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The stable structures of deuterated thiophene C4D4S were investigated at 155 (phase III), 115 (phase IV), 100 and 1.5 K (phase V) by neutron powder diffraction. At 155 K, thiophene is orthorhombic with space group Pbnm. Although there is some degree of in-plane orientational disorder, molecules begin to order along two symmetrically equivalent main orientations. At 115 K the structure is incommensurate, with a wavevector q ≃ 0.55a*. At 100 K and below, there is a doubling of the a cell parameter and the structure space group is P21. For the first time, it is shown that, unlike C4H4S, phase V of C4D4S is not an orientational glass: thiophene molecules are perfectly ordered and are oriented within the molecular plane along two alternating directions, corresponding to the two main orientations observed at 155 K. This ordering probably originates in the slowing down of the in-plane reorientational dynamics upon deuteration.
Supporting information
CCDC references: 705588; 705589; 705590
The synthesis of deuterated thiophene was performed as described in Dunstetter et al. Chem. Phys. 175, 475 (1993)
Program(s) used to refine structure: FULLPROF for 100K, 1point5K, 155K; (Jana2000; Petricek and Dusek, 2000) for 115K. Molecular graphics: Diamond for 100K, 1point5K, 155K. Software used to prepare material for publication: (Jana2000; Petricek and Dusek, 2000) for 115K.
(100K) deuterated thiophene
top
Crystal data top
C4D4S | V = 842.93 (2) Å3 |
Mr = 88 | Z = 8 |
Monoclinic, P21 | vanadium sample holder |
Hall symbol: P 2yb | Neutron radiation, λ = 2.450000 Å |
a = 11.05278 (19) Å | T = 100 K |
b = 7.50396 (9) Å | colourless |
c = 10.1632 (2) Å | ?, ? × ? × ? mm |
β = 89.996 (6)° | |
Data collection top
Powder diffractometer | 2θmin = 1.952°, 2θmax = 159.852°, 2θstep = 0.100° |
Radiation source: nuclear reactor, G41, Saclay | |
Refinement top
Rp = 3.706 | Excluded region(s): 32.40 33.75 |
Rwp = 4.731 | Profile function: manual |
Rexp = 1.827 | 40 parameters |
RBragg = 5.592 | 0 restraints |
χ2 = NOT FOUND | |
1580 data points | Preferred orientation correction: no |
Crystal data top
C4D4S | β = 89.996 (6)° |
Mr = 88 | V = 842.93 (2) Å3 |
Monoclinic, P21 | Z = 8 |
a = 11.05278 (19) Å | Neutron radiation, λ = 2.450000 Å |
b = 7.50396 (9) Å | T = 100 K |
c = 10.1632 (2) Å | ?, ? × ? × ? mm |
Data collection top
Powder diffractometer | 2θmin = 1.952°, 2θmax = 159.852°, 2θstep = 0.100° |
Refinement top
Rp = 3.706 | χ2 = NOT FOUND |
Rwp = 4.731 | 1580 data points |
Rexp = 1.827 | 40 parameters |
RBragg = 5.592 | 0 restraints |
Special details top
Experimental. Sample was first cooled quickly down to 1.5 K (metastable phase sequence), then heated up to 160 K, at which temperature it was kept for a few hours until the transformation from metastable phase II to stable phase III was complete |
Geometry. rigid body group non refined |
Refinement. Rigid-body Rietvelt refinement of powder data using TLS matrices (4 molecules) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
PI1 | −0.16882 | 0.18453 | −0.11888 | 0.00000 | |
PI2 | −0.04977 | 0.09072 | −0.07876 | 0.00000 | |
PI3 | −0.21796 | 0.24508 | 0.01646 | 0.00000 | |
