SUPPLEMENTARY INFORMATION

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1 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 ( ljb@sun.ac.za) nature materials 1

2 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) 2 nature MATERIALS

3 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 nature materials 3

4 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: C 8 H 10 O 2, M = , light brown needle, mm 3, orthorhombic, space group P (No. 19), a = (14), b = (4), c = (4) Å, V = 820.3(4) Å 3, Z = 4, D c = g/cm 3, F 000 = 296, CCD area detector, MoKα radiation, λ = Å, T = 225(2)K, 2θ max = 50.0º, 4261 reflections collected, 1451 unique (R int = ). 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 = , wr2 = , R indices based on 1000 reflections with I >2sigma(I) (refinement on F 2 ), 93 parameters, 0 restraints. Lp and absorption corrections were applied; μ = mm -1. Absolute structure parameter = 2(3) (Flack, H. D. Acta Cryst. 1983, A39, ). 4 nature MATERIALS

5 Figure S1 Packing diagram of 1 at 225K viewed along [100]. nature materials 5

6 1.2 Crystal data of 240: C 8 H 10 O 2, M = , light brown needle, mm 3, orthorhombic, space group P (No. 19), a = (17), b = (4), c = (5) Å, V = 824.1(5) Å 3, Z = 4, D c = g/cm 3, F 000 = 296, CCD area detector, MoKα radiation, λ = Å, T = 240(2)K, 2θ max = 49.9º, 4296 reflections collected, 1444 unique (R int = ). 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 = , wr2 = , R indices based on 965 reflections with I >2sigma(I) (refinement on F 2 ), 93 parameters, 0 restraints. Lp and absorption corrections were applied; μ = mm -1. Absolute structure parameter = 2(3) (Flack, H. D. Acta Cryst. 1983, A39, ). Figure S2 Packing diagram of 1 at 240K viewed along [100]. 6 nature MATERIALS

7 1.3 Crystal data of 255: C 8 H 10 O 2, M = , light brown needle, mm 3, orthorhombic, space group P (No. 19), a = (17), b = (4), c = (5) Å, V = 829.3(5) Å 3, Z = 4, D c = g/cm 3, F 000 = 296, CCD area detector, MoKα radiation, λ = Å, T = 255(2)K, 2θ max = 49.9º, 4334 reflections collected, 1459 unique (R int = ). 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 = , wr2 = , R indices based on 931 reflections with I >2sigma(I) (refinement on F 2 ), 93 parameters, 0 restraints. Lp and absorption corrections were applied; μ = mm -1. Absolute structure parameter = -1(3) (Flack, H. D. Acta Cryst. 1983, A39, ). Figure S3 Packing diagram of 1 at 255K viewed along [100]. nature materials 7

8 1.4 Crystal data of 270: C 8 H 10 O 2, M = , light brown needle, mm 3, orthorhombic, space group P (No. 19), a = (16), b = (4), c = (5) Å, V = 832.0(5) Å 3, Z = 4, D c = g/cm 3, F 000 = 296, CCD area detector, MoKα radiation, λ = Å, T = 270(2)K, 2θ max = 50.0º, 4334 reflections collected, 1463 unique (R int = ). 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 = , wr2 = , R indices based on 863 reflections with I >2sigma(I) (refinement on F 2 ), 93 parameters, 0 restraints. Lp and absorption corrections were applied; μ = mm -1. Absolute structure parameter = 1(3) (Flack, H. D. Acta Cryst. 1983, A39, ). Figure S4 Packing diagram of 1 at 270K viewed along [100]. 8 nature MATERIALS

9 1.5 Crystal data of 285: C 8 H 10 O 2, M = , light brown needle, mm 3, orthorhombic, space group P (No. 19), a = (15), b = (4), c = (4) Å, V = 836.2(4) Å 3, Z = 4, D c = g/cm 3, F 000 = 296, CCD area detector, MoKα radiation, λ = Å, T = 285(2)K, 2θ max = 50.2º, 4394 reflections collected, 1482 unique (R int = ). 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 = , wr2 = , R indices based on 872 reflections with I >2sigma(I) (refinement on F 2 ), 93 parameters, 0 restraints. Lp and absorption corrections were applied; μ = mm -1. Absolute structure parameter = -1(2) (Flack, H. D. Acta Cryst. 1983, A39, ). Figure S5 Packing diagram of 1 at 285K viewed along [100]. nature materials 9

10 1.6 Crystal data of 300: C 8 H 10 O 2, M = , light brown needle, mm 3, orthorhombic, space group P (No. 19), a = (16), b = (4), c = (5) Å, V = 838.2(5) Å 3, Z = 4, D c = g/cm 3, F 000 = 296, CCD area detector, MoKα radiation, λ = Å, T = 300(2)K, 2θ max = 50.0º, 4376 reflections collected, 1475 unique (R int = ). 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 = , wr2 = , R indices based on 832 reflections with I >2sigma(I) (refinement on F 2 ), 93 parameters, 0 restraints. Lp and absorption corrections were applied; μ = mm -1. Absolute structure parameter = 1(3) (Flack, H. D. Acta Cryst. 1983, A39, ). Figure S6 Packing diagram of 1 at 300K viewed along [100]. 10 nature MATERIALS

