Formation and Subsequent Reactivity of a N2-Stabilized Cobalt‒Hydride Complex
Krogman, Jeremy P.; Foxman, Bruce M.; Thomas, Christine M.; Organometallics 34 (2015) 3159–; doi:10.1021/acs.organomet.5b00182

data_4085967
_publ_section_title
;
 Formation and Subsequent Reactivity of a N2-Stabilized Cobalt--Hydride
 Complex
;
_journal_issue                   13
_journal_name_full               Organometallics
_journal_page_first              3159
_journal_paper_doi               10.1021/acs.organomet.5b00182
_journal_volume                  34
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C65.00 H93.00 Cl2.00 Co1 N3 O3.00 P3 Si1 Zr1'
_chemical_formula_sum            'C65 H93 Cl2 Co N3 O3 P3 Si Zr'
_chemical_formula_weight         1306.53
_space_group_IT_number           198
_symmetry_cell_setting           cubic
_symmetry_space_group_name_Hall  'P 2ac 2ab 3'
_symmetry_space_group_name_H-M   'P 21 3'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_audit_creation_date             2015-05-08
_audit_creation_method           CRYSTALS_ver_14.61
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.9609(17)
_cell_length_b                   18.9609(17)
_cell_length_c                   18.9609(17)
_cell_measurement_reflns_used    9077
_cell_measurement_temperature    120
_cell_measurement_theta_max      30
_cell_measurement_theta_min      3
_cell_volume                     6816.7(11)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.035
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       1
_diffrn_reflns_number            6642
_diffrn_reflns_theta_full        30.007
_diffrn_reflns_theta_max         30.007
_diffrn_reflns_theta_min         1.519
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.607
_exptl_absorpt_correction_T_max  0.81
_exptl_absorpt_correction_T_min  0.80
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
; 
 Analytical Absorption (De Meulenaer & Tompa, 1965) 
;
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.273
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             2751.985
_exptl_crystal_size_max          0.450
_exptl_crystal_size_mid          0.370
_exptl_crystal_size_min          0.350
_platon_squeeze_details
;
During the structure solution, electron density difference maps 
revealed that there was considerable disorder involving the two 
independent DCM solvate molecules, one molecule of which could 
not be successfully modeled.  From history, the remaining solvate 
was likely DCM in a volume of 556.8 \%A3 per unit cell (8.2%).  
It appeared that the cavity areas contained about four DCM molecules, 
located on crystallographic 3 axes at (-0.032, -0.032, -0.032) and 
symmetry-related positions. as shown in the ab 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 new 
structure factor set.  PLATON reported a total electron density 
of 164 e- per unit cell, likely representing about four DCM 
molecules, consistent with our earlier observations.  Use of the 
SQUEEZE technique resulted in a decrease of ca. 1.9 % in R.  
;
_refine_diff_density_max         0.80
_refine_diff_density_min         -0.40
_refine_ls_abs_structure_details 'Flack (1983), 3046 Friedel-pairs'
_refine_ls_abs_structure_Flack   0.002(4)
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   1.0307
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     250
_refine_ls_number_reflns         6642
_refine_ls_number_restraints     5
_refine_ls_R_factor_all          0.0318
_refine_ls_R_factor_gt           0.0273
_refine_ls_shift/su_max          0.0028911
_refine_ls_shift/su_mean         0.0000766
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.03P)^2^ + 3.84P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0713
_refine_ls_wR_factor_gt          0.0662
_refine_ls_wR_factor_ref         0.0713
_reflns_limit_h_max              18
_reflns_limit_h_min              -18
_reflns_limit_k_max              18
_reflns_limit_k_min              0
_reflns_limit_l_max              26
_reflns_limit_l_min              1
_reflns_number_gt                6088
_reflns_number_total             6642
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   1.52
_oxford_diffrn_Wilson_scale      93.08
_oxford_refine_ls_r_factor_ref   0.0318
_oxford_refine_ls_scale          0.10974(2)
_oxford_reflns_number_all        6642
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title 'JK_814_0m in P2(1)3'
_cod_data_source_file            om5b00182_si_002.cif
_cod_data_source_block           8
_cod_depositor_comments
'Adding full bibliography for 4085963--4085969.cif.'
_cod_original_sg_symbol_H-M      'P 21 3 '
_cod_original_formula_sum
'C65.00 H93.00 Cl2.00 Co1 N3 O3.00 P3 Si1 Zr1'
_cod_database_code               4085967
_platon_squeeze_void_probe_radius 1.20