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_4128259
_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_formula_moiety         'C19 H17 Br Mn N4 O3, 1(F6 P)'
_chemical_formula_sum            'C19 H17 Br F6 Mn N4 O3 P'
_chemical_formula_weight         629.18
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-07-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.9097(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.72670(10)
_cell_length_b                   29.1116(5)
_cell_length_c                   10.7432(2)
_cell_measurement_reflns_used    9249
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      61.678
_cell_measurement_theta_min      3.036
_cell_volume                     2299.44(7)
_computing_cell_refinement       'SAINT V8.38A (Bruker AXS, 2016)'
_computing_data_reduction        'SAINT V8.38A (Bruker AXS, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      110.0
_diffrn_measured_fraction_theta_full 0.957
_diffrn_measured_fraction_theta_max 0.957
_diffrn_measurement_device_type  'Bruker CCD Detector'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_av_unetI/netI     0.0191
_diffrn_reflns_Laue_measured_fraction_full 0.957
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            28108
_diffrn_reflns_point_group_measured_fraction_full 0.957
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        61.674
_diffrn_reflns_theta_max         61.674
_diffrn_reflns_theta_min         3.036
_exptl_absorpt_coefficient_mu    8.105
_exptl_absorpt_correction_T_max  0.7520
_exptl_absorpt_correction_T_min  0.5009
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1196 before and 0.0442 after correction. The Ratio of minimum to maximum transmission is 0.6661. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.817
_exptl_crystal_description       plate
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.105
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.032
_refine_diff_density_max         0.593
_refine_diff_density_min         -0.345
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         3441
_refine_ls_number_restraints     357
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.0274
_refine_ls_R_factor_gt           0.0271
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0373P)^2^+3.2035P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0709
_refine_ls_wR_factor_ref         0.0711
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3387
_reflns_number_total             3441
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b13657_si_002.cif
_cod_data_source_block           cu_mn_ssy_036_03_0m
_cod_database_code               4128259
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.781
_shelx_estimated_absorpt_t_min   0.483
_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. Shared sites
{F1, F1A}
{F2, F2A}
{P1, P1A}
3. Restrained distances
 P1-F1 \\sim P1A-F1A
 with sigma of 0.02
 P1-F2 \\sim P1A-F2A
 with sigma of 0.02
 P1-F3 \\sim P1A-F3A
 with sigma of 0.02
 P1-F4 \\sim P1A-F4A
 with sigma of 0.02
 P1-F5 \\sim P1A-F5A
 with sigma of 0.02
 P1-F6 \\sim P1A-F6A
 with sigma of 0.02
 F1-F2 \\sim F1A-F2A
 with sigma of 0.04
 F1-F3 \\sim F1A-F3A
 with sigma of 0.04
 F1-F4 \\sim F1A-F4A
 with sigma of 0.04
 F1-F5 \\sim F1A-F5A
 with sigma of 0.04
 F1-F6 \\sim F1A-F6A
 with sigma of 0.04
 F2-F3 \\sim F2A-F3A
 with sigma of 0.04
 F2-F4 \\sim F2A-F4A
 with sigma of 0.04
 F2-F5 \\sim F2A-F5A
 with sigma of 0.04
 F2-F6 \\sim F2A-F6A
 with sigma of 0.04
 F3-F4 \\sim F3A-F4A
 with sigma of 0.04
 F3-F5 \\sim F3A-F5A
 with sigma of 0.04
 F3-F6 \\sim F3A-F6A
 with sigma of 0.04
 F4-F5 \\sim F4A-F5A
 with sigma of 0.04
 F4-F6 \\sim F4A-F6A
 with sigma of 0.04
 F5-F6 \\sim F5A-F6A
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
F4 \\sim P1 \\sim F1 \\sim F2 \\sim F3 \\sim F5 \\sim F6 \\sim F4A \\sim F1A
\\sim P1A \\sim F5A \\sim F3A \\sim F6A \\sim F2A: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(P1) = Uanis(P1A)
Uanis(F1) = Uanis(F1A)
Uanis(F2) = Uanis(F2A)
5. Rigid body (RIGU) restrains
 F4, P1, F1, F2, F3, F5, F6, F4A, F1A, P1A, F5A, F3A, F6A, F2A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
6. Others
 Sof(F1A)=Sof(P1A)=Sof(F5A)=Sof(F4A)=Sof(F3A)=Sof(F6A)=Sof(F2A)=1-FVAR(1)
 Sof(P1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C8(H8), C9(H9), C10(H10), C13(H13), C14(H14), C15(H15)
7.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              76778
_shelx_hkl_checksum              46142
_olex2_submission_special_instructions 'No special instructions were received'