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Supplementary Information
Exceptionally Large Positive and Negative Anisotropic Thermal Expansion of an Organic Crystalline Material
Dinabandhu Das, Tia Jacobs and Leonard J. Barbour*
Department of Chemistry and Polymer Science, University of Stellenbosch, Stellenbosch
7600, South Africa
* Correspondence to: Leonard J. Barbour (E-mail: [email protected])
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Table of contents
1. Single crystal X-ray diffraction
1.1 Crystal data of 225 (Figure S1)
1.2 Crystal data of 240 (Figure S2)
1.3 Crystal data of 255 (Figure S3)
1.4 Crystal data of 270 (Figure S4)
1.5 Crystal data of 285 (Figure S5)
1.6 Crystal data of 300 (Figure S6)
1.7 Crystal data of 315 (Figure S7)
1.8 Crystal data of 330 (Figure S8)
2. Differential scanning calorimetry (Figure S9 and Figure S10)
3. Photomicrographs of 1 at different temperatures (Figure S11)
4. Tilt angle at different temperature (Figure S12)
5. Thermal ellipsoid plot at different temperature (Figure S13)
6. Molecular volume plot at different temperature (Figure S14)
7. Finger print plot at different temperature (Figure S15)
8. Unit cell parameters of 1 at different temperatures (Table S1)
9. Thermal expansion coefficients of 1 (Table S2)
10. C�−C−C angles in the C−C≡C−C≡C−C spine at different temperatures (Table S3)
11. C−C bond distances in C−C≡C−C≡C−C spine at different temperatures (Table
S4)
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12. Linear thermal expansion coefficients of selected materials (Table S5)
13. Reversibility of the thermal expansion of 1 - unit cell determinations of (S,S)-
octa-3,5-diyn-2,7-diol (1) at two different temperatures (Table S6)
14. Description of Animations (Video S1- Video S5)
15. Cryogenic Powder X-ray Diffraction (Figure S16 – Figure S21)
16. Unit cell parameters derived from single-crystal data (SCD) and cryogenic
powder diffraction experiments (XRPD) (Figure S22 – Figure S24)
17. References
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1. Single crystal X-ray diffraction:
Single crystal X-ray data were collected on Bruker SMART Apex diffractometer equipped
with a CCD area detector. A crystal was glued to a thin glass fiber and enveloped in a
temperature-controlled stream of dry nitrogen gas during intensity data collection. The
temperature of the crystal was controlled using an Oxford Cryosystream Plus cryostat. The
single-crystal data were initially recorded at 330 K and then successive datasets were
collected at intervals of 15K as the temperature was slowly decreased to 225 K.
1.1 Crystal data of 225:
C8H10O2, M = 138.16, light brown needle, 0.42 × 0.12 × 0.11 mm3, orthorhombic, space
group P212121 (No. 19), a = 4.6159(14), b = 11.699(4), c = 15.191(4) Å, V = 820.3(4) Å3, Z
= 4, Dc = 1.119 g/cm3, F000 = 296, CCD area detector, MoKα radiation, λ = 0.71073 Å, T
= 225(2)K, 2θmax = 50.0º, 4261 reflections collected, 1451 unique (Rint = 0.0542). The
structure was solved and refined using the programs SHELXS-97 (Sheldrick, 1990) and
SHELXL-97 (Sheldrick, 1997) respectively. The program X-Seed (Barbour, 1999) was
used as an interface to the SHELX programs, and to prepare the figures. Final GooF =
1.042, R1 = 0.0604, wR2 = 0.1140, R indices based on 1000 reflections with I >2sigma(I)
(refinement on F2), 93 parameters, 0 restraints. Lp and absorption corrections were
applied; μ = 0.080 mm-1. Absolute structure parameter = 2(3) (Flack, H. D. Acta Cryst.
1983, A39, 876-881).
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Figure S1 Packing diagram of 1 at 225K viewed along [100].
