Electrocatalytic H<sub>2</sub>O Reduction with f-Elements: Mechanistic Insight and Overpotential Tuning in a Series of Lanthanide Complexes.
Halter, Dominik P.; Palumbo, Chad T.; Ziller, Joseph W.; Gembicky, Milan; Rheingold, Arnold L.; Evans, William J.; Meyer, Karsten; Journal of the American Chemical Society 140 (2018) 2587–2594; doi:10.1021/jacs.7b11532

data_4131830
_publ_section_title
;
 Electrocatalytic H<sub>2</sub>O Reduction with f-Elements: Mechanistic
 Insight and Overpotential Tuning in a Series of Lanthanide Complexes.
;
_journal_issue                   7
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2587
_journal_page_last               2594
_journal_paper_doi               10.1021/jacs.7b11532
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C63 H75.66 Nd O3.33'
_chemical_formula_sum            'C63 H75.66 Nd O3.33'
_chemical_formula_weight         1030.41
_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   mixed
_audit_creation_date             2016-08-25
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.23 svn.r3337 for OlexSys, GUI svn.r5217)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.846(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.4694(6)
_cell_length_b                   36.8012(18)
_cell_length_c                   11.9740(6)
_cell_measurement_reflns_used    9920
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.69
_cell_measurement_theta_min      2.16
_cell_volume                     4837.2(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX-II CCD'
_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       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Ultra'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Double Bounce Multilayer Mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0423
_diffrn_reflns_av_unetI/netI     0.0279
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            62194
_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         25.713
_diffrn_reflns_theta_min         1.855
_diffrn_source                   'Micro Focus Rotating Anode'
_diffrn_source_type              'Bruker TXS'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.123
_exptl_absorpt_correction_T_max  0.4903
_exptl_absorpt_correction_T_min  0.4392
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0668 before and 0.0452 after correction.
The Ratio of minimum to maximum transmission is 0.8958.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.415
_exptl_crystal_description       block
_exptl_crystal_F_000             2161
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.025
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.660
_refine_diff_density_min         -1.145
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.350
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     724
_refine_ls_number_reflns         9182
_refine_ls_number_restraints     128
_refine_ls_restrained_S_all      1.342
_refine_ls_R_factor_all          0.0525
_refine_ls_R_factor_gt           0.0461
_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^)+(0.0001P)^2^+13.4958P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0829
_refine_ls_wR_factor_ref         0.0844
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8410
_reflns_number_total             9182
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b11532_si_002.cif
_cod_data_source_block           uci_evansv2
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/saulius/struct/COD-crude-data/automatic-downloads/DataCite-retrospective/ACS/depositions/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_database_code               4131830
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C18-C13 = C19-C18 = C20-C18 = C21-C18 = C21-C24 = C22-C19 = C23-C20 = C22-C27
 = C24-C27 = C24-C26 = C23-C26 = C23-C25 = C22-C25
 1.54 with sigma of 0.02
 C18B-C13B = C19B-C18B = C18B-C20B = C18B-C21B = C24B-C21B = C23B-C20B = C19B-
 C22B = C22B-C27B = C24B-C27B = C24B-C26B = C23B-C26B = C23B-C25B = C25B-C22B
 1.54 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O2) = Uanis(O2B)
Uanis(C12) = Uanis(C12B)
Uanis(C13) = Uanis(C13B)
Uanis(C14) = Uanis(C14B)
Uanis(C15) = Uanis(C15B)
Uanis(C17) = Uanis(C17B)
Uanis(C16) = Uanis(C16B)
Uanis(C11) = Uanis(C11B)
4. Rigid body (RIGU) restrains
 C26B, C24B, C13B, C21B, C18B, C22B, C27B, C20B, C19B, C25B, C23B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H10C)=Sof(H10D)=Sof(C26B)=Sof(H26C)=Sof(H26D)=Sof(O1)=Sof(H1A)=Sof(H1B)=
 Sof(C24B)=Sof(H24B)=Sof(C21B)=Sof(H21C)=Sof(H21D)=Sof(C18B)=Sof(C17B)=
 Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(O2B)=Sof(C22B)=Sof(H22B)=Sof(C27B)=Sof(H27C)=
 Sof(H27D)=Sof(C20B)=Sof(H20C)=Sof(H20D)=Sof(C19B)=Sof(H19C)=Sof(H19D)=
 Sof(C25B)=Sof(H25C)=Sof(H25D)=Sof(C12B)=Sof(C13B)=Sof(C14B)=Sof(H14B)=
 Sof(C15B)=Sof(C16B)=Sof(H16B)=Sof(C11B)=Sof(C23B)=Sof(H23B)=1-FVAR(1)
 Sof(H10A)=Sof(H10B)=Sof(O2)=Sof(C11)=Sof(C12)=Sof(C13)=Sof(C14)=Sof(H14)=
 Sof(C15)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(C21)=Sof(H21A)=
 Sof(H21B)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=Sof(C25)=
 Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(C27)=Sof(H27A)=Sof(H27B)=
 FVAR(1)
6.a Rotating group:
 O1(H1A,H1B)
6.b Ternary CH refined with riding coordinates:
 C40(H40), C41(H41), C42(H42), C58(H58), C59(H59), C60(H60), C22(H22),
 C23(H23), C24(H24), C24B(H24B), C22B(H22B), C23B(H23B)
6.c Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C10(H10C,H10D), C28(H28A,H28B), C37(H37A,H37B), C38(H38A,
 H38B), C39(H39A,H39B), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B),
 C46(H46A,H46B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C61(H61A,H61B),
  C62(H62A,H62B), C63(H63A,H63B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,
 H21B), C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C26B(H26C,H26D),
 C21B(H21C,H21D), C27B(H27C,H27D), C20B(H20C,H20D), C19B(H19C,H19D), C25B(H25C,
 H25D)
6.d Aromatic/amide H refined with riding coordinates:
 C32(H32), C34(H34), C50(H50), C52(H52), C14(H14), C16(H16), C14B(H14B),
 C16B(H16B)
6.e Fitted hexagon refined as free rotating group:
 C12B(C13B,C14B,C15B,C16B,C11B)
6.f Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C35(H35A,H35B,H35C),
 C53(H53A,H53B,H53C), C17(H17A,H17B,H17C), C17B(H17D,H17E,H17F)
;
_shelx_res_checksum              24431
_shelx_hkl_checksum              14943
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'