The crystal structures of C4Br4S and C4Br4Se have been determined from X-ray powder diffraction data, using direct-space search techniques. In the case of C4Br4S two crystalline phases occur, a stable orthorhombic and a metastable monoclinic phase. For the orthorhombic phase two different structural models were found that fit the experimental data equally well. The diversity in crystal structure models and packings of C4Br4S is explained.
Supporting information
| Crystallographic Information File (CIF) https://doi.org/10.1107/S010876810703652X/av5088sup1.cif Contains datablocks C4Br4Sa_publ, C4Br4Sab_publ, C4Br4Sb_publ, C4Br4S2G_publ, C4Br4S2S_publ, C4Br4Se_publ, C4Br4S2G_phase_1, C4Br4S2G_phase_2, C4Br4S2S_phase_1, C4Br4S2S_phase_2, C4Br4S2G_p_01, C4Br4S2S_p_01, C4Br4S2G_overall, C4Br4S2S_overall |
| Rietveld powder data file (CIF format) https://doi.org/10.1107/S010876810703652X/av5088sup2.rtv Contains datablock C4Br4Sb_publ |
| Rietveld powder data file (CIF format) https://doi.org/10.1107/S010876810703652X/av5088sup3.rtv Contains datablock C4Br4Sab_publ |
| Rietveld powder data file (CIF format) https://doi.org/10.1107/S010876810703652X/av5088sup4.rtv Contains datablocks C4Br4S2G_publ, C4Br4S2G_overall, C4Br4S2G_phase_1, C4Br4S2G_phase_2, C4Br4S2G_p_01 |
| Rietveld powder data file (CIF format) https://doi.org/10.1107/S010876810703652X/av5088sup5.rtv Contains datablocks C4Br4S2S_publ, C4Br4S2S_overall, C4Br4S2S_phase_1, C4Br4S2S_phase_2, C4Br4S2S_p_01 |
| Rietveld powder data file (CIF format) https://doi.org/10.1107/S010876810703652X/av5088sup6.rtv Contains datablock C4Br4Se_publ |
CCDC references: 665697; 665698; 665699; 665700; 665701; 665702; 665703; 665704
Crystal data top
C4Br4S | c = 8.824 (4) Å |
Mr = 399.72 | β = 109.181 (3)° |
Monoclinic, Pn | V = 418.1 (5) Å3 |
a = 12.419 (5) Å | Z = 2 |
b = 4.0397 (17) Å | |
Refinement top
Preferred orientation correction: Spherical Harmonic ODF
PHASE 4 spherical harmonic order= 4
The sample symmetry is: cylindrical (fiber texture)
Index = 2 0 -2 Coeff= -0.2896
Index = 2 0 0 Coeff= 0.6004
Index = 2 0 2 Coeff= 0.1875
Index = 4 0 -4 Coeff= 0.0771
Index = 4 0 -2 Coeff= 0.1331
Index = 4 0 0 Coeff= 0.3744
Index = 4 0 2 Coeff= 0.2432
Index = 4 0 4 Coeff= 0.1470 | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S11 | 0.5249 (6) | 0.086 (5) | 0.7188 (8) | 0.01226* | |
C11 | 0.3956 (12) | 0.125 (9) | 0.7364 (12) | 0.01226* | |
C12 | 0.3146 (10) | 0.235 (7) | 0.5964 (11) | 0.01226* | |
C13 | 0.3581 (9) | 0.223 (7) | 0.4673 (10) | 0.01226* | |
C14 | 0.4725 (12) | 0.135 (10) | 0.5204 (14) | 0.01226* | |
