The title compound, trisodium vanadium oxide trisulfide, has been synthesized by the reaction of the elements in an Li2O/Na2S flux at 723 K. The structure comprises isolated tetrahedral VOS33- anions separated by Na+ cations. The anion has symmetry m. Bond distances include V-O = 1.673 (2) Å, and V-S = 2.1746 (4) and 2.1971 (6) Å. Each Na+ cation is coordinated in a distorted octahedron by one O and five S atoms.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 153 K
- Mean (V-O) = 0.003 Å
- R factor = 0.017
- wR factor = 0.044
- Data-to-parameter ratio = 19.8
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.95
PLAT031_ALERT_4_B Refined Extinction Parameter within Range ...... 1.80 Sigma
Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio
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 28.79
From the CIF: _reflns_number_total 872
Count of symmetry unique reflns 507
Completeness (_total/calc) 171.99%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 365
Fraction of Friedel pairs measured 0.720
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
2 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
2 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
1 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: SHELXTL.
Trisodium vanadium oxide trisulfide
top
Crystal data top
Na3(VOS3) | F(000) = 448 |
Mr = 232.09 | Dx = 2.275 Mg m−3 |
Orthorhombic, Cmc21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2c -2 | Cell parameters from 3805 reflections |
a = 9.6673 (11) Å | θ = 2.7–28.8° |
b = 11.9122 (14) Å | µ = 2.47 mm−1 |
c = 5.8846 (7) Å | T = 153 K |
V = 677.66 (14) Å3 | Flat needle, red |
Z = 4 | 0.58 × 0.16 × 0.04 mm |
Data collection top
Bruker SMART-1000 CCD diffractometer | 872 independent reflections |
Radiation source: fine-focus sealed tube | 867 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
0.3° ω scans | θmax = 28.8°, θmin = 2.7° |
Absorption correction: integration (XPREP; Sheldrick, 2000) | h = −12→12 |
Tmin = 0.337, Tmax = 0.902 | k = −15→15 |
3902 measured reflections | l = −7→7 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.03P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.017 | (Δ/σ)max = 0.006 |
wR(F2) = 0.044 | Δρmax = 0.65 e Å−3 |
S = 1.15 | Δρmin = −0.37 e Å−3 |
872 reflections | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
44 parameters | Extinction coefficient: 0.0009 (5) |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.21 (2) |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Na1 | 1.0000 | 0.88164 (8) | 1.0000 | 0.0152 (2) | |
Na2 | 0.79336 (7) | 0.61995 (5) | 0.98035 (19) | 0.01556 (15) | |
