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_7229461
_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         'C46 H19 F15 N4 O2, C H3 O'
_chemical_formula_sum            'C47 H22 F15 N4 O3'
_chemical_formula_weight         975.68
_chemical_name_systematic
5,10,15-tris(pentafluorophenyl)-20-(3,4-dimethoxyphenyl)porphyrin
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-12-03
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_audit_update_record
;
2017-03-07 deposited with the CCDC.
2017-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.961(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5360(2)
_cell_length_b                   26.8989(6)
_cell_length_c                   15.0809(3)
_cell_measurement_reflns_used    16483
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      75.7160
_cell_measurement_theta_min      4.3830
_cell_volume                     4398.56(16)
_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      120
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9996
_diffrn_measured_fraction_theta_max 0.8255
_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    5.00    --  -43.17  57.00 120.00   97
  2  \w   -113.00 -17.00   1.00    5.00    --  -43.17 -57.00 -30.00   96
  3  \w   -116.00 -21.00   1.00    5.00    --  -43.17 -38.00 -60.00   95
  4  \w   -116.00 -21.00   1.00    5.00    --  -43.17 -38.00-150.00   95
  5  \w      1.00  83.00   1.00    5.00    --   43.17 -99.00-180.00   82
  6  \w     23.00  98.00   1.00    5.00    --   43.17-125.00 -60.00   75
  7  \w     85.00 178.00   1.00   20.00    --  111.00  53.00 -15.22   93
  8  \w     39.00 121.00   1.00   20.00    --  111.00-125.00  30.00   82
  9  \w     40.00 135.00   1.00   20.00    --  111.00 -45.00 -30.00   95
 10  \w     37.00 142.00   1.00   20.00    --  111.00 -77.00  30.00  105
 11  \w     94.00 178.00   1.00   20.00    --  111.00 125.00 -60.00   84
 12  \w     30.00 109.00   1.00   20.00    --  111.00 -94.00-180.00   79
 13  \w     30.00 109.00   1.00   20.00    --  111.00 -94.00 150.00   79
 14  \w     30.00 109.00   1.00   20.00    --  111.00 -94.00 -90.00   79
 15  \w     36.00 135.00   1.00   20.00    --  111.00 -30.00 150.00   99
 16  \w     66.00 178.00   1.00   20.00    --  111.00  15.00 -60.00  112
 17  \w     30.00 109.00   1.00   20.00    --  111.00 -94.00  30.00   79
 18  \w     40.00 135.00   1.00   20.00    --  111.00 -45.00-180.00   95
 19  \w     31.00 156.00   1.00   20.00    --  111.00 -15.00 -30.00  125
 20  \w     83.00 178.00   1.00   20.00    --  111.00  65.00 131.51   95
 21  \w     39.00 121.00   1.00   20.00    --  111.00-125.00 150.00   82
 22  \w     37.00 142.00   1.00   20.00    --  111.00 -77.00 -60.00  105
 23  \w     39.00 121.00   1.00   20.00    --  111.00-125.00 -90.00   82
 24  \w     41.00 139.00   1.00   20.00    --  111.00 -61.00  30.00   98
 25  \w     87.00 178.00   1.00   20.00    --  111.00  30.00 -30.00   91
 26  \w     30.00 109.00   1.00   20.00    --  111.00 -94.00-150.00   79
 27  \w   -117.00 -44.00   1.00    5.00    --  -43.17 -77.00-180.00   73
 28  \w   -113.00 -17.00   1.00    5.00    --  -43.17 -57.00  90.00   96
;
_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      0.0111506000
_diffrn_orient_matrix_UB_12      0.0551091000
_diffrn_orient_matrix_UB_13      0.0296890000
_diffrn_orient_matrix_UB_21      -0.1028831000
_diffrn_orient_matrix_UB_22      0.0134767000
_diffrn_orient_matrix_UB_23      -0.0930243000
_diffrn_orient_matrix_UB_31      -0.0972776000
_diffrn_orient_matrix_UB_32      -0.0079769000
_diffrn_orient_matrix_UB_33      0.0476839000
_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  0.0660
_diffrn_reflns_av_unetI/netI     0.0400
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            35755
_diffrn_reflns_point_group_measured_fraction_full 0.850
_diffrn_reflns_point_group_measured_fraction_max 0.826