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1.2 Crystal data of 240:
C8H10O2, M = 138.16, light brown needle, 0.42 × 0.12 × 0.11 mm3, orthorhombic, space
group P212121 (No. 19), a = 4.6857(17), b = 11.656(4), c = 15.089(5) Å, V = 824.1(5) Å3, Z
= 4, Dc = 1.114 g/cm3, F000 = 296, CCD area detector, MoKα radiation, λ = 0.71073 Å, T
= 240(2)K, 2θmax = 49.9º, 4296 reflections collected, 1444 unique (Rint = 0.0504). The
structure was solved and refined using the programs SHELXS-97 (Sheldrick, 1990) and
SHELXL-97 (Sheldrick, 1997) respectively. The program X-Seed (Barbour, 1999) was
used as an interface to the SHELX programs, and to prepare the figures. Final GooF =
1.019, R1 = 0.0595, wR2 = 0.1153, R indices based on 965 reflections with I >2sigma(I)
(refinement on F2), 93 parameters, 0 restraints. Lp and absorption corrections were
applied; μ = 0.079 mm-1. Absolute structure parameter = 2(3) (Flack, H. D. Acta Cryst.
1983, A39, 876-881).
Figure S2 Packing diagram of 1 at 240K viewed along [100].
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1.3 Crystal data of 255:
C8H10O2, M = 138.16, light brown needle, 0.42 × 0.12 × 0.11 mm3, orthorhombic, space
group P212121 (No. 19), a = 4.7427(17), b = 11.638(4), c = 15.025(5) Å, V = 829.3(5) Å3, Z
= 4, Dc = 1.107 g/cm3, F000 = 296, CCD area detector, MoKα radiation, λ = 0.71073 Å, T
= 255(2)K, 2θmax = 49.9º, 4334 reflections collected, 1459 unique (Rint = 0.0551). The
structure was solved and refined using the programs SHELXS-97 (Sheldrick, 1990) and
SHELXL-97 (Sheldrick, 1997) respectively. The program X-Seed (Barbour, 1999) was
used as an interface to the SHELX programs, and to prepare the figures. Final GooF =
1.027, R1 = 0.0602, wR2 = 0.1237, R indices based on 931 reflections with I >2sigma(I)
(refinement on F2), 93 parameters, 0 restraints. Lp and absorption corrections were
applied; μ = 0.079 mm-1. Absolute structure parameter = -1(3) (Flack, H. D. Acta Cryst.
1983, A39, 876-881).
Figure S3 Packing diagram of 1 at 255K viewed along [100].
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1.4 Crystal data of 270:
C8H10O2, M = 138.16, light brown needle, 0.42 × 0.12 × 0.11 mm3, orthorhombic, space
group P212121 (No. 19), a = 4.7853(16), b = 11.618(4), c = 14.965(5) Å, V = 832.0(5) Å3, Z
= 4, Dc = 1.103 g/cm3, F000 = 296, CCD area detector, MoKα radiation, λ = 0.71073 Å, T
= 270(2)K, 2θmax = 50.0º, 4334 reflections collected, 1463 unique (Rint = 0.0523). The
structure was solved and refined using the programs SHELXS-97 (Sheldrick, 1990) and
SHELXL-97 (Sheldrick, 1997) respectively. The program X-Seed (Barbour, 1999) was
used as an interface to the SHELX programs, and to prepare the figures. Final GooF =
0.954, R1 = 0.0549, wR2 = 0.1046, R indices based on 863 reflections with I >2sigma(I)
(refinement on F2), 93 parameters, 0 restraints. Lp and absorption corrections were applied; μ
= 0.078 mm-1. Absolute structure parameter = 1(3) (Flack, H. D. Acta Cryst. 1983, A39,
876-881).
Figure S4 Packing diagram of 1 at 270K viewed along [100].
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1.5 Crystal data of 285:
C8H10O2, M = 138.16, light brown needle, 0.42 × 0.12 × 0.11 mm3, orthorhombic, space
group P212121 (No. 19), a = 4.8194(15), b = 11.615(4), c = 14.938(4) Å, V = 836.2(4) Å3, Z
= 4, Dc = 1.097 g/cm3, F000 = 296, CCD area detector, MoKα radiation, λ = 0.71073 Å, T
= 285(2)K, 2θmax = 50.2º, 4394 reflections collected, 1482 unique (Rint = 0.0518). The
structure was solved and refined using the programs SHELXS-97 (Sheldrick, 1990) and
SHELXL-97 (Sheldrick, 1997) respectively. The program X-Seed (Barbour, 1999) was
used as an interface to the SHELX programs, and to prepare the figures. Final GooF =
0.957, R1 = 0.0519, wR2 = 0.1033, R indices based on 872 reflections with I >2sigma(I)
(refinement on F2), 93 parameters, 0 restraints. Lp and absorption corrections were
applied; μ = 0.078 mm-1. Absolute structure parameter = -1(2) (Flack, H. D. Acta Cryst.
