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_7713490
_publ_section_title
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 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         'C84 H98 B2 F2 N4, C6 H14'
_chemical_formula_sum            'C90 H112 B2 F2 N4'
_chemical_formula_weight         1309.45
_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
_audit_creation_date             2023-06-29
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-29 deposited with the CCDC.	2023-07-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.2415(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.86146(9)
_cell_length_b                   35.6092(3)
_cell_length_c                   21.07021(16)
_cell_measurement_reflns_used    11304
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      73.5830
_cell_measurement_theta_min      4.2860
_cell_volume                     8043.50(11)
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 8.1297
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.990
_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    -32.00  47.00   1.00    2.00    --   36.95 -38.00-120.00   79
  2  \w    -18.00  55.00   1.00    2.00    --   36.95 -38.00 120.00   73
  3  \w     30.00 104.00   1.00    2.00    --   36.95  57.00  30.00   74
  4  \w    -21.00  53.00   1.00    2.00    --   36.95 -77.00-120.00   74
  5  \w     61.00 131.00   1.00   30.00    --  111.00 -64.00-180.00   70
  6  \w     95.00 172.00   1.00   30.00    --  111.00  64.00 -60.00   77
  7  \w     46.00  92.00   1.00   30.00    --  111.00 -92.00  90.00   46
  8  \w     44.00  83.00   1.00   30.00    --  111.00 -92.00-180.00   39
  9  \w    114.00 177.00   1.00   30.00    --  111.00  38.00-180.00   63
 10  \w     91.00 175.00   1.00   30.00    --  111.00  64.00-120.00   84
 11  \w     95.00 121.00   1.00   30.00    --  111.00  64.00-150.00   26
 12  \w    129.00 173.00   1.00   30.00    --  111.00  64.00-150.00   44
 13  \w     67.00 146.00   1.00   30.00    --  111.00 178.00  90.00   79
;
_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  0.0229
_diffrn_reflns_av_unetI/netI     0.0352
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -43
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            31437
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.117
_diffrn_reflns_theta_min         4.124
_exptl_absorpt_coefficient_mu    0.494
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.98142
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.081
_exptl_crystal_description       block
_exptl_crystal_F_000             2832
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.485
_refine_diff_density_min         -0.514
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     907
_refine_ls_number_reflns         15693
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0709
_refine_ls_R_factor_gt           0.0561
_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^)+(0.0720P)^2^+3.5334P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1430
_refine_ls_wR_factor_ref         0.1545
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12694
_reflns_number_total             15693
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02048g2.cif
_cod_data_source_block           3-F
_cod_original_cell_volume        8043.49(11)
_cod_database_code               7713490
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.930
_shelx_estimated_absorpt_t_min   0.866
_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
 C89_$1-C88_$1 = C90_$1-C89_$1 = C90-C90_$1
 1.53 with sigma of 0.008
 C86-C85 = C87-C86 = C87_$2-C87
 1.53 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
C88 \\sim C89 \\sim C90: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
C85 \\sim C86 \\sim C87: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
Uanis(C20) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4.a Ternary CH refined with riding coordinates:
 C7(H7), C49(H49), C58(H58), C16(H16), C19(H19), C61(H61), C73(H73), C31(H31),
 C70(H70), C28(H28)
4.b Secondary CH2 refined with riding coordinates:
 C90(H90A,H90B), C87(H87A,H87B), C89(H89A,H89B), C86(H86A,H86B)
4.c Aromatic/amide H refined with riding coordinates:
 C50(H50), C2(H2), C8(H8), C3(H3), C80(H80), C38(H38), C44(H44), C56(H56),
 C78(H78), C36(H36), C54(H54), C45(H45), C14(H14), C55(H55), C12(H12), C13(H13),
  C68(H68), C66(H66), C26(H26), C67(H67), C24(H24), C25(H25)
4.d Idealised Me refined as rotating group:
 C82(H82A,H82B,H82C), C42(H42A,H42B,H42C), C40(H40A,H40B,H40C), C84(H84A,H84B,
 H84C), C83(H83A,H83B,H83C), C59(H59A,H59B,H59C), C41(H41A,H41B,H41C), C17(H17A,
 H17B,H17C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C60(H60A,H60B,H60C),
 C18(H18A,H18B,H18C), C71(H71A,H71B,H71C), C74(H74A,H74B,H74C), C32(H32A,H32B,
 H32C), C33(H33A,H33B,H33C), C72(H72A,H72B,H72C), C30(H30A,H30B,H30C), C75(H75A,
 H75B,H75C), C21(H21A,H21B,H21C), C29(H29A,H29B,H29C), C20(H20A,H20B,H20C),
 C85(H85A,H85B,H85C), C88(H88A,H88B,H88C)
;
_shelx_res_checksum              98930
_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
;