Mn(ii) betadiketonates: structural diversity from deceptively minor alterations to synthetic protocols
Ibrahim, Mukaila A.; Boeré, René T.; Preuss, Kathryn E.; RSC Advances 15 (2025) 32299–32308; doi:10.1039/D5RA03587B

data_7250842
_publ_section_title
;
 Mn(ii) betadiketonates: structural diversity from deceptively minor
 alterations to synthetic protocols
;
_journal_issue                   39
_journal_name_full               'RSC Advances'
_journal_page_first              32299
_journal_page_last               32308
_journal_paper_doi               10.1039/D5RA03587B
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C18 H18 F12 Mn O6'
_chemical_formula_sum            'C18 H18 F12 Mn O6'
_chemical_formula_weight         613.26
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-14
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-05 deposited with the CCDC.	2025-08-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.4825(8)
_cell_length_b                   19.6279(8)
_cell_length_c                   7.7219(4)
_cell_measurement_reflns_used    9893
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      27.44
_cell_measurement_theta_min      2.83
_cell_volume                     2346.6(2)
_computing_cell_refinement       APEX4
_computing_data_collection       'APEX4 (Bruker AXS, 2021)'
_computing_data_reduction        APEX4
_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      150.03
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker Kappa APEX-DUO CMOS PHOTON II'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0278
_diffrn_reflns_av_unetI/netI     0.0128
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            40469
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.466
_diffrn_reflns_theta_min         2.075
_exptl_absorpt_coefficient_mu    0.691
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6773
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Krause et al., 2015)'
_exptl_crystal_colour            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.736
_exptl_crystal_description       Shard
_exptl_crystal_F_000             1228
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.365
_refine_diff_density_min         -0.302
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     212
_refine_ls_number_reflns         2764
_refine_ls_number_restraints     79
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0308
_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^)+(0.0316P)^2^+1.7840P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0767
_refine_ls_wR_factor_ref         0.0812
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2423
_reflns_number_total             2764
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra03587b2.cif
_cod_data_source_block           7_[Mn(hfac)2THF(THF2)]
_cod_database_code               7250842
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.892
_shelx_estimated_absorpt_t_min   0.820
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C7-C8 = C10-C11
 1.51 with sigma of 0.01
 C6-C7 = C8-C9 = C10-C11 = C12-C13
 1.5 with sigma of 0.01
 O3-C6 = O3-C9 = O4-C10 = O4-C13
 1.45 with sigma of 0.01
 F4-F5 \\sim F5-F6 \\sim F6-F4 \\sim F4A-F5A \\sim F5A-F6A \\sim F6A-F4A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(F6A) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F4A)
\\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F5A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(F1) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F2) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C6) = Uanis(C9)
Uanis(C13) = Uanis(C10)
Uanis(C7) = Uanis(C8)
Uanis(C12) = Uanis(C11)
Ueq(C6), Ueq(C9), Ueq(C13), Ueq(C10): fixed at 0.001 with sigma of 0.1
Ueq(C10), Ueq(C13), Ueq(C6), Ueq(C9): fixed at 0.057 with sigma of 0.1
Ueq(C9), Ueq(C6), Ueq(C13), Ueq(C10): fixed at 0.05 with sigma of 0.1
Uvol(C13) \\sim Uvol(C10) \\sim Uvol(C6) \\sim Uvol(C9): with sigma of 0.1
4. Others
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(1)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
 Fixed Sof: C6(0.5) H6A(0.5) H6B(0.5) C7(0.5) H7A(0.5) H7B(0.5) C8(0.5)
 H8A(0.5) H8B(0.5) C9(0.5) H9A(0.5) H9B(0.5) C10(0.5) H10A(0.5) H10B(0.5)
 C11(0.5) H11A(0.5) H11B(0.5) C12(0.5) H12A(0.5) H12B(0.5) C13(0.5) H13A(0.5)
 H13B(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,
 H11B), C12(H12A,H12B), C13(H13A,H13B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2)
;
_shelx_res_checksum              10380
_olex2_submission_special_instructions 'No special instructions were received'