Ligand-to-metal charge transfer facilitates photocatalytic oxygen atom transfer (OAT) with <i>cis</i>-dioxo molybdenum(vi)-Schiff base complexes.
Dreher, Thorsten; Geciauskas, Lukas; Steinfeld, Samuel; Procacci, Barbara; Whitwood, Adrian C.; Lynam, Jason M.; Douthwaite, Richard E.; Duhme-Klair, Anne-K; Chemical science 15 (2024) 16186–16195; doi:10.1039/d4sc02784a

data_1572529
_publ_section_title
;
 Ligand-to-metal charge transfer facilitates photocatalytic oxygen atom
 transfer (OAT) with <i>cis</i>-dioxo molybdenum(vi)-Schiff base
 complexes.
;
_journal_issue                   39
_journal_name_full               'Chemical science'
_journal_page_first              16186
_journal_page_last               16195
_journal_paper_doi               10.1039/d4sc02784a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C19 H19 Mo N O9 S'
_chemical_formula_sum            'C19 H19 Mo N O9 S'
_chemical_formula_weight         533.35
_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
_audit_creation_date             2022-11-04
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-12-07 deposited with the CCDC.	2024-08-28 downloaded from the CCDC.
;
_cell_angle_alpha                89.8034(16)
_cell_angle_beta                 87.7720(16)
_cell_angle_gamma                74.1423(16)
_cell_formula_units_Z            4
_cell_length_a                   7.97347(14)
_cell_length_b                   14.0397(3)
_cell_length_c                   18.8868(4)
_cell_measurement_reflns_used    8402
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      76.4400
_cell_measurement_theta_min      5.7830
_cell_volume                     2032.23(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_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)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.968
_diffrn_measured_fraction_theta_max 0.969
_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    -64.00 -19.00   0.50    1.00    --  -48.95 125.00 -60.00   90
  2  \w   -103.00 -76.00   0.50    1.00    --  -48.95-125.00 120.00   54
  3  \w    -25.00  24.00   0.50    1.00    --  -48.95  37.00-120.00   98
  4  \w   -112.00 -74.00   0.50    1.00    --  -48.95-125.00  30.00   76
  5  \w    -58.00   6.00   0.50    1.00    --  -48.95  57.00 120.00  128
  6  \w   -119.00 -90.00   0.50    1.00    --  -48.95-125.00 -90.00   58
  7  \w   -119.00 -94.00   0.50    1.00    --  -48.95-125.00 -60.00   50
  8  \w      8.00  64.00   0.50    1.00    --   48.95 -57.00 -90.00  112
  9  \w    -22.00   4.00   0.50    1.00    --   48.95 -57.00 -90.00   52
 10  \w     67.00 123.00   0.50    4.00    --  107.75 -57.00-180.00  112
 11  \w    119.00 178.00   0.50    4.00    --  107.75  37.00-180.00  118
 12  \w     38.00 111.00   0.50    4.00    --  107.75 -77.00-180.00  146
 13  \w     84.00 112.00   0.50    4.00    --  107.75 -77.00 -30.00   56
 14  \w     42.00 120.00   0.50    4.00    --  107.75 -19.00   0.00  156
 15  \w     40.00  82.00   0.50    4.00    --  107.75-125.00 150.00   84
 16  \w    139.00 174.00   0.50    4.00    --  107.75  57.00 -60.00   70
 17  \w     44.00 104.00   0.50    4.00    --  107.75 -99.00-180.00  120
 18  \w     76.00 105.00   0.50    4.00    --  107.75 -99.00 -30.00   58
 19  \w    103.00 177.00   0.50    4.00    --  107.75  19.00 -30.00  148
 20  \w     37.00  72.00   0.50    4.00    --  107.75 -99.00 -30.00   70
 21  \w    101.00 177.00   0.50    4.00    --  107.75  19.00-120.00  152
 22  \w     96.00 134.00   0.50    4.00    --  107.75  57.00 -60.00   76
 23  \w     38.00 105.00   0.50    4.00    --  107.75 -99.00  60.00  134
 24  \w     69.00  94.00   0.50    4.00    --  107.75 -99.00  90.00   50
 25  \w     35.00  77.00   0.50    4.00    --  107.75 -77.00 -30.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1665068000
_diffrn_orient_matrix_UB_12      -0.0770327000
_diffrn_orient_matrix_UB_13      -0.0278192000
_diffrn_orient_matrix_UB_21      -0.0964245000
_diffrn_orient_matrix_UB_22      -0.0185155000
_diffrn_orient_matrix_UB_23      -0.0654765000
_diffrn_orient_matrix_UB_31      0.0581663000
_diffrn_orient_matrix_UB_32      0.0820721000
_diffrn_orient_matrix_UB_33      -0.0400337000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0315
_diffrn_reflns_Laue_measured_fraction_full 0.968
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            12797
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.122
_diffrn_reflns_theta_max         67.122
_diffrn_reflns_theta_min         4.011
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.731
_exptl_absorpt_correction_T_max  0.817
_exptl_absorpt_correction_T_min  0.745
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.743
_exptl_crystal_description       block
_exptl_crystal_F_000             1080
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: methanol and dimethylsulfoxide'
_exptl_crystal_size_max          0.102
_exptl_crystal_size_mid          0.099
_exptl_crystal_size_min          0.075
_refine_diff_density_max         0.695
_refine_diff_density_min         -0.801
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     582
_refine_ls_number_reflns         12797
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0490
_refine_ls_R_factor_gt           0.0440
_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^)+(0.0811P)^2^+0.7636P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1166
_refine_ls_wR_factor_ref         0.1203
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11365
_reflns_number_total             12797
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.7333\% 
around [0.90 0.44 0.08] (reciprocal) or [1.00 0.00 0.00] (direct)
;
_cod_data_source_file            d4sc02784a2.cif
_cod_data_source_block           akdk22011_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 1572529--1572533.cif.'
_cod_database_code               1572529
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C19 H19 Mo1 N1 O9 S1'
_chemical_oxdiff_usercomment     'Lukas Geciauskas LG-1-006'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5773(8)
 0.4227(8)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C8) = Uanis(C8A)
Uanis(N1A) = Uanis(N1)
Uanis(C27) = Uanis(C27A)
Uanis(N2) = Uanis(N2A)
4. Others
 Sof(C8A)=Sof(H8A)=Sof(N1A)=1-FVAR(1)
 Sof(C8)=Sof(H8)=Sof(N1)=FVAR(1)
 Sof(C27A)=Sof(H27A)=Sof(N2A)=1-FVAR(2)
 Sof(C27)=Sof(H27)=Sof(N2)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C7(H7), C8(H8), C8A(H8A), C11(H11), C12(H12), C14(H14),
 C22(H22), C23(H23), C26(H26), C27(H27), C27A(H27A), C30(H30), C31(H31),
 C33(H33)
5.b Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,
 H38B,H38C)
;
_shelx_res_checksum              37230
_shelx_hkl_checksum              44621
_olex2_date_sample_data_collection 2022-11-01
_olex2_date_sample_submission    2022-10-31
_olex2_exptl_crystal_mounting_method 'oil on 75 micrometre micromount'
_olex2_submission_original_sample_id LG-1-006
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.350
_oxdiff_exptl_absorpt_empirical_full_min 0.812
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2