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_7133080
_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         'C54 H58 B2 N6 O2 S2'
_chemical_formula_sum            'C54 H58 B2 N6 O2 S2'
_chemical_formula_weight         908.80
_chemical_name_systematic        'B,O-chelated PPAB'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-11-02
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-03-23 deposited with the CCDC.	2024-05-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.615(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   20.7040(10)
_cell_length_b                   6.2953(3)
_cell_length_c                   18.9378(9)
_cell_measurement_reflns_used    17514
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.8200
_cell_measurement_theta_min      2.0410
_cell_volume                     2339.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (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 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 7.111
_diffrn_detector_type            'Rigaku Saturn724+ area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.949
_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   22.00    --  -15.00  45.00   0.00  360
  2  \w   -105.00  75.00   0.50   22.00    --  -15.00  45.00  90.00  360
  3  \w   -105.00  75.00   0.50   22.00    --  -15.00  45.00 180.00  360
  4  \w   -105.00  75.00   0.50   22.00    --  -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      -0.0087690000
_diffrn_orient_matrix_UB_12      -0.0299754000
_diffrn_orient_matrix_UB_13      0.0318891000
_diffrn_orient_matrix_UB_21      -0.0347831000
_diffrn_orient_matrix_UB_22      -0.0062914000
_diffrn_orient_matrix_UB_23      -0.0221149000
_diffrn_orient_matrix_UB_31      0.0044441000
_diffrn_orient_matrix_UB_32      -0.1084167000
_diffrn_orient_matrix_UB_33      -0.0075198000
_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  0.0645
_diffrn_reflns_av_unetI/netI     0.0569
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            47021
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.797
_diffrn_reflns_theta_min         2.076
_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    0.164
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72340
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
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    1.290
_exptl_crystal_description       plate
_exptl_crystal_F_000             964
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.387
_refine_diff_density_min         -0.462
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     382
_refine_ls_number_reflns         6930
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.1328
_refine_ls_R_factor_gt           0.0714
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0697P)^2^+1.3703P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1487
_refine_ls_wR_factor_ref         0.1740
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4151
_reflns_number_total             6930
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc01586j2.cif
_cod_data_source_block           shimizu_autored
_cod_depositor_comments
'Adding full bibliography for 7133080--7133081.cif.'
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7133080
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         S2O2N6C54B2H58
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.959
_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
 C5-C19
 1.54 with sigma of 0.01
 C19-C20
 1.54 with sigma of 0.01
 C20-C21
 1.54 with sigma of 0.01
 C21-C22
 1.54 with sigma of 0.01
 C22-C23
 1.54 with sigma of 0.01
 C24-C25
 1.54 with sigma of 0.01
 C25-C26
 1.54 with sigma of 0.01
 C26-C27
 1.54 with sigma of 0.01
 C5-C20
 2.54 with sigma of 0.02
 C19-C21
 2.54 with sigma of 0.02
 C20-C22
 2.54 with sigma of 0.02
 C21-C23
 2.54 with sigma of 0.02
 C22-C24
 2.54 with sigma of 0.02
 C23-C25
 2.54 with sigma of 0.02
 C24-C26
 2.54 with sigma of 0.02
 C25-C27
 2.54 with sigma of 0.02
 C5-C28
 1.54 with sigma of 0.01
 C28-C29
 1.54 with sigma of 0.01
 C29-C30
 1.54 with sigma of 0.01
 C30-C31
 1.54 with sigma of 0.01
 C31-C32
 1.54 with sigma of 0.01
 C32-C33
 1.54 with sigma of 0.01
 C33-C34
 1.54 with sigma of 0.01
 C34-C35
 1.54 with sigma of 0.01
 C35-C36
 1.54 with sigma of 0.01
 C5-C29
 2.54 with sigma of 0.02
 C28-C30
 2.54 with sigma of 0.02
 C29-C31
 2.54 with sigma of 0.02
 C30-C32
 2.54 with sigma of 0.02
 C31-C33
 2.54 with sigma of 0.02
 C32-C34
 2.54 with sigma of 0.02
 C33-C35
 2.54 with sigma of 0.02
 C34-C36
 2.54 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C19 \\sim C21 \\sim C23 \\sim C24 \\sim C25 \\sim C27: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim
C36: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=
 Sof(H30B)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(C33)=
 Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C35)=Sof(H35A)=Sof(H35B)=
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=1-FVAR(1)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(C21)=Sof(H21A)=
 Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(C24)=
 Sof(H24A)=Sof(H24B)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,
 H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B), C28(H28A,H28B),
 C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B),
  C34(H34A,H34B), C35(H35A,H35B)
5.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18)
5.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C36(H36A,H36B,H36C)
;
_shelx_res_checksum              27301
_shelx_hkl_checksum              71750
_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 1.558
_oxdiff_exptl_absorpt_empirical_full_min 0.489