Synthesis, structure, and spectral and electrochemical properties of new visible to NIR absorbing 3-pyrrolyl BODIPY derivatives.
Behera, Kanhu Charan; Chauhan, Pinky; Tiwari, Shubham; Ravikanth, Mangalampalli; Organic & biomolecular chemistry 23 (2025) 935–947; doi:10.1039/d4ob01735h

data_7160273
_publ_section_title
;
 Synthesis, structure, and spectral and electrochemical properties of new
 visible to NIR absorbing 3-pyrrolyl BODIPY derivatives.
;
_journal_issue                   4
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              935
_journal_page_last               947
_journal_paper_doi               10.1039/d4ob01735h
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         '0.25(C36 H24 B F2 N5 S2), 0.25(C H Cl3)'
_chemical_formula_sum            'C9.25 H6.25 B0.25 Cl0.75 F0.5 N1.25 S0.5'
_chemical_formula_weight         189.72
_chemical_name_systematic        'bis(benzothiazolyl) -3-pyrrolyl BODIPY'
_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
_audit_creation_date             2024-07-25
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-25 deposited with the CCDC.	2024-11-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.932(2)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   22.4102(6)
_cell_length_b                   8.0136(2)
_cell_length_c                   19.3890(4)
_cell_measurement_reflns_used    13655
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      27.8110
_cell_measurement_theta_min      1.8250
_cell_volume                     3439.78(15)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'PROGRAM:BIS V6.2.16/2021-10-22 && APEX4 2021.4-0                                '
_computing_data_reduction        'CrysAlisPro 1.171.43.105a (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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_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  \f    -89.73 150.27   1.50    5.00  31.11 -18.16 -31.50    --   160
  2  \w   -122.88  22.62   1.50    5.00    --  -18.16 -59.25  71.08   97
  3  \w    -76.17   6.33   1.50    5.00    --  -18.16  89.85  18.34   55
  4  \w   -122.88  22.62   1.50    5.00    --  -18.16 -59.25  20.08   97
  5  \w    -76.17   6.33   1.50    5.00    --  -18.16  89.85 -32.66   55
  6  \w   -122.88  22.62   1.50    5.00    --  -18.16 -59.25-135.92   97
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0232786000
_diffrn_orient_matrix_UB_12      -0.0182856000
_diffrn_orient_matrix_UB_13      -0.0281473000
_diffrn_orient_matrix_UB_21      0.0219120000
_diffrn_orient_matrix_UB_22      -0.0120161000
_diffrn_orient_matrix_UB_23      -0.0222765000
_diffrn_orient_matrix_UB_31      0.0018884000
_diffrn_orient_matrix_UB_32      -0.0857868000
_diffrn_orient_matrix_UB_33      0.0091389000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0647
_diffrn_reflns_av_unetI/netI     0.0308
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            51295
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.127
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.436
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80445
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic greenish green'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.465
_exptl_crystal_description       block
_exptl_crystal_F_000             1552
_exptl_crystal_preparation       Luminescent
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.806
_refine_diff_density_min         -0.866
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     452
_refine_ls_number_reflns         6045
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0485
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0396P)^2^+3.9550P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0981
_refine_ls_wR_factor_ref         0.1036
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5278
_reflns_number_total             6045
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01735h2.cif
_cod_data_source_block           mr_pc_tribr_autored
_cod_depositor_comments
'Adding full bibliography for 7160273--7160275.cif.'
_cod_original_cell_volume        3439.77(15)
_cod_original_formula_sum        'C9.25 H6.25 B0.25 Cl0.75 F0.50 N1.25 S0.50'
_cod_database_code               7160273
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.958
_shelx_estimated_absorpt_t_min   0.880
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C01C(H01E)
1.b Aromatic/amide H refined with riding coordinates:
 N3(H008), C8(H00F), C21(H00M), C14(H00P), C7(H00R), C18(H00S), C28(H00T),
 C11(H00U), C19(H00W), C20(H00Y), C12(H00Z), C25(H010), C1(H012), C26(H013),
 C35(H014), C27(H015), C31(H016), C3(H017), C32(H018), C34(H019), C2(H01A)
1.c Idealised Me refined as rotating group:
 C36(H01B,H01C,H01D)
;
_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 2.244
_oxdiff_exptl_absorpt_empirical_full_min 0.411