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_7250839
_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         'C30 H28 F18 Mn3 O14'
_chemical_formula_sum            'C30 H28 F18 Mn3 O14'
_chemical_formula_weight         1119.34
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-14
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-04-05 deposited with the CCDC.	2025-08-20 downloaded from the CCDC.
;
_cell_angle_alpha                85.497(2)
_cell_angle_beta                 76.820(2)
_cell_angle_gamma                84.015(2)
_cell_formula_units_Z            2
_cell_length_a                   10.7690(2)
_cell_length_b                   11.5144(3)
_cell_length_c                   16.9696(4)
_cell_measurement_reflns_used    24222
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      79.9350
_cell_measurement_theta_min      3.8420
_cell_volume                     2034.35(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.88a (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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_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   -108.00 -33.00   0.50    2.89    --  -38.50 -19.00 -90.00  150
  2  \w    -50.00  24.00   0.50    2.89    --  -38.50  57.00   0.00  148
  3  \w    -86.00  -6.00   0.50    2.89    --  -38.50 125.00  60.00  160
  4  \w    -18.00  51.00   0.50    2.89    --   47.81 -38.00 120.00  138
  5  \w     42.00 117.00   0.50    2.89    --   47.81  19.00-120.00  150
  6  \w     45.00 114.00   0.50    2.89    --   47.81  38.00-120.00  138
  7  \w     28.00  97.00   0.50    2.89    --   47.81-125.00 120.00  138
  8  \w    -18.00  51.00   0.50    2.89    --   47.81 -38.00-120.00  138
  9  \w    -17.00  71.00   0.50    2.89    --   47.81 -77.00 -90.00  176
 10  \w    -18.00  51.00   0.50    2.89    --   47.81 -38.00   0.00  138
 11  \w     45.00 114.00   0.50   11.58    --  111.00 -38.00 150.00  138
 12  \w     42.00 106.00   0.50   11.58    --  111.00 -91.00 120.00  128
 13  \w     47.00 134.00   0.50   11.58    --  111.00 -77.00 120.00  174
 14  \w     47.00 134.00   0.50   11.58    --  111.00 -77.00  30.00  174
 15  \w     46.00 109.00   0.50   11.58    --  111.00-111.00 -90.00  126
 16  \w    108.00 177.00   0.50   11.58    --  111.00  38.00 150.00  138
 17  \w    107.00 177.00   0.50   11.58    --  111.00  41.00-176.09  140
 18  \w     46.00 109.00   0.50   11.58    --  111.00-111.00  30.00  126
 19  \w     46.00 109.00   0.50   11.58    --  111.00-111.00-150.00  126
 20  \w     99.00 174.00   0.50   11.58    --  111.00  58.00  25.19  150
 21  \w     42.00 106.00   0.50   11.58    --  111.00 -91.00  30.00  128
 22  \w     48.00 125.00   0.50   11.58    --  111.00 -63.00  90.00  154
 23  \w     46.00 109.00   0.50   11.58    --  111.00-111.00   0.00  126
 24  \w     47.00 117.00   0.50   11.58    --  111.00 -50.00  60.00  140
 25  \w     42.00 115.00   0.50   11.58    --  111.00 -25.00-180.00  146
 26  \w     61.00 146.00   0.50   11.58    --  111.00 178.00  30.00  170
 27  \w     42.00 106.00   0.50   11.58    --  111.00 -91.00  90.00  128
 28  \w     42.00 115.00   0.50   11.58    --  111.00 -25.00 -90.00  146
 29  \w     45.00 114.00   0.50   11.58    --  111.00 -38.00-120.00  138
 30  \w     46.00 109.00   0.50   11.58    --  111.00-111.00  60.00  126
 31  \w     76.00 101.00   0.50   11.58    --  111.00 -77.00-150.00   50
 32  \w     82.00 109.00   0.50   11.58    --  111.00-111.00-180.00   54
 33  \w    134.00 160.00   0.50   11.58    --  111.00  12.00 -30.00   52
 34  \w    111.00 137.00   0.50   11.58    --  111.00  38.00  60.00   52
 35  \w     47.00  92.00   0.50   11.58    --  111.00 -50.00-120.00   90
 36  \w     47.00 117.00   0.50   11.58    --  111.00 -50.00 120.00  140
 37  \w    117.00 167.00   0.50   11.58    --  111.00  12.00-120.00  100
 38  \w    105.00 152.00   0.50   11.58    --  111.00 111.00 120.00   94