1983, A39, 876-881).
Figure S5 Packing diagram of 1 at 285K viewed along [100].
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1.6 Crystal data of 300:
C8H10O2, M = 138.16, light brown needle, 0.42 × 0.12 × 0.11 mm3, orthorhombic, space
group P212121 (No. 19), a = 4.8450(16), b = 11.607(4), c = 14.905(5) Å, V = 838.2(5) Å3, Z
= 4, Dc = 1.095 g/cm3, F000 = 296, CCD area detector, MoKα radiation, λ = 0.71073 Å, T
= 300(2)K, 2θmax = 50.0º, 4376 reflections collected, 1475 unique (Rint = 0.0526). The
structure was solved and refined using the programs SHELXS-97 (Sheldrick, 1990) and
SHELXL-97 (Sheldrick, 1997) respectively. The program X-Seed (Barbour, 1999) was
used as an interface to the SHELX programs, and to prepare the figures. Final GooF =
0.963, R1 = 0.0576, wR2 = 0.1198, R indices based on 832 reflections with I >2sigma(I)
(refinement on F2), 93 parameters, 0 restraints. Lp and absorption corrections were
applied; μ = 0.078 mm-1. Absolute structure parameter = 1(3) (Flack, H. D. Acta Cryst.
1983, A39, 876-881).
Figure S6 Packing diagram of 1 at 300K viewed along [100].
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1.7 Crystal data of 315:
C8H10O2, M = 138.16, light brown needle, 0.42 × 0.12 × 0.11 mm3, orthorhombic, space
group P212121 (No. 19), a = 4.8683(16), b = 11.607(4), c = 14.883(5) Å, V = 841.0(5) Å3, Z
= 4, Dc = 1.091 g/cm3, F000 = 296, CCD area detector, MoKα radiation, λ = 0.71073 Å, T
= 315(2)K, 2θmax = 49.9º, 4327 reflections collected, 1462 unique (Rint = 0.0467). The
structure was solved and refined using the programs SHELXS-97 (Sheldrick, 1990) and
SHELXL-97 (Sheldrick, 1997) respectively. The program X-Seed (Barbour, 1999) was
used as an interface to the SHELX programs, and to prepare the figures. Final GooF =
0.959, R1 = 0.0533, wR2 = 0.1187, R indices based on 830 reflections with I >2sigma(I)
(refinement on F2), 93 parameters, 0 restraints. Lp and absorption corrections were
applied; μ = 0.078 mm-1. Absolute structure parameter = 3(3) (Flack, H. D. Acta Cryst.
1983, A39, 876-881).
Figure S7 Packing diagram of 1 at 315K viewed along [100].
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1.8 Crystal data of 330:
C8H10O2, M = 138.16, light brown needle, 0.39 × 0.12 × 0.11 mm3, orthorhombic, space
group P212121 (No. 19), a = 4.8797(10), b = 11.596(2), c = 14.873(3) Å, V = 841.6(3) Å3, Z
= 4, Dc = 1.090 g/cm3, F000 = 296, CCD area detector, MoKα radiation, λ = 0.71073 Å, T
= 330(2)K, 2θmax = 50.0º, 4218 reflections collected, 1474 unique (Rint = 0.0402). The
structure was solved and refined using the programs SHELXS-97 (Sheldrick, 1990) and
SHELXL-97 (Sheldrick, 1997) respectively. The program X-Seed (Barbour, 1999) was
used as an interface to the SHELX programs, and to prepare the figures. Final GooF =
1.030, R1 = 0.0511, wR2 = 0.1220, R indices based on 1016 reflections with I >2sigma(I)
(refinement on F2), 93 parameters, 0 restraints. Lp and absorption corrections were
applied; μ = 0.078 mm-1. Absolute structure parameter = 0(2) (Flack, H. D. Acta Cryst.
1983, A39, 876-881).
Figure S8 Packing diagram of 1 at 330K viewed along [100].
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2. Differential scanning calorimetry.
