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_4127532
_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 Co1.9 N8 Ni2.1 O14, Cl O4, 11(H2 O)'
_chemical_formula_sum            'C50 H67 Cl Co1.9 N8 Ni2.1 O29'
_chemical_formula_weight         1514.82
_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                 100.1181(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.0492(2)
_cell_length_b                   24.3545(4)
_cell_length_c                   21.4569(4)
_cell_measurement_reflns_used    52283
_cell_measurement_temperature    160.01(10)
_cell_measurement_theta_max      29.5400
_cell_measurement_theta_min      2.2590
_cell_volume                     6198.65(19)
_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      160.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     -8.00  89.00   0.50   65.00    --    9.59  38.00 -30.00  194
  2  \w     -8.00  89.00   0.50   65.00    --    9.59  38.00  90.00  194
  3  \w     38.00  90.00   0.50   65.00    --    9.59 178.00 120.00  104
  4  \w     38.00  90.00   0.50   65.00    --    9.59 178.00  30.00  104
  5  \w     -9.00  83.00   0.50   65.00    --    9.59  57.00-150.00  184
  6  \w    -27.00  25.00   0.50   65.00    --  -10.52 -99.00  30.00  104
  7  \w    -27.00  22.00   0.50   65.00    --    9.59 -99.00 -90.00   98
  8  \w     35.00  91.00   0.50   65.00    --    9.59-178.00-120.00  112
  9  \w    -28.00  69.00   0.50   65.00    --  -10.52  38.00-180.00  194
;
_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      0.0194907000
_diffrn_orient_matrix_UB_12      0.0227278000
_diffrn_orient_matrix_UB_13      -0.0157359000
_diffrn_orient_matrix_UB_21      0.0160215000
_diffrn_orient_matrix_UB_22      0.0135435000
_diffrn_orient_matrix_UB_23      0.0294753000
_diffrn_orient_matrix_UB_31      0.0541843000
_diffrn_orient_matrix_UB_32      -0.0121776000
_diffrn_orient_matrix_UB_33      0.0034342000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0324
_diffrn_reflns_av_unetI/netI     0.0180
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            128647
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.575
_diffrn_reflns_theta_min         1.910
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.265
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.406
_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    1.623
_exptl_crystal_description       prism
_exptl_crystal_F_000             3128
_exptl_crystal_size_max          0.479
_exptl_crystal_size_mid          0.108
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.804
_refine_diff_density_min         -0.835
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     925
_refine_ls_number_reflns         17391
_refine_ls_number_restraints     116
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.0422
_refine_ls_R_factor_gt           0.0370
_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^)+(0.0418P)^2^+12.4898P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1052
_refine_ls_wR_factor_ref         0.1076
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15475
_reflns_number_total             17391
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01356_si_002.cif
_cod_data_source_block           1891355(2-u-OAc-CoxNi4-x-ClO4final)
_cod_original_cell_volume        6198.63(19)
_cod_original_formula_sum        'C50 H67 Cl Co1.90 N8 Ni2.10 O29'
_cod_database_code               4127532
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H67 Cl N8 Ni4 O29'
_shelx_estimated_absorpt_t_max   0.906
_shelx_estimated_absorpt_t_min   0.582
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     29.51
_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
{Ni1, Co1}
{Ni2, Co2}
{Ni4, Co4}
{Ni3, Co3}
3. Restrained distances
 O27-O29
 2.3 with sigma of 0.008
 O27A-O29A
 2.3 with sigma of 0.008
 O29-O26
 2.3 with sigma of 0.01
 O29A-O26A
 2.3 with sigma of 0.01
 O27-O28
 2.3 with sigma of 0.01
 O26A-O28
 2.3 with sigma of 0.006
 O28-O29
 2.3 with sigma of 0.01
 O26-O28
 2.3 with sigma of 0.006
 O26-O27
 2.3 with sigma of 0.01
 Cl1-O29A \\sim Cl1-O29 \\sim Cl1-O27A \\sim Cl1-O27 \\sim Cl1-O28 \\sim
Cl1-O26A \\sim Cl1-O26
 with sigma of 0.002
4. Uiso/Uaniso restraints and constraints
O26 \\sim O26A \\sim O27 \\sim O27A \\sim O29 \\sim O29A: within 2A with sigma
of 0.005 and sigma for terminal atoms of 0.005
Uanis(Ni1) = Uanis(Co1)
Uanis(Ni2) = Uanis(Co2)
Uanis(Ni4) = Uanis(Co4)
Uanis(Ni3) = Uanis(Co3)
5. Rigid body (RIGU) restrains
 Cl1, O26, O26A, O27, O27A, O28, O29, O29A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O26A)=Sof(O27A)=Sof(O29A)=1-FVAR(1)
 Sof(O26)=Sof(O27)=Sof(O29)=FVAR(1)
 Fixed Sof: Co1(0.5) Co2(0.5) Co3(0.45) Co4(0.45) Ni1(0.5) Ni2(0.5) Ni3(0.55)
 Ni4(0.55)
7.a Free rotating group:
 O15(H15A,H15B), O16(H16A,H16B), O17(H17A,H17B), O18(H18A,H18B), O19(H19A,
 H19B), O20(H20A,H20B), O21(H21A,H21B), O22(H22A), O23(H23A,H23B), O24(H24A,
 H24B), O25(H25A,H25B)
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              77936
_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 1.613
_oxdiff_exptl_absorpt_empirical_full_min 0.732