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_7713493
_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         'C92 H114 B2 F2 Mg N4 O2, 5(C6 H6)'
_chemical_formula_sum            'C122 H144 B2 F2 Mg N4 O2'
_chemical_formula_weight         1782.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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
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2023-06-29 deposited with the CCDC.	2023-07-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.278(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.2816(2)
_cell_length_b                   36.4512(8)
_cell_length_c                   26.0374(5)
_cell_measurement_reflns_used    6111
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      72.5390
_cell_measurement_theta_min      4.0790
_cell_volume                     10643.1(4)
_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      150.15
_diffrn_detector_area_resol_mean 16.2595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.968
_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    -34.00  63.00   1.00    4.00    --   37.05 -19.00-180.00   97
  2  \w     35.00  90.00   1.00    4.00    --   37.05-125.00  30.00   55
  3  \w     28.00 104.00   1.00    4.00    --   37.05  57.00  90.00   76
  4  \w    -34.00  58.00   1.00    4.00    --   37.05 -19.00 120.00   92
  5  \w     46.00 130.00   1.00   20.00    --  111.00 -38.00  90.00   84
  6  \w     44.00 109.00   1.00   20.00    --  111.00 -77.00  30.00   65
  7  \w     43.00 130.00   1.00   20.00    --  111.00 -38.00   0.00   87
  8  \w    104.00 178.00   1.00   20.00    --  111.00 111.00 150.00   74
  9  \w     56.00 106.00   1.00   20.00    --  111.00 -92.00 120.00   50
 10  \w     49.00 105.00   1.00   20.00    --  111.00 -92.00-120.00   56
 11  \w     96.00 178.00   1.00   20.00    --  111.00  50.00-120.00   82
;
_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  0.0612
_diffrn_reflns_av_unetI/netI     0.1101
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       45
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            40055
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.898
_diffrn_reflns_theta_min         4.019
_exptl_absorpt_coefficient_mu    0.566
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84187
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.112
_exptl_crystal_description       plate
_exptl_crystal_F_000             3840
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.710
_refine_diff_density_min         -0.489
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1303
_refine_ls_number_reflns         20866
_refine_ls_number_restraints     328
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.1563
_refine_ls_R_factor_gt           0.0925
_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^)+(0.1485P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2435
_refine_ls_wR_factor_ref         0.2897
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11002
_reflns_number_total             20866
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02048g2.cif
_cod_data_source_block           4
_cod_database_code               7713493
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.849
_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
 C16-C18A = C18-C16 = C17-C16 = C16-C17A
 1.53 with sigma of 0.008
 C89A-C90A = C90-C89 = C90A-C91A = C91-C90 = C91A-C92A = C92-C91
 1.53 with sigma of 0.008
 O2-C89A = O2-C89 = O2-C92A = O2-C92
 1.4 with sigma of 0.008
 C17-C18 = C17A-C18A
 2.5 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
C18 \\sim C18A \\sim C16 \\sim C17A \\sim C17: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01 within 2A
