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_4127529
_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 Co1.52 N8 Ni2.48 O14, B F4, 3(H2 O), 8(O)'
_chemical_formula_sum            'C50 H67 B Co1.54 F4 N8 Ni2.46 O25'
_chemical_formula_weight         1502.10
_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             2019-01-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.719(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.9719(3)
_cell_length_b                   24.6331(6)
_cell_length_c                   21.5467(5)
_cell_measurement_reflns_used    24623
_cell_measurement_temperature    160.00(10)
_cell_measurement_theta_max      30.4500
_cell_measurement_theta_min      2.4180
_cell_volume                     6221.8(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      160.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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  83.00   0.50   90.00    --   11.61  57.00  90.00  160
  2  \w     64.00  90.00   0.50   90.00    --   11.61 178.00   0.00   52
  3  \w    -55.00  65.00   0.50   90.00    --   11.61   0.00-120.00  240
  4  \w    -10.00  16.00   0.50   90.00    --  -12.54 -99.00   0.00   52
  5  \w    -27.00   4.00   0.50   90.00    --  -12.54 -99.00 -30.00   62
  6  \w    -20.00   9.00   0.50   90.00    --  -12.54 -99.00 -60.00   58
  7  \w    -27.00   1.00   0.50   90.00    --  -12.54 -99.00-180.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0126481000
_diffrn_orient_matrix_UB_12      -0.0203295000
_diffrn_orient_matrix_UB_13      -0.0237057000
_diffrn_orient_matrix_UB_21      -0.0564289000
_diffrn_orient_matrix_UB_22      0.0101305000
_diffrn_orient_matrix_UB_23      -0.0089705000
_diffrn_orient_matrix_UB_31      0.0178001000
_diffrn_orient_matrix_UB_32      0.0177119000
_diffrn_orient_matrix_UB_33      -0.0220743000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0311
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            68983
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.507
_diffrn_reflns_theta_min         2.100
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.235
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.699
_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            'clear dark violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.604
_exptl_crystal_description       prism
_exptl_crystal_F_000             3098
_exptl_crystal_size_max          0.297
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.056
_refine_diff_density_max         1.630
_refine_diff_density_min         -1.065
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     940
_refine_ls_number_reflns         18930
_refine_ls_number_restraints     142
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0518
_refine_ls_R_factor_gt           0.0408
_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^)+(0.0665P)^2^+5.5759P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1168
_refine_ls_wR_factor_ref         0.1229
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15671
_reflns_number_total             18930
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01356_si_002.cif
_cod_data_source_block           1891352(2-u-oac-coxni4-x-bf4final)
_cod_database_code               4127529
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H72 B F4 N8 Co4 O28'
_reflns_odcompleteness_completeness 99.74
_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
{Co4, Ni4}
{Co3, Ni3}
{Co1, Ni1}
{Co2, Ni2}
3. Restrained distances
 F4A-F2A
 2.2 with sigma of 0.005
 F4A-F1A
 2.25 with sigma of 0.01
 F1A-F2A
 2.25 with sigma of 0.005
 F4A-F3A
 2.25 with sigma of 0.002
 F3A-F2A
 2.25 with sigma of 0.005
 F1A-F3A
 2.24 with sigma of 0.005
 F4B-F3B
 2.25 with sigma of 0.005
 F2B-F3B
 2.25 with sigma of 0.005
 F1B-F4B
 2.25 with sigma of 0.005
 F2B-F1B
 2.25 with sigma of 0.005
 F1B-F3B
 2.25 with sigma of 0.02
 F2A-B1 \\sim F2B-B1 \\sim F3A-B1 \\sim F3B-B1 \\sim F1A-B1 \\sim F1B-B1 \\sim
F4A-B1 \\sim F4B-B1
 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(Co4) = Uanis(Ni4)
Uanis(Co3) = Uanis(Ni3)
Uanis(Co1) = Uanis(Ni1)
Uanis(Co2) = Uanis(Ni2)
5. Rigid body (RIGU) restrains
 F1A, F1B, F2A, F2B, F3A, F3B, F4A, F4B, B1
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
6. Others
 1*[Sof(O23C)]+1*[Sof(O23B)]+1*[Sof(O23A)]=1 with esd of 0.00001
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=1-FVAR(4)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=FVAR(4)
 Sof(O21B)=Sof(O21D)=1-FVAR(5)
 Sof(O21A)=Sof(O21C)=FVAR(5)
 Fixed Sof: Co1(0.44) Co2(0.44) Co3(0.32) Co4(0.32) Ni1(0.56) Ni2(0.56)
 Ni3(0.68) Ni4(0.68)
7.a Free rotating group:
 O15(H15a,H15b), O19(H19a,H19b), O24(H24a,H24b)
7.b Aromatic/amide H refined with riding coordinates:
 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), 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              36728
_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 1.694
_oxdiff_exptl_absorpt_empirical_full_min 0.602