Speciation and Dynamics in the [Co4V2W18O68]10‒/Co(II)aq/CoOx Catalytic Water Oxidation System
Sullivan, Kevin P.; Wieliczko, Marika; Kim, Mooeung; Yin, Qiushi; Collins-Wildman, Daniel L.; Mehta, Anil K.; Bacsa, John; Lu, Xinlin; Geletii, Yurii V.; Hill, Craig L.; ACS Catalysis 8 (2018) 11952–; doi:10.1021/acscatal.7b01030

data_4515790
_publ_section_title
;
 Speciation and Dynamics in the [Co4V2W18O68]10--/Co(II)aq/CoOx Catalytic
 Water Oxidation System
;
_journal_issue                   12
_journal_name_full               'ACS Catalysis'
_journal_page_first              11952
_journal_paper_doi               10.1021/acscatal.7b01030
_journal_volume                  8
_journal_year                    2018
_chemical_formula_moiety
'C2 H3 Co2 N O34 V W8.48, 3(C2 H3 N), 0.52(W), 3(C16 H36 N)'
_chemical_formula_sum            'C56 H120 Co2 N7 O34 V W9'
_chemical_formula_weight         3259.03
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-03-24
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2017.03.21 svn.r3399 for OlexSys, GUI svn.r5332)
;
_cell_angle_alpha                90
_cell_angle_beta                 109.886(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4162(2)
_cell_length_b                   32.8597(6)
_cell_length_c                   20.2434(4)
_cell_measurement_reflns_used    50248
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      32.3450
_cell_measurement_theta_min      1.3340
_cell_volume                     9017.7(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2016.5-1 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.992
_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     -5.76 200.24   0.50   20.00    --   31.63  73.80  64.24  412
  2  \w     25.24 200.24   0.50   20.00    --   31.63  73.80 109.24  350
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'APEX2 Mo source'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0394098000
_diffrn_orient_matrix_UB_12      0.0044361000
_diffrn_orient_matrix_UB_13      0.0123390000
_diffrn_orient_matrix_UB_21      -0.0189320000
_diffrn_orient_matrix_UB_22      0.0143135000
_diffrn_orient_matrix_UB_23      -0.0275185000
_diffrn_orient_matrix_UB_31      -0.0286907000
_diffrn_orient_matrix_UB_32      -0.0155472000
_diffrn_orient_matrix_UB_33      -0.0218911000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0493
_diffrn_reflns_av_unetI/netI     0.0409
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            66266
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.575
_diffrn_reflns_theta_min         1.519
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           35
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_source_voltage           45
_exptl_absorpt_coefficient_mu    11.958
_exptl_absorpt_correction_T_max  0.02831
_exptl_absorpt_correction_T_min  0.00773
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015) Spherical absorption correction using equivalent radius and absorption coefficient. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.400
_exptl_crystal_description       prism
_exptl_crystal_F_000             6080
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.283
_exptl_crystal_size_min          0.182
_refine_diff_density_max         5.332
_refine_diff_density_min         -2.464
_refine_diff_density_rms         0.531
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.163
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1023
_refine_ls_number_reflns         25085
_refine_ls_number_restraints     1212
_refine_ls_restrained_S_all      1.139
_refine_ls_R_factor_all          0.1281
_refine_ls_R_factor_gt           0.1151
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0875P)^2^+830.1605P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2831
_refine_ls_wR_factor_ref         0.2904
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21096
_reflns_number_total             25085
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs7b01030_si_002.cif
_cod_data_source_block           co4v4tba
_cod_database_code               4515790
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C96H214N6O40W12
