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_7160486
_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         'C77 H93 Br4 N4, C2 H3 N, Cl'
_chemical_formula_sum            'C79 H96 Br4 Cl N5'
_chemical_formula_weight         1470.69
_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
_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                79.138(2)
_cell_angle_beta                 89.814(2)
_cell_angle_gamma                75.745(3)
_cell_formula_units_Z            2
_cell_length_a                   10.0551(3)
_cell_length_b                   19.2736(6)
_cell_length_c                   22.0454(6)
_cell_measurement_reflns_used    13604
_cell_measurement_temperature    100
_cell_measurement_theta_max      18.4820
_cell_measurement_theta_min      1.5160
_cell_volume                     4062.4(2)
_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 0.995
_diffrn_measured_fraction_theta_max 0.777
_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    1.00    --    0.00  45.00   0.00  180
  2  \w      0.00 180.00   1.00    1.00    --    0.00  45.00 -90.00  180
  3  \w      0.00 180.00   1.00    1.00    --    0.00  45.00-180.00  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      0.0346866000
_diffrn_orient_matrix_UB_12      -0.0169788000
_diffrn_orient_matrix_UB_13      0.0045758000
_diffrn_orient_matrix_UB_21      0.0169968000
_diffrn_orient_matrix_UB_22      0.0073279000
_diffrn_orient_matrix_UB_23      -0.0162894000
_diffrn_orient_matrix_UB_31      0.0175138000
_diffrn_orient_matrix_UB_32      0.0128693000
_diffrn_orient_matrix_UB_33      0.0088417000
_diffrn_radiation_monochromator  synchrotron
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.4129
_diffrn_reflns_av_R_equivalents  0.1352
_diffrn_reflns_av_unetI/netI     0.1296
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.777
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            158658
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.777
_diffrn_reflns_theta_full        14.344
_diffrn_reflns_theta_max         21.706
_diffrn_reflns_theta_min         1.496
_diffrn_source                   synchrotron
_exptl_absorpt_coefficient_mu    0.489
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69391
_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 colourless'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.202
_exptl_crystal_description       needle
_exptl_crystal_F_000             1524
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.230
_refine_diff_density_min         -1.906
_refine_diff_density_rms         0.160
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.173
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     899
_refine_ls_number_reflns         37954
_refine_ls_number_restraints     814
_refine_ls_restrained_S_all      1.162
_refine_ls_R_factor_all          0.1869
_refine_ls_R_factor_gt           0.1428
_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^)+(0.0512P)^2^+28.6714P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2530
_refine_ls_wR_factor_ref         0.2718
_reflns_Friedel_coverage         0.000
_reflns_number_gt                26002
_reflns_number_total             37954
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00212e2.cif
_cod_data_source_block           Me1-2_Cl
_cod_depositor_comments
'Adding full bibliography for 7160486--7160487.cif.'
_cod_database_code               7160486
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.792
_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. Restrained distances
 C00T-C01V \\sim C00T-C2
 with sigma of 0.02
 C01V-C02E \\sim C2-C1
 with sigma of 0.02
 C01V-C02G \\sim C2-C02H
 with sigma of 0.02
 C01V-C10 \\sim C2-C10A
 with sigma of 0.02
 C00T-C02E \\sim C00T-C1
 with sigma of 0.04
 C00T-C02G \\sim C00T-C02H
 with sigma of 0.04
 C00T-C10 \\sim C00T-C10A
 with sigma of 0.04
 C02E-C02G \\sim C1-C02H
 with sigma of 0.04
 C02E-C10 \\sim C1-C10A
 with sigma of 0.04
 C02G-C10 \\sim C02H-C10A
 with sigma of 0.04
 C01T-C029 \\sim C01T-C0
 with sigma of 0.02
 C01T-C02D \\sim C01T-C3
 with sigma of 0.02
 C01T-C02F \\sim C01T-C4
 with sigma of 0.02
3. Rigid bond restraints
 C02F, C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. 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
5. Others
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=
 Sof(C02H)=Sof(H5)=Sof(HU)=Sof(HV)=Sof(C2)=1-FVAR(1)
 Sof(C01V)=Sof(C02E)=Sof(H2)=Sof(HO)=Sof(HP)=Sof(C02G)=Sof(H4)=Sof(HS)=Sof(HT)=
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(1)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C0)=Sof(H0A)=Sof(H0B)=Sof(H0C)=Sof(C4)=
 Sof(H4A)=Sof(H4B)=Sof(H4C)=1-FVAR(2)
 Sof(C029)=Sof(H02V)=Sof(H02W)=Sof(H02X)=Sof(C02D)=Sof(H1)=Sof(HM)=Sof(HN)=
 Sof(C02F)=Sof(H3)=Sof(HQ)=Sof(HR)=FVAR(2)
 Fixed Sof: H006(0.5) H007(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 N006(H006), N007(H007), N008(H008), C00F(H00F), C00O(H00O), C00S(H00S),
 C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z), C011(H011), C012(H012),
 C013(H013), C017(H017), C01D(H01D), C01E(H01E), C01F(H01F), C01I(H01J),
 C01J(H01K)
6.b Idealised Me refined as rotating group:
 C01G(H01A,H01B,H01C), C01H(H01G,H01H,H01I), C01O(H01L,H01M,H01N), C01P(H01O,
 H01P,H01Q), C01Q(H01R,H01S,H01T), C01R(H01U,H01V,H01W), C01W(H01X,H01Y,H),
 C01Y(H01Z,HA,HB), C01Z(H01,HC,HD), C020(H02A,H02B,H02C), C021(H02D,H02E,H02F),
 C022(H02G,H02H,H02I), C023(H02J,H02K,H02L), C025(H02M,H02N,H02O), C026(H6,HE,
 HF), C027(H02P,H02Q,H02R), C028(H02S,H02T,H02U), C029(H02V,H02W,H02X),
 C02A(H02Y,HG,HH), C02B(H02Z,HI,HJ), C02C(H02,HK,HL), C02D(H1,HM,HN), C02E(H2,
 HO,HP), C02F(H3,HQ,HR), C02G(H4,HS,HT), C10(H10A,H10B,H10C), C1(H1A,H1B,H1C),
 C10A(H10D,H10E,H10F), C02H(H5,HU,HV), C3(H3A,H3B,H3C), C0(H0A,H0B,H0C), C4(H4A,
 H4B,H4C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              28883
_shelx_fab_checksum              4302
_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 1.391
_oxdiff_exptl_absorpt_empirical_full_min 0.715