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_4127528
_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 Co1.64 N8 Ni2.36 O14, 2(F6 P)'
_chemical_formula_sum            'C48 H46 Co1.66 F12 N8 Ni2.34 O14 P2'
_chemical_formula_weight         1484.07
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -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                88.324(2)
_cell_angle_beta                 73.699(2)
_cell_angle_gamma                64.454(3)
_cell_formula_units_Z            2
_cell_length_a                   12.2745(3)
_cell_length_b                   13.3722(4)
_cell_length_c                   19.5727(4)
_cell_measurement_reflns_used    23362
_cell_measurement_temperature    183.00(10)
_cell_measurement_theta_max      31.0840
_cell_measurement_theta_min      3.3350
_cell_volume                     2766.35(15)
_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      183.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_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    -12.00  80.00   0.50   40.00    --    6.20  57.00-120.00  184
  2  \w     38.00  87.00   0.50   40.00    --    6.20 178.00  30.00   98
  3  \w     38.00  87.00   0.50   40.00    --    6.20 178.00  60.00   98
  4  \w    -19.00  81.00   0.50   40.00    --    6.20  77.00  90.00  200
  5  \w    -25.00  67.00   0.50   40.00    --   -7.14  57.00  60.00  184
  6  \w    -25.00  55.00   0.50   40.00    --   -7.14  57.00   0.00  160
  7  \w    -35.00  25.00   0.50   40.00    --   -7.14  84.00 177.00  120
  8  \w    -87.00  10.00   0.50   40.00    --   -7.14 -38.00 -30.00  194
  9  \w    -27.00  42.00   0.50   40.00    --    6.20 -99.00 -60.00  138
 10  \w    -27.00  29.00   0.50   40.00    --   -7.14 -99.00-120.00  112
 11  \w    -27.00  42.00   0.50   40.00    --    6.20 -99.00 150.00  138
;
_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      -0.0385676000
_diffrn_orient_matrix_UB_12      -0.0270557000
_diffrn_orient_matrix_UB_13      0.0153385000
_diffrn_orient_matrix_UB_21      0.0325075000
_diffrn_orient_matrix_UB_22      -0.0414928000
_diffrn_orient_matrix_UB_23      -0.0298783000
_diffrn_orient_matrix_UB_31      0.0445650000
_diffrn_orient_matrix_UB_32      -0.0326291000
_diffrn_orient_matrix_UB_33      0.0179677000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0179
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            20297
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.356
_diffrn_reflns_theta_min         2.180
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.445
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77428
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.9b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.782
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             1501
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.121
_refine_diff_density_max         1.455
_refine_diff_density_min         -1.028
_refine_diff_density_rms         0.134
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     902
_refine_ls_number_reflns         20297
_refine_ls_number_restraints     443
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.0734
_refine_ls_R_factor_gt           0.0601
_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^)+(0.1205P)^2^+3.0868P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1749
_refine_ls_wR_factor_ref         0.1896
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16164
_reflns_number_total             20297
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01356_si_002.cif
_cod_data_source_block           1891350(2-CoxNi4-x-PF6_twin1_hklf5_02)
_cod_original_cell_volume        2766.35(14)
_cod_database_code               4127528
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C48 F12 N8 Co4 O14 P2'
_shelx_estimated_absorpt_t_max   0.845
_shelx_estimated_absorpt_t_min   0.771
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.8336(7)
 0.1664(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Shared sites
{Co3, Ni3}
{Co4, Ni4}
{Co1, Ni1}
{Co2, Ni2}
4. Restrained distances
 F10A-F8A
 2.1 with sigma of 0.04
 F9B-F12B
 2.1 with sigma of 0.04
 F11B-F12B
 2.1 with sigma of 0.04
 F7B-F12B
 2.1 with sigma of 0.04
 F10B-F11B
 2.1 with sigma of 0.04
 F7A-F12A
 2.1 with sigma of 0.04
 F12A-F8A
 2.1 with sigma of 0.04
 F12A-F9A
 2.1 with sigma of 0.04
 F7A-F9A
 2.1 with sigma of 0.04
 F11A-F12A
 2.1 with sigma of 0.04
 F12A-F7A
 2.2 with sigma of 0.04
 P1-F4A \\sim P1-F4B \\sim P1-F5A \\sim P1-F5B \\sim P1-F6A \\sim P1-F3B \\sim
P1-F1 \\sim P1-F2 \\sim P1-F3A
 \\sim P1-F6B
 with sigma of 0.005
 P2-F9B \\sim P2-F9A \\sim P2-F7B \\sim P2-F7A \\sim P2-F10A \\sim P2-F10B
\\sim P2-F8B \\sim P2-F11A \\sim P2-
 F12B \\sim P2-F12A \\sim P2-F11B \\sim P2-F8A
 with sigma of 0.005
5. Uiso/Uaniso restraints and constraints
F7A \\sim F7B \\sim F8A \\sim F8B \\sim F9A \\sim F9B \\sim F10A \\sim F10B
\\sim F11A \\sim F11B \\sim F12A \\sim F12B: within 1.9A with sigma of 0.006
and sigma for terminal atoms of 0.006
Uanis(Co3) = Uanis(Ni3)
Uanis(Co4) = Uanis(Ni4)
Uanis(Co1) = Uanis(Ni1)
Uanis(Co2) = Uanis(Ni2)
6. Rigid body (RIGU) restrains
 P1, F1, F2, F3A, F3B, F4A, F4B, F5A, F5B, F6A, F6B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 P2, F7A, F7B, F8A, F8B, F9A, F9B, F10A, F10B, F11A, F11B, F12A, F12B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
7. Others
 Sof(F3B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(1)
 Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(1)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12B)=1-FVAR(2)
 Sof(F7B)=Sof(F8B)=Sof(F9B)=Sof(F10B)=Sof(F11B)=Sof(F12A)=FVAR(2)
 Fixed Sof: Co1(0.44) Co2(0.44) Co3(0.38) Co4(0.38) Ni1(0.56) Ni2(0.56)
 Ni3(0.62) Ni4(0.62)
8.a Rotating group:
 O11(H11A,H11B), O14(H14A,H14B)
8.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)
8.c Idealised Me refined as rotating group:
 C46(H46A,H46B,H46C), C48(H48A,H48B,H48C)
8.d Idealised tetrahedral OH refined as rotating group:
 O5(H5), O6(H6), O7(H7), O8(H8)
;
_shelx_hkl_checksum              35798
_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 1.517
_oxdiff_exptl_absorpt_empirical_full_min 0.641
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by -179.9887\% 
 around [0.82 0.41 0.41] (reciprocal) or [1.00 0.03 0.02] (direct)
;