Synergistic Effects of Imidazolium-Functionalization on fac-Mn(CO)<sub>3</sub> Bipyridine Catalyst Platforms for Electrocatalytic Carbon Dioxide Reduction.
Sung, Siyoung; Li, Xiaohui; Wolf, Lucienna M.; Meeder, Jeremy R.; Bhuvanesh, Nattamai S.; Grice, Kyle A.; Panetier, Julien A.; Nippe, Michael; Journal of the American Chemical Society 141 (2019) 6569–6582; doi:10.1021/jacs.8b13657

data_4128260
_publ_section_title
;
 Synergistic Effects of Imidazolium-Functionalization on
 fac-Mn(CO)<sub>3</sub> Bipyridine Catalyst Platforms for Electrocatalytic
 Carbon Dioxide Reduction.
;
_journal_issue                   16
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6569
_journal_page_last               6582
_journal_paper_doi               10.1021/jacs.8b13657
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H23 Br Mn N4 O3, F6 P'
_chemical_formula_sum            'C22 H23 Br F6 Mn N4 O3 P'
_chemical_formula_weight         671.26
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.937(2)
_cell_length_b                   12.188(4)
_cell_length_c                   26.580(8)
_cell_measurement_reflns_used    4741
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      21.471
_cell_measurement_theta_min      5.216
_cell_volume                     2571.2(13)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      110.0
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1022
_diffrn_reflns_av_unetI/netI     0.0590
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            38614
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.651
_diffrn_reflns_theta_min         5.216
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.206
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6065
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0834 before and 0.0726 after correction. The Ratio of minimum to maximum transmission is 0.8139. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.734
_exptl_crystal_description       block
_exptl_crystal_F_000             1344
_exptl_crystal_size_max          0.207
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.073
_refine_diff_density_max         0.436
_refine_diff_density_min         -0.400
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 1606 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     354
_refine_ls_number_reflns         4787
_refine_ls_number_restraints     94
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.0506
_refine_ls_R_factor_gt           0.0377
_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^)+(0.0331P)^2^+1.5217P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0758
_refine_ls_wR_factor_ref         0.0804
_reflns_Friedel_coverage         0.745
_reflns_Friedel_fraction_full    0.985
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                4170
_reflns_number_total             4787
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b13657_si_003.cif
_cod_data_source_block           mnsy041
_cod_database_code               4128260
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.856
_shelx_estimated_absorpt_t_min   0.658
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 N4A-C13 \\sim N4-C15
 with sigma of 0.01
 C14-C13 \\sim C15-C14A
 with sigma of 0.01
 N4-C18 \\sim N4A-C17
 with sigma of 0.01
 C18-C14A \\sim C17-C14
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
N4 \\sim C14A \\sim C14 \\sim N4A \\sim C17 \\sim C18: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04
Uanis(N4) = Uanis(C14A)
Uanis(N4A) = Uanis(C14)
4. Rigid body (RIGU) restrains
 N4, C14A, C14, N4A, C17, C18
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
5. Others
 Sof(N4A)=Sof(C14A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(H18D)=Sof(H18E)=
 Sof(H18F)=1-FVAR(1)
 Sof(N4)=Sof(C14)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(H18A)=Sof(H18B)=Sof(H18C)=
 FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
6.b Me refined with riding coordinates:
 C17(H17A,H17B,H17C), C17(H17D,H17E,H17F)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9)
6.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C18(H18D,H18E,
 H18F), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              19441
_shelx_hkl_checksum              16927
_olex2_submission_special_instructions 'No special instructions were received'