Macrocycle- and metal-centered reduction of metal tetraphenylporphyrins where the metal is copper(II), nickel(II) and iron(II).
Nazarov, Dmitry I.; Andronov, Mikhail G.; Kuzmin, Aleksey V.; Khasanov, Salavat S.; Yudanova, Evgeniya I.; Shestakov, Alexander F.; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Konarev, Dmitri V.; Dalton transactions (Cambridge, England : 2003) 50 (2021) 15620–15632; doi:10.1039/d1dt02573b

data_7708755
_publ_section_title
;
 Macrocycle- and metal-centered reduction of metal tetraphenylporphyrins
 where the metal is copper(II), nickel(II) and iron(II).
;
_journal_issue                   43
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              15620
_journal_page_last               15632
_journal_paper_doi               10.1039/d1dt02573b
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety         'C44 H28 N4 Ni, C13 H30 P, C7 H8'
_chemical_formula_sum            'C64 H66 N4 Ni P'
_chemical_formula_weight         980.88
_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             2021-07-23
_audit_creation_method
;
FinalCif V85 by Daniel Kratzert, Freiburg 2021,
https://github.com/dkratzert/FinalCif
;
_audit_update_record
;
2021-07-23 deposited with the CCDC.	2021-09-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 126.742(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.0766(4)
_cell_length_b                   17.4210(3)
_cell_length_c                   27.8842(10)
_cell_measurement_reflns_used    11812
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.1470
_cell_measurement_theta_min      1.8360
_cell_volume                     5090.3(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4566
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.874
_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    -87.00   5.00   1.00  128.00    --  -12.20 -37.00-150.00   92
  2  \w    -76.00  25.00   1.00  128.00    --  -12.20 -19.00 -90.00  101
  3  \w    -67.00 -39.00   1.00  128.00    --  -12.20 -37.00   0.00   28
  4  \w    -30.00  13.00   1.00  128.00    --  -12.20 -57.00 150.00   43
  5  \w    -33.00  -6.00   1.00  128.00    --  -12.20 -57.00   0.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, AtlasS2, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0285037000
_diffrn_orient_matrix_UB_12      0.0035081000
_diffrn_orient_matrix_UB_13      0.0309631000
_diffrn_orient_matrix_UB_21      -0.0204094000
_diffrn_orient_matrix_UB_22      -0.0376710000
_diffrn_orient_matrix_UB_23      0.0001071000
_diffrn_orient_matrix_UB_31      0.0579239000
_diffrn_orient_matrix_UB_32      -0.0150161000
_diffrn_orient_matrix_UB_33      0.0069998000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0469
_diffrn_reflns_av_unetI/netI     0.0859
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.874
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            39961
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.874
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.696
_diffrn_reflns_theta_min         1.691
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.459
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97587
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_description       block
_exptl_crystal_F_000             2084
_exptl_crystal_size_max          0.449
_exptl_crystal_size_mid          0.189
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.694
_refine_diff_density_min         -0.687
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     679
_refine_ls_number_reflns         12628
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.1048
_refine_ls_R_factor_gt           0.0592
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0190P)^2^+5.9448P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0982
_refine_ls_wR_factor_ref         0.1230
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8428
_reflns_number_total             12628
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02573b2.cif
_cod_data_source_block           exp_1534_int1
_cod_database_code               7708755
_chemical_oxdiff_formula         C65H58N8Ni11P1Br1
_shelx_shelxl_version_number     2018/3
_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 1.027
_oxdiff_exptl_absorpt_empirical_full_min 0.975
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_shelx_estimated_absorpt_t_min   0.821
_shelx_estimated_absorpt_t_max   0.961
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C21A-C210 \\sim C21B-C210
 with sigma of 0.02
 C2-C22B \\sim C1-C22A
 with sigma of 0.02
 C22A-C21A \\sim C22B-C21B
 with sigma of 0.02
 P21-C26A \\sim P21-C26B
 with sigma of 0.02
 C24A-C205 \\sim C24B-C205
 with sigma of 0.02
 C27B-C208 \\sim C27A-C208
 with sigma of 0.02
 C27B-C26B \\sim C27A-C26A
 with sigma of 0.02
 C23B-C202 \\sim C23A-C202
 with sigma of 0.02
 C24B-C23B \\sim C24A-C23A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C23B) = Uanis(C23A)
Uanis(C27B) = Uanis(C27A)
Uanis(C24A) = Uanis(C24B)
Uanis(C26B) = Uanis(C26A)
4. Others
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C21B)=Sof(H21C)=Sof(H21D)=Sof(C22B)=
 Sof(H22C)=Sof(H22D)=Sof(H21G)=Sof(H21H)=1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(C22A)=
 Sof(H22A)=Sof(H22B)=Sof(H21E)=Sof(H21F)=FVAR(1)
 Sof(C23B)=Sof(H23C)=Sof(H23D)=Sof(C24B)=Sof(H24C)=Sof(H24D)=Sof(H20F)=
 Sof(H20G)=Sof(H20K)=Sof(H20L)=Sof(H20M)=1-FVAR(2)
 Sof(C23A)=Sof(H23A)=Sof(H23B)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H20D)=
 Sof(H20E)=Sof(H20H)=Sof(H20I)=Sof(H20J)=FVAR(2)
 Sof(C26B)=Sof(H26C)=Sof(H26D)=Sof(C27B)=Sof(H27C)=Sof(H27D)=Sof(H20P)=
 Sof(H20Q)=1-FVAR(3)
 Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(C27A)=Sof(H27A)=Sof(H27B)=Sof(H20N)=
 Sof(H20O)=FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C21A(H21A,H21B), C21B(H21C,H21D), C22A(H22A,H22B), C22B(H22C,H22D), C23A(H23A,
 H23B), C23B(H23C,H23D), C24A(H24A,H24B), C24B(H24C,H24D), C26A(H26A,H26B),
 C26B(H26C,H26D), C27A(H27A,H27B), C27B(H27C,H27D), C202(H20D,H20E), C202(H20F,
 H20G), C208(H20N,H20O), C208(H20P,H20Q), C210(H21E,H21F), C210(H21G,H21H)
5.b Aromatic/amide H refined with riding coordinates:
 C103(H103), C104(H104), C108(H108), C109(H109), C113(H113), C114(H114),
 C118(H118), C119(H119), C122(H122), C123(H123), C124(H124), C125(H125),
 C126(H126), C128(H128), C129(H129), C130(H130), C131(H131), C132(H132),
 C134(H134), C135(H135), C136(H136), C137(H137), C138(H138), C140(H140),
 C141(H141), C142(H142), C143(H143), C144(H144), C302(H302), C303(H303),
 C304(H304), C305(H305), C306(H306)
5.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C201(H20A,H20B,H20C), C205(H20H,H20I,H20J),
 C205(H20K,H20L,H20M), C209(H20R,H20S,H20T), C307(H30A,H30B,H30C)
;
_shelx_res_checksum              65833