Multi-electron redox processes at a Zr(iv) center facilitated by an appended redox-active cobalt-containing metalloligand.
Krogman, Jeremy P.; Bezpalko, Mark W.; Foxman, Bruce M.; Thomas, Christine M.; Dalton transactions (Cambridge, England : 2003) 45 (2016) 11182–11190; doi:10.1039/c6dt01498d

data_7039561
_publ_section_title
;
 Multi-electron redox processes at a Zr(iv) center facilitated by an
 appended redox-active cobalt-containing metalloligand.
;
_journal_issue                   27
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              11182
_journal_page_last               11190
_journal_paper_doi               10.1039/c6dt01498d
_journal_volume                  45
_journal_year                    2016
_chemical_formula_moiety         'C59 H95 Co1 N5 O1 P3 Zr1'
_chemical_formula_sum            'C59 H95 Co N5 O P3 Zr'
_chemical_formula_weight         1133.52
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_audit_creation_date             2015-03-23
_audit_creation_method           CRYSTALS_ver_14.61
_audit_update_record
;
2016-03-22 deposited with the CCDC.
2016-06-15 downloaded from the CCDC.
;
_cell_angle_alpha                87.6338(11)
_cell_angle_beta                 86.3298(11)
_cell_angle_gamma                69.9841(12)
_cell_formula_units_Z            4
_cell_length_a                   15.3717(4)
_cell_length_b                   16.3072(4)
_cell_length_c                   27.7262(7)
_cell_measurement_reflns_used    9983
_cell_measurement_temperature    120
_cell_measurement_theta_max      24
_cell_measurement_theta_min      2
_cell_volume                     6515.5(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 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  0.062
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            20534
_diffrn_reflns_theta_full        24.044
_diffrn_reflns_theta_max         24.044
_diffrn_reflns_theta_min         1.329
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.527
_exptl_absorpt_correction_T_max  0.96
_exptl_absorpt_correction_T_min  0.92
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
; 
 Analytical Absorption (De Meulenaer & Tompa, 1965) 
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.155
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2416.000
_exptl_crystal_size_max          0.210
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.080
_platon_squeeze_details
;
During the structure solution, only two toluene solvate 
molecules could be located and successfully refined or 
modeled; electron density difference maps revealed that 
there was considerable disorder involving at least 
three additional toluene molecules per unit cell.  
From history, the remaining solvate was confirmed as 
toluene in a volume of 837.3 \%A3 per unit cell (12.9%).  
It appeared that the cavity areas contained approximately 
three (but perhaps more) toluene, located near the center 
of symmetry at (0, 0, .5) and in a long channel centered 
at the general position (0.5, 0.651, 0) as shown in the 
projection below.  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 new structure factor set.  
PLATON reported a total electron density of 178 e- per unit cell, 
likely representing 3-4 toluene molecules, consistent with our 
earlier observations.  Use of the SQUEEZE technique resulted 
in a decrease of ca. 3.0 % in R. 
;
_refine_diff_density_max         1.09
_refine_diff_density_min         -0.93
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   0.9702
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1254
_refine_ls_number_reflns         20534
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0716
_refine_ls_R_factor_gt           0.0468
_refine_ls_shift/su_max          0.0073762
_refine_ls_shift/su_mean         0.0000925
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.05P)^2^ + 9.15P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1088
_refine_ls_wR_factor_gt          0.1013
_refine_ls_wR_factor_ref         0.1088
_reflns_limit_h_max              17
_reflns_limit_h_min              -17
_reflns_limit_k_max              18
_reflns_limit_k_min              -18
_reflns_limit_l_max              31
_reflns_limit_l_min              0
_reflns_number_gt                15320
_reflns_number_total             20534
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   1.44
_oxford_diffrn_Wilson_scale      340.20
_oxford_refine_ls_r_factor_ref   0.0716
_oxford_refine_ls_scale          0.080340(10)
_oxford_reflns_number_all        20534
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title 'JK_858_0m in P-1'
_cod_data_source_file            c6dt01498d2.cif
_cod_data_source_block           6
_cod_depositor_comments
'Adding full bibliography for 7039558--7039562.cif.'
_cod_original_cell_volume        6515.52(16)
_cod_original_sg_symbol_H-M      'P -1 '
_cod_original_formula_sum        'C59 H95 Co1 N5 O1 P3 Zr1'
_cod_database_code               7039561