One- and two-electron reductions of a bulky BODIPY compound
Pascoe, Liam M.; Lim, Li Feng; Kallmeier, Fabian; Cox, Nicholas; Brothers, Penelope Jane; Hicks, Jamie; Dalton Transactions  (2023) –; doi:10.1039/D3DT02048G

data_7713489
_publ_section_title
;
 One- and two-electron reductions of a bulky BODIPY compound
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02048G
_journal_year                    2023
_chemical_formula_moiety         'B Br4, C42 H49 B Br N2, C6 H6'
_chemical_formula_sum            'C48 H55 B2 Br5 N2'
_chemical_formula_weight         1081.11
_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
_audit_creation_date             2023-06-27
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-07-14 deposited with the CCDC.	2023-07-14 downloaded from the CCDC.
;
_cell_angle_alpha                75.759(3)
_cell_angle_beta                 75.100(3)
_cell_angle_gamma                83.917(3)
_cell_formula_units_Z            2
_cell_length_a                   11.5135(4)
_cell_length_b                   13.7856(5)
_cell_length_c                   16.3179(5)
_cell_measurement_reflns_used    8052
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.6510
_cell_measurement_theta_min      4.8700
_cell_volume                     2423.46(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector_area_resol_mean 8.1297
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.967
_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    -28.00  56.00   1.00    1.00    --   37.05 -38.00-120.00   84
  2  \w     29.00  84.00   1.00    1.00    --   37.05-125.00  60.00   55
  3  \w     12.00 104.00   1.00    1.00    --   37.05  19.00  60.00   92
  4  \w     23.00  76.00   1.00    1.00    --   37.05 -99.00 120.00   53
  5  \w     20.00 102.00   1.00    1.00    --   37.05  57.00-150.00   82
  6  \w     29.00  84.00   1.00    1.00    --   37.05-125.00 -60.00   55
  7  \w     12.00 104.00   1.00    1.00    --   37.05  19.00 150.00   92
  8  \w     78.00 154.00   1.00    4.00    --  111.00 -12.00-180.00   76
  9  \w     42.00  69.00   1.00    4.00    --  111.00-111.00 -90.00   27
 10  \w     43.00 137.00   1.00    4.00    --  111.00 -77.00 150.00   94
 11  \w     63.00 146.00   1.00    4.00    --  111.00 178.00  90.00   83
 12  \w     84.00 109.00   1.00    4.00    --  111.00-111.00 -90.00   25
 13  \w     96.00 178.00   1.00    4.00    --  111.00  38.00  30.00   82
 14  \w     41.00 109.00   1.00    4.00    --  111.00-111.00 150.00   68
 15  \w     97.00 178.00   1.00    4.00    --  111.00  50.00 -90.00   81
 16  \w    111.00 177.00   1.00    4.00    --  111.00 111.00-150.00   66
 17  \w     65.00 127.00   1.00    4.00    --  111.00 -50.00-150.00   62
 18  \w     46.00 129.00   1.00    4.00    --  111.00 -38.00 -60.00   83
 19  \w     41.00 109.00   1.00    4.00    --  111.00-111.00  60.00   68
 20  \w     41.00 126.00   1.00    4.00    --  111.00 -25.00  90.00   85
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0250
_diffrn_reflns_av_unetI/netI     0.0405
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            16455
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.776
_diffrn_reflns_theta_min         3.862
_exptl_absorpt_coefficient_mu    5.264
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85001
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.482
_exptl_crystal_description       block
_exptl_crystal_F_000             1084
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.420
_refine_diff_density_min         -2.414
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     576
_refine_ls_number_reflns         9500
_refine_ls_number_restraints     128
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0655
_refine_ls_R_factor_gt           0.0582
_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^)+(0.1028P)^2^+5.1771P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1675
_refine_ls_wR_factor_ref         0.1758
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8208
_reflns_number_total             9500
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02048g2.cif
_cod_data_source_block           2
_cod_database_code               7713489
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.817
_shelx_estimated_absorpt_t_min   0.451
_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
 C20A-C19 = C20-C19 = C21A-C19 = C21-C19
 1.53 with sigma of 0.008
 C29-C28 = C29A-C28A = C30A-C28A = C30-C28 = C28-C27 = C28A-C27
 1.53 with sigma of 0.008
 C20-C21 = C20A-C21A
 2.5 with sigma of 0.008
 C29-C30 = C29A-C30A
 2.5 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
C19 \\sim C20A \\sim C20 \\sim C21A \\sim C21: within 2A with sigma of 0.008
and sigma for terminal atoms of 0.016 within 2A
C28 \\sim C29 \\sim C30 \\sim C28A \\sim C29A \\sim C30A: within 2A with sigma
of 0.008 and sigma for terminal atoms of 0.016 within 2A
Uanis(B1) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.002
4. Others
 Sof(H19A)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21A)=Sof(H21D)=
 Sof(H21E)=Sof(H21F)=1-FVAR(1)
 Sof(H19)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C20)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=FVAR(1)
 Sof(C29A)=Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C28A)=Sof(H28A)=Sof(C30A)=
 Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(2)
 Sof(C28)=Sof(H28)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C29)=Sof(H29A)=
 Sof(H29B)=Sof(H29C)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C31(H31), C19(H19), C19(H19A), C16(H16), C28(H28), C28A(H28A)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C12(H12), C25(H25), C26(H26), C13(H13), C24(H24),
 C8(H8), C14(H14), C46(H46), C47(H47), C38(H38), C48(H48), C36(H36), C45(H45),
 C44(H44), C43(H43)
5.c Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C33(H33A,H33B,H33C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C41(H41A,H41B,H41C), C32(H32A,H32B,H32C), C30(H30A,
 H30B,H30C), C21(H21A,H21B,H21C), C20(H20A,H20B,H20C), C29(H29A,H29B,H29C),
 C20A(H20D,H20E,H20F), C21A(H21D,H21E,H21F), C29A(H29D,H29E,H29F), C30A(H30D,
 H30E,H30F)
;
_shelx_res_checksum              45730
_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
;