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_4127526
_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         'C48 H46 Co2.3 N8 Ni1.7 O14, 2(Cl O3), O'
_chemical_formula_sum            'C48 H48 Cl2 Co2.3 N8 Ni1.7 O21'
_chemical_formula_weight         1379.19
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/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                 116.299(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.4421(9)
_cell_length_b                   12.0160(3)
_cell_length_c                   21.2212(8)
_cell_measurement_reflns_used    19074
_cell_measurement_temperature    183.05(10)
_cell_measurement_theta_max      37.5440
_cell_measurement_theta_min      2.7060
_cell_volume                     5130.3(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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      183.05(10)
_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      3.00 100.00   1.00   40.00    --   30.02  59.00   9.99   97
  2  \w    -40.00  57.00   1.00   40.00    --   30.02 -60.00-140.69   97
  3  \w      3.00 100.00   1.00   40.00    --   30.02  59.00 -23.80   97
  4  \w    -49.00  67.00   1.00   40.00    --   30.02 -19.00  30.00  116
  5  \w    -40.00  57.00   1.00   40.00    --   30.02 -60.00 -47.88   97
  6  \w      3.00  32.00   1.00   40.00    --   30.02  60.00  89.48   29
  7  \w      3.00 100.00   1.00   40.00    --   30.02  57.00-180.00   97
;
_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      -0.0103064000
_diffrn_orient_matrix_UB_12      -0.0096657000
_diffrn_orient_matrix_UB_13      -0.0363293000
_diffrn_orient_matrix_UB_21      -0.0096821000
_diffrn_orient_matrix_UB_22      0.0565451000
_diffrn_orient_matrix_UB_23      -0.0072299000
_diffrn_orient_matrix_UB_31      0.0322833000
_diffrn_orient_matrix_UB_32      0.0139202000
_diffrn_orient_matrix_UB_33      0.0042504000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0401
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            64059
_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         36.316
_diffrn_reflns_theta_min         2.450
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.541
_exptl_absorpt_correction_T_max  0.749
_exptl_absorpt_correction_T_min  0.654
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.786
_exptl_crystal_description       block
_exptl_crystal_F_000             2815
_exptl_crystal_size_max          0.491
_exptl_crystal_size_mid          0.357
_exptl_crystal_size_min          0.346
_refine_diff_density_max         1.423
_refine_diff_density_min         -0.927
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     467
_refine_ls_number_reflns         12436
_refine_ls_number_restraints     249
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0410
_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^)+(0.0454P)^2^+9.5854P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1009
_refine_ls_wR_factor_ref         0.1171
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9691
_reflns_number_total             12436
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01356_si_002.cif
_cod_data_source_block           1891348(2-CoxNi4-x-ClO3final)
_cod_original_formula_sum        'C48 H48 Cl2 Co2.30 N8 Ni1.70 O21'
_cod_database_code               4127526
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Co4 C48 N8 O18 H46 Cl2'
_shelx_estimated_absorpt_t_max   0.618
_shelx_estimated_absorpt_t_min   0.518
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     36.23
_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
{Co2, Ni2}
{Co1, Ni1}
3. Restrained distances
 O3-H3
 0.84 with sigma of 0.02
 Cl2-O11 \\sim Cl1-O8 \\sim Cl1-O9 \\sim Cl1-O13 \\sim Cl2-O13 \\sim Cl2-O12
 with sigma of 0.002
 Ni1-O5B \\sim Co1-O5A
 with sigma of 0.005
 O5B-C23B \\sim O5A-C23A
 with sigma of 0.005
 C24B-C23B \\sim C24A-C23A
 with sigma of 0.005
 O6B-C23B \\sim O6A-C23A
 with sigma of 0.005
4. Uiso/Uaniso restraints and constraints
Cl1 \\sim Cl2 \\sim O8 \\sim O9 \\sim O10 \\sim O11 \\sim O12 \\sim O13: within
2A with sigma of 0.005 and sigma for terminal atoms of 0.005
O5A \\sim O5B \\sim O6A \\sim O6B \\sim C23A \\sim C23B \\sim C24A \\sim C24B:
within 2A with sigma of 0.002 and sigma for terminal atoms of 0.08
Uanis(Co2) = Uanis(Ni2)
Uanis(Co1) = Uanis(Ni1)
5. Rigid body (RIGU) restrains
 O5A, O5B, O6A, O6B, C23A, C23B, C24A, C24B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
6. Others
 Sof(Cl2)=Sof(O11)=Sof(O12)=Sof(O13)=1-FVAR(1)
 Sof(Cl1)=Sof(O8)=Sof(O9)=Sof(O10)=FVAR(1)
 Sof(O5B)=Sof(O6B)=Sof(C23B)=Sof(C24B)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(2)
 Sof(O5A)=Sof(O6A)=Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(2)
 Fixed Sof: Co1(0.6) Co2(0.55) Ni1(0.4) Ni2(0.45) O14(0.5)
7.a Rotating group:
 O7(H7A)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3A), C4(H4A), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C13(H13), C14(H14), C15(H15), C19(H19), C20(H20), C21(H21), C22(H22)
7.c Idealised Me refined as rotating group:
 C24A(H24A,H24B,H24C), C24B(H24D,H24E,H24F)
7.d Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_shelx_hkl_checksum              40642
_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 1.126
_oxdiff_exptl_absorpt_empirical_full_min 0.869