Electrocatalyst decomposition pathways: torsional strain in a second sphere proton relay shuts off CO2RR in a Re(2,2’-bipyridyl)(CO)3X type electrocatalyst
Dubrawski, Zack; Chang, Chia Yun; Carr, Cody; Gelfand, Benjamin Sidney; Piers, Warren; Dalton Transactions  (2022) –; doi:10.1039/D2DT02876J

data_7711658
_publ_section_title
;
 Electrocatalyst decomposition pathways: torsional strain in a second
 sphere proton relay shuts off CO2RR in a Re(2,2&#x2019;-bipyridyl)(CO)3X
 type electrocatalyst
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02876J
_journal_year                    2022
_chemical_formula_moiety
'C23 H14 Cl N3 O3 Re, 4(C3 H2.5 F0.5), C20 H30 Co'
_chemical_formula_sum            'C55 H54 Cl Co F2 N3 O3 Re'
_chemical_formula_weight         1123.59
_space_group_crystal_system      orthorhombic
_space_group_IT_number           63
_space_group_name_Hall           '-C 2c 2'
_space_group_name_H-M_alt        'C m c m'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-08
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-05-27 deposited with the CCDC.	2022-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.5535(17)
_cell_length_b                   21.0599(7)
_cell_length_c                   21.3570(14)
_cell_measurement_reflns_used    6384
_cell_measurement_temperature    173.0
_cell_measurement_theta_max      72.296
_cell_measurement_theta_min      4.101
_cell_volume                     9694.3(10)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      173.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0909
_diffrn_reflns_av_unetI/netI     0.0827
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            17382
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        66.552
_diffrn_reflns_theta_max         66.552
_diffrn_reflns_theta_min         2.934
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           0.64
_diffrn_source_power             0.0285952
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           44.68
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.438
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5326
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1069 before and 0.0652 after correction.
The Ratio of minimum to maximum transmission is 0.7067.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.540
_exptl_crystal_description       plate
_exptl_crystal_F_000             4528
_exptl_crystal_size_max          0.252
_exptl_crystal_size_mid          0.234
_exptl_crystal_size_min          0.052
_refine_diff_density_max         1.665
_refine_diff_density_min         -1.339
_refine_diff_density_rms         0.131
_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     486
_refine_ls_number_reflns         4426
_refine_ls_number_restraints     937
_refine_ls_restrained_S_all      1.143
_refine_ls_R_factor_all          0.0971
_refine_ls_R_factor_gt           0.0619
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0634P)^2^+98.8632P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1433
_refine_ls_wR_factor_ref         0.1615
