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_7708757
_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
'C80 H100 Cs2 Cu N8 O12, C62 H64 Cs Cu N6 O6, C18 H36 Cs N2 O6'
_chemical_formula_sum            'C160 H200 Cs4 Cu2 N16 O24'
_chemical_formula_weight         3390.07
_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                 94.8160(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.0683(2)
_cell_length_b                   43.0660(5)
_cell_length_c                   17.5575(2)
_cell_measurement_reflns_used    42722
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.2490
_cell_measurement_theta_min      2.0450
_cell_volume                     15120.7(3)
_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_temperature      100(2)
_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 0.985
_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    -65.00  53.00   0.50   32.00    --   16.58 -37.00 150.00  236
  2  \w    -52.00  48.00   0.50   32.00    --   16.58 -37.00  30.00  200
  3  \w     31.00  57.00   0.50   32.00    --   16.58  57.00 120.00   52
  4  \w    -18.00  -9.50   0.50   32.00    --   16.58  57.00 -30.00   17
;
_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      -0.0189042000
_diffrn_orient_matrix_UB_12      -0.0054941000
_diffrn_orient_matrix_UB_13      -0.0332250000
_diffrn_orient_matrix_UB_21      -0.0148102000
_diffrn_orient_matrix_UB_22      -0.0114561000
_diffrn_orient_matrix_UB_23      0.0222036000
_diffrn_orient_matrix_UB_31      -0.0260993000
_diffrn_orient_matrix_UB_32      0.0104811000
_diffrn_orient_matrix_UB_33      0.0068445000
_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  0.0247
_diffrn_reflns_av_unetI/netI     0.0369
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       55
_diffrn_reflns_limit_k_min       -53
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            83385
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.103
_diffrn_reflns_theta_min         1.678
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.305
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97096
_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    1.489
_exptl_crystal_description       block
_exptl_crystal_F_000             6968
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.314
_refine_diff_density_max         1.331
_refine_diff_density_min         -1.747
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1877
_refine_ls_number_reflns         32866
_refine_ls_number_restraints     22
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0463
_refine_ls_R_factor_gt           0.0359
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0373P)^2^+22.2178P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0856
_refine_ls_wR_factor_ref         0.0901
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27979
_reflns_number_total             32866
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02573b2.cif
_cod_data_source_block           exp_1531_int1
_cod_database_code               7708757
_chemical_oxdiff_formula         C112H132N8O12Cu1Cs2
_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 1.033
_oxdiff_exptl_absorpt_empirical_full_min 0.955
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_shelx_estimated_absorpt_t_min   0.610
_shelx_estimated_absorpt_t_max   0.685
_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
2. Restrained distances
 O31B-C311 \\sim O31A-C311
 with sigma of 0.02
 O31B-C32B \\sim O31A-C32A
 with sigma of 0.02
 C32B-C31B \\sim C32A-C31A
 with sigma of 0.02
 O303-C31A \\sim O303-C31B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C32B \\sim C32A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
O31B \\sim O31A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
C31A \\sim C31B: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
Uanis(O31B) = Uanis(O31A)
4. Others
 Sof(O31B)=Sof(C31B)=Sof(H31C)=Sof(H31D)=Sof(C32B)=Sof(H32C)=Sof(H32D)=
 Sof(H31G)=Sof(H31H)=1-FVAR(1)
 Sof(O31A)=Sof(C31A)=Sof(H31A)=Sof(H31B)=Sof(C32A)=Sof(H32A)=Sof(H32B)=
 Sof(H31E)=Sof(H31F)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C31A(H31A,H31B), C31B(H31C,H31D), C32A(H32A,H32B), C32B(H32C,H32D), C201(H20A,
 H20B), C202(H20C,H20D), C203(H20E,H20F), C204(H20G,H20H), C205(H20I,H20J),
 C206(H20K,H20L), C207(H20M,H20N), C208(H20O,H20P), C209(H20Q,H20R), C210(H21A,
 H21B), C211(H21C,H21D), C212(H21E,H21F), C213(H21G,H21H), C214(H21I,H21J),
 C215(H21K,H21L), C216(H21M,H21N), C217(H21O,H21P), C218(H21Q,H21R), C301(H30A,
 H30B), C302(H30C,H30D), C303(H30E,H30F), C304(H30G,H30H), C305(H30I,H30J),
 C306(H30K,H30L), C307(H30M,H30N), C308(H30O,H30P), C311(H31E,H31F), C311(H31G,
 H31H), C312(H31I,H31J), C313(H31K,H31L), C314(H31M,H31N), C315(H31O,H31P),
 C316(H31Q,H31R), C317(H31S,H31T), C318(H31U,H31V), C501(H50A,H50B), C502(H50C,
 H50D), C503(H50E,H50F), C504(H50G,H50H), C505(H50I,H50J), C506(H50K,H50L),
 C507(H50M,H50N), C508(H50O,H50P), C509(H50Q,H50R), C510(H51A,H51B), C511(H51C,
 H51D), C512(H51E,H51F), C513(H51G,H51H), C514(H51I,H51J), C515(H51K,H51L),
 C516(H51M,H51N), C517(H51O,H51P), C518(H51Q,H51R), C601(H60A,H60B), C602(H60C,
 H60D), C603(H60E,H60F), C604(H60G,H60H), C605(H60I,H60J), C606(H60K,H60L),
 C607(H60M,H60N), C608(H60O,H60P), C609(H60Q,H60R), C610(H61A,H61B), C611(H61C,
 H61D), C612(H61E,H61F), C613(H61G,H61H), C614(H61I,H61J), C615(H61K,H61L),
 C616(H61M,H61N), C617(H61O,H61P), C618(H61Q,H61R)
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), C403(H403), C404(H404),
 C408(H408), C409(H409), C413(H413), C414(H414), C418(H418), C419(H419),
 C422(H422), C423(H423), C424(H424), C425(H425), C426(H426), C428(H428),
 C429(H429), C430(H430), C431(H431), C432(H432), C434(H434), C435(H435),
 C436(H436), C437(H437), C438(H438), C440(H440), C441(H441), C442(H442),
 C443(H443), C444(H444)
;
_shelx_res_checksum              9544