Experimental and theoretical comprehension of ESIPT fluorophores based on a 2-(2'-hydroxyphenyl)-3,3'-dimethylindole (HDMI) scaffold.
Stoerkler, Timothée; Ulrich, Gilles; Retailleau, Pascal; Laurent, Adèle D; Jacquemin, Denis; Massue, Julien; Chemical science 15 (2024) 7206–7218; doi:10.1039/d4sc01937g

data_1571447
_publ_section_title
;
 Experimental and theoretical comprehension of ESIPT fluorophores based on
 a 2-(2'-hydroxyphenyl)-3,3'-dimethylindole (HDMI) scaffold.
;
_journal_issue                   19
_journal_name_full               'Chemical science'
_journal_page_first              7206
_journal_page_last               7218
_journal_paper_doi               10.1039/d4sc01937g
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C16 H13 Br2 N O'
_chemical_formula_sum            'C16 H13 Br2 N O'
_chemical_formula_weight         395.095
_chemical_name_systematic
"'2,4-dibromo-6-(3,3-dimethyl-3H-indol-2-yl)phenol'"
_space_group_crystal_system      monoclinic
_space_group_IT_number           11
_space_group_name_Hall           '-P 2yb'
_space_group_name_H-M_alt        'P 1 21/m 1'
_symmetry_Int_Tables_number      11
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-28
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-05-02 deposited with the CCDC.	2024-04-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.234(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.6747(5)
_cell_length_b                   6.9706(5)
_cell_length_c                   12.3186(6)
_cell_measurement_reflns_used    4968
_cell_measurement_temperature    173.01(10)
_cell_measurement_theta_max      29.7400
_cell_measurement_theta_min      2.5640
_cell_volume                     711.44(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.9986
_diffrn_measured_fraction_theta_max 0.9990
_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    -20.00  99.00   0.50    7.50    --    9.20  57.00  90.00  238
  2  \w    -39.00  80.00   0.50    7.50    --   -9.80  57.00-150.00  238
  3  \w    -41.00  80.00   0.50    7.50    --   -9.80  38.00-180.00  242
  4  \w    -39.00  80.00   0.50    7.50    --   -9.80  57.00  60.00  238
  5  \w    -20.00   5.00   0.50    7.50    --    9.20  57.00 -90.00   50
  6  \w    -41.00  80.00   0.50    7.50    --   -9.80  38.00   0.00  242
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0081930000
_diffrn_orient_matrix_UB_12      0.0825046000
_diffrn_orient_matrix_UB_13      0.0315215000
_diffrn_orient_matrix_UB_21      0.0846870000
_diffrn_orient_matrix_UB_22      0.0014210000
_diffrn_orient_matrix_UB_23      0.0260449000
_diffrn_orient_matrix_UB_31      0.0094701000
_diffrn_orient_matrix_UB_32      0.0595569000
_diffrn_orient_matrix_UB_33      -0.0442898000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0477
_diffrn_reflns_av_unetI/netI     0.0387
_diffrn_reflns_Laue_measured_fraction_full 0.9986
_diffrn_reflns_Laue_measured_fraction_max 0.9990
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            17279
_diffrn_reflns_point_group_measured_fraction_full 0.9986
_diffrn_reflns_point_group_measured_fraction_max 0.9990
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         28.68
_diffrn_reflns_theta_min         2.55
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.690
_exptl_absorpt_correction_T_max  0.942
_exptl_absorpt_correction_T_min  0.661
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.844
_exptl_crystal_description       prism
_exptl_crystal_F_000             387.390
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane / methanol'
_exptl_crystal_size_max          0.121
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.049
_refine_diff_density_max         0.4113
_refine_diff_density_min         -0.5865
_refine_diff_density_rms         0.1006
_refine_ls_d_res_high            0.7404
_refine_ls_d_res_low             7.9776
_refine_ls_goodness_of_fit_ref   1.0353
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     187
_refine_ls_number_reflns         1983
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.0301
_refine_ls_R_factor_all          0.0331
_refine_ls_R_factor_gt           0.0199
_refine_ls_shift/su_max          0.0006
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0110P)^2^+0.0166P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0326
_refine_ls_wR_factor_ref         0.0347
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              11
_reflns_limit_h_min              -11
_reflns_limit_k_max              9
_reflns_limit_k_min              0
_reflns_limit_l_max              16
_reflns_limit_l_min              0
_reflns_number_gt                1595
_reflns_number_total             1983
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4sc01937g2.cif
_cod_data_source_block           TS711
_cod_depositor_comments
'Adding full bibliography for 1571447--1571448.cif.'
_cod_database_code               1571447
_chemical_oxdiff_formula         'C16 H13 Br2 N O'
_chemical_oxdiff_usercomment     '173 K'
_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
 C7-H7 \\sim C6-H6 \\sim C5-H5 \\sim C8-H8 \\sim C14-H14 \\sim C12-H12
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(H1) \\sim Ueq, Uanis(H8) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.03
;
_olex2_refine_details
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
 - for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster charges
or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       ORCA 5.0
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   Normal
   METHOD:         R2SCAN
   BASIS SET:      def2-TZVP
   CHARGE:         0
   MULTIPLICITY:   2
   DATE:           2023-04-28_11-17-56
;
_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 1.622
_oxdiff_exptl_absorpt_empirical_full_min 0.583