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_1575180
_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         'C23 H16 F4 N2 O2'
_chemical_formula_sum            'C23 H16 F4 N2 O2'
_chemical_formula_weight         428.38
_chemical_name_systematic
2-(4-(diphenylamino)-3-methylpyridin-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 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                 98.3760(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.1449(2)
_cell_length_b                   7.30850(10)
_cell_length_c                   17.1746(2)
_cell_measurement_reflns_used    14599
_cell_measurement_temperature    122.99(10)
_cell_measurement_theta_max      80.0880
_cell_measurement_theta_min      5.1720
_cell_volume                     1880.72(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_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  (Sheldrick, 2015)'
_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 1.000
_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     44.00 122.00   0.50    0.10    --   50.49  43.00 -85.00  156
  2  \w    100.00 125.00   0.50    0.14    --  111.50  61.00-150.00   50
  3  \w    108.00 160.00   0.50    0.14    --  111.50  30.00-150.00  104
  4  \w    133.00 160.00   0.50    0.14    --  111.50  61.00-150.00   54
  5  \w    105.00 178.00   0.50    0.14    --  111.50  43.00 -85.00  146
  6  \w     66.00 114.00   0.50    0.14    --  111.50   0.00  60.00   96
  7  \w   -122.00 -43.00   0.50    0.10    --  -50.49 -43.00 122.00  158
  8  \w   -122.00 -73.00   0.50    0.10    --  -50.49-125.00 -90.00   98
  9  \w   -122.00 -73.00   0.50    0.10    --  -50.49-125.00-180.00   98
 10  \w   -160.00 -83.00   0.50    0.14    --  -90.00 -43.00 122.00  154
 11  \w   -122.00 -73.00   0.50    0.10    --  -50.49-125.00  60.00   98
 12  \w     40.00  66.00   0.50    0.14    --  111.50 -30.00 150.00   52
 13  \w     66.00  92.00   0.50    0.14    --  111.50 -61.00 150.00   52
 14  \w     94.00 125.00   0.50    0.14    --  111.50 -61.00 150.00   62
 15  \w     48.00  75.00   0.50    0.14    --  111.50 -45.00  60.00   54
 16  \w     43.00  69.00   0.50    0.14    --  111.50 -45.00  30.00   52
 17  \w     59.00 118.00   0.50    0.14    --  111.50 -61.00   0.00  118
 18  \w     41.00  68.00   0.50    0.14    --  111.50 -45.00 -30.00   54
 19  \w     41.00  76.00   0.50    0.14    --  111.50 -45.00 -90.00   70
 20  \w     41.00  76.00   0.50    0.14    --  111.50 -45.00-150.00   70
 21  \w     45.00  70.00   0.50    0.14    --  111.50 -45.00   0.00   50
 22  \w     41.00  76.00   0.50    0.14    --  111.50 -45.00  90.00   70
 23  \w     41.00  74.00   0.50    0.14    --  111.50 -43.00 122.00   66
 24  \w     99.00 149.00   0.50    0.14    --  111.50 125.00 120.00  100
 25  \w     40.00  66.00   0.50    0.14    --  111.50 -30.00  30.00   52
 26  \w    -20.00  57.00   0.50    0.10    --   50.49 -43.00 122.00  154
 27  \w     40.00  65.00   0.50    0.14    --  111.50 -30.00   0.00   50
 28  \w     40.00  65.00   0.50    0.14    --  111.50 -30.00 -30.00   50
 29  \w     40.00  66.00   0.50    0.14    --  111.50 -30.00-180.00   52
 30  \w    -57.00  21.00   0.50    0.10    --  -50.49  43.00 -85.00  156
 31  \w    -76.00 -18.00   0.50    0.14    --  -90.00  43.00 -85.00  116
 32  \w    -85.00 -18.00   0.50    0.14    --  -90.00 125.00   0.00  134
 33  \w     41.00  92.00   0.50    0.14    --  111.50 -94.00   0.00  102
;
_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      -0.0654399000
_diffrn_orient_matrix_UB_12      -0.1071666000
_diffrn_orient_matrix_UB_13      -0.0604406000
_diffrn_orient_matrix_UB_21      0.0754096000
_diffrn_orient_matrix_UB_22      -0.0349017000
_diffrn_orient_matrix_UB_23      -0.0494586000
_diffrn_orient_matrix_UB_31      0.0245553000
_diffrn_orient_matrix_UB_32      -0.1781260000
_diffrn_orient_matrix_UB_33      0.0460525000
_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     0.0200
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            20323
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.325
_diffrn_reflns_theta_min         3.638
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.069
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70111
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
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    1.513
_exptl_crystal_description       irregular
_exptl_crystal_F_000             880
_exptl_crystal_preparation       oil
_exptl_crystal_recrystallization_method acetone
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.422
_refine_diff_density_min         -0.481
_refine_diff_density_rms         0.046
_refine_ls_extinction_coef       0.0021(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   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     282
_refine_ls_number_reflns         4021
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0419
_refine_ls_R_factor_gt           0.0393
_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^)+(0.0380P)^2^+1.1641P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0945
_refine_ls_wR_factor_ref         0.0965
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3694
_reflns_number_total             4021
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04257g2.cif
_cod_data_source_block           pm2_164_acetone_a_auto
_cod_depositor_comments
'Adding full bibliography for 1575172--1575185.cif.'
_cod_database_code               1575180
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C20H16F4N2O2
_chemical_oxdiff_usercomment     'Pale yellow block'
_shelx_estimated_absorpt_t_max   0.901
_shelx_estimated_absorpt_t_min   0.740
_diffrn_oxdiff_digest_hkl
;
013672baacc2b8eb823f15ab9eedf0e6c7f785
;
_reflns_odcompleteness_completeness 99.86
_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.a Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C15(H15), C12(H12), C10(H10), C2(H2), C8(H8), C1(H1),
 C11(H11), C9(H9), C4(H4), C6(H6), C5(H5)
2.b Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C)
;
_shelx_res_checksum              16117
_olex2_exptl_crystal_mounting_method oil
_olex2_submission_original_sample_id '3a 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 1.268
_oxdiff_exptl_absorpt_empirical_full_min 0.722