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A detailed synchrotron X-ray diffraction (XRD) study performed with a single crystal of BaVS3 (barium vanadium trisulfide) in the temperature range between 10 and 295 K is reported. Aside from the known tetragonal–orthorhombic (240 K) and orthorhombic–monoclinic (69 K) phase transitions, in the 130 < T ≤ 295 K range the overall structure can be viewed as a host–guest (H–G) composite. The BaS3 matrix is the host, while the V-chains form the guest. The two subsystems lock in at TLOCK = 130 ± 20 K. This temperature is marked by a symmetry change from orthorhombic to monoclinic. This results in the formation of twins, implying a structural phase transition identified here for the first time. From the refined structural data, it is possible to follow, starting already at 295 K downwards, the stepwise transformation of VS6 octahedra into VS5 tetragonal pyramids as the origin of the structure evolution. The new findings will yield a better understanding of the complex electronic phase diagram of BaVS3.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520620016108/dk5104sup1.cif
Contains datablocks global, I, II, III, IV, V, VI, VII, VIII, IX, X

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520620016108/dk5104Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520620016108/dk5104IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520620016108/dk5104IIIsup4.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520620016108/dk5104IVsup5.hkl
Contains datablock IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520620016108/dk5104Vsup6.hkl
Contains datablock V

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520620016108/dk5104VIsup7.hkl
Contains datablock VI

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520620016108/dk5104VIIsup8.hkl
Contains datablock VII

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520620016108/dk5104VIIIsup9.hkl
Contains datablock VIII

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520620016108/dk5104IXsup10.hkl
Contains datablock IX

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520620016108/dk5104Xsup11.hkl
Contains datablock X

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052520620016108/dk5104sup12.pdf
Supporting information

CCDC references: 2049661; 2049662; 2049663; 2049664; 2049665; 2049666; 2049667; 2049668; 2049669; 2049670

Computing details top

For all structures, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to refine structure: JANA2006 (Petčíček et al., 2014).

