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_1544266
_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_absolute_configuration syn
_chemical_formula_moiety         'C20 H26 Cl2 Co N4'
_chemical_formula_sum            'C20 H26 Cl2 Co N4'
_chemical_formula_weight         452.28
_chemical_name_systematic        C4
_space_group_crystal_system      orthorhombic
_space_group_IT_number           20
_space_group_name_Hall           'C 2c 2'
_space_group_name_H-M_alt        'C 2 2 21'
_symmetry_space_group_name_Hall  'C 2c 2'
_symmetry_space_group_name_H-M   'C 2 2 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-12-16
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4959)
;
_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                   11.8914(7)
_cell_length_b                   12.9438(7)
_cell_length_c                   15.3741(9)
_cell_measurement_reflns_used    145
_cell_measurement_temperature    100
_cell_measurement_theta_max      45
_cell_measurement_theta_min      3
_cell_volume                     2366.4(2)
_computing_data_reduction        SAINT
_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 0.989
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device_type  'Bruker Proteum X8'
_diffrn_measurement_method       'Phi and omega scan'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_number            26322
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         67.745
_diffrn_reflns_theta_min         5.050
_exptl_absorpt_coefficient_mu    7.841
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.4637
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1539 before and 0.1217 after correction.
The Ratio of minimum to maximum transmission is 0.6158.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            purple
_exptl_crystal_colour_primary    purple
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_description       block
_exptl_crystal_F_000             940
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: '
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.641
_refine_diff_density_min         -0.501
_refine_diff_density_rms         0.100
_refine_ls_abs_structure_details
;
 Flack x determined using 831 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.004(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     145
_refine_ls_number_reflns         2120
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0661
_refine_ls_R_factor_gt           0.0633
_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^)+(0.0776P)^2^+17.4115P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1615
_refine_ls_wR_factor_ref         0.1640
_reflns_Friedel_coverage         0.749
_reflns_Friedel_fraction_full    0.975
_reflns_Friedel_fraction_max     0.972
_reflns_number_gt                2017
_reflns_number_total             2120
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cy01265e2.cif
_cod_data_source_block           cxy145_0m-sr
_cod_database_code               1544266
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained planarity
 N2, C10, C9, C8, C7, C6
 with sigma of 0.1
 N1, C5, C4, C3, C2, C1
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Uanis(N2) = Uanis(N1)
Uanis(C10) = Uanis(C5)
Uanis(C9) = Uanis(C4)
Uanis(C8) = Uanis(C3)
Uanis(C7) = Uanis(C2)
Uanis(C6) = Uanis(C1)
Uanis(C12) = Uanis(C11)
4. Same fragment restrains
{C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
{C6, C7, C8, C9, C10} sigma for 1-2: 0.02, 1-3: 0.04
as
{C1, C2, C3, C4, C5}
5. Others
 Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(N1)=1-FVAR(1)
 Sof(C6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(N2)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C13(H13)
6.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10)
;
_olex2_exptl_crystal_mounting_method 'nylon loop'
_olex2_submission_original_sample_id 3-280
_olex2_submission_special_instructions 'No special instructions were received'