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_1572530
_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 H15 Mo N O5 S, C2 H6 O S'
_chemical_formula_sum            'C17 H21 Mo N O6 S2'
_chemical_formula_weight         495.41
_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             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                90
_cell_angle_beta                 93.9945(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.51400(14)
_cell_length_b                   6.72111(8)
_cell_length_c                   23.5861(3)
_cell_measurement_reflns_used    7746
_cell_measurement_temperature    109.95(10)
_cell_measurement_theta_max      76.4600
_cell_measurement_theta_min      3.5510
_cell_volume                     1978.96(4)
_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      109.95(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -81.00  18.00   0.50    2.50    --  -48.70 101.00 -36.00  198
  2  \w     10.00  36.00   0.50    2.50    --   48.70-101.00-140.00   52
  3  \w     71.00  96.00   0.50   10.00    --  107.75-101.00-140.00   50
  4  \w    116.00 177.00   0.50   10.00    --  107.75 101.00 -36.00  122
  5  \w   -120.00 -37.00   0.50    2.50    --  -48.70 -57.00-150.00  166
  6  \w   -117.00 -74.00   0.50    2.50    --  -48.70-125.00   0.00   86
  7  \w   -117.00 -82.00   0.50    2.50    --  -48.70-125.00  90.00   70
  8  \w   -118.00 -93.00   0.50    2.50    --  -48.70-125.00  30.00   50
  9  \w     45.00  80.00   0.50   10.00    --  107.75 -99.00  30.00   70
 10  \w     85.00 162.00   0.50   10.00    --  107.75  77.00 120.00  154
 11  \w     57.00 113.00   0.50   10.00    --  107.75 -37.00-180.00  112
 12  \w     65.00  91.00   0.50   10.00    --  107.75 -99.00 120.00   52
 13  \w     57.00  82.00   0.50   10.00    --  107.75 -99.00 -30.00   50
 14  \w    104.00 177.00   0.50   10.00    --  107.75  37.00-120.00  146
 15  \w     41.00 102.00   0.50   10.00    --  107.75 -99.00 -60.00  122
 16  \w     33.00  96.00   0.50   10.00    --  107.75 -19.00 -60.00  126
 17  \w     41.00 100.00   0.50   10.00    --  107.75 -99.00-180.00  118
 18  \w     52.00 121.00   0.50   10.00    --  107.75 -57.00   0.00  138
;
_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      0.0139554000
_diffrn_orient_matrix_UB_12      0.0062449000
_diffrn_orient_matrix_UB_13      0.0653639000
_diffrn_orient_matrix_UB_21      -0.0365375000
_diffrn_orient_matrix_UB_22      -0.2184885000
_diffrn_orient_matrix_UB_23      0.0025471000
_diffrn_orient_matrix_UB_31      0.1170791000
_diffrn_orient_matrix_UB_32      -0.0691128000
_diffrn_orient_matrix_UB_33      -0.0021839000
_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  0.0293
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            12118
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.071
_diffrn_reflns_theta_max         67.071
_diffrn_reflns_theta_min         3.541
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.697
_exptl_absorpt_correction_T_max  0.832
_exptl_absorpt_correction_T_min  0.613
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.663
_exptl_crystal_description       plate
_exptl_crystal_F_000             1008
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Diethylether and dimethylsulfoxide'
_exptl_crystal_size_max          0.115
_exptl_crystal_size_mid          0.054
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.632
_refine_diff_density_min         -0.357
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     349
_refine_ls_number_reflns         3512
_refine_ls_number_restraints     88
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0287
_refine_ls_R_factor_gt           0.0258
_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^)+(0.0309P)^2^+1.4631P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0643
_refine_ls_wR_factor_ref         0.0658
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3216
_reflns_number_total             3512
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02784a2.cif
_cod_data_source_block           akdk22013
_cod_depositor_comments
'Adding full bibliography for 1572529--1572533.cif.'
