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_1575182
_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         'C17 H12 N2'
_chemical_formula_sum            'C17 H12 N2'
_chemical_formula_weight         244.29
_chemical_name_systematic        9-(pyridin-4-yl)-9H-carbazole
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.55330(4)
_cell_length_b                   12.55218(7)
_cell_length_c                   23.37782(14)
_cell_measurement_reflns_used    39607
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      79.9520
_cell_measurement_theta_min      3.9570
_cell_volume                     2509.90(2)
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(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 0.998
_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   -109.00 -18.00   0.50    0.60    --  -90.00  76.00-115.00  182
  2  \w    -56.00  21.00   0.50    0.60    --  -50.51  37.00-120.00  154
  3  \w    -70.00  21.00   0.50    0.60    --  -50.51  76.00-115.00  182
  4  \w    -70.00  21.00   0.50    0.60    --  -50.51  77.00 -30.00  182
  5  \w    -94.00 -18.00   0.50    0.60    --  -90.00  15.00  60.00  152
  6  \w   -121.00 -31.00   0.50    0.60    --  -50.51 -76.00 118.00  180
  7  \w   -161.00 -71.00   0.50    0.60    --  -90.00 -76.00 118.00  180
  8  \w   -119.00 -73.00   0.50    0.60    --  -50.51-125.00   0.00   92
  9  \w     41.00 131.00   0.50    0.60    --  111.50 -76.00 118.00  180
 10  \w    -20.00  70.00   0.50    0.60    --   50.51 -76.00 118.00  180
 11  \w     41.00  76.00   0.50    0.60    --  111.50 -45.00  90.00   70
 12  \w     41.00 125.00   0.50    0.60    --  111.50 -61.00-120.00  168
 13  \w     41.00  76.00   0.50    0.60    --  111.50 -45.00-180.00   70
 14  \w     41.00  76.00   0.50    0.60    --  111.50 -45.00   0.00   70
 15  \w     41.00  67.00   0.50    0.60    --  111.50 -45.00 -30.00   52
 16  \w     43.00  76.00   0.50    0.60    --  111.50 -45.00 -90.00   66
 17  \w     40.00  66.00   0.50    0.60    --  111.50 -30.00-120.00   52
 18  \w     40.00  65.00   0.50    0.60    --  111.50 -30.00 150.00   50
 19  \w     41.00  76.00   0.50    0.60    --  111.50 -45.00 120.00   70
 20  \w     40.00  66.00   0.50    0.60    --  111.50 -30.00  30.00   52
 21  \w     40.00  66.00   0.50    0.60    --  111.50 -30.00 -30.00   52
 22  \w     40.00  66.00   0.50    0.60    --  111.50 -30.00  90.00   52
 23  \w     95.00 169.00   0.50    0.60    --  111.50 125.00 -60.00  148
 24  \w     95.00 178.00   0.50    0.60    --  111.50 125.00-180.00  166
 25  \w     31.00 121.00   0.50    0.60    --   50.51  76.00-115.00  180
 26  \w     92.00 178.00   0.50    0.60    --  111.50  76.00-115.00  172
 27  \w     98.00 178.00   0.50    0.60    --  111.50  61.00  30.00  160
 28  \w    104.00 178.00   0.50    0.60    --  111.50  45.00  90.00  148
 29  \w    108.00 178.00   0.50    0.60    --  111.50  30.00   0.00  140
 30  \w     80.00 111.00   0.50    0.60    --  111.50   0.00  30.00   62
 31  \w     63.00 118.00   0.50    0.60    --  111.50   0.00 -30.00  110
 32  \w     63.00 118.00   0.50    0.60    --  111.50   0.00 -60.00  110
 33  \w     63.00 118.00   0.50    0.60    --  111.50   0.00-120.00  110
 34  \w     47.00  88.00   0.50    0.60    --  111.50 -94.00   0.00   82
 35  \w     43.00 111.00   0.50    0.60    --  111.50-125.00-120.00  136
 36  \w     44.00 106.00   0.50    0.60    --  111.50 -99.00-110.74  124
 37  \w     41.00 106.00   0.50    0.60    --  111.50 -94.00 -60.00  130
 38  \w     57.00 108.00   0.50    0.60    --  111.50-110.00  46.86  102
 39  \w     80.00 106.00   0.50    0.60    --  111.50 -97.00 113.48   52