(I) top
Crystal data top
BaVS3F(000) = 1016
Mr = 284.5Dx = 4.359 Mg m3
Monoclinic, ImSynchrotron radiation, λ = 0.70814 Å
Hall symbol: I -2yCell parameters from 4005 reflections
a = 11.456 (1) Åθ = 2.5–28.4°
b = 6.764 (1) ŵ = 12.18 mm1
c = 11.188 (1) ÅT = 10 K
β = 90.048 (9)°Irregular, grey
V = 866.94 (9) Å30.05 × 0.03 × 0.02 mm
Z = 8
Data collection top
Dectris-CrysAlisPro-abstract goniometer imported dectris images
diffractometer
1186 reflections with I > 3σ(I)
Radiation source: synchrotronRint = 0.030
Synchrotron monochromatorθmax = 28.4°, θmin = 2.5°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
h = 1515
Tmin = 0.671, Tmax = 1.000k = 88
4005 measured reflectionsl = 1111
1187 independent reflections
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
R[F > 3σ(F)] = 0.016(Δ/σ)max = 0.028
wR(F) = 0.027Δρmax = 0.37 e Å3
S = 1.16Δρmin = 0.42 e Å3
1187 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
110 parametersExtinction coefficient: 70 (30)
0 restraintsAbsolute structure: 587 of Friedel pairs used in the refinement
0 constraintsAbsolute structure parameter: 0.097 (19)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba10.33648600.1236030.0108 (3)
Ba20.33423 (6)00.37488 (10)0.0121 (4)
Ba30.34143 (4)00.62323 (4)0.0114 (3)
Ba40.33819 (7)00.86942 (10)0.0099 (2)
V20.0250 (3)00.23737 (18)0.0070 (6)
V30.0235 (3)00.4968 (2)0.0125 (7)
V10.0235 (3)00.73899 (19)0.0078 (6)
V40.0234 (3)00.9872 (2)0.0100 (5)
S10.8264 (7)00.1185 (6)0.0132 (11)
S20.8301 (8)00.3752 (6)0.0122 (10)
S30.8276 (7)00.6207 (6)0.0129 (10)
S40.8297 (8)00.8658 (6)0.0142 (11)
S50.0814 (7)0.2429 (5)0.1271 (5)0.0111 (7)
S60.0859 (7)0.2440 (5)0.3793 (5)0.0107 (7)
S70.0801 (7)0.2463 (5)0.6282 (5)0.0108 (8)
S80.0848 (7)0.2451 (5)0.8773 (5)0.0103 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.0071 (6)0.0193 (3)0.0060 (5)00.0029 (5)0
Ba20.0075 (7)0.0193 (3)0.0095 (8)00.0010 (6)0
Ba30.0090 (8)0.0193 (3)0.0058 (5)00.0018 (5)0
Ba40.0055 (5)0.0196 (3)0.0048 (5)00.0036 (4)0
V20.0015 (11)0.0151 (4)0.0043 (14)00.0018 (10)0
V30.0048 (12)0.0234 (5)0.0094 (15)00.0001 (9)0
V10.0027 (11)0.0125 (4)0.0080 (15)00.0015 (10)0
V40.0049 (12)0.0217 (4)0.0034 (10)00.0032 (12)0
S10.004 (2)0.0210 (11)0.0149 (19)00.0058 (13)0
S20.012 (2)0.0174 (9)0.0072 (15)00.0019 (14)0
S30.002 (2)0.0225 (11)0.0141 (18)00.0030 (13)0
S40.017 (3)0.0154 (8)0.0100 (17)00.0051 (15)0
S50.0058 (18)0.0203 (8)0.0072 (9)0.0045 (8)0.0030 (14)0.0008 (10)
S60.0069 (17)0.0166 (7)0.0087 (11)0.0044 (8)0.0061 (14)0.0015 (8)
S70.0046 (19)0.0198 (7)0.0080 (10)0.0030 (8)0.0030 (14)0.0006 (10)
S80.0090 (17)0.0158 (7)0.0062 (9)0.0027 (8)0.0046 (14)0.0016 (8)
Geometric parameters (Å, º) top
Ba1—S2i3.403 (8)V3—S62.453 (6)
Ba1—S3ii3.3837 (3)V3—S6v2.453 (6)
Ba1—S3iii3.3837 (3)V3—S72.314 (5)
Ba1—S4iv3.454 (7)V3—S7v2.314 (5)
Ba1—S53.353 (7)V1—V42.828 (3)
Ba1—S5v3.353 (7)V1—S3x2.158 (8)
Ba1—S6vi3.356 (6)V1—S4i2.635 (9)
Ba1—S6vii3.356 (6)V1—S72.392 (6)
Ba1—S7viii3.277 (7)V1—S7v2.392 (6)
Ba1—S7ix3.277 (7)V1—S82.374 (5)
Ba1—S8vi3.441 (6)V1—S8v2.374 (5)
Ba1—S8vii3.441 (6)V4—S1xx2.695 (8)
Ba2—S1x3.409 (7)V4—S4i2.163 (9)
Ba2—S3x3.315 (7)V4—S5xxiii2.364 (5)
Ba2—S4viii3.3839 (2)V4—S5xxiv2.364 (5)
Ba2—S4vi3.3839 (2)V4—S82.407 (6)
Ba2—S5xi3.454 (6)V4—S8v2.407 (6)
Ba2—S5xii3.454 (6)S1—S5i3.353 (10)
Ba2—S63.289 (7)S1—S5xxv3.353 (10)
Ba2—S6v3.289 (7)S1—S6i3.499 (8)
Ba2—S7ii3.394 (6)S1—S6xxv3.499 (8)
Ba2—S7xiii3.394 (6)S1—S7viii3.304 (10)
Ba2—S8iii3.349 (7)S1—S7ix3.304 (10)
Ba2—S8xiv3.349 (7)S1—S8iv3.327 (8)
Ba3—S1xi3.3868 (4)S1—S8xxvi3.327 (8)
Ba3—S1xv3.3868 (4)S2—S5x3.381 (8)
Ba3—S2i3.399 (8)S2—S5xxvii3.381 (8)
Ba3—S4i3.349 (8)S2—S6x3.363 (11)
Ba3—S5xvi3.253 (7)S2—S6xxvii3.363 (11)
Ba3—S5xvii3.253 (7)S2—S7x3.442 (8)
Ba3—S6xviii3.449 (6)S2—S7xxvii3.442 (8)
Ba3—S6xix3.449 (6)S2—S8iii3.297 (11)
Ba3—S73.426 (7)S2—S8xiv3.297 (11)
Ba3—S7v3.426 (7)S3—S5xvi3.315 (10)
Ba3—S8vi3.356 (6)S3—S5xvii3.315 (10)
Ba3—S8vii3.356 (6)S3—S6i3.317 (8)
Ba4—S1xx3.364 (7)S3—S6xxv3.317 (8)
Ba4—S2xvi3.3839 (3)S3—S7i3.339 (10)
Ba4—S2xviii3.3839 (3)S3—S7xxv3.339 (10)
Ba4—S3x3.371 (7)S3—S8i3.464 (8)
Ba4—S5xi3.349 (6)S3—S8xxv3.464 (8)
Ba4—S5xii3.349 (6)S4—S6xv3.290 (11)
Ba4—S6xv3.326 (7)S4—S6xxi3.290 (11)
Ba4—S6xxi3.326 (7)S4—S7x3.303 (8)
Ba4—S7xi3.494 (6)S4—S7xxvii3.303 (8)
Ba4—S7xii3.494 (6)S4—S8x3.363 (11)
Ba4—S83.344 (7)S4—S8xxvii3.363 (11)
Ba4—S8v3.344 (7)S5—S5v3.286 (5)
V2—V32.955 (3)S5—S5xxviii3.478 (5)
V2—V4xxii2.854 (3)S5—S6v3.412 (9)
V2—S1x2.159 (8)S5—S8xxix3.380 (9)
V2—S2i2.713 (9)S6—S6xxx3.464 (4)
V2—S52.389 (6)S6—S6v3.300 (4)
V2—S5v2.389 (6)S6—S7v3.371 (9)
V2—S62.394 (5)S7—S7v3.331 (5)
V2—S6v2.394 (5)S7—S7xxviii3.433 (5)
V3—V12.763 (3)S7—S8v3.369 (9)
V3—S2i2.161 (9)S8—S8xxx3.448 (4)
V3—S3x2.638 (8)S8—S8v3.316 (4)
V3—V2—V4xxii157.96 (16)V3—V1—V4157.80 (16)
S1x—V2—S2i176.6 (3)S3x—V1—S4i174.8 (3)
S1x—V2—S594.8 (2)S3x—V1—S794.3 (2)
S1x—V2—S5v94.8 (2)S3x—V1—S7v94.3 (2)
S1x—V2—S6100.3 (3)S3x—V1—S899.6 (3)
S1x—V2—S6v100.3 (3)S3x—V1—S8v99.6 (3)
S2i—V2—S582.7 (2)S4i—V1—S782.0 (2)
S2i—V2—S5v82.7 (2)S4i—V1—S7v82.0 (2)
S2i—V2—S682.1 (2)S4i—V1—S884.2 (2)
S2i—V2—S6v82.1 (2)S4i—V1—S8v84.2 (2)
S5—V2—S5v86.9 (2)S7—V1—S7v88.3 (2)
S5—V2—S6164.9 (3)S7—V1—S8166.2 (3)
S5—V2—S6v90.99 (18)S7—V1—S8v89.93 (18)
S5v—V2—S690.99 (18)S7v—V1—S889.93 (18)
S5v—V2—S6v164.9 (3)S7v—V1—S8v166.2 (3)
S6—V2—S6v87.13 (18)S8—V1—S8v88.57 (19)
V2—V3—V1157.94 (16)V2xxiii—V4—V1157.82 (16)
S2i—V3—S3x172.7 (3)S1xx—V4—S4i174.2 (3)
S2i—V3—S693.4 (2)S1xx—V4—S5xxiii82.7 (2)
S2i—V3—S6v93.4 (2)S1xx—V4—S5xxiv82.7 (2)
S2i—V3—S7100.5 (3)S1xx—V4—S881.2 (2)
S2i—V3—S7v100.5 (3)S1xx—V4—S8v81.2 (2)
S3x—V3—S681.2 (2)S4i—V4—S5xxiii101.4 (3)
S3x—V3—S6v81.2 (2)S4i—V4—S5xxiv101.4 (3)
S3x—V3—S784.5 (2)S4i—V4—S894.6 (2)
S3x—V3—S7v84.5 (2)S4i—V4—S8v94.6 (2)
S6—V3—S6v84.5 (2)S5xxiii—V4—S5xxiv88.04 (19)
S6—V3—S7165.4 (3)S5xxiii—V4—S8163.9 (3)
S6—V3—S7v89.95 (18)S5xxiii—V4—S8v90.21 (18)
S6v—V3—S789.95 (18)S5xxiv—V4—S890.21 (18)
S6v—V3—S7v165.4 (3)S5xxiv—V4—S8v163.9 (3)
S7—V3—S7v92.1 (2)S8—V4—S8v87.1 (2)
Symmetry codes: (i) x+1, y, z; (ii) x1/2, y1/2, z1/2; (iii) x1/2, y+1/2, z1/2; (iv) x+1, y, z1; (v) x, y, z; (vi) x+1/2, y+1/2, z1/2; (vii) x+1/2, y1/2, z1/2; (viii) x+1/2, y1/2, z1/2; (ix) x+1/2, y+1/2, z1/2; (x) x1, y, z; (xi) x1/2, y1/2, z+1/2; (xii) x1/2, y+1/2, z+1/2; (xiii) x1/2, y+1/2, z1/2; (xiv) x1/2, y1/2, z1/2; (xv) x1/2, y+1/2, z+1/2; (xvi) x+1/2, y1/2, z+1/2; (xvii) x+1/2, y+1/2, z+1/2; (xviii) x+1/2, y+1/2, z+1/2; (xix) x+1/2, y1/2, z+1/2; (xx) x1, y, z+1; (xxi) x1/2, y1/2, z+1/2; (xxii) x, y, z1; (xxiii) x, y, z+1; (xxiv) x, y, z+1; (xxv) x+1, y, z; (xxvi) x+1, y, z1; (xxvii) x1, y, z; (xxviii) x, y+1, z; (xxix) x, y, z1; (xxx) x, y1, z.
(II) top
Crystal data top
BaVS3F(000) = 1016
Mr = 284.5Dx = 4.357 Mg m3
Monoclinic, ImSynchrotron radiation, λ = 0.70814 Å
Hall symbol: I -2yCell parameters from 4010 reflections
a = 11.458 (1) Åθ = 2.5–28.4°
b = 6.764 (1) ŵ = 12.18 mm1
c = 11.190 (1) ÅT = 40 K
β = 90.045 (1)°Irregular, grey
V = 867.25 (9) Å30.05 × 0.03 × 0.02 mm
Z = 8
Data collection top
Dectris-CrysAlisPro-abstract goniometer imported dectris images
diffractometer
1185 reflections with I > 2σ(I)
Radiation source: synchrotronRint = 0.031
Synchrotron monochromatorθmax = 28.4°, θmin = 2.5°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
h = 1515
Tmin = 0.632, Tmax = 1.000k = 88
4010 measured reflectionsl = 1111
1185 independent reflections
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
R[F > 3σ(F)] = 0.027(Δ/σ)max = 0.043
wR(F) = 0.036Δρmax = 0.87 e Å3
S = 1.45Δρmin = 1.07 e Å3
1185 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
110 parametersExtinction coefficient: 60 (40)
0 restraintsAbsolute structure: 586 of Friedel pairs used in the refinement
0 constraintsAbsolute structure parameter: 0.11 (2)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba10.33648600.1236030.0113 (3)
Ba20.33472 (7)00.37543 (11)0.0136 (4)
Ba30.34085 (5)00.62344 (5)0.0130 (3)
Ba40.33846 (8)00.87039 (11)0.0121 (3)
V20.0272 (4)00.2392 (2)0.0110 (8)
V30.0216 (4)00.4975 (3)0.0118 (8)
V10.0257 (4)00.7411 (3)0.0125 (8)
V40.0214 (4)00.9889 (3)0.0123 (8)
S10.8283 (7)00.1184 (8)0.0185 (10)
S20.8285 (8)00.3773 (7)0.0131 (9)
S30.8293 (7)00.6210 (8)0.0179 (9)
S40.8285 (8)00.8692 (8)0.0183 (12)
S50.0884 (9)0.2413 (6)0.1295 (6)0.0122 (9)
S60.0785 (8)0.2433 (5)0.3789 (6)0.0100 (9)
S70.0874 (9)0.2457 (7)0.6304 (7)0.0122 (9)
S80.0775 (8)0.2456 (5)0.8771 (6)0.0099 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.0040 (6)0.0224 (4)0.0074 (4)00.0029 (4)0
Ba20.0091 (9)0.0224 (4)0.0092 (8)00.0006 (5)0
Ba30.0091 (8)0.0231 (4)0.0067 (4)00.0033 (5)0
Ba40.0047 (7)0.0225 (4)0.0091 (5)00.0039 (4)0
V20.0047 (17)0.0216 (10)0.0066 (14)00.0005 (14)0
V30.0044 (17)0.0244 (10)0.0066 (12)00.0039 (13)0
V10.0069 (18)0.0219 (10)0.0085 (14)00.0013 (15)0
V40.0045 (17)0.0240 (10)0.0083 (14)00.0052 (14)0
S10.002 (2)0.0240 (13)0.029 (3)00.0001 (1)0
S20.014 (2)0.0209 (13)0.0048 (14)00.0014 (14)0
S30.003 (2)0.0224 (13)0.028 (2)00.0001 (1)0
S40.013 (2)0.0203 (13)0.022 (3)00.0025 (16)0
S50.007 (2)0.0272 (10)0.0024 (12)0.0013 (12)0.0024 (19)0.0005 (11)
S60.005 (2)0.0173 (9)0.0075 (14)0.0044 (9)0.0036 (17)0.0026 (10)
S70.008 (2)0.0280 (9)0.0005 (13)0.0013 (12)0.0015 (19)0.0006 (11)
S80.006 (2)0.0169 (8)0.0071 (13)0.0037 (10)0.0041 (16)0.0025 (9)
Geometric parameters (Å, º) top
Ba1—S2i3.412 (9)V3—S62.405 (7)
Ba1—S3ii3.3831 (2)V3—S6v2.405 (7)
Ba1—S3iii3.3831 (2)V3—S72.353 (7)
Ba1—S4iv3.416 (9)V3—S7v2.353 (7)
Ba1—S53.279 (9)V1—V42.825 (4)
Ba1—S5v3.279 (9)V1—S3x2.135 (9)
Ba1—S6vi3.386 (7)V1—S4i2.675 (10)
Ba1—S6vii3.386 (7)V1—S72.445 (8)
Ba1—S7viii3.351 (9)V1—S7v2.445 (8)
Ba1—S7ix3.351 (9)V1—S82.330 (6)
Ba1—S8vi3.460 (7)V1—S8v2.330 (6)
Ba1—S8vii3.460 (7)V4—S1xx2.645 (9)
Ba2—S1x3.431 (9)V4—S4i2.180 (10)
Ba2—S3x3.329 (9)V4—S5xxiii2.393 (7)
Ba2—S4viii3.3835 (3)V4—S5xxiv2.393 (7)
Ba2—S4vi3.3835 (3)V4—S82.368 (7)
Ba2—S5xi3.453 (7)V4—S8v2.368 (7)
Ba2—S5xii3.453 (7)S1—S5i3.399 (12)
Ba2—S63.366 (9)S1—S5xxv3.399 (12)
Ba2—S6v3.366 (9)S1—S7viii3.256 (11)
Ba2—S7ii3.357 (7)S1—S7ix3.256 (11)
Ba2—S7xiii3.357 (7)S1—S8iv3.350 (10)
Ba2—S8iii3.271 (8)S1—S8xxvi3.350 (10)
Ba2—S8xiv3.271 (8)S2—S5x3.355 (10)
Ba3—S1xi3.3855 (4)S2—S5xxvii3.355 (10)
Ba3—S1xv3.3855 (4)S2—S6x3.304 (12)
Ba3—S2i3.367 (9)S2—S6xxvii3.304 (12)
Ba3—S4i3.367 (9)S2—S7x3.422 (10)
Ba3—S5xvi3.333 (9)S2—S7xxvii3.422 (10)
Ba3—S5xvii3.333 (9)S2—S8iii3.351 (11)
Ba3—S6xviii3.469 (7)S2—S8xiv3.351 (11)
Ba3—S6xix3.469 (7)S3—S5xvi3.270 (11)
Ba3—S73.347 (9)S3—S5xvii3.270 (11)
Ba3—S7v3.347 (9)S3—S6i3.342 (10)
Ba3—S8vi3.382 (7)S3—S6xxv3.342 (10)
Ba3—S8vii3.382 (7)S3—S7i3.393 (11)
Ba4—S1xx3.368 (9)S3—S7xxv3.393 (11)
Ba4—S2xvi3.3848 (4)S3—S8i3.479 (11)
Ba4—S2xviii3.3848 (4)S3—S8xxv3.479 (11)
Ba4—S3x3.390 (9)S4—S5xx3.472 (10)
Ba4—S5xi3.321 (7)S4—S5xxviii3.472 (10)
Ba4—S5xii3.321 (7)S4—S6xv3.351 (12)
Ba4—S6xv3.254 (8)S4—S6xxi3.351 (12)
Ba4—S6xxi3.254 (8)S4—S7x3.291 (10)
Ba4—S7xi3.486 (7)S4—S7xxvii3.291 (10)
Ba4—S7xii3.486 (7)S4—S8x3.302 (12)
Ba4—S83.422 (9)S4—S8xxvii3.302 (12)
Ba4—S8v3.422 (9)S5—S5v3.264 (6)
V2—V32.944 (4)S5—S6v3.384 (11)
V2—V4xxii2.857 (4)S5—S8xxix3.403 (11)
V2—S1x2.136 (9)S6—S6xxx3.472 (5)
V2—S2i2.751 (9)S6—S6v3.292 (5)
V2—S52.435 (8)S6—S7v3.395 (11)
V2—S5v2.435 (8)S7—S7v3.323 (6)
V2—S62.345 (6)S7—S7xxxi3.441 (6)
V2—S6v2.345 (6)S7—S8v3.347 (11)
V3—V12.779 (4)S8—S8xxx3.441 (5)
V3—S2i2.183 (9)S8—S8v3.323 (5)
V3—S3x2.602 (9)
V3—V2—V4xxii157.80 (19)V3—V1—V4157.7 (2)
S1x—V2—S2i174.9 (3)S3x—V1—S4i173.4 (3)
S1x—V2—S595.9 (3)S3x—V1—S795.4 (3)
S1x—V2—S5v95.9 (3)S3x—V1—S7v95.4 (3)
S1x—V2—S6103.1 (3)S3x—V1—S8102.3 (3)
S1x—V2—S6v103.1 (3)S3x—V1—S8v102.3 (3)
S2i—V2—S580.4 (3)S4i—V1—S779.9 (3)
S2i—V2—S5v80.4 (3)S4i—V1—S7v79.9 (3)
S2i—V2—S680.4 (3)S4i—V1—S882.3 (3)
S2i—V2—S6v80.4 (3)S4i—V1—S8v82.3 (3)
S5—V2—S5v84.2 (2)S7—V1—S7v85.6 (3)
S5—V2—S6160.6 (4)S7—V1—S8162.0 (4)
S5—V2—S6v90.1 (2)S7—V1—S8v89.0 (2)
S5v—V2—S690.1 (2)S7v—V1—S889.0 (2)
S5v—V2—S6v160.6 (4)S7v—V1—S8v162.0 (4)
S6—V2—S6v89.2 (2)S8—V1—S8v90.9 (2)
V2—V3—V1157.8 (2)V2xxiii—V4—V1157.7 (2)
S2i—V3—S3x174.0 (3)S1xx—V4—S4i175.3 (3)
S2i—V3—S692.0 (3)S1xx—V4—S5xxiii84.7 (3)
S2i—V3—S6v92.0 (3)S1xx—V4—S5xxiv84.7 (3)
S2i—V3—S797.9 (3)S1xx—V4—S883.6 (3)
S2i—V3—S7v97.9 (3)S1xx—V4—S8v83.6 (3)
S3x—V3—S683.7 (3)S4i—V4—S5xxiii98.7 (3)
S3x—V3—S6v83.7 (3)S4i—V4—S5xxiv98.7 (3)
S3x—V3—S786.3 (3)S4i—V4—S893.0 (3)
S3x—V3—S7v86.3 (3)S4i—V4—S8v93.0 (3)
S6—V3—S6v86.4 (2)S5xxiii—V4—S5xxiv86.0 (2)
S6—V3—S7169.8 (4)S5xxiii—V4—S8168.2 (3)
S6—V3—S7v91.0 (2)S5xxiii—V4—S8v91.3 (2)
S6v—V3—S791.0 (2)S5xxiv—V4—S891.3 (2)
S6v—V3—S7v169.8 (4)S5xxiv—V4—S8v168.2 (3)
S7—V3—S7v89.8 (2)S8—V4—S8v89.1 (2)
Symmetry codes: (i) x+1, y, z; (ii) x1/2, y1/2, z1/2; (iii) x1/2, y+1/2, z1/2; (iv) x+1, y, z1; (v) x, y, z; (vi) x+1/2, y+1/2, z1/2; (vii) x+1/2, y1/2, z1/2; (viii) x+1/2, y1/2, z1/2; (ix) x+1/2, y+1/2, z1/2; (x) x1, y, z; (xi) x1/2, y1/2, z+1/2; (xii) x1/2, y+1/2, z+1/2; (xiii) x1/2, y+1/2, z1/2; (xiv) x1/2, y1/2, z1/2; (xv) x1/2, y+1/2, z+1/2; (xvi) x+1/2, y1/2, z+1/2; (xvii) x+1/2, y+1/2, z+1/2; (xviii) x+1/2, y+1/2, z+1/2; (xix) x+1/2, y1/2, z+1/2; (xx) x1, y, z+1; (xxi) x1/2, y1/2, z+1/2; (xxii) x, y, z1; (xxiii) x, y, z+1; (xxiv) x, y, z+1; (xxv) x+1, y, z; (xxvi) x+1, y, z1; (xxvii) x1, y, z; (xxviii) x1, y, z+1; (xxix) x, y, z1; (xxx) x, y1, z; (xxxi) x, y+1, z.
(III) top
Crystal data top
BaS3VF(000) = 508
Mr = 284.5Dx = 4.364 Mg m3
Monoclinic, CmSynchrotron radiation, λ = 0.70814 Å
Hall symbol: C -2yCell parameters from 1782 reflections
a = 11.496 (9) Åθ = 3.5–28.5°
b = 6.742 (7) ŵ = 12.17 mm1
c = 5.597 (5) ÅT = 70 K
β = 90.012 (6)°Irregular, grey
V = 433.8 (7) Å30.05 × 0.03 × 0.02 mm
Z = 4
Data collection top
Dectris-CrysAlisPro-abstract goniometer imported dectris images
diffractometer
769 reflections with I > 3σ(I)
Radiation source: synchrotronRint = 0.025
Synchrotron monochromatorθmax = 28.5°, θmin = 3.5°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
h = 1415
Tmin = 0.529, Tmax = 1.000k = 08
1782 measured reflectionsl = 55
770 independent reflections
Refinement top
Refinement on F2 constraints
R[F > 3σ(F)] = 0.048Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
wR(F) = 0.065(Δ/σ)max = 0.035
S = 5.44Δρmax = 2.26 e Å3
770 reflectionsΔρmin = 1.77 e Å3
53 parametersAbsolute structure: 367 of Friedel pairs used in the refinement
0 restraintsAbsolute structure parameter: 0.05 (5)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba10.33605300.0003030.0131 (4)
Ba20.33852 (10)00.5010 (5)0.0120 (4)
V10.0205 (5)00.2417 (14)0.0164 (11)
V20.0238 (6)00.2635 (12)0.0093 (10)
S10.1730 (15)00.014 (3)0.013 (2)
S20.0833 (13)0.2459 (8)0.000 (3)0.0148 (12)
S30.1689 (15)00.506 (3)0.0117 (19)
S40.0836 (12)0.2427 (7)0.495 (3)0.0132 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.0170 (8)0.0143 (4)0.0079 (9)00.0003 (12)0
Ba20.0130 (6)0.0145 (5)0.0084 (8)00.0016 (11)0
V10.0164 (17)0.0118 (9)0.021 (3)00.003 (3)0
V20.0094 (14)0.0165 (10)0.002 (3)00.003 (2)0
S10.015 (5)0.0205 (18)0.005 (4)00.000 (4)0
S20.021 (3)0.0151 (12)0.008 (2)0.0047 (16)0.002 (3)0.003 (2)
S30.016 (4)0.0109 (15)0.008 (3)00.002 (3)0
S40.0136 (18)0.0124 (11)0.014 (2)0.0067 (16)0.002 (3)0.0021 (18)
Geometric parameters (Å, º) top
Ba1—S1i3.374 (7)V1—S3v2.60 (2)
Ba1—S1ii3.374 (7)V1—S4v2.318 (14)
Ba1—S23.346 (14)V1—S4xvi2.318 (14)
Ba1—S2i3.319 (14)V2—S12.658 (19)
Ba1—S2iii3.346 (14)V2—S22.321 (14)
Ba1—S2iv3.319 (14)V2—S2iii2.321 (14)
Ba1—S3v3.364 (19)V2—S32.15 (2)
Ba1—S33.425 (19)V2—S42.426 (14)
Ba1—S4vi3.440 (17)V2—S4iii2.426 (14)
Ba1—S4ii3.399 (16)S1—S23.38 (2)
Ba1—S4vii3.440 (17)S1—S2x3.28 (2)
Ba1—S4viii3.399 (16)S1—S2iii3.38 (2)
Ba2—S13.323 (18)S1—S2xii3.28 (2)
Ba2—S1ix3.446 (18)S1—S4v3.49 (2)
Ba2—S2x3.405 (17)S1—S43.31 (2)
Ba2—S2xi3.399 (17)S1—S4xvi3.49 (2)
Ba2—S2xii3.405 (17)S1—S4iii3.31 (2)
Ba2—S2xiii3.399 (17)S2—S2iii3.316 (10)
Ba2—S3x3.372 (7)S2—S2xvii3.426 (10)
Ba2—S3xiv3.372 (7)S2—S3v3.37 (2)
Ba2—S43.357 (13)S2—S33.43 (2)
Ba2—S4xiv3.308 (13)S2—S4xvi3.42 (2)
Ba2—S4iii3.357 (13)S2—S4iii3.37 (2)
Ba2—S4xv3.308 (13)S3—S43.33 (2)
V1—V2v2.816 (12)S3—S4ii3.33 (2)
V1—V22.873 (12)S3—S4iii3.33 (2)
V1—S12.264 (19)S3—S4viii3.33 (2)
V1—S22.451 (14)S4—S4xviii3.469 (10)
V1—S2iii2.451 (14)S4—S4iii3.273 (9)
V2v—V1—V2159.3 (3)V1—V2—V1ix159.3 (3)
S1—V1—S291.6 (6)S1—V2—S285.3 (5)
S1—V1—S2iii91.6 (6)S1—V2—S2iii85.3 (5)
S1—V1—S3v173.7 (7)S1—V2—S3172.5 (7)
S1—V1—S4v99.2 (5)S1—V2—S481.2 (5)
S1—V1—S4xvi99.2 (5)S1—V2—S4iii81.2 (5)
S2—V1—S2iii85.1 (5)S2—V2—S2iii91.2 (5)
S2—V1—S3v83.8 (5)S2—V2—S399.9 (6)
S2—V1—S4v168.8 (6)S2—V2—S4166.2 (6)
S2—V1—S4xvi91.5 (4)S2—V2—S4iii90.4 (4)
S2iii—V1—S3v83.8 (5)S2iii—V2—S399.9 (6)
S2iii—V1—S4v91.5 (4)S2iii—V2—S490.4 (4)
S2iii—V1—S4xvi168.8 (6)S2iii—V2—S4iii166.2 (6)
S3v—V1—S4v85.2 (5)S3—V2—S493.3 (6)
S3v—V1—S4xvi85.2 (5)S3—V2—S4iii93.3 (6)
S4v—V1—S4xvi89.8 (5)S4—V2—S4iii84.8 (4)
Symmetry codes: (i) x+1/2, y1/2, z; (ii) x+1/2, y+1/2, z; (iii) x, y, z; (iv) x+1/2, y+1/2, z; (v) x, y, z1; (vi) x+1/2, y+1/2, z1; (vii) x+1/2, y1/2, z1; (viii) x+1/2, y1/2, z; (ix) x, y, z+1; (x) x1/2, y1/2, z; (xi) x1/2, y1/2, z+1; (xii) x1/2, y+1/2, z; (xiii) x1/2, y+1/2, z+1; (xiv) x1/2, y+1/2, z; (xv) x1/2, y1/2, z; (xvi) x, y, z1; (xvii) x, y+1, z; (xviii) x, y1, z.
(IV) top
Crystal data top
BaS3VF(000) = 508
Mr = 284.5Dx = 4.354 Mg m3
Monoclinic, CmSynchrotron radiation, λ = 0.70000 Å
Hall symbol: C -2yCell parameters from 3199 reflections
a = 11.485 (7) Åθ = 3.5–31.8°
b = 6.751 (5) ŵ = 11.79 mm1
c = 5.597 (3) ÅT = 100 K
β = 90.011 (5)°Irregular, grey
V = 434.0 (5) Å30.05 × 0.03 × 0.02 mm
Z = 4
Data collection top
Mar345 image plate
diffractometer
1934 reflections with I > 3σ(I)
Radiation source: synchrotronRint = 0.031
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
θmax = 31.8°, θmin = 3.5°
Tmin = 0.627, Tmax = 1.000h = 1717
3199 measured reflectionsk = 99
1935 independent reflectionsl = 88
Refinement top
Refinement on F0 constraints
R[F > 3σ(F)] = 0.032Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
wR(F) = 0.045(Δ/σ)max = 0.048
S = 3.27Δρmax = 1.39 e Å3
1935 reflectionsΔρmin = 1.76 e Å3
59 parametersAbsolute structure: 806 of Friedel pairs used in the refinement
0 restraintsAbsolute structure parameter: 0.05 (4)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba10.3351 (3)00.4995 (9)0.0094 (9)
Ba20.338683000.0088 (9)
V10.0225 (10)00.2424 (16)0.007 (2)
V20.0211 (10)00.2593 (15)0.011 (2)
S10.173 (2)00.015 (3)0.006 (3)
S20.0785 (19)0.2431 (19)0.000 (2)0.009 (2)
S30.167 (2)00.512 (2)0.006 (3)
S40.0861 (18)0.2462 (18)0.493 (2)0.007 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.0116 (16)0.0096 (19)0.0070 (9)00.0016 (10)0
Ba20.0113 (18)0.007 (2)0.0079 (9)00.0034 (11)0
V10.004 (3)0.011 (5)0.007 (2)00.001 (3)0
V20.015 (4)0.009 (5)0.010 (2)00.000 (3)0
S10.005 (5)0.006 (6)0.006 (4)00.0016 (16)0
S20.012 (5)0.010 (4)0.005 (2)0.002 (3)0.002 (3)0.001 (3)
S30.008 (6)0.004 (6)0.005 (4)00.004 (2)0
S40.006 (4)0.004 (5)0.012 (3)0.001 (2)0.002 (3)0.002 (2)
Geometric parameters (Å, º) top
Ba1—S13.291 (19)V1—S2vii2.425 (17)
Ba1—S1i3.429 (19)V1—S3xii2.58 (2)
Ba1—S2ii3.437 (14)V1—S4xii2.343 (15)
Ba1—S2iii3.440 (14)V1—S4xvi2.343 (15)
Ba1—S2iv3.437 (14)V2—S12.62 (2)
Ba1—S2v3.440 (14)V2—S22.288 (15)
Ba1—S3ii3.3763 (6)V2—S2vii2.288 (15)
Ba1—S3vi3.3763 (6)V2—S32.19 (2)
Ba1—S43.308 (19)V2—S42.447 (17)
Ba1—S4vi3.354 (19)V2—S4vii2.447 (17)
Ba1—S4vii3.308 (19)S1—S23.33 (3)
Ba1—S4viii3.354 (19)S1—S2ii3.34 (3)
Ba2—S1ix3.3792 (12)S1—S2vii3.33 (3)
Ba2—S1x3.3792 (12)S1—S2iv3.34 (3)
Ba2—S23.41 (2)S1—S43.31 (2)
Ba2—S2ix3.26 (2)S1—S4vii3.31 (2)
Ba2—S2vii3.41 (2)S2—S2vii3.282 (19)
Ba2—S2xi3.26 (2)S2—S2xvii3.469 (19)
Ba2—S3xii3.370 (18)S2—S3xii3.345 (19)
Ba2—S33.478 (18)S2—S33.454 (19)
Ba2—S4xiii3.426 (13)S2—S4xvi3.41 (2)
Ba2—S4x3.361 (13)S2—S4vii3.35 (2)
Ba2—S4xiv3.426 (13)S3—S43.35 (3)
Ba2—S4xv3.361 (13)S3—S4x3.32 (3)
V1—V2xii2.834 (12)S3—S4vii3.35 (3)
V1—V22.852 (12)S3—S4xv3.32 (3)
V1—S12.25 (2)S4—S4xviii3.427 (17)
V1—S22.425 (17)S4—S4vii3.324 (17)
V2xii—V1—V2159.7 (5)V1—V2—V1i159.7 (5)
S1—V1—S290.6 (6)S1—V2—S285.1 (6)
S1—V1—S2vii90.6 (6)S1—V2—S2vii85.1 (6)
S1—V1—S3xii172.6 (8)S1—V2—S3171.4 (8)
S1—V1—S4xii99.5 (7)S1—V2—S481.4 (6)
S1—V1—S4xvi99.5 (7)S1—V2—S4vii81.4 (6)
S2—V1—S2vii85.2 (6)S2—V2—S2vii91.6 (6)
S2—V1—S3xii83.9 (6)S2—V2—S3100.9 (7)
S2—V1—S4xii169.4 (8)S2—V2—S4166.2 (9)
S2—V1—S4xvi91.3 (5)S2—V2—S4vii89.8 (5)
S2vii—V1—S3xii83.9 (6)S2vii—V2—S3100.9 (7)
S2vii—V1—S4xii91.3 (5)S2vii—V2—S489.8 (5)
S2vii—V1—S4xvi169.4 (8)S2vii—V2—S4vii166.2 (9)
S3xii—V1—S4xii85.7 (6)S3—V2—S492.3 (6)
S3xii—V1—S4xvi85.7 (6)S3—V2—S4vii92.3 (6)
S4xii—V1—S4xvi90.4 (6)S4—V2—S4vii85.6 (6)
Symmetry codes: (i) x, y, z+1; (ii) x1/2, y1/2, z; (iii) x1/2, y1/2, z+1; (iv) x1/2, y+1/2, z; (v) x1/2, y+1/2, z+1; (vi) x1/2, y+1/2, z; (vii) x, y, z; (viii) x1/2, y1/2, z; (ix) x+1/2, y1/2, z; (x) x+1/2, y+1/2, z; (xi) x+1/2, y+1/2, z; (xii) x, y, z1; (xiii) x+1/2, y+1/2, z1; (xiv) x+1/2, y1/2, z1; (xv) x+1/2, y1/2, z; (xvi) x, y, z1; (xvii) x, y+1, z; (xviii) x, y1, z.
(V) top
Crystal data top
BaVS3F(000) = 508
Mr = 284.5Dx = 4.336 Mg m3
Monoclinic, CmSynchrotron radiation, λ = 0.70814 Å
Hall symbol: C -2yCell parameters from 1319 reflections
a = 11.5839 (7) Åθ = 3.5–28.7°
b = 6.7016 (5) ŵ = 12.12 mm1
c = 5.5956 (3) ÅT = 150 K
β = 90°Irregular, grey
V = 434.39 (5) Å30.05 × 0.03 × 0.02 mm
Z = 4
Data collection top
Dectris-CrysAlisPro-abstract goniometer imported dectris images
diffractometer
1409 reflections with I > 3σ(I)
Radiation source: synchrotronRint = 0.023
Synchrotron monochromatorθmax = 28.7°, θmin = 3.5°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
h = 1414
Tmin = 0.658, Tmax = 1.000k = 88
3834 measured reflectionsl = 55
1409 independent reflections
Refinement top
Refinement on F28 constraints
R[F > 3σ(F)] = 0.046Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
wR(F) = 0.072(Δ/σ)max = 0.018
S = 4.83Δρmax = 2.16 e Å3
1409 reflectionsΔρmin = 1.62 e Å3
30 parametersAbsolute structure: 653 of Friedel pairs used in the refinement
0 restraintsAbsolute structure parameter: 0.02 (4)
Special details top

