Far-red fluorescence and chiroptical properties of pyrrolopyrrole aza-BODIPYs induced by the <i>B</i>,<i>O</i>-chelation.
Fukami, Shuhei; Mori, Shigeki; Harada, Takunori; Shimizu, Soji; Chemical communications (Cambridge, England) 60 (2024) 6170–6173; doi:10.1039/d4cc01586j

data_7133081
_publ_section_title
;
 Far-red fluorescence and chiroptical properties of pyrrolopyrrole
 aza-BODIPYs induced by the <i>B</i>,<i>O</i>-chelation.
;
_journal_issue                   48
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6170
_journal_page_last               6173
_journal_paper_doi               10.1039/d4cc01586j
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C38 H46 B2 F4 N6 S4'
_chemical_formula_sum            'C38 H46 B2 F4 N6 S4'
_chemical_formula_weight         812.67
_chemical_name_systematic        Thienyl-thiazole-PPAB
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-03-27
_audit_creation_method
;
Olex2 1.5
(compiled 2024.01.12 svn.r2f8d729c for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-03-27 deposited with the CCDC.	2024-05-21 downloaded from the CCDC.
;
_cell_angle_alpha                75.307(4)
_cell_angle_beta                 71.596(4)
_cell_angle_gamma                76.096(4)
_cell_formula_units_Z            1
_cell_length_a                   7.7011(3)
_cell_length_b                   11.6851(6)
_cell_length_c                   11.8911(6)
_cell_measurement_reflns_used    11285
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.7480
_cell_measurement_theta_min      1.8190
_cell_volume                     967.05(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'DTREK_VERSION=d*TREK version 9.9.9.10 W9RSSI -- Jul 7 2017'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (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  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 7.111
_diffrn_detector_type            'Rigaku Saturn724+ area detector'
_diffrn_measured_fraction_theta_full 0.999
_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   -105.00  75.00   0.50    1.00    --  -15.00  45.00   0.00  360
  2  \w   -105.00  75.00   0.50    1.00    --  -15.00  45.00  90.00  360
  3  \w   -105.00  75.00   0.50    1.00    --  -15.00  45.00 180.00  360
  4  \w   -105.00  75.00   0.50    1.00    --  -15.00  45.00 270.00  360
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Rigaku Varimax with Saturn'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0890589000
_diffrn_orient_matrix_UB_12      0.0367787000
_diffrn_orient_matrix_UB_13      0.0060899000
_diffrn_orient_matrix_UB_21      -0.0134641000
_diffrn_orient_matrix_UB_22      -0.0095491000
_diffrn_orient_matrix_UB_23      0.0632793000
_diffrn_orient_matrix_UB_31      0.0400694000
_diffrn_orient_matrix_UB_32      0.0511651000
_diffrn_orient_matrix_UB_33      -0.0079708000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0560
_diffrn_reflns_av_unetI/netI     0.0547
_diffrn_reflns_Laue_measured_fraction_full 0.999
_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       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            18533
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.989
_diffrn_reflns_theta_min         1.830
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'MicroMax 007'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.303
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66313
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.395
_exptl_crystal_description       plate
_exptl_crystal_F_000             426
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.324
_refine_diff_density_min         -0.355
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     290
_refine_ls_number_reflns         4659
_refine_ls_number_restraints     109
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0645
_refine_ls_R_factor_gt           0.0476
_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^)+(0.0444P)^2^+0.3660P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0997
_refine_ls_wR_factor_ref         0.1065
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3693
_reflns_number_total             4659
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc01586j2.cif
_cod_data_source_block           shimizu_autored_CCDC1
_cod_depositor_comments
'Adding full bibliography for 7133080--7133081.cif.'
_cod_original_cell_volume        967.05(9)
_cod_database_code               7133081
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C38H46B2F4N6S4
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.936
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C2-C20
 1.45 with sigma of 0.02
 S3-C20
 1.75 with sigma of 0.01
 S3-C23
 1.75 with sigma of 0.01
 C20-C21
 1.4 with sigma of 0.05
 C21-C22
 1.35 with sigma of 0.01
 C22-C23
 1.35 with sigma of 0.01
 S3-C21
 2.58 with sigma of 0.05
 S3-C22
 2.58 with sigma of 0.05
 C20-C23
 2.47 with sigma of 0.05
3. Rigid bond restraints
 S3, C20, C21, C22, C23
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
S2 \\sim C7 \\sim C8 \\sim C9 \\sim C10: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
S3 \\sim C20 \\sim C21 \\sim C22 \\sim C23: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Uanis(S3) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C23) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Others
 Fixed Sof: S2(0.83) C7(0.83) C8(0.83) H8(0.83) C9(0.83) H9(0.83) C10(0.83)
 H10(0.83) S3(0.17) C20(0.17) C21(0.17) H21(0.17) C22(0.17) H22(0.17) C23(0.17)
 H23(0.17)
6.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,
 H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B)
6.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C9(H9), C10(H10), C21(H21), C22(H22), C23(H23)
6.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_shelx_res_checksum              89595
_shelx_hkl_checksum              38266
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.487
_oxdiff_exptl_absorpt_empirical_full_min 0.555