PI4 | −0.03606 | 0.09900 | 0.05862 | 0.00000 | |
PI5 | −0.13729 | 0.19191 | 0.11593 | 0.00000 | |
PI6 | 0.01547 | 0.02737 | −0.13986 | 0.00000 | |
PI7 | −0.29892 | 0.31591 | 0.03811 | 0.00000 | |
PI8 | 0.03695 | 0.04589 | 0.11393 | 0.00000 | |
PI9 | −0.14745 | 0.21513 | 0.21832 | 0.00000 | |
PJ1 | −0.09499 | −0.23615 | −0.40713 | 0.00000 | |
PJ2 | −0.20634 | −0.11818 | −0.43744 | 0.00000 | |
PJ3 | −0.03416 | −0.24737 | −0.54398 | 0.00000 | |
PJ4 | −0.20616 | −0.07185 | −0.57146 | 0.00000 | |
PJ5 | −0.10253 | −0.14960 | −0.63558 | 0.00000 | |
PJ6 | −0.27550 | −0.07404 | −0.37235 | 0.00000 | |
PJ7 | 0.04636 | −0.31552 | −0.57149 | 0.00000 | |
PJ8 | −0.27144 | 0.00807 | −0.62025 | 0.00000 | |
PJ9 | −0.08267 | −0.13357 | −0.73704 | 0.00000 | |
PO1 | 0.32042 | 0.19398 | 0.12189 | 0.00000 | |
PO2 | 0.43830 | 0.08976 | 0.09331 | 0.00000 | |
PO3 | 0.28495 | 0.25784 | −0.01762 | 0.00000 | |
PO4 | 0.46340 | 0.09598 | −0.04220 | 0.00000 | |
PO5 | 0.37110 | 0.19714 | −0.10897 | 0.00000 | |
PO6 | 0.49567 | 0.02126 | 0.16043 | 0.00000 | |
PO7 | 0.20905 | 0.33541 | −0.04693 | 0.00000 | |
PO8 | 0.53835 | 0.03629 | −0.09032 | 0.00000 | |
PO9 | 0.37023 | 0.22055 | −0.21193 | 0.00000 | |
PP1 | 0.41729 | −0.21585 | −0.60670 | 0.00000 | |
PP2 | 0.30133 | −0.11390 | −0.56667 | 0.00000 | |
PP3 | 0.47709 | −0.24839 | −0.47118 | 0.00000 | |
PP4 | 0.29841 | −0.09383 | −0.42919 | 0.00000 | |
PP5 | 0.40419 | −0.17477 | −0.37172 | 0.00000 | |
PP6 | 0.23126 | −0.06326 | −0.62792 | 0.00000 | |
PP7 | 0.55980 | −0.31463 | −0.44942 | 0.00000 | |
PP8 | 0.22972 | −0.02940 | −0.37391 | 0.00000 | |
PP9 | 0.42241 | −0.17683 | −0.26922 | 0.00000 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
PI1 | 0.00239 | 0.00571 | 0.00909 | −0.00146 | −0.00071 | 0.00001 |
PI2 | 0.00172 | 0.00619 | 0.01034 | −0.00087 | 0.00083 | −0.00025 |
PI3 | 0.00148 | 0.00625 | 0.01061 | −0.00081 | 0.00063 | −0.00017 |
PI4 | 0.00224 | 0.00773 | 0.01084 | −0.00068 | −0.00145 | 0.00023 |
PI5 | 0.00414 | 0.00728 | 0.00879 | −0.00112 | 0.00011 | −0.00035 |
PI6 | 0.00455 | 0.01348 | 0.01398 | 0.00184 | 0.00312 | −0.00097 |
PI7 | 0.00304 | 0.01384 | 0.01561 | 0.00220 | 0.00189 | −0.00051 |
PI8 | 0.00506 | 0.01683 | 0.01532 | 0.00204 | −0.00430 | 0.00070 |
PI9 | 0.01100 | 0.01542 | 0.00892 | 0.00065 | 0.00056 | −0.00112 |
PJ1 | 0.00247 | 0.00529 | 0.00906 | −0.00135 | −0.00039 | 0.00048 |
PJ2 | 0.00167 | 0.00648 | 0.01039 | −0.00102 | 0.00097 | −0.00015 |
PJ3 | 0.00147 | 0.00642 | 0.01061 | −0.00090 | 0.00075 | −0.00015 |
PJ4 | 0.00250 | 0.00679 | 0.01064 | −0.00034 | −0.00106 | 0.00056 |
PJ5 | 0.00406 | 0.00731 | 0.00893 | −0.00126 | 0.00065 | 0.00057 |
PJ6 | 0.00431 | 0.01466 | 0.01419 | 0.00123 | 0.00365 | −0.00050 |
PJ7 | 0.00307 | 0.01424 | 0.01556 | 0.00196 | 0.00228 | −0.00051 |
PJ8 | 0.00584 | 0.01398 | 0.01471 | 0.00306 | −0.00318 | 0.00163 |
PJ9 | 0.01074 | 0.01560 | 0.00936 | 0.00018 | 0.00220 | 0.00167 |
PO1 | 0.00227 | 0.00575 | 0.00922 | −0.00145 | 0.00081 | −0.00002 |
PO2 | 0.00195 | 0.00595 | 0.01012 | −0.00085 | −0.00082 | 0.00036 |
PO3 | 0.00169 | 0.00600 | 0.01040 | −0.00077 | −0.00069 | 0.00027 |
PO4 | 0.00208 | 0.00766 | 0.01101 | −0.00057 | 0.00131 | −0.00026 |
