Selective light driven reduction of CO<sub>2</sub> to HCOOH in water using a {MoV<sub>9</sub>}<sub>n</sub> (n = 1332-3600) based soft-oxometalate (SOM).
Barman, Soumitra; Das, Santu; S S, Sreejith; Garai, Somnath; Pochamoni, Ramudu; Roy, Soumyajit; Chemical communications (Cambridge, England) 54 (2018) 2369–2372; doi:10.1039/c7cc09520a

data_7121250
_publ_section_title
;
 Selective light driven reduction of CO<sub>2</sub> to HCOOH in water
 using a {MoV<sub>9</sub>}<sub>n</sub> (n = 1332-3600) based
 soft-oxometalate (SOM).
;
_journal_issue                   19
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              2369
_journal_page_last               2372
_journal_paper_doi               10.1039/c7cc09520a
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety         'Mo O28 V9, H20 Na2 O10, 3(H4 N)'
_chemical_formula_sum            'H32 Mo N3 Na2 O38 V9'
_chemical_formula_weight         1282.66
_chemical_name_common            'Mo-doped Decavanadate'
_chemical_name_systematic        NaNH4MoV9
_chemical_properties_physical    Photo-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   difmap
_audit_creation_date             2017-09-20
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2017-09-21 deposited with the CCDC.
2018-02-07 downloaded from the CCDC.
;
_cell_angle_alpha                69.439(10)
_cell_angle_beta                 87.119(9)
_cell_angle_gamma                66.575(10)
_cell_formula_units_Z            1
_cell_length_a                   8.7249(9)
_cell_length_b                   10.4654(11)
_cell_length_c                   11.1884(13)
_cell_measurement_reflns_used    2550
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      27.3120
_cell_measurement_theta_min      2.3930
_cell_volume                     872.93(19)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15(10)
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0205
_diffrn_reflns_av_unetI/netI     0.0324
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            5354
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.025
_diffrn_reflns_theta_max         25.025
_diffrn_reflns_theta_min         1.955
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.789
_exptl_absorpt_correction_T_max  0.0470
_exptl_absorpt_correction_T_min  0.0234
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0434 before and 0.0366 after correction.
The Ratio of minimum to maximum transmission is 0.4979.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear dark orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.440
_exptl_crystal_description       block
_exptl_crystal_F_000             628
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Water'
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.770
_refine_diff_density_min         -1.430
_refine_diff_density_rms         0.145
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     277
_refine_ls_number_reflns         3058
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0670
_refine_ls_R_factor_gt           0.0587
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0915P)^2^+4.5452P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1742
_refine_ls_wR_factor_ref         0.1827
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2613
_reflns_number_total             3058
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc09520a2.cif
_cod_data_source_block           v9Mo
_cod_depositor_comments          'Adding full bibliography for 7121250.cif.'
_cod_original_cell_volume        872.93(18)
_cod_database_code               7121250
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   0.808
_shelx_estimated_absorpt_t_min   0.664
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All N(H,H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Shared sites
{V1, Mo1}
{V2, Mo2}
3. Restrained distances
 O14-H14A = O14-H14B
 0.87 with sigma of 0.02
 O15-H15A = O15-H15B
 0.87 with sigma of 0.02
 O18-H18A = O18-H18B
 0.87 with sigma of 0.02
 O16-H16A = O16-H16B
 0.87 with sigma of 0.02
 N2-H2D
 1 with sigma of 0.02
 N1-H1D
 1 with sigma of 0.02
 H14A-H14B
 1.38 with sigma of 0.04
 H15A-H15B
 1.38 with sigma of 0.04
 H18A-H18B
 1.38 with sigma of 0.04
 H16A-H16B
 1.38 with sigma of 0.04
 Na1-H14A \\sim Na1-H14B
 with sigma of 0.02
 Na1-H15A \\sim Na1-H15B
 with sigma of 0.02
 Na1-H18A \\sim Na1-H18B
 with sigma of 0.02
 Na1-H16A \\sim Na1-H16B
 with sigma of 0.02
 H2D-H2A \\sim H2D-H2B \\sim H2D-H2C
 with sigma of 0.02
 H1D-H1A \\sim H1D-H1B \\sim H1D-H1C
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(V1) = Uanis(Mo1)
Uanis(V2) = Uanis(Mo2)
5. Others
 Fixed Sof: V1(0.75) Mo1(0.25) V2(0.75) Mo2(0.25) N1(0.75) H1A(0.75) H1B(0.75)
 H1C(0.75) N2(0.75) H2A(0.75) H2B(0.75) H2C(0.75) H2D(0.75) H1D(0.75)
6.a Riding coordinates:
 N1(H1A,H1B,H1C), N2(H2A,H2B,H2C)
6.b Rotating group:
 O17(H17A,H17B)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop with superglue'
_olex2_submission_original_sample_id V9Mo
_olex2_submission_special_instructions 'No special instructions were received'