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_4127543
_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 N8 Ni4 O14, F6 P, 6(H2 O), 5(O)'
_chemical_formula_sum            'C50 H67 F6 N8 Ni4 O25 P'
_chemical_formula_weight         1559.92
_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                 100.613(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.0535(3)
_cell_length_b                   24.6786(6)
_cell_length_c                   21.4781(5)
_cell_measurement_reflns_used    39589
_cell_measurement_temperature    160.00(10)
_cell_measurement_theta_max      28.4410
_cell_measurement_theta_min      2.2600
_cell_volume                     6279.7(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 0.999
_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     -7.00  83.00   0.50   83.00    --    5.52  38.00   0.00  180
  2  \w     38.00  85.00   0.50   83.00    --    5.52 178.00 120.00   94
  3  \w    -19.00  60.00   0.50   83.00    --   -6.45  38.00 -60.00  158
  4  \w    -27.00  39.00   0.50   83.00    --    5.52 -99.00-180.00  132
  5  \w    -27.00  39.00   0.50   83.00    --    5.52 -99.00-120.00  132
  6  \w    -26.00  15.00   0.50   83.00    --   -6.45 -99.00-150.00   82
;
_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      -0.0057346000
_diffrn_orient_matrix_UB_12      0.0062287000
_diffrn_orient_matrix_UB_13      -0.0326877000
_diffrn_orient_matrix_UB_21      -0.0051367000
_diffrn_orient_matrix_UB_22      0.0278870000
_diffrn_orient_matrix_UB_23      0.0069014000
_diffrn_orient_matrix_UB_31      0.0593722000
_diffrn_orient_matrix_UB_32      0.0030237000
_diffrn_orient_matrix_UB_33      0.0037053000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0570
_diffrn_reflns_av_unetI/netI     0.0351
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            81161
_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         28.282
_diffrn_reflns_theta_min         1.989
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.311
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.642
_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 greenish green'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.650
_exptl_crystal_description       prism
_exptl_crystal_F_000             3216
_exptl_crystal_size_max          0.378
_exptl_crystal_size_mid          0.073
_exptl_crystal_size_min          0.065
_refine_diff_density_max         1.630
_refine_diff_density_min         -1.857
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.124
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     943
_refine_ls_number_reflns         15562
_refine_ls_number_restraints     309
_refine_ls_restrained_S_all      1.160
_refine_ls_R_factor_all          0.0679
_refine_ls_R_factor_gt           0.0596
_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^)+(0.0481P)^2^+30.6263P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1497
_refine_ls_wR_factor_ref         0.1532
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13500
_reflns_number_total             15562
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01356_si_002.cif
_cod_data_source_block           1891384(2-u-OAc-Ni4-PF6final)
_cod_original_cell_volume        6279.6(3)
_cod_database_code               4127543
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H59 F6 N8 Ni4 O25 P'
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_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. Restrained distances
 F4A-F1A
 2.2 with sigma of 0.008
 F2A-F4A
 2.2 with sigma of 0.008
 F6A-F2A
 2.2 with sigma of 0.008
 F6A-F1A
 2.2 with sigma of 0.008
 F2B-F5B
 2.2 with sigma of 0.008
 F5B-F1B
 2.2 with sigma of 0.008
 F5B-F6B
 2.2 with sigma of 0.008
 F3B-F6B
 2.2 with sigma of 0.008
 F3B-F1B
 2.2 with sigma of 0.006
 F4B-F5B
 2.2 with sigma of 0.02
 F3B-F4B
 2.2 with sigma of 0.02
 F2B-F4B
 2.2 with sigma of 0.008
 F4B-F1B
 2.2 with sigma of 0.02
 F6B-F2B
 2.2 with sigma of 0.02
 F3B-F2B
 2.2 with sigma of 0.008
 F1B-F4B
 2.2 with sigma of 0.008
 F6A-F5A
 2.2 with sigma of 0.008
 F3A-F6A
 2.2 with sigma of 0.008
 F4A-F5A
 2.2 with sigma of 0.008
 F2A-F3A
 2.2 with sigma of 0.008
 F3A-F1A
 2.2 with sigma of 0.008
 P1-F2A \\sim P1-F2B \\sim P1-F3B \\sim P1-F3A \\sim P1-F1B \\sim P1-F1A \\sim
P1-F4B \\sim P1-F4A \\sim P1-
 F6A \\sim P1-F6B \\sim P1-F5A \\sim P1-F5B
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
F2A \\sim F2B \\sim F5A \\sim F5B \\sim F6B \\sim F6A \\sim F1B \\sim F1A \\sim
F4A \\sim F4B \\sim F3B \\sim F3A: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.005
4. Rigid body (RIGU) restrains
 F2A, F2B, F3B, F3A, F6A, F6B, F5A, F5B, F1B, F1A, F4B, P1, F4A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F5B)=Sof(F6B)=Sof(F4A)=Sof(F3B)=Sof(F2B)=Sof(F1B)=1-FVAR(1)
 Sof(F6A)=Sof(F1A)=Sof(F4B)=Sof(F2A)=Sof(F3A)=Sof(F5A)=FVAR(1)
6.a Free rotating group:
 O20(H20A,H20B), O15(H15A,H15B), O21(H21A,H21B), O25(H25A,H25B), O17(H17A,
 H17B), O23(H23A,H23B)
6.b Aromatic/amide H refined with riding coordinates:
 C30(H30), C15(H15), C35(H35), C34(H34), C33(H33), C9(H9), C24(H24), C8(H8A),
 C36(H36), C12(H12), C3(H3), C10(H10), C41(H41), C13(H13), C44(H44), C25(H25),
 C26(H26), C2(H2), C14(H14), C31(H31), C43(H43), C23(H23), C1(H1), C37(H37),
 C21(H21), C11(H11), C22(H22), C4(H4), C42(H42), C19(H19), C32(H32), C20(H20)
6.c Idealised Me refined as rotating group:
 C50(H50A,H50B,H50C), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C)
6.d Idealised tetrahedral OH refined as rotating group:
 O7(H7), O6(H6), O5(H5), O8(H8)
;
_shelx_hkl_checksum              64000
_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 7.014
_oxdiff_exptl_absorpt_empirical_full_min 0.706