Br11 | 0.3733 (8) | 0.122 (3) | 0.9395 (8) | 0.01226* | |
Br12 | 0.1862 (6) | 0.484 (3) | 0.5967 (12) | 0.01226* | |
Br13 | 0.2969 (8) | 0.476 (3) | 0.2774 (9) | 0.01226* | |
Br14 | 0.5668 (6) | 0.096 (4) | 0.3896 (9) | 0.01226* | |
Geometric parameters (Å, º) top
S11—C11 | 1.670 (9) | C14—S11 | 1.667 (9) |
S11—C12 | 2.549 (9) | C14—C13 | 1.387 (8) |
S11—C13 | 2.550 (8) | C14—Br13 | 2.860 (10) |
S11—C14 | 1.667 (9) | C14—Br14 | 1.902 (7) |
S11—Br11 | 3.125 (9) | Br11—S11 | 3.125 (9) |
S11—Br14 | 3.116 (9) | Br11—C11 | 1.901 (8) |
C11—S11 | 1.670 (9) | Br11—C12 | 2.908 (8) |
C11—C12 | 1.386 (8) | Br11—Br12 | 3.474 (11) |
C11—Br11 | 1.901 (8) | Br12—C11 | 2.877 (10) |
C11—Br12 | 2.877 (10) | Br12—C12 | 1.885 (9) |
C12—S11 | 2.549 (9) | Br12—Br11 | 3.474 (11) |
C12—C11 | 1.386 (8) | Br12—Br13 | 3.518 (13) |
C12—C13 | 1.413 (7) | Br13—C12 | 2.918 (9) |
C12—Br11 | 2.908 (8) | Br13—C13 | 1.896 (9) |
C12—Br12 | 1.885 (9) | Br13—C14 | 2.860 (10) |
C12—Br13 | 2.918 (9) | Br13—Br12 | 3.518 (13) |
C13—S11 | 2.550 (8) | Br13—Br14 | 3.520 (12) |
C13—C12 | 1.413 (7) | Br14—S11 | 3.116 (9) |
C13—C14 | 1.387 (8) | Br14—C14 | 1.902 (7) |
C13—Br13 | 1.896 (9) | Br14—Br13 | 3.520 (12) |
| | | |
C11—S11—C14 | 91.8 (4) | C12—C13—C14 | 110.9 (6) |
S11—C11—C12 | 112.7 (6) | C12—C13—Br13 | 123.0 (8) |
S11—C11—Br11 | 122.0 (8) | C14—C13—Br13 | 120.3 (10) |
C12—C11—Br11 | 123.7 (6) | S11—C14—C13 | 112.8 (5) |
C11—C12—C13 | 110.5 (5) | S11—C14—Br14 | 121.5 (6) |
C11—C12—Br12 | 122.4 (9) | C13—C14—Br14 | 125.6 (6) |
C13—C12—Br12 | 124.6 (7) | | |
Crystal data top
C4Br4S | b = 4.034 (3) Å |
Mr = 399.72 | c = 16.350 (12) Å |
Orthorhombic, Pca21 | V = 833.8 (19) Å3 |
a = 12.643 (10) Å | Z = 4 |
Refinement top
Preferred orientation correction: Spherical Harmonic ODF
PHASE 4 spherical harmonic order= 4
The sample symmetry is: cylindrical (fiber texture)
Index = 2 0 0 Coeff= 0.1174
Index = 2 0 2 Coeff= 0.3335
Index = 4 0 0 Coeff= 0.0494
Index = 4 0 2 Coeff= 0.0110
Index = 4 0 4 Coeff= -0.1731 | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S21 | 0.4287 (11) | 0.891 (7) | 0.2800 (8) | 0.01529* | |
C21 | 0.340 (2) | 0.814 (15) | 0.3525 (6) | 0.01529* | |
C22 | 0.241 (2) | 0.687 (14) | 0.3213 (5) | 0.01529* | |
C23 | 0.246 (2) | 0.658 (14) | 0.2361 (4) | 0.01529* | |
C24 | 0.345 (2) | 0.797 (16) | 0.2065 (5) | 0.01529* | |
Br21 | 0.3691 (16) | 0.960 (6) | 0.4641 (7) | 0.01529* | |
Br22 | 0.1230 (17) | 0.493 (6) | 0.3868 (11) | 0.01529* | |
Br23 | 0.1240 (12) | 0.505 (4) | 0.1695 (11) | 0.01529* | |
Br24 | 0.3812 (14) | 0.906 (6) | 0.0949 (7) | 0.01529* | |
