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_1575176
_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                89.004(2)
_cell_angle_beta                 81.638(2)
_cell_angle_gamma                89.699(2)
_cell_formula_units_Z            2
_cell_length_a                   11.0644(2)
_cell_length_b                   15.0753(4)
_cell_length_c                   16.1709(4)
_cell_measurement_reflns_used    16060
_cell_measurement_temperature    292.45(10)
_cell_measurement_theta_max      79.0570
_cell_measurement_theta_min      3.9940
_cell_volume                     2668.20(11)
_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      air
_diffrn_ambient_temperature      292.45(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.976
_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 -52.00   0.50    1.02    --  -47.91-163.00  46.00   78
  2  \w    -79.00  -6.00   0.50    1.02    --  -47.91 116.00 -76.00  146
  3  \w   -112.00 -81.00   0.50    1.02    --  -47.91 163.00  72.00   62
  4  \w     40.00  88.00   0.50    1.02    --   47.91-116.00-164.00   96
  5  \w     93.00 118.00   0.50    1.02    --   47.91 163.00  72.00   50
  6  \w     73.00  98.00   0.50    1.02    --   47.91-163.00  46.00   50
  7  \w   -118.00 -93.00   0.50    4.07    --  -91.75-163.00  46.00   50
  8  \w   -131.00-106.00   0.50    4.07    --  -91.75-116.00-164.00   50
  9  \w    -96.00 -71.00   0.50    4.07    --  -91.75 163.00  72.00   50
 10  \w    -77.00 -52.00   0.50    4.07    --  -91.75 116.00 -76.00   50
 11  \w     89.00 114.00   0.50    4.07    --  113.25 163.00  72.00   50
 12  \w     93.00 119.00   0.50    4.07    --  113.25-163.00  46.00   52
 13  \w     56.00 103.00   0.50    4.07    --  113.25-116.00-164.00   94
 14  \w    111.00 141.00   0.50    4.07    --  113.25 116.00 -76.00   60
 15  \w    -63.00  23.00   0.50    1.02    --  -47.91  57.00  90.00  172
 16  \w    -56.00  28.00   0.50    1.02    --  -47.91  19.00-150.00  168
 17  \w    -19.00  29.00   0.50    1.02    --   47.91 -19.00 -60.00   96
 18  \w     34.00  61.00   0.50    1.02    --   47.91 -19.00 -60.00   54
 19  \w     36.00  80.00   0.50    1.02    --   47.91  37.00 -60.00   88
 20  \w    -46.00 -20.00   0.50    4.07    --  -91.75  45.00 -30.00   52
 21  \w   -144.00 -75.00   0.50    4.07    --  -91.75 -61.00 -90.00  138
 22  \w     39.00  66.00   0.50    4.07    --  113.25 -30.00 120.00   54
 23  \w     39.00  64.00   0.50    4.07    --  113.25 -30.00-180.00   50
 24  \w     43.00  76.00   0.50    4.07    --  113.25 -45.00 150.00   66
 25  \w     39.00  66.00   0.50    4.07    --  113.25 -30.00  30.00   54
 26  \w     42.00 106.00   0.50    4.07    --  113.25 -94.00-180.00  128
 27  \w     39.00  66.00   0.50    4.07    --  113.25 -30.00   0.00   54
 28  \w     52.00 104.00   0.50    4.07    --  113.25 -94.00   0.00  104
 29  \w     39.00  65.00   0.50    4.07    --  113.25 -30.00 -30.00   52
 30  \w     46.00  75.00   0.50    4.07    --  113.25 -45.00-150.00   58
 31  \w     39.00  66.00   0.50    4.07    --  113.25 -30.00  60.00   54
 32  \w    146.00 172.00   0.50    4.07    --  113.25 125.00-120.00   52
 33  \w     51.00  89.00   0.50    4.07    --  113.25 -15.00 120.00   76
 34  \w     94.00 125.00   0.50    4.07    --  113.25 -15.00 120.00   62
 35  \w    105.00 130.00   0.50    4.07    --  113.25 125.00  30.00   50
 36  \w    133.00 162.00   0.50    4.07    --  113.25 125.00  30.00   58
 37  \w     40.00  65.00   0.50    4.07    --  113.25 -30.00 -90.00   50
 38  \w     39.00  65.00   0.50    4.07    --  113.25 -30.00  90.00   52
 39  \w     95.00 123.00   0.50    4.07    --  113.25 125.00-120.00   56
 40  \w     46.00  75.00   0.50    4.07    --  113.25 -45.00   0.00   58
 41  \w     53.00 106.00   0.50    4.07    --  113.25 -94.00 -60.00  106
 42  \w     70.00 101.00   0.50    4.07    --  113.25 -94.00  30.00   62
 43  \w     46.00  71.00   0.50    4.07    --  113.25 -45.00 -60.00   50
 44  \w     60.00 104.00   0.50    4.07    --  113.25 -94.00  90.00   88
 45  \w     40.00  65.00   0.50    4.07    --  113.25 -30.00 150.00   50
 46  \w     45.00  70.00   0.50    4.07    --  113.25 -94.00 -30.00   50
 47  \w     44.00  71.00   0.50    4.07    --  113.25 -45.00-180.00   54
 48  \w     42.00  76.00   0.50    4.07    --  113.25 -45.00  60.00   68
 49  \w     79.00 106.00   0.50    4.07    --  113.25 -94.00 -30.00   54
 50  \w    128.00 175.00   0.50    4.07    --  113.25  30.00 -60.00   94
 51  \w     69.00 104.00   0.50    4.07    --  113.25 -94.00-150.00   70
