Synthesis of Hetero-multinuclear Metal Complexes by Site-Selective Redox Switching and Transmetalation on a Homo-multinuclear Complex.
Ube, Hitoshi; Endo, Kenichi; Sato, Hiroyasu; Shionoya, Mitsuhiko; Journal of the American Chemical Society 141 (2019) 10384–10389; doi:10.1021/jacs.9b04123

data_4128045
_publ_section_title
;
 Synthesis of Hetero-multinuclear Metal Complexes by Site-Selective Redox
 Switching and Transmetalation on a Homo-multinuclear Complex.
;
_journal_issue                   26
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10384
_journal_page_last               10389
_journal_paper_doi               10.1021/jacs.9b04123
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety
'C170.68 H116.03 Co4 N33 O8.68 Zn3, 0.5(Ce1 N6 O18)'
_chemical_formula_sum            'C170.68 H116.03 Ce0.5 Co4 N36 O17.67 Zn3'
_chemical_formula_weight         3455.80
_chemical_properties_physical    Efflorescent
_space_group_crystal_system      trigonal
_space_group_IT_number           165
_space_group_name_Hall           '-P 3 2"c'
_space_group_name_H-M_alt        'P -3 c 1'
_symmetry_space_group_name_Hall  '-P 3 2"c'
_symmetry_space_group_name_H-M   'P -3 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-06-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-06-20 deposited with the CCDC.    2019-06-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            4
_cell_length_a                   21.2460(4)
_cell_length_b                   21.2460(4)
_cell_length_c                   58.2102(12)
_cell_measurement_reflns_used    19434
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      72.2510
_cell_measurement_theta_min      3.0620
_cell_volume                     22755.4(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.20a (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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      93.15
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.995
_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    -27.00  89.00   0.50    3.88    --    0.00  38.00-150.00  232
  2  \w     14.00  40.00   0.50    3.88    --    0.00  38.00   0.00   52
  3  \w     10.00 115.00   0.50   35.41    --   98.20 -30.00   0.00  210
  4  \w     15.00  98.00   0.50   35.41    --   98.20 -77.00 -60.00  166
  5  \w     34.00 110.00   0.50   35.41    --   98.20 -61.00 -60.00  152
  6  \w     12.00  19.50   0.50   35.41    --   98.20 -45.00   0.00   15
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0491
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       65
_diffrn_reflns_limit_l_min       -69
_diffrn_reflns_number            54339
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.188
_diffrn_reflns_theta_min         2.401
_exptl_absorpt_coefficient_mu    3.768
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.30390
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.20a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.009
_exptl_crystal_description       plate
_exptl_crystal_F_000             7042
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Chloroform/methanol/water/diethyl ether'
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.188
_exptl_crystal_size_min          0.067
_refine_diff_density_max         0.986
_refine_diff_density_min         -0.892
_refine_diff_density_rms         0.123
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.147
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     837
_refine_ls_number_reflns         13847
_refine_ls_number_restraints     592
_refine_ls_restrained_S_all      1.131
_refine_ls_R_factor_all          0.1272
_refine_ls_R_factor_gt           0.0994
_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          0.2993
_refine_ls_wR_factor_ref         0.3230
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8248
_reflns_number_total             13847
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04123_si_003.cif
_cod_data_source_block           CoCo3L3X6
_cod_original_cell_volume        22755.4(10)
_cod_original_formula_sum        'C170.68 H116.03 Ce0.50 Co4 N36 O17.67 Zn3'
_cod_database_code               4128045
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.786
_shelx_estimated_absorpt_t_min   0.301
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C9-C8 \\sim C9-C10 \\sim C9A-C10A \\sim C9A-C8
 with sigma of 0.02
 N5-C10A \\sim N5-C10
 with sigma of 0.02
 C27A-C10A \\sim C27-C10
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C11 \\sim N5 \\sim C10 \\sim C27 \\sim C26: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C26 \\sim C27A \\sim C27 \\sim C10 \\sim C10A \\sim C9A \\sim C9: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
N8 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim N8A \\sim
C28A \\sim C29A \\sim C30A \\sim C31A \\sim C32A \\sim C33A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
N1A \\sim O1 \\sim O3 \\sim N1 \\sim O1A \\sim O2A \\sim O3A \\sim O2: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 C45, C44, C43, C42, C38, N10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N9, C37, C36, C41, C40, C39
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C27, C10, N5, C11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C33A, N8A, C31A, C32A, C28A, C29A, C30A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1A, N1A, O2A, O3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{N8, C28, C32, C31} sigma for 1-2: 0.02, 1-3: 0.04
as
{N8, C28, C29, C30}
{N8, C28, C29, C30, C31, C32, C33} sigma for 1-2: 0.02, 1-3: 0.04
as
{N8A, C28A, C29A, C30A, C31A, C32A, C33A}
{O1, O2, O3, N1} sigma for 1-2: 0.02, 1-3: 0.04
as
{O1A, O2A, O3A, N1A}
6. Others
 Sof(H26A)=Sof(N8A)=Sof(C28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=
 Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33D)=Sof(H33E)=
 Sof(H33F)=Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(N1A)=Sof(C9A)=Sof(C10A)=Sof(C27A)=
 Sof(H27A)=1-FVAR(1)
 Sof(C9)=Sof(C10)=Sof(H26)=Sof(C27)=Sof(H27)=Sof(N8)=Sof(C28)=Sof(C29)=
 Sof(H29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=Sof(C33)=
 Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(N1)=FVAR(1)
 Sof(Zn1A)=1-FVAR(2)
 Sof(Zn1)=Sof(O4)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=FVAR(2)
7.a Me refined with riding coordinates:
 C33(H33A,H33B,H33C), C33A(H33D,H33E,H33F)
7.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C17(H17), C20(H20), C21(H21), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26), C26(H26A), C27(H27), C34(H34), C35(H35),
 C37(H37), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46),
  C47(H47), C49(H49), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56),
 C57(H57), C29(H29), C30(H30), C31(H31), C32(H32), C29A(H29A), C30A(H30A),
 C31A(H31A), C32A(H32A), C27A(H27A)
7.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              39822
_shelx_hkl_checksum              12941
_shelx_fab_checksum              43512
_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
;