Geometric parameters (Å, º) top
S21—C21 | 1.660 (9) | C23—Br23 | 1.985 (8) |
S21—C24 | 1.648 (9) | C24—S21 | 1.648 (9) |
S21—Br21 | 3.116 (9) | C24—C23 | 1.453 (8) |
S21—Br24 | 3.086 (9) | C24—Br24 | 1.933 (9) |
C21—S21 | 1.660 (9) | Br21—S21 | 3.116 (9) |
C21—C22 | 1.451 (8) | Br21—C21 | 1.951 (9) |
C21—Br21 | 1.951 (9) | Br22—C22 | 1.993 (9) |
C22—C21 | 1.451 (8) | Br22—Br23 | 3.553 (13) |
C22—C23 | 1.400 (9) | Br23—C23 | 1.985 (8) |
C22—Br22 | 1.993 (9) | Br23—Br22 | 3.553 (13) |
C23—C22 | 1.400 (9) | Br24—S21 | 3.086 (9) |
C23—C24 | 1.453 (8) | Br24—C24 | 1.933 (9) |
| | | |
C21—S21—C24 | 92.5 (5) | C22—C23—C24 | 109.8 (7) |
S21—C21—C22 | 113.5 (5) | C22—C23—Br23 | 122.4 (8) |
S21—C21—Br21 | 119.1 (7) | C24—C23—Br23 | 127.2 (6) |
C22—C21—Br21 | 126.7 (10) | S21—C24—C23 | 113.6 (5) |
C21—C22—C23 | 109.8 (6) | S21—C24—Br24 | 118.9 (7) |
C21—C22—Br22 | 126.7 (9) | C23—C24—Br24 | 127.4 (8) |
C23—C22—Br22 | 122.4 (8) | | |
Crystal data top
C4Br4S | b = 3.9973 (4) Å |
Mr = 399.72 | c = 16.3267 (15) Å |
Orthorhombic, Pca21 | V = 819.7 (2) Å3 |
a = 12.5599 (12) Å | Z = 4 |
Refinement top
Preferred orientation correction: Spherical Harmonic ODF
PHASE 4 spherical harmonic order= 4
The sample symmetry is: cylindrical (fiber texture)
Index = 2 0 0 Coeff= 0.5624
Index = 2 0 2 Coeff= 0.2451
Index = 4 0 0 Coeff= 0.5976
Index = 4 0 2 Coeff= 0.0529
Index = 4 0 4 Coeff= -0.0365 | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S11 | 0.4235 (9) | 0.950 (4) | 0.2790 (6) | 0.025* | |
C11 | 0.337 (3) | 0.851 (17) | 0.3548 (6) | 0.025* | |
C12 | 0.238 (3) | 0.718 (18) | 0.3223 (7) | 0.025* | |
C13 | 0.235 (3) | 0.713 (18) | 0.2364 (8) | 0.025* | |
C14 | 0.3300 (19) | 0.888 (12) | 0.2060 (6) | 0.025* | |
Br11 | 0.3760 (15) | 0.955 (2) | 0.4641 (4) | 0.00786* | |
Br12 | 0.1244 (17) | 0.491 (3) | 0.3847 (6) | 0.00786* | |
Br13 | 0.1257 (15) | 0.489 (3) | 0.1679 (6) | 0.00786* | |
Br14 | 0.3800 (11) | 0.887 (2) | 0.0965 (4) | 0.00786* | |
Geometric parameters (Å, º) top
S11—C11 | 1.695 (11) | C13—Br13 | 1.986 (11) |
S11—C14 | 1.691 (12) | C14—S11 | 1.691 (12) |
S11—Br11 | 3.080 (9) | C14—C13 | 1.468 (12) |
S11—Br14 | 3.039 (10) | C14—Br14 | 1.895 (12) |
C11—S11 | 1.695 (11) | Br11—S11 | 3.080 (9) |
C11—C12 | 1.448 (11) | Br11—C11 | 1.898 (11) |
C11—Br11 | 1.898 (11) | Br12—C12 | 1.974 (12) |
C12—C11 | 1.448 (11) | Br12—Br13 | 3.540 (5) |
C12—C13 | 1.404 (11) | Br13—C13 | 1.986 (11) |
C12—Br12 | 1.974 (12) | Br13—Br12 | 3.540 (5) |
C13—C12 | 1.404 (11) | Br14—S11 | 3.039 (10) |
C13—C14 | 1.468 (12) | Br14—C14 | 1.895 (12) |
| | | |
C11—S11—C14 | 92.0 (8) | C12—C13—C14 | 108.0 (12) |
