Reactions of the Terminal NiII-OH Group in Substitution and Electrophilic Reactions with Carbon Dioxide and Other Substrates: Structural Definition of Binding Modes in an Intramolecular NiII...FeII Bridged Site
Deguang Huang; R. H. Holm; Journal of the American Chemical Society 132 (2010) 4693–4701; doi:10.1021/ja1003125

data_4102203
_publ_section_title
;
 Reactions of the Terminal NiII-OH Group in Substitution and Electrophilic
 Reactions with Carbon Dioxide and Other Substrates: Structural Definition
 of Binding Modes in an Intramolecular NiII...FeII Bridged Site
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4693
_journal_page_last               4701
_journal_paper_doi               10.1021/ja1003125
_journal_volume                  132
_journal_year                    2010
_chemical_formula_moiety         '2(C29 H33 Cl Fe N6 Ni O4), 2(C3 H6 O2)'
_chemical_formula_sum            'C64 H78 Cl2 Fe2 N12 Ni2 O12'
_chemical_formula_weight         1507.40
_chemical_name_common            2{[Ni(HCO2)FeCl(PyN2dien(Me3))].HCOOEt}
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method
;
SHELXL-97

The two solvated molecules, HCOOEt, were treated as disordered models in this
structure. One HCOOEt has only oxygen atoms disordered into two positions
with the occupancies of 0.73 and 0.27, but the other HCOOEt molecule applied
strong disorder for the whole molecule with each atom disordered into two
positions (50/50 occupancies). All the bond lengths of these two HCOOEt
molecules were constrained by command DFIX and their temperature factors
were evened out by using commands DELU and SIMU.

All the non-hydrogen atoms of these two HCOOEt molecules were anisotroped
and hydrogen atoms were added geometrically to one of molecules. The other
HCOOEt was not added hydrogen atoms due to its strongly disordered
structure. All the hydrogen atoms were included in the reported formula.

The distances of Ni1-Fe1 4.7922(9) and Ni2-Fe2 4.8139(9) were attached here
for reference use.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 112.377(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   17.3841(8)
_cell_length_b                   20.4346(11)
_cell_length_c                   19.4920(9)
_cell_measurement_reflns_used    6311
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      22.65
_cell_measurement_theta_min      2.29
_cell_volume                     6402.9(6)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0838
_diffrn_reflns_av_sigmaI/netI    0.0898
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            57610
_diffrn_reflns_theta_full        26.78
_diffrn_reflns_theta_max         26.78
_diffrn_reflns_theta_min         1.61
_exptl_absorpt_coefficient_mu    1.180
_exptl_absorpt_correction_T_max  0.8429
_exptl_absorpt_correction_T_min  0.7813
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            Orange-red
_exptl_crystal_density_diffrn    1.564
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3136
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.312
_refine_diff_density_min         -0.932
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     911
_refine_ls_number_reflns         13435
_refine_ls_number_restraints     175
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.1104
_refine_ls_R_factor_gt           0.0586
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0640P)^2^+8.3725P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1312
_refine_ls_wR_factor_ref         0.1568
_reflns_number_gt                8148
_reflns_number_total             13435
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja1003125_si_011.cif
_cod_data_source_block           Compound18
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_crystal_density_meas' value 'none' was changed to '?' - the
value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 3008 2015-01-20 13:52:24Z robertas 
;
_cod_original_cell_volume        6402.9(5)
_cod_original_sg_symbol_Hall     -P2ybc
_cod_database_code               4102203