Differential scanning calorimetry was carried out on powdered samples using a TA
Instruments Q100 calorimeter. Approximately 10 mg of the sample was sealed in a crimped
aluminum pan with a hole pierced in the lid. The experiment was carried out under nitrogen
purge.
20 30 40 50 60 70 80-7
-6
-5
-4
-3
-2
-1
0
Temperature (°C)
Hea
t Flo
w (W
/g)
Figure S9 DSC thermogram of 1 showing melting with an onset temperature of 67.3 °C
(340.5 K). The sample was heated from room temperature using a ramp rate of 2 °C min-1.
No phase change occurs before melting of the compound.
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-100 -50 0 50-40
-30
-20
-10
0
10
Temperature/°C
Hea
t Flo
w (W
/g)
Figure S10 DSC thermogram of 1. The sample was first heated to 60 °C, then cooled to -80
°C and then heated again until melting occurred (ramp rate 5 °C min-1).
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3. Photomicrographs of 1 at different temperatures:
245 K 260 K
275 K 290 K
305 K 323 K
Figure S11 Photomicrographs of a needle-shaped single crystal of ca 1.5 mm in length
glued to a thin glass fibre and placed in a temperature-controlled stream of nitrogen gas
(Oxford Cryostream Plus) at 325 K. The frames show large PTE along the crystallographic
a axis (i.e. the needle axis of the crystal) as the temperature is changed by ca 15 K between
photographs.
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4. Tilt angle at different temperatures
225K 240K
255K 270K
285K 300K
315K 330K
Figure S12. A perspective view of the columnar packing mode of compound 1 at different
temperature. The dumbbell-shaped molecules (shown in space-filling representation) stack
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with their linear C7C9C7C9C7C spines tilted at an angle of ϕ relative to the [100]
direction. Colors: gray, carbon; white, hydrogen; and red, oxygen.
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5. Thermal ellipsoid plots at different temperatures
225 K 240 K
255 K 270 K
285 K 300 K
315 K 330 K
Figure S13 Thermal ellipsoid plots of 1 at different temperatures. Atoms are shown with
70% probability thermal ellipsoids. Colors: carbon, grey; hydrogen, white; oxygen, red.
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6. Molecular volume plot at different temperature
225 K 240 K
255 K 270 K
285 K 300 K
315 K 330 K
Figure S14 Molecular volume plots of 1 at different temperatures. The semitransparent
yellow surface represents the space available to a sphere of radius 1.4Å within the packing
arrangement of all the surrounding molecules. Van der Waals surfaces that protrude from
this surface indicate intermolecular interactions.
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7. Finger print plot at different temperature
225 K 240 K
255 K 270 K
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285 K 300 K
325 K 330 K Figure S15 Fingerprint plots generated from Hirshfeld surfaces of 1 at different temperatures.
8. Table S1 Unit cell parameters of 1 at different temperatures: Temperature (K) a axis (Å) b axis (Å) c axis (Å) Volume (Å3)
225 4.6159 (14) 11.699 (4) 15.191 (4) 820.3 (4)
240 4.6857 (17) 11.656 (4) 15.089 (5) 824.1 (5)
255 4.7427 (17) 11.638 (4) 15.025 (5) 829.3 (5)
270 4.7853 (16) 11.618 (4) 14.965 (5) 832.0 (5)
285 4.8194 (15) 11.615 (4) 14.938 (4) 836.2 (4)
300 4.8450 (16) 11.607 (4) 14.905 (5) 838.2 (5)
315 4.8683 (16) 11.607 (4) 14.883 (5) 841.0 (5)
330 4.8797 (10) 11.596 (2) 14.873 (3) 841.6 (3)
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9. Table S2 Thermal expansion coefficients† of 1 Temperature (K) αa
* (×10-6 K-1) αb* (×10-6 K-1) αc
* (×10-6 K-1) αv** (×10-6 K-1)