Refinement. Structure is considered as a commensurate composite with Ccm21 space group for the BaS3 matrix and C2/m space group for the V-chain. The corresponding constrains are applied for the corresponding atomic sides.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba1a0.33666 (4)00.5079180.0127 (2)
Ba1b0.33666 (4)00.0079180.0127 (2)
V1a0.02090 (11)00.2505 (3)0.0131 (4)
V1b0.02090 (11)00.2505 (3)0.0131 (4)
S1a0.16932 (16)00.0029 (7)0.0126 (9)
S2a0.08307 (13)0.24518 (15)0.0226 (6)0.0102 (7)
S1b0.16932 (16)00.4971 (7)0.0126 (9)
S2b0.08307 (13)0.24518 (15)0.5226 (6)0.0102 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba1a0.0150 (4)0.0142 (3)0.0091 (5)00.0005 (3)0
Ba1b0.0150 (4)0.0142 (3)0.0091 (5)00.0005 (3)0
V1a0.0137 (7)0.0180 (6)0.0074 (9)00.0006 (5)0
V1b0.0137 (7)0.0180 (6)0.0074 (9)00.0006 (5)0
S1a0.0109 (12)0.0168 (13)0.010 (2)00.0001 (11)0
S2a0.0158 (10)0.0140 (10)0.0010 (15)0.0029 (5)0.0013 (10)0.0000 (5)
S1b0.0109 (12)0.0168 (13)0.010 (2)00.0001 (11)0
S2b0.0158 (10)0.0140 (10)0.0010 (15)0.0029 (5)0.0013 (10)0.0000 (5)
Geometric parameters (Å, º) top
Ba1a—S1a3.454 (3)V1a—S2avii2.356 (3)
Ba1a—S1ai3.354 (3)V1a—S1bxii2.225 (3)
Ba1a—S2aii3.340 (3)V1a—S2bxii2.401 (2)
Ba1a—S2aiii3.475 (3)V1a—S2bxvi2.401 (2)
Ba1a—S2aiv3.340 (3)V1b—S1a2.228 (3)
Ba1a—S2av3.475 (3)V1b—S2a2.403 (2)
Ba1a—S1bii3.3521 (5)V1b—S2avii2.403 (2)
Ba1a—S1bvi3.3521 (5)V1b—S1b2.600 (3)
Ba1a—S2b3.3669 (15)V1b—S2b2.353 (3)
Ba1a—S2bvi3.3272 (15)V1b—S2bvii2.353 (3)
Ba1a—S2bvii3.3669 (15)S1a—S2a3.357 (2)
Ba1a—S2bviii3.3272 (15)S1a—S2aii3.341 (2)
Ba1b—S1aix3.3521 (5)S1a—S2avii3.357 (2)
Ba1b—S1ax3.3521 (5)S1a—S2aiv3.341 (2)
Ba1b—S2a3.3669 (15)S1a—S2bxii3.278 (4)
Ba1b—S2aix3.3272 (15)S1a—S2bxvi3.278 (4)
Ba1b—S2avii3.3669 (15)S2a—S2avii3.2862 (15)
Ba1b—S2axi3.3272 (15)S2a—S2axvii3.4154 (15)
Ba1b—S1bxii3.454 (3)S2a—S1b3.278 (4)
Ba1b—S1b3.354 (3)S2a—S2bxvi3.396 (4)
Ba1b—S2bxiii3.340 (3)S2a—S2bvii3.396 (4)
Ba1b—S2bx3.475 (3)S1b—S2b3.357 (2)
Ba1b—S2bxiv3.340 (3)S1b—S2bx3.341 (2)
Ba1b—S2bxv3.475 (3)S1b—S2bvii3.357 (2)
V1a—V1bxii2.834 (2)S1b—S2bxv3.341 (2)
V1a—V1b2.845 (2)S2b—S2bxviii3.4154 (15)
V1a—S1a2.603 (3)S2b—S2bvii3.2862 (15)
V1a—S2a2.356 (3)
V1bxii—V1a—V1b160.36 (6)V1a—V1b—V1ai160.36 (6)
S1a—V1a—S2a85.04 (9)S1a—V1b—S2a92.81 (10)
S1a—V1a—S2avii85.04 (9)S1a—V1b—S2avii92.81 (10)
S1a—V1a—S1bxii172.76 (13)S1a—V1b—S1b172.55 (13)
S1a—V1a—S2bxii81.77 (9)S1a—V1b—S2b100.11 (9)
S1a—V1a—S2bxvi81.77 (9)S1a—V1b—S2bvii100.11 (9)
S2a—V1a—S2avii88.42 (9)S2a—V1b—S2avii86.26 (8)
S2a—V1a—S1bxii100.11 (9)S2a—V1b—S1b81.78 (9)
S2a—V1a—S2bxii166.80 (10)S2a—V1b—S2b166.93 (10)
S2a—V1a—S2bxvi91.09 (8)S2a—V1b—S2bvii91.11 (8)
S2avii—V1a—S1bxii100.11 (9)S2avii—V1b—S1b81.78 (9)
S2avii—V1a—S2bxii91.09 (8)S2avii—V1b—S2b91.11 (8)
S2avii—V1a—S2bxvi166.80 (10)S2avii—V1b—S2bvii166.93 (10)
S1bxii—V1a—S2bxii92.97 (10)S1b—V1b—S2b85.17 (9)
S1bxii—V1a—S2bxvi92.97 (10)S1b—V1b—S2bvii85.17 (9)
S2bxii—V1a—S2bxvi86.39 (8)S2b—V1b—S2bvii88.58 (10)
Symmetry codes: (i) x, y, z+1; (ii) x1/2, y1/2, z; (iii) x1/2, y1/2, z+1; (iv) x1/2, y+1/2, z; (v) x1/2, y+1/2, z+1; (vi) x1/2, y+1/2, z; (vii) x, y, z; (viii) x1/2, y1/2, z; (ix) x+1/2, y1/2, z; (x) x+1/2, y+1/2, z; (xi) x+1/2, y+1/2, z; (xii) x, y, z1; (xiii) x+1/2, y+1/2, z1; (xiv) x+1/2, y1/2, z1; (xv) x+1/2, y1/2, z; (xvi) x, y, z1; (xvii) x, y+1, z; (xviii) x, y1, z.
(VI) top
Crystal data top
BaS3VF(000) = 508
Mr = 284.5Dx = 4.327 Mg m3
Monoclinic, CmSynchrotron radiation, λ = 0.693 Å
Hall symbol: C -2yCell parameters from 1653 reflections
a = 11.5729 (7) Åθ = 3.5–28.7°
b = 6.7116 (5) ŵ = 12.09 mm1
c = 5.6015 (3) ÅT = 200 K
β = 90°Irregular, grey
V = 435.08 (5) Å30.05 × 0.03 × 0.02 mm
Z = 4
Data collection top
Dectris-CrysAlisPro-abstract goniometer imported dectris images
diffractometer
2191 reflections with I > 3σ(I)
Radiation source: synchrotronRint = 0.021
Synchrotron monochromatorθmax = 32.0°, θmin = 3.4°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
h = 1716
Tmin = 0.595, Tmax = 1.000k = 99
3593 measured reflectionsl = 88
2206 independent reflections
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
R[F > 3σ(F)] = 0.021(Δ/σ)max = 0.020
wR(F) = 0.026Δρmax = 0.62 e Å3
S = 1.15Δρmin = 0.80 e Å3
2206 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
31 parametersExtinction coefficient: 510 (40)
0 restraintsAbsolute structure: 974 of Friedel pairs used in the refinement
28 constraintsAbsolute structure parameter: 0.17 (3)
Special details top