 39  \w     43.00 107.00   0.50   11.58    --  111.00 -12.00  60.00  128
 40  \w    117.00 173.00   0.50   11.58    --  111.00  63.00  90.00  112
 41  \w     79.00 109.00   0.50   11.58    --  111.00-111.00 -60.00   60
 42  \w     47.00 108.00   0.50   11.58    --  111.00-111.00  90.00  122
 43  \w     63.00 106.00   0.50   11.58    --  111.00 -91.00 -30.00   86
 44  \w     76.00 109.00   0.50   11.58    --  111.00-111.00-120.00   66
 45  \w     43.00  68.00   0.50   11.58    --  111.00 -91.00-120.00   50
 46  \w     74.00 101.00   0.50   11.58    --  111.00 -91.00-120.00   54
 47  \w    108.00 169.00   0.50   11.58    --  111.00  38.00  90.00  122
 48  \w    112.00 166.00   0.50   11.58    --  111.00 111.00-150.00  108
 49  \w    128.00 170.00   0.50   11.58    --  111.00  12.00   0.00   84
 50  \w    114.00 140.00   0.50   11.58    --  111.00 178.00 -60.00   52
 51  \w     59.00 102.00   0.50   11.58    --  111.00 -91.00 -60.00   86
 52  \w     63.00  89.00   0.50   11.58    --  111.00 -77.00-120.00   52
 53  \w     48.00  77.00   0.50   11.58    --  111.00 -77.00   0.00   58
 54  \w     78.00 104.00   0.50   11.58    --  111.00 -77.00   0.00   52
 55  \w     84.00 109.00   0.50   11.58    --  111.00-111.00 -30.00   50
 56  \w     50.00  94.00   0.50   11.58    --  111.00 -50.00   0.00   88
 57  \w     57.00  83.00   0.50   11.58    --  111.00 -77.00 150.00   52
 58  \w    108.00 134.00   0.50   11.58    --  111.00 -77.00 150.00   52
 59  \w     80.00 106.00   0.50   11.58    --  111.00 -91.00  60.00   52
 60  \w     43.00  76.00   0.50   11.58    --  111.00 -91.00 -90.00   66
 61  \w    130.00 156.00   0.50   11.58    --  111.00  38.00 -90.00   52
 62  \w    126.00 175.00   0.50   11.58    --  111.00  77.00 -90.00   98
 63  \w     44.00  88.00   0.50   11.58    --  111.00 -21.00   9.96   88
;
_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      -0.1180773000
_diffrn_orient_matrix_UB_12      -0.0355189000
_diffrn_orient_matrix_UB_13      0.0640272000
_diffrn_orient_matrix_UB_21      0.0045226000
_diffrn_orient_matrix_UB_22      0.1075192000
_diffrn_orient_matrix_UB_23      0.0475442000
_diffrn_orient_matrix_UB_31      -0.0882984000
_diffrn_orient_matrix_UB_32      0.0730329000
_diffrn_orient_matrix_UB_33      -0.0485959000
_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  0.0320
_diffrn_reflns_av_unetI/netI     0.0252
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            44915
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.309
_diffrn_reflns_theta_min         2.679
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.822
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44014
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.88a (Rigaku Oxford Diffraction, 2023)
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    1.827
_exptl_crystal_description       block
_exptl_crystal_F_000             1114
_exptl_crystal_size_max          0.175
_exptl_crystal_size_mid          0.106
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.494
_refine_diff_density_min         -0.434
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     761
_refine_ls_number_reflns         8821
_refine_ls_number_restraints     235
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0339
_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^)+(0.0491P)^2^+1.8045P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0915
_refine_ls_wR_factor_ref         0.0940
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8107
_reflns_number_total             8821
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra03587b2.cif
_cod_data_source_block           3_[Mn3(tfac)6(OH2)2]
_cod_database_code               7250839
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C30H28F17Mn3O14
_chemical_oxdiff_usercomment
'Small block that is hopefully single but I have concerns. Cut from a big chunk.'
