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_7225767
_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         'C34 H42 Fe N10, 2(Cl4 Fe), 2(C H2 Cl2)'
_chemical_formula_sum            'C36 H46 Cl12 Fe3 N10'
_chemical_formula_weight         1211.78
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-07-28
_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                89.620(4)
_cell_angle_beta                 64.621(4)
_cell_angle_gamma                63.481(4)
_cell_formula_units_Z            2
_cell_length_a                   13.7303(12)
_cell_length_b                   14.9885(13)
_cell_length_c                   15.6987(13)
_cell_measurement_reflns_used    9151
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.16
_cell_measurement_theta_min      2.38
_cell_volume                     2542.7(4)
_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    'olex2.solve (Bourhis et al., 2013)'
_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 0.968
_diffrn_measured_fraction_theta_max 0.958
_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  0.0284
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_Laue_measured_fraction_full 0.968
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            36960
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         26.234
_diffrn_reflns_theta_min         1.475
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.514
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.6040
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1015 before and 0.0481 after correction.
The Ratio of minimum to maximum transmission is 0.8104.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.583
_exptl_crystal_description       shard
_exptl_crystal_F_000             1228
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.196
_refine_diff_density_min         -1.176
_refine_diff_density_rms         0.212
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.183
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     650
_refine_ls_number_reflns         9820
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.181
_refine_ls_R_factor_all          0.0994
_refine_ls_R_factor_gt           0.0966
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+74.1287P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2454
_refine_ls_wR_factor_ref         0.2466
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9239
_reflns_number_total             9820
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ra12788f2.cif
_cod_data_source_block           CPD_6
_cod_database_code               7225767
_shelxl_version_number           2014-3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(Cl1') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl2') \\sim Ueq, Uanis(Fe2') \\sim Ueq, Uanis(Cl4) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl4') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl3) \\sim Ueq, Uanis(Fe3') \\sim Ueq, Uanis(Cl6') \\sim Ueq, Uanis(Cl7)
\\sim Ueq, Uanis(Cl4) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
3. Others
 Sof(Fe2')=Sof(Cl1')=Sof(Cl2')=Sof(Cl3')=Sof(Cl4')=1-FVAR(1)
 Sof(Fe2)=Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=Sof(Cl4)=FVAR(1)
 Sof(Fe3')=Sof(Cl5')=Sof(Cl6')=Sof(Cl7')=Sof(Cl8')=1-FVAR(2)
 Sof(Fe3)=Sof(Cl5)=Sof(Cl6)=Sof(Cl7)=Sof(Cl8)=FVAR(2)
4.a Secondary CH2 refined with riding coordinates:
 C6(H6a,H6b), C12(H12a,H12b), C23(H23a,H23b), C29(H29a,H29b), C1A(H1Aa,H1Ab),
 C1B(H1Ba,H1Bb)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8), C9(H9), C10(H10), C15(H15), C20(H20), C25(H25), C26(H26),
 C27(H27), C32(H32)
4.c Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C5(H5a,H5b,H5c), C13(H13a,H13b,H13c), C17(H17a,H17b,H17c),
 C18(H18a,H18b,H18c), C22(H22a,H22b,H22c), C30(H30a,H30b,H30c), C34(H34a,H34b,
 H34c)
;