############################################################################ # This CIF contains general data collection # # items for all data sets collect on the # # Purdue University Mo D8 Quest # ############################################################################ ############################################################################ # Copy and edit the following section after the data_compoundname section # ############################################################################ _publ_contact_author_name 'Zeller, Matthias' _publ_contact_author_address ; Department of Chemistry Purdue University 560 Oval Dr. West Lafayette IN 47907-2084 USA ; _publ_contact_author_email 'zeller4@purdue.edu' _publ_contact_author_fax '1(765)4940239' _publ_contact_author_phone '1(765)4944572' ############################################################################ # The loop structure below should contain the names and addresses and # # footnotes of all authors, in the relevant order of publication. Repeat # # as necessary. # ############################################################################ loop_ _publ_author_name _publ_author_address 'Zeller, Matthias' ; Department of Chemistry Purdue University 560 Oval Dr. West Lafayette IN 47907-2084 USA ; ############################################################################ # These are the typical references for the Purdue University Cu D8 Quest # # instrument. Delete unused references, add additional references as # # needed. # ############################################################################ _publ_section_references ; Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R., Towler, M. (2004). J. Appl. Cryst. 37, 335--338. Bruker (2023). Apex5 v2023.9-2, SAINT V8.40B, Bruker AXS Inc.: Madison (WI), USA, 2023. Cooper, R. I., Gould, R. O., Parsons, S. and Watkin, D. J. (2002). The derivation of non-merohedral twin laws during refinement by analysis of poorly fitting intensity data and the refinement of non-merohedrally twinned crystal structures in the program CRYSTALS, J. Appl. Cryst. 35, 168-174. Farrugia, L. J. (2012). J Appl. Cryst. 45, 849-854. Groom, C. R. and Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662--671. H\"ubschle, C. B., Sheldrick, G. M. and Dittrich, B. (2011). J. Appl. Cryst. 44, 1281--1284. Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D. (2015). J. Appl. Cryst. 48, 3--10. Parsons, S., Flack, H., Wagner, T. (2013). Acta Cryst. B69, 249-259. Sheldrick, G.M. (2008). Acta Cryst. A64, 112--122. Sheldrick, G. M. (2008). CELL_NOW. Version 2008/4. University of G\"ottingen, Germany. Sheldrick, G. M. (2019). SHELXL2019. University of G\"ottingen, Germany. Sheldrick, G. M. (2015a). Crystal structure refinement with SHELXL, Acta Cryst. C71, 3--8. Sheldrick, G. M. (2015b). SHELXT--Integrated space-group and crystal-structure determination, Acta Cryst. A71 3--8. Sheldrick, G. M. (2012). TWINABS. Ver. 2012/1. Spek, A. L. (2003). J. Appl. Cryst. 36, 7--13. van der Sluis, P. & Spek, A. L. (1990). Acta Cryst. A46, 194-201. Westrip, S. P. (2010). J. Appl. Cryst. 43, 920--925. ; _publ_section_acknowledgements ; This material is based upon work supported by the National Science Foundation through the Major Research Instrumentation Program under Grant No. CHE 1625543. (Funding for the single crystal X-ray diffractometer). We thank the College of Science, Purdue University, for support for X-ray source and detector upgrades through the 2020 and 2023 Laboratory and University Core Facility Research Equipment Program. ; _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ; SADABS 2016/2: Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D. (2015). J. Appl. Cryst. 48, 3-10. ; _diffrn_source 'I-mu-S 3.0 microsource X-ray tube' _diffrn_source_current '1.1 mA' _diffrn_source_voltage '50 kV' _diffrn_radiation_monochromator 'HELIOS multilayer Montel optics' _diffrn_measurement_device 'four circle diffractometer' _diffrn_measurement_device_type 'Bruker AXS D8 Quest' _diffrn_detector_type 'PhotonIII_C14 charge-integrating and photon counting pixel array' _diffrn_measurement_method 'omega and phi scans' _diffrn_detector_area_resol_mean 7.4074 _computing_data_collection 'Apex5 v2023.9-2 (Bruker, 2023)' _computing_cell_refinement 'SAINT V8.40B (Bruker, 2020)' _computing_data_reduction 'SAINT V8.40B (Bruker, 2020)' _computing_structure_solution 'SHELXT (Sheldrick, 2015b)' _computing_structure_refinement ; SHELXL-2019/2 (Sheldrick, 2015a, 2019), SHELXLE Rev1613 (H\"ubschle et al., 2011) ; _atom_sites_solution_primary dual _atom_sites_solution_secondary difmap # If all H atoms in calculated positions: _refine_ls_hydrogen_treatment constr # If chiral space group: _chemical_absolute_configuration ad or syn # Disorder: _refine_special_details ; Fill in any special details about disorder, restraints or constraints used, omitted reflections, twinning, pseudosymmetry, use of squeeze etc here (see below for some standard text sections) Typical example text: The two disordered moieties were restrained to have similar geometries. Uij components of ADPs for disordered atoms closer to each other than 2.0 Angstrom were restrained to be similar. Subject to these conditions the occupancy ratio refined to ??? to ???. Water H atom positions were refined and O-H and H...H distances were restrained to 0.84(2) and 1.36(2) Angstrom, respectively. Some water H atom positions were further restrained based on hydrogen bonding considerations. Water H atom positions were initially refined and O-H and H...H distances were restrained to 0.84(2) and 1.36(2) Angstrom, respectively, while a damping factor was applied. Some water H atom positions were further restrained based on hydrogen bonding considerations. In the final refinement cycles the H atoms were constrained to ride on their carrying oxygen atom (AFIX 3) and the damping factor was removed. ; # Twinned Crystals: _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ; TWINABS 2012/1: Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D. (2015). J. Appl. Cryst. 