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_1572532
_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         'C17 H15 F2 Mo N O5, 0.5(C4 H8 O)'
_chemical_formula_sum            'C19 H19 F2 Mo N O5.5'
_chemical_formula_weight         483.29
_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             2023-03-13
_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                71.970(5)
_cell_angle_beta                 80.752(5)
_cell_angle_gamma                77.252(5)
_cell_formula_units_Z            2
_cell_length_a                   6.7559(4)
_cell_length_b                   12.1951(7)
_cell_length_c                   12.2098(7)
_cell_measurement_reflns_used    1838
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      75.7910
_cell_measurement_theta_min      6.1730
_cell_volume                     928.33(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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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   -101.00 -39.00   0.50    0.20    --  -48.70 148.00  96.00  124
  2  \w    -87.00 -61.00   0.50    0.20    --  -48.70-148.00  49.00   52
  3  \w    -80.00 -47.00   0.50    0.20    --  -48.70 123.00 -67.00   66
  4  \w     48.00  92.00   0.50    0.20    --   48.70-123.00-147.00   88
  5  \w     48.00  92.00   0.50    0.20    --   48.70-148.00  49.00   88
  6  \w     99.00 124.00   0.50    0.80    --  107.75 148.00  96.00   50
  7  \w     73.00 105.00   0.50    0.80    --  107.75-123.00-147.00   64
  8  \w     64.00  90.00   0.50    0.80    --  107.75-148.00  49.00   52
  9  \w    122.00 153.00   0.50    0.80    --  107.75 123.00 -67.00   62
 10  \w   -111.00 -74.00   0.50    0.20    --  -48.70-125.00 -60.00   74
 11  \w   -111.00 -81.00   0.50    0.20    --  -48.70-125.00 -90.00   60
 12  \w   -120.00 -29.00   0.50    0.20    --  -48.70 -77.00-120.00  182
 13  \w   -115.00 -74.00   0.50    0.20    --  -48.70-125.00  60.00   82
 14  \w   -113.00 -75.00   0.50    0.20    --  -48.70-125.00-150.00   76
 15  \w   -109.00 -76.00   0.50    0.20    --  -48.70-125.00-120.00   66
 16  \w     19.00  58.00   0.50    0.20    --   48.70 -99.00  30.00   78
 17  \w     38.00  97.00   0.50    0.80    --  107.75 -99.00  90.00  118
 18  \w    100.00 176.00   0.50    0.80    --  107.75  37.00-180.00  152
 19  \w     85.00 117.00   0.50    0.80    --  107.75 -37.00   0.00   64
 20  \w     39.00 119.00   0.50    0.80    --  107.75 -77.00 -60.00  160
 21  \w     80.00 106.00   0.50    0.80    --  107.75 -99.00-150.00   52
 22  \w    136.00 162.00   0.50    0.80    --  107.75 125.00-120.00   52
 23  \w     37.00  76.00   0.50    0.80    --  107.75 -99.00-150.00   78
 24  \w     39.00 102.00   0.50    0.80    --  107.75 -57.00-180.00  126
 25  \w    137.00 177.00   0.50    0.80    --  107.75  57.00 150.00   80
 26  \w     93.00 132.00   0.50    0.80    --  107.75  57.00 150.00   78
 27  \w     97.00 174.00   0.50    0.80    --  107.75  19.00 -60.00  154
 28  \w     54.00  99.00   0.50    0.80    --  107.75 -99.00 -90.00   90
 29  \w    101.00 132.00   0.50    0.80    --  107.75 125.00-180.00   62
 30  \w     39.00  64.00   0.50    0.80    --  107.75 -99.00 -60.00   50
 31  \w     67.00  95.00   0.50    0.80    --  107.75 -99.00 -60.00   56
 32  \w     40.00 106.00   0.50    0.80    --  107.75 -99.00 120.00  132
 33  \w     39.00  84.00   0.50    0.80    --  107.75 -99.00   0.00   90
 34  \w     35.00  77.00   0.50    0.80    --  107.75 -37.00   0.00   84
 35  \w    118.00 178.00   0.50    0.80    --  107.75  19.00-120.00  120
;
_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      -0.1213981000
_diffrn_orient_matrix_UB_12      0.1258976000
_diffrn_orient_matrix_UB_13      -0.0388359000
_diffrn_orient_matrix_UB_21      0.0785918000
_diffrn_orient_matrix_UB_22      0.0063263000
_diffrn_orient_matrix_UB_23      -0.1270450000
_diffrn_orient_matrix_UB_31      -0.1851890000
_diffrn_orient_matrix_UB_32      -0.0486256000
_diffrn_orient_matrix_UB_33      -0.0115982000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0266
_diffrn_reflns_av_unetI/netI     0.0287
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            9376
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.072
_diffrn_reflns_theta_max         67.072
_diffrn_reflns_theta_min         3.826
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.283
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.419
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.73a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.729
_exptl_crystal_description       irregular
_exptl_crystal_F_000             488
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Heptane and tetrahydrofuran'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.431
_refine_diff_density_min         -0.500
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     336
_refine_ls_number_reflns         3307
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0292
_refine_ls_R_factor_gt           0.0279
_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^)+(0.0257P)^2^+1.0117P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0660
_refine_ls_wR_factor_ref         0.0668
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3175
_reflns_number_total             3307
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02784a2.cif
_cod_data_source_block           akdk23005
_cod_depositor_comments
'Adding full bibliography for 1572529--1572533.cif.'
_cod_original_cell_volume        928.32(10)
_cod_original_formula_sum        'C19 H19 F2 Mo N O5.50'
_cod_database_code               1572532
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C19 H18.5 F2 Mo1 N1 O5.5'
_chemical_oxdiff_usercomment     'Samuel Steinfeld  SS-034-1'
_shelx_estimated_absorpt_t_max   0.744
_shelx_estimated_absorpt_t_min   0.366
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C18-C19 = C20-C19 = C20-C21
 1.5 with sigma of 0.01
 O6-C18 = O6-C21
 1.42 with sigma of 0.01
3. Others
 Sof(C7A)=Sof(H7A)=Sof(N1A)=1-FVAR(1)
 Sof(C7)=Sof(H7)=Sof(N1)=FVAR(1)
 Sof(C14A)=Sof(H14C)=Sof(H14D)=Sof(C15A)=Sof(H15C)=Sof(H15D)=Sof(C16A)=
 Sof(H16C)=Sof(H16D)=Sof(C17A)=Sof(H17C)=Sof(H17D)=1-FVAR(2)
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=
 Sof(H16B)=Sof(C17)=Sof(H17A)=Sof(H17B)=FVAR(2)
 Fixed Sof: C18(0.5) H18A(0.5) H18B(0.5) C19(0.5) H19A(0.5) H19B(0.5) C20(0.5)
 H20A(0.5) H20B(0.5) C21(0.5) H21A(0.5) H21B(0.5) O6(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C14A(H14C,H14D), C15(H15A,H15B), C15A(H15C,H15D), C16(H16A,
 H16B), C16A(H16C,H16D), C17(H17A,H17B), C17A(H17C,H17D), C18(H18A,H18B),
 C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B)
4.b 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              53030
_shelx_hkl_checksum              8397
_olex2_exptl_crystal_mounting_method 'oil on 200 micrometre micromount'
_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 1.124
_oxdiff_exptl_absorpt_empirical_full_min 0.906