Selective Electrochemical CO2 Conversion with a Hybrid Polyoxometalate
Kuramochi, Satoshi; Cameron, Jamie; Fukui, Tomoya; Jones, Kieran D.; Argent, Stephen; Kusaka, Shinpei; Shiraishi, Ryo; Tamaki, Yusuke; Yatsu, Taiki; Shiga, Takuya; Ishitani, Osamu; Oshio, Hiroki; Newton, Graham; Chemical Communications  (2023) –; doi:10.1039/D3CC02138F

data_7132014
_publ_section_title
;
 Selective Electrochemical CO2 Conversion with a Hybrid Polyoxometalate
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC02138F
_journal_year                    2023
_chemical_formula_moiety
'W17O63P4C66H53Ru2Cl2, 3 (C4H12N), 8 (C5H9NO), 120 (H2O)'
_chemical_formula_sum            'C118 H401 Cl2 N11 O191 P4 Ru2 W17'
_chemical_formula_weight         8553.84
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-07-20
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-07-20 deposited with the CCDC.	2023-08-02 downloaded from the CCDC.
;
_cell_angle_alpha                80.380(2)
_cell_angle_beta                 82.354(2)
_cell_angle_gamma                79.212(2)
_cell_formula_units_Z            2
_cell_length_a                   21.8379(6)
_cell_length_b                   22.3937(6)
_cell_length_c                   26.6266(7)
_cell_measurement_reflns_used    27427
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.5130
_cell_measurement_theta_min      1.6710
_cell_volume                     12541.4(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.63a (Rigaku OD, 2023)'
_computing_data_collection       'PROGRAM:BIS 2010'
_computing_data_reduction        'CrysAlisPro 1.171.43.63a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.953
_diffrn_measured_fraction_theta_max 0.953
_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      2.27 182.27   0.50   20.00    --   28.00  73.71 -25.73  360
  2  \w      2.27 122.27   0.50   20.00    --   28.00  73.71  64.27  240
  3  \w      2.27  62.27   0.50   20.00    --   28.00  73.71 154.27  120
;
_diffrn_measurement_device       'Bruker APEX-II CCD'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0041450000
_diffrn_orient_matrix_UB_12      -0.0173181000
_diffrn_orient_matrix_UB_13      0.0246974000
_diffrn_orient_matrix_UB_21      -0.0322978000
_diffrn_orient_matrix_UB_22      0.0021595000
_diffrn_orient_matrix_UB_23      -0.0025268000
_diffrn_orient_matrix_UB_31      0.0067191000
_diffrn_orient_matrix_UB_32      -0.0275274000
_diffrn_orient_matrix_UB_33      -0.0110370000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0577
_diffrn_reflns_av_unetI/netI     0.1241
_diffrn_reflns_Laue_measured_fraction_full 0.953
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            57896
_diffrn_reflns_point_group_measured_fraction_full 0.953
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         1.698
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    8.045
_exptl_absorpt_correction_T_max  0.42750
_exptl_absorpt_correction_T_min  0.41657
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.63a (Rigaku Oxford Diffraction, 2023)
Spherical absorption correction
using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.265
