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_4127520
_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 Co4 N8 O12, 6(O), 4(N O3)'
_chemical_formula_sum            'C44 H56 Co4 N12 O30'
_chemical_formula_weight         1468.72
_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                91.1275(17)
_cell_angle_beta                 100.3745(15)
_cell_angle_gamma                106.1227(17)
_cell_formula_units_Z            2
_cell_length_a                   11.7024(2)
_cell_length_b                   12.9555(3)
_cell_length_c                   19.8107(4)
_cell_measurement_reflns_used    36085
_cell_measurement_temperature    159.99(10)
_cell_measurement_theta_max      31.4970
_cell_measurement_theta_min      2.4410
_cell_volume                     2830.48(10)
_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      159.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_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     -5.00  81.00   0.50   40.00    --    4.50  38.00 -30.00  172
  2  \w     -5.00  84.00   0.50   40.00    --    4.50  19.00 -30.00  178
  3  \w     -5.00  28.00   0.50   40.00    --    4.50  38.00-120.00   66
  4  \w    -27.00  37.00   0.50   40.00    --    4.50 -99.00-180.00  128
  5  \w    -27.00  37.00   0.50   40.00    --    4.50 -99.00-150.00  128
  6  \w    -27.00  27.00   0.50   40.00    --   -5.60 -99.00-180.00  108
  7  \w    -27.00  27.00   0.50   40.00    --   -5.60 -99.00 -60.00  108
  8  \w     35.00  84.00   0.50   40.00    --    4.50-178.00  60.00   98
  9  \w    -27.00  37.00   0.50   40.00    --    4.50 -99.00 120.00  128
 10  \w    -78.00   8.00   0.50   40.00    --   -5.60 -57.00 -60.00  172
 11  \w    -84.00   4.00   0.50   40.00    --   -5.60 -19.00   0.00  176
;
_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      -0.0135908000
_diffrn_orient_matrix_UB_12      0.0224916000
_diffrn_orient_matrix_UB_13      0.0294520000
_diffrn_orient_matrix_UB_21      -0.0061957000
_diffrn_orient_matrix_UB_22      0.0455342000
_diffrn_orient_matrix_UB_23      -0.0179973000
_diffrn_orient_matrix_UB_31      -0.0625454000
_diffrn_orient_matrix_UB_32      -0.0261994000
_diffrn_orient_matrix_UB_33      -0.0118660000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0325
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            73069
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.282
_diffrn_reflns_theta_min         2.011
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.257
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.628
_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 pinkish violet'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   pinkish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.723
_exptl_crystal_description       prism
_exptl_crystal_F_000             1504
_exptl_crystal_size_max          0.225
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.048
_refine_diff_density_max         1.937
_refine_diff_density_min         -0.969
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1020
_refine_ls_number_reflns         14052
_refine_ls_number_restraints     388
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0517
_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^)+(0.0917P)^2^+4.4315P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1501
_refine_ls_wR_factor_ref         0.1575
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11854
_reflns_number_total             14052
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01356_si_002.cif
_cod_data_source_block           1891291(2(gem-aqua)-Co4-NO3final)
_cod_original_cell_volume        2830.49(10)
_cod_database_code               4127520
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C48 H49 Co4 N17 O22'
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.765
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 O75A-O77A
 2.15 with sigma of 0.005
 O75-O77
 2.15 with sigma of 0.005
 O77-O76
 2.15 with sigma of 0.005
 O89-O90
 2.15 with sigma of 0.005
 O89-O84
 2.15 with sigma of 0.005
 O90-O84
 2.15 with sigma of 0.005
 O81-O83
 2.15 with sigma of 0.005
 O74-O72
 2.15 with sigma of 0.005
 O73-O74
 2.15 with sigma of 0.005
 O73-O72
 2.15 with sigma of 0.005
 O74A-O73A
 2.15 with sigma of 0.005
 O74A-O72A
 2.15 with sigma of 0.005
 O73A-O72A
 2.15 with sigma of 0.005
 O70-O71
 2.15 with sigma of 0.005
 O69-O71
 2.15 with sigma of 0.005
 O69-O70
 2.15 with sigma of 0.005
 O17-O14
 2.15 with sigma of 0.005
 O20-O14
 2.15 with sigma of 0.005
 O20-O17
 2.15 with sigma of 0.005
 O90-N11 \\sim O89-N11 \\sim O84-N11
 with sigma of 0.005
 O75-N12B \\sim O75A-N12A \\sim O76-N12B \\sim O76A-N12A \\sim O77A-N12A \\sim
O77-N12B
 with sigma of 0.005
 O69-N9 \\sim O17-N9 \\sim O71-N9 \\sim O14-N9 \\sim O70-N9 \\sim O20-N9
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
O75 \\sim O76 \\sim O77 \\sim N12B: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002
O75 \\sim O75A \\sim O76 \\sim O76A \\sim O77 \\sim O77A \\sim N12A \\sim N12B:
within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
O72 \\sim O73 \\sim O74 \\sim N13A: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002
O72 \\sim O72A \\sim O73 \\sim O73A \\sim O74 \\sim O74A \\sim N13A \\sim N13B:
within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
O81 \\sim O82 \\sim O83 \\sim O88 \\sim N10: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002
O84 \\sim O89 \\sim O90 \\sim N11: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002
O20 \\sim O70 \\sim O14 \\sim O71 \\sim O17 \\sim O69: within 2A with sigma of
0.002 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 O69, O20, O70, O14, O71, O17, N9
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O72A)=Sof(O73A)=Sof(O74A)=Sof(N13B)=1-FVAR(1)
 Sof(O72)=Sof(O73)=Sof(O74)=Sof(N13A)=FVAR(1)
 Sof(O75A)=Sof(O76A)=Sof(O77A)=Sof(N12A)=1-FVAR(2)
 Sof(O75)=Sof(O76)=Sof(O77)=Sof(N12B)=FVAR(2)
 Sof(O4)=1-FVAR(3)
 Sof(O80)=FVAR(3)
 Sof(O5)=1-FVAR(4)
 Sof(O87)=FVAR(4)
 Sof(O14)=Sof(O17)=Sof(O20)=1-FVAR(5)
 Sof(O69)=Sof(O70)=Sof(O71)=FVAR(5)
 Fixed Sof: O81(0.5) O82(0.5) O83(0.5) O84(0.5) O85(0.25) O86(0.25) O88(0.5)
 O89(0.5) O90(0.5) O91(0.5) O92(0.25) O93(0.25) N10(0.5) N11(0.5)
6.a Rotating group:
 O65(H65A,H65B), O66(H66A,H66B), O67(H67A,H67B), O68(H68A,H68B)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12A),
  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(H42A), C43(H43),
 C44(H44)
6.c Idealised tetrahedral OH refined as rotating group:
 O12(H12), O27(H27), O42(H42), O57(H57)
;
_shelx_hkl_checksum              92698
_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 1.164
_oxdiff_exptl_absorpt_empirical_full_min 0.890