Hetero-metallic Active Sites Coupled with Strong Reductive Polyoxometalate for Selectively Photocatalytic CO2-to-CH4 Conversion in Water
Su, Zhong-Min; Xie, Shuai-Lei; Liu, Jiang; Dong, Long-Zhang; Li, Shun-Li; Lan, Ya-Qian; Chemical Science  (2018) –; doi:10.1039/C8SC03471K

data_1550000
_publ_section_title
;
 Hetero-metallic Active Sites Coupled with Strong Reductive
 Polyoxometalate for Selectively Photocatalytic CO2-to-CH4 Conversion in
 Water
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC03471K
_journal_year                    2018
_chemical_formula_moiety         '0.5(Co20 Mn60 Mo192 Na48 O1056 P136), 48(O)'
_chemical_formula_sum            'Co10 Mn30 Mo96 Na24 O576 P68'
_chemical_formula_weight         23321.46
_space_group_crystal_system      tetragonal
_space_group_IT_number           142
_space_group_name_Hall           '-I 4bd 2c'
_space_group_name_H-M_alt        'I 41/a c d'
_symmetry_space_group_name_Hall  '-I 4bd 2c'
_symmetry_space_group_name_H-M   'I 41/a c d :2'
_atom_sites_solution_primary     iterative
_audit_creation_date             2018-07-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5370)
;
_audit_update_record
;
2018-07-16 deposited with the CCDC.
2018-10-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   26.9679(5)
_cell_length_b                   26.9679(5)
_cell_length_c                   41.1540(18)
_cell_measurement_reflns_used    9190
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.465
_cell_measurement_theta_min      2.248
_cell_volume                     29930.0(15)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  CMOS-PHOTON100
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0348
_diffrn_reflns_av_unetI/netI     0.0194
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -53
_diffrn_reflns_number            83160
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.502
_diffrn_reflns_theta_min         2.768
_exptl_absorpt_coefficient_mu    3.128
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.7094
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0561 before and 0.0450 after correction. The Ratio of minimum to maximum transmission is 0.9514. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.588
_exptl_crystal_description       octahedral
_exptl_crystal_F_000             21888
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_platon_squeeze_details
;
TITL 111_a.res in I4(1)/acd
CELL   26.9679   26.9679   41.1540     90.00     90.00     90.00
SPGR I41/acd
Q101 0.443 0.568 0.063 !       5.69 eA-3
Q102 0.156 0.816 0.366 !       4.33 eA-3
C103 0.992 0.119 0.064 !       4.31 eA-3
C104 0.087 0.495 0.085 !       3.78 eA-3
C105 0.838 0.269 0.162 !       3.18 eA-3
C106 0.022 0.587 0.437 !       3.06 eA-3
C107 0.033 0.251 0.178 !       2.76 eA-3
C108 0.291 0.872 0.198 !       2.63 eA-3
C109 0.586 0.738 0.174 !       2.60 eA-3
C110 0.658 0.596 0.043 !       2.57 eA-3
C111 0.352 0.278 0.358 !       2.56 eA-3
C112 0.053 0.195 0.127 !       2.52 eA-3
C113 0.854 0.894 0.313 !       2.46 eA-3
C114 0.247 0.420 0.135 !       2.36 eA-3
Q115 0.171 0.578 0.154 !       2.24 eA-3
C116 0.905 0.257 0.142 !       2.20 eA-3
C117 0.759 0.016 0.119 !       2.13 eA-3
C118 0.750 0.465 0.369 !       2.06 eA-3
C119 0.892 0.955 0.417 !       1.97 eA-3
Q120 0.814 0.908 0.031 !       1.69 eA-3
C121 0.220 0.454 0.149 !       1.60 eA-3
Q122 0.227 0.776 0.078 !       1.58 eA-3
C123 0.324 0.134 0.351 !       1.58 eA-3
C124 0.741 0.945 0.389 !       1.57 eA-3
Q125 0.742 0.182 0.254 !       1.55 eA-3
Q126 0.275 0.857 0.420 !       1.49 eA-3
C127 0.218 0.463 0.129 !       1.48 eA-3
Q128 0.930 0.089 0.055 !       1.42 eA-3
Q129 0.876 0.240 0.033 !       1.40 eA-3
Q130 0.307 0.730 0.282 !       1.32 eA-3
Q131 0.212 0.362 0.219 !       1.21 eA-3
Q132 0.273 0.194 0.219 !       1.17 eA-3
Q133 0.296 0.797 0.257 !       1.17 eA-3
Q134 0.818 0.317 0.469 !       1.14 eA-3
C135 0.563 0.884 0.615 !       1.13 eA-3
