Structural modulation of the photophysical and electronic properties of pyrene-based 3D metal‒organic frameworks derived from s-block metals
Coleman, Christopher N.; Tapping, Patrick C.; Huxley, Michael T.; Kee, Tak W.; Huang, David M.; Doonan, Christian J.; Sumby, Christopher J.; CrystEngComm 23 (2021) 82–90; doi:10.1039/D0CE01505A

data_7242025
_publ_section_title
;
 Structural modulation of the photophysical and electronic properties of
 pyrene-based 3D metal--organic frameworks derived from s-block metals
;
_journal_issue                   1
_journal_name_full               CrystEngComm
_journal_page_first              82
_journal_page_last               90
_journal_paper_doi               10.1039/D0CE01505A
_journal_volume                  23
_journal_year                    2021
_chemical_formula_moiety         'C91 H51 K9 N O26.5'
_chemical_formula_sum            'C98.25 H83.25 K9 N3.25 O38.5'
_chemical_formula_weight         2277.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-09-02 deposited with the CCDC.	2020-11-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.59(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.329(4)
_cell_length_b                   36.085(7)
_cell_length_c                   15.194(3)
_cell_measurement_reflns_used    119477
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.989
_cell_measurement_theta_min      1.129
_cell_volume                     9471(3)
_computing_cell_refinement       'XDS (Kabsch, 1993)'
_computing_data_collection       'BluIce (McPhillips, 2002)'
_computing_data_reduction        'XDS (Kabsch, 1993)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.964
_diffrn_measured_fraction_theta_max 0.795
_diffrn_measurement_device_type  'ADSC Quantum 210r'
_diffrn_measurement_method       'Phi Scan'
_diffrn_radiation_monochromator  'Silicon Double Crystal'
_diffrn_radiation_source         'MX1 Beamline Australian Synchrotron'
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0282
_diffrn_reflns_av_unetI/netI     0.0175
_diffrn_reflns_Laue_measured_fraction_full 0.964
_diffrn_reflns_Laue_measured_fraction_max 0.795
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       47
_diffrn_reflns_limit_k_min       -47
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            119477
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.795
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.989
_diffrn_reflns_theta_min         1.129
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.505
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'XDS (Kabsch, 1993)'
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.597
_exptl_crystal_description       needle
_exptl_crystal_F_000             4698
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.07
_platon_squeeze_details
;                        
The SQUEEZE routine (see below) was used to remove the electron density 
relating to coordinated solvent molecules and the anion. 
The hydrogen atoms of the coordinated water molecules were 
not located either.  These atoms, comprising 2.25 DMF, 0.5 carbonate, and the 
hydrogen atoms of 8.25 water molecules, per asymmetric unit, were added to 
the formula.  Given the relatively small pore volume these atoms 
account for the majority of the electron density (121e) and void volume.
;
_refine_diff_density_max         1.921
_refine_diff_density_min         -0.528
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1205
_refine_ls_number_reflns         20002
_refine_ls_number_restraints     16
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0829
_refine_ls_R_factor_gt           0.0722
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1503P)^2^+8.5598P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2254
_refine_ls_wR_factor_ref         0.2364
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15913
_reflns_number_total             20002
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ce01505a3.cif
_cod_data_source_block           '[K(TBAPy)]_sqd'
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Multi-Scan' was
changed to 'multi-scan' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_original_formula_sum        'C98.25 H83.25 K9 N3.25 O38.50'
_cod_database_code               7242025
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 K1-O60B
 2.8 with sigma of 0.02
 K1-O60A
 2.8 with sigma of 0.02
 K7-O61A
 2.8 with sigma of 0.02
 K7-O61B
 2.8 with sigma of 0.02
 K4-O69B
 2.8 with sigma of 0.02
 K4-O69A
 2.8 with sigma of 0.02
 N72A-C71A
 1.4 with sigma of 0.02
 C71A-O70A
 -1.15 with sigma of 0.02
 N72A-C73B
 1.45 with sigma of 0.02
 C74B-C73B
 -2.3 with sigma of 0.02
 N72A-C74B
 1.44 with sigma of 0.02
 O70A-C71B
 1.15 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C73A) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Others
 Fixed Sof: O62A(0.5) O62B(0.5) O67(0.5) O69A(0.5) O69B(0.5) O61A(0.75)
 O60B(0.5) O60A(0.5) O61B(0.25) C73A(0.5) H73A(0.5) H73B(0.5) H73C(0.5)
 C74B(0.5) H74A(0.5) H74B(0.5) H74C(0.5) C71A(0.5) H71A(0.5) C71B(0.5)
 H71B(0.5) C73B(0.5) H73D(0.5) H73E(0.5) H73F(0.5) C74A(0.5) H74D(0.5)
 H74E(0.5) H74F(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C1A(H1A), C1B(H1B), C4A(H4A), C4B(H4B), C5A(H5A), C5B(H5B), C8A(H8A),
 C8B(H8B), C11A(H11A), C11B(H11B), C12A(H12A), C12B(H12B), C22A(H22A),
 C22B(H22B), C23A(H23A), C23B(H23B), C25A(H25A), C25B(H25B), C26A(H26A),
 C26B(H26B), C32A(H32A), C32B(H32B), C33A(H33A), C33B(H33B), C35A(H35A),
 C35B(H35B), C36A(H36A), C36B(H36B), C42A(H42A), C42B(H42B), C43A(H43A),
 C43B(H43B), C45A(H45A), C45B(H45B), C46A(H46A), C46B(H46B), C52A(H52A),
 C52B(H52B), C53A(H53A), C53B(H53B), C55A(H55A), C55B(H55B), C56A(H56A),
 C56B(H56B), C71A(H71A), C71B(H71B)
5.b Idealised Me refined as rotating group:
 C73A(H73A,H73B,H73C), C74B(H74A,H74B,H74C), C73B(H73D,H73E,H73F), C74A(H74D,
 H74E,H74F)
The structure has disordered coordinated solvent molecules surrounding
the potassium SBU; in all but one case where the DMF solvent is 100%
occupied and confined within a pocket the atoms of the coordinated solvent
beyond the donor atom were not modelled.  Also, a possible non-coordinated 
carbonate anion was not able to be modelled. The SQUEEZE routine (see below)
was used to remove the electron density relating to these solvent molecules 
and the anion. The hydrogen atoms of the coordinated water molecules were 
not located either.  These atoms, comprising 2.25 DMF, 0.5 carbonate, and the 
hydrogen atoms of 8.25 water molecules, per asymmetric unit, were added to 
the formula.
;
_olex2_submission_special_instructions 'No special instructions were received'