Metal-Metal Interactions in C3-Symmetric Diiron Imido Complexes Linked by Phosphinoamide Ligands
Subramaniam Kuppuswamy; Tamara M. Powers; Bruce M. Johnson; Mark W. Bezpalko; Carl K. Brozek; Bruce M. Foxman; Louise A. Berben; Christine M. Thomas; Inorganic Chemistry 52 (2013) 4802–4811; doi:10.1021/ic302108k

data_4334547
_publ_section_title
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 Metal-Metal Interactions in C3-Symmetric Diiron Imido Complexes Linked by
 Phosphinoamide Ligands
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_journal_name_full               'Inorganic Chemistry'
_journal_page_first              4802
_journal_page_last               4811
_journal_paper_doi               10.1021/ic302108k
_journal_volume                  52
_journal_year                    2013
_chemical_formula_moiety         'C48 H60 Fe2 N3 P4'
_chemical_formula_sum            'C48 H60 Fe2 N3 P4'
_chemical_formula_weight         914.61
_space_group_IT_number           165
_symmetry_cell_setting           trigonal
_symmetry_space_group_name_Hall  '-P 3 2"c'
_symmetry_space_group_name_H-M   'P -3 c 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_audit_creation_date             12-01-02
_audit_creation_method           CRYSTALS_ver_14.30
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            4
_cell_length_a                   16.1581(8)
_cell_length_b                   16.1581(8)
_cell_length_c                   23.4646(13)
_cell_measurement_reflns_used    9593
_cell_measurement_temperature    120
_cell_measurement_theta_max      29
_cell_measurement_theta_min      3
_cell_volume                     5305.5(5)
_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    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      120
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.049
_diffrn_reflns_limit_h_max       0
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            4716
_diffrn_reflns_theta_full        28.999
_diffrn_reflns_theta_max         28.999
_diffrn_reflns_theta_min         1.455
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.699
_exptl_absorpt_correction_T_max  0.94
_exptl_absorpt_correction_T_min  0.83
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
; 
 Analytical Absorption (De Meulenaer & Tompa, 1965) 
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.145
_exptl_crystal_description       plate
_exptl_crystal_F_000             1924.000
_exptl_crystal_size_max          0.340
_exptl_crystal_size_mid          0.270
_exptl_crystal_size_min          0.090
_platon_squeeze_details
;
During the structure solution, electron density difference 
maps revealed that there were considerable disordered solvent 
molecules.  Additional electron density corresponding to 
disordered solvent could not be successfully modeled.  From 
history, the remaining solvate was likely THF in a volume of 
902.5 \%A3 per unit cell (17.0%).  It appeared that the cavity
area contained more than four THF molecules, in part located 
near the centers of symmetry at (0, 0, 0) and near the 
crystallographic 3 axis at ca. z = 0.17 and symmetry-related 
positions,as shown in the ab projection.  The void volume
surrounds the crystallographic 3 axis at (0, 0, z), and is 
continuous along the c axis as shown in the bc projection.    
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 200 e- per 
unit cell, likely representing 4-5 THF 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         0.53
_refine_diff_density_min         -0.58
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.9980
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     172
_refine_ls_number_reflns         4716
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0468
_refine_ls_R_factor_gt           0.0277
_refine_ls_shift/su_max          0.0019402
_refine_ls_shift/su_mean         0.0003999
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.03P)^2^ + 2.65P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0773
_refine_ls_wR_factor_gt          0.0648
_refine_ls_wR_factor_ref         0.0773
_reflns_limit_h_max              0
_reflns_limit_h_min              -18
_reflns_limit_k_max              22
_reflns_limit_k_min              0
_reflns_limit_l_max              32
_reflns_limit_l_min              0
_reflns_number_gt                3295
_reflns_number_total             4716
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   1.62
_oxford_diffrn_Wilson_scale      126.62
_oxford_refine_ls_r_factor_ref   0.0468
_oxford_refine_ls_scale          0.092962(19)
_oxford_reflns_number_all        4716
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title 'sk_372_0m in P-3c1'
_cod_data_source_file            ic302108k_si_002_2.cif
_cod_data_source_block           3
_cod_original_sg_symbol_Hall     '-P 3 2"c '
_cod_original_sg_symbol_H-M      'P -3 c 1 '
_cod_database_code               4334547
_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   (  16,X'S) H   ( 161,X'S) H   ( 162,X'S) H   ( 163,X'S) 
END                                                                             
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_iucr_refine_instruction_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
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