Tetra-, tetradeca- and octadecametallic clusters of Mn
Brechin, Euan K.; Agapaki, Eleftheria; Canaj, Angelos; Nichol, Gary Stephen; Dalton Transactions  (2023) –; doi:10.1039/D3DT00732D

data_7712816
_publ_section_title
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 Tetra-, tetradeca- and octadecametallic clusters of Mn
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00732D
_journal_year                    2023
_chemical_formula_moiety         'C68 H102 Mn14 N8 O50, 1[C3H6O], 1[C2H3N]'
_chemical_formula_sum            'C73 H111 Mn14 N9 O51'
_chemical_formula_weight         2699.86
_space_group_crystal_system      orthorhombic
_space_group_IT_number           70
_space_group_name_Hall           '-F 2uv 2vw'
_space_group_name_H-M_alt        'F d d d :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-17
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6396)
;
_audit_update_record
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2022-12-29 deposited with the CCDC.	2023-04-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.1080(2)
_cell_length_b                   20.4454(4)
_cell_length_c                   76.1586(11)
_cell_measurement_reflns_used    21006
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      28.3420
_cell_measurement_theta_min      3.3850
_cell_volume                     23524.6(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (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      120.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.988
_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    -41.00  22.00   0.30   15.00    --  -17.45 -77.00-121.00  210
  2  \w    -42.00  60.00   0.30   15.00    --   19.01 -77.00-121.00  340
  3  \w    -42.00  24.00   0.30   15.00    --  -17.45 -77.00  90.00  220
  4  \w    -55.00  18.20   0.30   15.00    --  -17.45  77.00   4.00  244
  5  \w    -52.00   8.00   0.30   15.00    --  -17.45  77.00 -30.00  200
  6  \w    -41.00  38.50   0.30   15.00    --   19.01 -77.00 150.00  265
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0206249000
_diffrn_orient_matrix_UB_12      0.0272404000
_diffrn_orient_matrix_UB_13      0.0040591000
_diffrn_orient_matrix_UB_21      0.0169420000
_diffrn_orient_matrix_UB_22      0.0208010000
_diffrn_orient_matrix_UB_23      -0.0066555000
_diffrn_orient_matrix_UB_31      -0.0385961000
_diffrn_orient_matrix_UB_32      -0.0054697000
_diffrn_orient_matrix_UB_33      -0.0050982000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0419
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       97
_diffrn_reflns_limit_l_min       -97
_diffrn_reflns_number            49597
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.098
_diffrn_reflns_theta_min         3.138
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.531
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93295
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.99a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark brown'
_exptl_crystal_density_diffrn    1.525
_exptl_crystal_description       block
_exptl_crystal_F_000             10960
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of acetone and acetonitrile  by vapour diffusion'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.428
_refine_diff_density_min         -0.327
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     347
_refine_ls_number_reflns         6437
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0379
_refine_ls_R_factor_gt           0.0329
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0329P)^2^+93.3957P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0777
_refine_ls_wR_factor_ref         0.0799
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5755
_reflns_number_total             6437
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00732d2.cif
_cod_data_source_block           eb21208
_cod_original_sg_symbol_H-M      'F d d d'
_cod_database_code               7712816
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C34 H53 Mn7 N4 O25'
_chemical_oxdiff_usercomment     '@ 120 K EA9-acetone'
_shelx_estimated_absorpt_t_max   0.875
_shelx_estimated_absorpt_t_min   0.692
_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
 O12-C16A \\sim O11-C16A \\sim O12-C16 \\sim O11-C16
 with sigma of 0.02
 C17A-C16A \\sim C17-C16
 with sigma of 0.02
 C10-C11 \\sim C10-C11A
 with sigma of 0.02
3. Rigid bond restraints
 C10, C11A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C10, C11
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O11, O12, C16A, C17A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C10 \\sim C11A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C10 \\sim C11: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
O11 \\sim O12 \\sim C16A \\sim C17A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(C11) = Uanis(C11A)
5. Rigid body (RIGU) restrains
 O11, O12, C16A, C17A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O11, O12, C16, C17
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10, C11A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10, C11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C16A)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=1-FVAR(1)
 Sof(C16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(1)
 Sof(C11A)=Sof(H11D)=Sof(H11E)=Sof(H11F)=1-FVAR(2)
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=FVAR(2)
 Fixed Sof: H8A(0.5) H8B(0.5) H8C(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
7.b Me refined with riding coordinates:
 C11(H11A,H11B,H11C), C11A(H11D,H11E,H11F), C17(H17A,H17B,H17C), C17A(H17D,
 H17E,H17F)
7.c Aromatic/amide H refined with riding coordinates:
 C2(H2)
7.d Idealised Me refined as rotating group:
 C00U(H00A,H00B,H00C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C),
 C13(H13A,H13B,H13C), C15(H15A,H15B,H15C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 416 electrons were 
found in a volume of 5700\%A^3^ in 1 void per unit cell. 
This approximates with the presence of 
1[C3H6O], 1[C2H3N] per Formula Unit 
which account for 432 electrons 
per unit cell.  These solvent molecules were observed in a difference map but could not be reasonably modelled.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              91953
_shelx_hkl_checksum              33549
_shelx_fab_checksum              51222
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id EA9-acetone
_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 1.318
_oxdiff_exptl_absorpt_empirical_full_min 0.880