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_4335766
_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_formula_moiety         'C80 H72.00 N4 O1.00 P6 Pd2'
_chemical_formula_sum            'C80 H72 N4 O P6 Pd2'
_chemical_formula_weight         1504.12
_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             2012-11-26
_audit_creation_method           CRYSTALS_ver_14.52
_cell_angle_alpha                90
_cell_angle_beta                 105.280(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9704(4)
_cell_length_b                   34.0785(12)
_cell_length_c                   16.6454(6)
_cell_measurement_reflns_used    9763
_cell_measurement_temperature    135
_cell_measurement_theta_max      30
_cell_measurement_theta_min      2
_cell_volume                     7097.4(4)
_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    'USER DEFINED STRUCTURE SOLUTION'
_diffrn_ambient_temperature      135
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.051
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       47
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            20678
_diffrn_reflns_theta_full        30.006
_diffrn_reflns_theta_max         30.006
_diffrn_reflns_theta_min         1.195
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.691
_exptl_absorpt_correction_T_max  0.92
_exptl_absorpt_correction_T_min  0.81
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
; 
 Analytical Absorption (De Meulenaer & Tompa, 1965) 
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.408
_exptl_crystal_description       prism
_exptl_crystal_F_000             3080.000
_exptl_crystal_size_max          0.350
_exptl_crystal_size_mid          0.310
_exptl_crystal_size_min          0.120
_platon_squeeze_details
;
During the structure solution, electron density difference 
maps revealed that there were considerable disordered solvent 
molecules which could not be successfully modeled.  From history, 
the remaining solvate was likely diethyl ether in a volume of 
496.1 \%A3 per unit cell (7.0%).  It appeared that the cavity area 
contained ca. four ether molecules, located near the centers of 
symmetry at (1/2 , 0, 0) and (1/2 , 1/2,  1/2). 
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 
123 e- per unit cell, likely representing four ether molecules, 
consistent with our earlier observations.  Use of the SQUEEZE technique 
resulted in a decrease of ca. 1.0 % in R.   
;
_refine_diff_density_max         1.39
_refine_diff_density_min         -1.47
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.9989
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     830
_refine_ls_number_reflns         20678
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0604
_refine_ls_R_factor_gt           0.0453
_refine_ls_shift/su_max          0.0035949
_refine_ls_shift/su_mean         0.0000835
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.02P)^2^ +30.11P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1045
_refine_ls_wR_factor_gt          0.0990
_refine_ls_wR_factor_ref         0.1045
_reflns_limit_h_max              17
_reflns_limit_h_min              -18
_reflns_limit_k_max              47
_reflns_limit_k_min              0
_reflns_limit_l_max              23
_reflns_limit_l_min              0
_reflns_number_gt                16499
_reflns_number_total             20678
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   0.00
_oxford_diffrn_Wilson_scale      0.00
_oxford_refine_ls_r_factor_ref   0.0604
_oxford_refine_ls_scale          0.060243(5)
_oxford_reflns_number_all        20678
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title 'bfpan_848_0m in P2(1)/c'
_iucr_refine_instructions_details_constraints
;
BLOCK 
CONT SCALE 
CONT PD   (    1 ,X'S,U'S)  UNTIL P    (    6 ) 
CONT O    (    1 ,X'S,U[ISO])  UNTIL O    (    2 ) 
CONT N    (    1 ,X'S,U'S)  UNTIL C    (   76 ) 
CONT C    (   77 ,X'S,U[ISO])  UNTIL C    (  773 ) 
EQUIVALENCE PART(1001, OCC) 
CONTINUE    PART(1002, OCC) 
WEIGHT -1   PART(1002, OCC) 
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   (  14,X'S) H   ( 141,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   (  19,X'S) H   ( 191,X'S) H   ( 192,X'S) 
RIDE C   (  20,X'S) H   ( 201,X'S) H   ( 202,X'S) 
RIDE C   (  22,X'S) H   ( 221,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   (  28,X'S) H   ( 281,X'S) 
RIDE C   (  29,X'S) H   ( 291,X'S) 
RIDE C   (  30,X'S) H   ( 301,X'S) 
RIDE C   (  31,X'S) H   ( 311,X'S) 
RIDE C   (  32,X'S) H   ( 321,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   (  37,X'S) H   ( 371,X'S) 
RIDE C   (  38,X'S) H   ( 381,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) 
RIDE C   (  46,X'S) H   ( 461,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   (  52,X'S) H   ( 521,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   (  57,X'S) H   ( 571,X'S) H   ( 572,X'S) 
RIDE C   (  58,X'S) H   ( 581,X'S) H   ( 582,X'S) 
RIDE C   (  60,X'S) H   ( 601,X'S) 
RIDE C   (  61,X'S) H   ( 611,X'S) 
RIDE C   (  62,X'S) H   ( 621,X'S) 
RIDE C   (  63,X'S) H   ( 631,X'S) 
RIDE C   (  66,X'S) H   ( 661,X'S) 
RIDE C   (  67,X'S) H   ( 671,X'S) 
RIDE C   (  68,X'S) H   ( 681,X'S) 
RIDE C   (  69,X'S) H   ( 691,X'S) 
RIDE C   (  70,X'S) H   ( 701,X'S) 
RIDE C   (  72,X'S) H   ( 721,X'S) 
RIDE C   (  73,X'S) H   ( 731,X'S) 
RIDE C   (  74,X'S) H   ( 741,X'S) 
RIDE C   (  75,X'S) H   ( 751,X'S) 
RIDE C   (  76,X'S) H   ( 761,X'S) 
RIDE C   (  77,X'S) H   ( 771,X'S) H   ( 772,X'S) 
RIDE C   (  78,X'S) H   ( 781,X'S) H   ( 782,X'S) 
RIDE C   (  79,X'S) H   ( 791,X'S) H   ( 792,X'S) 
CONT                H   ( 793,X'S) H   ( 794,X'S) 
RIDE C   (  80,X'S) H   ( 801,X'S) H   (802,X'S) 
RIDE C   ( 771,X'S) H   (7711,X'S) H   (7712,X'S) 
RIDE C   ( 772,X'S) H   (7721,X'S) H   (7722,X'S) 
RIDE C   ( 773,X'S) H   (7731,X'S) H   (7732,X'S) 
END                                                                             
;
_iucr_refine_instructions_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
DISTANCE 1.540000 , 0.015000 = C(79) TO C(772) 
END                                                                             
;
_cod_data_source_file            ic4012873_si_002_1.cif
_cod_data_source_block           5
_cod_original_sg_symbol_H-M      'P 1 21/c 1 '
_cod_original_formula_sum        'C80 H72.00 N4 O1.00 P6 Pd2'
_cod_database_code               4335766