Structural, Kinetic, and DFT Studies of the Transfer Hydro-genation of Ketones Mediated by (Pyrazole)pyridine Iron(II) and Nickel(II) Complexes
Magubane, Makhosozane N.; Nyamato, George Simba; Ojwach, Stephen O.; Munro, Orde Q.; RSC Adv.  (2016) –; doi:10.1039/C6RA12788F

data_7225765
_publ_section_title
;
 Structural, Kinetic, and DFT Studies of the Transfer Hydro-genation of
 Ketones Mediated by (Pyrazole)pyridine Iron(II) and Nickel(II) Complexes
;
_journal_name_full               'RSC Adv.'
_journal_paper_doi               10.1039/C6RA12788F
_journal_year                    2016
_chemical_formula_moiety         'C15 H23 N5 Ni O3, H2 O, 2(Br)'
_chemical_formula_sum            'C15 H25 Br2 N5 Ni O4'
_chemical_formula_weight         557.93
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-06-06
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_audit_update_record
;
2016-05-16 deposited with the CCDC.
2016-06-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.777(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4314(8)
_cell_length_b                   11.0104(8)
_cell_length_c                   18.8608(13)
_cell_measurement_reflns_used    9928
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      30.48
_cell_measurement_theta_min      3.13
_cell_volume                     2103.9(3)
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0210
_diffrn_reflns_av_unetI/netI     0.0287
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            12399
_diffrn_reflns_point_group_measured_fraction_full 0.681
_diffrn_reflns_point_group_measured_fraction_max 0.654
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.479
_diffrn_reflns_theta_min         2.224
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.750
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.4630
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1002 before and 0.0454 after correction.
The Ratio of minimum to maximum transmission is 0.6206.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.761
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.445
_refine_diff_density_min         -0.386
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.014(5)
_refine_ls_extinction_coef       0.00042(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     281
_refine_ls_number_reflns         4201
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0153
_refine_ls_R_factor_gt           0.0150
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0132P)^2^+0.7200P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0368
_refine_ls_wR_factor_ref         0.0369
_reflns_Friedel_coverage         0.315
_reflns_Friedel_fraction_full    0.367
_reflns_Friedel_fraction_max     0.314
_reflns_number_gt                4128
_reflns_number_total             4201
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ra12788f2.cif
_cod_data_source_block           mo_so_mgc1_l3_db_0m
_cod_database_code               7225765
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.450
_shelx_estimated_absorpt_t_min   0.252
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 H2A-O2
 0.82 with sigma of 0.02
 O2-H2B
 0.82 with sigma of 0.02
 H1SA-O1S
 0.82 with sigma of 0.02
 O1S-H1SB
 0.82 with sigma of 0.02
 H1A-O1
 0.82 with sigma of 0.02
 O1-H1B
 0.82 with sigma of 0.02
 O3-H3B
 0.82 with sigma of 0.02
 O3-H3A
 0.82 with sigma of 0.02
3.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C8(H8), C9(H9), C13(H13)
3.b Idealised Me refined as rotating group:
 C1(H1C,H1D,H1E), C5(H5A,H5B,H5C), C11(H11A,H11B,H11C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              51845