V | 1.0000 | 0.70360 (2) | 0.5789 (2) | 0.00851 (10) | |
S1 | 1.0000 | 0.88180 (4) | 0.48267 (19) | 0.01130 (12) | |
S2 | 0.68988 (4) | 0.87609 (3) | 0.9639 (2) | 0.01272 (11) | |
O | 1.0000 | 0.69877 (12) | 0.8630 (4) | 0.0112 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Na1 | 0.0194 (5) | 0.0116 (4) | 0.0146 (5) | 0.000 | 0.000 | −0.0023 (3) |
Na2 | 0.0133 (3) | 0.0185 (3) | 0.0149 (3) | −0.0016 (2) | 0.0021 (3) | 0.0004 (3) |
V | 0.00835 (15) | 0.00893 (17) | 0.00826 (17) | 0.000 | 0.000 | 0.00038 (13) |
S1 | 0.0106 (2) | 0.0093 (2) | 0.0140 (2) | 0.000 | 0.000 | 0.00230 (18) |
S2 | 0.01136 (19) | 0.01397 (19) | 0.0128 (2) | −0.00304 (11) | 0.00159 (14) | 0.00061 (12) |
O | 0.0110 (7) | 0.0142 (9) | 0.0085 (8) | 0.000 | 0.000 | 0.0011 (5) |
Geometric parameters (Å, º) top
Na1—O | 2.3228 (19) | Na2—Na2iii | 3.9952 (14) |
Na1—S1i | 2.8198 (10) | Na2—Na1viii | 4.0042 (10) |
Na1—S1ii | 2.8403 (12) | Na2—Na1ix | 4.0144 (10) |
Na1—S2iii | 3.0063 (5) | V—O | 1.6726 (18) |
Na1—S2 | 3.0063 (5) | V—S2viii | 2.1746 (4) |
Na1—S1 | 3.0443 (12) | V—S2x | 2.1746 (4) |
Na1—V | 3.2616 (11) | V—S1 | 2.1971 (6) |
Na1—Na2 | 3.7042 (11) | V—Na2iii | 3.2501 (8) |
Na1—Na2iii | 3.7042 (11) | V—Na2x | 3.5774 (7) |
Na1—Na2iv | 4.0042 (10) | V—Na2viii | 3.5774 (7) |
Na1—Na2v | 4.0042 (10) | S1—Na1xi | 2.8198 (10) |
Na1—Na2vi | 4.0144 (10) | S1—Na2x | 2.8361 (7) |
Na2—O | 2.3128 (10) | S1—Na2viii | 2.8361 (8) |
Na2—S1v | 2.8361 (7) | S1—Na1xii | 2.8403 (12) |
Na2—S2v | 2.8504 (9) | S2—Vv | 2.1746 (4) |
Na2—S2vii | 2.9111 (7) | S2—Na2viii | 2.8504 (9) |
Na2—S2viii | 3.0439 (9) | S2—Na2xiii | 2.9111 (7) |
Na2—S2 | 3.2125 (7) | S2—Na2v | 3.0439 (9) |
Na2—V | 3.2501 (8) | O—Na2iii | 2.3128 (10) |
Na2—Vv | 3.5774 (7) | | |
| | | |
O—Na1—S1i | 157.62 (7) | O—Na2—Na2iii | 30.26 (4) |
O—Na1—S1ii | 110.35 (6) | S1v—Na2—Na2iii | 179.496 (17) |
S1i—Na1—S1ii | 92.03 (3) | S2v—Na2—Na2iii | 86.742 (16) |
O—Na1—S2iii | 87.411 (19) | S2vii—Na2—Na2iii | 86.810 (16) |
S1i—Na1—S2iii | 91.113 (19) | S2viii—Na2—Na2iii | 86.949 (15) |
S1ii—Na1—S2iii | 94.06 (2) | S2—Na2—Na2iii | 108.145 (13) |
O—Na1—S2 | 87.411 (19) | V—Na2—Na2iii | 52.075 (15) |
S1i—Na1—S2 | 91.113 (19) | Vv—Na2—Na2iii | 142.445 (11) |
S1ii—Na1—S2 | 94.06 (2) | Na1—Na2—Na2iii | 57.365 (14) |
S2iii—Na1—S2 | 171.51 (4) | O—Na2—Na1viii | 113.76 (4) |
O—Na1—S1 | 69.72 (5) | S1v—Na2—Na1viii | 45.18 (2) |
S1i—Na1—S1 | 87.89 (3) | S2v—Na2—Na1viii | 138.16 (3) |
S1ii—Na1—S1 | 179.93 (4) | S2vii—Na2—Na1viii | 90.64 (2) |
S2iii—Na1—S1 | 85.95 (2) | S2viii—Na2—Na1viii | 48.158 (16) |
