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_1549998
_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         'Mn Mo12 O62 P8, 8(C2 H10 N2), 12(H2 O)'
_chemical_formula_sum            'C16 H104 Mn Mo12 N16 O74 P8'
_chemical_formula_weight         3159.13
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-07-16 deposited with the CCDC.
2018-10-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.645(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.8641(14)
_cell_length_b                   15.9370(16)
_cell_length_c                   17.1695(17)
_cell_measurement_reflns_used    9951
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      27.66
_cell_measurement_theta_min      2.56
_cell_volume                     4336.3(7)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0426
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            57163
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.721
_diffrn_reflns_theta_min         1.744
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.088
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6547
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0726 before and 0.0449 after correction. The Ratio of minimum to maximum transmission is 0.8782. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.420
_exptl_crystal_description       plate
_exptl_crystal_F_000             3106
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.276
_refine_diff_density_min         -1.177
_refine_diff_density_rms         0.309
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.186
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     609
_refine_ls_number_reflns         10042
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.186
_refine_ls_R_factor_all          0.0625
_refine_ls_R_factor_gt           0.0418
_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^)+(0.0550P)^2^+13.1341P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0985
_refine_ls_wR_factor_ref         0.1144
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8174
_reflns_number_total             10042
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc03471k2.cif
_cod_data_source_block           NENU_607
_cod_database_code               1549998
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.903
_shelx_estimated_absorpt_t_min   0.645
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Others
 Fixed Sof: O5W(0.5) H5WA(0.5) H5WB(0.5) O1W(0.5) H1WA(0.5) H1WB(0.5) O6W(0.5)
 H6WA(0.5) H6WB(0.5) O8W(0.5) H8WA(0.5) H8WB(0.5)
3.a Riding coordinates:
 O4W(H4WA,H4WB), O5W(H5WA,H5WB), O1W(H1WA,H1WB), O6W(H6WA,H6WB), O8W(H8WA,H8WB)
3.b Free rotating group:
 O3W(H3WA,H3WB), O7W(H7WA,H7WB), O2W(H2WA,H2WB)
3.c Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C6(H6D,H6E), C5(H5D,H5E), C3(H3D,H3E), C2(H2D,H2E), C8(H8D,H8E),
 C7(H7A,H7B), C4(H4D,H4E)
3.d Idealised Me refined as rotating group:
 N6(H6A,H6B,H6C), N8(H8A,H8B,H8C), N1(H1C,H1D,H1E), N5(H5A,H5B,H5C), N3(H3A,
 H3B,H3C), N4(H4A,H4B,H4C), N2(H2A,H2B,H2C), N7(H7C,H7D,H7E)
;
_olex2_submission_special_instructions 'No special instructions were received'