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_4334128
_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         'C46 H76 Co1 N3 O2 P3 Zr1'
_chemical_formula_sum            'C46 H76 Co N3 O2 P3 Zr'
_chemical_formula_weight         946.20
_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             2012-08-16
_audit_creation_method           CRYSTALS_ver_14.43
_cell_angle_alpha                95.270(5)
_cell_angle_beta                 94.998(4)
_cell_angle_gamma                92.760(4)
_cell_formula_units_Z            2
_cell_length_a                   12.0854(8)
_cell_length_b                   12.7432(9)
_cell_length_c                   17.8468(12)
_cell_measurement_reflns_used    3443
_cell_measurement_temperature    120
_cell_measurement_theta_max      23
_cell_measurement_theta_min      2
_cell_volume                     2722.1(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 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.078
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            9599
_diffrn_reflns_theta_full        25.030
_diffrn_reflns_theta_max         25.030
_diffrn_reflns_theta_min         1.607
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.618
_exptl_absorpt_correction_T_max  0.96
_exptl_absorpt_correction_T_min  0.91
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
; 
 Analytical Absorption (De Meulenaer & Tompa, 1965) 
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.154
_exptl_crystal_description       prism
_exptl_crystal_F_000             1002
_exptl_crystal_size_max          0.230
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.060
_platon_squeeze_details
;
During the structure solution, electron density 
difference maps revealed that there were considerable 
disordered solvent molecules.  From history, the 
solvate was likely ethyl ether in a volume of 476.3 \%A3 
per unit cell (17.5%).  It appeared that the cavity 
area contained about four ether molecules, located 
near the center of symmetry at (0, 1/2, 1/2 ) as 
shown in the bc 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 ?solvate-free? structure factor set 
(only for the third independent molecule).  PLATON 
reported a total electron density of 143 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. 
5.0 % in R.   
;
_refine_diff_density_max         0.97
_refine_diff_density_min         -0.92
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.9489
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     509
_refine_ls_number_reflns         9599
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0764
_refine_ls_R_factor_gt           0.0451
_refine_ls_shift/su_max          0.0014415
_refine_ls_shift/su_mean         0.0000390
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.03P)^2^ + 2.77P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0925
_refine_ls_wR_factor_gt          0.0830
_refine_ls_wR_factor_ref         0.0925
_reflns_limit_h_max              14
_reflns_limit_h_min              -14
_reflns_limit_k_max              15
_reflns_limit_k_min              -15
_reflns_limit_l_max              21
_reflns_limit_l_min              0
_reflns_number_gt                6817
_reflns_number_total             9599
_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   0.0764
_oxford_refine_ls_scale          0.14211(4)
_oxford_reflns_number_all        9599
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title 'JK_173_0m in P-1'
_cod_data_source_file            ic302473j_si_002_02.cif
_cod_data_source_block           4
_cod_original_sg_symbol_H-M      'P -1 '
_cod_original_formula_sum        'C46 H76 Co1 N3 O2 P3 Zr1'
_cod_database_code               4334128
_iucr_refine_instructions_details_constraints
;
BLOCK 
CONT SCALE 
CONT ZR   (    1 ,X'S,U'S)  UNTIL O    (    2 ) 
CONT N    (    1 ,X'S,U'S)  UNTIL C    (   46 ) 
CONT H   (  21,X'S,U[ISO]) 
RIDE C   (   3,X'S) H   (  31,X'S) H   (  32,X'S) H   (  33,X'S) 
RIDE C   (   4,X'S) H   (  41,X'S) 
RIDE C   (   6,X'S) H   (  61,X'S) H   (  62,X'S) H   (  63,X'S) 
RIDE C   (   7,X'S) H   (  71,X'S) 
RIDE C   (   9,X'S) H   (  91,X'S) H   (  92,X'S) H   (  93,X'S) 
RIDE C   (  10,X'S) H   ( 101,X'S) 
RIDE C   (  11,X'S) H   ( 111,X'S) H   ( 112,X'S) H   ( 113,X'S) 
RIDE C   (  12,X'S) H   ( 121,X'S) H   ( 122,X'S) H   ( 123,X'S) 
RIDE C   (  13,X'S) H   ( 131,X'S) 
RIDE C   (  14,X'S) H   ( 141,X'S) H   ( 142,X'S) H   ( 143,X'S) 
RIDE C   (  15,X'S) H   ( 151,X'S) H   ( 152,X'S) H   ( 153,X'S) 
RIDE C   (  18,X'S) H   ( 181,X'S) H   ( 182,X'S) H   ( 183,X'S) 
RIDE C   (  19,X'S) H   ( 191,X'S) 
RIDE C   (  21,X'S) H   ( 211,X'S) H   ( 212,X'S) H   ( 213,X'S) 
RIDE C   (  22,X'S) H   ( 221,X'S) 
RIDE C   (  24,X'S) H   ( 241,X'S) H   ( 242,X'S) H   ( 243,X'S) 
RIDE C   (  25,X'S) H   ( 251,X'S) 
RIDE C   (  26,X'S) H   ( 261,X'S) H   ( 262,X'S) H   ( 263,X'S) 
RIDE C   (  27,X'S) H   ( 271,X'S) H   ( 272,X'S) H   ( 273,X'S) 
RIDE C   (  28,X'S) H   ( 281,X'S) 
RIDE C   (  29,X'S) H   ( 291,X'S) H   ( 292,X'S) H   ( 293,X'S) 
RIDE C   (  30,X'S) H   ( 301,X'S) H   ( 302,X'S) H   ( 303,X'S) 
RIDE C   (  33,X'S) H   ( 331,X'S) H   ( 332,X'S) H   ( 333,X'S) 
RIDE C   (  34,X'S) H   ( 341,X'S) 
RIDE C   (  36,X'S) H   ( 361,X'S) H   ( 362,X'S) H   ( 363,X'S) 
RIDE C   (  37,X'S) H   ( 371,X'S) 
RIDE C   (  39,X'S) H   ( 391,X'S) H   ( 392,X'S) H   ( 393,X'S) 
RIDE C   (  40,X'S) H   ( 401,X'S) 
RIDE C   (  41,X'S) H   ( 411,X'S) H   ( 412,X'S) H   ( 413,X'S) 
RIDE C   (  42,X'S) H   ( 421,X'S) H   ( 422,X'S) H   ( 423,X'S) 
RIDE C   (  43,X'S) H   ( 431,X'S) 
RIDE C   (  44,X'S) H   ( 441,X'S) H   ( 442,X'S) H   ( 443,X'S) 
RIDE C   (  45,X'S) H   ( 451,X'S) H   ( 452,X'S) H   ( 453,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 0.820000 , 0.020000 = O(2) TO H(21) 
END                                                                             
;