The quaternary vanadium thiophosphate CsVP2S7 (caesium vanadium diphosphorus heptasulfide) was synthesized by reacting a mixture of Cs2S3, V, P4S3 and S. The crystal structure is composed of VS6 octahedra, which are linked by bitetrahedral [P2S7] groups to form two-dimensional anionic [VP2S7]- layers. The layers are stacked perpendicular to the crystallographic c axis and are separated by the Cs+ ions. The VS6 octahedra, the [P2S7] groups and the Cs+ ions are located in special positions. CsVP2S7 is isostructural to KVP2S7 and RbVP2S7.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (S-P) = 0.004 Å
- R factor = 0.046
- wR factor = 0.100
- Data-to-parameter ratio = 23.2
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT035_ALERT_1_A No _chemical_absolute_configuration info given . ?
| Author Response: The compound is not chiral. Therefore, only the absolute
structure
is needed. This was determined and is in agreement with the selected
setting.
|
Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.37
PLAT199_ALERT_1_C Check the Reported cell_measurement_temperature 293
PLAT200_ALERT_1_C Check the Reported cell_ambient_temperature .... 293
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 27.03
From the CIF: _reflns_number_total 1205
Count of symmetry unique reflns 638
Completeness (_total/calc) 188.87%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 567
Fraction of Friedel pairs measured 0.889
Are heavy atom types Z>Si present yes
1 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
3 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: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: CIFTAB in SHELXTL (Bruker, 1998).
Caesium vanadium diphosphorus heptasulfide
top
Crystal data top
CsVP2S7 | F(000) = 440 |
Mr = 470.21 | Dx = 2.864 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 68 reflections |
a = 8.6010 (17) Å | θ = 10–15° |
b = 9.5176 (19) Å | µ = 5.77 mm−1 |
c = 6.7287 (13) Å | T = 293 K |
β = 98.17 (3)° | Plate, green |
V = 545.23 (19) Å3 | 0.15 × 0.05 × 0.05 mm |
Z = 2 | |
Data collection top
Philips PW1100 4-circle- diffractometer | 979 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.044 |
Graphite monochromator | θmax = 27.0°, θmin = 3.1° |
ω/θ scans | h = 0→10 |
Absorption correction: numerical X-SHAPE and X-RED (Stoe & Cie, 1998) | k = −12→12 |
Tmin = 0.701, Tmax = 0.738 | l = −8→8 |
1280 measured reflections | 3 standard reflections every 120 min |
1205 independent reflections | intensity decay: none |
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) + (0.0566P)2P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.100 | (Δ/σ)max < 0.001 |
S = 1.01 | Δρmax = 1.49 e Å−3 |
