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_4102208
_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         'C23 H22 N3 O3 Pd, C8 H20 N'
_chemical_formula_sum            'C31 H42 N4 O3 Pd'
_chemical_formula_weight         625.09
_chemical_name_common            (Et4N)[Pd(PyN2(Me2))OH]
_space_group_IT_number           36
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'C 2c -2'
_symmetry_space_group_name_H-M   'C m c 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method
;
SHELXL-97

The cation Et4N+ was treated as disordered model and all the atoms of it
was anisotroped in the following refinement. The temperature factors of
these atoms were evened out by using commands DELU and SIMU.

Hydrogen atoms was not added to Et4N+ due to its high symmetry
and disordered atoms on its ethylene chain, but these hydrogen atoms were
included in the reported formula.

The attempts to add hydrogen atom on -OH group by residual Fourier maps
was always failed. Therefore, it was added geometrically. The Et4N+
cation in this structure and 1H NMR spectrum of this compound
(see paper) supports the existence of this hydrgen atom.

There is no strong H bond acceptor (O/N) in an appropriate position
for the hydrogen atom of -OH group. Therefore, the hydrogen atoms
was defined to point to one of phenyl rings of ligand.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   14.461(5)
_cell_length_b                   13.742(5)
_cell_length_c                   14.839(5)
_cell_measurement_reflns_used    1699
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      20.38
_cell_measurement_theta_min      2.46
_cell_volume                     2948.9(18)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_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 0.973
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w 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  0.0640
_diffrn_reflns_av_sigmaI/netI    0.0717
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            7647
_diffrn_reflns_theta_full        25.82
_diffrn_reflns_theta_max         25.82
_diffrn_reflns_theta_min         2.04
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.667
_exptl_absorpt_correction_T_max  0.8893
_exptl_absorpt_correction_T_min  0.8781
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.408
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1304
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.662
_refine_diff_density_min         -0.467
_refine_diff_density_rms         0.099
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.01(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     211
_refine_ls_number_reflns         2612
_refine_ls_number_restraints     86
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0526
_refine_ls_R_factor_gt           0.0461
_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^)+(0.0610P)^2^+1.5639P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1104
_refine_ls_wR_factor_ref         0.1158
_reflns_number_gt                2331
_reflns_number_total             2612
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja1003125_si_016.cif
_cod_data_source_block           Compound20
_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        2948.8(18)
_cod_original_sg_symbol_Hall     C2c-2
_cod_database_code               4102208