Bis(napthobipyrrolyl)methene derived Hexapyrrolic BODIPY as a Single Molecule Helicate with Near Infrared Emission
Sahoo, Sipra Sucharita; Panda, Pradeepta; Chemical Communications  (2023) –; doi:10.1039/D3CC02336B

data_7131840
_publ_section_title
;
 Bis(napthobipyrrolyl)methene derived Hexapyrrolic BODIPY as a Single
 Molecule Helicate with Near Infrared Emission
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC02336B
_journal_year                    2023
_chemical_formula_moiety         'C61 H67 B F2 N6 O4, 0.5(C H Cl3), 0.5(C6 H14)'
_chemical_formula_sum            'C64.5 H74.5 B Cl1.5 F2 N6 O4'
_chemical_formula_weight         1099.78
_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   mixed
_audit_creation_date             2023-07-04
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-07-05 deposited with the CCDC.	2023-07-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.346(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.1630(5)
_cell_length_b                   31.5920(8)
_cell_length_c                   13.5347(4)
_cell_measurement_reflns_used    9928
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      24.2
_cell_measurement_theta_min      2.9
_cell_volume                     5937.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0376
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            57010
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.953
_exptl_absorpt_coefficient_mu    0.146
_exptl_absorpt_correction_T_max  0.94
_exptl_absorpt_correction_T_min  0.91
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.230
_exptl_crystal_description       block
_exptl_crystal_F_000             2336
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.459
_refine_diff_density_min         -0.293
_refine_diff_density_rms         0.046
_refine_ls_extinction_coef       0.0032(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     834
_refine_ls_number_reflns         10428
_refine_ls_number_restraints     520
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.1066
_refine_ls_R_factor_gt           0.0694
_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^)+(0.1297P)^2^+1.0257P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2036
_refine_ls_wR_factor_ref         0.2329
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6399
_reflns_number_total             10428
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc02336b2.cif
_cod_data_source_block           pkpbodipy
_cod_original_formula_sum        'C64.50 H74.50 B Cl1.50 F2 N6 O4'
_cod_database_code               7131840
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.958
_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
 C62-Cl1 = C62-Cl2 = C62-Cl3
 1.74 with sigma of 0.02
 Cl1-Cl2 = Cl2-Cl3 = Cl3-Cl1
 2.84 with sigma of 0.02
 C63-C64 = C64-C65 = C65-C66 = C66-C67 = C67-C68
 1.53 with sigma of 0.02
 C48-C49 = C48-C50 = C46-C48
 1.53 with sigma of 0.02
 C48'-C49' = C48'-C50'
 1.53 with sigma of 0.02
 C46-C50 = C46-C49 = C46-C50' = C46-C49'
 2.5 with sigma of 0.02
 C49-C50 = C49'-C50'
 2.5 with sigma of 0.02
 C63-C65 = C64-C66 = C65-C67 = C66-C68
 2.49 with sigma of 0.02
 N1-H1 = N2-H2 = N5-H5 = N6-H6
 0.9 with sigma of 0.02
 O2-C2 = O2'-C2'
 1.46 with sigma of 0.02
 C1-C2 = C1'-C2'
 1.53 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C62 \\sim Cl1 \\sim Cl2 \\sim Cl3 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim
C67 \\sim C68: within 6A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 6A
C46 \\sim C48 \\sim C49 \\sim C50 \\sim C48' \\sim C49' \\sim C50': within 3A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 3A
N1 \\sim H1: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 2A
N2 \\sim H2: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 2A
N5 \\sim H5: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 2A
N6 \\sim H6: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 2A
C1 \\sim C2 \\sim C1' \\sim C2' \\sim O2 \\sim O2': within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
4. Others
 Sof(C1')=Sof(H1'A)=Sof(H1'B)=Sof(H1'C)=Sof(C2')=Sof(H2'A)=Sof(H2'B)=Sof(O2')=
 1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(O2)=FVAR(1)
 Sof(C48')=Sof(H48')=Sof(C49')=Sof(H49D)=Sof(H49E)=Sof(H49F)=Sof(C50')=
 Sof(H50D)=Sof(H50E)=Sof(H50F)=1-FVAR(2)
 Sof(C48)=Sof(H48)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C50)=Sof(H50A)=
 Sof(H50B)=Sof(H50C)=FVAR(2)
 Fixed Sof: C62(0.5) H62(0.5) Cl1(0.5) Cl2(0.5) Cl3(0.5) C63(0.5) H63A(0.5)
 H63B(0.5) H63C(0.5) C64(0.5) H64A(0.5) H64B(0.5) C65(0.5) H65A(0.5) H65B(0.5)
 C66(0.5) H66A(0.5) H66B(0.5) C67(0.5) H67A(0.5) H67B(0.5) C68(0.5) H68A(0.5)
 H68B(0.5) H68C(0.5)
5.a Ternary CH refined with riding coordinates:
 C13(H13), C28(H28), C34(H34), C48(H48), C48'(H48'), C62(H62)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C2'(H2'A,H2'B), C10(H10A,H10B), C52(H52A,H52B), C60(H60A,H60B),
 C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), C67(H67A,H67B)
5.c Me refined with riding coordinates:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C),
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C35(H35A,H35B,H35C), C36(H36A,H36B,
 H36C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C49'(H49D,H49E,H49F),
 C50'(H50D,H50E,H50F), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C61(H61A,H61B,
 H61C)
5.d Aromatic/amide H refined with riding coordinates:
 C18(H18), C19(H19), C20(H20), C21(H21), C31(H31), C39(H39), C40(H40),
 C41(H41), C42(H42)
5.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C1'(H1'A,H1'B,H1'C), C63(H63A,H63B,H63C), C68(H68A,H68B,H68C)
;
_shelx_res_checksum              56496
_shelx_hkl_checksum              3094
_olex2_submission_special_instructions 'No special instructions were received'