48 3-10. ; _refine_special_details ; The crystal under investigation was found to be non-merohedrally twinned. The orientation matrices for the two components were identified using the program Cell_Now, with the two components being related by a 180 degree rotation around the real/reciprocal axis XX. The two components were integrated using Saint and corrected for absorption using twinabs, resulting in the following statistics: The exact twin matrix identified by the integration program was found to be: The structure was solved using dual methods with only the non-overlapping reflections of component 1. The structure was refined using the hklf 5 routine with all reflections of component 1 (including the overlapping ones), resulting in a BASF value of ????. The Rint value given is for all reflections and is based on agreement between observed single and composite intensities and those calculated from refined unique intensities and twin fractions (TWINABS (Sheldrick, 2012)). The data were corrected for absorption using twinabs, and the structure was solved using direct methods with only the non-overlapping reflections of component 1. The structure was refined using the hklf 5 routine with all reflections of component 1 (including the overlapping ones) with a resolution better than 0.75 Angstrom, resulting in a BASF value of ???. The total number of reflections given (_diffrn_reflns_number) is before the cutoff at 0.75 Angstrom. The Rint value (_diffrn_reflns_av_R_equivalents) given is for these reflections and is based on agreement between observed single and composite intensities and those calculated from refined unique intensities and twin fractions before the cutoff at 0.75 Angstrom (TWINABS (Sheldrick, 2012)). Integration proved problematic due to excessive multiple overlap of reflections, resulting in large numbers of rejected reflections. Attempts were made to adjust integration parameters to avoid excessive rejections (through adjustments to integration queue size, integration box slicing and twin overlap parameters, and omission of box size optimization), which led to less but still substantial numbers of rejected reflections, or to complete but severely deteriorated data (no box size optimization). With no acceptable quality complete data set obtainable through simultaneous integration of both twin domains, the data were instead handled as if not twinned, with only the major domain integrated, and converted into an hklf 5 type format hkl file after integration using the "Make HKLF5 File" routine as implemented in WinGX. The twin law matrix was used as obtained from SAINT, see above. The Overlap R1 and R2 values used were ???, i.e. reflections with a discriminator function less or equal to overlap radius of ??? were counted overlapped, all others as single. The discriminator function used was the "delta function on index non-integrality". No reflections were omitted. The structure was solved using dual methods with the hklf 4 type file and was refined using the hklf 5 type file, resulting in a BASF value of ???. A refinement using the incomplete data obtained through SAINT and TWINABS gave similar refinement statistics, but with higher overall R values (around ???% for R1) and with less well defined ADPs (two atoms NPD or close to NPD). No Rint value is obtainable for the hklf 5 type file using the WinGX routine. The value from TWINABS is given instead, which is for all reflections available and is based on agreement between observed single and composite intensities and those calculated from refined unique intensities and twin fractions (TWINABS (Sheldrick, 2012)). WinGX: Farrugia, L. J (2012). J Appl. Cryst. 45, 849-854. ROTAX: Richard I. Cooper, Robert O. Gould, Simon Parsons and David J. Watkin, The derivation of non-merohedral twin laws during refinement by analysis of poorly fitting intensity data and the refinement of non-merohedrally twinned crystal structures in the program CRYSTALS. J. Appl. Cryst. 2002. 35, 168-174. ; # Squeeze: _refine_special_details ; The structure contains additional ??? Ang3 of solvent accessible pores. No substantial electron density peaks were found in the solvent accessible pores (less than ?? electron per cubic Angstrom) and the residual electron density peaks are not arranged in an interpretable pattern. The structure factors were instead augmented via reverse Fourier transform methods using the SQUEEZE routine (P. van der Sluis & A.L. Spek (1990). Acta Cryst. A46, 194-201) as implemented in the program Platon. The resultant FAB file containing the structure factor contribution from the electron content of the pore space was used in together with the original hkl file in the further refinement. (The FAB file with details of the Squeeze results is appended to this cif file). The Squeeze procedure corrected for ?? electrons within the solvent accessible pores. ; # Combination of twinning and Squeeze: _refine_special_details ; In addition to the twinning, the structure also exhibits large volume sections consisting of highly disordered solvate or other small molecules. No satisfactory model for the solvate molecules could be developed, and the contribution of the solvate molecules was instead taken into account by reverse Fourier transform methods. The data were first detwinned (using the LIST 8 function of Shelxl2019) and then the cif and fcf files were subjected to the SQUEEZE routine as implemented in the program Platon. The resultant files were used in the further refinement. (Both the hklf 5 type HKL file and the detwinned FAB file are appended to this cif file). A volume of ??? cubic Angstrom per unit cell containing ??? electrons was corrected for. ;