PO5 | 0.00414 | 0.00728 | 0.00880 | −0.00117 | 0.00024 | 0.00043 |
PO6 | 0.00538 | 0.01266 | 0.01316 | 0.00188 | −0.00302 | 0.00136 |
PO7 | 0.00374 | 0.01296 | 0.01492 | 0.00235 | −0.00217 | 0.00081 |
PO8 | 0.00460 | 0.01657 | 0.01582 | 0.00237 | 0.00387 | −0.00079 |
PO9 | 0.01105 | 0.01539 | 0.00891 | 0.00050 | 0.00050 | 0.00139 |
PP1 | 0.00248 | 0.00554 | 0.00900 | −0.00139 | 0.00052 | −0.00026 |
PP2 | 0.00161 | 0.00645 | 0.01046 | −0.00097 | −0.00090 | 0.00016 |
PP3 | 0.00139 | 0.00644 | 0.01069 | −0.00089 | −0.00066 | 0.00013 |
PP4 | 0.00241 | 0.00733 | 0.01066 | −0.00051 | 0.00130 | −0.00041 |
PP5 | 0.00409 | 0.00737 | 0.00883 | −0.00116 | −0.00051 | −0.00017 |
PP6 | 0.00412 | 0.01447 | 0.01442 | 0.00145 | −0.00343 | 0.00060 |
PP7 | 0.00277 | 0.01442 | 0.01587 | 0.00196 | −0.00197 | 0.00041 |
PP8 | 0.00559 | 0.01562 | 0.01478 | 0.00253 | 0.00391 | −0.00120 |
PP9 | 0.01082 | 0.01577 | 0.00906 | 0.00051 | −0.00178 | −0.00046 |
Geometric parameters (Å, º) top
PI1—PI2 | 1.717 | PI4—PI5 | 1.442 |
PI2—PI4 | 1.368 | PI2—PI6 | 1.072 |
| | | |
PI3—PI1—PI2 | 91.90 | PI1—PI2—PI6 | 121.0 |
PI1—PI2—PI4 | 112.0 | PI2—PI4—PI5 | 120.0 |
(1point5K) deuterated thiophene
top
Crystal data top
C4D4S | β = 89.989 (5)° |
Mr = 88 | V = 826.85 (2) Å3 |
Monoclinic, P21 | Z = 8 |
Hall symbol: P 2yb | Neutron radiation, λ = 2.450000 Å |
a = 11.02171 (18) Å | T = 2 K |
b = 7.42951 (10) Å | colourless |
c = 10.09755 (18) Å | ?, ? × ? × ? mm |
Data collection top
Powder diffractometer | Scan method: step |
Radiation source: nuclear reactor, G41, Saclay | 2θmin = 1.955°, 2θmax = 159.855°, 2θstep = 0.100° |
Refinement top
Rp = 4.542 | Excluded region(s): 32.6 33.75 |
Rwp = 5.758 | Profile function: manual |
Rexp = 1.838 | 41 parameters |
RBragg = 5.051 | 0 restraints |
χ2 = NOT FOUND | |
1580 data points | Preferred orientation correction: no |
Crystal data top
C4D4S | β = 89.989 (5)° |
Mr = 88 | V = 826.85 (2) Å3 |
Monoclinic, P21 | Z = 8 |
a = 11.02171 (18) Å | Neutron radiation, λ = 2.450000 Å |
b = 7.42951 (10) Å | T = 2 K |
c = 10.09755 (18) Å | ?, ? × ? × ? mm |
Data collection top
Powder diffractometer | 2θmin = 1.955°, 2θmax = 159.855°, 2θstep = 0.100° |
Scan method: step | |
Refinement top
Rp = 4.542 | χ2 = NOT FOUND |
Rwp = 5.758 | 1580 data points |
Rexp = 1.838 | 41 parameters |
RBragg = 5.051 | 0 restraints |
Special details top
Experimental. Sample was first cooled quickly down to 1.5 K (metastable phase sequence), then heated up to 160 K, at which temperature it was kept for a few hours until the transformation from metastable phase II to stable phase III was complete |
Refinement. Rigid-body Rietvelt refinement of powder data using TLS matrices (4 molecules) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
PI1 | −0.17951 | 0.18477 | −0.13171 | 0.00000 | |
PI2 | −0.06055 | 0.08679 | −0.09409 | 0.00000 | |
PI3 | −0.22465 | 0.24905 | 0.00544 | 0.00000 | |
PI4 | −0.04340 | 0.09635 | 0.04367 | 0.00000 | |
PI5 | −0.14216 | 0.19401 | 0.10358 | 0.00000 | |
PI6 | 0.00247 | 0.02005 | −0.15700 | 0.00000 | |
PI7 | −0.30427 | 0.32336 | 0.02905 | 0.00000 | |
PI8 | 0.03035 | 0.04109 | 0.09761 | 0.00000 | |
PI9 | −0.14956 | 0.21899 | 0.20674 | 0.00000 | |
PJ1 | −0.08508 | −0.22948 | −0.40628 | 0.00000 | |
