Ligand Controlled Product Selectivity in the Electrochemical Carbon Dioxide Reduction Using Manganese Bipyridine Catalysts.
Rønne, Magnus Haugaard H; Cho, Dasol; Madsen, Monica R.; Jakobsen, Joakim B.; Eom, Seunghwan; Escoudé, Émile; Hammershøj, Hans Christian D; Nielsen, Dennis U.; Pedersen, Steen U.; Baik, Mu-Hyun; Skrydstrup, Troels; Daasbjerg, Kim; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.9b11806

data_4134233
_publ_section_title
;
 Ligand Controlled Product Selectivity in the Electrochemical Carbon
 Dioxide Reduction Using Manganese Bipyridine Catalysts.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b11806
_journal_year                    2020
_chemical_formula_moiety         'C35 H38 Br Mn N4 O3'
_chemical_formula_sum            'C35 H38 Br Mn N4 O3'
_chemical_formula_weight         697.54
_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     direct
_audit_creation_date             2019-09-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 103.9199(17)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.4608(2)
_cell_length_b                   29.8404(5)
_cell_length_c                   17.2593(3)
_cell_measurement_reflns_used    24263
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      27.9520
_cell_measurement_theta_min      1.7950
_cell_volume                     6729.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3590
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w      7.00  87.00   1.00   30.00    --   18.69-132.00 -23.00   80
  2  \w     10.00  90.00   1.00   30.00    --   18.69-137.00 159.00   80
  3  \w    -91.00 -10.00   1.00   30.00    --  -19.47 137.00-137.00   81
  4  \w    -88.00  -7.00   1.00   30.00    --  -19.47 132.00  45.00   81
  5  \w    -82.00 -35.00   1.00   30.00    --   18.69-178.00-180.00   47
  6  \w    -28.00 109.00   1.00   30.00    --   18.69  38.00 -90.00  137
  7  \w    -73.00 -48.00   1.00   30.00    --   18.69 -57.00 150.00   25
  8  \w    -28.00 109.00   1.00   30.00    --   18.69  38.00 120.00  137
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0004982000
_diffrn_orient_matrix_UB_12      -0.0231374000
_diffrn_orient_matrix_UB_13      -0.0095132000
_diffrn_orient_matrix_UB_21      -0.0017668000
_diffrn_orient_matrix_UB_22      -0.0053862000
_diffrn_orient_matrix_UB_23      0.0396847000
_diffrn_orient_matrix_UB_31      -0.0542395000
_diffrn_orient_matrix_UB_32      0.0004000000
_diffrn_orient_matrix_UB_33      -0.0113923000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0432
_diffrn_reflns_av_unetI/netI     0.0350
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            84269
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         1.701
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.619
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.595
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear brownish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.377
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2880
_exptl_crystal_size_max          0.253
_exptl_crystal_size_mid          0.198
_exptl_crystal_size_min          0.148
_refine_diff_density_max         1.994
_refine_diff_density_min         -1.996
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     794
_refine_ls_number_reflns         13754
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0770
_refine_ls_R_factor_gt           0.0603
_refine_ls_shift/su_max          0.017
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0874P)^2^+20.5498P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1631
_refine_ls_wR_factor_ref         0.1758
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11132
_reflns_number_total             13754
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b11806_si_002.cif
_cod_data_source_block           magnus_1
_cod_database_code               4134233
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'Mn C35 H38 N4 O3'
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C7B) = Uanis(C7A)
3.a Secondary CH2 refined with riding coordinates:
 C5A(H5AA,H5AB), C6A(H6AA,H6AB), C8A(H8AA,H8AB), C32A(H32A,H32B), C34A(H34A,
 H34B), C35A(H35A,H35B), C5B(H5BA,H5BB), C6B(H6BA,H6BB), C8B(H8BA,H8BB),
 C31B(H31A,H31B), C33B(H33D,H33E), C34B(H34C,H34D)
3.b Aromatic/amide H refined with riding coordinates:
 C10A(H10A), C11A(H11A), C12A(H12A), C13A(H13A), C16A(H16A), C17A(H17A),
 C18A(H18A), C21A(H21A), C22A(H22A), C23A(H23A), C26A(H26A), C27A(H27A),
 C28A(H28A), C29A(H29A), C10B(H10B), C11B(H11B), C12B(H12B), C13B(H13B),
 C16B(H16B), C17B(H17B), C18B(H18B), C21B(H21B), C22B(H22B), C23B(H23B),
 C26B(H26B), C27B(H27B), C28B(H28B), C29B(H29B)
3.c Idealised Me refined with riding coordinates:
 C7B(H7BA,H7BB,H7BC)
3.d Idealised Me refined as rotating group:
 C4A(H4AA,H4AB,H4AC), C7A(H7AA,H7AB,H7AC), C33A(H33A,H33B,H33C), C36A(H36A,
 H36B,H36C), C4B(H4BA,H4BB,H4BC), C32B(H32C,H32D,H32E), C35B(H35C,H35D,H35E)
;
_shelx_res_checksum              72755
_shelx_hkl_checksum              87377
_olex2_date_sample_data_collection 2019-02-22
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.132
_oxdiff_exptl_absorpt_empirical_full_min 0.896