11 1.7 Crystal data of 315: C 8 H 10 O 2, M = , light brown needle, mm 3, orthorhombic, space group P (No. 19), a = (16), b = (4), c = (5) Å, V = 841.0(5) Å 3, Z = 4, D c = g/cm 3, F 000 = 296, CCD area detector, MoKα radiation, λ = Å, T = 315(2)K, 2θ max = 49.9º, 4327 reflections collected, 1462 unique (R int = ). 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 = , wr2 = , R indices based on 830 reflections with I >2sigma(I) (refinement on F 2 ), 93 parameters, 0 restraints. Lp and absorption corrections were applied; μ = mm -1. Absolute structure parameter = 3(3) (Flack, H. D. Acta Cryst. 1983, A39, ). Figure S7 Packing diagram of 1 at 315K viewed along [100]. nature materials 11

12 1.8 Crystal data of 330: C 8 H 10 O 2, M = , light brown needle, mm 3, orthorhombic, space group P (No. 19), a = (10), b = (2), c = (3) Å, V = 841.6(3) Å 3, Z = 4, D c = g/cm 3, F 000 = 296, CCD area detector, MoKα radiation, λ = Å, T = 330(2)K, 2θ max = 50.0º, 4218 reflections collected, 1474 unique (R int = ). 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 = , wr2 = , R indices based on 1016 reflections with I >2sigma(I) (refinement on F 2 ), 93 parameters, 0 restraints. Lp and absorption corrections were applied; μ = mm -1. Absolute structure parameter = 0(2) (Flack, H. D. Acta Cryst. 1983, A39, ). Figure S8 Packing diagram of 1 at 330K viewed along [100]. 12 nature MATERIALS

13 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. 0-1 Heat Flow (W/g) Temperature ( C) 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. nature materials 13

14 10 0 Heat Flow (W/g) Temperature/ C 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 nature MATERIALS

15 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. nature materials 15

16 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 16 nature MATERIALS

17 with their linear C7C9C7C9C7C spines tilted at an angle of ϕ relative to the [100] direction. Colors: gray, carbon; white, hydrogen; and red, oxygen. nature materials 17

18 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 nature MATERIALS

19 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. nature materials 19

20 7. Finger print plot at different temperature 225 K 240 K 255 K 270 K 20 nature MATERIALS

21 285 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 (Å 3 ) (14) (4) (4) (4) (17) (4) (5) (5) (17) (4) (5) (5) (16) (4) (5) (5) (15) (4) (4) (4) (16) (4) (5) (5) (16) (4) (5) (5) (10) (2) (3) (3) nature materials 21

22 9. Table S2 Thermal expansion coefficients of 1 Temperature (K) α a * ( 10-6 K -1 ) α b * ( 10-6 K -1 ) α c * ( 10-6 K -1 ) α v ** ( 10-6 K -1 ) 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 T i refers to the thermal expansion over the temperature range 330 K to T i. * α a, α b and α c are linear thermal expansion coefficients ** α v 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-C C2-C3-C C3-C4-C C4-C5-C 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-C C2-C C3-C C4-C C5-C C1-C nature MATERIALS

23 12. Table S5 Linear thermal expansion coefficients of selected materials Compound Ag 3 Co(CN) 6 1 d-h 3 Co(CN) 6 2 ZrW 2 O 8 3,4 ZrW 2 O 8 3,4 Temperature (K) max α a (K -1 ) max α b (K -1 ) max α c (K -1 ) Low cordierite Cd(CN) Β-Quartz NaCl FMOF-1 9 (Under N 2 atmosphere) FMOF-1 9 (Under N 2 atmosphere) FMOF-1 (Under vacuum) (S,S)-Octa-3,5-diyn-2,7-diol (1) 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 (4) (2) (4) c / Å (5) (3) (5) V / Å (7) 824 (7) 830 (4) Mosaicity / nature materials 23

24 * 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 nature MATERIALS

25 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. nature materials 25

26 15. Cryogenic Powder X-ray Diffraction Powdered samples were placed in a sealed glass capillary.. X-ray powder diffractograms were measured using Cu K α radiation (λ= 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 _203K y Relative intensit Theta/degrees Figure S16 Experimental powder diffraction pattern of 1 at 203K 26 nature MATERIALS

27 _183K Relative intensity Theta/degrees Figure S17 Experimental powder diffraction pattern of 1 at 183K _163K Relative intensity Theta/degrees Figure S18 Experimental powder diffraction pattern of 1 at 163K nature materials 27

28 _143K Relative intensity Theta/degrees Figure S19 Experimental powder diffraction pattern of 1 at 143K _123K Relative intensity Theta/degrees Figure S20 Experimental powder diffraction pattern of 1 at 123K 28 nature MATERIALS

29 _103K Relative intensity Theta/degrees 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 2 1 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 DASH 11,12 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. nature materials 29

30 SCD Data XRPD data a Axis Temperature (K) Figure S22 Variation of a with temperature 11.8 b Axis XRPD Data SCD Data Temperature (K) Figure S23 Variation of b with temperature 30 nature MATERIALS

31 15.5 c Axis XRPD Data SCD Data Temperature (K) 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 Ag 3 [Co(CN) 6 ]. Science 319, (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, (2008). 3. Mary, T. A., Evans, J. S. O., Vogt, T. & Sleight, A. W. Negative Thermal Expansion from 0.3 to 1050 Kelvin in ZrW 2 O 8. Science 272, (1996). 4. Sleight, A. W. Isotropic negative thermal expansion. Annu. Rev. Mater. Sci. 28, (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, (1979). 6. Goodwin, A. L. & Kepert, C. J. Negative thermal expansion and low-frequency modes in cyanide-bridged framework materials. Phys. Rev. B 71, (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 nature materials 31

32 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, (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, (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, (2006). 12 Boultif, A & Louër, D. Indexing of powder diffraction patterns for low-symmetry lattices by the successive dichotomy method. J. Appl. Cryst. 24, (1991). 32 nature MATERIALS

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