{Co4O4} and {CoxNi4-xO4} Cubane Water Oxidation Catalysts as Surface Cut-Outs of Cobalt Oxides.
Song, Fangyuan; Moré, René; Schilling, Mauro; Smolentsev, Grigory; Azzaroli, Nicolo; Fox, Thomas; Luber, Sandra; Patzke, Greta R.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b07361

data_4126504
_publ_section_title
;
 {Co4O4} and {CoxNi4-xO4} Cubane Water Oxidation Catalysts as Surface
 Cut-Outs of Cobalt Oxides.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b07361
_journal_year                    2017
_chemical_formula_moiety         'C48 H46 Co4 N8 O14, 2(Cl O4)'
_chemical_formula_sum            'C48 H46 Cl2 Co4 N8 O22'
_chemical_formula_weight         1393.55
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2016-08-25
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 115.750(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.8068(9)
_cell_length_b                   12.1904(4)
_cell_length_c                   21.0805(7)
_cell_measurement_reflns_used    16236
_cell_measurement_temperature    183(2)
_cell_measurement_theta_max      29.3390
_cell_measurement_theta_min      2.5700
_cell_volume                     5278.9(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      183(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4498
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -14.00   88.00   0.5000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       12.1849   38.0000 -120.0000 204

  2 omega  -11.00   55.00   0.5000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       12.1849   38.0000    0.0000 132

  3 omega  -41.00  -13.00   0.5000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       12.1849  -57.0000   60.0000 56

  4 omega   -2.00   32.00   0.5000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       12.1849   57.0000  -60.0000 68

  5 omega   -9.00   86.00   0.5000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       12.1849   57.0000   90.0000 190

  6 omega  -17.00   22.00   0.5000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       12.1849   57.0000 -150.0000 78

  7 omega   16.00   62.00   0.5000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       12.1849   57.0000   30.0000 92

  8 omega  -62.00   42.00   0.5000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       12.1849  -57.0000  120.0000 208

  9 omega  -62.00   42.00   0.5000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       12.1849  -57.0000    0.0000 208

 10 omega  -62.00    0.00   0.5000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       12.1849  -57.0000  -60.0000 124

 11 omega  -62.00   42.00   0.5000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       12.1849  -57.0000 -120.0000 208

 12 omega  -87.00  -62.00   0.5000   45.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4036  -38.0000   60.0000 50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0279920000
_diffrn_orient_matrix_UB_12      0.0338211000
_diffrn_orient_matrix_UB_13      0.0106718000
_diffrn_orient_matrix_UB_21      -0.0189976000
_diffrn_orient_matrix_UB_22      0.0414661000
_diffrn_orient_matrix_UB_23      -0.0235833000
_diffrn_orient_matrix_UB_31      -0.0069524000
_diffrn_orient_matrix_UB_32      0.0229198000
_diffrn_orient_matrix_UB_33      0.0269154000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0449
_diffrn_reflns_av_unetI/netI     0.0206
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            54440
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.418
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.428
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69202
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.753
_exptl_crystal_description
;
;
_exptl_crystal_F_000             2832
_refine_diff_density_max         1.101
_refine_diff_density_min         -0.947
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     402
_refine_ls_number_reflns         5396
_refine_ls_number_restraints     79
_refine_ls_restrained_S_all      1.134
_refine_ls_R_factor_all          0.0702
_refine_ls_R_factor_gt           0.0589
_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^)+(0.0677P)^2^+30.2661P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1490
_refine_ls_wR_factor_ref         0.1585
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4494
_reflns_number_total             5396
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07361_si_002.cif
_cod_data_source_block           co-dpk-water-new-05
_cod_database_code               4126504
_chemical_oxdiff_formula         'Co4 C44 H44 O12 N8 Cl2'
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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, All O(H) groups, All O(H,H) groups
2. Restrained distances
 Cl1-O10 \\sim Cl1-O9 \\sim Cl1-O11 \\sim Cl1-O8 \\sim Cl2-O10 \\sim Cl2-O9
\\sim Cl2-O11 \\sim Cl2-O12
 with sigma of 0.005
3. Rigid body (RIGU) restrains
 Cl1, Cl2, O10, O9, O11, O8, O12
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
4. Others
 Sof(Cl2)=Sof(O12)=1-FVAR(1)
 Sof(Cl1)=Sof(O8)=FVAR(1)
5.a Rotating group:
 O5(H5A,H5B)
5.b Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C21(H21), C22(H22), C15(H15), C14(H14), C13(H13),
 C12(H12), C8(H8), C9(H9), C10(H10), C11(H11), C4(H4), C3(H3), C2(H2), C1(H1)
5.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C)
5.d Idealised tetrahedral OH refined as rotating group:
 O4(H4A), O2(H2A)
;
_shelx_res_checksum              79767
_shelx_hkl_checksum              69690
_shelx_shelxl_version_number     2016/4
_olex2_submission_special_instructions 'No special instructions were received'