PJ2 | −0.19950 | −0.11649 | −0.43733 | 0.00000 | |
PJ3 | −0.02907 | −0.25148 | −0.54585 | 0.00000 | |
PJ4 | −0.20499 | −0.08196 | −0.57407 | 0.00000 | |
PJ5 | −0.10243 | −0.16320 | −0.63939 | 0.00000 | |
PJ6 | −0.26699 | −0.06805 | −0.37098 | 0.00000 | |
PJ7 | 0.05156 | −0.32038 | −0.57383 | 0.00000 | |
PJ8 | −0.27338 | −0.00769 | −0.62391 | 0.00000 | |
PJ9 | −0.08654 | −0.15569 | −0.74289 | 0.00000 | |
PO1 | 0.32839 | 0.17870 | 0.11259 | 0.00000 | |
PO2 | 0.45091 | 0.08624 | 0.08155 | 0.00000 | |
PO3 | 0.28830 | 0.24106 | −0.02688 | 0.00000 | |
PO4 | 0.47418 | 0.09675 | −0.05511 | 0.00000 | |
PO5 | 0.37631 | 0.18994 | −0.12038 | 0.00000 | |
PO6 | 0.51230 | 0.02235 | 0.14785 | 0.00000 | |
PO7 | 0.20837 | 0.31172 | −0.05483 | 0.00000 | |
PO8 | 0.55143 | 0.04496 | −0.10494 | 0.00000 | |
PO9 | 0.37317 | 0.21469 | −0.22381 | 0.00000 | |
PP1 | 0.40797 | −0.25333 | −0.58597 | 0.00000 | |
PP2 | 0.29691 | −0.13415 | −0.55291 | 0.00000 | |
PP3 | 0.47166 | −0.26450 | −0.44970 | 0.00000 | |
PP4 | 0.29974 | −0.08721 | −0.41809 | 0.00000 | |
PP5 | 0.40491 | −0.16566 | −0.35596 | 0.00000 | |
PP6 | 0.22630 | −0.08964 | −0.61681 | 0.00000 | |
PP7 | 0.55293 | −0.33331 | −0.42389 | 0.00000 | |
PP8 | 0.23525 | −0.00644 | −0.36750 | 0.00000 | |
PP9 | 0.42682 | −0.14935 | −0.25435 | 0.00000 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
PI1 | 0.00085 | 0.00100 | 0.00369 | −0.00041 | −0.00031 | 0.00003 |
PI2 | 0.00068 | 0.00115 | 0.00422 | −0.00004 | 0.00033 | −0.00021 |
PI3 | 0.00059 | 0.00116 | 0.00433 | 0.00000 | 0.00026 | −0.00015 |
PI4 | 0.00083 | 0.00212 | 0.00445 | 0.00006 | −0.00058 | 0.00020 |
PI5 | 0.00159 | 0.00201 | 0.00356 | −0.00026 | −0.00001 | −0.00026 |
PI6 | 0.00209 | 0.00534 | 0.00579 | 0.00149 | 0.00124 | −0.00081 |
PI7 | 0.00149 | 0.00543 | 0.00650 | 0.00175 | 0.00079 | −0.00045 |
PI8 | 0.00208 | 0.00746 | 0.00643 | 0.00160 | −0.00171 | 0.00061 |
PI9 | 0.00445 | 0.00712 | 0.00363 | 0.00061 | 0.00007 | −0.00083 |
PJ1 | 0.00090 | 0.00082 | 0.00368 | −0.00034 | −0.00020 | 0.00025 |
PJ2 | 0.00062 | 0.00134 | 0.00422 | −0.00012 | 0.00039 | −0.00015 |
PJ3 | 0.00055 | 0.00130 | 0.00433 | −0.00006 | 0.00030 | −0.00013 |
PJ4 | 0.00096 | 0.00173 | 0.00443 | 0.00021 | −0.00047 | 0.00034 |
PJ5 | 0.00157 | 0.00205 | 0.00357 | −0.00029 | 0.00020 | 0.00021 |
PJ6 | 0.00186 | 0.00607 | 0.00580 | 0.00117 | 0.00146 | −0.00052 |
PJ7 | 0.00138 | 0.00582 | 0.00649 | 0.00157 | 0.00093 | −0.00042 |
PJ8 | 0.00248 | 0.00631 | 0.00637 | 0.00206 | −0.00139 | 0.00101 |
PJ9 | 0.00438 | 0.00731 | 0.00366 | 0.00049 | 0.00069 | 0.00059 |
PO1 | 0.00081 | 0.00102 | 0.00372 | −0.00042 | 0.00034 | 0.00000 |
PO2 | 0.00070 | 0.00118 | 0.00419 | −0.00006 | −0.00035 | 0.00021 |
PO3 | 0.00059 | 0.00120 | 0.00431 | −0.00002 | −0.00029 | 0.00016 |
PO4 | 0.00075 | 0.00220 | 0.00453 | 0.00004 | 0.00057 | −0.00015 |
PO5 | 0.00159 | 0.00201 | 0.00356 | −0.00027 | 0.00008 | 0.00028 |
PO6 | 0.00215 | 0.00543 | 0.00567 | 0.00142 | −0.00130 | 0.00082 |
PO7 | 0.00148 | 0.00559 | 0.00644 | 0.00166 | −0.00090 | 0.00047 |
PO8 | 0.00183 | 0.00772 | 0.00666 | 0.00152 | 0.00169 | −0.00047 |
PO9 | 0.00446 | 0.00712 | 0.00363 | 0.00056 | 0.00014 | 0.00089 |
