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_7713491
_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         'C84 H98.545 B2 Br1.455 N4 O0.545, C3 H7'
_chemical_formula_sum            'C87 H105.54 B2 Br1.46 N4 O0.55'
_chemical_formula_weight         1353.90
_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             2023-06-29
_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                82.352(3)
_cell_angle_beta                 77.952(4)
_cell_angle_gamma                85.009(3)
_cell_formula_units_Z            2
_cell_length_a                   11.6625(4)
_cell_length_b                   13.5508(5)
_cell_length_c                   25.3021(12)
_cell_measurement_reflns_used    6761
_cell_measurement_temperature    149.98(10)
_cell_measurement_theta_max      73.2980
_cell_measurement_theta_min      3.9360
_cell_volume                     3868.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (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)'
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 8.1297
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.963
_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    -54.00  25.00   1.00    3.00    --  -36.95  57.00 -30.00   79
  2  \w      6.00  76.00   1.00    3.00    --   36.95 -99.00 120.00   70
  3  \w     30.00  95.00   1.00    3.00    --   36.95  38.00-180.00   65
  4  \w     44.00 108.00   1.00    3.00    --   36.95  19.00 120.00   64
  5  \w     21.00  54.00   1.00    3.00    --   36.95 -57.00   0.00   33
  6  \w     23.00 100.00   1.00    3.00    --   36.95  57.00-120.00   77
  7  \w     62.00  89.00   1.00    3.00    --   36.95-125.00 -30.00   27
  8  \w      7.00  74.00   1.00    3.00    --   36.95 -99.00 -30.00   67
  9  \w     32.00  61.00   1.00    3.00    --   36.95-125.00 -30.00   29
 10  \w    -30.00  12.00   1.00    3.00    --   36.95 -57.00   0.00   42
 11  \w      9.00  42.00   1.00    3.00    --   36.95  19.00 120.00   33
 12  \w     42.00 129.00   1.00   12.00    --  111.00 -38.00   0.00   87
 13  \w     64.00 109.00   1.00   12.00    --  111.00-111.00-180.00   45
 14  \w     57.00 125.00   1.00   12.00    --  111.00 -50.00-150.00   68
 15  \w     77.00 109.00   1.00   12.00    --  111.00-111.00 -90.00   32
 16  \w     48.00 108.00   1.00   12.00    --  111.00 -77.00  60.00   60
 17  \w     52.00 109.00   1.00   12.00    --  111.00-111.00  60.00   57
 18  \w     43.00  70.00   1.00   12.00    --  111.00-111.00 -90.00   27
 19  \w     62.00 130.00   1.00   12.00    --  111.00 -38.00 -90.00   68
 20  \w     44.00 127.00   1.00   12.00    --  111.00 -38.00  90.00   83
 21  \w     54.00 122.00   1.00   12.00    --  111.00 -64.00 150.00   68
 22  \w     99.00 168.00   1.00   12.00    --  111.00  25.00   0.00   69
 23  \w     44.00 130.00   1.00   12.00    --  111.00 -77.00 -90.00   86
 24  \w     41.00 157.00   1.00   12.00    --  111.00 -12.00 150.00  116
;
_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_unetI/netI     0.0413
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            18726
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.710
_diffrn_reflns_theta_min         3.565
_exptl_absorpt_coefficient_mu    1.344
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85259
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (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    1.162
_exptl_crystal_description       prism
_exptl_crystal_F_000             1442
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.523
_refine_diff_density_min         -0.350
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     950