 40  \w     44.00  74.00   0.50    0.60    --  111.50 -97.00 113.48   60
 41  \w     41.00 106.00   0.50    0.60    --  111.50 -94.00 120.00  130
 42  \w     34.00  93.00   0.50    0.60    --   50.51-125.00  90.00  118
 43  \w     52.00 104.00   0.50    0.60    --  111.50 -94.00  30.00  104
 44  \w     47.00  99.00   0.50    0.60    --  111.50 -94.00 -30.00  104
 45  \w     41.00 106.00   0.50    0.60    --  111.50 -94.00 -90.00  130
 46  \w     41.00  66.00   0.50    0.60    --  111.50 -94.00-150.00   50
 47  \w     41.00 106.00   0.50    0.60    --  111.50 -94.00-180.00  130
 48  \w     81.00 106.00   0.50    0.60    --  111.50 -94.00-150.00   50
 49  \w     52.00  78.00   0.50    0.60    --  111.50 -94.00-120.00   52
 50  \w     49.00 106.00   0.50    0.60    --  111.50 -94.00  60.00  114
;
_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      0.0969457000
_diffrn_orient_matrix_UB_12      -0.0148815000
_diffrn_orient_matrix_UB_13      -0.0549697000
_diffrn_orient_matrix_UB_21      -0.0450399000
_diffrn_orient_matrix_UB_22      -0.1187768000
_diffrn_orient_matrix_UB_23      -0.0014051000
_diffrn_orient_matrix_UB_31      -0.1449233000
_diffrn_orient_matrix_UB_32      0.0270563000
_diffrn_orient_matrix_UB_33      -0.0363453000
_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  0.0355
_diffrn_reflns_av_unetI/netI     0.0151
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            53432
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.386
_diffrn_reflns_theta_min         3.782
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.600
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63253
_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 light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1024
_exptl_crystal_preparation       oil
_exptl_crystal_recrystallization_method 'ethyl acetate'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.135
_refine_diff_density_min         -0.186
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 2273 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.11(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     343
_refine_ls_number_reflns         5444
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0297
_refine_ls_R_factor_gt           0.0291
_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^)+(0.0388P)^2^+0.4071P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0729
_refine_ls_wR_factor_ref         0.0734
_reflns_Friedel_coverage         0.754
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                5319
_reflns_number_total             5444
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04257g2.cif
_cod_data_source_block           pm3_34_etoac_a_auto
_cod_depositor_comments
'Adding full bibliography for 1575172--1575185.cif.'
_cod_database_code               1575182
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C17H12N2
_chemical_oxdiff_usercomment     'Colourless block'
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.841
_diffrn_oxdiff_digest_hkl
;
019e388115c0d0a717f7a36da4af4d414d0559
;
_reflns_odcompleteness_completeness 99.93
_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.a Aromatic/amide H refined with riding coordinates:
 C19(H19), C33(H33), C28(H28), C31(H31), C25(H25), C32(H32), C21(H21),
 C20(H20), C26(H26), C34(H34), C27(H27), C22(H22), C2(H2), C11(H11), C16(H16),
 C14(H14), C17(H17), C15(H15), C8(H8), C10(H10), C3(H3), C9(H9), C4(H4), C5(H5)
;
_shelx_res_checksum              71717
_olex2_exptl_crystal_mounting_method oil
_olex2_submission_original_sample_id '4 123 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 1.937
_oxdiff_exptl_absorpt_empirical_full_min 0.626