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_7250841
_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         'C14 H12 F12 Mn O6'
_chemical_formula_sum            'C14 H12 F12 Mn O6'
_chemical_formula_weight         559.18
_chemical_properties_physical    Moisture-sensitive,Hygroscopic
_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             2025-08-15
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-08-16 deposited with the CCDC.	2025-08-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.799(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.9426(3)
_cell_length_b                   12.8936(3)
_cell_length_c                   14.0015(3)
_cell_measurement_reflns_used    10773
_cell_measurement_temperature    100.00(15)
_cell_measurement_theta_max      74.5440
_cell_measurement_theta_min      4.4470
_cell_volume                     2117.81(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(15)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.975
_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    -50.00  24.00   0.50    0.77    --  -38.50  57.00  90.00  148
  2  \w    -19.00  51.00   0.50    0.77    --   47.56 -38.00 -90.00  140
  3  \w     42.00 117.00   0.50    0.77    --   47.56  19.00 150.00  150
  4  \w     42.00 117.00   0.50    0.77    --   47.56  19.00 150.00  150
  5  \w     42.00 117.00   0.50    0.77    --   47.56  19.00   0.00  150
  6  \w     42.00 117.00   0.50    0.77    --   47.56  19.00   0.00  150
  7  \w    -19.00  51.00   0.50    0.77    --   47.56 -38.00 -90.00  140
  8  \w     28.00  97.00   0.50    0.77    --   47.56-125.00-150.00  138
  9  \w     36.00 105.00   0.50    3.09    --  100.13 -45.00 -60.00  138
 10  \w     38.00 113.00   0.50    3.09    --  100.13 -61.00 -60.00  150
 11  \w     32.00 104.00   0.50    3.09    --  100.13 -30.00  30.00  144
 12  \w     36.00 123.00   0.50    3.09    --  100.13 -77.00-150.00  174
 13  \w     36.00 105.00   0.50    3.09    --  100.13 -45.00-120.00  138
 14  \w     96.00 165.00   0.50    3.09    --  100.13  45.00 150.00  138
 15  \w     36.00 105.00   0.50    3.09    --  100.13 -45.00  30.00  138
 16  \w    103.00 165.00   0.50    3.09    --  100.13  77.00 150.00  124
 17  \w     31.00 170.00   0.50    3.09    --  100.13   0.00-180.00  278
 18  \w     44.00 114.00   0.50    0.77    --   47.56  38.00 -90.00  140
 19  \w     36.00 111.00   0.50    0.77    --   47.56  57.00-180.00  150
 20  \w    -19.00  51.00   0.50    0.77    --   47.56 -38.00-180.00  140
 21  \w     36.00  73.00   0.50    0.77    --   47.56  57.00   0.00   74
 22  \w     44.00 114.00   0.50    0.77    --   47.56  38.00  60.00  140
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0890097000
_diffrn_orient_matrix_UB_12      -0.0031412000
_diffrn_orient_matrix_UB_13      0.0948982000
_diffrn_orient_matrix_UB_21      0.0613474000
_diffrn_orient_matrix_UB_22      -0.0900879000
_diffrn_orient_matrix_UB_23      -0.0409073000
_diffrn_orient_matrix_UB_31      0.0743778000
_diffrn_orient_matrix_UB_32      0.0785618000
_diffrn_orient_matrix_UB_33      -0.0431349000
_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  0.0348
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            20736
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.008
_diffrn_reflns_theta_min         4.472
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.359
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60334
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.109a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.754
_exptl_crystal_description       prism
_exptl_crystal_F_000             1108
_exptl_crystal_size_max          0.147
_exptl_crystal_size_mid          0.138
_exptl_crystal_size_min          0.093
_refine_diff_density_max         0.510
_refine_diff_density_min         -0.412
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     390
_refine_ls_number_reflns         4248
_refine_ls_number_restraints     128
_refine_ls_restrained_S_all      1.140
_refine_ls_R_factor_all          0.0445
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0547P)^2^+1.6353P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1016
_refine_ls_wR_factor_ref         0.1056
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3805
_reflns_number_total             4248
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra03587b2.cif
_cod_data_source_block           5-[Mn(hfac)2DME]
_cod_database_code               7250841
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C14H12F12Mn1O6
_chemical_oxdiff_usercomment
'Small chunkc cut from larger, clear transparent light yellow crystal.'
_shelx_estimated_absorpt_t_max   0.589
_shelx_estimated_absorpt_t_min   0.455
_diffrn_oxdiff_digest_hkl
;
013acc1dfdd7c1ab3974e9731a052eea502f5a
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F1-C4 \\sim F1A-C4A
 with sigma of 0.02
 F4-C5 \\sim F4A-C5
 with sigma of 0.02
 F2-C4 \\sim F2A-C4A
 with sigma of 0.02
 F5-C5 \\sim F5A-C5
 with sigma of 0.02
 F6-C5 \\sim F6A-C5
 with sigma of 0.02
 F3-C4 \\sim F3A-C4A
 with sigma of 0.02
 C1-C4 \\sim C1-C4A
 with sigma of 0.02
 F4-C5 \\sim F4-C5A
 with sigma of 0.02
 F5-C5 \\sim F5-C5A
 with sigma of 0.02
 F1-F2 \\sim F1A-F2A
 with sigma of 0.04
 F6-C5 \\sim F6-C5A
 with sigma of 0.02
 F1-F3 \\sim F1A-F3A
 with sigma of 0.04
 F1-C1 \\sim F1A-C1
 with sigma of 0.04
 C3-C5 \\sim C3-C5A
 with sigma of 0.02
 C5-F5A \\sim C5A-F5A
 with sigma of 0.02
 F2-F3 \\sim F2A-F3A
 with sigma of 0.04
 F2-C1 \\sim F2A-C1
 with sigma of 0.04
 C5-F4A \\sim C5A-F4A
 with sigma of 0.02
 F3-C1 \\sim F3A-C1
 with sigma of 0.04
 C5-F6A \\sim C5A-F6A
 with sigma of 0.02
 F10A-C10 \\sim F10-C10
 with sigma of 0.02
 F11A-C10 \\sim F11-C10
 with sigma of 0.02
 F12A-C10 \\sim F12-C10
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F6 \\sim F6A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
Uanis(F10A) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F11A)
\\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F12A) \\sim Ueq, Uanis(F3A) \\sim Ueq,
Uanis(F3) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F1A) \\sim
Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(F12A) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F11A) \\sim Ueq, Uanis(F11)
\\sim Ueq, Uanis(F10A) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F2A) \\sim Ueq,
Uanis(F2) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F3) \\sim
Ueq, Uanis(F3A) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F5A) \\sim Ueq, Uanis(F4)
\\sim Ueq, Uanis(F4A) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F6A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F5A) \\sim Ueq, Uanis(F4A) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F2A)
\\sim Ueq, Uanis(F10A) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F12) \\sim Ueq:
with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(F6A) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C5) = Uanis(C5A)
Uanis(C4A) = Uanis(C4)
4. Others
 Sof(F3A)=Sof(C4A)=Sof(F2A)=Sof(F1A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(C4)=FVAR(1)
 Sof(F10)=Sof(F11)=Sof(F12)=1-FVAR(2)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(2)
 Sof(F5A)=Sof(F4A)=Sof(F6A)=Sof(C5A)=1-FVAR(3)
 Sof(F4)=Sof(F5)=Sof(F6)=Sof(C5)=FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7)
5.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              46498
_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 1.446
_oxdiff_exptl_absorpt_empirical_full_min 0.771