Planarisation or a twist? Using steric engineering to unlock the origin of mechanofluorochromic red-shifts.
McDonald, Peter W.; Goerigk, Lars; Ritchie, Chris; Chemical science 16 (2025) 15320–15332; doi:10.1039/d5sc04257g

data_1575177
_publ_section_title
;
 Planarisation or a twist? Using steric engineering to unlock the origin
 of mechanofluorochromic red-shifts.
;
_journal_issue                   34
_journal_name_full               'Chemical science'
_journal_page_first              15320
_journal_page_last               15332
_journal_paper_doi               10.1039/d5sc04257g
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '3(C22 H12 F4 N2 O2)'
_chemical_formula_sum            'C66 H36 F12 N6 O6'
_chemical_formula_weight         1237.01
_chemical_name_systematic
2-(4-(9H-carbazol-9-yl)pyridin-1-ium-1-yl)-4,4,5,5-tetrafluoro-3-oxocyclopent-1-en-1-olate
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-05-25
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-06-06 deposited with the CCDC.	2025-07-18 downloaded from the CCDC.
;
_cell_angle_alpha                89.1010(10)
_cell_angle_beta                 81.4950(10)
_cell_angle_gamma                88.9950(10)
_cell_formula_units_Z            2
_cell_length_a                   10.8897(2)
_cell_length_b                   15.0104(2)
_cell_length_c                   16.1121(2)
_cell_measurement_reflns_used    27123
_cell_measurement_temperature    122.99(10)
_cell_measurement_theta_max      80.2150
_cell_measurement_theta_min      3.9950
_cell_volume                     2604.07(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.70a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.70a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.70a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      122.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.977
_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    -91.00 -17.00   0.50    0.62    --  -50.51 132.00  48.00  148
  2  \w   -121.00 -66.00   0.50    0.62    --  -50.51-137.00 161.00  110
  3  \w   -120.00 -69.00   0.50    0.62    --  -50.51-132.00 -21.00  102
  4  \w    -95.00 -19.00   0.50    0.62    --  -50.51 137.00-135.00  152
  5  \w     41.00 102.00   0.50    0.62    --   50.51-137.00 161.00  122
  6  \w     38.00  98.00   0.50    0.62    --   50.51-132.00 -21.00  120
  7  \w    -95.00 -19.00   0.50    2.70    --  -90.00 137.00-135.00  152
  8  \w   -160.00 -69.00   0.50    2.70    --  -90.00-132.00 -21.00  182
  9  \w   -159.00 -66.00   0.50    2.70    --  -90.00-137.00 161.00  186
 10  \w    -91.00 -20.00   0.50    2.70    --  -90.00 132.00  48.00  142
 11  \w     41.00 121.00   0.50    2.70    --  111.50-137.00 161.00  160
 12  \w     91.00 178.00   0.50    2.70    --  111.50 132.00  48.00  174
 13  \w     42.00 117.00   0.50    2.70    --  111.50-132.00 -21.00  150
 14  \w     87.00 178.00   0.50    2.70    --  111.50 137.00-135.00  182
 15  \w    -99.00 -44.00   0.50    0.62    --  -50.51   0.00-150.00  110
 16  \w   -119.00 -93.00   0.50    0.62    --  -50.51-125.00  30.00   52
 17  \w    -98.00 -45.00   0.50    0.62    --  -50.51   0.00  60.00  106
 18  \w   -120.00 -33.00   0.50    0.62    --  -50.51 -77.00   0.00  174
 19  \w    -97.00 -49.00   0.50    0.62    --  -50.51   0.00 -30.00   96
 20  \w    -44.00 -18.00   0.50    2.70    --  -90.00  15.00 -60.00   52
 21  \w    -93.00 -65.00   0.50    2.70    --  -90.00  15.00 -60.00   56
 22  \w     61.00 103.00   0.50    2.70    --  111.50 -94.00   0.00   84
 23  \w     66.00 100.00   0.50    2.70    --  111.50 -94.00-180.00   68
 24  \w     41.00  66.00   0.50    2.70    --  111.50 -30.00 120.00   50
 25  \w     52.00 106.00   0.50    2.70    --  111.50 -94.00-120.00  108
 26  \w     66.00 118.00   0.50    2.70    --  111.50   0.00 -60.00  104
 27  \w     42.00 104.00   0.50    2.70    --  111.50 -94.00  30.00  124
 28  \w     48.00 108.00   0.50    2.70    --  111.50-106.00-128.07  120
 29  \w     63.00 105.00   0.50    2.70    --  111.50 -94.00 120.00   84
 30  \w     42.00  72.00   0.50    2.70    --  111.50 -45.00  30.00   60
 31  \w     44.00  76.00   0.50    2.70    --  111.50 -45.00   0.00   64
 32  \w     41.00  66.00   0.50    2.70    --  111.50 -45.00 120.00   50
 33  \w     40.00  65.00   0.50    2.70    --  111.50 -30.00   0.00   50
 34  \w     54.00 107.00   0.50    2.70    --  111.50-107.00  -5.49  106
 35  \w     67.00 113.00   0.50    2.70    --  111.50   0.00 150.00   92
 36  \w     91.00 117.00   0.50    2.70    --  111.50   0.00-180.00   52
 37  \w    143.00 169.00   0.50    2.70    --  111.50  15.00  30.00   52
 38  \w     42.00  75.00   0.50    2.70    --  111.50 -45.00 -90.00   66
 39  \w     41.00 105.00   0.50    2.70    --  111.50 -94.00 150.00  128
 40  \w     45.00  85.00   0.50    2.70    --  111.50 -77.00  60.00   80
