Utilization of Phosphinoamide Ligands in Homobimetallic Fe and Mn Complexes: The Effect of Disparate Coordination Environments on Metal-Metal Interactions and Magnetic and Redox Properties
Subramaniam Kuppuswamy; Mark W. Bezpalko; Tamara M. Powers; Mark M. Turnbull; Bruce M. Foxman; Christine M. Thomas; Inorganic Chemistry 51 (2012) 8225–8240; doi:10.1021/ic300776y

data_4329848
_publ_section_title
;
 Utilization of Phosphinoamide Ligands in Homobimetallic Fe and Mn
 Complexes: The Effect of Disparate Coordination Environments on
 Metal-Metal Interactions and Magnetic and Redox Properties
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              8225
_journal_page_last               8240
_journal_paper_doi               10.1021/ic300776y
_journal_volume                  51
_journal_year                    2012
_chemical_formula_moiety         'C60 H68 Fe2 N4 P4'
_chemical_formula_sum            'C60 H68 Fe2 N4 P4'
_chemical_formula_weight         1080.81
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     other
_audit_creation_date             11-05-14
_audit_creation_method           CRYSTALS_ver_14.21
_cell_angle_alpha                90
_cell_angle_beta                 117.149(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6193(9)
_cell_length_b                   44.242(3)
_cell_length_c                   11.7062(7)
_cell_measurement_reflns_used    6331
_cell_measurement_temperature    120
_cell_measurement_theta_max      24.56
_cell_measurement_theta_min      2.93
_cell_volume                     5815.5(7)
_computing_cell_refinement       'Apex2 (Bruker AXS, 2006)'
_computing_data_collection       'Apex2 (Bruker AXS, 2006)'
_computing_data_reduction        'Apex2 (Bruker AXS, 2006)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'Superflip (Palatinus & Chapuis, 2007)'
_diffrn_ambient_temperature      120
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Bruker Kappa Apex2'
_diffrn_measurement_method       '\f & \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.082
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       56
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            12677
_diffrn_reflns_theta_full        26.499
_diffrn_reflns_theta_max         27.040
_diffrn_reflns_theta_min         0.920
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.649
_exptl_absorpt_correction_T_max  0.95
_exptl_absorpt_correction_T_min  0.94
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
; 
 Analytical Absorption (De Meulenaer & Tompa, 1965) 
;
_exptl_crystal_colour            'red brown'
_exptl_crystal_density_diffrn    1.234
_exptl_crystal_description       prism
_exptl_crystal_F_000             2272
_exptl_crystal_size_max          0.335
_exptl_crystal_size_mid          0.094
_exptl_crystal_size_min          0.074
_platon_squeeze_details
;
During the structure solution, electron density difference 
maps revealed that there were considerable disordered 
solvent molecules.  From history, the solvate was likely 
Et2O in a volume of 470.6 \%A3 per unit cell (8.1%); 
the peaks could not be modeled successfully.  It appeared 
that the cavity areas contained about two diethyl ether 
molecules, located near the center of symmetry at  
(1/2, 1/2, 0) and (1/2, 0, 1/2 ) as cab be seen in the
ab projection in the experimental sction of the paper.  
Modeling with or without restraints was unsuccessful, 
as was step by step acquisition of peaks using 
successive electron density difference maps.  Thus, 
the structure factors were modified using the PLATON 
SQUEEZE technique, in order to produce a ?solvate-free? 
structure factor set  PLATON reported a total electron 
density of 97 e- per unit cell, likely representing 
2-3 diethyl ethere molecules, consistent with our earlier 
observations.  Use of the SQUEEZE technique resulted 
in a decrease of ca 2.1 % in R.  
;
_refine_diff_density_max         1.30
_refine_diff_density_min         -0.99
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.9993
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     631
_refine_ls_number_reflns         12677
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0894
_refine_ls_R_factor_gt           0.0476
_refine_ls_shift/su_max          0.0033982
_refine_ls_shift/su_mean         0.0000774
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.03P)^2^ + 4.48P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0959
_refine_ls_wR_factor_gt          0.0874
_refine_ls_wR_factor_ref         0.0959
_reflns_limit_h_max              14
_reflns_limit_h_min              -16
_reflns_limit_k_max              56
_reflns_limit_k_min              0
_reflns_limit_l_max              14
_reflns_limit_l_min              0
_reflns_number_gt                8253
_reflns_number_total             12677
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   1.36
_oxford_diffrn_Wilson_scale      299.72
_oxford_refine_ls_r_factor_ref   0.0894
_oxford_refine_ls_scale          0.078539(10)
_oxford_reflns_number_all        12677
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title 'sk065_0ma in P2(1)/c'
_cod_data_source_file            ic300776y_si_002_2.cif
_cod_data_source_block           4
_cod_depositor_comments
;
The following automatic conversions were performed:

'_atom_sites_solution_primary' value 'Other' changed to 'other'
according to the built-in table from CIF Core dictionary named
'cif_core.dic' version 2.4.1 from 2010-06-29.