_refine_ls_number_reflns         18726
_refine_ls_number_restraints     161
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0561
_refine_ls_R_factor_gt           0.0486
_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^)+(0.0783P)^2^+0.7837P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1260
_refine_ls_wR_factor_ref         0.1290
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16107
_reflns_number_total             18726
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9857\% 
around [-0.00 -0.00 1.00] (reciprocal) or [-0.39 -0.20 0.90] (direct)
;
_cod_data_source_file            d3dt02048g2.cif
_cod_data_source_block           3-Br
_cod_database_code               7713491
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.912
_shelx_estimated_absorpt_t_min   0.794
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5324(7)
 0.4676(7)
2. 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, All O(H) groups
3. Restrained distances
 C15-C16 = C16-C17 = C16-C18
 1.53 with sigma of 0.008
 C15-C16A = C16A-C17A = C16A-C18A
 1.53 with sigma of 0.008
 C23-C31 = C31-C32 = C31-C33
 1.53 with sigma of 0.008
 C23-C31A = C31A-C32A = C31A-C33A
 1.53 with sigma of 0.008
 C37-C41
 1.53 with sigma of 0.008
 C17-C18
 2.5 with sigma of 0.008
 C17A-C18A
 2.5 with sigma of 0.008
 C32-C33
 2.5 with sigma of 0.008
 C32A-C33A
 2.5 with sigma of 0.008
4. Uiso/Uaniso restraints and constraints
C16 \\sim C17 \\sim C18 \\sim C16A \\sim C17A \\sim C18A: within 2A with sigma
of 0.005 and sigma for terminal atoms of 0.01 within 2A
C31 \\sim C32 \\sim C33 \\sim C31A \\sim C32A \\sim C33A: within 2A with sigma
of 0.005 and sigma for terminal atoms of 0.01 within 2A
Uanis(C41) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O1) = Uanis(Br1)
Uanis(O2) = Uanis(Br2)
5. Others
 Sof(O1)=Sof(H1)=1-FVAR(1)
 Sof(Br1)=FVAR(1)
 Sof(O2)=Sof(H2A)=1-FVAR(2)
 Sof(Br2)=FVAR(2)
 Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=
 Sof(H17F)=Sof(C16A)=Sof(H16A)=1-FVAR(3)
 Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=Sof(H18A)=
 Sof(H18B)=Sof(H18C)=FVAR(3)
 Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C32A)=Sof(H32D)=Sof(H32E)=
 Sof(H32F)=Sof(C31A)=Sof(H31A)=1-FVAR(4)
 Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33)=Sof(H33A)=
 Sof(H33B)=Sof(H33C)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C45(H45), C7(H7), C28(H28), C61(H61), C70(H70), C19(H19), C58(H58), C73(H73),
 C31(H31), C16(H16), C16A(H16A), C31A(H31A)
6.b Secondary CH2 refined with riding coordinates:
 C87(H87A,H87B), C86(H86A,H86B)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8), C78(H78), C44(H44), C2(H2), C66(H66), C68(H68), C67(H67),
 C50(H50), C49(H49), C13(H13), C80(H80), C14(H14), C12(H12), C55(H55), C56(H56),
  C24(H24), C25(H25), C26(H26), C54(H54), C38(H38), C36(H36)
6.d Idealised Me refined as rotating group:
 C82(H82A,H82B,H82C), C84(H84A,H84B,H84C), C40(H40A,H40B,H40C), C42(H42A,H42B,
 H42C), C62(H62A,H62B,H62C), C21(H21A,H21B,H21C), C83(H83A,H83B,H83C), C60(H60A,
 H60B,H60C), C29(H29A,H29B,H29C), C20(H20A,H20B,H20C), C74(H74A,H74B,H74C),
 C30(H30A,H30B,H30C), C75(H75A,H75B,H75C), C63(H63A,H63B,H63C), C72(H72A,H72B,
 H72C), C71(H71A,H71B,H71C), C32(H32A,H32B,H32C), C85(H85A,H85B,H85C), C17(H17A,
 H17B,H17C), C18(H18A,H18B,H18C), C59(H59A,H59B,H59C), C33(H33A,H33B,H33C),
 C18A(H18D,H18E,H18F), C17A(H17D,H17E,H17F), C33A(H33D,H33E,H33F), C32A(H32D,
 H32E,H32F), C41(H41A,H41B,H41C)
6.e Idealised tetrahedral OH refined as rotating group:
 O2(H2A), O1(H1)
;
_shelx_res_checksum              2495
_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
;