An Efficient and Stable Hydrophobic Molecular Cobalt Catalyst for Water Electro-oxidation at Neutral pH
Chen, Ba-Tian; Morlanés, Natalia; Adogla, Enoch; Takanabe, Kazuhiro; Rodionov, Valentin O.; ACS Catalysis 6 (2016) 4647–; doi:10.1021/acscatal.6b01237

data_4513899
_publ_section_title
;
 An Efficient and Stable Hydrophobic Molecular Cobalt Catalyst for Water
 Electro-oxidation at Neutral pH
;
_journal_issue                   7
_journal_name_full               'ACS Catalysis'
_journal_page_first              4647
_journal_paper_doi               10.1021/acscatal.6b01237
_journal_volume                  6
_journal_year                    2016
_chemical_formula_moiety
'C57 H36 Cl Co F51 N7, Cl, 3(C4 H8 O), 2(H2 O)'
_chemical_formula_sum            'C69 H64 Cl2 Co F51 N7 O5'
_chemical_formula_weight         2170.10
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-10-13
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.1210(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.5991(11)
_cell_length_b                   14.5605(6)
_cell_length_c                   25.6393(11)
_cell_measurement_reflns_used    9691
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      25.66
_cell_measurement_theta_min      2.47
_cell_volume                     8822.2(7)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker APEXII v2014.9-0 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      200(2)
_diffrn_detector                 'Bruker PHOTON-100 area detector'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Quest'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0758
_diffrn_reflns_av_unetI/netI     0.0183
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            439740
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.026
_diffrn_reflns_theta_max         25.026
_diffrn_reflns_theta_min         2.155
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.414
_exptl_absorpt_correction_T_max  0.6939
_exptl_absorpt_correction_T_min  0.6323
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1588 before and 0.0707 after correction.
The Ratio of minimum to maximum transmission is 0.9112.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'pink / purple, dichroic'
_exptl_crystal_colour_modifier   pinkish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.634
_exptl_crystal_description       plate
_exptl_crystal_F_000             4348
_exptl_crystal_size_max          0.56
_exptl_crystal_size_mid          0.44
_exptl_crystal_size_min          0.24
_refine_diff_density_max         1.028
_refine_diff_density_min         -0.780
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1397
_refine_ls_number_reflns         15563
_refine_ls_number_restraints     1116
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.1033
_refine_ls_R_factor_gt           0.0871
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1502P)^2^+25.4028P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2466
