The quaternary thallium thiophosphate TlPbPS4 (thallium lead phosphorus tetrasulfide) was obtained by reacting elemental Pb with a melt, formed in situ, of Tl2S, P2S5 and S. The crystal structure is composed of parallel zigzag layers, which consist of condensed S6 distorted trigonal prisms alternately centred by Tl and Pb atoms. The layers are stacked perpendicular to the crystallographic a axis and are joined by [PS4] tetrahedra. TlPbPS4 is isostructural with TlEuPS4 and TlSnPS4.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (S-P) = 0.005 Å
- R factor = 0.046
- wR factor = 0.125
- Data-to-parameter ratio = 22.5
checkCIF/PLATON results
No syntax errors found
Alert level C
CRYSC01_ALERT_1_C No recognised colour has been given for crystal colour.
RINTA01_ALERT_3_C The value of Rint is greater than 0.10
Rint given 0.114
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.11
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT126_ALERT_1_C Error in or Uninterpretable Hall Symbol ....... P N M A
PLAT127_ALERT_1_C Implicit Hall Symbol Inconsistent with Explicit P n m a
Alert level G
ABSTM02_ALERT_3_G The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
Tmin and Tmax reported: 0.004 0.046
Tmin(prime) and Tmax expected: 0.015 0.090
RR(prime) = 0.567
Please check that your absorption correction is appropriate.
CHEMS02_ALERT_1_G Please check that you have entered the correct
_publ_requested_category classification of your compound;
FI or CI or EI for inorganic; FM or CM or EM for metal-organic;
FO or CO or EO for organic.
From the CIF: _publ_requested_category EO
From the CIF: _chemical_formula_sum:P1 Pb1 S4 Tl1
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
4 ALERT level G = General alerts; check
7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
3 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: IPDS Program Package (Stoe & Cie, 1998); cell refinement: IPDS Program Package (Stoe & Cie, 1998); data reduction: IPDS Program Package; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia,1997) and BS (Ozawa & Kang, 2004); software used to prepare material for publication: SHELXL97.
Thallium lead tetrathiophosphate
top
Crystal data top
TlPbPS4 | F(000) = 968 |
Mr = 570.77 | Dx = 5.405 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P n m a | Cell parameters from 921 reflections |
a = 12.0976 (9) Å | θ = 2.9–28.0° |
b = 6.5816 (5) Å | µ = 48.21 mm−1 |
c = 8.8093 (6) Å | T = 293 K |
V = 701.41 (9) Å3 | Platelets, dark |
Z = 4 | 0.08 × 0.06 × 0.05 mm |
Data collection top
Stoe IPDS diffractometer | 921 independent reflections |
Radiation source: fine-focus sealed tube | 743 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.114 |
ω scans | θmax = 28.0°, θmin = 2.9° |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998) | h = −15→15 |
Tmin = 0.005, Tmax = 0.046 | k = −8→8 |
4828 measured reflections | l = −11→11 |
Refinement top
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)] = 0.046 | w = 1/[σ2(Fo2) + (0.0775P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.125 | (Δ/σ)max < 0.001 |
S = 1.00 | Δρmax = 2.57 e Å−3 |
921 reflections | Δρmin = −3.30 e Å−3 |
41 parameters | Extinction correction: SHELXL97 |
0 restraints | Extinction coefficient: 0.0021 (3) |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Tl1 | 0.39716 (8) | 0.7500 | 0.62788 (8) | 0.0396 (3) | |
Pb1 | 0.63273 (6) | 0.2500 | 0.89495 (8) | 0.0307 (3) | |
P1 | 0.3444 (3) | 0.2500 | 0.8748 (4) | 0.0160 (7) | |
S1 | 0.4489 (4) | 0.2500 | 0.6937 (4) | 0.0268 (9) | |
S2 | 0.4309 (4) | 0.2500 | 1.0748 (4) | 0.0270 (9) | |
S3 | 0.2446 (2) | 0.0010 (5) | 0.8644 (4) | 0.0266 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Tl1 | 0.0477 (5) | 0.0418 (5) | 0.0294 (4) | 0.000 | −0.0038 (3) | 0.000 |
Pb1 | 0.0239 (4) | 0.0446 (5) | 0.0236 (4) | 0.000 | 0.0001 (2) | 0.000 |
P1 | 0.0177 (16) | 0.0130 (18) | 0.0174 (17) | 0.000 | −0.0009 (14) | 0.000 |
S1 | 0.033 (2) | 0.033 (2) | 0.0140 (16) | 0.000 | 0.0006 (17) | 0.000 |
S2 | 0.0243 (19) | 0.041 (3) | 0.0155 (17) | 0.000 | −0.0013 (16) | 0.000 |
S3 | 0.0278 (14) | 0.0182 (15) | 0.0338 (16) | −0.0035 (11) | −0.0050 (12) | 0.0010 (11) |
Geometric parameters (Å, º) top
Pb1—S1 | 2.844 (4) | P1—S1 | 2.035 (6) |
Pb1—S2 | 2.911 (4) | P1—S3 | 2.038 (4) |
Pb1—S3i | 3.070 (3) | P1—S3v | 2.038 (4) |
Pb1—S3ii | 3.070 (3) | P1—S2 | 2.050 (5) |
Pb1—S3iii | 3.120 (3) | S3—Pb1ii | 3.070 (3) |
Pb1—S3iv | 3.120 (3) | S3—Pb1vi | 3.120 (3) |
| | | |
S1—Pb1—S2 | 71.53 (12) | S3ii—Pb1—S3iv | 125.35 (2) |
S1—Pb1—S3i | 143.95 (6) | S3iii—Pb1—S3iv | 63.37 (11) |
S2—Pb1—S3i | 91.71 (9) | S1—P1—S3 | 109.45 (16) |
S1—Pb1—S3ii | 143.95 (6) | S1—P1—S3v | 109.45 (16) |
S2—Pb1—S3ii | 91.71 (9) | S3—P1—S3v | 107.1 (3) |
S3i—Pb1—S3ii | 65.09 (11) | S1—P1—S2 | 110.9 (3) |
S1—Pb1—S3iii | 83.26 (9) | S3—P1—S2 | 109.94 (15) |
S2—Pb1—S3iii | 139.66 (7) | S3v—P1—S2 | 109.94 (15) |
S3i—Pb1—S3iii | 125.35 (2) | P1—S1—Pb1 | 89.85 (17) |
S3ii—Pb1—S3iii | 90.764 (13) | P1—S2—Pb1 | 87.73 (17) |
S1—Pb1—S3iv | 83.26 (9) | P1—S3—Pb1ii | 96.62 (14) |
S2—Pb1—S3iv | 139.66 (7) | P1—S3—Pb1vi | 82.37 (13) |
S3i—Pb1—S3iv | 90.764 (13) | Pb1ii—S3—Pb1vi | 176.20 (12) |
Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) −x+1, −y, −z+2; (iii) x+1/2, y, −z+3/2; (iv) x+1/2, −y+1/2, −z+3/2; (v) x, −y+1/2, z; (vi) x−1/2, y, −z+3/2. |