Steric factors controlling regioselective and efficient <i>N</i>-methylation of β-tetrabromoporphyrins.
Suzuki, Wataru; Tanaka, Futo; Kizuki, Yusuke; Inoue, Ryo; Agou, Tomohiro; Umeyama, Tomokazu; Organic & biomolecular chemistry 23 (2025) 4686–4693; doi:10.1039/d5ob00212e

data_7160487
_publ_section_title
;
 Steric factors controlling regioselective and efficient
 <i>N</i>-methylation of &#x3b2;-tetrabromoporphyrins.
;
_journal_issue                   19
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4686
_journal_page_last               4693
_journal_paper_doi               10.1039/d5ob00212e
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C50 H39 Br4 N4 O4, C F3 O3 S, O'
_chemical_formula_sum            'C51 H39 Br4 F3 N4 O8 S'
_chemical_formula_weight         1244.43
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2024-08-05
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-21 deposited with the CCDC.	2025-04-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.902(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1008(4)
_cell_length_b                   26.9189(9)
_cell_length_c                   18.3963(9)
_cell_measurement_reflns_used    9734
_cell_measurement_temperature    100
_cell_measurement_theta_max      17.3120
_cell_measurement_theta_min      1.4890
_cell_volume                     5984.7(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.824
_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      0.00 180.00   1.00    3.00    --    0.00  45.00   0.00  180
  2  \w      0.00 180.00   1.00    3.00    --    0.00  45.00 -90.00  180
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'esperanto-CrysAlisPro-abstract goniometer imported esperanto images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0075806000
_diffrn_orient_matrix_UB_12      -0.0016231000
_diffrn_orient_matrix_UB_13      -0.0220080000
_diffrn_orient_matrix_UB_21      0.0122011000
_diffrn_orient_matrix_UB_22      0.0140589000
_diffrn_orient_matrix_UB_23      -0.0036785000
_diffrn_orient_matrix_UB_31      0.0309722000
_diffrn_orient_matrix_UB_32      -0.0059320000
_diffrn_orient_matrix_UB_33      -0.0027196000
_diffrn_radiation_monochromator  synchrotron
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.4129
_diffrn_reflns_av_R_equivalents  0.1914
_diffrn_reflns_av_unetI/netI     0.1642
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.824
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       45
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            157810
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.824
_diffrn_reflns_theta_full        14.344
_diffrn_reflns_theta_max         21.786
_diffrn_reflns_theta_min         1.467
_diffrn_source                   synchrotron
_exptl_absorpt_coefficient_mu    0.657
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70629
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            dark
_exptl_crystal_colour_modifier   dark
_exptl_crystal_density_diffrn    1.381
_exptl_crystal_description       needle
_exptl_crystal_F_000             2480
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.002
_refine_diff_density_min         -1.403
_refine_diff_density_rms         0.136
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.997
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     719
_refine_ls_number_reflns         29985
_refine_ls_number_restraints     629
_refine_ls_restrained_S_all      0.988
_refine_ls_R_factor_all          0.2070
_refine_ls_R_factor_gt           0.0956
_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^)+(0.1315P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2485
_refine_ls_wR_factor_ref         0.2951
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11189
_reflns_number_total             29985
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00212e2.cif
_cod_data_source_block           syn-1_OTf
_cod_depositor_comments
'Adding full bibliography for 7160486--7160487.cif.'
_cod_database_code               7160487
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.735
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Fixed Sof: C011(0.4) C01I(0.4) H01I(0.4) C01Q(0.4) H01Q(0.4) C01W(0.4)
 H01W(0.4) O01Z(0.6) C020(0.4) C021(0.6) H021(0.6) C025(0.6) H02D(0.6)
 H02E(0.6) H02F(0.6) C7(0.4) H7A(0.4) H7B(0.4) H7C(0.4) O12(0.4) C1(0.6)
 C8(0.6) H8(0.6) C22(0.6) H22(0.6) C2(0.4) H2(0.4) C18(0.6) H18(0.6) C46(0.6)
4.a Aromatic/amide H refined with riding coordinates:
 N00B(H00B), C00L(H00L), C00Q(H00Q), C00S(H00S), C00T(H00T), C00U(H00U),
 C00Z(H00Z), C018(H018), C01G(H01G), C01H(H01H), C01I(H01I), C01J(H01J),
 C01K(H01K), C01N(H01O), C01O(H01P), C01Q(H01Q), C01R(H01R), C01U(H01U),
 C01W(H01W), C01X(H01X), C021(H021), C8(H8), C22(H22), C2(H2), C18(H18)
4.b Idealised Me refined as rotating group:
 C01A(H01A,H01B,H01C), C01L(H01D,H01E,H01F), C01M(H01L,H01M,H01N), C023(H02A,
 H02B,H02C), C025(H02D,H02E,H02F), C029(H02G,H02H,H02I), C7(H7A,H7B,H7C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              19408
_shelx_fab_checksum              21143
_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 1.397
_oxdiff_exptl_absorpt_empirical_full_min 0.750