Refinement. Structure is considered as a commensurate composite with Ccm21 space group for the BaS3 matrix and C2/m space group for the V-chain. The corresponding constrains are applied for the corresponding atomic sides.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba1a0.33533 (5)00.5041910.01417 (15)
Ba1b0.33533 (5)00.0041910.01417 (15)
V1a0.01585 (9)00.2520 (3)0.0211 (3)
V1b0.01585 (9)00.2520 (3)0.0211 (3)
S1a0.16705 (13)00.0068 (6)0.0123 (10)
S2a0.08293 (11)0.24686 (16)0.0088 (10)0.0133 (7)
S1b0.16705 (13)00.4932 (6)0.0123 (10)
S2b0.08293 (11)0.24686 (16)0.5088 (10)0.0133 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba1a0.0150 (3)0.0148 (3)0.01268 (10)00.0002 (3)0
Ba1b0.0150 (3)0.0148 (3)0.01268 (10)00.0002 (3)0
V1a0.0186 (6)0.0335 (8)0.01127 (19)00.0023 (5)0
V1b0.0186 (6)0.0335 (8)0.01127 (19)00.0023 (5)0
S1a0.0141 (18)0.0102 (18)0.0125 (14)00.0004 (15)0
S2a0.0180 (16)0.0097 (14)0.0122 (8)0.0020 (8)0.0008 (13)0.0006 (6)
S1b0.0141 (18)0.0102 (18)0.0125 (14)00.0004 (15)0
S2b0.0180 (16)0.0097 (14)0.0122 (8)0.0020 (8)0.0008 (13)0.0006 (6)
Geometric parameters (Å, º) top
Ba1a—S1a3.462 (3)V1a—S1bxii2.258 (3)
Ba1a—S1ai3.361 (3)V1a—S2bxii2.418 (3)
Ba1a—S2aii3.388 (5)V1a—S2bxvi2.418 (3)
Ba1a—S2aiii3.431 (5)V1b—S1a2.272 (3)
Ba1a—S2aiv3.388 (5)V1b—S2a2.430 (3)
Ba1a—S2av3.431 (5)V1b—S2avii2.430 (3)
Ba1a—S1bii3.3565 (5)V1b—S1b2.511 (3)
Ba1a—S1bvi3.3565 (5)V1b—S2b2.328 (4)
Ba1a—S2b3.3582 (14)V1b—S2bvii2.328 (4)
Ba1a—S2bvi3.3314 (14)S1a—S2a3.3350 (18)
Ba1a—S2bvii3.3582 (14)S1a—S2aii3.3566 (18)
Ba1a—S2bviii3.3314 (14)S1a—S2avii3.3350 (18)
Ba1b—S1aix3.3565 (5)S1a—S2aiv3.3566 (18)
Ba1b—S1ax3.3565 (5)S1a—S2bxii3.325 (5)
Ba1b—S2a3.3582 (14)S1a—S2b3.469 (5)
Ba1b—S2aix3.3314 (14)S1a—S2bxvi3.325 (5)
Ba1b—S2avii3.3582 (14)S1a—S2bvii3.469 (5)
Ba1b—S2axi3.3314 (14)S2a—S2avii3.3137 (16)
Ba1b—S1bxii3.462 (3)S2a—S2axvii3.3979 (16)
Ba1b—S1b3.361 (3)S2a—S1bxii3.469 (5)
Ba1b—S2bxiii3.388 (5)S2a—S1b3.325 (5)
Ba1b—S2bx3.431 (5)S2a—S2bxvi3.395 (6)
Ba1b—S2bxiv3.388 (5)S2a—S2bvii3.395 (6)
Ba1b—S2bxv3.431 (5)S1b—S2b3.3350 (18)
V1a—V1bxii2.803 (2)S1b—S2bx3.3566 (18)
V1a—V1b2.847 (2)S1b—S2bvii3.3350 (18)
V1a—S1a2.523 (3)S1b—S2bxv3.3566 (18)
V1a—S2a2.341 (4)S2b—S2bxviii3.3979 (16)
V1a—S2avii2.341 (4)S2b—S2bvii3.3137 (16)
V1bxii—V1a—V1b165.08 (5)V1a—V1b—V1ai165.08 (5)
S1a—V1a—S2a86.47 (10)S1a—V1b—S2a90.27 (11)
S1a—V1a—S2avii86.47 (10)S1a—V1b—S2avii90.27 (11)
S1a—V1a—S1bxii173.78 (12)S1a—V1b—S1b172.92 (12)
S1a—V1a—S2bxii84.55 (10)S1a—V1b—S2b97.90 (10)
S1a—V1a—S2bxvi84.55 (10)S1a—V1b—S2bvii97.90 (10)
S2a—V1a—S2avii90.08 (13)S2a—V1b—S2avii85.96 (11)
S2a—V1a—S1bxii97.90 (10)S2a—V1b—S1b84.55 (10)
S2a—V1a—S2bxii170.87 (11)S2a—V1b—S2b171.31 (10)
S2a—V1a—S2bxvi91.01 (11)S2a—V1b—S2bvii91.03 (11)
S2avii—V1a—S1bxii97.90 (10)S2avii—V1b—S1b84.55 (10)
S2avii—V1a—S2bxii91.01 (11)S2avii—V1b—S2b91.03 (11)
S2avii—V1a—S2bxvi170.87 (11)S2avii—V1b—S2bvii171.31 (10)
S1bxii—V1a—S2bxii90.93 (11)S1b—V1b—S2b87.05 (10)
S1bxii—V1a—S2bxvi90.93 (11)S1b—V1b—S2bvii87.05 (10)
S2bxii—V1a—S2bxvi86.51 (11)S2b—V1b—S2bvii90.76 (13)
Symmetry codes: (i) x, y, z+1; (ii) x1/2, y1/2, z; (iii) x1/2, y1/2, z+1; (iv) x1/2, y+1/2, z; (v) x1/2, y+1/2, z+1; (vi) x1/2, y+1/2, z; (vii) x, y, z; (viii) x1/2, y1/2, z; (ix) x+1/2, y1/2, z; (x) x+1/2, y+1/2, z; (xi) x+1/2, y+1/2, z; (xii) x, y, z1; (xiii) x+1/2, y+1/2, z1; (xiv) x+1/2, y1/2, z1; (xv) x+1/2, y1/2, z; (xvi) x, y, z1; (xvii) x, y+1, z; (xviii) x, y1, z.
(VII) top
Crystal data top
BaVS3F(000) = 508
Mr = 284.5Dx = 4.336 Mg m3
Monoclinic, CmSynchrotron radiation, λ = 0.70814 Å
Hall symbol: C -2yCell parameters from 1812 reflections
a = 11.593 (7) Åθ = 3.5–28.6°
b = 6.708 (5) ŵ = 12.12 mm1
c = 5.604 (3) ÅT = 220 K
β = 90°Irregular, grey
V = 435.8 (5) Å30.05 × 0.03 × 0.02 mm
Z = 4
Data collection top
Dectris-CrysAlisPro-abstract goniometer imported dectris images
diffractometer
1464 reflections with I > 3σ(I)
Radiation source: synchrotronRint = 0.014
Synchrotron monochromatorθmax = 28.6°, θmin = 3.5°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
h = 1515
Tmin = 0.606, Tmax = 1.000k = 88
3944 measured reflectionsl = 55
1464 independent reflections
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
R[F > 3σ(F)] = 0.019(Δ/σ)max = 0.045
wR(F) = 0.040Δρmax = 0.96 e Å3
S = 2.83Δρmin = 0.72 e Å3
1464 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
32 parametersExtinction coefficient: 580 (40)
0 restraintsAbsolute structure: 668 of Friedel pairs used in the refinement
27 constraintsAbsolute structure parameter: 0.28 (2)
Special details top