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.08
_diffrn_reflns_theta_min         3.12
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.211
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.626
_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    1.473
_exptl_crystal_description       plate
_exptl_crystal_F_000             1964
_exptl_crystal_recrystallization_method
'The material was recrystallised by slow vapour diffusion of methanol into a solution f chloroform'
_exptl_crystal_size_max          0.514
_exptl_crystal_size_mid          0.224
_exptl_crystal_size_min          0.055
_refine_diff_density_max         0.730
_refine_diff_density_min         -0.515
_refine_diff_density_rms         0.104
_refine_ls_abs_structure_details
;
 Flack x determined using 2367 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.392
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     767
_refine_ls_number_reflns         7617
_refine_ls_number_restraints     397
_refine_ls_restrained_S_all      1.829
_refine_ls_R_factor_all          0.1079
_refine_ls_R_factor_gt           0.1043
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2897
_refine_ls_wR_factor_ref         0.3001
_reflns_Friedel_coverage         0.657
_reflns_Friedel_fraction_full    0.701
_reflns_Friedel_fraction_max     0.657
_reflns_number_gt                7026
_reflns_number_total             7617
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ra08734a2.cif
_cod_data_source_block           P3
_cod_database_code               7229461
_chemical_oxdiff_formula         'C46 H19 F15 N4 O2'
_chemical_oxdiff_usercomment     '@ 120 K A3B 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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 H4-H2
 0.84 with sigma of 0.02
3. Restrained planarity
 F21, F22, F24, F25, C39, C40, C41, C36, C37, C38
 with sigma of 0.1
 F6, F7, F8, F9, F10, C51, C52, C53, C48, C49, C50
 with sigma of 0.1
4. Rigid bond restraints
 O0AA, C1AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim C21 \\sim C22 \\sim C23 \\sim C24
\\sim C25 \\sim C26: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
O0AA \\sim C1AA: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
6. Rigid body (RIGU) restrains
 F11, F12, F13, F14, F15, C59, C58, C57, C56, C55, C54
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F6, F7, F8, F9, F10, C51, C52, C53, C48, C49, C50
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F21, F22, F23, F24, F25, C39, C40, C41, C36, C37, C38
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F16, F17, F18, F19, F20, C43, C42, C47, C46, C45, C44
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(F6)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(C51)=Sof(C52)=Sof(C53)=Sof(C48)=
 Sof(C49)=Sof(C50)=1-FVAR(1)
 Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(C59)=Sof(C58)=Sof(C57)=
 Sof(C56)=Sof(C55)=Sof(C54)=FVAR(1)
 Sof(F16)=Sof(F17)=Sof(F18)=Sof(F19)=Sof(F20)=Sof(C43)=Sof(C42)=Sof(C47)=
 Sof(C46)=Sof(C45)=Sof(C44)=1-FVAR(2)
 Sof(F21)=Sof(F22)=Sof(F23)=Sof(F24)=Sof(F25)=Sof(C39)=Sof(C40)=Sof(C41)=
 Sof(C36)=Sof(C37)=Sof(C38)=FVAR(2)
8.a Aromatic/amide H refined with riding coordinates:
 N2(H2), N4(H4), C2(H2A), C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C17(H17),
  C18(H18), C28(H28), C29(H29), C32(H32)
8.b Fitted hexagon refined as free rotating group:
 C39(C40,C41,C36,C37,C38), C43(C42,C47,C46,C45,C44), C51(C52,C53,C48,C49,C50),
 C59(C58,C57,C56,C55,C54)
8.c Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C1AA(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              3641
_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 paratone'
_olex2_submission_original_sample_id
5,10,15-tris(pentafluorophenyl)-20-(3,4-dimethoxyphenyl)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 4.074
_oxdiff_exptl_absorpt_empirical_full_min 0.581