_exptl_crystal_description       block
_exptl_crystal_F_000             8308
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: NMP, petroleum ether'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_exptl_crystal_size_rad          0.075
_refine_diff_density_max         2.112
_refine_diff_density_min         -2.152
_refine_diff_density_rms         0.227
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.991
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1685
_refine_ls_number_reflns         42251
_refine_ls_number_restraints     4078
_refine_ls_restrained_S_all      0.955
_refine_ls_R_factor_all          0.1185
_refine_ls_R_factor_gt           0.0675
_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^)+(0.0691P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1518
_refine_ls_wR_factor_ref         0.1718
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22782
_reflns_number_total             42251
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc02138f2.cif
_cod_data_source_block           1-TMA
_cod_database_code               7132014
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C120 H300 N25 O150 P4 Cl2 Ru2 W17 '
_shelx_estimated_absorpt_t_max   0.689
_shelx_estimated_absorpt_t_min   0.500
_olex2_refinement_description
;
1. Restrained distances
 C2X-C4X \\sim C4X-C5X \\sim C5X-C2X \\sim C3X-C2X \\sim C3X-C4X \\sim C3X-C5X
 with sigma of 0.01
 C22B-C12B \\sim C22D-C12D
 with sigma of 0.02
 W15-W16 \\sim W16-W17 \\sim W17-W15 \\sim W15A-W16A \\sim W16A-W17A \\sim
W17A-W15A
 with sigma of 0.02
 W15-O49 \\sim W17-O49 \\sim W15-O47 \\sim W16-O47 \\sim W16-O48 \\sim W17-O48
 with sigma of 0.02
 W17-O45 \\sim W17-O44 \\sim W16-O42 \\sim W16-O43 \\sim W15-O41 \\sim W15-O46
 with sigma of 0.02
 C24A-C14A \\sim C24C-C14C
 with sigma of 0.02
 P1F-C11C \\sim P1E-C11A
 with sigma of 0.02
 Ru1-Cl1 \\sim Ru2-Cl2
 with sigma of 0.02
 W11-O11 \\sim W10-O10 \\sim W12-O12 \\sim W13-O13 \\sim W14-O14 \\sim W9-O9
\\sim W8-O8 \\sim W7-O7 \\sim W6-
 O6 \\sim W5-O5 \\sim W4-O4 \\sim W3-O3
 with sigma of 0.02
 W3-O19 \\sim W4-O20
 with sigma of 0.02
 W1-O19 \\sim W2-O20
 with sigma of 0.02
 W1-O2G \\sim W2-O2G
 with sigma of 0.02
 W1-O18 \\sim W2-O18
 with sigma of 0.02
 W1-O1 \\sim W2-O2
 with sigma of 0.02
 P1F-O2F \\sim P1E-O2E
 with sigma of 0.02
 P1F-O4F \\sim P1E-O4E
 with sigma of 0.02
 P1E-O3E \\sim P1F-O3F
 with sigma of 0.02
 W3-O23 \\sim W4-O23
 with sigma of 0.02
 W3-O28 \\sim W4-O24
 with sigma of 0.02
 W5-O24 \\sim W8-O28
 with sigma of 0.02
 O33-W7 \\sim O33-W13
 with sigma of 0.02
 W14-O39 \\sim W13-O39 \\sim W12-O37 \\sim W11-O37 \\sim W9-O35 \\sim W10-O35
 with sigma of 0.02
 P1H-O5H \\sim P1H-O3H \\sim P1H-O4H
 with sigma of 0.02
 W14-O46 \\sim W9-O41 \\sim W10-O42 \\sim W11-O43 \\sim W13-O45 \\sim W12-O44
 with sigma of 0.02
 W13-W12 \\sim W13A-W12A
 with sigma of 0.02
 W12-W11 \\sim W12A-W11A
 with sigma of 0.02
 W11-W10 \\sim W11A-W10A
 with sigma of 0.02
 W10-W9 \\sim W10A-W9A
 with sigma of 0.02
 W9-W14 \\sim W9A-W14A
 with sigma of 0.02
 W14-W13 \\sim W14A-W13A
 with sigma of 0.02
 W7-W6 \\sim W7A-W6A
