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_1575181
_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         'C24 H18 F4 N2 O2'
_chemical_formula_sum            'C24 H18 F4 N2 O2'
_chemical_formula_weight         442.40
_chemical_name_systematic
2-(4-(diphenylamino)-3,5-dimethylpyridin-1-ium-1-yl)-4,4,5,5-tetrafluoro-3-oxocyclopent-1-en-1-olate
_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             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                90
_cell_angle_beta                 95.225(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.7285(3)
_cell_length_b                   17.8213(4)
_cell_length_c                   10.0082(2)
_cell_measurement_reflns_used    7903
_cell_measurement_temperature    292.36(10)
_cell_measurement_theta_max      79.6130
_cell_measurement_theta_min      4.5130
_cell_volume                     2083.19(8)
_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      292.36(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 0.979
_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     48.00  93.00   0.50    1.80    --  113.25 -94.00 120.00   90
  2  \w     46.00  80.00   0.50    1.80    --  113.25-125.00  60.00   68
  3  \w     85.00 110.00   0.50    1.80    --  113.25-125.00  30.00   50
  4  \w     67.00 106.00   0.50    1.80    --  113.25 -94.00 -60.00   78
  5  \w     48.00  92.00   0.50    1.80    --  113.25 -93.00 -95.00   88
  6  \w      8.00  68.00   0.50    0.43    --   47.91 -93.00 -95.00  120
  7  \w     42.00  76.00   0.50    1.80    --  113.25 -45.00  30.00   68
  8  \w     47.00  73.00   0.50    1.80    --  113.25 -45.00  90.00   52
  9  \w     42.00  67.00   0.50    1.80    --  113.25 -45.00 150.00   50
 10  \w     46.00  74.00   0.50    1.80    --  113.25 -45.00  60.00   56
 11  \w     42.00  74.00   0.50    1.80    --  113.25 -45.00   0.00   64
 12  \w     42.00  75.00   0.50    1.80    --  113.25 -45.00 -30.00   66
 13  \w     49.00  75.00   0.50    1.80    --  113.25 -45.00 -60.00   52
 14  \w     45.00  75.00   0.50    1.80    --  113.25 -45.00-120.00   60
 15  \w     42.00  75.00   0.50    1.80    --  113.25 -45.00 -90.00   66
 16  \w     39.00  64.00   0.50    1.80    --  113.25 -30.00-120.00   50
 17  \w     39.00  65.00   0.50    1.80    --  113.25 -30.00-150.00   52
 18  \w     41.00  66.00   0.50    1.80    --  113.25 -30.00-180.00   50
 19  \w     41.00  66.00   0.50    1.80    --  113.25 -30.00 -90.00   50
 20  \w     39.00  64.00   0.50    1.80    --  113.25 -30.00  30.00   50
 21  \w     40.00  65.00   0.50    1.80    --  113.25 -30.00 150.00   50
 22  \w     42.00  71.00   0.50    1.80    --  113.25 -45.00 120.00   58
 23  \w    111.00 136.00   0.50    1.80    --  113.25  15.00 -60.00   50
 24  \w    142.00 168.00   0.50    1.80    --  113.25  15.00 -60.00   52
 25  \w    108.00 148.00   0.50    1.80    --  113.25  93.00  16.00   80
 26  \w    122.00 171.00   0.50    1.80    --  113.25 125.00  90.00   98
 27  \w     41.00 120.00   0.50    0.43    --   47.91  57.00  90.00  158
 28  \w    -77.00  19.00   0.50    0.43    --  -47.91  93.00  16.00  192
 29  \w    -58.00  21.00   0.50    0.43    --  -47.91  37.00 150.00  158
 30  \w    -74.00 -49.00   0.50    1.80    --  -91.75  93.00  16.00   50
 31  \w    -68.00 -43.00   0.50    1.80    --  -91.75  30.00-120.00   50
 32  \w   -147.00-122.00   0.50    1.80    --  -91.75 -93.00 -95.00   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      0.0405315000
_diffrn_orient_matrix_UB_12      -0.0617157000
_diffrn_orient_matrix_UB_13      0.1011239000
_diffrn_orient_matrix_UB_21      0.1023139000
_diffrn_orient_matrix_UB_22      0.0493491000
_diffrn_orient_matrix_UB_23      0.0523423000
_diffrn_orient_matrix_UB_31      -0.0727014000
_diffrn_orient_matrix_UB_32      0.0350393000
_diffrn_orient_matrix_UB_33      0.1045533000
_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  0.0296
_diffrn_reflns_av_unetI/netI     0.0313
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            16214
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.810
_diffrn_reflns_theta_min         3.785
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.982
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65078
_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    1.411
_exptl_crystal_description       irregular
_exptl_crystal_F_000             912
_exptl_crystal_preparation       oil
_exptl_crystal_recrystallization_method dichloromethane/methanol
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.164
_refine_diff_density_min         -0.202
_refine_diff_density_rms         0.032
_refine_ls_extinction_coef       0.0012(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     339
_refine_ls_number_reflns         4445
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0486
_refine_ls_R_factor_gt           0.0406
_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^)+(0.0572P)^2^+0.2990P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1123
_refine_ls_wR_factor_ref         0.1197
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3655
_reflns_number_total             4445
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04257g2.cif
_cod_data_source_block           pm3_24_292k_a_auto
_cod_depositor_comments
'Adding full bibliography for 1575172--1575185.cif.'
_cod_database_code               1575181
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C24H18F4N2O2
_chemical_oxdiff_usercomment     'Yellow block at 292.3 K'
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.828
_diffrn_oxdiff_digest_hkl
;
017a7419874ebce1023fae7a6c80ffa204cf3a
;
_reflns_odcompleteness_completeness 99.64
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
 F4-C23 \\sim F4A-C23
 with sigma of 0.02
 F1-C23 \\sim F1A-C23
 with sigma of 0.02
 C23-F3 \\sim C23-F3A
 with sigma of 0.04
 C21-C22 \\sim C21-C22A
 with sigma of 0.02
 C21-F3 \\sim C21-F3A
 with sigma of 0.04
 C23-C22 \\sim C23-C22A
 with sigma of 0.02
 F3-F2 \\sim F3A-F2A
 with sigma of 0.04
 F3-C22 \\sim F3A-C22A
 with sigma of 0.02
 C21-F2 \\sim C21-F2A
 with sigma of 0.04
 C23-F2 \\sim C23-F2A
 with sigma of 0.04
 F2-C22 \\sim F2A-C22A
 with sigma of 0.02
3. Others
 Sof(F4A)=Sof(F1A)=1-FVAR(1)
 Sof(F4)=Sof(F1)=FVAR(1)
 Sof(F3A)=Sof(C22A)=Sof(F2A)=1-FVAR(2)
 Sof(F3)=Sof(F2)=Sof(C22)=FVAR(2)
4.a Aromatic/amide H refined with riding coordinates:
 C16(H16), C15(H15), C2(H2), C8(H8), C12(H12), C4(H4), C1(H1), C9(H9),
 C11(H11), C10(H10), C5(H5), C6(H6)
4.b Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              62643
_olex2_exptl_crystal_mounting_method oil
_olex2_submission_original_sample_id '5a 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 1.878
_oxdiff_exptl_absorpt_empirical_full_min 0.599