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_4127536
_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         'C44 H44 N8 Ni4 O12, 6(O), 4(N O3)'
_chemical_formula_sum            'C44 H56 N12 Ni4 O30'
_chemical_formula_weight         1467.84
_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             2018-08-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                91.5430(7)
_cell_angle_beta                 99.0305(8)
_cell_angle_gamma                106.2031(8)
_cell_formula_units_Z            2
_cell_length_a                   11.60874(12)
_cell_length_b                   12.86774(12)
_cell_length_c                   19.73943(15)
_cell_measurement_reflns_used    31068
_cell_measurement_temperature    160.00(10)
_cell_measurement_theta_max      78.0620
_cell_measurement_theta_min      3.5750
_cell_volume                     2788.63(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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 0.997
_diffrn_measured_fraction_theta_max 0.983
_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    -66.00  20.00   0.50    1.00    --  -51.91  57.00 120.00  172
  2  \w    -74.00  21.00   0.50    1.00    --  -51.91  77.00 -90.00  190
  3  \w    -94.00  -5.00   0.50    4.00    --  -84.25  15.00   0.00  178
  4  \w   -106.00 -11.00   0.50    4.00    --  -84.25  77.00  60.00  190
  5  \w   -124.00 -38.00   0.50    1.00    --  -51.91 -57.00 150.00  172
  6  \w   -127.00 -82.00   0.50    1.00    --  -51.91 -99.00  30.00   90
  7  \w   -126.00 -70.00   0.50    1.00    --  -51.91-125.00  60.00  112
  8  \w   -125.00 -30.00   0.50    1.00    --  -51.91 -77.00   0.00  190
  9  \w   -126.00 -70.00   0.50    1.00    --  -51.91-125.00-120.00  112
 10  \w     28.00  69.00   0.50    4.00    --  105.75 -30.00  30.00   82
 11  \w     53.00 109.00   0.50    4.00    --  105.75 -15.00  30.00  112
 12  \w     63.00 126.00   0.50    4.00    --  105.75 -77.00  60.00  126
 13  \w     78.00 112.00   0.50    4.00    --  105.75-111.00   0.00   68
 14  \w     75.00 110.00   0.50    4.00    --  105.75-111.00  90.00   70
 15  \w     63.00  90.00   0.50    4.00    --  105.75-127.00 154.00   54
 16  \w     51.00 112.00   0.50    4.00    --  105.75-111.00 150.00  122
 17  \w     45.00  91.00   0.50    4.00    --  105.75 -61.00   0.00   92
 18  \w     60.00 109.00   0.50    4.00    --  105.75 -94.00   0.00   98
 19  \w     93.00 121.00   0.50    4.00    --  105.75 -77.00 -90.00   56
 20  \w     80.00 112.00   0.50    4.00    --  105.75-111.00 -90.00   64
 21  \w     88.00 124.00   0.50    4.00    --  105.75 -77.00-180.00   72
 22  \w     87.00 112.00   0.50    4.00    --  105.75-111.00-180.00   50
 23  \w     59.00 105.00   0.50    4.00    --  105.75 -94.00 -90.00   92
 24  \w     49.00  77.00   0.50    4.00    --  105.75 -45.00   0.00   56
 25  \w     39.00  77.00   0.50    4.00    --  105.75 -45.00 -60.00   76
 26  \w     33.00 104.00   0.50    4.00    --  105.75 -94.00-120.00  142
 27  \w     36.00  97.00   0.50    4.00    --  105.75 -61.00-120.00  122
 28  \w     46.00 114.00   0.50    4.00    --  105.75 -15.00-180.00  136
 29  \w     96.00 177.00   0.50    4.00    --  105.75  61.00-180.00  162
 30  \w    143.00 175.00   0.50    4.00    --  105.75 111.00 -90.00   64
 31  \w    120.00 151.00   0.50    4.00    --  105.75 178.00 -60.00   62
 32  \w     99.00 178.00   0.50    4.00    --  105.75 111.00 -60.00  158
 33  \w    133.00 159.00   0.50    4.00    --  105.75  30.00 -90.00   52
 34  \w     99.00 155.00   0.50    4.00    --  105.75 111.00  30.00  112
 35  \w    149.00 175.00   0.50    4.00    --  105.75  45.00 120.00   52
 36  \w     96.00 159.00   0.50    4.00    --  105.75  77.00  30.00  126
 37  \w     99.00 129.00   0.50    4.00    --  105.75 111.00 -90.00   60
 38  \w     93.00 119.00   0.50    4.00    --  105.75 178.00 -90.00   52
 39  \w     66.00  92.00   0.50    4.00    --  105.75 178.00 -90.00   52
 40  \w     67.00  93.00   0.50    4.00    --  105.75 178.00 -60.00   52
 41  \w     59.00  94.00   0.50    4.00    --  105.75 178.00  30.00   70
 42  \w     59.00 151.00   0.50    4.00    --  105.75 178.00 120.00  184
 43  \w     91.00 148.00   0.50    4.00    --  105.75  77.00   0.00  114
 44  \w    101.00 120.00   0.50    4.00    --  105.75 178.00-180.00   38
;
_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      -0.0065588000