Refinement. Structure is considered as a commensurate composite with Ccm21 space group for the BaS3 matrix and C2/m space group for the V-chain. The corresponding constrains are applied for the corresponding atomic sides.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba1a0.33471 (3)00.5046 (4)0.01489 (16)
Ba1b0.33471 (3)00.0046 (4)0.01489 (16)
V1a0.01545 (6)00.25311 (9)0.0213 (2)
V1b0.01545 (6)00.25311 (9)0.0213 (2)
S1a0.16657 (9)00.0040 (15)0.0162 (6)
S2a0.08293 (7)0.24697 (8)0.0193 (13)0.0114 (5)
S1b0.16657 (9)00.5040 (15)0.0162 (6)
S2b0.08293 (7)0.24697 (8)0.5193 (13)0.0114 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba1a0.0146 (3)0.0141 (3)0.0160 (3)00.0008 (2)0
Ba1b0.0146 (3)0.0141 (3)0.0160 (3)00.0008 (2)0
V1a0.0212 (4)0.0301 (5)0.0125 (4)00.0011 (4)0
V1b0.0212 (4)0.0301 (5)0.0125 (4)00.0011 (4)0
S1a0.0107 (9)0.0153 (9)0.0226 (13)00.0003 (9)0
S2a0.0142 (8)0.0110 (7)0.0089 (10)0.0017 (3)0.0003 (9)0.0000 (3)
S1b0.0107 (9)0.0153 (9)0.0226 (13)00.0003 (9)0
S2b0.0142 (8)0.0110 (7)0.0089 (10)0.0017 (3)0.0003 (9)0.0000 (3)
Geometric parameters (Å, º) top
Ba1a—S1a3.416 (8)V1a—S1bxii2.218 (6)
Ba1a—S1ai3.411 (8)V1a—S2bxii2.382 (5)
Ba1a—S2aii3.345 (7)V1a—S2bxvi2.382 (5)
Ba1a—S2aiii3.480 (7)V1b—S1a2.240 (6)
Ba1a—S2aiv3.345 (7)V1b—S2a2.400 (5)
Ba1a—S2av3.480 (7)V1b—S2avii2.400 (5)
Ba1a—S1bii3.354 (5)V1b—S1b2.536 (5)
Ba1a—S1bvi3.354 (5)V1b—S2b2.363 (5)
Ba1a—S2b3.357 (3)V1b—S2bvii2.363 (5)
Ba1a—S2bvi3.342 (3)S1a—S2a3.334 (3)
Ba1a—S2bvii3.357 (3)S1a—S2aii3.365 (3)
Ba1a—S2bviii3.342 (3)S1a—S2avii3.334 (3)
Ba1b—S1aix3.354 (5)S1a—S2aiv3.365 (3)
Ba1b—S1ax3.354 (5)S1a—S2bxii3.326 (10)
Ba1b—S2a3.357 (3)S1a—S2b3.468 (10)
Ba1b—S2aix3.342 (3)S1a—S2bxvi3.326 (10)
Ba1b—S2avii3.357 (3)S1a—S2bvii3.468 (10)
Ba1b—S2axi3.342 (3)S2a—S2avii3.313 (5)
Ba1b—S1bxii3.416 (8)S2a—S2axvii3.395 (5)
Ba1b—S1b3.411 (8)S2a—S1bxii3.468 (10)
Ba1b—S2bxiii3.345 (7)S2a—S1b3.326 (10)
Ba1b—S2bx3.480 (7)S2a—S2bxvi3.398 (9)
Ba1b—S2bxiv3.345 (7)S2a—S2bvii3.398 (9)
Ba1b—S2bxv3.480 (7)S1b—S2b3.334 (3)
V1a—V1bxii2.790 (3)S1b—S2bx3.365 (3)
V1a—V1b2.859 (3)S1b—S2bvii3.334 (3)
V1a—S1a2.555 (5)S1b—S2bxv3.365 (3)
V1a—S2a2.385 (5)S2b—S2bxviii3.395 (5)
V1a—S2avii2.385 (5)S2b—S2bvii3.313 (5)
V1bxii—V1a—V1b165.43 (4)V1a—V1b—V1ai165.43 (4)
S1a—V1a—S2a84.83 (15)S1a—V1b—S2a91.80 (17)
S1a—V1a—S2avii84.83 (15)S1a—V1b—S2avii91.80 (17)
S1a—V1a—S1bxii176.5 (2)S1a—V1b—S1b175.1 (2)
S1a—V1a—S2bxii84.64 (16)S1a—V1b—S2b97.73 (16)
S1a—V1a—S2bxvi84.64 (16)S1a—V1b—S2bvii97.73 (16)
S2a—V1a—S2avii88.00 (17)S2a—V1b—S2avii87.29 (14)
S2a—V1a—S1bxii97.68 (16)S2a—V1b—S1b84.68 (16)
S2a—V1a—S2bxii169.47 (15)S2a—V1b—S2b170.37 (14)
S2a—V1a—S2bxvi90.96 (16)S2a—V1b—S2bvii91.03 (16)
S2avii—V1a—S1bxii97.68 (16)S2avii—V1b—S1b84.68 (16)
S2avii—V1a—S2bxii90.96 (16)S2avii—V1b—S2b91.03 (16)
S2avii—V1a—S2bxvi169.47 (15)S2avii—V1b—S2bvii170.37 (14)
S1bxii—V1a—S2bxii92.84 (18)S1b—V1b—S2b85.72 (15)
S1bxii—V1a—S2bxvi92.84 (18)S1b—V1b—S2bvii85.72 (15)
S2bxii—V1a—S2bxvi88.15 (14)S2b—V1b—S2bvii89.04 (17)
Symmetry codes: (i) x, y, z+1; (ii) x1/2, y1/2, z; (iii) x1/2, y1/2, z+1; (iv) x1/2, y+1/2, z; (v) x1/2, y+1/2, z+1; (vi) x1/2, y+1/2, z; (vii) x, y, z; (viii) x1/2, y1/2, z; (ix) x+1/2, y1/2, z; (x) x+1/2, y+1/2, z; (xi) x+1/2, y+1/2, z; (xii) x, y, z1; (xiii) x+1/2, y+1/2, z1; (xiv) x+1/2, y1/2, z1; (xv) x+1/2, y1/2, z; (xvi) x, y, z1; (xvii) x, y+1, z; (xviii) x, y1, z.
(VIII) top
Crystal data top
BaVS3F(000) = 508
Mr = 284.5Dx = 4.324 Mg m3
Monoclinic, CmSynchrotron radiation, λ = 0.7 Å
Hall symbol: C -2yCell parameters from 2084 reflections
a = 11.585 (7) Åθ = 3.5–32.4°
b = 6.724 (5) ŵ = 11.71 mm1
c = 5.610 (2) ÅT = 240 K
β = 90°Irregular, grey
V = 437.0 (4) Å30.05 × 0.03 × 0.02 mm
Z = 4
Data collection top
Mar345 image plate
diffractometer
1724 reflections with I > 3σ(I)
Radiation source: synchrotronRint = 0.018
Synchrotron monochromatorθmax = 32.4°, θmin = 3.5°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
h = 1717
Tmin = 0.623, Tmax = 1.000k = 1010
2084 measured reflectionsl = 78
1751 independent reflections
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
R[F > 3σ(F)] = 0.021(Δ/σ)max = 0.002
wR(F) = 0.033Δρmax = 1.27 e Å3
S = 2.02Δρmin = 0.98 e Å3
1751 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
32 parametersExtinction coefficient: 510 (60)
0 restraintsAbsolute structure: 573 of Friedel pairs used in the refinement
27 constraintsAbsolute structure parameter: 0.20 (5)
Special details top