S11—C11—C12 | 111.6 (9) | C12—C13—Br13 | 126.0 (12) |
S11—C11—Br11 | 117.9 (8) | C14—C13—Br13 | 125.9 (12) |
C12—C11—Br11 | 130.3 (11) | S11—C14—C13 | 113.3 (14) |
C11—C12—C13 | 113.2 (13) | S11—C14—Br14 | 115.8 (10) |
C11—C12—Br12 | 126.8 (15) | C13—C14—Br14 | 125.9 (15) |
C13—C12—Br12 | 119.3 (11) | | |
Crystal data top
C4Br4S | c = 8.816 (7) Å |
Mr = 399.72 | β = 109.452 (3)° |
Monoclinic, Pn | V = 411.9 (9) Å3 |
a = 12.376 (10) Å | Z = 2 |
b = 4.004 (3) Å | |
Refinement top
Preferred orientation correction: Spherical Harmonic ODF
PHASE 4 spherical harmonic order= 4
The sample symmetry is: cylindrical (fiber texture)
Index = 2 0 -2 Coeff= -0.0704
Index = 2 0 0 Coeff= -0.2127
Index = 2 0 2 Coeff= 0.1838
Index = 4 0 -4 Coeff= -0.0304
Index = 4 0 -2 Coeff= 0.0261
Index = 4 0 0 Coeff= 0.1302
Index = 4 0 2 Coeff= 0.0435
Index = 4 0 4 Coeff= 0.0993 | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S21 | 0.5267 (14) | 0.060 (11) | 0.7208 (15) | 0.025* | |
C21 | 0.399 (3) | 0.17 (2) | 0.741 (3) | 0.025* | |
C22 | 0.326 (3) | 0.331 (17) | 0.606 (2) | 0.025* | |
C23 | 0.364 (3) | 0.285 (18) | 0.474 (2) | 0.025* | |
C24 | 0.474 (3) | 0.16 (2) | 0.523 (3) | 0.025* | |
Br21 | 0.3705 (14) | 0.113 (6) | 0.9377 (15) | 0.00786* | |
Br22 | 0.1761 (10) | 0.481 (6) | 0.5920 (19) | 0.00786* | |
Br23 | 0.2911 (13) | 0.466 (6) | 0.2628 (12) | 0.00786* | |
Br24 | 0.5615 (12) | 0.078 (7) | 0.3852 (14) | 0.00786* | |
Geometric parameters (Å, º) top
S21—C21 | 1.698 (11) | C24—S21 | 1.692 (10) |
S21—C23 | 2.587 (10) | C24—C23 | 1.391 (10) |
S21—C24 | 1.692 (10) | C24—Br23 | 2.909 (11) |
S21—Br21 | 3.146 (11) | C24—Br24 | 1.900 (9) |
S21—Br24 | 3.129 (11) | Br21—S21 | 3.146 (11) |
C21—S21 | 1.698 (11) | Br21—C21 | 1.899 (9) |
C21—C22 | 1.394 (11) | Br21—Br22 | 3.517 (19) |
C21—Br21 | 1.899 (9) | Br22—C21 | 2.918 (11) |
C21—Br22 | 2.918 (11) | Br22—C22 | 1.910 (11) |
C22—C21 | 1.394 (11) | Br22—Br21 | 3.517 (19) |
C22—C23 | 1.405 (11) | Br23—C23 | 1.920 (11) |
C22—Br22 | 1.910 (11) | Br23—C24 | 2.909 (11) |
C23—S21 | 2.587 (10) | Br23—Br24 | 3.52 (2) |
C23—C22 | 1.405 (11) | Br24—S21 | 3.129 (11) |
C23—C24 | 1.391 (10) | Br24—C24 | 1.900 (9) |
C23—Br23 | 1.920 (11) | Br24—Br23 | 3.52 (2) |
| | | |
C21—S21—C24 | 89.9 (6) | C22—C23—C24 | 110.9 (9) |
S21—C21—C22 | 113.4 (9) | C22—C23—Br23 | 125.4 (11) |
S21—C21—Br21 | 121.9 (7) | C24—C23—Br23 | 122.1 (10) |
C22—C21—Br21 | 124.3 (8) | S21—C24—C23 | 113.8 (6) |
C21—C22—C23 | 109.9 (11) | S21—C24—Br24 | 121.1 (7) |
C21—C22—Br22 | 123.3 (10) | C23—C24—Br24 | 125.1 (9) |
C23—C22—Br22 | 124.7 (11) | | |