_diffrn_orient_matrix_UB_12      0.0074216000
_diffrn_orient_matrix_UB_13      0.0772586000
_diffrn_orient_matrix_UB_21      0.1241919000
_diffrn_orient_matrix_UB_22      -0.0231565000
_diffrn_orient_matrix_UB_23      0.0170309000
_diffrn_orient_matrix_UB_31      0.0648786000
_diffrn_orient_matrix_UB_32      0.1226356000
_diffrn_orient_matrix_UB_33      0.0045652000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0296
_diffrn_reflns_av_unetI/netI     0.0246
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            47865
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.381
_diffrn_reflns_theta_min         3.587
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.455
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.370
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.748
_exptl_crystal_description       prism
_exptl_crystal_F_000             1512
_exptl_crystal_size_max          0.239
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.033
_refine_diff_density_max         0.956
_refine_diff_density_min         -0.491
_refine_diff_density_rms         0.074
_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     967
_refine_ls_number_reflns         11652
_refine_ls_number_restraints     201
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0442
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0616P)^2^+2.8685P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1129
_refine_ls_wR_factor_ref         0.1162
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10484
_reflns_number_total             11652
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01356_si_002.cif
_cod_data_source_block           1891360(2(gem-aqua)-Ni4-NO3final)
_cod_database_code               4127536
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C88 H88 N24 Ni8 O60'
_shelx_estimated_absorpt_t_max   0.923
_shelx_estimated_absorpt_t_min   0.592
_reflns_odcompleteness_completeness 98.31
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     77.17
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 O9-H9B
 0.85 with sigma of 0.02
 O11-H11B
 0.85 with sigma of 0.02
 O25A-O27A
 2.15 with sigma of 0.005
 O26A-O25A
 2.15 with sigma of 0.005
 O27A-O26A
 2.15 with sigma of 0.005
 O29B-O30B
 2.15 with sigma of 0.005
 O28A-O30A
 2.15 with sigma of 0.005
 O34-O35
 2.15 with sigma of 0.005
 O34-O36
 2.15 with sigma of 0.005
 O35-O36
 2.15 with sigma of 0.005
 O31-O33
 2.15 with sigma of 0.005
 O31-O32
 2.15 with sigma of 0.005
 O32-O33
 2.15 with sigma of 0.005
 O29A-O30A
 2.15 with sigma of 0.005
 O28A-O29A
 2.15 with sigma of 0.005
 O28B-O30B
 2.15 with sigma of 0.005
 O28B-O29B
 2.15 with sigma of 0.005
 O26B-O25B
 2.15 with sigma of 0.005
 O27B-O25B
 2.15 with sigma of 0.005
 O26B-O27B
 2.15 with sigma of 0.005
 O28B-N11B \\sim O28A-N11A \\sim O29A-N11A \\sim O29B-N11B \\sim O30B-N11B
\\sim O30A-N11A
 with sigma of 0.005
 O25A-N10 \\sim O25B-N10 \\sim O26A-N10 \\sim O27A-N10 \\sim O27B-N10
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
O34 \\sim O35 \\sim O36: within 2A with sigma of 0.002 and sigma for terminal
atoms of 0.08
O28A \\sim O28B \\sim O29A \\sim O29B \\sim O30A \\sim O30B: within 2A with
sigma of 0.002 and sigma for terminal atoms of 0.08
O25A \\sim O25B \\sim O26A \\sim O26B \\sim O27A \\sim O27B: within 2A with
sigma of 0.002 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 O34, O35, O36, N13
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 O28A, O28B, O29A, O29B, O30A, O30B, N11A, N11B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 O25A, O25B, O26A, O26B, O27A, O27B, N10
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O25B)=Sof(O26B)=Sof(O27B)=1-FVAR(1)
 Sof(O25A)=Sof(O26A)=Sof(O27A)=FVAR(1)
 Sof(O28B)=Sof(O29B)=Sof(O30B)=Sof(N11B)=1-FVAR(2)
 Sof(O28A)=Sof(O29A)=Sof(O30A)=Sof(N11A)=FVAR(2)
 Fixed Sof: O16(0.5) O17(0.5) O18(0.5) O19(0.5) O20(0.5) O21(0.5) O31(0.5)
 O32(0.5) O33(0.5) O34(0.5) O35(0.5) O36(0.5) N12(0.5) N13(0.5)
6.a Rotating group:
 O9(H9A), O10(H10A,H10B), O11(H11A), O12(H12A,H12B)
6.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)
6.c Idealised tetrahedral OH refined as rotating group:
 O6(H6), O7(H7), O8(H8)
;
_shelx_hkl_checksum              18459
_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 1.221
_oxdiff_exptl_absorpt_empirical_full_min 0.789