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_4127525
_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(B1 F4)'
_chemical_formula_sum            'C48 H46 B2 Co2.3 F8 N8 Ni1.7 O14'
_chemical_formula_weight         1367.89
_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                 116.313(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.7806(17)
_cell_length_b                   12.0764(5)
_cell_length_c                   21.2581(13)
_cell_measurement_reflns_used    4462
_cell_measurement_temperature    183.05(10)
_cell_measurement_theta_max      26.3210
_cell_measurement_theta_min      3.1410
_cell_volume                     5242.3(7)
_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)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_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     29.00  54.00   1.00   50.00    --  -19.65  38.00  30.00   25
  2  \w    -94.00  10.00   1.00   50.00    --  -19.65 -57.00-120.00  104
  3  \w    -26.00   9.00   1.00   50.00    --  -19.65  38.00  30.00   35
  4  \w      1.00  47.00   1.00   50.00    --   20.59 -57.00  60.00   46
  5  \w    -48.00 -18.00   1.00   50.00    --   20.59 -57.00  60.00   30
;
_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      0.0305261000
_diffrn_orient_matrix_UB_12      -0.0270893000
_diffrn_orient_matrix_UB_13      0.0103913000
_diffrn_orient_matrix_UB_21      0.0129437000
_diffrn_orient_matrix_UB_22      0.0482513000
_diffrn_orient_matrix_UB_23      -0.0082249000
_diffrn_orient_matrix_UB_31      0.0103598000
_diffrn_orient_matrix_UB_32      0.0195827000
_diffrn_orient_matrix_UB_33      0.0347612000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0389
_diffrn_reflns_av_unetI/netI     0.0456
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            14098
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.368
_diffrn_reflns_theta_min         2.553
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.420
_exptl_absorpt_correction_T_max  0.892
_exptl_absorpt_correction_T_min  0.762
_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 purple'
_exptl_crystal_density_diffrn    1.733
_exptl_crystal_description       block
_exptl_crystal_F_000             2775
_exptl_crystal_size_max          0.387
_exptl_crystal_size_mid          0.267
_exptl_crystal_size_min          0.109
_refine_diff_density_max         1.564
_refine_diff_density_min         -0.720
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     464
_refine_ls_number_reflns         5353
_refine_ls_number_restraints     158
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0647
_refine_ls_R_factor_gt           0.0519
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0951P)^2^+12.2022P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1478
_refine_ls_wR_factor_ref         0.1615
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4336
_reflns_number_total             5353
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01356_si_002.cif
_cod_data_source_block           1891347(2-CoxNi4-x-BF4final)
_cod_original_cell_volume        5242.3(6)
_cod_original_formula_sum        'C48 H46 B2 Co2.30 F8 N8 Ni1.70 O14'
_cod_database_code               4127525
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C48 H46 B2 Co4 F8 N8 O14'
_shelx_estimated_absorpt_t_max   0.861
_shelx_estimated_absorpt_t_min   0.610
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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, All O(H) groups
2. Shared sites
{Co2, Ni2}
{Co1, Ni1}
3. Restrained distances
 O7-H7B
 0.84 with sigma of 0.02
 O5-C23A \\sim O5-C23B
 with sigma of 0.002
 O6A-C23A \\sim O6B-C23B
 with sigma of 0.002
 C24B-C23B \\sim C23A-C24A
 with sigma of 0.002
 F2A-B1A \\sim F1A-B1A \\sim F3A-B1A \\sim F4A-B1A \\sim F4B-B1B \\sim F1B-B1B
\\sim F3B-B1B \\sim F2B-B1B
 with sigma of 0.002
4. Uiso/Uaniso restraints and constraints
F1A \\sim F1B \\sim F2A \\sim F2B \\sim F3A \\sim F3B \\sim F4A \\sim F4B:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.005
Uanis(Co2) = Uanis(Ni2)
Uanis(Co1) = Uanis(Ni1)
5. Rigid body (RIGU) restrains
 O5, O6A, O6B, C23A, C23B, C24A, C24B
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
 F1A, F1B, F2A, F2B, F3A, F3B, F4A, F4B, B1A, B1B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=Sof(B1B)=1-FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(B1A)=FVAR(1)
 Sof(O6A)=Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H24C)=1-FVAR(2)
 Sof(O6B)=Sof(C23B)=Sof(C24B)=Sof(H24D)=Sof(H24E)=Sof(H24F)=FVAR(2)
 Fixed Sof: Co1(0.6) Co2(0.55) Ni1(0.4) Ni2(0.45)
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:
 O3(H3), O4(H4)
;
_shelx_hkl_checksum              74432
_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 1.393
_oxdiff_exptl_absorpt_empirical_full_min 0.742