Exceptionally Large Positive and Negative Anisotropic Thermal … · 2010-02-12 · used as an interface to the SHELX programs, and to prepare the figures. Final GooF = 0.954, R1

SUPPLEMENTARY INFORMATIONdoi: 10.1038/nmat2583

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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])

1

2 nature materials | www.nature.com/naturematerials

SUPPLEMENTARY INFORMATION doi: 10.1038/nmat2583

Table of contents

1. Single crystal X-ray diffraction

1.1 Crystal data of 225 (Figure S1)








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)

2



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

3



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).

4



Figure S1 Packing diagram of 1 at 225K viewed along [100].

5














1983, A39, 876-881).


6













applied; μ = 0.079 mm-1. Absolute structure parameter = -1(3) (Flack, H. D. Acta Cryst.

1983, A39, 876-881).


7












(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).


8













applied; μ = 0.078 mm-1. Absolute structure parameter = -1(2) (Flack, H. D. Acta Cryst.

1983, A39, 876-881).


9














1983, A39, 876-881).


10














1983, A39, 876-881).


11














1983, A39, 876-881).


12



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.

13



-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).

14



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.

15



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.

17



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.

18



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

20



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

22



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.

24



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.

25



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

26



5 10 15 20 25 30 35 40

20000

40000

60000

80000

100000

120000

2 Theta/degrees

Rel

ative

inte

nsity

1_183K

0


5 10 15 20 25 30 35 40

50000

100000

150000

200000

2 Theta/degrees

Rel

ative

inte

nsity

1_163K

0


27



5 10 15 20 25 30 35 40

50000

100000

150000

200000

2 Theta/degrees

Rel

ative

inte

nsity

1_143K

0


5 10 15 20 25 30 35 40

50000

100000

150000

200000

2 Theta/degrees

Rel

ative

inte

nsity

1_123K

0


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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


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.

29



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

30



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

17. References

1. Goodwin, A. L., Calleja, M., Conterio, M. J., Dove, M. T., Evans, J. S. O., Keen, D.

A., Peters, L. & Tucker, M. G. Colossal Positive and Negative Thermal Expansion

in the Framework Material Ag3[Co(CN)6]. Science 319, 794-797 (2008).

2. Goodwin, A. L., Keen, D. A., Tucker, M. G., Dove, M. T., Peters, L. & Evans, J. S.

O. Argentophilicity-Dependent Colossal Thermal Expansion in Extended Prussian

Blue Analogues. J. Am. Chem. Soc. 130, 9660-9661 (2008).

3. Mary, T. A., Evans, J. S. O., Vogt, T. & Sleight, A. W. Negative Thermal

Expansion from 0.3 to 1050 Kelvin in ZrW2O8. Science 272, 90-92 (1996).

4. Sleight, A. W. Isotropic negative thermal expansion. Annu. Rev. Mater. Sci. 28, 29-

43 (1998).

5. Hochella, Jr. M. F., Brown, Jr. G. E., Ross, F. K. & Gibbs, G. V. High-temperature

crystal chemistry of hydrous Mg- and Fe-cordierites. Am. Mineral. 64, 337-351

(1979).

6. Goodwin, A. L. & Kepert, C. J. Negative thermal expansion and low-frequency

modes in cyanide-bridged framework materials. Phys. Rev. B 71, 140301-140304

(2005).

7. Carpenter, M .A., Salje, E. K. H., Graeme-Barber, A., Wruck, B., Dove, M. T. &

Knight, K. S. Calibration of excess thermodynamic properties and elastic constant

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variations associated with the α ↔ β phase transition in quartz. Am. Mineral. 83, 2-

22 (1998).

8. Barron, T. H. K., Collins, J. G. & White, G. K. Thermal expansion of solids at low

temperature. Adv. Phys. 29, 609-730 (1980).

9. Yang, C., Wang, X. & Omary, M. A. Crystallographic Observation of Dynamic Gas

Adsorption Sites and Thermal Expansion in a Breathable Fluorous Metal–Organic

Framework. Angew. Chem. Int. Ed. 48, 2500-2505 (2009).

10. Present study

11. David, W. I. F., Shankland, K., van de Streek, J., Pidcock, E., Motherwell, W. D. S.

& Cole, J. C. DASH a program for crystal structure determination from powder

diffraction data, J. Appl. Cryst. 39, 910-915 (2006).

12 Boultif, A & Louër, D. Indexing of powder diffraction patterns for low-symmetry

lattices by the successive dichotomy method. J. Appl. Cryst. 24, 987-993 (1991).

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Exceptionally Large Positive and Negative Anisotropic Thermal … · 2010-02-12 · used as an interface to the SHELX programs, and to prepare the figures. Final GooF = 0.954, R1