_shelx_estimated_absorpt_t_max   0.577
_shelx_estimated_absorpt_t_min   0.307
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 O13-H13B = O13-H13A = O14-H14A = O14-H14B
 0.84 with sigma of 0.02
 F12-C19 \\sim F12A-C19
 with sigma of 0.02
 F10-C19 \\sim F10A-C19
 with sigma of 0.02
 C19-F11 \\sim C19-F11A
 with sigma of 0.02
 F4-C9 \\sim F4A-C9
 with sigma of 0.02
 F6-C9 \\sim F6A-C9
 with sigma of 0.02
 F5-C9 \\sim F5A-C9
 with sigma of 0.02
 F1-C5 \\sim F1A-C5
 with sigma of 0.02
 F2-C5 \\sim F2A-C5
 with sigma of 0.02
 F3-C5 \\sim F3A-C5
 with sigma of 0.02
 F7-C15 \\sim F7A-C15
 with sigma of 0.02
 F8-C15 \\sim F8A-C15
 with sigma of 0.02
 F9-C15 \\sim F9A-C15
 with sigma of 0.02
 F14-C25 \\sim F14A-C25
 with sigma of 0.02
 F13-C25 \\sim F13A-C25
 with sigma of 0.02
 F15-C25 \\sim F15A-C25
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F14) \\sim Ueq, Uanis(F8A) \\sim Ueq, Uanis(F6A) \\sim Ueq, Uanis(F7)
\\sim Ueq, Uanis(F12A) \\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F2A) \\sim Ueq,
Uanis(F4) \\sim Ueq, Uanis(F10A) \\sim Ueq, Uanis(F13) \\sim Ueq, Uanis(F20)
\\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F5A) \\sim Ueq, Uanis(F9) \\sim Ueq,
Uanis(F9A) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F13A) \\sim Ueq, Uanis(F15)
\\sim Ueq, Uanis(F11A) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F19) \\sim Ueq,
Uanis(F5) \\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F4A)
\\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F10) \\sim Ueq,
Uanis(F1A) \\sim Ueq, Uanis(F16) \\sim Ueq, Uanis(F7A) \\sim Ueq, Uanis(F11)
\\sim Ueq, Uanis(F14A) \\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F15A) \\sim Ueq,
Uanis(F18) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F1A) = Uanis(F1)
Uanis(F2) = Uanis(F2A)
4. Others
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(1)
 Sof(F12)=Sof(F10)=Sof(F11)=FVAR(1)
 Sof(F6A)=Sof(F4A)=Sof(F5A)=1-FVAR(2)
 Sof(F4)=Sof(F6)=Sof(F5)=FVAR(2)
 Sof(F3A)=Sof(F2A)=Sof(F1A)=1-FVAR(3)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(3)
 Sof(F9A)=Sof(F7A)=Sof(F8A)=1-FVAR(4)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(4)
 Sof(F14A)=Sof(F13A)=Sof(F15A)=1-FVAR(5)
 Sof(F14)=Sof(F13)=Sof(F15)=FVAR(5)
 Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(F19)=Sof(F20)=Sof(F21)=1-FVAR(6)
 Sof(F16)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(F17)=Sof(F18)=FVAR(6)
5.a Aromatic/amide H refined with riding coordinates:
 C17(H17), C12(H12), C7(H7), C22(H22), C2(H2), C27(H27)
5.b Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C14(H14C,H14D,H14E), C24(H24A,H24B,H24C), C20(H20A,H20B,
 H20C), C10(H10A,H10B,H10C), C30(H30A,H30B,H30C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              86951
_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 1.962
_oxdiff_exptl_absorpt_empirical_full_min 0.710