Automatic conversion script
Id: cif_fix_values 1891 2012-01-12 08:04:46Z andrius 
;
_cod_original_cell_volume        5815.6(7)
_cod_original_sg_symbol_H-M      'P 1 21/c 1 '
_cod_database_code               4329848
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, U'S 
RIDE C   (   2,X'S) H   (  21,X'S) 
RIDE C   (   3,X'S) H   (  31,X'S) 
RIDE C   (   4,X'S) H   (  41,X'S) 
RIDE C   (   5,X'S) H   (  51,X'S) 
RIDE C   (   6,X'S) H   (  61,X'S) 
RIDE C   (   8,X'S) H   (  81,X'S) 
RIDE C   (   9,X'S) H   (  91,X'S) 
RIDE C   (  10,X'S) H   ( 101,X'S) 
RIDE C   (  11,X'S) H   ( 111,X'S) 
RIDE C   (  12,X'S) H   ( 121,X'S) 
RIDE C   (  13,X'S) H   ( 131,X'S) 
RIDE C   (  14,X'S) H   ( 141,X'S) H   ( 142,X'S) H   ( 143,X'S) 
RIDE C   (  15,X'S) H   ( 151,X'S) H   ( 152,X'S) H   ( 153,X'S) 
RIDE C   (  17,X'S) H   ( 171,X'S) 
RIDE C   (  18,X'S) H   ( 181,X'S) 
RIDE C   (  19,X'S) H   ( 191,X'S) 
RIDE C   (  20,X'S) H   ( 201,X'S) 
RIDE C   (  21,X'S) H   ( 211,X'S) 
RIDE C   (  23,X'S) H   ( 231,X'S) 
RIDE C   (  24,X'S) H   ( 241,X'S) 
RIDE C   (  25,X'S) H   ( 251,X'S) 
RIDE C   (  26,X'S) H   ( 261,X'S) 
RIDE C   (  27,X'S) H   ( 271,X'S) 
RIDE C   (  28,X'S) H   ( 281,X'S) 
RIDE C   (  29,X'S) H   ( 291,X'S) H   ( 292,X'S) H   ( 293,X'S) 
RIDE C   (  30,X'S) H   ( 301,X'S) H   ( 302,X'S) H   ( 303,X'S) 
RIDE C   (  32,X'S) H   ( 321,X'S) 
RIDE C   (  33,X'S) H   ( 331,X'S) 
RIDE C   (  34,X'S) H   ( 341,X'S) 
RIDE C   (  35,X'S) H   ( 351,X'S) 
RIDE C   (  36,X'S) H   ( 361,X'S) 
RIDE C   (  38,X'S) H   ( 381,X'S) 
RIDE C   (  39,X'S) H   ( 391,X'S) 
RIDE C   (  40,X'S) H   ( 401,X'S) 
RIDE C   (  41,X'S) H   ( 411,X'S) 
RIDE C   (  42,X'S) H   ( 421,X'S) 
RIDE C   (  43,X'S) H   ( 431,X'S) 
RIDE C   (  44,X'S) H   ( 441,X'S) H   ( 442,X'S) H   ( 443,X'S) 
RIDE C   (  45,X'S) H   ( 451,X'S) H   ( 452,X'S) H   ( 453,X'S) 
RIDE C   (  47,X'S) H   ( 471,X'S) 
RIDE C   (  48,X'S) H   ( 481,X'S) 
RIDE C   (  49,X'S) H   ( 491,X'S) 
RIDE C   (  50,X'S) H   ( 501,X'S) 
RIDE C   (  51,X'S) H   ( 511,X'S) 
RIDE C   (  53,X'S) H   ( 531,X'S) 
RIDE C   (  54,X'S) H   ( 541,X'S) 
RIDE C   (  55,X'S) H   ( 551,X'S) 
RIDE C   (  56,X'S) H   ( 561,X'S) 
RIDE C   (  57,X'S) H   ( 571,X'S) 
RIDE C   (  58,X'S) H   ( 581,X'S) 
RIDE C   (  59,X'S) H   ( 591,X'S) H   ( 592,X'S) H   ( 593,X'S) 
RIDE C   (  60,X'S) H   ( 601,X'S) H   ( 602,X'S) H   ( 603,X'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;