C89 \\sim C90 \\sim C91 \\sim C92 \\sim C89A \\sim C90A \\sim C91A \\sim C92A:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C93 \\sim C98 \\sim C97 \\sim C96 \\sim C95 \\sim C94: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
C100: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01 within
2A
C101 \\sim C100 \\sim C99 \\sim C104 \\sim C103 \\sim C102: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C125 \\sim C123 \\sim C128 \\sim C127 \\sim C126 \\sim C124: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C118 \\sim C119 \\sim C120 \\sim C121 \\sim C122 \\sim C117: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C129 \\sim C130 \\sim C131 \\sim C132 \\sim C133 \\sim C134: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
4. Others
 Sof(H16A)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C18A)=Sof(H18D)=
 Sof(H18E)=Sof(H18F)=1-FVAR(1)
 Sof(H16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=Sof(H18A)=Sof(H18B)=
 Sof(H18C)=FVAR(1)
 Sof(C91A)=Sof(H91C)=Sof(H91D)=Sof(C89A)=Sof(H89C)=Sof(H89D)=Sof(C90A)=
 Sof(H90C)=Sof(H90D)=Sof(C92A)=Sof(H92C)=Sof(H92D)=1-FVAR(2)
 Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(C91)=Sof(H91A)=
 Sof(H91B)=Sof(C90)=Sof(H90A)=Sof(H90B)=FVAR(2)
 Sof(C125)=Sof(H125)=Sof(C124)=Sof(H124)=Sof(C126)=Sof(H126)=Sof(C127)=
 Sof(H127)=Sof(C128)=Sof(H128)=Sof(C123)=Sof(H123)=1-FVAR(3)
 Sof(C100)=Sof(H100)=Sof(C99)=Sof(H99)=Sof(C104)=Sof(H104)=Sof(C103)=Sof(H103)=
 Sof(C102)=Sof(H102)=Sof(C101)=Sof(H101)=FVAR(3)
 Fixed Sof: C118(0.5) H118(0.5) C119(0.5) H119(0.5) C120(0.5) H120(0.5)
 C121(0.5) H121(0.5) C122(0.5) H122(0.5) C117(0.5) H117(0.5) C129(0.5)
 H129(0.5) C130(0.5) H130(0.5) C131(0.5) H131(0.5) C132(0.5) H132(0.5)
 C133(0.5) H133(0.5) C134(0.5) H134(0.5)
5.a Ternary CH refined with riding coordinates:
 C7(H7), C49(H49), C31(H31), C73(H73), C58(H58), C28(H28), C61(H61), C16(H16),
 C16(H16A), C19(H19), C70(H70)
5.b Secondary CH2 refined with riding coordinates:
 C89(H89A,H89B), C92(H92A,H92B), C88(H88A,H88B), C85(H85A,H85B), C86(H86A,
 H86B), C87(H87A,H87B), C91(H91A,H91B), C90(H90A,H90B), C91A(H91C,H91D),
 C89A(H89C,H89D), C90A(H90C,H90D), C92A(H92C,H92D)
5.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C50(H50), C3(H3), C44(H44), C45(H45), C2(H2), C78(H78), C36(H36),
 C38(H38), C24(H24), C66(H66), C80(H80), C25(H25), C26(H26), C68(H68), C12(H12),
  C56(H56), C67(H67), C14(H14), C13(H13), C54(H54), C55(H55), C113(H113),
 C114(H114), C115(H115), C116(H116), C111(H111), C112(H112), C110(H110),
 C105(H105), C106(H106), C107(H107), C108(H108), C109(H109), C95(H95), C94(H94),
  C93(H93), C98(H98), C97(H97), C96(H96), C118(H118), C119(H119), C120(H120),
 C121(H121), C122(H122), C117(H117), C100(H100), C99(H99), C104(H104),
 C103(H103), C102(H102), C101(H101), C125(H125), C124(H124), C126(H126),
 C127(H127), C128(H128), C123(H123), C129(H129), C130(H130), C131(H131),
 C132(H132), C133(H133), C134(H134)
5.d Fitted hexagon refined as free rotating group:
 C113(C114,C115,C116,C111,C112), C110(C105,C106,C107,C108,C109), C95(C94,C93,
 C98,C97,C96), C118(C119,C120,C121,C122,C117), C100(C99,C104,C103,C102,C101),
 C125(C124,C126,C127,C128,C123), C129(C130,C131,C132,C133,C134)
5.e Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C84(H84A,H84B,H84C), C40(H40A,H40B,H40C), C82(H82A,H82B,
 H82C), C62(H62A,H62B,H62C), C83(H83A,H83B,H83C), C41(H41A,H41B,H41C), C63(H63A,
 H63B,H63C), C32(H32A,H32B,H32C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C),
 C29(H29A,H29B,H29C), C33(H33A,H33B,H33C), C71(H71A,H71B,H71C), C30(H30A,H30B,
 H30C), C72(H72A,H72B,H72C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C59(H59A,
 H59B,H59C), C60(H60A,H60B,H60C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C),
 C17A(H17D,H17E,H17F), C18A(H18D,H18E,H18F)
;
_shelx_res_checksum              6452
_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
;