C136 0.063 0.384 0.115 !       1.13 eA-3
Q137 0.523 0.282 0.157 !       1.11 eA-3
C138 0.930 0.738 0.374 !       1.09 eA-3
C139 0.614 0.320 0.358 !       1.05 eA-3
Q140 0.091 0.128 0.220 !       1.04 eA-3
Q141 0.312 0.196 0.220 !       0.94 eA-3
Q142 0.812 0.696 0.720 !       0.94 eA-3
Q143 0.054 0.438 0.970 !       0.94 eA-3
Q144 0.405 0.812 0.181 !       0.93 eA-3
Q145 0.769 0.187 0.493 !       0.91 eA-3
Q146 0.731 0.313 0.007 !       0.91 eA-3
Q147 0.231 0.187 0.993 !       0.91 eA-3
Q148 0.555 0.029 0.013 !       0.90 eA-3
Q149 0.562 0.712 0.180 !       0.88 eA-3
Q150 0.523 0.014 0.033 !       0.88 eA-3
C151 0.720 0.497 0.335 !       0.88 eA-3
C152 0.181 0.485 0.161 !       0.85 eA-3
Q153 0.874 0.182 0.258 !       0.85 eA-3
Q154 0.022 0.800 0.124 !       0.85 eA-3
Q155 0.931 0.924 0.032 !       0.84 eA-3
Q156 0.233 0.204 0.984 !       0.84 eA-3
Q157 0.564 0.010 0.000 !       0.84 eA-3
Q158 0.814 0.125 0.413 !       0.83 eA-3
Q159 0.866 0.449 0.228 !       0.82 eA-3
Q160 0.968 0.249 0.376 !       0.82 eA-3
Q161 0.219 0.413 0.277 !       0.82 eA-3
Q162 0.967 0.126 0.412 !       0.81 eA-3
Q163 0.303 0.773 0.338 !       0.81 eA-3
Q164 0.766 0.305 0.015 !       0.81 eA-3
C165 0.013 0.808 0.399 !       0.80 eA-3
Q166 0.795 0.358 0.392 !       0.79 eA-3
Q167 0.775 0.282 0.990 !       0.79 eA-3
Q168 0.454 0.405 0.483 !       0.79 eA-3
Q169 0.696 0.016 0.033 !       0.79 eA-3
Q170 0.291 0.759 0.438 !       0.78 eA-3
Q171 0.239 0.743 0.828 !       0.78 eA-3
Q172 0.739 0.243 0.328 !       0.78 eA-3
Q173 0.036 0.500 0.250 !       0.78 eA-3
Q174 0.275 0.720 0.995 !       0.78 eA-3
Q175 0.121 0.835 0.273 !       0.78 eA-3
C176 0.618 0.663 0.128 !       0.78 eA-3
Q177 0.133 0.280 0.468 !       0.78 eA-3
Q178 0.229 0.455 0.306 !       0.77 eA-3
Q179 0.452 0.041 0.468 !       0.77 eA-3
Q180 0.529 0.265 0.165 !       0.77 eA-3
Q181 0.299 0.054 0.472 !       0.77 eA-3
Q182 0.201 0.446 0.028 !       0.77 eA-3
Q183 0.482 0.627 0.290 !       0.76 eA-3
Q184 0.102 0.278 0.455 !       0.76 eA-3
Q185 0.299 0.445 0.965 !       0.76 eA-3
Q186 0.429 0.722 0.187 !       0.76 eA-3
Q187 0.225 0.836 0.488 !       0.76 eA-3
Q188 0.484 0.905 0.038 !       0.75 eA-3
Q189 0.416 0.839 0.367 !       0.75 eA-3
Q190 0.852 0.416 0.381 !       0.75 eA-3
Q191 0.648 0.084 0.119 !       0.75 eA-3
Q192 0.148 0.416 0.881 !       0.75 eA-3
Q193 0.853 0.214 0.439 !       0.75 eA-3
Q194 0.366 0.256 0.182 !       0.74 eA-3
C195 0.252 0.112 0.358 !       0.74 eA-3
C196 0.125 0.355 0.155 !       0.74 eA-3
Q197 0.817 0.705 0.229 !       0.74 eA-3
Q198 0.490 0.881 0.431 !       0.74 eA-3
Q199 0.388 0.073 0.178 !       0.74 eA-3
;
_refine_diff_density_max         1.511
_refine_diff_density_min         -1.148
_refine_diff_density_rms         0.134
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     455
_refine_ls_number_reflns         8600
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0400
_refine_ls_R_factor_gt           0.0316
_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^)+(0.0286P)^2^+400.1517P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0736
_refine_ls_wR_factor_ref         0.0768
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7411
_reflns_number_total             8600
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc03471k2.cif
_cod_data_source_block           NENU_606
_cod_original_cell_volume        29930.0(17)
_cod_database_code               1550000
_shelx_shelxl_version_number     2016/4
_olex2_refinement_description
;
1. Shared sites
{Mn3, Co3}
{Mn1, Co1}
{Mn2, Co2}
2. Uiso/Uaniso restraints and constraints
P5 \\sim O32: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(O32) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.2
Uanis(Mn3) = Uanis(Co3)
Uanis(Mn1) = Uanis(Co1)
Uanis(Mn2) = Uanis(Co2)
3. Others
 Fixed Sof: Mn3(0.375) Mn1(0.75) Mn2(0.75) Co3(0.125) Co1(0.25) Co2(0.25)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'