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3033
_reflns_number_total             4426
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02876j2.cif
_cod_data_source_block           zd-n16
_cod_database_code               7711658
_shelx_shelxl_version_number     2018/3
_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
 F1B_2-C1_2
 1.35 with sigma of 0.02
 C19-C17
 -2.25 with sigma of 0.02
 F1A_1-C1_1 = F1B_1-C6_1
 F1A_2-C1_2 = F1B_2-C6_2
 F1A_3-C1_3 = F1B_3-C6_3
 1.35 with sigma of 0.01
 F1A_1-C2_1 = F1A_1-C6_1 = F1B_1-C1_1 = F1B_1-C5_1
 F1A_2-C2_2 = F1A_2-C6_2 = F1B_2-C1_2 = F1B_2-C5_2
 F1A_3-C2_3 = F1A_3-C6_3 = F1B_3-C1_3 = F1B_3-C5_3
 2.35 with sigma of 0.01
 Re1-Cl1A \\sim Re1-Cl1B
 with sigma of 0.02
 O2A-C2A \\sim O2B-C2B \\sim C1-O1
 with sigma of 0.02
 Re1-C2A \\sim Re1-C2B \\sim Re1-C1
 with sigma of 0.02
 Re1-O2A \\sim Re1-O2B \\sim Re1-O1
 with sigma of 0.04
 Co1_10-C1A_10 \\sim Co1_10-C2A_10 \\sim Co1_10-C3A_10 \\sim Co1_10-C4A_10
\\sim Co1_10-C5A_10
 \\sim Co1_10-C11A_10 \\sim Co1_10-C12A_10 \\sim Co1_10-C13A_10 \\sim
Co1_10-C14A_10 \\sim Co1_10-
 C15A_10
 with sigma of 0.02
3. Restrained planarity
 C20, C17, C18, C21, N3, C19, C22
 with sigma of 0.1
 N1, C7, C3, C6, C4, C8, C5
 with sigma of 0.1
 F1A_1, F1B_1, C1_1, C2_1, C3_1, C4_1, C5_1, C6_1
 F1A_2, F1B_2, C1_2, C2_2, C3_2, C4_2, C5_2, C6_2
 F1A_3, F1B_3, C1_3, C2_3, C3_3, C4_3, C5_3, C6_3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Co1_10 \\sim C1A_10 \\sim C5A_10 \\sim C2A_10 \\sim C20A_10 \\sim C4A_10 \\sim
C10A_10 \\sim C3A_10 \\sim C16A_10 \\sim C6A_10 \\sim C8A_10: within 2A with
sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
Cl1B \\sim O2A \\sim C2A \\sim Cl1A \\sim O2B \\sim C2B: within 2A with sigma
of 0.003 and sigma for terminal atoms of 0.003 within 2A
N1 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim N2 \\sim C16
\\sim C15 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim N3: within 3A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 3A
F1A_1 \\sim F1B_1 \\sim C1_1 \\sim C2_1 \\sim C3_1 \\sim C4_1 \\sim C5_1 \\sim
C6_1 \\sim F1A_2 \\sim F1B_2 \\sim C1_2 \\sim C2_2 \\sim C3_2 \\sim C4_2 \\sim
C5_2 \\sim C6_2 \\sim F1A_3 \\sim F1B_3 \\sim C1_3 \\sim C2_3 \\sim C3_3 \\sim
C4_3 \\sim C5_3 \\sim C6_3: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Co1_10 \\sim C1A_10 \\sim C2A_10 \\sim C3A_10 \\sim C4A_10 \\sim C5A_10 \\sim
C6A_10 \\sim C7A_10 \\sim C8A_10 \\sim C9A_10 \\sim C10A_10 \\sim C11A_10 \\sim
C12A_10 \\sim C13A_10 \\sim C14A_10 \\sim C15A_10 \\sim C16A_10 \\sim C17A_10
\\sim C18A_10 \\sim C19A_10 \\sim C20A_10: within 1A with sigma of 0.003 and
sigma for terminal atoms of 0.003 within 1A
: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Co1_10) \\sim Ueq, Uanis(C1A_10) \\sim Ueq, Uanis(C2A_10) \\sim Ueq,
Uanis(C3A_10) \\sim Ueq, Uanis(C4A_10) \\sim Ueq, Uanis(C5A_10) \\sim Ueq,
Uanis(C6A_10) \\sim Ueq, Uanis(C7A_10) \\sim Ueq, Uanis(C8A_10) \\sim Ueq,
Uanis(C9A_10) \\sim Ueq, Uanis(C10A_10) \\sim Ueq, Uanis(C11A_10) \\sim Ueq,
Uanis(C12A_10) \\sim Ueq, Uanis(C13A_10) \\sim Ueq, Uanis(C14A_10) \\sim Ueq,