1205 reflections | Δρmin = −0.63 e Å−3 |
52 parameters | Absolute structure: Flack (1983) |
1 restraint | Absolute structure parameter: −0.03 (4) |
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 | |
P1 | 0.3030 (3) | 0.6425 (3) | 0.4194 (4) | 0.0169 (5) | |
S1 | 0.1582 (2) | 0.5244 (3) | 0.2257 (3) | 0.0214 (6) | |
S2 | 0.1928 (3) | 0.6633 (3) | 0.6648 (4) | 0.0235 (6) | |
S3 | 0.3703 (3) | 0.8139 (3) | 0.2801 (4) | 0.0252 (6) | |
S4 | 0.5000 | 0.5068 (4) | 0.5000 | 0.0175 (7) | |
V1 | 0.0000 | 0.4975 (2) | 0.5000 | 0.0167 (5) | |
Cs1 | 0.5000 | 0.39532 (12) | 0.0000 | 0.0370 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0134 (11) | 0.0173 (14) | 0.0202 (11) | −0.0010 (9) | 0.0027 (9) | 0.0009 (10) |
S1 | 0.0153 (11) | 0.0275 (15) | 0.0214 (12) | −0.0070 (11) | 0.0023 (9) | −0.0025 (11) |
S2 | 0.0214 (12) | 0.0228 (15) | 0.0284 (12) | −0.0062 (10) | 0.0109 (10) | −0.0090 (11) |
S3 | 0.0254 (13) | 0.0223 (14) | 0.0255 (13) | −0.0077 (11) | −0.0044 (10) | 0.0067 (11) |
S4 | 0.0171 (15) | 0.0133 (18) | 0.0219 (16) | 0.000 | 0.0015 (11) | 0.000 |
V1 | 0.0134 (10) | 0.0162 (13) | 0.0211 (11) | 0.000 | 0.0048 (8) | 0.000 |
Cs1 | 0.0264 (5) | 0.0629 (8) | 0.0216 (5) | 0.000 | 0.0029 (4) | 0.000 |
Geometric parameters (Å, º) top
P1—S3 | 2.008 (4) | S4—Cs1iii | 3.5277 (13) |
P1—S1 | 2.013 (3) | V1—S2vi | 2.439 (3) |
P1—S2 | 2.027 (4) | V1—S3vii | 2.453 (3) |
P1—S4 | 2.138 (3) | V1—S3viii | 2.453 (3) |
P1—Cs1 | 4.211 (3) | V1—S1vi | 2.457 (2) |
S1—V1 | 2.457 (2) | Cs1—S4ix | 3.5277 (13) |
S1—Cs1 | 3.705 (2) | Cs1—S3x | 3.548 (3) |
S1—Cs1i | 4.004 (3) | Cs1—S3xi | 3.548 (3) |
S2—V1 | 2.439 (3) | Cs1—S1xii | 3.705 (2) |
S2—Cs1ii | 3.711 (3) | Cs1—S2xiii | 3.711 (3) |
S2—Cs1iii | 4.108 (3) | Cs1—S2viii | 3.711 (3) |
S3—V1iv | 2.453 (3) | Cs1—S1x | 4.004 (3) |
S3—Cs1i | 3.548 (3) | Cs1—S1xi | 4.004 (3) |
S4—P1v | 2.138 (3) | Cs1—S2v | 4.108 (3) |
S4—Cs1 | 3.5277 (13) | Cs1—S2ix | 4.108 (3) |
| | | |
S3—P1—S1 | 110.13 (15) | S4—Cs1—S1 | 53.26 (4) |
S3—P1—S2 | 120.02 (16) | S4ix—Cs1—S1 | 113.50 (5) |
S1—P1—S2 | 105.32 (14) | S3x—Cs1—S1 | 65.52 (6) |
S3—P1—S4 | 109.79 (15) | S3xi—Cs1—S1 | 124.00 (6) |
S1—P1—S4 | 102.84 (15) | S1xii—Cs1—S1 | 141.26 (9) |
S2—P1—S4 | 107.33 (14) | S4—Cs1—S2xiii | 144.98 (6) |
S3—P1—Cs1 | 88.33 (12) | S4ix—Cs1—S2xiii | 62.54 (6) |
S1—P1—Cs1 | 61.64 (9) | S3x—Cs1—S2xiii | 89.55 (6) |
S2—P1—Cs1 | 151.62 (12) | S3xi—Cs1—S2xiii | 75.41 (6) |
S4—P1—Cs1 | 56.81 (6) | S1xii—Cs1—S2xiii | 59.95 (6) |
P1—S1—V1 | 85.96 (11) | S1—Cs1—S2xiii | 153.56 (6) |
P1—S1—Cs1 | 89.81 (10) | S4—Cs1—S2viii | 62.54 (6) |
V1—S1—Cs1 | 146.05 (10) | S4ix—Cs1—S2viii | 144.98 (6) |
