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_1572533
_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         'C15 H9 F6 Mo N O5, C4 H8 O'
_chemical_formula_sum            'C19 H17 F6 Mo N O6'
_chemical_formula_weight         565.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-10
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-12-07 deposited with the CCDC.	2024-08-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.217(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.3516(3)
_cell_length_b                   14.8110(3)
_cell_length_c                   11.4468(3)
_cell_measurement_reflns_used    10337
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      76.7250
_cell_measurement_theta_min      3.5740
_cell_volume                     2095.56(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.73a (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 0.991
_diffrn_measured_fraction_theta_max 0.991
_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   -103.00 -63.00   0.50    1.00    --  -48.70-140.00  92.00   80
  2  \w    -86.00 -46.00   0.50    1.00    --  -48.70 129.00 -21.00   80
  3  \w    -83.00 -58.00   0.50    1.00    --  -48.70 140.00 150.00   50
  4  \w   -118.00 -71.00   0.50    1.00    --  -48.70-129.00 -94.00   94
  5  \w     43.00  68.00   0.50    1.00    --   48.70-129.00 -94.00   50
  6  \w     50.00  75.00   0.50    1.00    --   48.70-140.00  92.00   50
  7  \w     89.00 137.00   0.50    4.00    --  107.75 140.00 150.00   96
  8  \w     82.00 112.00   0.50    4.00    --  107.75-129.00 -94.00   60
  9  \w     78.00 121.00   0.50    4.00    --  107.75-140.00  92.00   86
 10  \w    101.00 154.00   0.50    4.00    --  107.75 129.00 -21.00  106
 11  \w   -117.00 -83.00   0.50    1.00    --  -48.70-125.00  30.00   68
 12  \w   -117.00 -73.00   0.50    1.00    --  -48.70-125.00 -30.00   88
 13  \w     69.00 120.00   0.50    1.00    --   48.70  77.00 150.00  102
 14  \w     15.00  80.00   0.50    1.00    --   48.70 -99.00-150.00  130
 15  \w     26.00  65.00   0.50    1.00    --   48.70  77.00 150.00   78
 16  \w     36.00  83.00   0.50    4.00    --  107.75 -57.00  30.00   94
 17  \w     98.00 158.00   0.50    4.00    --  107.75  37.00-180.00  120
 18  \w    153.00 178.00   0.50    4.00    --  107.75  57.00-120.00   50
 19  \w    143.00 170.00   0.50    4.00    --  107.75 125.00  30.00   54
 20  \w     95.00 125.00   0.50    4.00    --  107.75 125.00  30.00   60
 21  \w     37.00 105.00   0.50    4.00    --  107.75 -99.00 -60.00  136
 22  \w    100.00 143.00   0.50    4.00    --  107.75 125.00  60.00   86
 23  \w    152.00 178.00   0.50    4.00    --  107.75 125.00  60.00   52
 24  \w    102.00 129.00   0.50    4.00    --  107.75  57.00-120.00   54
 25  \w     38.00 115.00   0.50    4.00    --  107.75 -37.00  30.00  154
 26  \w    130.00 156.00   0.50    4.00    --  107.75 129.00 -21.00   52
 27  \w   -103.00 -76.00   0.50    1.00    --  -48.70-125.00   0.00   54
 28  \w     44.00  80.00   0.50    1.00    --   48.70-125.00-180.00   72
 29  \w     80.00 106.00   0.50    4.00    --  107.75 -99.00 -90.00   52
 30  \w     37.00  62.00   0.50    4.00    --  107.75 -99.00 150.00   50
;
_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      0.0817125000
_diffrn_orient_matrix_UB_12      -0.0543492000
_diffrn_orient_matrix_UB_13      -0.0373684000
_diffrn_orient_matrix_UB_21      0.0462275000
_diffrn_orient_matrix_UB_22      0.0885655000
_diffrn_orient_matrix_UB_23      -0.0292448000
_diffrn_orient_matrix_UB_31      0.0820077000
_diffrn_orient_matrix_UB_32      0.0040068000
_diffrn_orient_matrix_UB_33      0.1374819000
_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     0.0172
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            6751
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.034
_diffrn_reflns_theta_max         67.034
_diffrn_reflns_theta_min         3.576
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.975
_exptl_absorpt_correction_T_max  0.656
_exptl_absorpt_correction_T_min  0.392
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.73a (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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.792
_exptl_crystal_description       block
_exptl_crystal_F_000             1128
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Heptane and tetrahydrofuran'
_exptl_crystal_size_max          0.193
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.094
_refine_diff_density_max         0.820
_refine_diff_density_min         -0.508
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     307
_refine_ls_number_reflns         6751
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0326
_refine_ls_R_factor_gt           0.0297
_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^)+(0.0426P)^2^+1.2447P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0773
_refine_ls_wR_factor_ref         0.0793
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6164
_reflns_number_total             6751
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9899\% 
around [-0.40 0.00 0.91] (reciprocal) or [-0.00 -0.00 1.00] (direct)
;
_cod_data_source_file            d4sc02784a2.cif
_cod_data_source_block           akdk23004_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 1572529--1572533.cif.'
_cod_original_cell_volume        2095.56(9)
_cod_database_code               1572533
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C16 H11 F6 Mo1 N1 O5 C4 H8 O'
_chemical_oxdiff_usercomment     'Samuel Steinfeld  SS-038-2'
_shelx_estimated_absorpt_t_max   0.604
_shelx_estimated_absorpt_t_min   0.392
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5076(8)
 0.4924(8)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C7A) = Uanis(C7)
Uanis(N1A) = Uanis(N1)
4. Others
 Sof(C7A)=Sof(H7A)=Sof(N1A)=1-FVAR(1)
 Sof(C7)=Sof(H7)=Sof(N1)=FVAR(1)
5.a Rotating group:
 O3(H3A,H3B)
5.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C7(H7), C7A(H7A), C9(H9), C11(H11), C12(H12)
;
_shelx_res_checksum              80363
_shelx_hkl_checksum              59697
_olex2_date_sample_data_collection 2023-02-28
_olex2_date_sample_submission    2023-02-24
_olex2_exptl_crystal_mounting_method 'oil on 200 micrometre micromount'
_olex2_submission_original_sample_id SS-038-2
_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 1.157
_oxdiff_exptl_absorpt_empirical_full_min 0.887
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2