Facile Supramolecular Engineering of Porphyrin cis Tautomers: The Case of β-Octabromo-<i>meso</i>-tetraarylporphyrins.
Thomas, Kolle E.; Slebodnick, Carla; Ghosh, Abhik; ACS omega 5 (2020) 8893–8901; doi:10.1021/acsomega.0c00517

data_4517541
_publ_section_title
;
 Facile Supramolecular Engineering of Porphyrin cis Tautomers: The Case of
 \b-Octabromo-<i>meso</i>-tetraarylporphyrins.
;
_journal_issue                   15
_journal_name_full               'ACS omega'
_journal_page_first              8893
_journal_page_last               8901
_journal_paper_doi               10.1021/acsomega.0c00517
_journal_volume                  5
_journal_year                    2020
_chemical_formula_moiety         'C48 H18 Br8 F12 N4, 2(C H4 O)'
_chemical_formula_sum            'C50 H26 Br8 F12 N4 O2'
_chemical_formula_weight         1582.03
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 112.8497(11)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   36.7959(4)
_cell_length_b                   10.19901(8)
_cell_length_c                   30.7172(3)
_cell_measurement_reflns_used    71729
_cell_measurement_temperature    99.99(11)
_cell_measurement_theta_max      77.5260
_cell_measurement_theta_min      3.8370
_cell_volume                     10623.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.16a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.16a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.16a (Rigaku OD, 2018)'
_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      99.99(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_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    -60.00  28.00   0.50    4.00    --  -47.45  19.00 -30.00  176
  2  \w     24.00  90.00   0.50    4.00    --   47.45-114.00  33.00  132
  3  \w     58.00 134.00   0.50   16.00    --  107.75-178.00-102.00  152
  4  \w     35.00 104.00   0.50   16.00    --  107.75-114.00  33.00  138
  5  \w     83.00 106.50   0.50   16.00    --  107.75-125.00 150.00   47
  6  \w     33.00  69.00   0.50   16.00    --  107.75 -30.00   0.00   72
  7  \w     38.00  77.00   0.50   16.00    --  107.75 -45.00  60.00   78
  8  \w     35.00 124.00   0.50   16.00    --  107.75 -61.00  60.00  178
  9  \w     94.00 178.00   0.50   16.00    --  107.75  15.00 150.00  168
 10  \w     99.00 178.00   0.50   16.00    --  107.75 114.00 124.00  158
 11  \w     95.00 178.00   0.50   16.00    --  107.75  30.00  60.00  166
 12  \w     95.00 178.00   0.50   16.00    --  107.75  45.00 -60.00  166
 13  \w     97.00 133.00   0.50   16.00    --  107.75  45.00 -90.00   72
 14  \w    106.00 132.00   0.50   16.00    --  107.75  30.00-120.00   52
 15  \w     91.00 178.00   0.50   16.00    --  107.75  61.00   0.00  174
 16  \w     85.00 178.00   0.50   16.00    --  107.75  78.00 110.08  186
 17  \w     85.00 178.00   0.50   16.00    --  107.75  77.00  30.00  186
 18  \w     60.00 120.00   0.50    4.00    --   47.45 178.00 -99.00  120
 19  \w     55.00  85.00   0.50   16.00    --  107.75 -20.00-122.17   60
 20  \w     36.00  77.00   0.50   16.00    --  107.75 -45.00-120.00   82
 21  \w     35.00  88.50   0.50   16.00    --  107.75 -77.00-180.00  107
 22  \w     36.00  61.00   0.50   16.00    --  107.75 -45.00-180.00   50
 23  \w     35.00 124.00   0.50   16.00    --  107.75 -61.00-120.00  178
 24  \w     33.00  69.00   0.50   16.00    --  107.75 -30.00 -90.00   72
 25  \w     35.00 131.00   0.50   16.00    --  107.75 -77.00  30.00  192
 26  \w     33.00  69.00   0.50   16.00    --  107.75 -30.00 120.00   72
 27  \w     35.00 124.00   0.50   16.00    --  107.75 -61.00 120.00  178
 28  \w     35.00 110.00   0.50   16.00    --  107.75-125.00  60.00  150
 29  \w     35.00  98.50   0.50   16.00    --  107.75 -94.00  90.00  127
 30  \w     35.00 131.00   0.50   16.00    --  107.75 -77.00  60.00  192
 31  \w     35.00  91.50   0.50   16.00    --  107.75 -77.00 150.00  113
 32  \w     33.00  67.00   0.50   16.00    --  107.75 -30.00 150.00   68
 33  \w    -87.00  -2.00   0.50    4.00    --  -47.45 114.00 124.00  170
 34  \w    -86.00 -13.00   0.50   16.00    --  -86.25 114.00 124.00  146
 35  \w   -131.00 -36.00   0.50   16.00    --  -86.25 178.00 -99.00  190
 36  \w   -159.00 -77.00   0.50   16.00    --  -86.25-114.00  33.00  164
 37  \w   -120.00 -38.00   0.50    4.00    --  -47.45-178.00-102.00  164
 38  \w   -120.00 -70.00   0.50    4.00    --  -47.45-125.00-150.00  100
 39  \w   -120.00 -70.00   0.50    4.00    --  -47.45-125.00-180.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0332237000
