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_1572531
_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         'C16 H17 Mo N O7'
_chemical_formula_sum            'C16 H17 Mo N O7'
_chemical_formula_weight         431.24
_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             2023-02-27
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-12-07 deposited with the CCDC.	2024-08-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.9309(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.93153(10)
_cell_length_b                   11.74560(18)
_cell_length_c                   20.3314(3)
_cell_measurement_reflns_used    5818
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      76.1820
_cell_measurement_theta_min      4.3140
_cell_volume                     1649.15(4)
_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   -123.00 -51.00   0.50    0.20    --  -48.70 -16.00 162.00  144
  2  \w    -61.00  -2.00   0.50    0.20    --  -48.70  16.00 -28.00  118
  3  \w     -6.00  19.00   0.50    0.20    --   48.70 -16.00 162.00   50
  4  \w     73.00 111.00   0.50    0.20    --   48.70  16.00 -28.00   76
  5  \w     47.00 106.00   0.50    0.80    --  107.75 -16.00 162.00  118
  6  \w     94.00 178.00   0.50    0.80    --  107.75  16.00 -28.00  168
  7  \w    -26.00  60.00   0.50    0.20    --   48.70 -19.00  30.00  172
  8  \w     42.00  75.00   0.50    0.20    --   48.70-125.00  90.00   66
  9  \w     45.00 116.00   0.50    0.80    --  107.75 -57.00  90.00  142
 10  \w     36.00 119.00   0.50    0.80    --  107.75 -19.00 -30.00  166
 11  \w     36.00 126.00   0.50    0.80    --  107.75 -77.00  90.00  180
 12  \w    110.00 153.00   0.50    0.80    --  107.75  37.00  30.00   86
 13  \w     39.00  65.00   0.50    0.80    --  107.75-125.00 150.00   52
 14  \w     42.00  94.00   0.50    0.80    --  107.75 -99.00 -90.00  104
 15  \w     86.00 111.00   0.50    0.80    --  107.75-125.00 150.00   50
 16  \w     81.00 106.00   0.50    0.80    --  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      0.1698990000
_diffrn_orient_matrix_UB_12      -0.0106853000
_diffrn_orient_matrix_UB_13      0.0537262000
_diffrn_orient_matrix_UB_21      -0.1438020000
_diffrn_orient_matrix_UB_22      -0.0258024000
_diffrn_orient_matrix_UB_23      0.0517541000
_diffrn_orient_matrix_UB_31      0.0149235000
_diffrn_orient_matrix_UB_32      -0.1281444000
_diffrn_orient_matrix_UB_33      -0.0148336000
_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  0.0334
_diffrn_reflns_av_unetI/netI     0.0329
_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       9
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            9124
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.039
_diffrn_reflns_theta_max         67.039
_diffrn_reflns_theta_min         4.351
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.876
_exptl_absorpt_correction_T_max  0.786
_exptl_absorpt_correction_T_min  0.342
_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 orangish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.737
_exptl_crystal_description       block
_exptl_crystal_F_000             872
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: methanol and tetrahydrofuran'
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.139
_exptl_crystal_size_min          0.102
_refine_diff_density_max         0.458
_refine_diff_density_min         -0.699
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     261
_refine_ls_number_reflns         2945
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0303
_refine_ls_R_factor_gt           0.0283
_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^)+(0.0210P)^2^+1.8646P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0665
_refine_ls_wR_factor_ref         0.0676
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2779
_reflns_number_total             2945
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02784a2.cif
_cod_data_source_block           akdk23003
_cod_depositor_comments
'Adding full bibliography for 1572529--1572533.cif.'
_cod_database_code               1572531
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C16 H17 Mo1 N1 O7'
_chemical_oxdiff_usercomment     'Samuel Steinfeld'
_shelx_estimated_absorpt_t_max   0.541
_shelx_estimated_absorpt_t_min   0.326
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C5A) = Uanis(C5)
Uanis(O4A) = Uanis(O4)
Uanis(C3) = Uanis(C3A)
Uanis(C2) = Uanis(C2A)
Uanis(C6) = Uanis(C6A)
Uanis(C4) = Uanis(C4A)
Uanis(C1) = Uanis(C1A)
Uanis(C14A) = Uanis(C14)
Uanis(C7A) = Uanis(C7)
Uanis(N1A) = Uanis(N1)
Uanis(O3) = Uanis(O3A)
3. Others
 Sof(C6A)=Sof(C5A)=Sof(H5A)=Sof(C4A)=Sof(C3A)=Sof(H3A)=Sof(C2A)=Sof(H2A)=
 Sof(C1A)=Sof(C7A)=Sof(H7A)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(N1A)=
 Sof(O3A)=Sof(O4A)=1-FVAR(1)
 Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(C5)=Sof(H5)=Sof(C6)=
 Sof(C7)=Sof(H7)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(N1)=Sof(O3)=Sof(O4)=
 FVAR(1)
4.a Riding coordinates:
 O7(H7B)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C5A(H5A), C3A(H3A), C2A(H2A), C7(H7), C7A(H7A),
 C9(H9), C11(H11), C12(H12)
4.c Fitted hexagon refined as free rotating group:
 C6A(C5A,C4A,C3A,C2A,C1A)
4.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              67676
_shelx_hkl_checksum              54350
_olex2_date_sample_data_collection 2023-02-20
_olex2_date_sample_submission    2023-02-16
_olex2_exptl_crystal_mounting_method 'oil on 200 micrometre micromount'
_olex2_submission_original_sample_id SS-025-1
_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 1.191
_oxdiff_exptl_absorpt_empirical_full_min 0.882