A molecular noble metal-free system for efficient visible light-driven reduction of CO<sub>2</sub> to CO.
Chen, Lingjing; Qin, Yanfei; Chen, Gui; Li, Mingya; Cai, Lirong; Qiu, Yongfu; Fan, Hongbo; Robert, Marc; Lau, Tai-Chu; Dalton transactions (Cambridge, England : 2003) 48 (2019) 9596–9602; doi:10.1039/c9dt00425d

data_7048960
_publ_section_title
;
 A molecular noble metal-free system for efficient visible light-driven
 reduction of CO<sub>2</sub> to CO.
;
_journal_issue                   26
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9596
_journal_page_last               9602
_journal_paper_doi               10.1039/c9dt00425d
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety         'C35 H24 Co N6, 0.5(C2 H3 N), 2(Cl O4)'
_chemical_formula_sum            'C36 H25.5 Cl2 Co N6.5 O8'
_chemical_formula_weight         806.96
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date
;
'Mon Jun 05 15:20:46 2017'
;
_audit_creation_method
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
;
_audit_update_record
;
2019-01-24 deposited with the CCDC.
2019-02-08 downloaded from the CCDC.
;
_cell_angle_alpha                78.865(2)
_cell_angle_beta                 81.873(2)
_cell_angle_gamma                76.817(3)
_cell_formula_units_Z            4
_cell_length_a                   11.4087(4)
_cell_length_b                   11.6129(4)
_cell_length_c                   26.4344(7)
_cell_measurement_reflns_used    7998
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      71.7730
_cell_measurement_theta_min      6.2060
_cell_volume                     3328.35(19)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1270
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_details
;
  1 omega   94.00  121.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -88.0000  111.0820 27

  2 omega   51.00   83.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -50.0000  120.0000 32

  3 omega   51.00   76.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -88.0000  111.0820 25

  4 omega   45.00  109.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -88.0000   60.0000 64

  5 omega   79.00  117.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -88.0000  -44.4850 38

  6 omega   78.00  105.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -88.0000  -98.8860 27

  7 omega   88.00  146.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -88.0000 -150.0000 58

  8 omega   50.00   80.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -50.0000  -60.0000 30

  9 omega   45.00   70.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -37.0000 -120.0000 25

 10 omega   48.00   83.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -50.0000 -150.0000 35

 11 omega   53.00   79.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -88.0000 -150.0000 26

 12 omega   40.00   68.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -37.0000 -180.0000 28

 13 omega   37.00   72.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -25.0000  -90.0000 35

 14 omega   38.00   72.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -25.0000  -60.0000 34

 15 omega   40.00   72.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -25.0000  -30.0000 32

 16 omega   42.00   71.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -37.0000   30.0000 29

 17 omega   46.00   71.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -25.0000   60.0000 25

 18 omega   40.00   66.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -37.0000   60.0000 26

 19 omega   39.00   65.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -25.0000    0.0000 26

 20 omega   45.00  100.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -88.0000   30.0000 55

 21 omega   41.00   66.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -88.0000  -44.4850 25

 22 omega   35.00   65.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       55.0000  -57.0000  -60.0000 30

 23 omega    0.00   84.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       55.0000 -125.0000  -60.0000 84

 24 omega   50.00   75.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000 -178.0000   90.0000 25

 25 omega   39.00   68.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -37.0000  150.0000 29

 26 omega   37.00  157.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -12.0000  120.0000 120

 27 omega   91.00  178.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   41.0000  -53.0000 87

 28 omega   88.00  114.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       55.0000  125.0000 -150.0000 26

 29 omega   77.00  113.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       55.0000  125.0000  -90.0000 36

 30 omega   73.00   98.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       55.0000  125.0000  -30.0000 25

 31 omega   43.00   69.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000  -60.0000 26

 32 omega   26.00  120.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       55.0000   77.0000   60.0000 94

 33 omega   74.00  100.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       55.0000  125.0000  150.0000 26

 34 omega   -4.00   29.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000  -60.0000 33

 35 omega  -13.00   60.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       55.0000  -37.0000  -90.0000 73

 36 omega   24.00   71.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       55.0000  -37.0000  120.0000 47

 37 omega   39.00  131.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -88.0000  150.0000 92

 38 omega  -31.00   11.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -41.0000  153.0000 42

 39 omega  -72.00  -37.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -41.0000  153.0000 35

 40 omega -111.00  -32.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -55.0000  125.0000   90.0000 79
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1233856000
_diffrn_orient_matrix_UB_12      -0.0114911000
_diffrn_orient_matrix_UB_13      0.0199192000
_diffrn_orient_matrix_UB_21      -0.0498141000
_diffrn_orient_matrix_UB_22      0.1148880000
_diffrn_orient_matrix_UB_23      0.0237346000
_diffrn_orient_matrix_UB_31      -0.0416043000
_diffrn_orient_matrix_UB_32      -0.0759267000
_diffrn_orient_matrix_UB_33      0.0510381000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0304
_diffrn_reflns_av_unetI/netI     0.0494
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            25000
_diffrn_reflns_theta_full        68.24
_diffrn_reflns_theta_max         68.24
_diffrn_reflns_theta_min         3.43
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.092
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61228
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.610
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1648
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.798
_refine_diff_density_min         -0.520
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     965
_refine_ls_number_reflns         12105
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0571
_refine_ls_R_factor_gt           0.0461
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0648P)^2^+2.1179P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1165
_refine_ls_wR_factor_ref         0.1232
_reflns_number_gt                10192
_reflns_number_total             12105
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c9dt00425d2.cif
_cod_data_source_block           053117a_jing
_cod_depositor_comments
'Adding full bibliography for 7048959--7048960.cif.'
_cod_original_cell_volume        3328.34(17)
_cod_original_formula_sum        'C36 H25.50 Cl2 Co N6.50 O8'
_cod_database_code               7048960
_cell_oxdiff_angle_alpha         78.865(2)
_cell_oxdiff_angle_beta          81.873(2)
_cell_oxdiff_angle_gamma         76.817(3)
_cell_oxdiff_length_a            11.4087(4)
_cell_oxdiff_length_b            11.6129(4)
_cell_oxdiff_length_c            26.4344(7)
_cell_oxdiff_measurement_reflns_used 7998
_cell_oxdiff_volume              3328.34(18)
_reflns_odcompleteness_completeness 99.37
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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
 N13-C71 = N13A-C71A
 1.15 with sigma of 0.01
 C71-C72 = C71A-C72A
 1.47 with sigma of 0.01
3. Others
 Fixed Sof: N13(0.65) C71(0.65) C72(0.65) H72A(0.65) H72B(0.65) H72C(0.65)
 N13A(0.35) C71A(0.35) C72A(0.35) H72D(0.35) H72E(0.35) H72F(0.35)
4.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C11(H11), C12(H12), C13(H13),
 C16(H16), C17(H17), C18(H18), C21(H21), C22(H22), C23(H23), C26(H26), C27(H27),
  C28(H28), C31(H31), C32(H32), C33(H33), C36(H36), C37(H37), C38(H38),
 C40(H40), C41(H41), C42(H42), C46(H46), C47(H47), C48(H48), C51(H51), C52(H52),
  C53(H53), C56(H56), C57(H57), C58(H58), C61(H61), C62(H62), C63(H63),
 C66(H66), C67(H67), C68(H68)
4.b Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C70(H70A,H70B,H70C), C72(H72A,H72B,H72C), C72A(H72D,H72E,
 H72F)
;
_olex2_submission_special_instructions 'No special instructions were received'