Synthesis, crystallographic characterization and homogeneous catalytic activity of novel unsymmetric porphyrins
Antonangelo, A. R.; Westrup, K. C. M.; Burt, L. A.; Bezzu, C. Grazia; Malewschik, T.; Machado, G. S.; Nunes, F. S.; McKeown, N. B.; Nakagaki, S.; RSC Adv. 7 (2017) 50610–; doi:10.1039/C7RA08734A

data_7229460
_publ_section_title
;
 Synthesis, crystallographic characterization and homogeneous catalytic
 activity of novel unsymmetric porphyrins
;
_journal_issue                   80
_journal_name_full               'RSC Adv.'
_journal_page_first              50610
_journal_paper_doi               10.1039/C7RA08734A
_journal_volume                  7
_journal_year                    2017
_chemical_formula_moiety         '2(C H Cl3), C48 H28 F10 N4 O4'
_chemical_formula_sum            'C50 H30 Cl6 F10 N4 O4'
_chemical_formula_weight         1153.48
_chemical_name_systematic
Cis-5,10-bis(pentafluorophenyl)-15,20-bis(3,4-dimethoxyphenyl)porphyrin
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2016-11-29
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.24 svn.r3356 for OlexSys, GUI svn.r5267)
;
_audit_update_record
;
2017-03-07 deposited with the CCDC.
2017-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.0320(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.0821(2)
_cell_length_b                   17.9808(2)
_cell_length_c                   22.7546(3)
_cell_measurement_reflns_used    16274
_cell_measurement_temperature    199.97(14)
_cell_measurement_theta_max      75.9410
_cell_measurement_theta_min      3.8650
_cell_volume                     4915.97(12)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43h (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43h (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43h (Rigaku OD, 2015)'
_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      200
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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    -70.00  27.00   1.00    8.00    --  -43.17  57.00  90.00   97
  2  \w    -66.00  29.00   1.00    8.00    --  -43.17  38.00-120.00   95
  3  \w   -113.00 -17.00   1.00    8.00    --  -43.17 -57.00 -60.00   96
  4  \w      1.00  83.00   1.00    8.00    --   43.17 -99.00-120.00   82
  5  \w     23.00  98.00   1.00    8.00    --   43.17-125.00 150.00   75
  6  \w     66.00 178.00   1.00   23.00    --  111.00  15.00 120.00  112
  7  \w     41.00 139.00   1.00   23.00    --  111.00 -61.00  30.00   98
  8  \w     37.00 142.00   1.00   23.00    --  111.00 -77.00  30.00  105
  9  \w     39.00 121.00   1.00   23.00    --  111.00-125.00  60.00   82
 10  \w     30.00 109.00   1.00   23.00    --  111.00 -94.00 -60.00   79
 11  \w     87.00 178.00   1.00   23.00    --  111.00  45.00-120.00   91
 12  \w     39.00 121.00   1.00   23.00    --  111.00-125.00   0.00   82
 13  \w     39.00 121.00   1.00   23.00    --  111.00-125.00-150.00   82
 14  \w     30.00 109.00   1.00   23.00    --  111.00 -94.00-150.00   79
 15  \w     81.00 178.00   1.00   23.00    --  111.00  71.00 -34.77   97
 16  \w     39.00 121.00   1.00   23.00    --  111.00-125.00 120.00   82
 17  \w     87.00 178.00   1.00   23.00    --  111.00  30.00-150.00   91
 18  \w     37.00 142.00   1.00   23.00    --  111.00 -77.00-120.00  105
 19  \w     30.00 109.00   1.00   23.00    --  111.00 -94.00-120.00   79
 20  \w     36.00 135.00   1.00   23.00    --  111.00 -30.00  30.00   99
 21  \w     87.00 178.00   1.00   23.00    --  111.00  30.00-180.00   91
 22  \w     36.00 135.00   1.00   23.00    --  111.00 -30.00-120.00   99
 23  \w     87.00 178.00   1.00   23.00    --  111.00  45.00 -60.00   91
 24  \w     30.00 109.00   1.00   23.00    --  111.00 -94.00   0.00   79
 25  \w     30.00 109.00   1.00   23.00    --  111.00 -94.00  90.00   79
 26  \w     94.00 178.00   1.00   23.00    --  111.00 125.00 -60.00   84
 27  \w     36.00 135.00   1.00   23.00    --  111.00 -30.00 150.00   99
;
_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      0.0012796000
_diffrn_orient_matrix_UB_12      -0.0613679000
_diffrn_orient_matrix_UB_13      0.0473369000
_diffrn_orient_matrix_UB_21      0.0074096000
_diffrn_orient_matrix_UB_22      -0.0596611000
_diffrn_orient_matrix_UB_23      -0.0480103000
_diffrn_orient_matrix_UB_31      0.1279764000
_diffrn_orient_matrix_UB_32      0.0040544000
_diffrn_orient_matrix_UB_33      0.0095184000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0661
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            39378
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.123
_diffrn_reflns_theta_min         3.139
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.974
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.874
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43h (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 reddish brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.559
_exptl_crystal_description       block
_exptl_crystal_F_000             2328
_exptl_crystal_preparation
'Crystallised by slow diffusion of methanol into a solution of the compound in chloroform'
_exptl_crystal_size_max          0.188
_exptl_crystal_size_mid          0.091
_exptl_crystal_size_min          0.085
_refine_diff_density_max         0.474
_refine_diff_density_min         -0.522
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     378
_refine_ls_number_reflns         5127
_refine_ls_number_restraints     38
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0708
_refine_ls_R_factor_gt           0.0659
_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^)+(0.1188P)^2^+5.4131P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1873
_refine_ls_wR_factor_ref         0.1943
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4550
_reflns_number_total             5127
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ra08734a2.cif
_cod_data_source_block           P2
_cod_database_code               7229460
_chemical_oxdiff_formula         'C48 H28 F10 N4 O4'
_chemical_oxdiff_usercomment     '@ 120 K CisA2B2 porphyrin'
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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 = H3-N3
 0.88 with sigma of 0.02
3. Rigid body (RIGU) restrains
 Cl2, Cl3, Cl1, C25
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl4, Cl5, Cl6, C26
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(Cl4)=Sof(Cl5)=Sof(Cl6)=Sof(C26)=Sof(H26)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=Sof(C25)=Sof(H25)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C25(H25), C26(H26)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1A), C5(H5), C6(H6), C10(H10), C12(H12), C15(H15), C16(H16)
5.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              90055
_shelx_shelxl_version_number     2014/7
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder with paratone'
_olex2_submission_original_sample_id 'Cis A2B2 porphyrin'
_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 1.869
_oxdiff_exptl_absorpt_empirical_full_min 0.716