Refinement. Structure is considered as a commensurate composite with Ccm21 space group for the BaS3 matrix and C2/m space group for the V-chain. The corresponding constrains are applied for the corresponding atomic sides.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba1a0.33427 (6)00.5014 (8)0.01674 (14)
Ba1b0.33427 (6)00.0014 (8)0.01674 (14)
V1a0.01168 (9)00.2553 (3)0.0282 (4)
V1b0.01168 (9)00.2553 (3)0.0282 (4)
S1a0.16583 (15)00.005 (3)0.0158 (8)
S2a0.08287 (13)0.24755 (18)0.006 (3)0.0153 (5)
S1b0.16583 (15)00.495 (3)0.0158 (8)
S2b0.08287 (13)0.24755 (18)0.506 (3)0.0153 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba1a0.0153 (3)0.0164 (3)0.01850 (16)00.0006 (3)0
Ba1b0.0153 (3)0.0164 (3)0.01850 (16)00.0006 (3)0
V1a0.0254 (7)0.0441 (10)0.0152 (4)00.0007 (7)0
V1b0.0254 (7)0.0441 (10)0.0152 (4)00.0007 (7)0
S1a0.0100 (10)0.0174 (12)0.0200 (18)00.0007 (10)0
S2a0.0134 (8)0.0145 (9)0.0179 (10)0.0023 (4)0.0004 (9)0.0004 (5)
S1b0.0100 (10)0.0174 (12)0.0200 (18)00.0007 (10)0
S2b0.0134 (8)0.0145 (9)0.0179 (10)0.0023 (4)0.0004 (9)0.0004 (5)
Geometric parameters (Å, º) top
Ba1a—S1a3.446 (13)V1a—S1bxii2.269 (9)
Ba1a—S1ai3.388 (13)V1a—S2bxii2.400 (8)
Ba1a—S2aii3.395 (12)V1a—S2bxvi2.400 (8)
Ba1a—S2aiii3.438 (12)V1b—S1a2.307 (10)
Ba1a—S2aiv3.395 (12)V1b—S2a2.434 (8)
Ba1a—S2av3.438 (12)V1b—S2avii2.434 (8)
Ba1a—S1bii3.362 (5)V1b—S1b2.457 (9)
Ba1a—S1bvi3.362 (5)V1b—S2b2.330 (9)
Ba1a—S2b3.355 (4)V1b—S2bvii2.330 (9)
Ba1a—S2bvi3.343 (4)S1a—S2a3.328 (4)
Ba1a—S2bvii3.355 (4)S1a—S2aii3.371 (4)
Ba1a—S2bviii3.343 (4)S1a—S2avii3.328 (4)
Ba1b—S1aix3.362 (5)S1a—S2aiv3.371 (4)
Ba1b—S1ax3.362 (5)S1a—S2bxii3.350 (17)
Ba1b—S2a3.355 (4)S1a—S2b3.451 (17)
Ba1b—S2aix3.343 (4)S1a—S2bxvi3.350 (17)
Ba1b—S2avii3.355 (4)S1a—S2bvii3.451 (17)
Ba1b—S2axi3.343 (4)S2a—S2avii3.329 (5)
Ba1b—S1bxii3.446 (13)S2a—S2axvii3.395 (5)
Ba1b—S1b3.388 (13)S2a—S1bxii3.451 (17)
Ba1b—S2bxiii3.395 (12)S2a—S1b3.350 (17)
Ba1b—S2bx3.438 (12)S2a—S2bxvi3.399 (17)
Ba1b—S2bxiv3.395 (12)S2a—S2bvii3.399 (17)
Ba1b—S2bxv3.438 (12)S1b—S2b3.328 (4)
V1a—V1bxii2.758 (3)S1b—S2bx3.371 (4)
V1a—V1b2.878 (3)S1b—S2bvii3.328 (4)
V1a—S1a2.491 (9)S1b—S2bxv3.371 (4)
V1a—S2a2.367 (9)S2b—S2bxviii3.395 (5)
V1a—S2avii2.367 (9)S2b—S2bvii3.329 (5)
V1bxii—V1a—V1b168.98 (5)V1a—V1b—V1ai168.98 (5)
S1a—V1a—S2a86.5 (3)S1a—V1b—S2a89.1 (3)
S1a—V1a—S2avii86.5 (3)S1a—V1b—S2avii89.1 (3)
S1a—V1a—S1bxii176.3 (4)S1a—V1b—S1b173.9 (4)
S1a—V1a—S2bxii86.4 (3)S1a—V1b—S2b96.2 (3)
S1a—V1a—S2bxvi86.4 (3)S1a—V1b—S2bvii96.2 (3)
S2a—V1a—S2avii89.4 (3)S2a—V1b—S2avii86.3 (3)
S2a—V1a—S1bxii96.2 (3)S2a—V1b—S1b86.4 (3)
S2a—V1a—S2bxii172.8 (3)S2a—V1b—S2b173.99 (15)
S2a—V1a—S2bxvi91.0 (3)S2a—V1b—S2bvii91.0 (3)
S2avii—V1a—S1bxii96.2 (3)S2avii—V1b—S1b86.4 (3)
S2avii—V1a—S2bxii91.0 (3)S2avii—V1b—S2b91.0 (3)
S2avii—V1a—S2bxvi172.8 (3)S2avii—V1b—S2bvii173.99 (15)
S1bxii—V1a—S2bxii90.9 (3)S1b—V1b—S2b88.0 (3)
S1bxii—V1a—S2bxvi90.9 (3)S1b—V1b—S2bvii88.0 (3)
S2bxii—V1a—S2bxvi87.8 (3)S2b—V1b—S2bvii91.2 (3)
Symmetry codes: (i) x, y, z+1; (ii) x1/2, y1/2, z; (iii) x1/2, y1/2, z+1; (iv) x1/2, y+1/2, z; (v) x1/2, y+1/2, z+1; (vi) x1/2, y+1/2, z; (vii) x, y, z; (viii) x1/2, y1/2, z; (ix) x+1/2, y1/2, z; (x) x+1/2, y+1/2, z; (xi) x+1/2, y+1/2, z; (xii) x, y, z1; (xiii) x+1/2, y+1/2, z1; (xiv) x+1/2, y1/2, z1; (xv) x+1/2, y1/2, z; (xvi) x, y, z1; (xvii) x, y+1, z; (xviii) x, y1, z.
(IX) top
Crystal data top
BaVS3Dx = 4.312 Mg m3
Mr = 284.5Synchrotron radiation, λ = 0.70814 Å
Trigonal, P3m1Cell parameters from 1783 reflections
Hall symbol: P 3;-2"θ = 3.5–28.6°
a = 6.7164 (2) ŵ = 12.05 mm1
c = 5.6088 (2) ÅT = 250 K
V = 219.12 (1) Å3Irregular, grey
Z = 20.05 × 0.03 × 0.02 mm
F(000) = 254
Data collection top
Dectris-CrysAlisPro-abstract goniometer imported dectris images
diffractometer
196 reflections with I > 3σ(I)
Radiation source: synchrotronRint = 0.034
Synchrotron monochromatorθmax = 28.6°, θmin = 3.5°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
h = 88
Tmin = 0.649, Tmax = 1.000k = 88
2069 measured reflectionsl = 55
196 independent reflections
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.00034225F2)
R[F > 3σ(F)] = 0.034(Δ/σ)max = 0.018
wR(F) = 0.146Δρmax = 1.67 e Å3
S = 1.67Δρmin = 1.94 e Å3
196 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
13 parametersExtinction coefficient: 600 (400)
0 restraintsAbsolute structure: 0 of Friedel pairs used in the refinement
12 constraints
Special details top

