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_1544269
_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         'C12 H30 Cl Co N4, Cl, 2(H2 O)'
_chemical_formula_sum            'C12 H34 Cl2 Co N4 O2'
_chemical_formula_weight         396.26
_chemical_name_systematic        C8
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-01-27
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.19 svn.r3143 for OlexSys, GUI svn.r4992)
;
_audit_update_record
;
2015-03-03 deposited with the CCDC.
2016-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                83.343(3)
_cell_angle_beta                 81.332(3)
_cell_angle_gamma                61.722(3)
_cell_formula_units_Z            2
_cell_length_a                   9.0263(11)
_cell_length_b                   9.1900(11)
_cell_length_c                   13.2981(16)
_cell_measurement_reflns_used    8108
_cell_measurement_temperature    100
_cell_measurement_theta_max      68.55
_cell_measurement_theta_min      3.37
_cell_volume                     959.1(2)
_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
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.962
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0734
_diffrn_reflns_av_unetI/netI     0.0584
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            16339
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.500
_diffrn_reflns_theta_min         3.366
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    9.651
_exptl_absorpt_correction_T_max  0.3490
_exptl_absorpt_correction_T_min  0.1271
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1501 before and 0.1089 after correction.
The Ratio of minimum to maximum transmission is 0.3642.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.372
_exptl_crystal_description       plate
_exptl_crystal_F_000             422
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: '
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.688
_refine_diff_density_min         -0.641
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     212
_refine_ls_number_reflns         3390
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0503
_refine_ls_R_factor_gt           0.0488
_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^)+(0.0933P)^2^+0.2555P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1316
_refine_ls_wR_factor_ref         0.1333
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3249
_reflns_number_total             3390
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cy01265e2.cif
_cod_data_source_block           cxy163_p-1
_cod_database_code               1544269
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O1-H1D = O1-H1C = O2-H2C = O2-H2D
 0.99 with sigma of 0.02
 H1D-H1C = H2C-H2D
 1.58 with sigma of 0.04
3.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C10(H10A,H10B), C9(H9A,H9B), C6(H6A,H6B), C2(H2A,H2B), C1(H1A,H1B)
3.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C3(H3A,H3B,H3C), C8(H8A,H8B,H8C), C4(H4A,H4B,H4C),
 C11(H11A,H11B,H11C), C7(H7A,H7B,H7C)
;
_olex2_submission_special_instructions 'No special instructions were received'