Uanis(C15A_10) \\sim Ueq, Uanis(C16A_10) \\sim Ueq, Uanis(C17A_10) \\sim Ueq,
Uanis(C18A_10) \\sim Ueq, Uanis(C19A_10) \\sim Ueq, Uanis(C20A_10) \\sim Ueq:
with sigma of 0.005 and sigma for terminal atoms of 0.01
5. Rigid body (RIGU) restrains
 C1A_10, C2A_10, C3A_10, C4A_10, C5A_10, C6A_10, C7A_10, C8A_10, C9A_10, C10A_10
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C11A_10, C12A_10, C13A_10, C14A_10, C15A_10, C16A_10, C17A_10, C18A_10,
 C19A_10, C20A_10
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Others
 Sof(Cl1B)=Sof(O2B)=Sof(C2B)=0.5*(1-FVAR(2))
 Sof(Cl1A)=Sof(O2A)=Sof(C2A)=0.5*FVAR(2)
 Fixed Sof: N1(0.5) N2(0.5) C16(0.5) H16(0.5) C15(0.5) H15(0.5) C9(0.5)
 C10(0.5) H10(0.5) C11(0.5) H11(0.5) C12(0.5) H12(0.5) C13(0.5) C14(0.5)
 C17(0.5) C3(0.5) C4(0.5) H4(0.5) C5(0.5) H5(0.5) C6(0.5) H6(0.5) C7(0.5)
 H7(0.5) C8(0.5) H8(0.5) C18(0.5) C19(0.5) H19(0.5) C20(0.5) H20(0.5) C21(0.5)
 H21(0.5) C22(0.5) H22(0.5) N3(0.5) F1A(0.25) F1B(0.25) C1(0.5) H1(0.25)
 C2(0.5) H2(0.5) C3(0.5) H3(0.5) C4(0.5) H4(0.5) C5(0.5) H5(0.5) C6(0.5)
 H6(0.25) F1A(0.125) F1B(0.125) C1(0.25) H1(0.125) C2(0.25) H2(0.25) C3(0.25)
 H3(0.25) C4(0.25) H4(0.25) C5(0.25) H5(0.25) C6(0.25) H6(0.125) F1A(0.125)
 F1B(0.125) C1(0.25) H1(0.125) C2(0.25) H2(0.25) C3(0.25) H3(0.25) C4(0.25)
 H4(0.25) C5(0.25) H5(0.25) C6(0.25) H6(0.125) H4A(0.5) H4B(0.5) H4C(0.5)
 Co1(0.25) C1A(0.25) C2A(0.25) C3A(0.25) C4A(0.25) C5A(0.25) C6A(0.25)
 H6AA(0.25) H6AB(0.25) H6AC(0.25) C7A(0.25) H7AA(0.25) H7AB(0.25) H7AC(0.25)
 C8A(0.25) H8AA(0.25) H8AB(0.25) H8AC(0.25) C9A(0.25) H9AA(0.25) H9AB(0.25)
 H9AC(0.25) C10A(0.25) H10A(0.25) H10B(0.25) H10C(0.25) C11A(0.25) C12A(0.25)
 C13A(0.25) C14A(0.25) C15A(0.25) C16A(0.25) H16A(0.25) H16B(0.25) H16C(0.25)
 C17A(0.25) H17A(0.25) H17B(0.25) H17C(0.25) C18A(0.25) H18A(0.25) H18B(0.25)
 H18C(0.25) C19A(0.25) H19A(0.25) H19B(0.25) H19C(0.25) C20A(0.25) H20A(0.25)
 H20B(0.25) H20C(0.25)
7.a Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C6A(H6AA,H6AB,H6AC),
 C7A(H7AA,H7AB,H7AC), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC), C10A(H10A,H10B,
 H10C), C16A(H16A,H16B,H16C), C17A(H17A,H17B,H17C), C18A(H18A,H18B,H18C),
 C19A(H19A,H19B,H19C), C20A(H20A,H20B,H20C)
7.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C15(H15), C10(H10), C11(H11), C12(H12), C4(H4), C5(H5), C6(H6),
 C7(H7), C8(H8), C19(H19), C20(H20), C21(H21), C22(H22), C1(H1), C2(H2), C3(H3),
  C4(H4), C5(H5), C6(H6), C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6),
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6)
7.c Fitted hexagon refined as free rotating group:
 C9(C10,C11,C12,C13,C14), C3(C4,C5,C6,C7,C8), C18(C19,C20,C21,C22,N3), C1(C2,
 C3,C4,C5,C6), C1(C2,C3,C4,C5,C6), C1(C2,C3,C4,C5,C6)
7.d Cp* refined as free rotating group:
 C1A(C2A,C3A,C4A,C5A,C6A,C7A,C8A,C9A,C10A), C11A(C12A,C13A,C14A,C15A,C16A,C17A,
 C18A,C19A,C20A)
;
_shelx_res_checksum              39337
_shelx_hkl_checksum              23087
_olex2_submission_special_instructions 'No special instructions were received'