PP1 | 0.00094 | 0.00074 | 0.00369 | −0.00035 | 0.00014 | −0.00033 |
PP2 | 0.00059 | 0.00139 | 0.00425 | −0.00014 | −0.00039 | 0.00012 |
PP3 | 0.00052 | 0.00132 | 0.00435 | −0.00006 | −0.00029 | 0.00012 |
PP4 | 0.00105 | 0.00155 | 0.00440 | 0.00024 | 0.00043 | −0.00041 |
PP5 | 0.00154 | 0.00202 | 0.00363 | −0.00034 | −0.00031 | −0.00035 |
PP6 | 0.00171 | 0.00626 | 0.00593 | 0.00111 | −0.00148 | 0.00043 |
PP7 | 0.00131 | 0.00587 | 0.00655 | 0.00156 | −0.00088 | 0.00038 |
PP8 | 0.00273 | 0.00577 | 0.00628 | 0.00213 | 0.00128 | −0.00119 |
PP9 | 0.00428 | 0.00724 | 0.00386 | 0.00034 | −0.00102 | −0.00101 |
Geometric parameters (Å, º) top
PI1—PI2 | 1.717 | PI4—PI5 | 1.442 |
PI2—PI4 | 1.368 | PI2—PI6 | 1.072 |
| | | |
PI3—PI1—PI2 | 91.90 | PI1—PI2—PI6 | 121.0 |
PI1—PI2—PI4 | 112.0 | PI2—PI4—PI5 | 120.0 |
(155K) deuterated thiophene
top
Crystal data top
C4D4S | V = 432.13 (1) Å3 |
Mr = 88 | Z = 4 |
Orthorhombic, PBNM | Neutron radiation, λ = 2.450000 Å |
Hall symbol: -P 2c 2ab | T = 155 K |
a = 5.5226 (1) Å | colourless |
b = 7.62000 (9) Å | ?, ? × ? × ? mm |
c = 10.2688 (2) Å | |
Data collection top
Powder diffractometer | 2θmin = 1.949°, 2θmax = 159.849°, 2θstep = 0.100° |
Radiation source: nuclear reactor, G41, Saclay | |
Refinement top
Rp = 2.788 | Excluded region(s): 32.30 33.75 and 58.05 58.75 |
Rwp = 3.756 | Profile function: manual |
Rexp = 1.756 | 31 parameters |
RBragg = 3.919 | 0 restraints |
χ2 = NOT FOUND | |
1580 data points | Preferred orientation correction: no |
Crystal data top
C4D4S | V = 432.13 (1) Å3 |
Mr = 88 | Z = 4 |
Orthorhombic, PBNM | Neutron radiation, λ = 2.450000 Å |
a = 5.5226 (1) Å | T = 155 K |
b = 7.62000 (9) Å | ?, ? × ? × ? mm |
c = 10.2688 (2) Å | |
Data collection top
Powder diffractometer | 2θmin = 1.949°, 2θmax = 159.849°, 2θstep = 0.100° |
Refinement top
Rp = 2.788 | χ2 = NOT FOUND |
Rwp = 3.756 | 1580 data points |
Rexp = 1.756 | 31 parameters |
RBragg = 3.919 | 0 restraints |
Special details top
Experimental. Sample was first cooled quickly down to 1.5 K (metastable phase sequence), then heated up to 160 K, at which temperature it was kept for a few hours until the transformation from metastable phase II to stable phase III was complete |
Refinement. Rigid-body Rietvelt refinement of powder data using TLS matrices (3 molecules on the same site with different orientations and different occupations) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
PI1 | −0.05910 | 0.19653 | 0.14236 | 0.00000 | 1.000 (6) |
PI2 | 0.16548 | 0.09378 | 0.19029 | 0.00000 | 1.000 (6) |
PI3 | −0.18083 | 0.24668 | 0.27285 | 0.00000 | 1.000 (6) |
PI4 | 0.16595 | 0.08872 | 0.32713 | 0.00000 | 1.000 (6) |
PI5 | −0.04248 | 0.18074 | 0.37682 | 0.00000 | 1.000 (6) |
PI6 | 0.30443 | 0.03325 | 0.13434 | 0.00000 | 1.000 (6) |
PI7 | −0.34291 | 0.31904 | 0.28868 | 0.00000 | 1.000 (6) |
PI8 | 0.29779 | 0.02727 | 0.38690 | 0.00000 | 1.000 (6) |
PI9 | −0.08188 | 0.19489 | 0.47742 | 0.00000 | 1.000 (6) |
PJ1 | −0.11123 | 0.28002 | 0.26437 | 0.00000 | 0.057 (5) |
PJ2 | −0.00876 | 0.22302 | 0.13068 | 0.00000 | 0.057 (5) |
PJ3 | −0.01573 | 0.13209 | 0.35387 | 0.00000 | 0.057 (5) |
PJ4 | 0.12345 | 0.06661 | 0.14529 | 0.00000 | 0.057 (5) |
