Synthesis, Structure, and Reactivity of an Anionic Zr-Oxo Relevant to CO2 Reduction by a Zr/Co Heterobimetallic Complex
Jeremy P. Krogman; Mark W. Bezpalko; Bruce M. Foxman; Christine M. Thomas; Inorganic Chemistry 52 (2013) 3022–3031; doi:10.1021/ic302473j

data_4334127
_publ_section_title
;
 Synthesis, Structure, and Reactivity of an Anionic Zr-Oxo Relevant to CO2
 Reduction by a Zr/Co Heterobimetallic Complex
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              3022
_journal_page_last               3031
_journal_paper_doi               10.1021/ic302473j
_journal_volume                  52
_journal_year                    2013
_chemical_formula_moiety         'C47.80 H78.60 Cl0.55 Co1 N3 O1.45 P3 Zr1'
_chemical_formula_sum            'C47.8 H78.6 Cl0.55 Co N3 O1.45 P3 Zr'
_chemical_formula_weight         981.14
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             10-01-20
_audit_creation_method           CRYSTALS_ver_14.01
_cell_angle_alpha                96.375(4)
_cell_angle_beta                 95.645(4)
_cell_angle_gamma                94.154(3)
_cell_formula_units_Z            2
_cell_length_a                   12.1536(10)
_cell_length_b                   12.7685(9)
_cell_length_c                   17.6635(14)
_cell_measurement_reflns_used    9984
_cell_measurement_temperature    120
_cell_measurement_theta_max      29
_cell_measurement_theta_min      3
_cell_volume                     2701.3(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    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      120
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.991
_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  0.042
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            15637
_diffrn_reflns_theta_full        29.120
_diffrn_reflns_theta_max         30.021
_diffrn_reflns_theta_min         2.334
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.651
_exptl_absorpt_correction_T_max  0.92
_exptl_absorpt_correction_T_min  0.88
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
; 
 Analytical Absorption (De Meulenaer & Tompa, 1965) 
;
_exptl_crystal_colour            'orange red'
_exptl_crystal_density_diffrn    1.206
_exptl_crystal_description       prism
_exptl_crystal_F_000             1038.701
_exptl_crystal_size_max          0.387
_exptl_crystal_size_mid          0.193
_exptl_crystal_size_min          0.129
_platon_squeeze_details
;
During the structure solution, electron density difference 
maps revealed that there were considerable disordered solvent 
molecules (from history, likely diethyl ether or THF) in a 
volume of 337.4 \%A3 per unit cell (12.5%); the peaks could 
not be modeled successfully.  It appeared that the cavity area 
contained about two diethyl ether molecules, centered near
 +- (0.294, 0.741, 0.267).  An initially satisfactory solution 
was obtained for the independent diethyl ether molecule; 
however, residual peaks in the same area of 1.5 -- 2.0 e- 
suggested alternative partial occupancy of THF.  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 60 e- per 
unit cell, likely representing two diethyl ether molecules 
(and/or substitution by THF), consistent with our earlier 
observations.  Use of the SQUEEZE technique resulted in a 
decrease of ca 2.5 % in R. 
;
_refine_diff_density_max         0.83
_refine_diff_density_min         -0.91
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.9949
_refine_ls_hydrogen_treatment    none
_refine_ls_matrix_type           full
_refine_ls_number_parameters     551
_refine_ls_number_reflns         15637
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0597
_refine_ls_R_factor_gt           0.0432
_refine_ls_shift/su_max          0.0045397
_refine_ls_shift/su_mean         0.3893191
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.04P)^2^ + 4.41P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1091
_refine_ls_wR_factor_gt          0.1051
_refine_ls_wR_factor_ref         0.1091
_reflns_limit_h_max              16
_reflns_limit_h_min              -17
_reflns_limit_k_max              17
_reflns_limit_k_min              -17
_reflns_limit_l_max              24
_reflns_limit_l_min              0
_reflns_number_gt                12093
_reflns_number_total             15637
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   1.61
_oxford_diffrn_Wilson_scale      54.44
_oxford_refine_ls_r_factor_ref   0.0597
_oxford_refine_ls_scale          0.14137(3)
_oxford_reflns_number_all        15637
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title 'cmt30_0m in P-1'
_cod_data_source_file            ic302473j_si_002_01.cif
_cod_data_source_block           3
_cod_original_sg_symbol_H-M      'P -1 '
_cod_original_formula_sum        'C47.80 H78.60 Cl0.55 Co1 N3 O1.45 P3 Zr1'
_cod_database_code               4334127