P1—S1—Cs1i | 84.21 (11) | S3x—Cs1—S2viii | 75.41 (6) |
V1—S1—Cs1i | 100.51 (9) | S3xi—Cs1—S2viii | 89.55 (6) |
Cs1—S1—Cs1i | 112.55 (6) | S1xii—Cs1—S2viii | 153.56 (6) |
P1—S2—V1 | 86.14 (12) | S1—Cs1—S2viii | 59.95 (6) |
P1—S2—Cs1ii | 148.66 (13) | S2xiii—Cs1—S2viii | 106.97 (9) |
V1—S2—Cs1ii | 109.13 (8) | S4—Cs1—S1x | 125.51 (7) |
P1—S2—Cs1iii | 92.75 (11) | S4ix—Cs1—S1x | 87.10 (6) |
V1—S2—Cs1iii | 100.99 (9) | S3x—Cs1—S1x | 51.32 (5) |
Cs1ii—S2—Cs1iii | 110.11 (7) | S3xi—Cs1—S1x | 103.88 (6) |
P1—S3—V1iv | 115.70 (13) | S1xii—Cs1—S1x | 112.55 (6) |
P1—S3—Cs1i | 97.41 (11) | S1—Cs1—S1x | 101.61 (4) |
V1iv—S3—Cs1i | 117.51 (10) | S2xiii—Cs1—S1x | 53.27 (5) |
P1v—S4—P1 | 105.7 (2) | S2viii—Cs1—S1x | 63.18 (6) |
P1v—S4—Cs1 | 108.42 (7) | S4—Cs1—S1xi | 87.10 (6) |
P1—S4—Cs1 | 92.71 (7) | S4ix—Cs1—S1xi | 125.51 (7) |
P1v—S4—Cs1iii | 92.71 (7) | S3x—Cs1—S1xi | 103.88 (6) |
P1—S4—Cs1iii | 108.42 (7) | S3xi—Cs1—S1xi | 51.32 (5) |
Cs1—S4—Cs1iii | 144.99 (12) | S1xii—Cs1—S1xi | 101.61 (4) |
S2—V1—S2vi | 99.35 (16) | S1—Cs1—S1xi | 112.55 (6) |
S2—V1—S3vii | 163.10 (9) | S2xiii—Cs1—S1xi | 63.18 (6) |
S2vi—V1—S3vii | 87.99 (9) | S2viii—Cs1—S1xi | 53.27 (5) |
S2—V1—S3viii | 87.99 (9) | S1x—Cs1—S1xi | 56.32 (7) |
S2vi—V1—S3viii | 163.10 (9) | S4—Cs1—S2v | 51.46 (5) |
S3vii—V1—S3viii | 89.17 (14) | S4ix—Cs1—S2v | 104.46 (6) |
S2—V1—S1 | 82.00 (9) | S3x—Cs1—S2v | 152.36 (6) |
S2vi—V1—S1 | 90.23 (9) | S3xi—Cs1—S2v | 52.07 (6) |
S3vii—V1—S1 | 82.78 (9) | S1xii—Cs1—S2v | 62.18 (5) |
S3viii—V1—S1 | 105.93 (10) | S1—Cs1—S2v | 93.15 (5) |
S2—V1—S1vi | 90.23 (9) | S2xiii—Cs1—S2v | 113.26 (3) |
S2vi—V1—S1vi | 82.00 (9) | S2viii—Cs1—S2v | 110.11 (7) |
S3vii—V1—S1vi | 105.93 (10) | S1x—Cs1—S2v | 155.91 (5) |
S3viii—V1—S1vi | 82.78 (9) | S1xi—Cs1—S2v | 100.47 (5) |
S1—V1—S1vi | 168.01 (17) | S4—Cs1—S2ix | 104.46 (6) |
S4—Cs1—S4ix | 144.99 (12) | S4ix—Cs1—S2ix | 51.46 (5) |
S4—Cs1—S3x | 116.79 (5) | S3x—Cs1—S2ix | 52.07 (6) |
S4ix—Cs1—S3x | 71.38 (5) | S3xi—Cs1—S2ix | 152.36 (6) |
S4—Cs1—S3xi | 71.38 (5) | S1xii—Cs1—S2ix | 93.15 (5) |
S4ix—Cs1—S3xi | 116.79 (5) | S1—Cs1—S2ix | 62.18 (5) |
S3x—Cs1—S3xi | 154.77 (9) | S2xiii—Cs1—S2ix | 110.11 (7) |
S4—Cs1—S1xii | 113.50 (5) | S2viii—Cs1—S2ix | 113.26 (3) |
S4ix—Cs1—S1xii | 53.26 (4) | S1x—Cs1—S2ix | 100.47 (5) |
S3x—Cs1—S1xii | 124.00 (6) | S1xi—Cs1—S2ix | 155.91 (5) |
S3xi—Cs1—S1xii | 65.52 (6) | S2v—Cs1—S2ix | 103.25 (8) |
Symmetry codes: (i) x−1/2, y+1/2, z; (ii) x−1/2, y+1/2, z+1; (iii) x, y, z+1; (iv) x+1/2, y+1/2, z; (v) −x+1, y, −z+1; (vi) −x, y, −z+1; (vii) x−1/2, y−1/2, z; (viii) −x+1/2, y−1/2, −z+1; (ix) x, y, z−1; (x) −x+1/2, y−1/2, −z; (xi) x+1/2, y−1/2, z; (xii) −x+1, y, −z; (xiii) x+1/2, y−1/2, z−1. |