Molybdenum(IV) β-diketonate complexes as highly active catalysts for allylic substitution reactions.
Masero, Fabio; Mougel, Victor; Chemical communications (Cambridge, England) 59 (2023) 4636–4639; doi:10.1039/d3cc00572k

data_7131419
_publ_section_title
;
 Molybdenum(IV) &#x3b2;-diketonate complexes as highly active catalysts
 for allylic substitution reactions.
;
_journal_issue                   31
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              4636
_journal_page_last               4639
_journal_paper_doi               10.1039/d3cc00572k
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety         'C12 H14 F6 Mo O10 S2'
_chemical_formula_sum            'C12 H14 F6 Mo O10 S2'
_chemical_formula_weight         592.29
_chemical_name_systematic        molybdenum-bis(acac)-bis(triflate)
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-02
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-06 deposited with the CCDC.	2023-03-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.611(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.2697(3)
_cell_length_b                   12.9257(5)
_cell_length_c                   19.5683(6)
_cell_measurement_reflns_used    3875
_cell_measurement_temperature    100.01
_cell_measurement_theta_max      76.4840
_cell_measurement_theta_min      6.3910
_cell_volume                     2062.33(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01
_diffrn_detector                 'Image Plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.976
_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    -74.00  -3.00   0.50    2.45    --  -47.39  91.00 115.00  142
  2  \w      7.00  52.00   0.50    2.45    --   47.39 -91.00   2.00   90
  3  \w    -77.00 -49.00   0.50    9.79    --  -91.75  91.00 115.00   56
  4  \w   -132.00-105.00   0.50    9.79    --  -91.75 -91.00   2.00   54
  5  \w     64.00  90.00   0.50    9.79    --  113.25 -91.00   2.00   52
  6  \w    103.00 178.00   0.50    9.79    --  113.25  91.00 115.00  150
  7  \w   -117.00 -73.00   0.50    2.45    --  -47.39-125.00-120.00   88
  8  \w   -117.00 -74.00   0.50    2.45    --  -47.39-125.00-180.00   86
  9  \w   -117.00 -77.00   0.50    2.45    --  -47.39-125.00  60.00   80
 10  \w   -119.00 -75.00   0.50    2.45    --  -47.39-125.00  90.00   88
 11  \w    -49.00 -23.00   0.50    9.79    --  -91.75  45.00 -90.00   52
 12  \w    103.00 153.00   0.50    9.79    --  113.25  45.00-150.00  100
 13  \w     55.00 102.00   0.50    9.79    --  113.25 -77.00   0.00   94
 14  \w     42.00  70.00   0.50    9.79    --  113.25 -61.00  60.00   56
 15  \w     43.00  69.00   0.50    9.79    --  113.25 -61.00 120.00   52
 16  \w     42.00  70.00   0.50    9.79    --  113.25 -61.00-150.00   56
 17  \w    141.00 178.00   0.50    9.79    --  113.25 125.00  60.00   74
 18  \w     52.00 105.00   0.50    9.79    --  113.25 -77.00  30.00  106
 19  \w    109.00 165.00   0.50    9.79    --  113.25  45.00-180.00  112
 20  \w     43.00  71.00   0.50    9.79    --  113.25 -61.00  90.00   56
 21  \w    113.00 152.00   0.50    9.79    --  113.25 125.00-180.00   78
 22  \w     51.00  92.00   0.50    9.79    --  113.25-125.00 150.00   82
 23  \w     96.00 125.00   0.50    9.79    --  113.25 125.00  60.00   58
 24  \w     43.00 100.00   0.50    9.79    --  113.25 -95.00-120.00  114
 25  \w     44.00  86.00   0.50    9.79    --  113.25-125.00   0.00   84
 26  \w     42.00  97.00   0.50    9.79    --  113.25 -77.00 150.00  110
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku R-AXIS SPIDER IP'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0713792000
_diffrn_orient_matrix_UB_12      -0.0561442000
_diffrn_orient_matrix_UB_13      -0.0577892000
_diffrn_orient_matrix_UB_21      -0.1119770000
_diffrn_orient_matrix_UB_22      -0.0932860000
_diffrn_orient_matrix_UB_23      0.0063743000
_diffrn_orient_matrix_UB_31      -0.1344606000
_diffrn_orient_matrix_UB_32      0.0483868000
_diffrn_orient_matrix_UB_33      -0.0547527000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0363
_diffrn_reflns_av_unetI/netI     0.0412
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            7189
_diffrn_reflns_point_group_measured_fraction_full 0.601
_diffrn_reflns_point_group_measured_fraction_max 0.576
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.930
_diffrn_reflns_theta_min         4.584
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.079
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78326
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.908
_exptl_crystal_description       plate
_exptl_crystal_F_000             1176
_exptl_crystal_recrystallization_method
'from acetonitrile at -35 degree Celsius.'
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.755
_refine_diff_density_min         -1.120
_refine_diff_density_rms         0.105
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.009(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     284
_refine_ls_number_reflns         2598
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0396
_refine_ls_R_factor_gt           0.0382
_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^)+(0.0602P)^2^+6.1475P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0991
_refine_ls_wR_factor_ref         0.1000
_reflns_Friedel_coverage         0.179
_reflns_Friedel_fraction_full    0.202
_reflns_Friedel_fraction_max     0.175
_reflns_number_gt                2516
_reflns_number_total             2598
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc00572k2.cif
_cod_data_source_block           fma_605_1
_cod_depositor_comments
'Adding full bibliography for 7131417--7131422.cif.'
_cod_database_code               7131419
_shelx_shelxl_version_number     2019/1
_chemical_oxdiff_formula         MoO12C10S2F6H14
_chemical_oxdiff_usercomment     'dark plate, DCM/Et2O'
_shelx_estimated_absorpt_t_max   0.924
_shelx_estimated_absorpt_t_min   0.738
_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.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8)
2.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C5(H5A,H5B,H5C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              18941
_shelx_hkl_checksum              85098
_olex2_date_sample_data_collection 2022-02-07
_olex2_date_sample_submission    2022-02-07
_olex2_exptl_crystal_mounting_method 'in a glovebox.'
_olex2_submission_original_sample_id FMA_605_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 1.573
_oxdiff_exptl_absorpt_empirical_full_min 0.649