225 514.9 -84.6 -203.6 241.0240 441.7 -57.5 -161.4 231.0255 374.3 -48.3 -136.3 194.9270 322.4 -31.6 -103.1 190.1285 274.6 -36.4 -97.1 142.6300 237.0 -31.6 -71.7 134.7315 155.7 -63.2 -44.8 47.5330 † All coefficients are calculated relative to the parameters determined at 330 K – i.e. the initial state of the material. Therefore, the coefficient at each temperature Ti refers to the thermal expansion over the temperature range 330 K to Ti. *αa, αb and αc are linear thermal expansion coefficients **αv is the volumetric thermal expansion coefficient 10. Table S3 C −C−C angles in the C−C≡C−C≡C−C spine at different temperatures: Angle 225K 240K 255K 270K 285K 300K 315K 330K
C1-C2-C3 178.00 177.65 177.52 177.91 178.71 177.90 177.52 178.80
C2-C3-C4 178.37 178.78 178.19 178.93 178.04 178.79 178.64 178.07
C3-C4-C5 179.35 178.21 178.69 177.70 178.55 178.12 178.06 178.74
C4-C5-C6 177.59 178.50 178.56 178.74 178.27 179.16 178.38 178.35
11. Table S4 C−C bond distances in C−C≡C−C≡C−C spine at different temperatures: Bond 225K 240K 255K 270K 285K 300K 315K 330K
C1-C2 1.470 1.463 1.457 1.462 1.475 1.450 1.461 1.458
C2-C3 1.195 1.195 1.200 1.188 1.183 1.194 1.197 1.197
C3-C4 1.373 1.373 1.375 1.383 1.373 1380 1.388 1.375
C4-C5 1.201 1.191 1.188 1.189 1.195 1.186 1.181 1.190
C5-C6 1.457 1.460 1.477 1.476 1.468 1.465 1.459 1.467
C1-C6 6.694 6.688 6.693 6.695 6.690 6.672 6.682 6.684
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12. Table S5 Linear thermal expansion coefficients of selected materials
Compound Temperature
(K)
max αa(K-1) max αb(K-1) max αc(K-1)
Ag3Co(CN)61 10-500 132×10-6 -130×10-6
d-H3Co(CN)62 4-300 14.8×10-6 -2.4×10-6
ZrW2O83,4 0.4-430 -9.1×10-6
ZrW2O83,4 430-950 -4.9×10-6
Low cordierite5 600-1050 6×10-6 5×10-6 -0.6×10-6
Cd(CN)26 150-375 -20.4×10-6
Β-Quartz7 900 1.9×10-6 -1.1×10-6
NaCl8 293 39.6×10-6
FMOF-19
(Under N2 atmosphere)
119-295 1.4×10-3 -1.3×10-3
FMOF-19
(Under N2 atmosphere)
90-119 -1.3×10-2 1.2×10-2
FMOF-1 (Under vacuum)9 90-295 230×10-6 -170×10-6
(S,S)-Octa-3,5-diyn-2,7-diol
(1)10
225-330 515×10-6 -85×10-6 -204×10-6
13. Table S6 Reversibility of the thermal expansion of 1 – unit cell determinations of (S,S)-octa-3,5-diyn-2,7-diol (1) at two different temperatures.*
330 K (initial) 240 K 330 K (final)
a / Å 4.87 (1) 4.68 (1) 4.87 (2)
b / Å 11.53 (4) 11.67 (2) 11.54 (4)
c / Å 14.77 (5) 15.12 (3) 14.79 (5)
V / Å3 829 (7) 824 (7) 830 (4)
Mosaicity / ° 0.62 0.67 0.59
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* The crystal system is orthorhombic. The first unit cell was determined at 330 K. Then the
temperature was decreased at a rate of 0.5 K min-1 to 240 K and the unit cell was
redetermined. Thereafter, the temperature was increased at a rate of 0.5 K min-1 to 330 K,
and the unit cell once again redetermined.
14. Description of Animations
All of the animations show changes in the crystal due to changes in temperature. Each
animation begins with a frame recorded at the lowest temperature in the series, and each
successive frame represents a change in temperature by 15 K. After the maximum recorded
temperature is reached, the frames are repeated in reverse order. In reality the crystal was
only cooled from either 330 to 225 K, or 323 to 245 K in ca 15 K intervals and not heated.
However, reversibility of the process was verified by measuring the unit cell parameters at
330 K, then at 240 K after cooling at 0.5 K min-1, and then again at 330 K after heating at
0.5 K min-1.
Video S1 Constructed from the photomicrographs shown in Fig. S11. The crystal is glued
to a thin glass fiber and positioned in a temperature-controlled stream of nitrogen gas. The
individual frames represent snapshots recorded at 15 K intervals.