_refine_ls_wR_factor_ref         0.2662
_reflns_number_gt                12678
_reflns_number_total             15563
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs6b01237_si_002.cif
_cod_data_source_block           en_f51co
_cod_depositor_comments          'Adding full bibliography for 4513899.cif.'
_cod_database_code               4513899
_shelx_estimated_absorpt_t_max   0.907
_shelx_estimated_absorpt_t_min   0.801
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Shared sites
{F18A, F18B}
{F19A, F19B}
{F20A, F20B}
{F21A, F21B}
{C31A, C31B}
{C32A, C32B}
3. Restrained distances
 C13-C12 = C14-C13 = C15-C14 = C16-C15 = C17-C16 = C18-C17 = C19-C18
 1.55 with sigma of 0.02
 F2-C12 = F1-C12 = F3-C13 = F4-C13 = F5-C14 = F6-C14 = F7-C15 = F8-C15 = F9-
 C16 = F10-C16 = F12-C17 = F11-C17 = F13-C18 = F14-C18 = F16-C19 = F15-C19 =
 F17-C19
 1.35 with sigma of 0.02
 C50B-C49 \\sim C50A-C49
 with sigma of 0.01
 F17-C19 \\sim F15-C19 \\sim F16-C19
 with sigma of 0.01
 C8S-C7S \\sim C6S-C5S
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uiso(O3S) = Uiso(C9S) = Uiso(C10S) = Uiso(C11S) = Uiso(C12S)
Uanis(C50A) = Uanis(C50B)
Uanis(C51A) = Uanis(C51B)
Uanis(C52A) = Uanis(C52B)
Uanis(C53A) = Uanis(C53B)
Uanis(C54A) = Uanis(C54B)
Uanis(C55A) = Uanis(C55B)
Uanis(C56A) = Uanis(C56B)
Uanis(C57A) = Uanis(C57B)
Uanis(C33A) = Uanis(C33B)
Uanis(C34A) = Uanis(C34B)
Uanis(C35A) = Uanis(C35B)
Uanis(C36A) = Uanis(C36B)
Uanis(C37A) = Uanis(C37B)
Uanis(C38A) = Uanis(C38B)
Uanis(C33A) = Uanis(C33B)
Uanis(C34A) = Uanis(C34B)
Uanis(C35A) = Uanis(C35B)
Uanis(C36A) = Uanis(C36B)
Uanis(C37A) = Uanis(C37B)
Uanis(C38A) = Uanis(C38B)
Uanis(F18A) = Uanis(F18B)
Uanis(F19A) = Uanis(F19B)
Uanis(F20A) = Uanis(F20B)
Uanis(F21A) = Uanis(F21B)
Uanis(C31A) = Uanis(C31B)
Uanis(C32A) = Uanis(C32B)
Uanis(F31B) = Uanis(F31A)
Uanis(F25A) = Uanis(F24B)
Uanis(F30B) = Uanis(F30A)
Uanis(F40A) = Uanis(F40B) = Uanis(F39A) = Uanis(F39B)
Uanis(F48A) = Uanis(F47B)
Uanis(F45A) = Uanis(F46B)
Uanis(F49A) = Uanis(F50B)
5. Rigid body (RIGU) restrains
 C35A, C36A, C37A, C38A, F26A, F27A, F28A, F29A, F30A, F31A, F32A, F33A, F34A,
 C35B, C36B, C37B, C38B, F26B, F27B, F28B, F29B, F30B, F31B, F32B, F33B, F34B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C14, C15, C16, C17, C18, C19, F5, F6, F7, F8, F9, F10, F11, F12, F13, F14,
 F15, F16, F17
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C57A, F49A, F50A, F51A, C57B, F49B, F50B, F51B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{C12, C13, C14, C15, C16, C17, C18, C19, F1, F2, F3, F4, F5, F6, F7, F8, F9,
F10, F11, F12, F13, F14, F15, F16, F17} sigma for 1-2: 0.02, 1-3: 0.04
as
{C31A, C32A, C33A, C34A, C35A, C36A, C37A, C38A, F18A, F19A, F20A, F21A, F22A,
F23A, F24A, F25A, F26A, F27A, F28A, F29A, F30A, F31A, F32A, F33A, F34A}
{C12, C13, C14, C15, C16, C17, C18, C19, F1, F2, F3, F4, F5, F6, F7, F8, F9,
