Copper(II) tetrakis(pentafluorophenyl)porphyrin: Highly Active Copper-based Molecular Catalyst for Electrochemical CO2 Reduction
Kosugi, Kento; Kashima, Hina; Kondo, Mio; Masaoka, Shigeyuki; Chemical Communications  (2022) –; doi:10.1039/D1CC05880K

data_7129506
_publ_section_title
;
 Copper(II) tetrakis(pentafluorophenyl)porphyrin: Highly Active
 Copper-based Molecular Catalyst for Electrochemical CO2 Reduction
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC05880K
_journal_year                    2022
_chemical_formula_moiety         'C44 H8 Cu F20 N4, 2(C2 H3 N)'
_chemical_formula_sum            'C48 H14 Cu F20 N6'
_chemical_formula_weight         1118.19
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-09-20 deposited with the CCDC.	2022-01-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.758(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.9205(7)
_cell_length_b                   11.2461(5)
_cell_length_c                   15.0429(6)
_cell_measurement_reflns_used    8713
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      27.9580
_cell_measurement_theta_min      2.3630
_cell_volume                     2120.99(19)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_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_temperature      123(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.854
_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    -24.00  27.00   0.50   90.00    --  -11.26 -99.00 -60.00  102
  2  \w     34.00  59.00   0.50   90.00    --   12.36-161.00 -24.00   50
  3  \w     26.00  51.00   0.50   90.00    --   12.36-117.00 126.00   50
  4  \w    -25.00  21.00   0.50   90.00    --  -11.26 -99.00  30.00   92
  5  \w    -26.00  48.00   0.50   90.00    --   12.36 -99.00  60.00  148
  6  \w    -19.00  27.00   0.50   90.00    --  -11.26 -99.00-120.00   92
  7  \w    -66.00 -38.00   0.50   90.00    --  -11.26-178.00 -90.00   56
  8  \w    -76.00 -51.00   0.50   90.00    --  -11.26-178.00 -60.00   50
  9  \w    -44.00 -18.00   0.50   90.00    --  -11.26 117.00-146.00   52
 10  \w    -82.00 -57.00   0.50   90.00    --  -11.26 161.00   4.00   50
 11  \w     39.00  82.00   0.50   90.00    --   12.36 178.00  30.00   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0125725000
_diffrn_orient_matrix_UB_12      0.0614219000
_diffrn_orient_matrix_UB_13      -0.0075822000
_diffrn_orient_matrix_UB_21      -0.0500209000
_diffrn_orient_matrix_UB_22      -0.0112049000
_diffrn_orient_matrix_UB_23      0.0002823000
_diffrn_orient_matrix_UB_31      0.0233098000
_diffrn_orient_matrix_UB_32      0.0090965000
_diffrn_orient_matrix_UB_33      0.0517680000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0378
_diffrn_reflns_av_unetI/netI     0.0406
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.854
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            24245
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.854
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.086
_diffrn_reflns_theta_min         2.354
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.650
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64468
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.751
_exptl_crystal_description       plate
_exptl_crystal_F_000             1106
_exptl_crystal_size_max          1.043
_exptl_crystal_size_mid          0.308
_exptl_crystal_size_min          0.105
_refine_diff_density_max         0.725
_refine_diff_density_min         -0.297
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.160
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     402
_refine_ls_number_reflns         5827
_refine_ls_number_restraints     435
_refine_ls_restrained_S_all      1.155
_refine_ls_R_factor_all          0.1455
_refine_ls_R_factor_gt           0.0954
_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^)+(0.0863P)^2^+2.7596P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2199
_refine_ls_wR_factor_ref         0.2428
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3483
_reflns_number_total             5827
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc05880k2.cif
_cod_data_source_block           cupfp_2nd
_cod_original_cell_volume        2120.99(18)
_cod_database_code               7129506
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         C44H8F20N4Cu
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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. Uiso/Uaniso restraints and constraints
Uanis(C204) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(F109) \\sim Ueq, Uanis(F210) \\sim Ueq, Uanis(F110) \\sim Ueq,
Uanis(C105) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C201)=Sof(C202)=Sof(C203)=Sof(C204)=Sof(C205)=Sof(C206)=Sof(F207)=
 Sof(F208)=Sof(F209)=Sof(F210)=Sof(F211)=1-FVAR(1)
 Sof(F107)=Sof(C106)=Sof(C101)=Sof(C102)=Sof(C103)=Sof(C104)=Sof(C105)=
 Sof(F108)=Sof(F110)=Sof(F111)=Sof(F109)=FVAR(1)
5.a Free rotating group:
 C201(C202,C203,C204,C205,C206,F207,F208,F209,F210,F211)
5.b Aromatic/amide H refined with riding coordinates:
 C00C(H00C), C00I(H00I), C00L(H00L), C00Q(H00Q)
5.c Fitted hexagon refined as free rotating group:
 C106(C101,C102,C103,C104,C105)
5.d Idealised Me refined as rotating group:
 C010(H01A,H01B,H01C)
;
_shelx_res_checksum              17999
_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 1.540
_oxdiff_exptl_absorpt_empirical_full_min 0.514