The effects of chelating N4ligand coordination on Co(ii)-catalysed photochemical conversion of CO2to CO: reaction mechanism and DFT calculations
Wang, Feng; Cao, Bei; To, Wai-Pong; Tse, Chun-Wai; Li, Kai; Chang, Xiao-Yong; Zang, Chao; Chan, Sharon Lai-Fung; Che, Chi-Ming; Catal. Sci. Technol. 6 (2016) 7408–; doi:10.1039/C6CY01265E

data_1544267
_publ_section_title
;
 The effects of chelating N4ligand coordination on Co(ii)-catalysed
 photochemical conversion of CO2to CO: reaction mechanism and DFT
 calculations
;
_journal_issue                   20
_journal_name_full               'Catal. Sci. Technol.'
_journal_page_first              7408
_journal_paper_doi               10.1039/C6CY01265E
_journal_volume                  6
_journal_year                    2016
_chemical_formula_moiety         'C17 H24 Cl2 Co N4'
_chemical_formula_sum            'C17 H24 Cl2 Co N4'
_chemical_formula_weight         414.23
_chemical_name_systematic        C6
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_symmetry_space_group_name_Hall  '-P 2n 2ab'
_symmetry_space_group_name_H-M   'P b c n'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-02-25
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-03-03 deposited with the CCDC.
2016-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.2357(14)
_cell_length_b                   8.2893(8)
_cell_length_c                   15.2974(17)
_cell_measurement_reflns_used    27330
_cell_measurement_temperature    115(2)
_cell_volume                     1805.2(3)
_computing_cell_refinement       'APEX2 (Bruker, 2014)'
_computing_data_collection       'APEX2 (Bruker, 2014)'
_computing_data_reduction        'SAINT (Bruker, 2014)'
_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      114.99
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type
'Bruker D8 Venture with PHOTON100 CMOS detector'
_diffrn_measurement_method       '\w scan'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0271
_diffrn_reflns_av_unetI/netI     0.0123
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            27330
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.520
_diffrn_reflns_theta_min         2.663
_diffrn_source                   'micro focus'
_exptl_absorpt_coefficient_mu    1.253
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6367
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/2 (Bruker,2014/2) was used for absorption correction.
wR2(int) was 0.1412 before and 0.0444 after correction.
The Ratio of minimum to maximum transmission is 0.8539.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.524
_exptl_crystal_description       plate
_exptl_crystal_F_000             860
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: '
_exptl_crystal_size_max          0.466
_exptl_crystal_size_mid          0.162
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.339
_refine_diff_density_min         -0.244
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     133
_refine_ls_number_reflns         2083
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0258
_refine_ls_R_factor_gt           0.0216
_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^)+(0.0208P)^2^+1.2763P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0517
_refine_ls_wR_factor_ref         0.0540
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1876
_reflns_number_total             2083
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cy01265e2.cif
_cod_data_source_block           mo_chem0035_b0ma
_cod_database_code               1544267
_shelx_estimated_absorpt_t_max   0.854
_shelx_estimated_absorpt_t_min   0.593
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C8-H8AB = C8-H8BC = C8-H8AA = C8-H8BD
 0.98 with sigma of 0.01
 C9-H9A
 0.98 with sigma of 0.005
 C9-H9B = C9-H9A
 0.98 with sigma of 0.005
 H8AB-H8AA = H8BC-H8BD
 1.605 with sigma of 0.005
 H8AB-C9
 2.07 with sigma of 0.02
 H8AA-C9
 2.07 with sigma of 0.02
 H9A-H9B
 1.6 with sigma of 0.04
3. Others
 Fixed Sof: C9(0.5) H8BC(0.5) H8BD(0.5) H8AB(0.5) H8AA(0.5) H9A(0.5) H9B(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C3(H3), C2(H2)
4.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              14336
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'