_cod_database_code               1572530
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C17 H21 Mo1 N1 O6 S2'
_chemical_oxdiff_usercomment     'Lukas Geciauskas LG-1-016'
_shelx_estimated_absorpt_t_max   0.780
_shelx_estimated_absorpt_t_min   0.471
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C16-C17 \\sim C16A-C17A
 with sigma of 0.02
 C1-C6 \\sim C13A-C8A
 with sigma of 0.02
 C1-C2 \\sim C13A-C12A
 with sigma of 0.02
 C16A-O6A \\sim O6A-C17A \\sim C17-O6 \\sim O6-C16
 with sigma of 0.02
 C1-C3 \\sim C13A-C11A
 with sigma of 0.04
 S2A-O6A \\sim S2-O6
 with sigma of 0.02
 S2-C16 \\sim S2A-C16A \\sim S2-C17 \\sim S2A-C17A
 with sigma of 0.02
 C1-C5 \\sim C13A-C9A
 with sigma of 0.04
 C1-C7 \\sim C13A-C7
 with sigma of 0.04
 C1-N1A \\sim C13A-N1A
 with sigma of 0.04
 O4A-C13A \\sim O3-C1
 with sigma of 0.02
 C6-C2 \\sim C8A-C12A
 with sigma of 0.04
 C6-C7 \\sim C8A-C7
 with sigma of 0.02
 C6-N1A \\sim C8A-N1A
 with sigma of 0.02
 C6A-C5A \\sim C9-C8
 with sigma of 0.02
 C6-C5 \\sim C8A-C9A
 with sigma of 0.02
 C6-C4 \\sim C8A-C10A
 with sigma of 0.04
 C8-C13 \\sim C1A-C6A
 with sigma of 0.02
 C2A-C1A \\sim C12-C13
 with sigma of 0.02
 C4A-C3A \\sim C10-C11
 with sigma of 0.02
 C11-C12 \\sim C2A-C3A
 with sigma of 0.02
 C4A-C5A \\sim C10-C9
 with sigma of 0.02
 C5-C7 \\sim C9A-C7
 with sigma of 0.04
 C2-C3 \\sim C12A-C11A
 with sigma of 0.02
 C4-C5 \\sim C10A-C9A
 with sigma of 0.02
 C2-C4 \\sim C12A-C10A
 with sigma of 0.04
 C3-C5 \\sim C11A-C9A
 with sigma of 0.04
 C5-N1A \\sim C9A-N1A
 with sigma of 0.04
 C3-C4 \\sim C11A-C10A
 with sigma of 0.02
 Mo4-O4A \\sim Mo1-O3
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C17A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1A) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C8)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C6) \\sim Ueq, Uanis(C8A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C1) \\sim Ueq, Uanis(C13A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C16A) = Uanis(C16)
Uanis(O3) = Uanis(O4A)
Uanis(O6) = Uanis(O6A)
Uanis(S2A) = Uanis(S2)
Uanis(C13A) = Uanis(C1)
Uanis(C1) = Uanis(C13A)
Uanis(N1) = Uanis(N1A)
Uanis(C6A) = Uanis(C8)
Uanis(C8A) = Uanis(C6)
Uanis(C7A) = Uanis(C7)
Uanis(C12) = Uanis(C2A)
Uanis(C13) = Uanis(C1A)
Uanis(C4A) = Uanis(C10)
Uanis(C3A) = Uanis(C11)
Uanis(C5A) = Uanis(C9)
Uanis(C9A) = Uanis(C5)
Uanis(C12A) = Uanis(C2)
Uanis(C10A) = Uanis(C4)
Uanis(C11A) = Uanis(C3)
4. Others
 Sof(C1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=
 Sof(H5A)=Sof(C6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=
 Sof(H10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H14D)=
 Sof(H14E)=Sof(H14F)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(N1A)=Sof(O3A)=Sof(O4A)=
 Sof(O5A)=Sof(S1A)=Sof(Mo4)=1-FVAR(1)
 Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=
 Sof(C6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=
 Sof(H11)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(H15A)=
 Sof(H15B)=Sof(H15C)=Sof(Mo1)=Sof(N1)=Sof(O3)=Sof(O4)=Sof(O5)=Sof(S1)=FVAR(1)
 Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=
 Sof(H17F)=Sof(O6A)=Sof(S2A)=1-FVAR(2)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(O6)=Sof(S2)=FVAR(2)
5.a Riding coordinates:
 C16A(H16D,H16E,H16F), C17A(H17D,H17E,H17F)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C2A(H2A), C3(H3), C3A(H3A), C4(H4), C4A(H4A), C5(H5), C5A(H5A),
 C7(H7), C7A(H7A), C9(H9), C9A(H9A), C10(H10), C10A(H10A), C11(H11), C11A(H11A),
  C12(H12), C12A(H12A)
5.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C14(H14D,H14E,H14F), C15(H15A,H15B,H15C), C15(H15D,H15E,
 H15F), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              15067
_shelx_hkl_checksum              88986
_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-1-016
_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 1.182
_oxdiff_exptl_absorpt_empirical_full_min 0.821