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_4038458
_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         '2(C H2 Cl2), C88 H80 N4 O12, 1[CH2Cl2]'
_chemical_formula_sum            'C90 H86 Cl4 N4 O12'
_chemical_formula_weight         1557.42
_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
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.4280(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.99280(10)
_cell_length_b                   15.59830(10)
_cell_length_c                   29.9124(3)
_cell_measurement_reflns_used    21809
_cell_measurement_temperature    153.00(10)
_cell_measurement_theta_max      64.5570
_cell_measurement_theta_min      2.7540
_cell_volume                     8370.07(11)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_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 0.986
_diffrn_measured_fraction_theta_max 0.986
_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    -67.00  18.00   1.00    1.00    --  -42.31  38.00  90.00   85
  2  \w   -105.00  20.00   1.00    1.00    --  -42.31   0.00  30.00  125
  3  \w     64.00 153.00   1.00    1.96    --   88.61  45.00-150.00   89
  4  \w    102.00 147.00   1.00    1.96    --   88.61 125.00   0.00   45
  5  \w     94.00 158.00   1.00    1.96    --   88.61 125.00  60.00   64
  6  \w     66.00 165.00   1.00    1.96    --   88.61  30.00  60.00   99
  7  \w     60.00 152.00   1.00    1.96    --   88.61  30.00-180.00   92
  8  \w     46.00 117.00   1.00    1.96    --   88.61 -30.00   0.00   71
  9  \w     23.00 122.00   1.00    1.96    --   88.61-125.00  30.00   99
 10  \w     13.00 121.00   1.00    1.96    --   88.61 -77.00  30.00  108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0145631000
_diffrn_orient_matrix_UB_12      0.0756350000
_diffrn_orient_matrix_UB_13      -0.0312982000
_diffrn_orient_matrix_UB_21      0.0389344000
_diffrn_orient_matrix_UB_22      0.0492204000
_diffrn_orient_matrix_UB_23      0.0398536000
_diffrn_orient_matrix_UB_31      0.0751313000
_diffrn_orient_matrix_UB_32      -0.0401678000
_diffrn_orient_matrix_UB_33      -0.0100335000
_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  0.0369
_diffrn_reflns_av_unetI/netI     0.0306
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            47801
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        64.643
_diffrn_reflns_theta_max         64.642
_diffrn_reflns_theta_min         3.197
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.790
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.281
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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            'clear greenish blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.236
_exptl_crystal_description       block
_exptl_crystal_F_000             3272
_exptl_crystal_recrystallization_method
'crystallized from DCM, CF3COOH, CH3OH'
_exptl_crystal_size_max          0.621
_exptl_crystal_size_mid          0.362
_exptl_crystal_size_min          0.276
_refine_diff_density_max         1.031
_refine_diff_density_min         -1.644
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1010
_refine_ls_number_reflns         13901
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0886
_refine_ls_R_factor_gt           0.0805
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1475P)^2^+10.2432P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2274
_refine_ls_wR_factor_ref         0.2381
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11965
_reflns_number_total             13901
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00293_si_003.cif
_cod_data_source_block           19jux_pg02
_cod_database_code               4038458
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C92 H106 N4 O8'
_chemical_oxdiff_usercomment     PG-50-cis-a2b2
_shelx_estimated_absorpt_t_max   0.638
_shelx_estimated_absorpt_t_min   0.403
_reflns_odcompleteness_completeness 99.96
_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) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl31-C300 \\sim Cl32-C300 \\sim Cl21-C200
 with sigma of 0.02
 C121-C117 \\sim C118-C117 \\sim C122-C117 \\sim C119-C117 \\sim C123-C117
\\sim C120-C117
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C120) = Uanis(C123) = Uanis(C119) = Uanis(C122) = Uanis(C118) =
Uanis(C121)
4. Others
 Sof(C121)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C122)=Sof(H12G)=Sof(H12H)=
 Sof(H12I)=Sof(C123)=Sof(H12J)=Sof(H12K)=Sof(H12L)=1-FVAR(1)
 Sof(C118)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C119)=Sof(H11D)=Sof(H11E)=
 Sof(H11F)=Sof(C120)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C200(H20A,H20B), C300(H30A,H30B)
5.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C17(H17), C33(H33), C34(H34), C36(H36), C37(H37), N41(H41),
 C44(H44), C45(H45), C46(H46), C47(H47), C52(H52), C53(H53), C55(H55), C56(H56),
  C64(H64), C67(H67), C82(H82), C83(H83), C85(H85), C86(H86), N91(H91),
 C94(H94), C97(H97), C112(H112), C113(H113), C115(H115), C116(H116)
5.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C27(H27A,H27B,H27C), C38(H38A,H38B,H38C), C39(H39A,H39B,
 H39C), C40(H40A,H40B,H40C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,
 H60B,H60C), C73(H73A,H73B,H73C), C77(H77A,H77B,H77C), C88(H88A,H88B,H88C),
 C89(H89A,H89B,H89C), C90(H90A,H90B,H90C), C103(H10A,H10B,H10C), C107(H10D,H10E,
 H10F), C118(H11A,H11B,H11C), C119(H11D,H11E,H11F), C120(H12A,H12B,H12C),
 C121(H12D,H12E,H12F), C122(H12G,H12H,H12I), C123(H12J,H12K,H12L)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 176 electrons were
found in a volume of 728\%A^3 in 1 void per unit cell.
This is consistent with the presence of 
1[CH2Cl2] per Asymmetric Unit 
which account for 168 electrons 
per unit cell.
;
_olex2_date_sample_data_collection 2019-03-06
_olex2_date_sample_submission    2019-03-05
_olex2_exptl_crystal_mounting_method 'mounted on a loop'
_olex2_submission_original_sample_id PG50-cis-A2B2
_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 1.176
_oxdiff_exptl_absorpt_empirical_full_min 0.872