Refinement. Structure is considered as a commensurate composite with P63/mmc space group for the BaS3 matrix and P3/m space group for the V-chain. The corresponding constrains are applied for the corresponding atomic sides.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba1a0.3333330.6666670.50.0170 (13)
Ba1b0.3333330.66666700.0170 (13)
V1a000.2593 (16)0.0339 (19)
V1b000.2598 (16)0.0339 (19)
S1a0.16378 (19)0.16378 (19)00.018 (3)
S1b0.16378 (19)0.1637830.50.018 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba1a0.0149 (15)0.0149 (15)0.021 (3)0.0074 (7)00
Ba1b0.0149 (15)0.0149 (15)0.021 (3)0.0074 (7)00
V1a0.040 (2)0.040 (2)0.021 (4)0.0201 (11)00
V1b0.040 (2)0.040 (2)0.021 (4)0.0201 (11)00
S1a0.018 (3)0.018 (3)0.025 (6)0.013 (2)0.0002 (7)0.0002 (7)
S1b0.018 (3)0.018 (3)0.025 (6)0.013 (2)0.0002 (7)0.0002 (7)
Geometric parameters (Å, º) top
Ba1a—S1ai3.4286 (9)V1a—V1b2.912 (13)
Ba1a—S1aii3.4286 (9)V1a—S1a2.397 (6)
Ba1a—S1aiii3.4286 (9)V1a—S1aiii2.397 (6)
Ba1a—S1aiv3.4286 (9)V1a—S1ax2.397 (6)
Ba1a—S1av3.4286 (9)V1a—S1bxxi2.335 (5)
Ba1a—S1avi3.4286 (9)V1a—S1bxviii2.335 (5)
Ba1a—S1b3.3584 (7)V1a—S1bxxii2.335 (5)
Ba1a—S1bvii3.3584 (7)V1b—S1a2.399 (5)
Ba1a—S1bviii3.3584 (7)V1b—S1aiii2.399 (5)
Ba1a—S1bix3.3584 (7)V1b—S1ax2.399 (5)
Ba1a—S1bx3.3584 (15)V1b—S1b2.333 (5)
Ba1a—S1bxi3.3584 (15)V1b—S1biii2.333 (5)
Ba1b—S1axii3.3584 (10)V1b—S1bx2.333 (5)
Ba1b—S1a3.3584 (10)S1a—S1axiv3.416 (2)
Ba1b—S1axiii3.3584 (16)S1a—S1aiii3.300 (2)
Ba1b—S1axiv3.3584 (16)S1a—S1ax3.300 (2)
Ba1b—S1axv3.3584 (16)S1a—S1axxiii3.416 (2)
Ba1b—S1ax3.3584 (16)S1a—S1bxviii3.3904 (7)
Ba1b—S1bxvi3.4286 (7)S1a—S1biii3.3904 (7)
Ba1b—S1bxvii3.4286 (7)S1a—S1bxxii3.3904 (9)
Ba1b—S1bxviii3.4286 (7)S1a—S1bx3.3904 (9)
Ba1b—S1biii3.4286 (7)S1b—S1biii3.3001 (15)
Ba1b—S1bxix3.4286 (7)S1b—S1bviii3.4163 (15)
Ba1b—S1bxx3.4286 (7)S1b—S1bxxiv3.416 (2)
V1a—V1bxxi2.697 (13)S1b—S1bx3.300 (2)
V1bxxi—V1a—V1b180V1a—V1b—V1axxv180
S1a—V1a—S1aiii87.0 (3)S1a—V1b—S1aiii86.9 (2)
S1a—V1a—S1ax87.0 (3)S1a—V1b—S1ax86.9 (2)
S1a—V1a—S1bxxi178.0 (4)S1a—V1b—S1b177.9 (3)
S1a—V1a—S1bxviii91.52 (3)S1a—V1b—S1biii91.52 (3)
S1a—V1a—S1bxxii91.52 (4)S1a—V1b—S1bx91.52 (4)
S1aiii—V1a—S1ax87.0 (3)S1aiii—V1b—S1ax86.9 (2)
S1aiii—V1a—S1bxxi91.52 (4)S1aiii—V1b—S1b91.52 (4)
S1aiii—V1a—S1bxviii178.0 (4)S1aiii—V1b—S1biii177.9 (3)
S1aiii—V1a—S1bxxii91.52 (3)S1aiii—V1b—S1bx91.52 (3)
S1ax—V1a—S1bxxi91.52 (5)S1ax—V1b—S1b91.52 (5)
S1ax—V1a—S1bxviii91.52 (2)S1ax—V1b—S1biii91.52 (2)
S1ax—V1a—S1bxxii178.0 (4)S1ax—V1b—S1bx177.9 (3)
S1bxxi—V1a—S1bxviii89.9 (3)S1b—V1b—S1biii90.0 (2)
S1bxxi—V1a—S1bxxii89.9 (3)S1b—V1b—S1bx90.0 (3)
S1bxviii—V1a—S1bxxii89.9 (3)S1biii—V1b—S1bx90.0 (2)
Symmetry codes: (i) x, y+1, z; (ii) x, y+1, z+1; (iii) y, xy, z; (iv) y, xy, z+1; (v) x+y+1, x+1, z; (vi) x+y+1, x+1, z+1; (vii) x+1, y+1, z; (viii) y, xy+1, z; (ix) y+1, xy+1, z; (x) x+y, x, z; (xi) x+y, x+1, z; (xii) x1, y1, z; (xiii) y1, xy1, z; (xiv) y, xy1, z; (xv) x+y, x1, z; (xvi) x, y1, z1; (xvii) x, y1, z; (xviii) y, xy, z1; (xix) x+y1, x1, z1; (xx) x+y1, x1, z; (xxi) x, y, z1; (xxii) x+y, x, z1; (xxiii) x+y+1, x, z; (xxiv) x+y1, x, z; (xxv) x, y, z+1.
(X) top
Crystal data top
BaVS3Dx = 4.305 Mg m3
Mr = 284.5Synchrotron radiation, λ = 0.6622 Å
Trigonal, P3m1Cell parameters from 2946 reflections
Hall symbol: P 3;-2"θ = 3.3–24.4°
a = 6.7180 (5) ŵ = 10.01 mm1
c = 5.6150 (2) ÅT = 295 K
V = 219.46 (2) Å3Irregular, grey
Z = 20.05 × 0.03 × 0.02 mm
F(000) = 254
Data collection top
Dectris-CrysAlisPro-abstract goniometer imported dectris images
diffractometer
168 reflections with I > 2σ(I)
Radiation source: synchrotronRint = 0.038
Synchrotron monochromatorθmax = 24.4°, θmin = 3.3°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
h = 88
Tmin = 0.556, Tmax = 1.000k = 88
2946 measured reflectionsl = 66
173 independent reflections
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.00034225F2)
R[F > 3σ(F)] = 0.028(Δ/σ)max = 0.001
wR(F) = 0.063Δρmax = 0.76 e Å3
S = 3.13Δρmin = 0.73 e Å3
173 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
13 parametersExtinction coefficient: 2700 (700)
0 restraintsAbsolute structure: 0 of Friedel pairs used in the refinement
12 constraintsAbsolute structure parameter: not applicable for the particular case
Special details top

