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_1575174
_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         428.39
_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
_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                 98.5(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.31(18)
_cell_length_b                   7.35(8)
_cell_length_c                   17.30(9)
_cell_measurement_reflns_used    2416
_cell_measurement_temperature    100
_cell_measurement_theta_max      0.8660
_cell_measurement_theta_min      0.1060
_cell_volume                     1925(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.105a 64-bit (release 11-01-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix-ED
_diffrn_measured_fraction_theta_full 0.857
_diffrn_measured_fraction_theta_max 0.857
_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    -58.00  56.00   0.50    2.50    --    0.00   0.00   0.00  228
  2  \w    -55.00  58.00   0.50    2.00    --    0.00   0.00   0.00  226
;
_diffrn_measurement_device       'electron diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy-ED, HyPix-ED, electron source at 200keV'
_diffrn_measurement_method       'continuous rotation electron diffraction'
_diffrn_radiation_wavelength     0.0251
_diffrn_reflns_av_R_equivalents  0.1493
_diffrn_reflns_av_unetI/netI     0.1184
_diffrn_reflns_Laue_measured_fraction_full 0.857
_diffrn_reflns_Laue_measured_fraction_max 0.857
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            15364
_diffrn_reflns_point_group_measured_fraction_full 0.857
_diffrn_reflns_point_group_measured_fraction_max 0.857
_diffrn_reflns_theta_full        0.863
_diffrn_reflns_theta_max         0.863
_diffrn_reflns_theta_min         0.109
_exptl_absorpt_coefficient_mu    0.000
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.13485
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.109a (Rigaku Oxford Diffraction, 2024)
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    1.479
_exptl_crystal_description       'nanoparticle grain'
_exptl_crystal_F_000             327
_exptl_crystal_recrystallization_method acetone
_refine_diff_density_max         0.106
_refine_diff_density_min         -0.131
_refine_diff_density_rms         0.031
_refine_ls_extinction_coef       608(44)
_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   1.199
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     282
_refine_ls_number_reflns         2991
_refine_ls_number_restraints     258
_refine_ls_restrained_S_all      1.153
_refine_ls_R_factor_all          0.1763
_refine_ls_R_factor_gt           0.1372
_refine_ls_shift/su_max          0.264
_refine_ls_shift/su_mean         0.031
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0728P)^2^+1.4057P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2986
_refine_ls_wR_factor_ref         0.3134
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2260
_reflns_number_total             2991
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04257g2.cif
_cod_data_source_block           1112_1113
_cod_depositor_comments
'Adding full bibliography for 1575172--1575185.cif.'
_cod_original_cell_volume        1924(32)
_cod_database_code               1575174
_shelx_shelxl_version_number     2019/3
_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. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C10(H10), C12(H12), C5(H5), C4(H4), C17(H17), C8(H8),
 C9(H9), C6(H6), C1(H1), C2(H2), C11(H11)
3.b Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C)
;
_shelx_res_checksum              10038
_olex2_submission_original_sample_id '3a G 100 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
;