Mechanistically Driven Control over Cubane Oxo Cluster Catalysts.
Song, Fangyuan; Al-Ameed, Karrar; Schilling, Mauro; Fox, Thomas; Luber, Sandra; Patzke, Greta R.; Journal of the American Chemical Society 141 (2019) 8846–8857; doi:10.1021/jacs.9b01356

data_4127534
_publ_section_title
;
 Mechanistically Driven Control over Cubane Oxo Cluster Catalysts.
;
_journal_issue                   22
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8846
_journal_page_last               8857
_journal_paper_doi               10.1021/jacs.9b01356
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety
'C50 H45 Co2.36 N8 Ni1.64 O14, F6 P, 8(H2 O), 3(O)'
_chemical_formula_sum            'C50 H67 Co2.36 F6 N8 Ni1.64 O25 P'
_chemical_formula_weight         1560.44
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2018-08-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.632(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1050(3)
_cell_length_b                   24.6661(8)
_cell_length_c                   21.5614(6)
_cell_measurement_reflns_used    30169
_cell_measurement_temperature    183.00(14)
_cell_measurement_theta_max      30.5200
_cell_measurement_theta_min      2.5960
_cell_volume                     6327.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.9b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.9b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.9b (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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      183.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4498
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -25.00  22.00   1.00   50.00    --  -18.78 -99.00 -60.00   47
  2  \w     35.00 108.00   1.00   50.00    --   19.56 178.00 -90.00   73
  3  \w     35.00 108.00   1.00   50.00    --   19.56 178.00 -30.00   73
  4  \w    -69.00 108.00   1.00   50.00    --   19.56   0.00  90.00  177
  5  \w    -25.00  22.00   1.00   50.00    --  -18.78 -99.00-150.00   47
  6  \w     -5.00  94.00   1.00   50.00    --   19.56  38.00-180.00   99
  7  \w     32.00  71.00   1.00   50.00    --   19.56-178.00  60.00   39
  8  \w    -55.00  25.00   1.00   50.00    --   19.56 -38.00   0.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0058411000
_diffrn_orient_matrix_UB_12      0.0036223000
_diffrn_orient_matrix_UB_13      0.0331033000
_diffrn_orient_matrix_UB_21      -0.0245506000
_diffrn_orient_matrix_UB_22      -0.0258148000
_diffrn_orient_matrix_UB_23      0.0025752000
_diffrn_orient_matrix_UB_31      0.0539751000
_diffrn_orient_matrix_UB_32      -0.0121327000
_diffrn_orient_matrix_UB_33      0.0043953000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0557
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            123706
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.508
_diffrn_reflns_theta_min         2.268
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.218
_exptl_absorpt_correction_T_max  0.913
_exptl_absorpt_correction_T_min  0.708
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.9b (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            'metallic dark violet'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.638
_exptl_crystal_description       prism
_exptl_crystal_F_000             3207
_exptl_crystal_size_max          0.53
_exptl_crystal_size_mid          0.287
_exptl_crystal_size_min          0.085
_refine_diff_density_max         1.594
_refine_diff_density_min         -1.608
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     956
_refine_ls_number_reflns         19306
_refine_ls_number_restraints     326
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0724
_refine_ls_R_factor_gt           0.0504
_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^)+(0.0760P)^2^+10.6951P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1371
_refine_ls_wR_factor_ref         0.1538
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14758
_reflns_number_total             19306
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01356_si_002.cif
_cod_data_source_block           1891357(2-u-oac-coxni4-x-pf6final)
_cod_database_code               4127534
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H67 F6 N8 Co4 O25 P'
_shelx_estimated_absorpt_t_max   0.904
_shelx_estimated_absorpt_t_min   0.565
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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. Shared sites
{Co1, Ni1}
{Co2, Ni2}
{Co3, Ni3}
{Co4, Ni4}
3. Restrained distances
 O15-H15A
 0.85 with sigma of 0.02
 O15-H15B
 0.85 with sigma of 0.02
 O25-H25A
 0.87 with sigma of 0.02
 O25-H25B
 0.87 with sigma of 0.02
 F3A-F6A
 2.2 with sigma of 0.006
 F3A-F5A
 2.2 with sigma of 0.006
 F6A-F2A
 2.2 with sigma of 0.01
 F5A-F2A
 2.2 with sigma of 0.01
 F4A-F6A
 2.2 with sigma of 0.02
 F1A-F4A
 2.2 with sigma of 0.01
 F2A-F3A
 2.2 with sigma of 0.01
 F3A-F1A
 2.2 with sigma of 0.01
 F6A-F1A
 2.2 with sigma of 0.01
 F1-F3
 2.2 with sigma of 0.004
 F2-F4
 2.2 with sigma of 0.004
 F4-F5
 2.2 with sigma of 0.002
 F3-F6
 2.2 with sigma of 0.002
 F4-F6
 2.2 with sigma of 0.008
 F3-F2
 2.2 with sigma of 0.004
 F4-F2
 2.2 with sigma of 0.008
 F5-F3
 2.2 with sigma of 0.002
 F5-F2
 2.2 with sigma of 0.004
 F2-F6
 2.2 with sigma of 0.004
 F1-F5
 2.2 with sigma of 0.004
 F1-F6
 2.2 with sigma of 0.004
 F4-F1
 2.2 with sigma of 0.004
 P1-F4A \\sim P1-F4 \\sim P1-F6 \\sim P1-F3A \\sim P1-F3 \\sim P1-F5 \\sim
P1-F5A \\sim P1-F2 \\sim P1-F2A ~
 P1-F1 \\sim P1-F6A \\sim P1-F1A
 with sigma of 0.002
4. Uiso/Uaniso restraints and constraints
F1 \\sim F1A \\sim F3A \\sim F3 \\sim F6A \\sim F6 \\sim F4 \\sim F4A \\sim F5A
\\sim F5 \\sim F2 \\sim F2A: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.005
Uanis(Co1) = Uanis(Ni1)
Uanis(Co2) = Uanis(Ni2)
Uanis(Co3) = Uanis(Ni3)
Uanis(Co4) = Uanis(Ni4)
5. Rigid body (RIGU) restrains
 P1, F1, F1A, F2, F2A, F3, F3A, F4A, F4, F5, F5A, F6, F6A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F1A)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6A)=1-FVAR(1)
 Sof(F1)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6)=FVAR(1)
 Fixed Sof: Co1(0.65) Co2(0.65) Co3(0.53) Co4(0.53) Ni1(0.35) Ni2(0.35)
 Ni3(0.47) Ni4(0.47)
7.a Free rotating group:
 O15(H15A,H15B), O17(H17A,H17B), O18(H18A,H18B), O19(H19A,H19B), O21(H21A,
 H21B), O22(H22A,H22B), O24(H24A,H24B)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C8(H8A), C9(H9), C10(H10), C11(H11), C12(H12),
  C13(H13), C14(H14), C15(H15), C19(H19), C20(H20), C21(H21), C22(H22),
 C23(H23), C24(H24), C25(H25), C26(H26), C30(H30), C31(H31), C32(H32), C33(H33),
  C34(H34), C35(H35), C36(H36), C37(H37), C41(H41), C42(H42), C43(H43), C44(H44)
7.c Idealised Me refined as rotating group:
 C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C50(H50A,H50B,H50C)
7.d Idealised tetrahedral OH refined as rotating group:
 O5(H5), O6(H6), O7(H7), O8(H8)
;
_shelx_hkl_checksum              55162
_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 1.236
_oxdiff_exptl_absorpt_empirical_full_min 0.688