An amide-based second coordination sphere promotes the dimer pathway of Mn-catalyzed CO2-to-CO reduction at low overpotential
Yang, Yong; Ertem, Mehmed Z.; Duan, Lele; Chemical Science 12 (2021) 4779–4788; doi:10.1039/D0SC05679K

data_1560367
_publ_section_title
;
 An amide-based second coordination sphere promotes the dimer pathway of
 Mn-catalyzed CO2-to-CO reduction at low overpotential
;
_journal_issue                   13
_journal_name_full               'Chemical Science'
_journal_page_first              4779
_journal_page_last               4788
_journal_paper_doi               10.1039/D0SC05679K
_journal_volume                  12
_journal_year                    2021
_chemical_formula_moiety         'C31 H43 K Mn N3 O11, C4 H8 O'
_chemical_formula_sum            'C35 H51 K Mn N3 O12'
_chemical_formula_weight         799.82
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-10-08 deposited with the CCDC.	2021-02-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.907(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4091(12)
_cell_length_b                   15.768(3)
_cell_length_c                   25.766(5)
_cell_measurement_reflns_used    2085
_cell_measurement_temperature    100
_cell_measurement_theta_max      24.724
_cell_measurement_theta_min      2.58
_cell_volume                     3808.7(11)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker PHOTO 100 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker CMOS 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  0.0377
_diffrn_reflns_av_unetI/netI     0.0309
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            33070
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        24.761
_diffrn_reflns_theta_max         24.761
_diffrn_reflns_theta_min         2.704
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.520
_exptl_absorpt_correction_T_max  0.7451
_exptl_absorpt_correction_T_min  0.6378
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1119 before and 0.0606 after correction. The Ratio of minimum to maximum transmission is 0.8560. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.395
_exptl_crystal_description       block
_exptl_crystal_F_000             1688
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.455
_refine_diff_density_min         -0.781
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     643
_refine_ls_number_reflns         6480
_refine_ls_number_restraints     453
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.1054
_refine_ls_R_factor_gt           0.0845
_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^)+(0.1133P)^2^+12.8101P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2174
_refine_ls_wR_factor_ref         0.2382
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5078
_reflns_number_total             6480
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc05679k3.cif
_cod_data_source_block           cxy0685_0m
_cod_depositor_comments
'Adding full bibliography for 1560367--1560369.cif.'
_cod_original_cell_volume        3808.6(11)
_cod_database_code               1560367
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C36-C37 = C39-C38 = C41-C40 = C43-C42 = C33-C32 = C34-C35
 1.52 with sigma of 0.02
 O7-C36 = O8-C37 = O8-C38 = O9-C39 = O9-C40 = O7-C35 = O10-C42 = O5-C43 = O5-
 C32 = O6-C33
 1.42 with sigma of 0.02
 O6-C34
 1.42 with sigma of 0.02
 C23-O17
 1.42 with sigma of 0.02
 C24-C25 = C26-C27 = C17-C16 = C19-C18 = C21-C20 = C23-C22
 1.52 with sigma of 0.02
 O18-C26 = O13-C27 = O13-C16 = O14-C17 = O14-C18 = O15-C19 = O15-C20 = O16-C21
 = O16-C22 = O18-C25 = O17-C24
 1.42 with sigma of 0.02
