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_7131422
_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         'C23 H38 F3 Mo O8 S'
_chemical_formula_sum            'C23 H38 F3 Mo O8 S'
_chemical_formula_weight         627.53
_chemical_name_systematic
'molybdenum oxo bis(dipivaloylmethanate) triflate'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.0456(2)
_cell_length_b                   17.89060(10)
_cell_length_c                   17.08060(10)
_cell_measurement_reflns_used    23400
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.7560
_cell_measurement_theta_min      2.4690
_cell_volume                     5820.00(8)
_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  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'Image Plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.982
_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    104.00 178.00   0.50    0.78    --  111.50  30.00   0.00  148
  2  \w    127.00 174.00   0.50    0.78    --  111.50  30.00 -60.00   94
  3  \w     99.00 170.00   0.50    0.78    --  111.50  61.00  30.00  142
  4  \w    124.00 178.00   0.50    0.78    --  111.50  15.00 120.00  108
  5  \w     42.00  85.00   0.50    0.78    --  111.50-125.00 120.00   86
  6  \w     41.00  69.00   0.50    0.78    --  111.50 -61.00 150.00   56
  7  \w     38.00  64.00   0.50    0.20    --   49.56-130.00  17.00   52
  8  \w     48.00 111.00   0.50    0.78    --  111.50-125.00-180.00  126
  9  \w     49.00  95.00   0.50    0.78    --  111.50 -77.00 -90.00   92
 10  \w     41.00  66.00   0.50    0.78    --  111.50 -61.00 -60.00   50
 11  \w     42.00  67.00   0.50    0.78    --  111.50 -59.00  74.00   50
 12  \w    -26.00  23.00   0.50    0.20    --  -49.56  19.00-150.00   98
 13  \w    -49.00 -23.00   0.50    0.78    --  -90.00  61.00  30.00   52
 14  \w    -27.00  11.00   0.50    0.20    --  -49.56  19.00 120.00   76
 15  \w   -130.00-104.00   0.50    0.78    --  -90.00 -59.00  74.00   52
 16  \w   -117.00 -73.00   0.50    0.20    --  -49.56-125.00  30.00   88
 17  \w   -140.00-115.00   0.50    0.78    --  -90.00-130.00  17.00   50
 18  \w   -116.00 -73.00   0.50    0.20    --  -49.56-125.00-150.00   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku R-AXIS SPIDER IP'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0388
_diffrn_reflns_av_unetI/netI     0.0413
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            31035
_diffrn_reflns_point_group_measured_fraction_full 0.847
_diffrn_reflns_point_group_measured_fraction_max 0.810
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.158
_diffrn_reflns_theta_min         2.470
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_exptl_absorpt_coefficient_mu    4.892
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84614
_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            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.432
_exptl_crystal_description       block
_exptl_crystal_F_000             2600
_exptl_crystal_recrystallization_method
'from acetonitrile at -35 degree celsius'
_exptl_crystal_size_max          0.162
_exptl_crystal_size_mid          0.096
_exptl_crystal_size_min          0.056
_refine_diff_density_max         0.486
_refine_diff_density_min         -0.588
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.464(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     766
_refine_ls_number_reflns         10297
_refine_ls_number_restraints     337
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.0314
_refine_ls_R_factor_gt           0.0304
_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^)+(0.0386P)^2^+3.4084P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0780
_refine_ls_wR_factor_ref         0.0785
_reflns_Friedel_coverage         0.593
_reflns_Friedel_fraction_full    0.682
_reflns_Friedel_fraction_max     0.625
_reflns_number_gt                10006
_reflns_number_total             10297
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc00572k2.cif
_cod_data_source_block           fma_681_2_old
_cod_depositor_comments
'Adding full bibliography for 7131417--7131422.cif.'
_cod_database_code               7131422
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.771
_shelx_estimated_absorpt_t_min   0.505
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.536(9)
 0.464(9)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 S003-O8BB \\sim S003-O8BA \\sim S003-O7BB \\sim S003-O7BA
 with sigma of 0.02
 F1AB-C23A \\sim F1AA-C23A \\sim F3AB-C23A \\sim F3AA-C23A \\sim F2AB-C23A
\\sim F2AA-C23A
 with sigma of 0.02
 S004-O8AA \\sim S004-O8AB \\sim S004-O7AA \\sim S004-O7AB
 with sigma of 0.02
 F2BA-C23B \\sim F2BB-C23B \\sim F1BB-C23B \\sim F3BA-C23B \\sim F1BA-C23B
\\sim F3BB-C23B
 with sigma of 0.02
4. Rigid bond restraints
 S003, C23B, F1BB, F2BB, F3BB, O7BB, O8BB, F1BA, F2BA, F3BA, O7BA, O8BA
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 S004, C23A, F1AB, F2AB, F3AB, O7AB, O8AB, F1AA, F2AA, F3AA, O7AA, O8AA
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Uiso/Uaniso restraints and constraints
Uanis(O7BA) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O8BB) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O8AA) \\sim Ueq, Uanis(O8AB) \\sim Ueq, Uanis(O7AA) \\sim Ueq,
Uanis(O7AB) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(F1AA) \\sim Ueq, Uanis(F1AB) \\sim Ueq, Uanis(F2AA) \\sim Ueq,
Uanis(F2AB) \\sim Ueq, Uanis(F3AA) \\sim Ueq, Uanis(F3AB) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
6. Rigid body (RIGU) restrains
 S004, C23A, F1AB, F2AB, F3AB, O7AB, O8AB, F1AA, F2AA, F3AA, O7AA, O8AA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S003, C23B, F1BB, F2BB, F3BB, O7BB, O8BB, F1BA, F2BA, F3BA, O7BA, O8BA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(F1BB)=Sof(F2BB)=Sof(F3BB)=Sof(O7BB)=Sof(O8BB)=1-FVAR(1)
 Sof(F1BA)=Sof(F2BA)=Sof(F3BA)=Sof(O7BA)=Sof(O8BA)=FVAR(1)
 Sof(F1AB)=Sof(F2AB)=Sof(F3AB)=Sof(O7AB)=Sof(O8AB)=1-FVAR(2)
 Sof(F1AA)=Sof(F2AA)=Sof(F3AA)=Sof(O7AA)=Sof(O8AA)=FVAR(2)
8.a Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C15A(H15A), C4B(H4B), C15B(H15B)
8.b Idealised Me refined as rotating group:
 C1A(H1AA,H1AB,H1AC), C7A(H7AA,H7AB,H7AC), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,
 H9AC), C10A(H10A,H10B,H10C), C11A(H11A,H11B,H11C), C12A(H12A,H12B,H12C),
 C18A(H18A,H18B,H18C), C19A(H19A,H19B,H19C), C20A(H20A,H20B,H20C), C21A(H21A,
 H21B,H21C), C22A(H22A,H22B,H22C), C1B(H1BA,H1BB,H1BC), C7B(H7BA,H7BB,H7BC),
 C8B(H8BA,H8BB,H8BC), C9B(H9BA,H9BB,H9BC), C10B(H10D,H10E,H10F), C11B(H11D,H11E,
 H11F), C12B(H12D,H12E,H12F), C18B(H18D,H18E,H18F), C19B(H19D,H19E,H19F),
 C20B(H20D,H20E,H20F), C21B(H21D,H21E,H21F), C22B(H22D,H22E,H22F)
;
_shelx_res_checksum              79883
_shelx_hkl_checksum              99144
_olex2_date_sample_data_collection 2022-05-30
_olex2_date_sample_submission    2022-05-30
_olex2_submission_original_sample_id FMA_681
_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
;