On the role of torsional dynamics in the solid-state fluorescent properties of a new bifluorene–tetracarboxylic acid and its supramolecular assemblies: a structural and TD-DFT investigation
Podda, Enrico; Arca, Massimiliano; Pintus, Anna; Lippolis, Vito; Caltagirone, Claudia; Coles, Simon J.; Orton, James B.; Ennas, Guido; Picci, Giacomo; Davies, Robert P.; Aragoni, M. Carla; CrystEngComm 25 (2023) 1058–1066; doi:10.1039/D2CE01552H

data_7246141
_publ_section_title
;
 On the role of torsional dynamics in the solid-state fluorescent
 properties of a new bifluorene--tetracarboxylic acid and its
 supramolecular assemblies: a structural and TD-DFT investigation
;
_journal_issue                   7
_journal_name_full               CrystEngComm
_journal_page_first              1058
_journal_page_last               1066
_journal_paper_doi               10.1039/D2CE01552H
_journal_volume                  25
_journal_year                    2023
_chemical_formula_moiety         'C33 H26 Cd2 O11'
_chemical_formula_sum            'C33 H26 Cd2 O11'
_chemical_formula_weight         823.34
_space_group_crystal_system      orthorhombic
_space_group_IT_number           36
_space_group_name_Hall           'C 2c -2'
_space_group_name_H-M_alt        'C m c 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-20
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-10-21 deposited with the CCDC.	2023-01-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   27.4335(7)
_cell_length_b                   18.9368(6)
_cell_length_c                   12.7660(5)
_cell_measurement_reflns_used    6985
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      69.4600
_cell_measurement_theta_min      2.9310
_cell_volume                     6632.0(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -67.00 -41.00   0.50    6.00    --    0.00  42.00-113.00   52
  2  \w    -24.00   1.00   0.50    6.00    --    0.00  42.00-113.00   50
  3  \w   -178.00 -19.00   0.50   42.00    --  -90.00  42.00-113.00  318
  4  \w    -89.00  69.00   0.50    6.00    --    0.00  39.00 -60.00  316
  5  \w    -19.00   6.00   0.50   42.00    --    5.00  42.00-113.00   50
  6  \w   -115.00 -82.00   0.50   42.00    --  -90.00  39.00   0.00   66
  7  \w   -166.00-121.00   0.50   42.00    --  -90.00  20.00 -30.00   90
  8  \w    -90.00 -64.00   0.50   42.00    --  -90.00  20.00 -30.00   52
  9  \w   -179.00  -1.00   0.50   42.00    --  -90.00  49.00 120.00  356
 10  \w   -113.00  -1.00   0.50   42.00    --  -90.00  49.00-180.00  224
 11  \w   -164.00-118.00   0.50   42.00    --  -90.00  49.00-180.00   92
 12  \w    -44.00  -4.00   0.50   42.00    --  -90.00  39.00   0.00   80
 13  \w   -160.00 -74.00   0.50   42.00    --  -90.00  39.00  30.00  172
 14  \w   -156.00-107.00   0.50   42.00    --  -90.00  10.00-150.00   98
 15  \w    -41.00 -15.00   0.50   42.00    --  -90.00  10.00-150.00   52
 16  \w   -142.00 -96.00   0.50   42.00    --  -90.00  20.00-120.00   92
 17  \w   -129.00 -93.00   0.50   42.00    --  -90.00  30.00  30.00   72
 18  \w   -177.00-151.00   0.50   42.00    --  -90.00  39.00   0.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0038274000
_diffrn_orient_matrix_UB_12      -0.0635989000
_diffrn_orient_matrix_UB_13      -0.0748546000
_diffrn_orient_matrix_UB_21      -0.0536680000
_diffrn_orient_matrix_UB_22      -0.0103798000
_diffrn_orient_matrix_UB_23      0.0321183000
_diffrn_orient_matrix_UB_31      -0.0161111000
_diffrn_orient_matrix_UB_32      0.0496858000
_diffrn_orient_matrix_UB_33      -0.0889789000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0790
_diffrn_reflns_av_unetI/netI     0.0664
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            29109
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.243
_diffrn_reflns_theta_min         2.835
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.775
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63147
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.37a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.649
_exptl_crystal_description       needle
_exptl_crystal_F_000             3264
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.005
_refine_diff_density_min         -0.935
_refine_diff_density_rms         0.130
_refine_ls_abs_structure_details
;
 Flack x determined using 1644 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     437
_refine_ls_number_reflns         6102
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0889
_refine_ls_R_factor_gt           0.0650
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1069P)^2^+15.8982P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1674
_refine_ls_wR_factor_ref         0.1821
_reflns_Friedel_coverage         0.872
_reflns_Friedel_fraction_full    0.965
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                4540
_reflns_number_total             6102
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ce01552h2.cif
_cod_data_source_block           2020ep008_1a
_cod_depositor_comments
'Adding full bibliography for 7246140--7246143.cif.'
_cod_database_code               7246141
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C33 H24 O8 Cd2'
_chemical_oxdiff_usercomment     374
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.564
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 O10-H10
 0.85 with sigma of 0.01
 H10-O2_$3
 1.9 with sigma of 0.05
 H10_$2-H10
 1.35 with sigma of 0.04
 H9-O5_$4
 1.9 with sigma of 0.05
 H9_$5-H9_$6
 1.35 with sigma of 0.04
 H13-O13
 0.85 with sigma of 0.01
 H13_$1-H13
 1.35 with sigma of 0.04
3. Others
 Fixed Sof: H12A(0.5) H12B(0.5)
4.a Rotating group:
 O9(H9), O11(H11A,H11B)
4.b Secondary CH2 refined with riding coordinates:
 O12(H12A,H12B), C17(H17A,H17B)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C7(H7), C10(H10A), C13(H13A), C14(H14), C20(H20), C23(H23),
 C24(H24), C27(H27), C28(H28), C31(H31)
4.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C33(H33A,H33B,H33C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              52808
_shelx_hkl_checksum              78819
_shelx_fab_checksum              81014
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.602
_oxdiff_exptl_absorpt_empirical_full_min 0.623