Pictet–Spengler Synthesis of Twist Quinoline-Fused BODIPYs as Heavy-Atom-Free Photosensitizers
Li, Wanwan; Gong, Qingbao; Wu, Qinghua; Guo, Luying; Guo, Xing; Guo, Dianjun; Jiao, Lijuan; Hao, Erhong; Chemical Communications  (2023) –; doi:10.1039/D3CC04460B

data_7132146
_publ_section_title
;
 Pictet--Spengler Synthesis of Twist Quinoline-Fused BODIPYs as
 Heavy-Atom-Free Photosensitizers
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC04460B
_journal_year                    2023
_chemical_formula_moiety         'C31 H24 B F2 N3'
_chemical_formula_sum            'C31 H24 B F2 N3'
_chemical_formula_weight         487.34
_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             2023-09-15
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-09-15 deposited with the CCDC.	2023-09-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.660(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3821(12)
_cell_length_b                   18.3455(15)
_cell_length_c                   11.4591(12)
_cell_measurement_reflns_used    9894
_cell_measurement_temperature    300.00
_cell_measurement_theta_max      24.483
_cell_measurement_theta_min      2.833
_cell_volume                     2435.6(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker D8 Venture diffractometer'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      300.00
_diffrn_detector                 'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0693
_diffrn_reflns_av_unetI/netI     0.0271
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            65120
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.156
_diffrn_reflns_theta_max         25.156
_diffrn_reflns_theta_min         2.832
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.089
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6277
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1083 before and 0.0747 after correction.
The Ratio of minimum to maximum transmission is 0.8423.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_description       block
_exptl_crystal_F_000             1016
_exptl_crystal_recrystallization_method
'The crystals were growth by means of evaporation of a mixture of n-hexane and toluene at RT.'
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.363
_refine_diff_density_min         -0.428
_refine_diff_density_rms         0.049
_refine_ls_extinction_coef       0.014(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     430
_refine_ls_number_reflns         4352
_refine_ls_number_restraints     703
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0841
_refine_ls_R_factor_gt           0.0626
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0771P)^2^+2.0030P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1601
_refine_ls_wR_factor_ref         0.1786
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3257
_reflns_number_total             4352
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04460b2.cif
_cod_data_source_block           3a
_cod_database_code               7132146
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.989
_exptl_crystal_mounting_method
'Crystals were removed from the crystallisation vial and immediately coated with polybutenes oil (CAS: 9003-29-6) on a glass slide. A suitable single crystal coated with polybutenes oil as less as possible was sealed in capillary tube filled with argon. The capillary tube with single crystal was mounted on copper pin with solid paraffin.'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C17A-C16 \\sim C17-C16
 with sigma of 0.02
 C5-C23 \\sim C5-C23A
 with sigma of 0.02
 C29-C24 \\sim C29A-C24A
 with sigma of 0.02
 C30-C26 \\sim C30A-C26A
 with sigma of 0.02
 C31-C28 \\sim C31A-C28A
 with sigma of 0.02
3. Restrained planarity
 C5, C23, C24, C25, C26, C27, C28, C29, C30, C31
 with sigma of 0.1
 C5, C23A, C24A, C25A, C26A, C27A, C28A, C29A, C30A, C31A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C19A \\sim C17A
\\sim C22A \\sim C20A \\sim C18A \\sim C21A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim
C31 \\sim C23A \\sim C24A \\sim C25A \\sim C26A \\sim C27A \\sim C28A \\sim
C29A \\sim C30A \\sim C31A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
5. Rigid body (RIGU) restrains
 C16, C17, C18, C19, C20, C21, C22, C19A, C17A, C22A, C20A, C18A, C21A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C5, C23, C24, C25, C26, C27, C28, C29, C30, C31, C23A, C24A, C25A, C26A, C27A,
  C28A, C29A, C30A, C31A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
6. Others
 Sof(C17A)=Sof(C22A)=Sof(H22A)=Sof(C21A)=Sof(H21A)=Sof(C20A)=Sof(H20A)=
 Sof(C19A)=Sof(H19A)=Sof(C18A)=Sof(H18A)=1-FVAR(1)
 Sof(C17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=
 Sof(H21)=Sof(C22)=Sof(H22)=FVAR(1)
 Sof(C23A)=Sof(C24A)=Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(C27A)=Sof(H27A)=
 Sof(C28A)=Sof(C29A)=Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C30A)=Sof(H30D)=
 Sof(H30E)=Sof(H30F)=Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=1-FVAR(2)
 Sof(C23)=Sof(C24)=Sof(C25)=Sof(H25)=Sof(C26)=Sof(C27)=Sof(H27)=Sof(C28)=
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=FVAR(2)
7.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C7(H7), C12(H12), C13(H13), C14(H14), C15(H15),
 C25(H25), C27(H27), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22),
 C22A(H22A), C21A(H21A), C20A(H20A), C19A(H19A), C18A(H18A), C25A(H25A),
 C27A(H27A)
7.b Fitted hexagon refined as free rotating group:
 C23(C24,C25,C26,C27,C28), C17(C18,C19,C20,C21,C22), C17A(C22A,C21A,C20A,C19A,
 C18A), C23A(C24A,C25A,C26A,C27A,C28A)
7.c Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C29A(H29D,H29E,
 H29F), C30A(H30D,H30E,H30F), C31A(H31D,H31E,H31F)
;
_shelx_res_checksum              29047
_olex2_submission_special_instructions 'No special instructions were received'