PJ5 | 0.11925 | 0.01188 | 0.27962 | 0.00000 | 0.057 (5) |
PJ6 | −0.02799 | 0.28558 | 0.03865 | 0.00000 | 0.057 (5) |
PJ7 | −0.04102 | 0.11561 | 0.45583 | 0.00000 | 0.057 (5) |
PJ8 | 0.21414 | −0.00301 | 0.07025 | 0.00000 | 0.057 (5) |
PJ9 | 0.20649 | −0.10270 | 0.31494 | 0.00000 | 0.057 (5) |
PK1 | 0.10677 | 0.10793 | 0.16597 | 0.00000 | 0.086 (5) |
PK2 | 0.17544 | 0.15948 | 0.30693 | 0.00000 | 0.086 (5) |
PK3 | −0.16169 | 0.16543 | 0.16035 | 0.00000 | 0.086 (5) |
PK4 | −0.02651 | 0.23426 | 0.36910 | 0.00000 | 0.086 (5) |
PK5 | −0.22941 | 0.23784 | 0.28088 | 0.00000 | 0.086 (5) |
PK6 | 0.34443 | 0.14463 | 0.35542 | 0.00000 | 0.086 (5) |
PK7 | −0.28575 | 0.15576 | 0.08143 | 0.00000 | 0.086 (5) |
PK8 | −0.03294 | 0.28180 | 0.46616 | 0.00000 | 0.086 (5) |
PK9 | −0.40255 | 0.28832 | 0.30547 | 0.00000 | 0.086 (5) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
PI1 | 0.02591 | 0.00859 | 0.01474 | −0.00505 | −0.00513 | 0.00000 |
PI2 | 0.02695 | 0.01006 | 0.01501 | 0.00300 | 0.00130 | −0.00175 |
PI3 | 0.01735 | 0.00937 | 0.02040 | −0.00161 | 0.00308 | −0.00059 |
PI4 | 0.03245 | 0.01157 | 0.01522 | 0.00178 | −0.00234 | 0.00313 |
PI5 | 0.03525 | 0.01111 | 0.01431 | −0.00762 | 0.00620 | 0.00054 |
PI6 | 0.04434 | 0.02103 | 0.02208 | 0.00945 | 0.00784 | −0.00596 |
PI7 | 0.02196 | 0.01976 | 0.03430 | 0.00426 | 0.00730 | −0.00209 |
PI8 | 0.05533 | 0.02355 | 0.02217 | 0.00664 | −0.01073 | 0.00833 |
PI9 | 0.07083 | 0.02265 | 0.01547 | −0.01854 | 0.01389 | −0.00037 |
PJ1 | 0.01786 | 0.00691 | 0.01756 | −0.00095 | 0.00194 | −0.00043 |
PJ2 | 0.02774 | 0.00902 | 0.01336 | −0.00535 | −0.00467 | 0.00001 |
PJ3 | 0.03296 | 0.00930 | 0.01420 | −0.00573 | 0.00345 | 0.00159 |
PJ4 | 0.03685 | 0.01036 | 0.01553 | 0.00066 | 0.00176 | −0.00342 |
PJ5 | 0.03905 | 0.00804 | 0.01791 | 0.00428 | −0.00102 | 0.00176 |
PJ6 | 0.05654 | 0.01746 | 0.01433 | −0.01326 | −0.01164 | 0.00238 |
PJ7 | 0.06678 | 0.01927 | 0.01494 | −0.01598 | 0.00750 | 0.00315 |
PJ8 | 0.06827 | 0.02021 | 0.02094 | 0.00217 | 0.00928 | −0.00930 |
PJ9 | 0.07114 | 0.01296 | 0.02753 | 0.01344 | −0.00510 | 0.00525 |
PK1 | 0.02821 | 0.00882 | 0.01395 | −0.00013 | 0.00056 | −0.00208 |
PK2 | 0.02275 | 0.01108 | 0.01296 | −0.00011 | −0.00123 | 0.00169 |
PK3 | 0.02422 | 0.01017 | 0.01850 | −0.00606 | −0.00607 | 0.00027 |
PK4 | 0.03218 | 0.01041 | 0.01385 | −0.00666 | 0.00636 | −0.00044 |
PK5 | 0.01783 | 0.01186 | 0.02303 | −0.00205 | 0.00432 | −0.00084 |
PK6 | 0.03226 | 0.02494 | 0.01772 | 0.00144 | −0.00781 | 0.00479 |
PK7 | 0.04290 | 0.02219 | 0.02506 | −0.01393 | −0.01730 | 0.00190 |
PK8 | 0.06642 | 0.02056 | 0.01445 | −0.01620 | 0.01323 | −0.00262 |
PK9 | 0.02179 | 0.02563 | 0.03824 | 0.00214 | 0.01059 | −0.00281 |
Geometric parameters (Å, º) top
PI1—PI2 | 1.717 | PI4—PI5 | 1.442 |
PI2—PI4 | 1.368 | PI2—PI6 | 1.072 |
| | | |
PI3—PI1—PI2 | 91.90 | PI1—PI2—PI6 | 121.0 |
PI1—PI2—PI4 | 112.0 | PI2—PI4—PI5 | 120.0 |
Crystal data top
C4D4S | V = 423.17 Å3 |
Mr = 84.1 | Z = 4 |
Monoclinic, P21(α0γ)0† | F(000) = 135 |
q = 0.55243a* | Dx = 1.320 Mg m−3 |
a = 5.5169 Å | Neutron radiation, λ = 2.45 Å |
b = 7.5335 Å | T = 115 K |
c = 10.1817 Å | ?, ? × ? × ? mm |
β = 89.996° | |
† Symmetry operations: (1) x1, x2, x3, x4; (2) −x1, 1/2+x2, −x3, −x4.
