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_7711659
_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         'C30 H24 N5 O3 Re, C6 H6'
_chemical_formula_sum            'C36 H30 N5 O3 Re'
_chemical_formula_weight         766.85
_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             2021-12-13
_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                 91.8983(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.8205(8)
_cell_length_b                   13.4145(12)
_cell_length_c                   26.571(2)
_cell_measurement_reflns_used    9434
_cell_measurement_temperature    173.0
_cell_measurement_theta_max      29.119
_cell_measurement_theta_min      2.158
_cell_volume                     3142.2(5)
_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 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 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  0.0499
_diffrn_reflns_av_unetI/netI     0.0395
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            42912
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.137
_diffrn_reflns_theta_min         1.534
_diffrn_source                   'fine focus X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_type              Siemens
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.912
_exptl_absorpt_correction_T_max  0.5637
_exptl_absorpt_correction_T_min  0.4185
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0971 before and 0.0445 after correction.
The Ratio of minimum to maximum transmission is 0.7424.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.621
_exptl_crystal_description       plate
_exptl_crystal_F_000             1520
_exptl_crystal_size_max          0.284
_exptl_crystal_size_mid          0.228
_exptl_crystal_size_min          0.048
_refine_diff_density_max         0.744
_refine_diff_density_min         -0.522
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     531
_refine_ls_number_reflns         8443
_refine_ls_number_restraints     962
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0388
_refine_ls_R_factor_gt           0.0262
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0162P)^2^+1.5126P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0488
_refine_ls_wR_factor_ref         0.0519
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6961
_reflns_number_total             8443
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02876j2.cif
_cod_data_source_block           zd-m75
_cod_original_cell_volume        3142.3(5)
_cod_database_code               7711659
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.834
_shelx_estimated_absorpt_t_min   0.403
_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
 C5-C4 \\sim C5A-C4 \\sim C9-C4 \\sim C9A-C4
 with sigma of 0.02
 C4-C6 \\sim C4-C8 \\sim C4-C6A \\sim C4-C8A
 with sigma of 0.04
 N1-C5 \\sim N1-C5A \\sim N1-C9 \\sim N1-C9A
 with sigma of 0.04
 C19-N3 \\sim C19-N3A
 with sigma of 0.02
 C19-C20 \\sim C19-C20A
 with sigma of 0.02
 C19-C21 \\sim C19-C21A
 with sigma of 0.04
 C19-C23 \\sim C19-C23A
 with sigma of 0.04
 C18-C20 \\sim C18-C20A
 with sigma of 0.04
 C18-N3 \\sim C18-N3A
 with sigma of 0.04
3. Restrained planarity
 N1, C4, C5A, C6A, C7A, C8A, C9A
 with sigma of 0.1
 N1, C4, C5, C6, C7, C8, C9
 with sigma of 0.1
 C18, C19, C20, C21, C22, C23, N3
 with sigma of 0.1
 C18, C19, C20A, C21A, C22A, C23A, N3A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C5A \\sim C6A \\sim C7A
\\sim C8A \\sim C9A: within 2A with sigma of 0.02 and sigma for terminal atoms
of 0.02 within 2A
C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim N3 \\sim C20A \\sim C21A
\\sim C22A \\sim C23A \\sim N3A: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.02 within 2A
: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.02 within 2A
Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim
Ueq, Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C6A)
\\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C9A) \\sim Ueq:
with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(C20A) \\sim Ueq,
Uanis(C21A) \\sim Ueq, Uanis(C22A) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(N3A)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
: with sigma of 0.005 and sigma for terminal atoms of 0.01
5. Rigid body (RIGU) restrains
 C4, C5A, C6A, C7A, C8A, C9A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C4, C5, C6, C7, C8, C9
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C19, C20, C21, C22, C23, N3
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C19, C20A, C21A, C22A, C23A, N3A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C1S_1, C2S_1, C3S_1, C4S_1, C5S_1, C6S_1
 C1S_2, C2S_2, C3S_2, C4S_2, C5S_2, C6S_2
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Same fragment restrains
{C5, C6, C7, C8, C9} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C5A, C6A, C7A, C8A, C9A}
{C20, C21, C22, C23, N3} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C20A, C21A, C22A, C23A, N3A}
7. Others
 Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=
 Sof(C9A)=Sof(H9A)=1-FVAR(1)
 Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=
 Sof(H9)=FVAR(1)
 Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=
 Sof(H23A)=Sof(N3A)=1-FVAR(2)
 Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=
 Sof(N3)=FVAR(2)
 Sof(C1S)=Sof(H1S)=Sof(C2S)=Sof(H2S)=Sof(C3S)=Sof(H3S)=Sof(C4S)=Sof(H4S)=
 Sof(C5S)=Sof(H5S)=Sof(C6S)=Sof(H6S)=1-FVAR(3)
 Sof(C1S)=Sof(H1S)=Sof(C2S)=Sof(H2S)=Sof(C3S)=Sof(H3S)=Sof(C4S)=Sof(H4S)=
 Sof(C5S)=Sof(H5S)=Sof(C6S)=Sof(H6S)=FVAR(3)
8.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C5A(H5A), C6A(H6A), C7A(H7A),
 C8A(H8A), C9A(H9A), C11(H11), C12(H12), C13(H13), C16(H16), C17(H17), C20(H20),
  C21(H21), C22(H22), C23(H23), C20A(H20A), C21A(H21A), C22A(H22A), C23A(H23A),
 C24(H24), C25(H25), C27(H27), C28(H28), C1S(H1S), C2S(H2S), C3S(H3S), C4S(H4S),
  C5S(H5S), C6S(H6S), C1S(H1S), C2S(H2S), C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S)
8.b Fitted hexagon refined as free rotating group:
 C1S(C2S,C3S,C4S,C5S,C6S), C1S(C2S,C3S,C4S,C5S,C6S)
8.c Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              54795
_shelx_hkl_checksum              85550
_olex2_submission_special_instructions 'No special instructions were received'