1
Supporting Information for
Reversible control of crystalline rotors by squeezing their hydrogen bond cloud across a halogen bond-mediated phase transition
Cyprien Lemouchi, Hiroshi M. Yamamoto, Reizo Kato, Sergey Simonov, Leokadiya Zorina, Antonio Rodríguez-Fortea, Enric Canadell, Pawel Wzietek, Konstantinos Iliopoulos, Denis Gindre, Michael Chrysos and Patrick Batail*
This file contains:
Figure S1. Temperature dependence of unit cell parameters for 2.
Figure S2. Relative orientation of an inner rotator and its surrounding phenyl platforms for
= 0°.
Table S1. Crystallographic data.
Table S2. C–H···I–C (Å) and C–I···I–C (Å) interactions in 2.
Table S3. Calculated energies as a function of for 2 at 90 K and 298 K
Figure S1. Temperature dependence of unit cell parameters for 2. For clarity of the description of the relative changes, lattice parameters for the low-temperature phase are transformed to high-temperature triclinic unit cell. Doubling of the lattice at the transition temperature is not considered here.
6.9 6.92 6.94 6.96 6.98 7
80 110 140 170 200 230 260 290
a (Å)
T (K)
cooling heating
9.1 9.12 9.14 9.16
80 110 140 170 200 230 260 290
b (Å)
T (K)
cooling heating
83.2 83.4 83.6 83.8 84 84.2
80 110 140 170 200 230 260 290
γ angle (°)
T (K)
cooling heating
640 650 660
80 110 140 170 200 230 260 290
V (Å3)
T (K)
cooling heating
3
Table S1. Crystal data, data collection and refinement details for 2
Temperature / K 293 90
λ / Å 0.71073 0.71073
Chemical formula C24H12F6I4 C24H12F6I4
Molecular weight 921.94 921.94
Crystal system triclinic triclinic
a / Å 7.0104(3) 9.0986(5)
b / Å 9.1585(6) 11.2261(7)
c / Å 10.9366(6) 13.7829(6)
/ ° 80.332(6) 112.913(5)
β / º 73.993(4) 96.345(5)
/ ° 84.208(4) 93.942(5)
V / Å3 664.26(6) 1279.1(1)
Space group, Z P1, 1 P1, 2
F(000) 422 844
ρcalc. / g·cm-3 2.305 2.394
μ / cm-1 47.44 49.27
Tmin, Tmax 0.5422, 0.7460 0.5564, 0.7479
2θmax / º 60.0 79.6
Reflections collected 26080 75631
Independent reflections 3855 15628
Rint 0.0344 0.0296
No. of parameters 199 307
GooF on F2 1.085 1.075
R1 [I>2(I)] 0.0429 0.0262
wR2[I>2(I)] 0.1120 0.0491
5
Table S2. C–H···I–C (Å) and C–I···I–C (Å) interactions in 2 and BIBCO3; the same, yet activated16 interactions in the radical cation salt, -(EDT-TTF-I2)2•+[(Pb5/6[lead
vacancy]1/6I2)1/3–]325 and Dehnicke-Weiss’s [PPh4+][ diiodoacetylene][I–]26
2
Rotator-Stator Stator-Stator
C–H···I–C (Å) C–H···F–C (Å) C–I···I–C (Å)
293 K total rotor site
occupancies:
0.3 + 0.2 + 0.3 + 0.2
30% occupancy 3.304 3.343
30% occupancy 2.640
2.894 in-plane:
3.991 transverse:
4.041 20% occupancy
3.231 3.338 3.352
20% occupancy 2.520 2.655
90 K one single site
3.211 3.270 3.294 3.347
2.714 2.803 2.797
in-plane:
4.188 3.796 transverse:
3.901
BIBCO3
295 K 3.089
3.278 3.325
4.005 4.062
90 K
3.072 3.094 3.107 3.237 3.251 3.274 3.296 3.307 3.309 3.344
3.933 3.952 3.967 3.973 3.996 4.008
F F
I
F F
I F
I F
I
I I
C–H···Br– (Å)14f 3.2932(7)
-(EDT-TTF-I2)2•+[(Pb5/6(lead vacancy)1/6I2)1/3–]325
C–H···I–C (Å) 1
C–H···(I–Pb)anion (Å) 2
C–I···(I–Pb)anion (Å) 3
3.019 2.746 3.788
S S
I I S S S
S H
HH H
S S I
I S
S S
S H HH
H I I
I I I I
I I I I I I
1 2
3
1/2
1/2
7
[PPh4+][ diiodoacetylene[I–] 26 C–I···I– (Å)
3.271 and 3.351
25 T. Devic, M. Evain, Y. Moelo, E. Canadell, P. Auban-Senzier, M. Fourmigué and P. Batail, J. Am. Chem. Soc. 2003, 125, 3295- 3301; T. Devic, E. Canadell, P. Auban-Senzier and P. Batail, J. Mater. Chem. 2004, 14, 135-137.
26 M. Ghassemzadeh, K. Harms, K. Dehnicke and D. Fenske, Z. Naturforsch. B 1994, 49, 593-601; M. Ghassemzadeh, J. Magull, D. Fenske and K. Dehnicke, Z. Naturforsh. B 1996, 51, 1579-1582; J. Grebe, G. Geiseler, K. Harms and K. Dehnicke, Z.
Naturforsh. B 1999, 54, 77-86.
Table S3. Calculated energies (see Figure 7c) as a function of for 2 at 90 K (left) and 298 K (right) when the six CH2 groups as well as the iodine atoms of the six fragments representing the environment are allowed to relax.
Figure S2. Relative orientation of an inner rotator and its surrounding phenyl platforms for
= 0°. is the dihedral angle that involves one C—C bond axle of a rotator blade and the normal to one vicinal phenyl ring, as shown by red dashed lines.
Structure 298 K
(deg) E (au) E rel (kcal/mol)
0 -115866.8032000 0.37
10 -115866.8035106 0.18
20 -115866.8027587 0.65
30 -115866.8027241 0.67
40 -115866.8028505 0.59
50 -115866.8033954 0.25
60 -115866.8037931 0.00
70 -115866.8031711 0.39
80 -115866.8025690 0.77
90 -115866.8027315 0.67
100 -115866.8030960 0.44
110 -115866.8032623 0.33
120 -115866.8034276 0.23
Structure 90 K
(deg) E (au) E rel (kcal/mol)
0 -115866.8219840 0.01
10 -115866.8211673 0.52
20 -115866.8196810 1.46
30 -115866.8178000 2.64
40 -115866.8177680 2.66
50 -115866.8176340 2.74
60 -115866.8188890 1.95
70 -115866.8188490 1.98
80 -115866.8181856 2.39
90 -115866.8184254 2.24
100 -115866.8200739 1.21
110 -115866.8216411 0.23
120 -115866.8219999 0.00