|
Data collection top
2θmin = 1.8°, 2θmax = 159.7°, 2θstep = 0.1° | |
Refinement top
Rp = 0.071 | Excluded region(s): from 32.3 to 33.750 |
Rwp = 0.090 | Profile function: Pseudo-Voigt |
Rexp = 0.063 | 4 parameters |
R(F) = 0.050 | Weighting scheme based on measured s.u.'s |
χ2 = NOT FOUND | (Δ/σ)max = 0.003 |
1580 data points | Preferred orientation correction: none |
Crystal data top
C4D4S | β = 89.996° |
Mr = 84.1 | V = 423.17 Å3 |
Monoclinic, P21(α0γ)0† | Z = 4 |
q = 0.55243a* | Neutron radiation, λ = 2.45 Å |
a = 5.5169 Å | T = 115 K |
b = 7.5335 Å | ?, ? × ? × ? mm |
c = 10.1817 Å | |
† Symmetry operations: (1) x1, x2, x3, x4; (2) −x1, 1/2+x2, −x3, −x4.
|
Data collection top
2θmin = 1.8°, 2θmax = 159.7°, 2θstep = 0.1° | |
Refinement top
Rp = 0.071 | χ2 = NOT FOUND |
Rwp = 0.090 | 1580 data points |
Rexp = 0.063 | 4 parameters |
R(F) = 0.050 | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C2aa | −0.417418 | 0.260057 | 0.01975 | 0.0981* | 0.25 |
C3aa | −0.091183 | 0.07546 | 0.067842 | −0.0233* | 0.25 |
C4aa | −0.270495 | 0.192889 | 0.12115 | 0.0273* | 0.25 |
D1aa | −0.001716 | −0.016969 | −0.127671 | −0.0549* | 0.25 |
D2aa | −0.561956 | 0.349934 | 0.03889 | −0.08* | 0.25 |
D3aa | 0.040488 | 0.008643 | 0.125635 | −0.0795* | 0.25 |
D4aa | −0.286241 | 0.222625 | 0.222776 | −0.0166* | 0.25 |
C2ab | −0.447559 | 0.239697 | −0.028477 | 0.0981* | 0.25 |
C3ab | −0.069406 | 0.112334 | −0.065229 | −0.0233* | 0.25 |
C4ab | −0.287961 | 0.175731 | −0.125283 | 0.0273* | 0.25 |
D1ab | 0.062341 | 0.094703 | 0.134737 | −0.0549* | 0.25 |
D2ab | −0.620521 | 0.292778 | −0.052901 | −0.08* | 0.25 |
D3ab | 0.078063 | 0.057748 | −0.118692 | −0.0795* | 0.25 |
D4ab | −0.320186 | 0.173261 | −0.228125 | −0.0166* | 0.25 |
C1ca | −0.424862 | −0.08698 | −0.452408 | 0.0416* | 0.25 |
C2ca | −0.081723 | −0.24308 | −0.538829 | 0.0349* | 0.25 |
C3ca | −0.436747 | −0.091318 | −0.590437 | −0.013* | 0.25 |
C4ca | −0.230987 | −0.184906 | −0.642249 | 0.0137* | 0.25 |
D1ca | −0.560731 | −0.023569 | −0.394914 | −0.0557* | 0.25 |
D2ca | 0.080752 | −0.315376 | −0.556462 | −0.076* | 0.25 |
D3ca | −0.575085 | −0.034883 | −0.649709 | −0.0871* | 0.25 |
D4ca | −0.2002 | −0.205412 | −0.744115 | 0.0023* | 0.25 |
C1cb | −0.424 (2) | −0.0826 (14) | 0.5226 (16) | 0.0416* | 0.25 |
C2cb | −0.075 (2) | −0.2381 (14) | 0.6031 (16) | 0.0349* | 0.25 |
C3cb | −0.407 (2) | −0.0625 (14) | 0.6597 (16) | −0.013* | 0.25 |
C4cb | −0.198 (2) | −0.1558 (14) | 0.7079 (16) | 0.0137* | 0.25 |
D1cb | −0.567 (2) | −0.0235 (14) | 0.4676 (16) | −0.0557* | 0.25 |