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N5-C9 = N4_$1-C5_$1 = N3-C7 = N1-C1
 1.137 with sigma of 0.005
 C9-C10 = C5-C6 = C7-C8 = C1-C2
 1.456 with sigma of 0.005
 N5-C10 = N4-C6 = N3-C8 = N1-C2
 2.593 with sigma of 0.005
 C12_1-C11_1 = C20_1-C19_1 = C16_1-C15_1 = C19_1-C18_1
 C12_3-C11_3 = C20_3-C19_3 = C16_3-C15_3 = C19_3-C18_3
 C12_2-C11_2 = C20_2-C19_2 = C16_2-C15_2 = C19_2-C18_2
 1.52 with sigma of 0.004
 C23_1-C22_1 = C11_1-C10_1 = C22_1-C21_1 = C14_1-C13_1
 C23_3-C22_3 = C11_3-C10_3 = C22_3-C21_3 = C14_3-C13_3
 C23_2-C22_2 = C11_2-C10_2 = C22_2-C21_2 = C14_2-C13_2
 1.52 with sigma of 0.004
3. Uiso/Uaniso restraints and constraints
Uanis(C12_1) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of
0.004
Uanis(C6) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C20_2) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of
0.004
: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(W1') = Uanis(W1)
Uanis(W7') = Uanis(W7)
Uanis(W3') = Uanis(W3)
Uanis(W6) = Uanis(W6')
Uanis(W5) = Uanis(W5')
Uanis(W8) = Uanis(W8')
Uanis(W9') = Uanis(W9)
Uanis(W4') = Uanis(W4)
Uanis(W2') = Uanis(W2)
4. Rigid body (RIGU) restrains
 W2, O8, W6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 W1, O21, W7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 W3, O3, W1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 W9, O16
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 W7, O23, O22, O12, O21, O9
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C1, C2, N1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O17, O1, W1, W2, O3, O10, O11, O21, O34, O2, O7, O8, O27, O33, W3, V1, W7, W8,
  W1', W5, W6, W2', O4, O5, O14, O32, O20, O9, O12, O22, O23, O13, O18, O19, O6,
  O24, O28, O29, O25, O26, W4, W9, Co2, Co1, O15, O30, O31, O16, W9', N1, W4',
 C1, C2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C6, N4, C5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N5, C9, C10
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N3, C7, C8
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N5_1, C9_1, C13_1, C17_1, C21_1, C10_1, C14_1, C18_1, C22_1, C11_1, C15_1,
 C19_1, C23_1, C12_1, C16_1, C20_1, C24_1
 N5_3, C9_3, C13_3, C17_3, C21_3, C10_3, C14_3, C18_3, C22_3, C11_3, C15_3,
 C19_3, C23_3, C12_3, C16_3, C20_3, C24_3
 N5_2, C9_2, C13_2, C17_2, C21_2, C10_2, C14_2, C18_2, C22_2, C11_2, C15_2,
 C19_2, C23_2, C12_2, C16_2, C20_2, C24_2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Same fragment restrains
{N5_3, C9_3, C10_3, C11_3, C12_3, C13_3, C14_3, C15_3, C16_3, C17_3, C18_3,
C19_3, C20_3, C21_3, C22_3, C23_3, C24_3}
{N5_2, C9_2, C10_2, C11_2, C12_2, C13_2, C14_2, C15_2, C16_2, C17_2, C18_2,
C19_2, C20_2, C21_2, C22_2, C23_2, C24_2}
as
{N5_1, C9_1, C10_1, C11_1, C12_1, C13_1, C14_1, C15_1, C16_1, C17_1, C18_1,
C19_1, C20_1, C21_1, C22_1, C23_1, C24_1} sigma for 1-2: 0.001 1-3: 0.004
6. Others
 Sof(W1')=Sof(W2')=Sof(W7')=Sof(W3')=Sof(W6')=Sof(W5')=Sof(W8')=Sof(W9')=
 Sof(W4')=1-FVAR(1)
 Sof(W1)=Sof(W2)=Sof(W3)=Sof(W4)=Sof(W5)=Sof(W6)=Sof(W7)=Sof(W8)=Sof(W9)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B), C14(H14A,H14B),
 C15(H15A,H15B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C21(H21A,H21B),
  C22(H22A,H22B), C23(H23A,H23B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B),
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C17(H17A,H17B), C18(H18A,H18B),
  C19(H19A,H19B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C9(H9A,H9B),
 C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B),
  C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C21(H21A,H21B), C22(H22A,
 H22B), C23(H23A,H23B)
7.b Idealised Me refined with riding coordinates:
 C16(H16A,H16B,H16C), C24(H24A,H24B,H24C), C16(H16A,H16B,H16C)
7.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C2(H2A,H2B,H2C), C10(H10A,H10B,H10C), C6(H6A,H6B,H6C),
 C12(H12A,H12B,H12C), C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C24(H24A,H24B,
 H24C), C12(H12A,H12B,H12C), C20(H20A,H20B,H20C), C12(H12A,H12B,H12C), C20(H20A,
 H20B,H20C), C24(H24A,H24B,H24C)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id Co4V4TBA
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 38.223
_oxdiff_exptl_absorpt_empirical_full_min 0.412