Video S2 Constructed from the images shown in Fig. S12. As the temperature increases,
the relatively bulky end groups increase slightly in steric bulk, but remain tethered by the
O–H···O hydrogen bonds. This causes the molecules to slide over one another with a
concomitant, but cooperative change in orientation relative to the crystallographic a axis
(horizontal).
Video S3 Constructed from the images shown in Fig. S13. As expected, the thermal
ellipsoids of the atoms increase in size with rising temperature. This effect changes the
steric bulk of the molecule.
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Video S4 Constructed from the images shown in Fig. S14. The semitransparent yellow
surface represents the space available to the molecule within the packing arrangement of all
its neighboring molecules. The animation shows how this volume increases with increasing
temperature as the molecules cooperatively increase in bulk. The result is that the van der
Waals interaction energies become weaker with increasing temperature.
Video S5 Constructed from the images shown in Fig. S15. The fingerprint plot generated
from the Hirshfeld surface of the molecule shows how the van der Waals interactions
weaken with increasing temperature, but also that the hydrogen bond geometry remains
relatively consistent throughout. The two long “horns” extending towards the lower left
region of the plot represent the H···O interactions of the O···O hydrogen bonds that serve as
pivot points of the spring-like arrangement of the molecules.
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15. Cryogenic Powder X-ray Diffraction
Powdered samples were placed in a sealed glass capillary.. X-ray powder diffractograms
were measured using Cu Kα radiation (λ= 1.5418 Å, 40 kV and 30 mA) on a PANalytical
instrument operating in Debye-Scherrer geometry. The first diffractorgam (2θ range from
5º to 40º) was measured at 203 K, after which successive patterns were measured at 20 K
intervals. The sample was cooled at a rate of 0.7 K min−1 between measurements. A
polymorphic phase transformation was observed between 220 and 200 K.
5 10 15 20 25 30 35 40
20000
40000
60000
80000
100000
120000
2 Theta/degrees
Rel
ative
inte
nsit
0
y
1_203K
Figure S16 Experimental powder diffraction pattern of 1 at 203K
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5 10 15 20 25 30 35 40
20000
40000
60000
80000
100000
120000
2 Theta/degrees
Rel
ative
inte
nsity
1_183K
0
Figure S17 Experimental powder diffraction pattern of 1 at 183K
5 10 15 20 25 30 35 40
50000
100000
150000
200000
2 Theta/degrees
Rel
ative
inte
nsity
1_163K
0
Figure S18 Experimental powder diffraction pattern of 1 at 163K
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5 10 15 20 25 30 35 40
50000
100000
150000
200000
2 Theta/degrees
Rel
ative
inte
nsity
1_143K
0
Figure S19 Experimental powder diffraction pattern of 1 at 143K
5 10 15 20 25 30 35 40
50000
100000
150000
200000
2 Theta/degrees
Rel
ative
inte
nsity
1_123K
0
Figure S20 Experimental powder diffraction pattern of 1 at 123K
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5 10 15 20 25 30 35 40
50000
100000
150000
200000
2 Theta/degrees
Rel
ative
inte
nsity
1_103K
0
Figure S21 Experimental powder diffraction pattern of 1 at 103K
16. Unit cell parameters derived from single-crystal data (SCD) and cryogenic powder
diffraction experiments (XRPD)
The three mutually perpendicular 21 screw axes preclude direct determination of unit cell
parameters from the powder data at low angle (i.e. the (100), (010) and (001) reflections are
systematically absent). We therefore used the program DASH11,12 to determine the unit cell
parameters - in all cases it was difficult to obtain accurate values for the known phase as it
continues to cool because of significant high-angle overlap of the peaks of the mixture of phases.
Given the difficulties involved in determining unit cell parameters from the powder data, the level
of confidence in the values reported below is not high.
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100 150 200 250 300 350
4.5
4.6
4.7
4.8
4.9
Temperature (K)
aA
xis
SCD Data
XRPD data
Figure S22 Variation of a with temperature
100 150 200 250 300 35011.55
11.6
11.65
11.7
11.75
11.8
Temperature (K)
b A
xis
SCD Data
XRPD Data
Figure S23 Variation of b with temperature
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100 150 200 250 300 35014.8
14.9
15
15.1
15.2
15.3
15.4
15.5
Temperature (K)
c A
xis
SCD Data
XRPD Data
Figure S24 Variation of c with temperature
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