Skip to main content Accessibility help
×
Home

Crystal structure of 1-propanethiol–Co2(dobdc) from laboratory X-ray powder diffraction data

  • Jonathan B. Lefton (a1), Kyle B. Pekar (a1), Daniel Sethio (a1), Elfi Kraka (a1) and Tomče Runčevski (a1)...

Abstract

Laboratory X-ray powder diffraction was used to solve and refine the crystal structures of appended guest molecules within the pores of metal–organic frameworks (MOFs). Herein, we report the crystal structure of 1-propanethiol adsorbed in the pores of Co2(dobdc) (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate, MOF-74). Soaking the activated MOF in neat 1-propanethiol resulted in the formation of 1-propanethiol–Co2(dobdc). The thiol appendant MOF maintained the crystal symmetry, with a rhombohedral space group R-3 and unit-cell parameters a = 25.9597(9) Å, c = 6.8623(5) Å, and V = 4005.0(4) Å3. As expected, the thiol sulfur formed a bond with the open cobalt metal site. The alkane chain was directed toward the center of the pore, participating in numerous van der Waals weak interactions with neighboring molecules. For the final Rietveld refinement, soft restrains were applied using bond distances obtained by periodic density functional theory (DFT) geometry optimization.

Copyright

Corresponding author

a)Author to whom correspondence should be addressed. Electronic mail: truncevski@smu.edu

References

Hide All
Andreev, Y. G., MacGlashan, G. S., and Bruce, P. G. (1997). “Ab initio solution of a complex crystal structure from powder-diffraction data using simulated-annealing method and a high degree of molecular flexibility,” Phys. Rev. B 55, 1201112017.
Bloch, E. D., Murray, L. J., Queen, W. L., Chavan, S., Maximoff, S. N., Bigi, J. P., Krishna, R., Peterson, V. K., Grandjean, F., Long, G. J., Smit, B., Bordiga, S., Brown, C. M., and Long, J. R. (2011). “Selective binding of O2 over N2 in a redox-active metal-organic framework with open iron(II) coordination sites,” J. Am. Chem. Soc. 133, 1481414822.
Bloch, E. D., Queen, W. L., Krishna, R., Zadrozny, J. M., Brown, C. M., and Long, J. R. (2012). “Hydrocarbon separations in a metal-organic framework with open iron(II) coordination sites,” Science 335, 16061610.
Dietzel, P. D. C., Panella, P., Hirscher, M., Blom, R., and Fjellvag, H. (2006). “Hydrogen adsorption in a nickel based coordination polymer with open metal sites in the cylindrical cavities of the desolvated framework,” Chem. Commun. 959961.
Dietzel, P. D. C., Johnsen, R. E., Fjellvag, H., Bordiga, S., Groppo, E., Chavan, S., and Blom, R. (2008). “Adsorption properties and structure of CO2 adsorbed on open coordination sites of metal–organic framework Ni2(dhtp) from gas adsorption, IR spectroscopy and X-ray diffraction,” Chem. Commun. 51255127.
Dovesi, R., Erba, A., Orlando, R., Zicovich-Wilson, C. M., Civalleri, B., Maschio, L., Rèrat, M., Casassa, S., Baima, J., Salustro, S., and Kirtman, B. (2017). “Quantum-mechanical condensed matter simulations with CRYSTAL,” WIREs Comput. Mol. Sci. 8, 1360.
Geier, S. J., Mason, J. A., Bloch, E. D., Queen, W. L., Hudson, M. R., Brown, C. M., and Long, J. R. (2013). “Selective adsorption of ethylene over ethane and propylene over propane in the metal–organic frameworks M 2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn),” Chem. Sci. 4, 20542061.
Gilat, G. (1972). “Analysis of methods for calculating spectral properties in solids,” J. Comp. Phys. 10, 432.
Gonzalez, M. I., Mason, J. A., Bloch, E. D., Teat, S. J., Gagnon, K. J., Morrison, G. Y., Queen, W. L., and Long, J. R. (2017). “Structural characterization of framework–gas interactions in the metal–organic framework Co2(dobdc) by in situ single-crystal X-ray diffraction,” Chem. Sci. 8, 43874398.
Gonzalez, M. I., Kapelewski, M. T., Bloch, E. D., Milner, P. J., Reed, D. A., Hudson, M. R., Mason, J. A., Barin, G., Brown, C. M., and Long, J. R. (2018). “Separation of xylene isomers through multiple metal site interactions in metal−organic frameworks,” J. Am. Chem. Soc. 140, 34123422.
Grimme, S., Ehrlich, S., and Goerigk, L. (2011). “Effect of the damping function in dispersion corrected density functional theory,” J. Comput. Chem. 21, 14561465.
Kizzie, A. C., Wong-Foy, A. G., and Matzger, A. J. (2011). “Effect of humidity on the performance of microporous coordination polymers as adsorbents for CO2 capture,” Langmuir 27, 63686373.
Liu, Y., Kabbour, H., Brown, C. M., Neumann, D. A., and Ahn, C. C. (2008). “Increasing the density of adsorbed hydrogen with coordinatively unsaturated metal centers in metal−organic frameworks,” Langmuir 24, 47724777.
Magdysyuk, O. V., Adams, F., Liermann, H.-P., Spanopoulos, I., Trikalitis, P. N., Hirscher, M., Morris, R. E., Duncan, M. J., McCormick, L. J., and Dinnebier, R. E. (2014). “Understanding the adsorption mechanism of noble gases Kr and Xe in CPO-27-Ni, CPO-27-Mg, and ZIF-8,” Phys. Chem. Chem. Phys. 16, 2390823914.
Pawley, G. S. (1981). “Unit-cell refinement from powder diffraction scans,” J. Appl. Crystallogr. 14, 357361.
Peintinger, M. P., Oliveira, D. V., and Bredow, T. (2013). “Consistent Gaussian basis sets of triple-zeta valence with polarization quality for solid-state calculations,” J. Comput. Chem. 34, 451.
Perdew, J. P., Burke, K., and Ernzerhof, M. (1996). “Generalized gradient approximation made simple,” Phys. Rev. Lett. 77, 38653868.
Queen, W. L., Hudson, M. R., Bloch, E. D., Mason, J. A., Gonzalez, M. I., Lee, J. S., Gygi, D., Howe, J. D., Lee, K., Darwish, T. A., James, M., Peterson, V. K., Teat, S. J., Smit, B., Neaton, J. B., Long, J. R., and Brown, C. M. (2014). “Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M 2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn),” Chem. Sci. 5, 45694581.
Rietveld, H. M. (1969). “A profile refinement method for nuclear and magnetic structures,” J. Appl. Crystallogr. 2, 6571.
Sumida, K., Brown, C. M., Herm, Z. R., Chavan, S., Bordiga, S., and Long, J. R. (2011). “Hydrogen storage properties and neutron scattering studiesof Mg2(dobdc)—a metal–organic framework with open Mg2+ adsorption sites,” Chem. Commun. 47, 11571159.

Keywords

Crystal structure of 1-propanethiol–Co2(dobdc) from laboratory X-ray powder diffraction data

  • Jonathan B. Lefton (a1), Kyle B. Pekar (a1), Daniel Sethio (a1), Elfi Kraka (a1) and Tomče Runčevski (a1)...

Metrics

Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed