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_7711657
_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 N3 O3 Re, 0.5(C5 H12)'
_chemical_formula_sum            'C25.5 H20 N3 O3 Re'
_chemical_formula_weight         602.64
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-05-27 deposited with the CCDC.	2022-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.5883(13)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.8011(5)
_cell_length_b                   10.7352(3)
_cell_length_c                   21.1945(6)
_cell_measurement_reflns_used    9722
_cell_measurement_temperature    173.0
_cell_measurement_theta_max      72.562
_cell_measurement_theta_min      9.365
_cell_volume                     4428.6(2)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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 0.975
_diffrn_measured_fraction_theta_max 0.975
_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  0.0644
_diffrn_reflns_av_unetI/netI     0.0720
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            3809
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        66.576
_diffrn_reflns_theta_max         66.576
_diffrn_reflns_theta_min         4.244
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           0.64
_diffrn_source_power             0.0285824
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           44.66
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    11.008
_exptl_absorpt_correction_T_max  0.523212
_exptl_absorpt_correction_T_min  0.348046
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.

Final HKLF 4 output contains 68399 reflections, Rint = 0.0746
 (21815 with I > 3sig(I), Rint = 0.0644)
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.808
_exptl_crystal_description       plate
_exptl_crystal_F_000             2344
_exptl_crystal_size_max          0.168
_exptl_crystal_size_mid          0.075
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.499
_refine_diff_density_min         -0.968
_refine_diff_density_rms         0.153
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     349
_refine_ls_number_reflns         3809
_refine_ls_number_restraints     164
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0395
_refine_ls_R_factor_gt           0.0360
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0559P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0843
_refine_ls_wR_factor_ref         0.0866
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3404
_reflns_number_total             3809
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02876j2.cif
_cod_data_source_block           zd-m33
_cod_original_formula_sum        'C25.50 H20 N3 O3 Re'
_cod_database_code               7711657
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.734
_shelx_estimated_absorpt_t_min   0.259
_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. Restrained distances
 C2S-C1S = C3S-C2S = C4S-C3S = C5S-C4S
 1.52 with sigma of 0.02
 C1S-C3S = C2S-C4S = C3S-C5S
 2.49 with sigma of 0.04
 N1-C4 \\sim N1-C4A
 with sigma of 0.02
 C9A-N1 \\sim C9-N1 \\sim C5A-N1 \\sim C5-N1
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C4 \\sim C4A \\sim C5 \\sim C5A \\sim C6 \\sim C6A \\sim C7 \\sim C7A \\sim C8
\\sim C8A \\sim C9 \\sim C9A: within 0.7A with sigma of 0.01 and sigma for
terminal atoms of 0.01 within 0.7A
C5S \\sim C1S \\sim C2S \\sim C3S \\sim C4S: within 3A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 3A
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(C4A) \\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 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=
 Sof(H8A)=Sof(C9A)=Sof(H9A)=1-FVAR(1)
 Sof(C4)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=
 Sof(C9)=Sof(H9)=FVAR(1)
 Fixed Sof: C1S(0.5) H1SA(0.5) H1SB(0.5) H1SC(0.5) C2S(0.5) H2SA(0.5)
 H2SB(0.5) C3S(0.5) H3SA(0.5) H3SB(0.5) C4S(0.5) H4SA(0.5) H4SB(0.5) C5S(0.5)
 H5SA(0.5) H5SB(0.5) H5SC(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB)
5.b 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)
5.c Fitted hexagon refined as free rotating group:
 C4(C5,C6,C7,C8,C9), C4A(C5A,C6A,C7A,C8A,C9A)
5.d Idealised Me refined as rotating group:
 C1S(H1SA,H1SB,H1SC), C5S(H5SA,H5SB,H5SC)
;
_shelx_res_checksum              83399
_shelx_hkl_checksum              2033
_olex2_submission_special_instructions 'No special instructions were received'