Multimetallic Complexes Featuring a Bridging N-heterocyclic Phosphido/Phosphenium Ligand: Synthesis, Structure, and Theoretical Investigation
Baofei Pan; Deirdra A. Evers-McGregor; Mark W. Bezpalko; Bruce M. Foxman; Christine M. Thomas; Inorganic Chemistry 52 (2013) 9583–9589; doi:10.1021/ic4012873

data_4335767
_publ_section_title
;
 Multimetallic Complexes Featuring a Bridging N-heterocyclic
 Phosphido/Phosphenium Ligand: Synthesis, Structure, and Theoretical
 Investigation
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              9583
_journal_page_last               9589
_journal_paper_doi               10.1021/ic4012873
_journal_volume                  52
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C76 H64 N4 P6 Pt2'
_chemical_formula_sum            'C76 H64 N4 P6 Pt2'
_chemical_formula_weight         1609.39
_space_group_IT_number           120
_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_Hall  'I -4 -2c'
_symmetry_space_group_name_H-M   'I -4 c 2'
_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                90
_cell_formula_units_Z            4
_cell_length_a                   16.6096(4)
_cell_length_b                   16.6096(4)
_cell_length_c                   25.8471(7)
_cell_measurement_reflns_used    9914
_cell_measurement_temperature    120
_cell_measurement_theta_max      30
_cell_measurement_theta_min      2
_cell_volume                     7130.7(3)
_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  0.039
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            5205
_diffrn_reflns_theta_full        29.992
_diffrn_reflns_theta_max         29.992
_diffrn_reflns_theta_min         1.576
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.098
_exptl_absorpt_correction_T_max  0.59
_exptl_absorpt_correction_T_min  0.42
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
; 
 Analytical Absorption (De Meulenaer & Tompa, 1965) 
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.499
_exptl_crystal_description       prism
_exptl_crystal_F_000             3176
_exptl_crystal_size_max          0.210
_exptl_crystal_size_mid          0.210
_exptl_crystal_size_min          0.130
_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 either ether or THF in a volume of 1090.1 \%A3 
per unit cell (15.3%).  It appeared that the cavity area 
contained about eight THF and/or ether molecules, located 
near the 222 position at (0, 0, 1/4) and symmetry-related 
positions, as shown in the ab projection above. 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 301 e- per 
unit cell, likely representing 8 THF and/or ether 
molecules, consistent with our earlier observations.  
Use of the SQUEEZE technique resulted in a decrease of 
ca. 0.9 % in R.
;
_refine_diff_density_max         1.08
_refine_diff_density_min         -1.29
_refine_ls_abs_structure_details 'Flack (1983), 2418 Friedel-pairs'
_refine_ls_abs_structure_Flack   -0.013(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.9722
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     200
_refine_ls_number_reflns         5205
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0195
_refine_ls_R_factor_gt           0.0154
_refine_ls_shift/su_max          0.0023650
_refine_ls_shift/su_mean         0.0002843
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.00P)^2^ + 0.75P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0342
_refine_ls_wR_factor_gt          0.0329
_refine_ls_wR_factor_ref         0.0342
_reflns_limit_h_max              23
_reflns_limit_h_min              0
_reflns_limit_k_max              23
_reflns_limit_k_min              0
_reflns_limit_l_max              36
_reflns_limit_l_min              0
_reflns_number_gt                4542
_reflns_number_total             5205
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   1.31
_oxford_diffrn_Wilson_scale      928.96
_oxford_refine_ls_r_factor_ref   0.0195
_oxford_refine_ls_scale          0.0340893(11)
_oxford_reflns_number_all        5205
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title 'bfpan_727_0m in I4/mcm'
_cod_data_source_file            ic4012873_si_002_2.cif
_cod_data_source_block           6
_cod_original_sg_symbol_H-M      'I -4 c 2 '
_cod_database_code               4335767
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, U'S 
RIDE C   (   4,X'S) H   (  41,X'S) H   (  42,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   (  15,X'S) H   ( 151,X'S) 
RIDE C   (  16,X'S) H   ( 161,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   (  22,X'S) H   ( 221,X'S) 
RIDE C   (  23,X'S) H   ( 231,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                                                                             
;