Formation of the tetranuclear, tetrakis-terminal-imido Mn4IV(NtBu)8 cubane cluster by four-electron reductive elimination of tBuN[double bond, length as m-dash]NtBu. The role of the s-block ion in stabilization of high-oxidation state intermediates
Shivaiah Vaddypally; Sandeep K. Kondaveeti; John H. Roudebush; Robert J. Cava; Michael J. Zdilla; Chem.Commun. 50 (2014) 1061–; doi:10.1039/c3cc42165a

data_7110330
_publ_section_title
;
 Formation of the tetranuclear, tetrakis-terminal-imido Mn4IV(NtBu)8
 cubane cluster by four-electron reductive elimination of tBuN[double
 bond, length as m-dash]NtBu. The role of the s-block ion in stabilization
 of high-oxidation state intermediates
;
_journal_name_full               Chem.Commun.
_journal_page_first              1061
_journal_paper_doi               10.1039/c3cc42165a
_journal_volume                  50
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H72 Mn4 N8'
_chemical_formula_sum            'C32 H72 Mn4 N8'
_chemical_formula_weight         788.73
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           36
_space_group_name_Hall           'C 2c -2'
_space_group_name_H-M_alt        'C m c 21'
_symmetry_space_group_name_Hall  'C 2c -2'
_symmetry_space_group_name_H-M   'C m c 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.636(2)
_cell_length_b                   12.5912(18)
_cell_length_c                   19.216(2)
_cell_measurement_reflns_used    7553
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      27.873
_cell_measurement_theta_min      2.922
_cell_volume                     4025.1(9)
_computing_cell_refinement       'SAINT (Bruker AXS)'
_computing_data_collection       'COSMO (Bruker AXS)'
_computing_data_reduction        'SADABS (Bruker AXS)'
_computing_molecular_graphics
;
ORTEP III (Burnett/Johnson, 2000) and Pov-Ray 3.62
;
_computing_structure_refinement  'SHELXL-2013 (Sheldrick)'
_computing_structure_solution    'SHELXS-2013 (Sheldrick)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 8.333
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device_type  'Bruker KAPPA APEX II DUO'
_diffrn_measurement_method       'omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0224
_diffrn_reflns_av_unetI/netI     0.0394
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            7701
_diffrn_reflns_point_group_measured_fraction_full 0.829
_diffrn_reflns_point_group_measured_fraction_max 0.785
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.983
_diffrn_reflns_theta_min         2.935
_diffrn_source                   'fine-foucs sealed tube'
_exptl_absorpt_coefficient_mu    1.257
_exptl_absorpt_correction_T_max  0.9172
_exptl_absorpt_correction_T_min  0.6332
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
7862 Corrected reflections written to file 
Estimated minimum and maximum transmission:  0.5954  0.7456
Additional spherical absorption correction applied with mu*r =  0.2000
Lambda/2 correction factor = 0.0015
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.302
_exptl_crystal_description       block
_exptl_crystal_F_000             1680
_exptl_crystal_size_max          0.400
_exptl_crystal_size_mid          0.260
_exptl_crystal_size_min          0.070
_refine_diff_density_max         0.650
_refine_diff_density_min         -0.626
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details
;
 Flack x determined using 1278 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.054(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.113
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     260
_refine_ls_number_reflns         3938
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.121
_refine_ls_R_factor_all          0.0406
_refine_ls_R_factor_gt           0.0364
_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^)+(0.0168P)^2^+12.7221P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0876
_refine_ls_wR_factor_ref         0.0922
_reflns_Friedel_coverage         0.552
_reflns_Friedel_fraction_full    0.661
_reflns_Friedel_fraction_max     0.576
_reflns_number_gt                3722
_reflns_number_total             3938
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c3cc42165a.txt
_cod_data_source_block           2
_cod_original_cell_volume        4025.0(9)
_cod_database_code               7110330
_shelx_estimated_absorpt_t_min   0.633
_shelx_estimated_absorpt_t_max   0.917
_shelxl_version_number           2013-3
_shelx_res_checksum              32312
_shelx_hkl_checksum              58167