P1 | −147.2 (18) | O2—P1—O3—Tlv | 17.3 (12) |
O1—Tl—O5—P2 | 21.0 (16) | O2—P1—O3—Tlvi | −169.5 (12) |
O3i—Tl—O5—P2 | 141.3 (16) | O4—P1—O3—Tlv | −94.9 (11) |
O2ii—Tl—O5—P2 | −62.7 (16) | O4—P1—O3—Tlvi | 78.3 (13) |
O3iii—Tl—O5—P2 | −146.7 (16) | O1—P1—O4—P2 | −10.4 (19) |
O1—Tl—O3i—P1i | −8.6 (12) | O2—P1—O4—P2 | 109.5 (17) |
O5—Tl—O3i—P1i | −91.2 (10) | O3—P1—O4—P2 | −139.6 (17) |
O1—Tl—O2ii—P1ii | 2.5 (17) | O5—P2—O4—P1 | 43.4 (19) |
O5—Tl—O2ii—P1ii | 88.2 (17) | O6—P2—O4—P1 | −83.9 (17) |
O5—Tl—O3iii—P1iii | 89.2 (12) | O7—P2—O4—P1 | 153.5 (16) |
O1—Tl—O7iv—P2iv | −139.6 (18) | O4—P2—O5—Tl | −45.2 (17) |
O2—P1—O1—Tl | −143.2 (16) | O6—P2—O5—Tl | 78.6 (17) |
O3—P1—O1—Tl | 94 (2) | O7—P2—O5—Tl | −152.0 (14) |
O4—P1—O1—Tl | −26 (2) | O4—P2—O7—Tlvii | 134.2 (16) |
O1—P1—O2—Tlii | 46 (2) | O5—P2—O7—Tlvii | −113.7 (17) |
O3—P1—O2—Tlii | 177.1 (14) | O6—P2—O7—Tlvii | 16 (2) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1, −y, −z+1; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1/2, −y+1/2, z+1/2; (v) −x+3/2, y−1/2, −z+3/2; (vi) x+1/2, −y+1/2, z+1/2; (vii) x+1/2, −y+1/2, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O5viii | 0.8500 | 2.2300 | 3.06 (2) | 165.00 |
Symmetry code: (viii) −x+3/2, y−1/2, −z+1/2. |