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_4127535
_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 N8 Ni4 O14, 2(N O3), 1.42(O)'
_chemical_formula_sum            'C48 H47.6 N10 Ni4 O21.42'
_chemical_formula_weight         1342.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/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                 116.4557(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.5327(3)
_cell_length_b                   11.87693(11)
_cell_length_c                   21.4511(2)
_cell_measurement_reflns_used    15964
_cell_measurement_temperature    160.00(10)
_cell_measurement_theta_max      76.9440
_cell_measurement_theta_min      4.2890
_cell_volume                     5139.55(11)
_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 1.000
_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    -61.00  25.00   0.50    1.00    --  -51.66  38.00 150.00  172
  2  \w    -61.00  25.00   0.50    1.00    --  -51.66  38.00  30.00  172
  3  \w    -65.00  21.00   0.50    1.00    --  -51.66  56.00-122.00  172
  4  \w     43.00 129.00   0.50    1.00    --   51.66  38.00-180.00  172
  5  \w     96.00 178.00   0.50    4.00    --  105.75  15.00-180.00  164
  6  \w    148.00 174.00   0.50    4.00    --  105.75  48.00 -55.50   52
  7  \w     94.00 178.00   0.50    4.00    --  105.75  51.00  72.21  168
  8  \w     95.00 178.00   0.50    4.00    --  105.75  48.00 109.36  166
  9  \w     99.00 177.00   0.50    4.00    --  105.75  51.00 124.95  156
 10  \w     94.00 178.00   0.50    4.00    --  105.75  45.00   0.00  168
 11  \w     97.00 178.00   0.50    4.00    --  105.75  30.00-120.00  162
 12  \w     97.00 178.00   0.50    4.00    --  105.75  30.00-180.00  162
 13  \w     64.00  91.00   0.50    4.00    --  105.75 -56.00 -65.45   54
 14  \w     36.00  72.00   0.50    4.00    --  105.75 -49.00 -14.82   72
 15  \w     33.00  93.00   0.50    4.00    --  105.75 -56.00 -31.23  120
 16  \w     28.00  53.00   0.50    4.00    --  105.75 -30.00-150.00   50
 17  \w     33.00  70.00   0.50    4.00    --  105.75 -45.00-120.00   74
 18  \w     30.00  66.00   0.50    4.00    --  105.75 -44.00-100.44   72
 19  \w     34.00  65.00   0.50    4.00    --  105.75 -52.00 -64.74   62
 20  \w     30.00  57.00   0.50    4.00    --  105.75 -30.00   0.00   54
 21  \w     32.00  78.00   0.50    4.00    --  105.75 -53.00  49.09   92
 22  \w     48.00  76.00   0.50    4.00    --  105.75 -45.00  90.00   56
 23  \w     43.00  82.00   0.50    4.00    --  105.75 -52.00 147.57   78
 24  \w     38.00  76.00   0.50    4.00    --  105.75 -45.00 164.58   76
 25  \w     31.00  79.00   0.50    4.00    --  105.75 -47.00 128.08   96
 26  \w     30.00  59.00   0.50    4.00    --  105.75 -30.00 150.00   58
 27  \w     30.00  69.00   0.50    4.00    --  105.75 -30.00 -90.00   78
 28  \w    -61.00  28.00   0.50    1.00    --  -51.66  19.00 150.00  178
 29  \w     39.00  65.00   0.50    4.00    --  105.75 -45.00 -90.00   52
 30  \w    111.00 137.00   0.50    4.00    --  105.75  30.00-150.00   52
 31  \w     34.00  60.00   0.50    4.00    --  105.75 -15.00-150.00   52
;
_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      0.0500428000
_diffrn_orient_matrix_UB_12      0.0900554000
_diffrn_orient_matrix_UB_13      0.0447238000
_diffrn_orient_matrix_UB_21      -0.0121278000
_diffrn_orient_matrix_UB_22      -0.0334126000
_diffrn_orient_matrix_UB_23      0.0627804000
_diffrn_orient_matrix_UB_31      0.0563883000
_diffrn_orient_matrix_UB_32      -0.0871809000
_diffrn_orient_matrix_UB_33      0.0221626000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            30292
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.382
_diffrn_reflns_theta_min         4.320
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.462
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.560
_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            'clear greenish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.735
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             2756
_exptl_crystal_size_max          0.167
_exptl_crystal_size_mid          0.126
_exptl_crystal_size_min          0.068
_refine_diff_density_max         0.700
_refine_diff_density_min         -0.457
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     462
_refine_ls_number_reflns         5419
_refine_ls_number_restraints     221
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0508
_refine_ls_R_factor_gt           0.0463
_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^)+(0.0733P)^2^+11.8044P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1256
_refine_ls_wR_factor_ref         0.1293
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4880
_reflns_number_total             5419
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01356_si_002.cif
_cod_data_source_block           1891359(2-Ni4-NO3final)
_cod_original_cell_volume        5139.54(11)
_cod_original_formula_sum        'C48 H47.60 N10 Ni4 O21.42'
_cod_database_code               4127535
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C48 H46 N10 Ni4 O20'
_reflns_odcompleteness_completeness 99.25
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     77.17
_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
 O6B-C24B
 2.35 with sigma of 0.005
 O6A-C24A
 2.35 with sigma of 0.005
 O5A-C24A
 2.35 with sigma of 0.005
 O5B-C24B
 2.35 with sigma of 0.005
 O9A-O10A
 2.16 with sigma of 0.005
 O8A-O10A
 2.16 with sigma of 0.005
 O9A-O8A
 2.16 with sigma of 0.005
 O8B-O10B
 2.16 with sigma of 0.005
 O10B-O9B
 2.16 with sigma of 0.005
 O8B-O9B
 2.16 with sigma of 0.005
 Ni1-O5A \\sim Ni1-O5B
 with sigma of 0.005
 O5A-C23A \\sim O5B-C23B
 with sigma of 0.005
 O6B-C23B \\sim O6A-C23A
 with sigma of 0.005
 C24B-C23B \\sim C24A-C23A
 with sigma of 0.005
 O9A-N5A \\sim O10A-N5A \\sim O8A-N5A \\sim O8B-N5B \\sim O10B-N5B \\sim O9B-N5B
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
O5A \\sim O5B \\sim O6A \\sim O6B \\sim C23A \\sim C23B \\sim C24A \\sim C24B:
within 2A with sigma of 0.002 and sigma for terminal atoms of 0.08
O8A \\sim O8B \\sim O9A \\sim O9B \\sim O10A \\sim O10B: within 2A with sigma
of 0.002 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 O5A, O5B, O6A, O6B, C23A, C23B, C24A, C24B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 O8A, O8B, O9A, O9B, O10A, O10B, N5A, N5B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O8B)=Sof(O9B)=Sof(O10B)=Sof(N5B)=1-FVAR(1)
 Sof(O8A)=Sof(O9A)=Sof(O10)=Sof(O10A)=Sof(N5A)=FVAR(1)
 Sof(O5B)=Sof(O6B)=Sof(C23B)=Sof(C24B)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(2)
 Sof(O5A)=Sof(O6A)=Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(2)
6.a Rotating group:
 O7(H7A,H7B)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3A), C4(H4A), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C13(H13), C14(H14), C15(H15), C19(H19), C20(H20), C21(H21), C22(H22)
6.c Idealised Me refined as rotating group:
 C24A(H24A,H24B,H24C), C24B(H24D,H24E,H24F)
6.d Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4)
;
_shelx_hkl_checksum              16826
_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 1.399
_oxdiff_exptl_absorpt_empirical_full_min 0.724