 with sigma of 0.02
 W6-W5 \\sim W6A-W5A
 with sigma of 0.02
 W5-W4 \\sim W5A-W4A
 with sigma of 0.02
 W4-W3 \\sim W4A-W3A
 with sigma of 0.02
 W5-W11 \\sim W5A-W11A
 with sigma of 0.02
 W6-W12 \\sim W6A-W12A
 with sigma of 0.02
 W7-W13 \\sim W7A-W13A
 with sigma of 0.02
 W3-W9 \\sim W3A-W9A
 with sigma of 0.02
 W4-W10 \\sim W4A-W10A
 with sigma of 0.02
 W5-W2 \\sim W5A-W2A
 with sigma of 0.02
 W4-W2 \\sim W4A-W2A
 with sigma of 0.02
 W3-W1 \\sim W3A-W1A
 with sigma of 0.02
 W1-W2 \\sim W1A-W2A
 with sigma of 0.02
2. Restrained planarity
 N1S, C2S, C3S, C4S, C5S, C6S, O7S
 with sigma of 0.1
 N1V, C2V, C3V, C4V, C5V, C6V, O7V
 with sigma of 0.1
 N1T, C2T, C3T, C4T, C5T, C6T, O7T
 with sigma of 0.1
 N1U, C2U, C3U, C4U, C5U, C6U, O7U
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C27D) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(O19) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C11A, C16A, C15A, C14A, C13A, C12A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C11A, C12A, C13A, C14A, C15A, C16A}
{N11B, C12B, C13B, C14B, C15B, C16B, C17B} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N21B, C22B, C23B, C24B, C25B, C26B, C27B}
{N1S, C2S, C3S, C4S, C5S, C6S, O7S} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1U, C2U, C3U, C4U, C5U, C6U, O7U}
{N21A, C26A, C25A, C24A, C23A, C22A, N41A, C42A, C43A, C44A, C45A, C46A} sigma
for 1-2: 0.02, 1-3: 0.04
as in
{N21A, C22A, C23A, C24A, C25A, C26A, N31A, C32A, C33A, C34A, C35A, C36A}
{N1W, C4W, C5W, C2W, C3W} sigma for 1-2: 0.02, 1-3: 0.04
{N1W, C5W, C2W, C3W, C4W} sigma for 1-2: 0.02, 1-3: 0.04
{N1W, C5W, C4W, C3W, C2W} sigma for 1-2: 0.02, 1-3: 0.04
{N1W, C3W, C4W, C5W, C2W} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1W, C2W, C3W, C4W, C5W}
{C11A, C16A, C15A, C14A, C13A, C12A} sigma for 1-2: 0.02, 1-3: 0.04
{C11A, C12A, C13A, C14A, C15A, C16A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C11C, C12C, C13C, C14C, C15C, C16C}
{N1S, C2S, C3S, C4S, C5S, C6S, O7S} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1T, C2T, C3T, C4T, C5T, C6T, O7T}
{N21A, C22A, C23A, C24A, C25A, C26A, N31A, C32A, C33A, C34A, C35A, C36A, N41A,
C42A, C43A, C44A, C45A, C46A} sigma for 1-2: 0.02, 1-3: 0.04
{N21C, C26C, C25C, C24C, C23C, C22C, N41C, C42C, C43C, C44C, C45C, C46C} sigma
for 1-2: 0.02, 1-3: 0.04
{N21A, C26A, C25A, C24A, C23A, C22A, N41A, C42A, C43A, C44A, C45A, C46A} sigma
for 1-2: 0.02, 1-3: 0.04
as in
{N21C, C22C, C23C, C24C, C25C, C26C, N31C, C32C, C33C, C34C, C35C, C36C, N41C,
C42C, C43C, C44C, C45C, C46C}
{N1S, C2S, C3S, C4S, C5S, C6S, O7S} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1V, C2V, C3V, C4V, C5V, C6V, O7V}
{N1W, C4W, C5W, C2W, C3W} sigma for 1-2: 0.02, 1-3: 0.04
{N1W, C2W, C3W, C4W, C5W} sigma for 1-2: 0.02, 1-3: 0.04
{N1W, C3W, C4W, C5W, C2W} sigma for 1-2: 0.02, 1-3: 0.04
{N1W, C5W, C4W, C3W, C2W} sigma for 1-2: 0.02, 1-3: 0.04
{N1W, C5W, C2W, C3W, C4W} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1X, C2X, C3X, C4X, C5X}
{N11B, C12B, C13B, C14B, C15B, C16B, C17B} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N11D, C12D, C13D, C14D, C15D, C16D, C17D}