F10, F11, F12, F13, F14, F15, F16, F17} sigma for 1-2: 0.02, 1-3: 0.04
as
{C31B, C32B, C33B, C34B, C35B, C36B, C37B, C38B, F18B, F19B, F20B, F21B, F22B,
F23B, F24B, F25B, F26B, F27B, F28B, F29B, F30B, F31B, F32B, F33B, F34B}
{C12, C13, C14, C15, C16, C17, C18, C19, F1, F2, F3, F4, F5, F6, F7, F8, F9,
F10, F11, F12, F13, F14, F15, F16, F17} sigma for 1-2: 0.02, 1-3: 0.04
as
{C50A, C51A, C52A, C53A, C54A, C55A, C56A, C57A, F35A, F36A, F37A, F38A, F39A,
F40A, F41A, F42A, F43A, F44A, F45A, F46A, F47A, F48A, F49A, F50A, F51A}
{C12, C13, C14, C15, C16, C17, C18, C19, F1, F2, F3, F4, F5, F6, F7, F8, F9,
F10, F11, F12, F13, F14, F15, F16, F17} sigma for 1-2: 0.02, 1-3: 0.04
as
{C50B, C51B, C52B, C53B, C54B, C55B, C56B, C57B, F35B, F36B, F37B, F38B, F39B,
F40B, F41B, F42B, F43B, F44B, F45B, F46B, F47B, F48B, F49B, F50B, F51B}
{O2S, C5S, C6S, C7S, C8S} sigma for 1-2: 0.02, 1-3: 0.04
as
{O3S, C9S, C10S, C11S, C12S}
7. Others
 Sof(H49C)=Sof(H49D)=Sof(C50B)=Sof(C51B)=Sof(C52B)=Sof(C53B)=Sof(C54B)=
 Sof(C55B)=Sof(C56B)=Sof(C57B)=Sof(F35B)=Sof(F36B)=Sof(F37B)=Sof(F38B)=
 Sof(F39B)=Sof(F40B)=Sof(F41B)=Sof(F42B)=Sof(F43B)=Sof(F44B)=Sof(F45B)=
 Sof(F46B)=Sof(F47B)=Sof(F48B)=Sof(F49B)=Sof(F50B)=Sof(F51B)=1-FVAR(1)
 Sof(H49A)=Sof(H49B)=Sof(C50A)=Sof(C51A)=Sof(C52A)=Sof(C53A)=Sof(C54A)=
 Sof(C55A)=Sof(C56A)=Sof(C57A)=Sof(F35A)=Sof(F36A)=Sof(F37A)=Sof(F38A)=
 Sof(F39A)=Sof(F40A)=Sof(F41A)=Sof(F42A)=Sof(F43A)=Sof(F44A)=Sof(F45A)=
 Sof(F46A)=Sof(F47A)=Sof(F48A)=Sof(F49A)=Sof(F50A)=Sof(F51A)=FVAR(1)
 Sof(H30C)=Sof(H30D)=Sof(C31B)=Sof(C32B)=Sof(C33B)=Sof(C34B)=Sof(C35B)=
 Sof(C36B)=Sof(C37B)=Sof(C38B)=Sof(F18B)=Sof(F19B)=Sof(F20B)=Sof(F21B)=
 Sof(F22B)=Sof(F23B)=Sof(F24B)=Sof(F25B)=Sof(F26B)=Sof(F27B)=Sof(F28B)=
 Sof(F29B)=Sof(F30B)=Sof(F31B)=Sof(F32B)=Sof(F33B)=Sof(F34B)=1-FVAR(2)
 Sof(H30A)=Sof(H30B)=Sof(C31A)=Sof(C32A)=Sof(C33A)=Sof(C34A)=Sof(C35A)=
 Sof(C36A)=Sof(C37A)=Sof(C38A)=Sof(F18A)=Sof(F19A)=Sof(F20A)=Sof(F21A)=
 Sof(F22A)=Sof(F23A)=Sof(F24A)=Sof(F25A)=Sof(F26A)=Sof(F27A)=Sof(F28A)=
 Sof(F29A)=Sof(F30A)=Sof(F31A)=Sof(F32A)=Sof(F33A)=Sof(F34A)=FVAR(2)
 Sof(O5S)=1-FVAR(3)
 Sof(O4S)=FVAR(3)
 Sof(O7S)=1-FVAR(4)
 Sof(O6S)=FVAR(4)
8.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C20(H20A,H20B),
 C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B), C30(H30C,H30D), C39(H39A,H39B),
  C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B), C49(H49C,H49D), C1S(H1SA,
 H1SB), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB), C5S(H5SA,H5SB),
 C6S(H6SA,H6SB), C7S(H7SA,H7SB), C8S(H8SA,H8SB), C9S(H9SA,H9SB), C10S(H10C,
 H10D), C11S(H11C,H11D), C12S(H12A,H12B)
8.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C23(H23), C24(H24), C25(H25), C26(H26),
 C42(H42), C43(H43), C44(H44), C45(H45)
;
_shelx_res_checksum              47633
_shelx_hkl_checksum              12320
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'