Covalent Metal-Metal-Bonded Mn<sub>4</sub> Tetrahedron Inscribed within a Four-Coordinate Manganese Cubane Cluster, As Evidenced by Unexpected Temperature-Independent Diamagnetism.
Vaddypally, Shivaiah; Jovinelli, Daniel J.; McKendry, Ian G.; Zdilla, Michael J.; Inorganic chemistry 56 (2017) 3733–3737; doi:10.1021/acs.inorgchem.7b00152

data_4349413
_publ_section_title
;
 Covalent Metal-Metal-Bonded Mn<sub>4</sub> Tetrahedron Inscribed within a
 Four-Coordinate Manganese Cubane Cluster, As Evidenced by Unexpected
 Temperature-Independent Diamagnetism.
;
_journal_issue                   7
_journal_name_full               'Inorganic chemistry'
_journal_page_first              3733
_journal_page_last               3737
_journal_paper_doi               10.1021/acs.inorgchem.7b00152
_journal_volume                  56
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H72 Mn4 N8, 2(F3 P0.5)'
_chemical_formula_sum            'C32 H72 F6 Mn4 N8 P'
_chemical_formula_weight         933.70
_chemical_name_systematic
;
tris[bis(tert-butylimido)manganese(IV)bis(tert-butylimido)manganese(V)
hexafluorophosphate
;
_space_group_crystal_system      trigonal
_space_group_IT_number           160
_space_group_name_Hall           'R 3 -2"'
_space_group_name_H-M_alt        'R 3 m :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-07-25
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   13.260(2)
_cell_length_b                   13.260(2)
_cell_length_c                   22.193(3)
_cell_measurement_reflns_used    2610
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      23.90
_cell_measurement_theta_min      2.55
_cell_volume                     3379.4(9)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'COSMO (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.01
_diffrn_detector_area_resol_mean 8.333
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0267
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            6698
_diffrn_reflns_point_group_measured_fraction_full 0.908
_diffrn_reflns_point_group_measured_fraction_max 0.897
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         27.918
_diffrn_reflns_theta_min         1.997
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.187
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6384
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0569 before and 0.0459 after correction.
The Ratio of minimum to maximum transmission is 0.8562.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_description       block
_exptl_crystal_F_000             1467
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.743
_refine_diff_density_min         -0.593
_refine_diff_density_rms         0.083
_refine_ls_abs_structure_details
;
 Flack x determined using 680 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.047(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     166
_refine_ls_number_reflns         1819
_refine_ls_number_restraints     129
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0678
_refine_ls_R_factor_gt           0.0633
_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^)+(0.1016P)^2^+10.0589P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1743
_refine_ls_wR_factor_ref         0.1784
_reflns_Friedel_coverage         0.789
_reflns_Friedel_fraction_full    0.817
_reflns_Friedel_fraction_max     0.794
_reflns_number_gt                1665
_reflns_number_total             1819
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00152_si_002.cif
_cod_data_source_block           split3_olex
_cod_original_cell_volume        3379.1(12)
_cod_original_sg_symbol_H-M      'R 3 m'
_cod_database_code               4349413
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.815
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-C1
 1.45 with sigma of 0.01
 N2-C2
 1.45 with sigma of 0.001
 N3-C3
 1.45 with sigma of 0.001
 N4-C4
 1.45 with sigma of 0.001
 Mn2-N4
 1.66 with sigma of 0.002
 C1-C11 = C1-C12 = C1-C13
 1.54 with sigma of 0.01
 C2-C21 = C2-C22 = C2-C23
 1.54 with sigma of 0.001
 C3-C31
 1.54 with sigma of 0.001
 C4-C41 = C4-C42 = C4-C43
 1.54 with sigma of 0.001
 N1-C11 = N1-C12 = N1-C13
 2.44 with sigma of 0.02
 N2-C21 = N2-C22 = N2-C23
 2.44 with sigma of 0.002
 N3-C31
 2.44 with sigma of 0.002
 N4-C41 = N4-C42 = N4-C43
 2.44 with sigma of 0.002
 C11-C12 = C12-C13 = C13-C11
 2.52 with sigma of 0.02
 C21-C22 = C22-C23 = C23-C21
 2.52 with sigma of 0.002
 C41-C42 = C42-C43 = C43-C41
 2.52 with sigma of 0.002
3. Rigid bond restraints
 Mn2, N4, C4, C41, C42, C43
 with sigma for 1-2 distances of 0.03 and sigma for 1-3 distances of 0.03
 C1, C11, C12, C13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N2, C2, C21, C22, C23
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
Mn2 \\sim N4 \\sim C4 \\sim C41 \\sim C42 \\sim C43: within 2A with sigma of
0.03 and sigma for terminal atoms of 0.06
C2 \\sim C21: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.002
C1 \\sim C11 \\sim C12 \\sim C12: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N2 \\sim C2 \\sim C21 \\sim C22 \\sim C23: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002
5. Others
 Fixed Sof: N4(0.5) C1(0.5) C11(0.5) H11A(0.5) H11B(0.5) H11C(0.5) C12(0.5)
 H12A(0.5) H12B(0.5) H12C(0.5) C13(0.5) H13A(0.5) H13B(0.5) H13C(0.5)
 C2(0.16667) C21(0.16667) H21A(0.16667) H21B(0.16667) H21C(0.16667)
 C22(0.16667) H22A(0.16667) H22B(0.16667) H22C(0.16667) C23(0.16667)
 H23A(0.16667) H23B(0.16667) H23C(0.16667) C31(0.5) H31A(0.5) H31B(0.5)
 H31C(0.5) C4(0.5) C41(0.5) H41A(0.5) H41B(0.5) H41C(0.5) C42(0.5) H42A(0.5)
 H42B(0.5) H42C(0.5) C43(0.5) H43A(0.5) H43B(0.5) H43C(0.5)
6.a Me refined with riding coordinates:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C31(H31A,H31B,H31C), C41(H41A,
 H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C)
;
_shelx_res_checksum              20395
_shelx_hkl_checksum              1157
_olex2_submission_special_instructions 'No special instructions were received'