_diffrn_orient_matrix_UB_12      0.0537237000
_diffrn_orient_matrix_UB_13      -0.0447246000
_diffrn_orient_matrix_UB_21      0.0241533000
_diffrn_orient_matrix_UB_22      -0.0362089000
_diffrn_orient_matrix_UB_23      -0.0294943000
_diffrn_orient_matrix_UB_31      -0.0194397000
_diffrn_orient_matrix_UB_32      -0.1363861000
_diffrn_orient_matrix_UB_33      -0.0097048000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0737
_diffrn_reflns_av_unetI/netI     0.0318
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       46
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            177057
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.524
_diffrn_reflns_theta_min         3.823
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.997
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.413
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.16a (Rigaku Oxford Diffraction, 2018)
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            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.978
_exptl_crystal_description       plate
_exptl_crystal_F_000             6064
_exptl_crystal_size_max          0.124
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.011
_refine_diff_density_max         1.062
_refine_diff_density_min         -0.634
_refine_diff_density_rms         0.134
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.127
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1505
_refine_ls_number_reflns         22336
_refine_ls_number_restraints     153
_refine_ls_restrained_S_all      1.126
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0476
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0595P)^2^+33.8368P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1209
_refine_ls_wR_factor_ref         0.1241
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20330
_reflns_number_total             22336
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao0c00517_si_003.cif
_cod_data_source_block           cs2495
_cod_depositor_comments
'Adding full bibliography for 4517540--4517541.cif.'
_cod_original_cell_volume        10623.00(19)
_cod_database_code               4517541
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C50 H26 Br8 F12 N4 O2'
_chemical_oxdiff_usercomment
'Abhik Ghosh / Thomas Kolle Ekaney (Tromso)  Br8P-CF3PP'
_reflns_odcompleteness_completeness 95.48
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     80.95
_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. Restrained distances
 N1-H1 = N4-H4
 0.88 with sigma of 0.02
 O1-H1S = O2-H2S
 0.84 with sigma of 0.02
 N5-H5 = N8-H8
 0.88 with sigma of 0.02
 O3-H3S = O4-H4S
 0.84 with sigma of 0.02
 H3S-N6
 2 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C27A) = Uanis(C27B)
Uanis(C48A) = Uanis(C48B)
4. Rigid body (RIGU) restrains
 F1A, F2A, F1B, F2B, F3, C27A, C27B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F10A, F11A, F10B, F11B, F12, C48A, C48B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F19A, F20A, F21A, F19B, F20B, F21B, C91
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F4A, F5A, F6A, F4B, F5B, F6B, C34
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F1B)=Sof(F2B)=Sof(C27B)=1-FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(C27A)=FVAR(1)
 Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(2)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(2)
 Sof(F10B)=Sof(F11B)=Sof(C48B)=1-FVAR(3)
 Sof(F10A)=Sof(F11A)=Sof(C48A)=FVAR(3)
 Sof(F19B)=Sof(F20B)=Sof(F21B)=1-FVAR(4)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=FVAR(4)
6.a Aromatic/amide H refined with riding coordinates:
 C22(H22), C23(H23), C25(H25), C26(H26), C29(H29), C30(H30), C32(H32),
 C33(H33), C36(H36), C37(H37), C39(H39), C40(H40), C43(H43), C44(H44), C46(H46),
  C47(H47), C72(H72), C73(H73), C75(H75), C76(H76), C79(H79), C80(H80),
 C82(H82), C83(H83), C86(H86), C87(H87), C89(H89), C90(H90), C93(H93), C94(H94),
  C96(H96), C97(H97)
6.b Idealised Me refined as rotating group:
 C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C99(H99A,H99B,H99C), C100(H10A,H10B,
 H10C)
;
_shelx_res_checksum              81197
_shelx_hkl_checksum              43491
_olex2_date_sample_data_collection 2018-09-10
_olex2_date_sample_submission    2018-09-10
_olex2_submission_original_sample_id Br8P-CF3PP
_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 2.589
_oxdiff_exptl_absorpt_empirical_full_min 0.522