 41  \w     42.00  72.00   0.50    2.70    --  111.50 -94.00 -60.00   60
 42  \w     74.00 100.00   0.50    2.70    --  111.50 -94.00 -60.00   52
 43  \w    119.00 177.00   0.50    2.70    --  111.50  45.00 -90.00  116
 44  \w     46.00  71.00   0.50    2.70    --  111.50 -45.00 150.00   50
 45  \w     42.00 108.00   0.50    2.70    --  111.50 -15.00 -90.00  132
 46  \w     70.00 105.00   0.50    2.70    --  111.50 -94.00  60.00   70
 47  \w     41.00  73.00   0.50    2.70    --  111.50 -45.00-150.00   64
 48  \w    109.00 135.00   0.50    2.70    --  111.50  15.00  30.00   52
 49  \w     49.00  76.00   0.50    2.70    --  111.50 -45.00-180.00   54
 50  \w     40.00  65.00   0.50    2.70    --  111.50 -30.00 150.00   50
 51  \w     45.00  70.00   0.50    2.70    --  111.50 -45.00 -60.00   50
 52  \w     41.00  73.00   0.50    2.70    --  111.50 -45.00  60.00   64
 53  \w     97.00 123.00   0.50    2.70    --  111.50  77.00 150.00   52
 54  \w    152.00 177.00   0.50    2.70    --  111.50  77.00 150.00   50
 55  \w     49.00 106.00   0.50    2.70    --  111.50 -94.00 -90.00  114
 56  \w     40.00  65.00   0.50    2.70    --  111.50 -30.00  60.00   50
 57  \w     40.00  65.00   0.50    2.70    --  111.50 -30.00 -90.00   50
 58  \w     62.00 102.00   0.50    2.70    --  111.50 -94.00 -30.00   80
 59  \w     57.00  82.00   0.50    2.70    --  111.50 -61.00  30.00   50
 60  \w     93.00 125.00   0.50    2.70    --  111.50 -61.00  30.00   64
 61  \w     40.00  65.00   0.50    2.70    --  111.50 -30.00  90.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0230814000
_diffrn_orient_matrix_UB_12      -0.0218665000
_diffrn_orient_matrix_UB_13      -0.0941776000
_diffrn_orient_matrix_UB_21      0.0069919000
_diffrn_orient_matrix_UB_22      0.1002570000
_diffrn_orient_matrix_UB_23      -0.0217925000
_diffrn_orient_matrix_UB_31      0.1410115000
_diffrn_orient_matrix_UB_32      -0.0029940000
_diffrn_orient_matrix_UB_33      0.0020116000
_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  0.0521
_diffrn_reflns_av_unetI/netI     0.0377
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            54561
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.199
_diffrn_reflns_theta_min         4.020
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.136
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78876
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.70a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.578
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1260
_exptl_crystal_preparation       oil
_exptl_crystal_recrystallization_method dichloromethane/methanol
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.764
_refine_diff_density_min         -0.529
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     839
_refine_ls_number_reflns         11112
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0494
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0462P)^2^+2.0699P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1122
_refine_ls_wR_factor_ref         0.1168
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9578
_reflns_number_total             11112
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04257g2.cif
_cod_data_source_block           pm3_36_dcm_meoh_a2_auto
_cod_depositor_comments
'Adding full bibliography for 1575172--1575185.cif.'
_cod_database_code               1575177
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C22H12F4N2O2
_chemical_oxdiff_usercomment     'yellow block'
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.895
_diffrn_oxdiff_digest_hkl
;
01a178c12e7061962898ff080504eb7f632367
;
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C19-C20 \\sim C19-C20A
 with sigma of 0.02
 C21-F2 \\sim C21-F2A
 with sigma of 0.04
 C21-C20 \\sim C21-C20A
 with sigma of 0.02
 C20-F3 \\sim C20A-F3A
 with sigma of 0.02
 C19-F2 \\sim C19-F2A
 with sigma of 0.04
 C20-F2 \\sim C20A-F2A
 with sigma of 0.02
 C21-F3 \\sim C21-F3A
 with sigma of 0.04
 F3-F2 \\sim F3A-F2A
 with sigma of 0.04
 C19-F3 \\sim C19-F3A
 with sigma of 0.04
3. Others
 Sof(C20A)=Sof(F3A)=Sof(F2A)=1-FVAR(1)
 Sof(C20)=Sof(F3)=Sof(F2)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C38(H38), C39(H39), C58(H58), C60(H60), C59(H59), C16(H16), C37(H37),
 C15(H15), C49(H49), C14(H14), C33(H33), C36(H36), C17(H17), C61(H61), C2(H2),
 C24(H24), C55(H55), C27(H27), C25(H25), C52(H52), C30(H30), C47(H47), C11(H11),
  C46(H46), C26(H26), C5(H5), C54(H54), C32(H32), C48(H48), C8(H8), C10(H10),
 C31(H31), C3(H3), C53(H53), C4(H4), C9(H9)
;
_shelx_res_checksum              1181
_olex2_exptl_crystal_mounting_method oil
_olex2_submission_original_sample_id '4a 123 K'
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.090
_oxdiff_exptl_absorpt_empirical_full_min 0.559