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_4102200
_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         'C28 H34 N6 O2, H2 Cl2, C H4 O, H0.5 O0.25'
_chemical_formula_sum            'C29 H40.5 Cl2 N6 O3.25'
_chemical_formula_weight         596.07
_chemical_name_common            '[H2PyN2dien(Me3)](2HCl).MeOH.0.25H2O'
_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
_atom_sites_solution_secondary   difmap
_audit_creation_method
;
SHELXL-97

This structure was solved from a twin data with BASF of 0.25. The data was
run for absorption correction by TWINABS before the hkl data was generated
for refinement. The occupancy of H2O was defined to be 0.25 by SHELXTL
program and two hydrogen atoms this water molecule were added by Foriour
maps, but their positons was fixed by using command AFIX 3.

Two extra hydrogen atoms were included in formula for a balance of
charge of two chloride anions in this compound, even they could not be defined
from the residual Foriour maps.

In this compound, the main structure of macrocyclic ligand is netural
accompanied by two chloride anions outside. Obviously
these two chloride anions should be presented as two HCl molecules which
formed a amine salt with the main amine macrocyclic ligand. This definition
was supported by the reaction from which HCl molecules were generated
by reaction of carbonyl chloride and primary amine (see paper).
;
_cell_angle_alpha                73.508(5)
_cell_angle_beta                 77.465(5)
_cell_angle_gamma                83.423(5)
_cell_formula_units_Z            2
_cell_length_a                   7.857(2)
_cell_length_b                   13.443(4)
_cell_length_c                   15.249(5)
_cell_measurement_reflns_used    2696
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      25.55
_cell_measurement_theta_min      2.39
_cell_volume                     1505.1(8)
_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      113(2)
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_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  0.0000
_diffrn_reflns_av_sigmaI/netI    0.0520
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            5621
_diffrn_reflns_theta_full        25.68
_diffrn_reflns_theta_max         25.68
_diffrn_reflns_theta_min         1.58
_exptl_absorpt_coefficient_mu    0.258
_exptl_absorpt_correction_T_max  0.9698
_exptl_absorpt_correction_T_min  0.9267
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   TWINABS
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.315
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       column
_exptl_crystal_F_000             633
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.859
_refine_diff_density_min         -0.416
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     372
_refine_ls_number_reflns         5621
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0778
_refine_ls_R_factor_gt           0.0608
_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^)+(0.0799P)^2^+1.3165P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1498
_refine_ls_wR_factor_ref         0.1620
_reflns_number_gt                4608
_reflns_number_total             5621
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja1003125_si_008.cif
_cod_data_source_block           Compound13
_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_sg_symbol_Hall     -P1
_cod_original_formula_sum        'C29 H40.50 Cl2 N6 O3.25'
_cod_database_code               4102200