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_4102207
_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         'C24 H22 N3 Ni O5, C8 H20 N, H2 O'
_chemical_formula_sum            'C32 H44 N4 Ni O6'
_chemical_formula_weight         639.42
_chemical_name_common            '(Et4N)[Ni(PyN2(Me2))HCO3] H2O'
_space_group_IT_number           58
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  '-P 2 2n'
_symmetry_space_group_name_H-M   'P n n m'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method
;
SHELXL-97

This compound contains three components, a anion of main structure, a Et4N
cation and a H2O solvated molecule. Only half of them were shown as
independent components due to an existence of mirror symmetry.

The methylene atoms on Et4N cation was treated as diordered model in two
positions with occupancies of 50/50 and their bond lengths were contrained by
the DFIX command. All the temperature factors of Et4N atoms were
evened out by using commands DELU and SIMU in the following refinement.
The H2O molecule was placed with an occupancy of 0.5 and the other 0.5 H2O
can be generated by the mirror symmetry. In this case all the hydrogens on Et4N
and H2O were not added due to their disordered positions, but they were
included in the reported molecular formula. Meanwhile, the lackage of addition
of hydrogen atoms to the Et4N cation might cause the increasing of Solvent
Accessible VOIDS.

The disordered H2O (50/50) by an mirror symmetry might give rise to a short
intermolecular interaction between H2O molecule and the carbonyl group on main
structure, since the real position of H2O has been replaced by two disordered
oxygen atoms.

The hightest Fourier map in the final refinement was tried placed as a second
H2O molecule, but this definition resulted in an extremely large temperature
factor for this atom, with no any peak around this atom for disordered
positions. Moreover, no hydrogen acceptor could be found for a H2O molecule in
this position. Therefore, this placement of a second H2O was thought incorrect.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   17.494(3)
_cell_length_b                   12.920(2)
_cell_length_c                   14.762(2)
_cell_measurement_reflns_used    5524
_cell_measurement_temperature    97(2)
_cell_measurement_theta_max      27.20
_cell_measurement_theta_min      2.33
_cell_volume                     3336.5(9)
_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      97(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.0386
_diffrn_reflns_av_sigmaI/netI    0.0204
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            38079
_diffrn_reflns_theta_full        27.50
_diffrn_reflns_theta_max         27.54
_diffrn_reflns_theta_min         2.33
_exptl_absorpt_coefficient_mu    0.628
_exptl_absorpt_correction_T_max  0.9693
_exptl_absorpt_correction_T_min  0.9228
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.273
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1360
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.258
_refine_diff_density_min         -0.770
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.196
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     232
_refine_ls_number_reflns         3988
_refine_ls_number_restraints     87
_refine_ls_restrained_S_all      1.222
_refine_ls_R_factor_all          0.0861
_refine_ls_R_factor_gt           0.0777
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1005P)^2^+5.6597P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2093
_refine_ls_wR_factor_ref         0.2158
_reflns_number_gt                3526
_reflns_number_total             3988
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja1003125_si_015.cif
_cod_data_source_block           Compound6
_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        3336.6(9)
_cod_original_sg_symbol_Hall     -P22n
_cod_database_code               4102207