Refinement. Structure is considered as a commensurate composite with P63/mmc space group for the BaS3 matrix and P3/m space group for the V-chain. The corresponding constrains are applied for the corresponding atomic sides.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba1a0.3333330.6666670.50.0183 (7)
Ba1b0.3333330.66666700.0183 (7)
V1a000.2540 (9)0.0337 (9)
V1b000.2558 (9)0.0337 (9)
S1a0.16500 (10)0.16500 (10)00.0171 (13)
S1b0.16500 (10)0.1649980.50.0171 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba1a0.0171 (9)0.0171 (9)0.0206 (10)0.0086 (4)00
Ba1b0.0171 (9)0.0171 (9)0.0206 (10)0.0086 (4)00
V1a0.0410 (12)0.0410 (12)0.0192 (14)0.0205 (6)00
V1b0.0410 (12)0.0410 (12)0.0192 (14)0.0205 (6)00
S1a0.0187 (15)0.0187 (15)0.017 (2)0.0117 (10)0.0000 (3)0.0000 (3)
S1b0.0187 (15)0.0187 (15)0.017 (2)0.0117 (10)0.0000 (3)0.0000 (3)
Geometric parameters (Å, º) top
Ba1a—S1ai3.4233 (5)V1a—V1b2.862 (7)
Ba1a—S1aii3.4233 (5)V1a—S1a2.392 (3)
Ba1a—S1aiii3.4233 (5)V1a—S1aiii2.392 (3)
Ba1a—S1aiv3.4233 (5)V1a—S1ax2.392 (3)
Ba1a—S1av3.4233 (5)V1a—S1bxxi2.365 (3)
Ba1a—S1avi3.4233 (5)V1a—S1bxviii2.365 (3)
Ba1a—S1b3.3591 (8)V1a—S1bxxii2.365 (3)
Ba1a—S1bvii3.3591 (8)V1b—S1a2.398 (3)
Ba1a—S1bviii3.3591 (6)V1b—S1aiii2.398 (3)
Ba1a—S1bix3.3591 (6)V1b—S1ax2.398 (3)
Ba1a—S1bx3.3591 (9)V1b—S1b2.359 (3)
Ba1a—S1bxi3.3591 (9)V1b—S1biii2.359 (3)
Ba1b—S1axii3.3591 (9)V1b—S1bx2.359 (3)
Ba1b—S1a3.3591 (9)S1a—S1axiv3.3926 (13)
Ba1b—S1axiii3.3591 (9)S1a—S1aiii3.3254 (13)
Ba1b—S1axiv3.3591 (9)S1a—S1ax3.3254 (13)
Ba1b—S1axv3.3591 (9)S1a—S1axxiii3.3926 (13)
Ba1b—S1ax3.3591 (9)S1a—S1bxviii3.4012 (4)
Ba1b—S1bxvi3.4233 (4)S1a—S1biii3.4012 (4)
Ba1b—S1bxvii3.4233 (4)S1a—S1bxxii3.4012 (5)
Ba1b—S1bxviii3.4233 (4)S1a—S1bx3.4012 (5)
Ba1b—S1biii3.4233 (4)S1b—S1biii3.3254 (9)
Ba1b—S1bxix3.4233 (4)S1b—S1bviii3.3926 (9)
Ba1b—S1bxx3.4233 (4)S1b—S1bxxiv3.3926 (11)
V1a—V1bxxi2.753 (7)S1b—S1bx3.3254 (11)
V1bxxi—V1a—V1b180V1a—V1b—V1axxv180
S1a—V1a—S1aiii88.09 (15)S1a—V1b—S1aiii87.81 (14)
S1a—V1a—S1ax88.09 (15)S1a—V1b—S1ax87.81 (14)
S1a—V1a—S1bxxi179.1 (2)S1a—V1b—S1b178.7 (2)
S1a—V1a—S1bxviii91.287 (16)S1a—V1b—S1biii91.281 (17)
S1a—V1a—S1bxxii91.29 (2)S1a—V1b—S1bx91.28 (2)
S1aiii—V1a—S1ax88.09 (15)S1aiii—V1b—S1ax87.81 (14)
S1aiii—V1a—S1bxxi91.29 (2)S1aiii—V1b—S1b91.28 (2)
S1aiii—V1a—S1bxviii179.1 (2)S1aiii—V1b—S1biii178.7 (2)
S1aiii—V1a—S1bxxii91.287 (17)S1aiii—V1b—S1bx91.281 (17)
S1ax—V1a—S1bxxi91.29 (2)S1ax—V1b—S1b91.28 (2)
S1ax—V1a—S1bxviii91.287 (13)S1ax—V1b—S1biii91.281 (13)
S1ax—V1a—S1bxxii179.1 (2)S1ax—V1b—S1bx178.7 (2)
S1bxxi—V1a—S1bxviii89.33 (15)S1b—V1b—S1biii89.61 (15)
S1bxxi—V1a—S1bxxii89.33 (15)S1b—V1b—S1bx89.61 (15)
S1bxviii—V1a—S1bxxii89.33 (15)S1biii—V1b—S1bx89.61 (15)
Symmetry codes: (i) x, y+1, z; (ii) x, y+1, z+1; (iii) y, xy, z; (iv) y, xy, z+1; (v) x+y+1, x+1, z; (vi) x+y+1, x+1, z+1; (vii) x+1, y+1, z; (viii) y, xy+1, z; (ix) y+1, xy+1, z; (x) x+y, x, z; (xi) x+y, x+1, z; (xii) x1, y1, z; (xiii) y1, xy1, z; (xiv) y, xy1, z; (xv) x+y, x1, z; (xvi) x, y1, z1; (xvii) x, y1, z; (xviii) y, xy, z1; (xix) x+y1, x1, z1; (xx) x+y1, x1, z; (xxi) x, y, z1; (xxii) x+y, x, z1; (xxiii) x+y+1, x, z; (xxiv) x+y1, x, z; (xxv) x, y, z+1.
 

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