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_7250844
_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
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-06
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-07-07 deposited with the CCDC.	2025-08-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.621(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.5361(3)
_cell_length_b                   6.81320(10)
_cell_length_c                   27.8521(5)
_cell_measurement_reflns_used    21849
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      79.7580
_cell_measurement_theta_min      3.2130
_cell_volume                     3954.39(11)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_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_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.990
_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    -42.00  28.00   0.50    1.78    --  -38.50  38.00 -30.00  140
  2  \w    -50.00  24.00   0.50    1.78    --  -38.50  57.00  90.00  148
  3  \w   -101.00 -27.00   0.50    1.78    --  -38.50 -56.00-175.95  148
  4  \w    -42.00  28.00   0.50    1.78    --  -38.50  38.00  30.00  140
  5  \w     42.00 117.00   0.50    1.78    --   47.56  19.00-120.00  150
  6  \w     28.00  97.00   0.50    1.78    --   47.56-125.00-180.00  138
  7  \w     44.00 114.00   0.50    1.78    --   47.56  38.00 120.00  140
  8  \w     28.00  97.00   0.50    1.78    --   47.56-125.00 -90.00  138
  9  \w     42.00 117.00   0.50    1.78    --   47.56  19.00 -30.00  150
 10  \w     44.00 114.00   0.50    1.78    --   47.56  38.00 -30.00  140
 11  \w     45.00 114.00   0.50    7.10    --  111.00 -38.00  30.00  138
 12  \w     46.00 109.00   0.50    7.10    --  111.00-111.00 150.00  126
 13  \w     42.00 106.00   0.50    7.10    --  111.00 -91.00 -90.00  128
 14  \w     42.00 115.00   0.50    7.10    --  111.00 -25.00  30.00  146
 15  \w     46.00 109.00   0.50    7.10    --  111.00-111.00   0.00  126
 16  \w     46.00 109.00   0.50    7.10    --  111.00-111.00  30.00  126
 17  \w    105.00 175.00   0.50    7.10    --  111.00  50.00-180.00  140
 18  \w     46.00 109.00   0.50    7.10    --  111.00-111.00 120.00  126
 19  \w     48.00 125.00   0.50    7.10    --  111.00 -63.00  60.00  154
 20  \w     42.00 106.00   0.50    7.10    --  111.00 -91.00-180.00  128
 21  \w     42.00 115.00   0.50    7.10    --  111.00 -25.00 -60.00  146
 22  \w     45.00 114.00   0.50    7.10    --  111.00 -38.00-180.00  138
 23  \w    108.00 177.00   0.50    7.10    --  111.00  38.00  30.00  138
 24  \w     42.00 115.00   0.50    7.10    --  111.00 -25.00-180.00  146
 25  \w     46.00 109.00   0.50    7.10    --  111.00-111.00-120.00  126
 26  \w     42.00 106.00   0.50    7.10    --  111.00 -91.00  30.00  128
 27  \w     97.00 174.00   0.50    7.10    --  111.00  63.00-180.00  154
 28  \w    104.00 177.00   0.50    7.10    --  111.00 111.00 -90.00  146
 29  \w    108.00 177.00   0.50    7.10    --  111.00  38.00-150.00  138
 30  \w     42.00 121.00   0.50    7.10    --  111.00 -12.00-120.00  158
 31  \w     45.00 114.00   0.50    7.10    --  111.00 -38.00 -30.00  138
 32  \w     48.00 125.00   0.50    7.10    --  111.00 -63.00 -60.00  154
 33  \w     46.00 109.00   0.50    7.10    --  111.00-111.00  90.00  126
 34  \w     46.00 109.00   0.50    7.10    --  111.00-111.00 -90.00  126
 35  \w     45.00 114.00   0.50    7.10    --  111.00 -38.00 150.00  138
 36  \w    104.00 177.00   0.50    7.10    --  111.00 111.00-120.00  146
 37  \w    101.00 178.00   0.50    7.10    --  111.00  12.00-150.00  154
 38  \w     47.00 134.00   0.50    7.10    --  111.00 -77.00 -60.00  174
 39  \w     46.00 109.00   0.50    7.10    --  111.00-111.00 -60.00  126
 40  \w    108.00 177.00   0.50    7.10    --  111.00  38.00-120.00  138
 41  \w    108.00 177.00   0.50    7.10    --  111.00  38.00 150.00  138
 42  \w     97.00 133.00   0.50    7.10    --  111.00  63.00   0.00   72
 43  \w     75.00 101.00   0.50    7.10    --  111.00-111.00-150.00   52
 44  \w     52.00 116.00   0.50    7.10    --  111.00 -50.00 120.00  128
 45  \w     74.00 100.00   0.50    7.10    --  111.00 -77.00  60.00   52
 46  \w     62.00 104.00   0.50    7.10    --  111.00 -91.00 -60.00   84
