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_7131420
_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         '2(C11 H19 Cl Mo0.5 O2), C2 H3 N'
_chemical_formula_sum            'C24 H41 Cl2 Mo N O4'
_chemical_formula_weight         574.42
_chemical_name_systematic
'Molybdenum bis(dipivaloylmethanate) dichloride'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                 92.743(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.9632(5)
_cell_length_b                   18.9755(7)
_cell_length_c                   13.6819(6)
_cell_measurement_reflns_used    9839
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      30.50
_cell_measurement_theta_min      2.61
_cell_volume                     2843.0(2)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            5259
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_min         2.563
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.676
_exptl_absorpt_correction_T_max  100
_exptl_absorpt_correction_T_min  100
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0681 before and 0.0471 after correction.
 
For component 2:
 wR2(int) was 0.0713 before and 0.0576 after correction.
 The Ratio of minimum to maximum transmission is 0.90.

Final HKLF 4 output contains 85510 reflections, Rint = 0.0915
 (38738 with I > 3sig(I), Rint = 0.0529)
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_description       block
_exptl_crystal_F_000             1200
_exptl_crystal_recrystallization_method
'from acetonitrile at -35 degree Celsius.'
_exptl_crystal_size_max          0.368
_exptl_crystal_size_mid          0.154
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.955
_refine_diff_density_min         -0.773
_refine_diff_density_rms         0.146
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.191
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     306
_refine_ls_number_reflns         5259
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.190
_refine_ls_R_factor_all          0.0825
_refine_ls_R_factor_gt           0.0626
_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^)+29.1152P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1231
_refine_ls_wR_factor_ref         0.1377
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4735
_reflns_number_total             5259
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc00572k2.cif
_cod_data_source_block           twin4
_cod_depositor_comments
'Adding full bibliography for 7131417--7131422.cif.'
_cod_database_code               7131420
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.789
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7764(15)
 0.2236(15)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C6B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.002
Uanis(C1A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C4B(H4B)
4.b Idealised Me refined as rotating group:
 C8A(H8AA,H8AB,H8AC), C1A(H1AA,H1AB,H1AC), C7A(H7AA,H7AB,H7AC), C10A(H10A,H10B,
 H10C), C11A(H11A,H11B,H11C), C9A(H9AA,H9AB,H9AC), C11B(H11D,H11E,H11F),
 C10B(H10D,H10E,H10F), C8B(H8BA,H8BB,H8BC), C1B(H1BA,H1BB,H1BC), C7B(H7BA,H7BB,
 H7BC), C9B(H9BA,H9BB,H9BC), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              35155
_shelx_hkl_checksum              20432
_olex2_date_sample_data_collection 2021-03-14
_olex2_date_sample_submission    2021-03-14
_olex2_submission_original_sample_id FMA_408
_olex2_submission_special_instructions 'No special instructions were received'