Sub-<i>m</i>-benziporphyrin: a subcarbaporphyrinoid and its B<sup>III</sup> complex with an unprecedented planar tridentate 14π-aromatic network.
Liu, Le; Song, Shuangji; Lee, Jiyeon; Rao, Yutao; Xu, Ling; Zhou, Mingbo; Yin, Bangshao; Oh, Juwon; Kim, Jiwon; Osuka, Atsuhiro; Song, Jianxin; Chemical science 16 (2025) 1155–1160; doi:10.1039/d4sc07199a

data_1573433
_publ_section_title
;
 Sub-<i>m</i>-benziporphyrin: a subcarbaporphyrinoid and its
 B<sup>III</sup> complex with an unprecedented planar tridentate
 14&#x3c0;-aromatic network.
;
_journal_issue                   3
_journal_name_full               'Chemical science'
_journal_page_first              1155
_journal_page_last               1160
_journal_paper_doi               10.1039/d4sc07199a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C50 H41 B N2 O2'
_chemical_formula_sum            'C50 H41 B N2 O2'
_chemical_formula_weight         712.66
_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             2023-11-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-08-25 deposited with the CCDC.	2024-12-09 downloaded from the CCDC.
;
_cell_angle_alpha                92.220(3)
_cell_angle_beta                 94.235(3)
_cell_angle_gamma                98.658(4)
_cell_formula_units_Z            4
_cell_length_a                   14.4553(6)
_cell_length_b                   15.1300(6)
_cell_length_c                   21.0270(7)
_cell_measurement_reflns_used    7753
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      71.4710
_cell_measurement_theta_min      3.1060
_cell_volume                     4528.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0697
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     19.00  94.00   1.00    2.00    --   34.73  38.00  60.00   75
  2  \w     26.00  98.00   1.00    2.00    --   34.73  57.00  90.00   72
  3  \w     42.00 120.00   1.00    8.00    --  105.88 -45.00  90.00   78
  4  \w     87.00 124.00   1.00    8.00    --  105.88 -77.00 150.00   37
  5  \w     81.00 107.00   1.00    8.00    --  105.88 -94.00  30.00   26
  6  \w     54.00 116.00   1.00    8.00    --  105.88-111.00   0.00   62
  7  \w     68.00 101.00   1.00    8.00    --  105.88 -94.00 -90.00   33
  8  \w     58.00 124.00   1.00    8.00    --  105.88 -30.00-120.00   66
  9  \w     88.00 148.00   1.00    8.00    --  105.88  45.00-120.00   60
 10  \w    105.00 164.00   1.00    8.00    --  105.88  61.00 -90.00   59
 11  \w     98.00 124.00   1.00    8.00    --  105.88  61.00 -60.00   26
 12  \w     67.00 161.00   1.00    8.00    --  105.88  15.00-150.00   94
 13  \w     62.00 107.00   1.00    8.00    --  105.88 -94.00-180.00   45
 14  \w     36.00  79.00   1.00    2.00    --   34.73-125.00-180.00   43
 15  \w      7.00  74.00   1.00    2.00    --   34.73 -99.00-150.00   67
 16  \w     42.00 122.00   1.00    8.00    --  105.88 -61.00 -30.00   80
 17  \w     40.00  88.00   1.00    2.00    --   34.73-125.00  30.00   48
 18  \w     38.00 105.00   1.00    8.00    --  105.88 -94.00 120.00   67
 19  \w     38.00 122.00   1.00    8.00    --  105.88 -30.00 -30.00   84
 20  \w     38.00 122.00   1.00    8.00    --  105.88 -45.00-150.00   84
 21  \w     -8.00  60.00   1.00    2.00    --   34.73 -19.00-120.00   68
 22  \w    -31.00  49.00   1.00    2.00    --   34.73 -57.00-120.00   80
 23  \w    -24.00  53.00   1.00    2.00    --   34.73 -38.00 120.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0752026000
_diffrn_orient_matrix_UB_12      0.0748758000
_diffrn_orient_matrix_UB_13      0.0317104000
_diffrn_orient_matrix_UB_21      -0.0735170000
_diffrn_orient_matrix_UB_22      0.0638402000
_diffrn_orient_matrix_UB_23      0.0009162000
_diffrn_orient_matrix_UB_31      -0.0252466000
_diffrn_orient_matrix_UB_32      -0.0308758000
_diffrn_orient_matrix_UB_33      0.0663685000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0562
_diffrn_reflns_av_unetI/netI     0.0897
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            29740
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.600
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         2.958
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.487
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62092
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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    1.045
_exptl_crystal_description       plate
_exptl_crystal_F_000             1504
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.401
_refine_diff_density_min         -0.704
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1005
_refine_ls_number_reflns         15982
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0881
_refine_ls_R_factor_gt           0.0622
_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^)+(0.0718P)^2^+2.0713P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1525
_refine_ls_wR_factor_ref         0.1684
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11576
_reflns_number_total             15982
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07199a2.cif
_cod_data_source_block           exp_3498_sq
_cod_depositor_comments
'Adding full bibliography for 1573430--1573435.cif.'
_cod_database_code               1573433
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C100 H100 N2 O1 B1'
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.909
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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. Uiso/Uaniso restraints and constraints
Uanis(C61) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C60) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C70) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C83) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C61)
\\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(N1) \\sim Ueq,
Uanis(N2) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(C69) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(B1) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C100) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
3.a Aromatic/amide H refined with riding coordinates:
 C62(H62), C67(H67), C95(H95), C96(H96), C97(H97), C68(H68), C87(H87),
 C37(H37), C42(H42), C89(H89), C75(H75), C72(H72), C44(H44), C2(H2), C73(H73),
 C63(H63), C53(H53), C77(H77), C17(H17), C56(H56), C31(H31), C36(H36), C81(H81),
  C4(H4), C3(H3), C79(H79), C82(H82), C28(H28), C34(H34), C25(H25), C32(H32),
 C33(H33), C80(H80), C23(H23), C18(H18), C74(H74), C24(H24), C26(H26), C13(H13),
  C10(H10)
3.b Idealised Me refined as rotating group:
 C59(H59A,H59B,H59C), C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C51(H51A,H51B,
 H51C), C47(H47A,H47B,H47C), C100(H10A,H10B,H10C), C14(H14A,H14B,H14C),
 C49(H49A,H49B,H49C), C93(H93A,H93B,H93C), C48(H48A,H48B,H48C), C55(H55A,H55B,
 H55C), C46(H46A,H46B,H46C), C50(H50A,H50B,H50C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              15094
_shelx_fab_checksum              47835
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.641
_oxdiff_exptl_absorpt_empirical_full_min 0.604