D2cb | 0.085 (2) | −0.3142 (14) | 0.6181 (16) | −0.076* | 0.25 |
D3cb | −0.527 (2) | 0.0100 (14) | 0.7205 (16) | −0.0871* | 0.25 |
D4cb | −0.147 (2) | −0.1599 (14) | 0.8085 (16) | 0.0023* | 0.25 |
Experimental details
| (100K) | (1point5K) | (155K) | (115K) |
Crystal data |
Chemical formula | C4D4S | C4D4S | C4D4S | C4D4S |
Mr | 88 | 88 | 88 | 84.1 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21 | Orthorhombic, PBNM | Monoclinic, P21(α0γ)0† |
Temperature (K) | 100 | 2 | 155 | 115 |
a, b, c (Å) | 11.05278 (19), 7.50396 (9), 10.1632 (2) | 11.02171 (18), 7.42951 (10), 10.09755 (18) | 5.5226 (1), 7.62000 (9), 10.2688 (2) | ? |
α, β, γ (°) | 90, 89.996 (6), 90 | 90, 89.989 (5), 90 | 90, 90, 90 | 5.5169, 7.5335, 10.1817 |
V (Å3) | 842.93 (2) | 826.85 (2) | 432.13 (1) | 90, 89.996, 90 |
Z | 8 | 8 | 4 | 423.17 |
Radiation type | Neutron, λ = 2.450000 Å | Neutron, λ = 2.450000 Å | Neutron, λ = 2.450000 Å | ? |
Specimen shape, size (mm) | ?, ? × ? × ? | ?, ? × ? × ? | ?, ? × ? × ? | ? |
|
Data collection |
Diffractometer | Powder diffractometer | Powder diffractometer | Powder diffractometer | ? |
Specimen mounting | ? | ? | ? | ? |
Data collection mode | ? | ? | ? | ? |
Scan method | ? | Step | ? | ? |
2θ values (°) | 2θmin = 1.952 2θmax = 159.852 2θstep = 0.100 | 2θmin = 1.955 2θmax = 159.855 2θstep = 0.100 | 2θmin = 1.949 2θmax = 159.849 2θstep = 0.100 | 2θmin = 1.8 2θmax = 159.7 2θstep = 0.1 |
|
Refinement |
R factors and goodness of fit | Rp = 3.706, Rwp = 4.731, Rexp = 1.827, RBragg = 5.592, χ2 = NOT FOUND | Rp = 4.542, Rwp = 5.758, Rexp = 1.838, RBragg = 5.051, χ2 = NOT FOUND | Rp = 2.788, Rwp = 3.756, Rexp = 1.756, RBragg = 3.919, χ2 = NOT FOUND | Rp = 0.071, Rwp = 0.090, Rexp = 0.063, R(F) = 0.050, χ2 = NOT FOUND |
No. of data points | 1580 | 1580 | 1580 | 1580 |
No. of parameters | 40 | 41 | 31 | 4 |
No. of restraints | 0 | 0 | 0 | ? |
Selected geometric parameters (Å, º) for (100K) topPI1—PI2 | 1.717 | PI4—PI5 | 1.442 |
PI2—PI4 | 1.368 | PI2—PI6 | 1.072 |
| | | |
PI3—PI1—PI2 | 91.90 | PI1—PI2—PI6 | 121.0 |
PI1—PI2—PI4 | 112.0 | PI2—PI4—PI5 | 120.0 |
Selected geometric parameters (Å, º) for (1point5K) topPI1—PI2 | 1.717 | PI4—PI5 | 1.442 |
PI2—PI4 | 1.368 | PI2—PI6 | 1.072 |
| | | |
PI3—PI1—PI2 | 91.90 | PI1—PI2—PI6 | 121.0 |
PI1—PI2—PI4 | 112.0 | PI2—PI4—PI5 | 120.0 |
Selected geometric parameters (Å, º) for (155K) topPI1—PI2 | 1.717 | PI4—PI5 | 1.442 |
PI2—PI4 | 1.368 | PI2—PI6 | 1.072 |
| | | |
PI3—PI1—PI2 | 91.90 | PI1—PI2—PI6 | 121.0 |
PI1—PI2—PI4 | 112.0 | PI2—PI4—PI5 | 120.0 |
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