 O12-C28 = O12-C31 = O19-C48 = O19-C51
 1.43 with sigma of 0.02
 C48-C49 = C50-C51 = C50-C49 = C29-C28 = C31-C30 = C30-C29
 1.52 with sigma of 0.02
 O8-C39 = C38-O9 = O10-C43 = O5-C42 = O6-C35 = C34-O7
 2.37 with sigma of 0.04
 O9-C41 = C40-O10 = O5-C33 = C32-O6 = O7-C37 = C36-O8
 2.37 with sigma of 0.04
 C25-O17 = C24-O18 = O13-C17 = C16-O14 = O15-C21 = O16-C20
 2.37 with sigma of 0.04
 O18-C27 = C26-O13 = O14-C19 = C18-O15 = O16-C23 = C22-O17
 2.37 with sigma of 0.04
 O12-C30
 2.26 with sigma of 0.04
 C48-C51
 2.26 with sigma of 0.04
 C28-C30 = C31-C29 = C50-C48 = C49-C51
 2.37 with sigma of 0.04
 C30-O12
 2.35 with sigma of 0.04
 O12-C29
 2.35 with sigma of 0.04
 K1-O13 \\sim K1-O14 \\sim K1-O15 \\sim K1-O16 \\sim K1-O17 \\sim K1-O18
 with sigma of 0.02
 O11-C47 \\sim O11-C44
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C34 \\sim C35 \\sim O7 \\sim C36 \\sim C37 \\sim O8 \\sim C38 \\sim C39 \\sim
O9 \\sim C40 \\sim C41 \\sim O10 \\sim C42 \\sim C43 \\sim O5 \\sim C32 \\sim
C33 \\sim O6: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C22 \\sim C23 \\sim O17 \\sim C24 \\sim C25 \\sim O18 \\sim C26 \\sim C27 \\sim
O13 \\sim C16 \\sim C17 \\sim O14 \\sim C18 \\sim C19 \\sim O15 \\sim C20 \\sim
C21 \\sim O16: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C49 \\sim C50 \\sim C51 \\sim C30 \\sim O19 \\sim C31 \\sim O12 \\sim C48 \\sim
C29 \\sim C28: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O8) = Uanis(O16)
Uanis(O17) = Uanis(O9)
Uanis(O18) = Uanis(O10)
Uanis(O13) = Uanis(O5)
Uanis(O14) = Uanis(O6)
Uanis(O15) = Uanis(O7)
4. Others
 Sof(O6)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(O5)=Sof(O7)=Sof(C33)=Sof(H33A)=
 Sof(H33B)=Sof(O9)=Sof(O10)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C32)=Sof(H32A)=
 Sof(H32B)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(O8)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C41)=Sof(H41A)=
 Sof(H41B)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C36)=
 Sof(H36A)=Sof(H36B)=1-FVAR(1)
 Sof(O18)=Sof(O13)=Sof(O15)=Sof(O14)=Sof(O16)=Sof(O17)=Sof(C21)=Sof(H21A)=
 Sof(H21B)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(C16)=
 Sof(H16A)=Sof(H16B)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C19)=Sof(H19A)=Sof(H19B)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(C20)=Sof(H20A)=
 Sof(H20B)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C25)=
 Sof(H25A)=Sof(H25B)=FVAR(1)
 Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(O19)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C50)=
 Sof(H50A)=Sof(H50B)=Sof(C49)=Sof(H49A)=Sof(H49B)=1-FVAR(2)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(O12)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C29)=
 Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=Sof(H30B)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C45(H45A,H45B), C46(H46A,H46B), C44(H44A,H44B), C47(H47A,H47B), C21(H21A,
 H21B), C26(H26A,H26B), C23(H23A,H23B), C16(H16A,H16B), C22(H22A,H22B),
 C19(H19A,H19B), C24(H24A,H24B), C17(H17A,H17B), C20(H20A,H20B), C18(H18A,H18B),
  C27(H27A,H27B), C25(H25A,H25B), C40(H40A,H40B), C33(H33A,H33B), C42(H42A,
 H42B), C32(H32A,H32B), C43(H43A,H43B), C35(H35A,H35B), C34(H34A,H34B),
 C39(H39A,H39B), C41(H41A,H41B), C37(H37A,H37B), C38(H38A,H38B), C36(H36A,H36B),
  C31(H31A,H31B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B), C48(H48A,
 H48B), C51(H51A,H51B), C50(H50A,H50B), C49(H49A,H49B)
5.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), N3(H3), C4(H4), C3(H3A), C2(H2), C1(H1)
5.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_olex2_submission_special_instructions 'No special instructions were received'