 52  \w     46.00  74.00   0.50    4.07    --  113.25 -45.00  90.00   56
 53  \w     73.00 118.00   0.50    4.07    --  113.25 -15.00 -60.00   90
 54  \w     47.00  72.00   0.50    4.07    --  113.25 -61.00 150.00   50
 55  \w     96.00 128.00   0.50    4.07    --  113.25 -61.00 150.00   64
 56  \w     78.00 103.00   0.50    4.07    --  113.25 -94.00 120.00   50
 57  \w     62.00  99.00   0.50    4.07    --  113.25 -94.00  60.00   74
 58  \w     71.00 106.00   0.50    4.07    --  113.25 -94.00-120.00   70
 59  \w    115.00 171.00   0.50    4.07    --  113.25  15.00-180.00  112
 60  \w     41.00  66.00   0.50    4.07    --  113.25 -30.00 -60.00   50
 61  \w     93.00 119.00   0.50    4.07    --  113.25  77.00  60.00   52
 62  \w    133.00 177.00   0.50    4.07    --  113.25  77.00  60.00   88
 63  \w     72.00  97.00   0.50    4.07    --  113.25 -94.00 -90.00   50
 64  \w     43.00  72.00   0.50    4.07    --  113.25 -45.00 -30.00   58
;
_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      -0.0007054000
_diffrn_orient_matrix_UB_12      0.0871792000
_diffrn_orient_matrix_UB_13      0.0483832000
_diffrn_orient_matrix_UB_21      -0.0491086000
_diffrn_orient_matrix_UB_22      -0.0500483000
_diffrn_orient_matrix_UB_23      0.0817628000
_diffrn_orient_matrix_UB_31      0.1318852000
_diffrn_orient_matrix_UB_32      -0.0184708000
_diffrn_orient_matrix_UB_33      0.0157658000
_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  0.0388
_diffrn_reflns_av_unetI/netI     0.0404
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_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            40925
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.066
_diffrn_reflns_theta_min         3.996
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.109
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90384
_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    1.540
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1260
_exptl_crystal_preparation       oil
_exptl_crystal_recrystallization_method acetone
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.497
_refine_diff_density_min         -0.314
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     858
_refine_ls_number_reflns         11375
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0632
_refine_ls_R_factor_gt           0.0488
_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^)+(0.0461P)^2^+1.0525P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1269
_refine_ls_wR_factor_ref         0.1350
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9072
_reflns_number_total             11375
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04257g2.cif
_cod_data_source_block           pm3_36_292k_acetone_auto
_cod_depositor_comments
'Adding full bibliography for 1575172--1575185.cif.'
_cod_database_code               1575176
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C22H12F4N2O2
_chemical_oxdiff_usercomment     'Yellow irregular block at 292.5 K'
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.843
_diffrn_oxdiff_digest_hkl
;
01b7770302eb39196049a2d7fe20a150e2cfd2
;
_reflns_odcompleteness_completeness 99.73
_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
 F1-C21 \\sim F1A-C21
 with sigma of 0.02
 C21-F4 \\sim C21-F4A
 with sigma of 0.02
 F3-C21 \\sim F3A-C21
 with sigma of 0.04
 F3-C20 \\sim F3A-C20A
 with sigma of 0.02
 F2-C19 \\sim F2A-C19
 with sigma of 0.04
 F2-C20 \\sim F2A-C20A
 with sigma of 0.02
 F3-C19 \\sim F3A-C19
 with sigma of 0.04
 C19-C20 \\sim C19-C20A
 with sigma of 0.02
 C20-C21 \\sim C20A-C21
 with sigma of 0.02
 F2-C21 \\sim F2A-C21
 with sigma of 0.04
 F3-F2 \\sim F3A-F2A
 with sigma of 0.04
3. Others
 Sof(F1A)=Sof(F4A)=1-FVAR(1)
 Sof(F1)=Sof(F4)=FVAR(1)
 Sof(F3A)=Sof(C20A)=Sof(F2A)=1-FVAR(2)
 Sof(F3)=Sof(F2)=Sof(C20)=FVAR(2)
4.a Aromatic/amide H refined with riding coordinates:
 C37(H37), C61(H61), C36(H36), C59(H59), C60(H60), C38(H38), C16(H16),
 C15(H15), C39(H39), C58(H58), C14(H14), C17(H17), C33(H33), C24(H24), C49(H49),
  C55(H55), C46(H46), C11(H11), C2(H2), C27(H27), C30(H30), C52(H52), C26(H26),
 C54(H54), C48(H48), C25(H25), C8(H8), C32(H32), C5(H5), C47(H47), C31(H31),
 C53(H53), C10(H10), C3(H3), C9(H9), C4(H4)
;
_shelx_res_checksum              3669
_olex2_exptl_crystal_mounting_method oil
_olex2_submission_original_sample_id '4a 292 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 1.727
_oxdiff_exptl_absorpt_empirical_full_min 0.547