S2—Na1—S1 | 85.95 (2) | S2—Na2—Na1viii | 76.27 (2) |
O—Na1—V | 29.13 (5) | V—Na2—Na1viii | 85.62 (2) |
S1i—Na1—V | 128.49 (4) | Vv—Na2—Na1viii | 63.63 (2) |
S1ii—Na1—V | 139.48 (4) | Na1—Na2—Na1viii | 114.08 (2) |
S2iii—Na1—V | 86.10 (2) | Na2iii—Na2—Na1viii | 135.094 (14) |
S2—Na1—V | 86.10 (2) | O—Na2—Na1ix | 154.94 (4) |
S1—Na1—V | 40.597 (18) | S1v—Na2—Na1ix | 44.620 (14) |
O—Na1—Na2 | 36.86 (2) | S2v—Na2—Na1ix | 91.32 (2) |
S1i—Na1—Na2 | 147.126 (14) | S2vii—Na2—Na1ix | 48.287 (17) |
S1ii—Na1—Na2 | 91.82 (3) | S2viii—Na2—Na1ix | 94.43 (2) |
S2iii—Na1—Na2 | 121.14 (3) | S2—Na2—Na1ix | 116.91 (2) |
S2—Na1—Na2 | 56.047 (15) | V—Na2—Na1ix | 132.22 (2) |
S1—Na1—Na2 | 88.24 (2) | Vv—Na2—Na1ix | 81.417 (19) |
V—Na1—Na2 | 55.184 (18) | Na1—Na2—Na1ix | 167.21 (3) |
O—Na1—Na2iii | 36.86 (2) | Na2iii—Na2—Na1ix | 134.948 (14) |
S1i—Na1—Na2iii | 147.126 (15) | Na1viii—Na2—Na1ix | 61.093 (19) |
S1ii—Na1—Na2iii | 91.82 (3) | O—V—S2viii | 107.23 (3) |
S2iii—Na1—Na2iii | 56.047 (15) | O—V—S2x | 107.23 (3) |
S2—Na1—Na2iii | 121.14 (3) | S2viii—V—S2x | 115.15 (2) |
S1—Na1—Na2iii | 88.24 (2) | O—V—S1 | 106.91 (5) |
V—Na1—Na2iii | 55.184 (18) | S2viii—V—S1 | 109.968 (17) |
Na2—Na1—Na2iii | 65.27 (3) | S2x—V—S1 | 109.968 (17) |
O—Na1—Na2iv | 103.92 (4) | O—V—Na2iii | 42.53 (3) |
S1i—Na1—Na2iv | 91.73 (2) | S2viii—V—Na2iii | 127.68 (2) |
S1ii—Na1—Na2iv | 45.096 (15) | S2x—V—Na2iii | 64.763 (17) |
S2iii—Na1—Na2iv | 48.966 (17) | S1—V—Na2iii | 118.920 (19) |
S2—Na1—Na2iv | 139.12 (3) | O—V—Na2 | 42.53 (3) |
S1—Na1—Na2iv | 134.905 (15) | S2viii—V—Na2 | 64.763 (17) |
V—Na1—Na2iv | 122.223 (19) | S2x—V—Na2 | 127.68 (2) |
Na2—Na1—Na2iv | 113.58 (3) | S1—V—Na2 | 118.920 (19) |
Na2iii—Na1—Na2iv | 68.659 (16) | Na2iii—V—Na2 | 75.85 (3) |
O—Na1—Na2v | 103.92 (4) | O—V—Na1 | 42.53 (6) |
S1i—Na1—Na2v | 91.74 (2) | S2viii—V—Na1 | 121.357 (14) |
S1ii—Na1—Na2v | 45.096 (15) | S2x—V—Na1 | 121.357 (14) |
S2iii—Na1—Na2v | 139.12 (3) | S1—V—Na1 | 64.38 (2) |
S2—Na1—Na2v | 48.966 (17) | Na2iii—V—Na1 | 69.34 (2) |
S1—Na1—Na2v | 134.905 (15) | Na2—V—Na1 | 69.34 (2) |
V—Na1—Na2v | 122.223 (19) | O—V—Na2x | 100.50 (3) |
Na2—Na1—Na2v | 68.659 (16) | S2viii—V—Na2x | 151.07 (2) |
Na2iii—Na1—Na2v | 113.58 (3) | S2x—V—Na2x | 62.407 (16) |
Na2iv—Na1—Na2v | 90.19 (3) | S1—V—Na2x | 52.447 (11) |
O—Na1—Na2vi | 130.78 (3) | Na2iii—V—Na2x | 79.089 (15) |
S1i—Na1—Na2vi | 44.949 (14) | Na2—V—Na2x | 141.74 (3) |
S1ii—Na1—Na2vi | 91.62 (2) | Na1—V—Na2x | 74.996 (16) |
S2iii—Na1—Na2vi | 46.290 (14) | O—V—Na2viii | 100.50 (3) |
S2—Na1—Na2vi | 135.89 (3) | S2viii—V—Na2viii | 62.407 (16) |
S1—Na1—Na2vi | 88.32 (2) | S2x—V—Na2viii | 151.07 (2) |
