Investigations of low-symmetrical tetraaryltetrabenzoporphyrins produced by mixed condensation reactions.
Ruppel, Michael; Gazetas, Lampros-Pascal; Lungerich, Dominik; Hampel, Frank; Jux, Norbert; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00293

data_4038457
_publ_section_title
;
 Investigations of low-symmetrical tetraaryltetrabenzoporphyrins produced
 by mixed condensation reactions.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00293
_journal_year                    2020
_chemical_formula_moiety         'C H2 Cl2, C80 H74 N4 O4, 0.8[CH2Cl2]'
_chemical_formula_sum            'C81 H76 Cl2 N4 O4'
_chemical_formula_weight         1240.35
_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             2020-04-07
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.1090(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.81190(10)
_cell_length_b                   27.3640(4)
_cell_length_c                   23.5338(3)
_cell_measurement_reflns_used    10535
_cell_measurement_temperature    153.00(10)
_cell_measurement_theta_max      63.6660
_cell_measurement_theta_min      4.0830
_cell_volume                     6952.39(15)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      153.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6144
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.962
_diffrn_measured_fraction_theta_max 0.962
_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   -107.00 -65.00   1.00    1.00    --  -42.31-137.00  82.00   42
  2  \w    -70.00  31.00   1.00    1.00    --  -42.31  57.00 120.00  101
  3  \w     59.00 156.00   1.00    2.54    --   87.05  30.00-180.00   97
  4  \w      4.00 103.00   1.00    2.54    --   87.05 -94.00 120.00   99
  5  \w     32.00  90.00   1.00    2.54    --   87.05-125.00 -90.00   58
  6  \w     33.00 110.00   1.00    2.54    --   87.05-125.00  90.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0661803000
_diffrn_orient_matrix_UB_12      0.0224620000
_diffrn_orient_matrix_UB_13      0.0534500000
_diffrn_orient_matrix_UB_21      0.0264432000
_diffrn_orient_matrix_UB_22      -0.0516192000
_diffrn_orient_matrix_UB_23      0.0237780000
_diffrn_orient_matrix_UB_31      0.1236044000
_diffrn_orient_matrix_UB_32      -0.0009440000
_diffrn_orient_matrix_UB_33      -0.0295998000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0306
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            21182
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        63.824
_diffrn_reflns_theta_max         63.824
_diffrn_reflns_theta_min         3.738
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.250
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.575
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark violet'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.185
_exptl_crystal_description       block
_exptl_crystal_F_000             2624
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM/TFA and methanol  by solvent layering'
_exptl_crystal_size_max          0.301
_exptl_crystal_size_mid          0.182
_exptl_crystal_size_min          0.147
_refine_diff_density_max         0.731
_refine_diff_density_min         -1.302
_refine_diff_density_rms         0.064
_refine_ls_extinction_coef       0.00046(9)
_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   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     836
_refine_ls_number_reflns         11068
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0812
_refine_ls_R_factor_gt           0.0697
_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^)+(0.1211P)^2^+6.2034P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1942
_refine_ls_wR_factor_ref         0.2086
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9079
_reflns_number_total             11068
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00293_si_002.cif
_cod_data_source_block           19jux_mr04
_cod_database_code               4038457
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C80 H74 N4 O4'
_shelx_estimated_absorpt_t_max   0.838
_shelx_estimated_absorpt_t_min   0.705
_diffrn_oxdiff_digest_frames
;
011a8c6ed5c004d10c03808b4aeed97cf800496373a
;
_diffrn_oxdiff_digest_hkl
;
0158324e1e9654ecd79f82b38f406ce62ff72e
;
_reflns_odcompleteness_completeness 98.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     61.08
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl2-C200 \\sim Cl2A-C200 \\sim Cl1-C200 \\sim Cl1A-C200
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Cl2) = Uanis(Cl2A) = Uanis(Cl1) = Uanis(Cl1A)
4. Others
 Sof(Cl1A)=Sof(Cl2A)=Sof(H20C)=Sof(H20D)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(H20B)=Sof(H20A)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C200(H20B,H20A), C200(H20C,H20D)
5.b Aromatic/amide H refined with riding coordinates:
 N11(H11), N61(H61), C14(H14), C15(H15), C16(H16), C17(H17), C22(H22),
 C23(H23), C25(H25), C26(H26), C34(H34), C35(H35), C36(H36), C37(H37), C42(H42),
  C44(H44), C46(H46), C64(H64), C65(H65), C66(H66), C67(H67), C72(H72),
 C73(H73), C75(H75), C76(H76), C84(H84), C85(H85), C86(H86), C87(H87), C92(H92),
  C94(H94), C96(H96)
5.c Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,
 H50C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C80(H80A,
 H80B,H80C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C), C100(H10A,H10B,H10C),
 C102(H10D,H10E,H10F), C103(H10G,H10H,H10I), C104(H10J,H10K,H10L)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_date_sample_data_collection 2019-08-21
_olex2_diffrn_ambient_temperature_device 'Cryojet - Oxford Instruments'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop in perfluoroether oil'
_olex2_submission_original_sample_id MR244-trans
_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 1.126
_oxdiff_exptl_absorpt_empirical_full_min 0.922