 47  \w     55.00  98.00   0.50    7.10    --  111.00 -91.00  90.00   86
 48  \w     69.00 107.00   0.50    7.10    --  111.00-111.00 -30.00   76
 49  \w    130.00 156.00   0.50    7.10    --  111.00  38.00  60.00   52
 50  \w     78.00 106.00   0.50    7.10    --  111.00-103.00 156.00   56
 51  \w     51.00  76.00   0.50    7.10    --  111.00 -50.00   0.00   50
 52  \w    144.00 170.00   0.50    7.10    --  111.00 111.00 150.00   52
 53  \w    117.00 143.00   0.50    7.10    --  111.00  77.00-120.00   52
 54  \w    135.00 161.00   0.50    7.10    --  111.00  77.00 -90.00   52
 55  \w     81.00 114.00   0.50    7.10    --  111.00 -25.00-150.00   66
 56  \w     82.00 109.00   0.50    7.10    --  111.00 -52.00  -5.14   54
 57  \w    106.00 134.00   0.50    7.10    --  111.00 178.00 -30.00   56
 58  \w     91.00 117.00   0.50    7.10    --  111.00 -85.00 -43.51   52
;
_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      0.0348528000
_diffrn_orient_matrix_UB_12      -0.1048685000
_diffrn_orient_matrix_UB_13      0.0483051000
_diffrn_orient_matrix_UB_21      0.0163818000
_diffrn_orient_matrix_UB_22      0.2001748000
_diffrn_orient_matrix_UB_23      0.0257781000
_diffrn_orient_matrix_UB_31      -0.0630804000
_diffrn_orient_matrix_UB_32      -0.0059431000
_diffrn_orient_matrix_UB_33      0.0165026000
_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  0.0672
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            40093
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.425
_diffrn_reflns_theta_min         3.280
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.811
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.226
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.878
_exptl_crystal_description       needle
_exptl_crystal_F_000             2216
_exptl_crystal_size_max          0.505
_exptl_crystal_size_mid          0.074
_exptl_crystal_size_min          0.048
_refine_diff_density_max         1.200
_refine_diff_density_min         -1.708
_refine_diff_density_rms         0.154
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     321
_refine_ls_number_reflns         4294
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0977
_refine_ls_R_factor_gt           0.0941
_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^)+(0.0575P)^2^+104.9626P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2398
_refine_ls_wR_factor_ref         0.2417
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3979
_reflns_number_total             4294
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra03587b2.cif
_cod_data_source_block           rb23008i2f2
_cod_database_code               7250844
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C14 H12 F12 Mn O2'
_chemical_oxdiff_usercomment     ' Repeat on a larger crystal '
_shelx_estimated_absorpt_t_max   0.736
_shelx_estimated_absorpt_t_min   0.130
_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 O(H,H) groups
2. Restrained distances
 O6-H6B = O6-H6A
 0.84 with sigma of 0.02
 F5-C4 \\sim F5A-C4A
 with sigma of 0.02
 F6-C4 \\sim F6A-C4A
 with sigma of 0.02
 F4-C4 \\sim F4A-C4A
 with sigma of 0.02
 C4-C3 \\sim C4A-C3
 with sigma of 0.02
 F5-F6 \\sim F5A-F6A
 with sigma of 0.04
 F5-F4 \\sim F5A-F4A
 with sigma of 0.04
 F5-C3 \\sim F5A-C3
 with sigma of 0.04
 F6-F4 \\sim F6A-F4A
 with sigma of 0.04
 F6-C3 \\sim F6A-C3
 with sigma of 0.04
 F4-C3 \\sim F4A-C3
 with sigma of 0.04
 Mn1-O1 \\sim Mn1A-O1
 with sigma of 0.02
 Mn1-O2 \\sim Mn1A-O2
 with sigma of 0.02
 Mn1-O3 \\sim Mn1A-O3
 with sigma of 0.02
 Mn1-O4 \\sim Mn1A-O4
 with sigma of 0.02
 Mn1-O5 \\sim Mn1A-O5
 with sigma of 0.02
 Mn1-O6 \\sim Mn1A-O6
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C4) = Uanis(C4A)
Uanis(F5) = Uanis(F5A)
Uanis(F6) = Uanis(F6A)
Uanis(F4A) = Uanis(F4)
Uanis(Mn1) = Uanis(Mn1A)
4. Others
 Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(C4A)=1-FVAR(1)
 Sof(F4)=Sof(F5)=Sof(F6)=Sof(C4)=FVAR(1)
 Sof(Mn1A)=1-FVAR(2)
 Sof(Mn1)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7)
;
_shelx_res_checksum              97021
_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 3.081
_oxdiff_exptl_absorpt_empirical_full_min 0.547