V—Na1—Na2vi | 115.97 (2) | S1—V—Na2viii | 52.447 (11) |
Na2—Na1—Na2vi | 167.21 (3) | Na2iii—V—Na2viii | 141.74 (3) |
Na2iii—Na1—Na2vi | 102.311 (9) | Na2—V—Na2viii | 79.089 (15) |
Na2iv—Na1—Na2vi | 61.531 (16) | Na1—V—Na2viii | 74.996 (16) |
Na2v—Na1—Na2vi | 121.60 (3) | Na2x—V—Na2viii | 104.89 (2) |
O—Na2—S1v | 150.24 (4) | V—S1—Na1xi | 162.99 (3) |
O—Na2—S2v | 104.02 (5) | V—S1—Na2x | 89.663 (16) |
S1v—Na2—S2v | 92.99 (2) | Na1xi—S1—Na2x | 90.432 (15) |
O—Na2—S2vii | 110.31 (4) | V—S1—Na2viii | 89.663 (16) |
S1v—Na2—S2vii | 92.78 (2) | Na1xi—S1—Na2viii | 90.432 (15) |
S2v—Na2—S2vii | 92.67 (2) | Na2x—S1—Na2viii | 178.99 (3) |
O—Na2—S2viii | 69.49 (5) | V—S1—Na1xii | 104.90 (3) |
S1v—Na2—S2viii | 93.33 (2) | Na1xi—S1—Na1xii | 92.11 (3) |
S2v—Na2—S2viii | 173.43 (3) | Na2x—S1—Na1xii | 89.725 (18) |
S2vii—Na2—S2viii | 88.81 (2) | Na2viii—S1—Na1xii | 89.725 (18) |
O—Na2—S2 | 82.78 (4) | V—S1—Na1 | 75.02 (3) |
S1v—Na2—S2 | 72.286 (19) | Na1xi—S1—Na1 | 87.96 (3) |
S2v—Na2—S2 | 91.84 (2) | Na2x—S1—Na1 | 90.275 (18) |
S2vii—Na2—S2 | 164.61 (3) | Na2viii—S1—Na1 | 90.275 (18) |
S2viii—Na2—S2 | 88.38 (2) | Na1xii—S1—Na1 | 179.93 (4) |
O—Na2—V | 29.27 (4) | Vv—S2—Na2viii | 111.47 (2) |
S1v—Na2—V | 128.34 (3) | Vv—S2—Na2xiii | 118.18 (2) |
S2v—Na2—V | 133.28 (3) | Na2viii—S2—Na2xiii | 90.78 (2) |
S2vii—Na2—V | 104.33 (2) | Vv—S2—Na1 | 146.04 (3) |
S2viii—Na2—V | 40.257 (14) | Na2viii—S2—Na1 | 90.78 (3) |
S2—Na2—V | 83.010 (16) | Na2xiii—S2—Na1 | 85.42 (2) |
O—Na2—Vv | 119.64 (4) | Vv—S2—Na2v | 74.980 (19) |
S1v—Na2—Vv | 37.890 (14) | Na2viii—S2—Na2v | 173.43 (3) |
S2v—Na2—Vv | 82.73 (2) | Na2xiii—S2—Na2v | 87.04 (2) |
S2vii—Na2—Vv | 129.48 (2) | Na1—S2—Na2v | 82.88 (3) |
S2viii—Na2—Vv | 101.24 (2) | Vv—S2—Na2 | 80.728 (18) |
S2—Na2—Vv | 36.865 (11) | Na2viii—S2—Na2 | 91.61 (2) |
V—Na2—Vv | 115.15 (2) | Na2xiii—S2—Na2 | 158.350 (15) |
O—Na2—Na1 | 37.05 (4) | Na1—S2—Na2 | 73.03 (2) |
S1v—Na2—Na1 | 123.05 (2) | Na2v—S2—Na2 | 88.17 (2) |
S2v—Na2—Na1 | 85.66 (2) | V—O—Na2iii | 108.20 (5) |
S2vii—Na2—Na1 | 144.17 (3) | V—O—Na2 | 108.20 (5) |
S2viii—Na2—Na1 | 89.39 (2) | Na2iii—O—Na2 | 119.47 (7) |
S2—Na2—Na1 | 50.919 (15) | V—O—Na1 | 108.34 (8) |
V—Na2—Na1 | 55.475 (19) | Na2iii—O—Na1 | 106.09 (5) |
Vv—Na2—Na1 | 85.872 (18) | Na2—O—Na1 | 106.09 (5) |
Symmetry codes: (i) −x+2, −y+2, z+1/2; (ii) x, y, z+1; (iii) −x+2, y, z; (iv) x+1/2, −y+3/2, z+1/2; (v) −x+3/2, −y+3/2, z+1/2; (vi) x+1/2, y+1/2, z; (vii) −x+3/2, y−1/2, z; (viii) −x+3/2, −y+3/2, z−1/2; (ix) x−1/2, y−1/2, z; (x) x+1/2, −y+3/2, z−1/2; (xi) −x+2, −y+2, z−1/2; (xii) x, y, z−1; (xiii) −x+3/2, y+1/2, z. |