Increasing the rate of hydrogen oxidation without increasing the overpotential: a bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay
Darmon, Jonathan M.; Kumar, Neeraj; Hulley, Elliott B.; Weiss, Charles J.; Raugei, Simone; Bullock, R. Morris; Helm, Monte L.; Chem. Sci. 6 (2015) 2737–; doi:10.1039/C5SC00398A

data_1518781
_publ_section_title
;
 Increasing the rate of hydrogen oxidation without increasing the
 overpotential: a bio-inspired iron molecular electrocatalyst with an
 outer coordination sphere proton relay
;
_journal_issue                   5
_journal_name_full               'Chem. Sci.'
_journal_page_first              2737
_journal_paper_doi               10.1039/C5SC00398A
_journal_volume                  6
_journal_year                    2015
_chemical_formula_moiety         'C25 H42 F4 Fe N3 P2, C32 H12 B F24, C6 H5 F'
_chemical_formula_sum            'C63 H59 B F29 Fe N3 P2'
_chemical_formula_weight         1537.73
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2014-02-20
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_audit_update_record
;
2015-01-29 deposited with the CCDC.
2015-03-04 downloaded from the CCDC.
;
_cell_angle_alpha                90.4567(18)
_cell_angle_beta                 92.9881(18)
_cell_angle_gamma                96.475(2)
_cell_formula_units_Z            4
_cell_length_a                   12.7767(5)
_cell_length_b                   13.8940(5)
_cell_length_c                   38.0545(13)
_cell_measurement_reflns_used    9833
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.803
_cell_measurement_theta_min      2.301
_cell_volume                     6702.5(4)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.988
_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  0.0447
_diffrn_reflns_av_unetI/netI     0.0400
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            142333
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.733
_diffrn_reflns_theta_min         1.475
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.396
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7994
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0769 before and 0.0637 after correction.
The Ratio of minimum to maximum transmission is 0.7994.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.524
_exptl_crystal_description       block
_exptl_crystal_F_000             3120
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.37
_exptl_crystal_size_min          0.36
_refine_diff_density_max         1.122
_refine_diff_density_min         -0.729
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1923
_refine_ls_number_reflns         28123
_refine_ls_number_restraints     629
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0655
_refine_ls_R_factor_gt           0.0511
_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^)+(0.0473P)^2^+11.3475P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1220
_refine_ls_wR_factor_ref         0.1288
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22763
_reflns_number_total             28123
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5sc00398a2.cif
_cod_data_source_block           eh064_01
_cod_depositor_comments          'Adding full bibliography for 1518781.cif.'
_cod_database_code               1518781
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.871
_shelx_estimated_absorpt_t_min   0.864
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F58A-C128 = F58-C121
 1.3 with sigma of 0.001
 F58-C122 \\sim F58-C126
 with sigma of 0.001
 F58A-C133 \\sim F58A-C129
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
C122 \\sim H122 \\sim C123 \\sim H123 \\sim C124 \\sim H124 \\sim H125 \\sim
C126 \\sim H126 \\sim C121 \\sim C133 \\sim H133 \\sim C128 \\sim C129 \\sim
H129 \\sim C130 \\sim H130 \\sim H131 \\sim C132 \\sim H132 \\sim F58 \\sim
F58A \\sim C131 \\sim C125: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 C117, C116, C115, C118, C120, C119
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C89, F33, F34, F35
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C89, F33A, F34A, F35A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C82, F30, F31, F32
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C82, F30A, F31A, F32A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C90, F36, F37, F38
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C90, F36A, F37A, F38A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C121, C122, C123, C124, C125, C126
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C128, C129, C130, C131, C132, C133
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: F33(0.73759) F35(0.73759) F37(0.59688) F38(0.59688) F36(0.59688)
 F34(0.73759) F32(0.67394) F31(0.67394) F30(0.67394) C122(0.60402)
 H122(0.60402) C123(0.60402) H123(0.60402) C124(0.60402) H124(0.60402)
 C125(0.60402) H125(0.60402) C126(0.60402) H126(0.60402) C121(0.60402)
 C133(0.39598) H133(0.39598) C128(0.39598) C129(0.39598) H129(0.39598)
 C130(0.39598) H130(0.39598) C131(0.39598) H131(0.39598) C132(0.39598)
 H132(0.39598) F58(0.60402) F34A(0.26241) F35A(0.26241) F33A(0.26241)
 F32A(0.32606) F30A(0.32606) F31A(0.32606) F58A(0.39598) F36A(0.40312)
 F38A(0.40312) F37A(0.40312)
6.a Ternary CH refined with riding coordinates:
 N3(H3), N6(H6)
6.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C15(H15A,H15B), C13(H13A,H13B), C11(H11A,H11B), C19(H19A,
 H19B), C21(H21A,H21B), C17(H17A,H17B), C22(H22A,H22B), C23(H23A,H23B),
 C40(H40A,H40B), C45(H45A,H45B), C42(H42A,H42B), C36(H36A,H36B), C38(H38A,H38B),
  C48(H48A,H48B), C46(H46A,H46B), C44(H44A,H44B), C47(H47A,H47B)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C4(H4), C3(H3A), C2(H2), C94(H94), C104(H104), C108(H108), C96(H96),
 C30(H30), C112(H112), C92(H92), C110(H110), C100(H100), C102(H102), C88(H88),
 C28(H28), C27(H27), C86(H86), C84(H84), C29(H29), C54(H54), C62(H62), C72(H72),
  C52(H52), C76(H76), C68(H68), C80(H80), C64(H64), C60(H60), C70(H70),
 C56(H56), C78(H78), C119(H119), C118(H118), C120(H120), C116(H116), C117(H117),
  C122(H122), C123(H123), C124(H124), C125(H125), C126(H126), C133(H133),
 C129(H129), C130(H130), C131(H131), C132(H132)
6.d Fitted hexagon refined as free rotating group:
 C122(C123,C124,C125,C126,C121), C133(C128,C129,C130,C131,C132)
6.e Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C25(H25A,H25B,H25C), C18(H18A,H18B,H18C), C24(H24A,H24B,
 H24C), C14(H14A,H14B,H14C), C12(H12A,H12B,H12C), C49(H49A,H49B,H49C), C41(H41A,
 H41B,H41C), C43(H43A,H43B,H43C), C39(H39A,H39B,H39C), C37(H37A,H37B,H37C),
 C50(H50A,H50B,H50C)
;
_shelx_res_checksum              80558