{N11B, C12B, C13B, C14B, C15B, C16B, C17B} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N21D, C22D, C23D, C24D, C25D, C26D, C27D}
6. Others
 Sof(N1S)=Sof(C2S)=Sof(C3S)=Sof(H3SA)=Sof(H3SB)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=
 Sof(C5S)=Sof(H5SA)=Sof(H5SB)=Sof(C6S)=Sof(H6SA)=Sof(H6SB)=Sof(H6SC)=Sof(O7S)=
 FVAR(1)
 Sof(N1U)=Sof(C2U)=Sof(C3U)=Sof(H3UA)=Sof(H3UB)=Sof(C4U)=Sof(H4UA)=Sof(H4UB)=
 Sof(C5U)=Sof(H5UA)=Sof(H5UB)=Sof(C6U)=Sof(H6UA)=Sof(H6UB)=Sof(H6UC)=Sof(O7U)=
 FVAR(2)
 Sof(N1V)=Sof(C2V)=Sof(C3V)=Sof(H3VA)=Sof(H3VB)=Sof(C4V)=Sof(H4VA)=Sof(H4VB)=
 Sof(C5V)=Sof(H5VA)=Sof(H5VB)=Sof(C6V)=Sof(H6VA)=Sof(H6VB)=Sof(H6VC)=Sof(O7V)=
 FVAR(3)
 Sof(W16A)=Sof(W15A)=Sof(W17A)=Sof(W13A)=Sof(W10A)=Sof(W11A)=Sof(W12A)=
 Sof(W9A)=Sof(W14A)=Sof(W7A)=Sof(W4A)=Sof(W6A)=Sof(W5A)=Sof(W3A)=Sof(W2A)=
 Sof(W1A)=1-FVAR(4)
 Sof(W1)=Sof(O1)=Sof(O2)=Sof(W2)=Sof(O3)=Sof(W3)=Sof(W4)=Sof(O4)=Sof(W5)=
 Sof(O5)=Sof(W6)=Sof(O6)=Sof(W7)=Sof(O7)=Sof(W8)=Sof(O8)=Sof(O9)=Sof(W9)=
 Sof(W10)=Sof(O10)=Sof(O11)=Sof(W11)=Sof(W12)=Sof(O12)=Sof(O13)=Sof(W13)=
 Sof(W14)=Sof(O14)=Sof(W15)=Sof(O15)=Sof(O16)=Sof(W16)=Sof(W17)=Sof(O17)=
 Sof(O18)=Sof(O19)=Sof(O20)=Sof(O21)=Sof(O22)=Sof(O23)=Sof(O24)=Sof(O25)=
 Sof(O26)=Sof(O27)=Sof(O28)=Sof(O29)=Sof(O30)=Sof(O31)=Sof(O32)=Sof(O33)=
 Sof(O34)=Sof(O35)=Sof(O36)=Sof(O37)=Sof(O38)=Sof(O39)=Sof(O40)=Sof(O41)=
 Sof(O42)=Sof(O43)=Sof(O44)=Sof(O45)=Sof(O46)=Sof(O47)=Sof(O48)=Sof(O49)=
 Sof(P1G)=Sof(O2G)=Sof(O3G)=Sof(O4G)=Sof(O5G)=Sof(P1H)=Sof(O2H)=Sof(O3H)=
 Sof(O4H)=Sof(O5H)=FVAR(4)
 Uiso(N1T)=Uiso(C2T)=Uiso(C3T)=Uiso(C4T)=Uiso(C5T)=Uiso(C6T)=Uiso(O7T)=FVAR(5)
 Uiso(N1S)=Uiso(C2S)=Uiso(C3S)=Uiso(C4S)=Uiso(C5S)=Uiso(C6S)=Uiso(O7S)=FVAR(6)
7.a Secondary CH2 refined with riding coordinates:
 C3S(H3SA,H3SB), C4S(H4SA,H4SB), C5S(H5SA,H5SB), C3T(H3TA,H3TB), C4T(H4TA,
 H4TB), C5T(H5TA,H5TB), C3U(H3UA,H3UB), C4U(H4UA,H4UB), C5U(H5UA,H5UB),
 C3V(H3VA,H3VB), C4V(H4VA,H4VB), C5V(H5VA,H5VB)
7.b Me refined with riding coordinates:
 C17B(H17A,H17B,H17C), C27B(H27A,H27B,H27C), C17D(H17D,H17E,H17F), C27D(H27D,
 H27E,H27F), C6S(H6SA,H6SB,H6SC), C6T(H6TA,H6TB,H6TC), C6U(H6UA,H6UB,H6UC),
 C6V(H6VA,H6VB,H6VC), C2W(H2WA,H2WB,H2WC), C3W(H3WA,H3WB,H3WC), C4W(H4WA,H4WB,
 H4WC), C5W(H5WA,H5WB,H5WC), C2X(H2XA,H2XB,H2XC), C3X(H3XA,H3XB,H3XC), C4X(H4XA,
 H4XB,H4XC), C5X(H5XA,H5XB,H5XC)
7.c Aromatic/amide H refined with riding coordinates:
 C12A(H12A), C13A(H13A), C15A(H15A), C16A(H16A), C23A(H23A), C25A(H25A),
 C33A(H33A), C34A(H34A), C35A(H35A), C36A(H36A), C43A(H43A), C44A(H44A),
 C45A(H45A), C46A(H46A), C13B(H13B), C15B(H15B), C16B(H16B), C23B(H23B),
 C25B(H25B), C26B(H26B), C12C(H12C), C13C(H13C), C15C(H15C), C16C(H16C),
 C23C(H23C), C25C(H25C), C33C(H33C), C34C(H34C), C35C(H35C), C36C(H36C),
 C43C(H43C), C44C(H44C), C45C(H45C), C46C(H46C), C13D(H13D), C15D(H15D),
 C16D(H16D), C23D(H23D), C25D(H25D), C26D(H26D)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              22951
_shelx_hkl_checksum              10441
_shelx_fab_checksum              59985
_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 1.573
_oxdiff_exptl_absorpt_empirical_full_min 0.614