Enhancing the Reactivity of Nickel(II) in Hydrogen Evolution Reactions (HER) by β-Hydrogenation of Porphyrinoid Ligands
Wu, Zhuo-Yan; Wang, Teng; Meng, Yin-Shan; Rao, Yu; Gao, Song; Zheng, Jie; Wang, Bing-Wu; Zhang, Jun-Long; Chem. Sci.  (2017) –; doi:10.1039/C7SC02073B

data_1546349
_publ_section_title
;
 Enhancing the Reactivity of Nickel(II) in Hydrogen Evolution Reactions
 (HER) by \b-Hydrogenation of Porphyrinoid Ligands
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC02073B
_journal_year                    2017
_chemical_formula_moiety         'C44 H8 F20 N4 Ni'
_chemical_formula_sum            'C44 H8 F20 N4 Ni'
_chemical_formula_weight         1031.25
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      tetragonal
_space_group_IT_number           122
_space_group_name_Hall           'I -4 2bw'
_space_group_name_H-M_alt        'I -4 2 d'
_symmetry_space_group_name_Hall  'I -4 2bw'
_symmetry_space_group_name_H-M   'I -4 2 d'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-12-19
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2017-01-18 deposited with the CCDC.
2017-06-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.4001(2)
_cell_length_b                   15.4001(2)
_cell_length_c                   15.3253(4)
_cell_measurement_reflns_used    14251
_cell_measurement_temperature    180.01(10)
_cell_measurement_theta_max      29.5140
_cell_measurement_theta_min      3.7170
_cell_volume                     3634.60(12)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      180.01(10)
_diffrn_detector_area_resol_mean 10.3914
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_details
;
  1 omega    6.00   75.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4628 -132.0000   34.1141 69

  2 omega    3.00   72.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4628 -127.0000  159.9459 69

  3 omega  -13.00   89.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4628   38.0000  -90.0000 102

  4 omega   -5.00   89.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4628   38.0000 -180.0000 94

  5 omega  -13.00   87.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4628   38.0000    0.0000 100

  6 omega  -22.00   83.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4628    0.0000  120.0000 105

  7 omega   21.00   88.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4628 -151.0000  -54.0000 67

  8 omega  -17.00   27.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.5566  -99.0000    0.0000 44
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0384704000
_diffrn_orient_matrix_UB_12      0.0218481000
_diffrn_orient_matrix_UB_13      -0.0129723000
_diffrn_orient_matrix_UB_21      -0.0248559000
_diffrn_orient_matrix_UB_22      0.0370866000
_diffrn_orient_matrix_UB_23      -0.0113836000
_diffrn_orient_matrix_UB_31      0.0049447000
_diffrn_orient_matrix_UB_32      0.0163889000
_diffrn_orient_matrix_UB_33      0.0429346000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0537
_diffrn_reflns_av_unetI/netI     0.0249
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            31387
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.257
_diffrn_reflns_theta_min         3.243
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.681
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84884
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.885
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2032
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.314
_refine_diff_density_min         -0.240
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 983 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.011(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     156
_refine_ls_number_reflns         2633
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0432
_refine_ls_R_factor_gt           0.0353
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0426P)^2^+4.1840P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0874
_refine_ls_wR_factor_ref         0.0933
_reflns_Friedel_coverage         0.788
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.948
_reflns_number_gt                2380
_reflns_number_total             2633
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc02073b2.cif
_cod_data_source_block           1
_cod_original_cell_volume        3634.59(15)
_cod_database_code               1546349
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'c44 h12 f20 n4 ni'
_reflns_odcompleteness_completeness 99.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C11(H11)
;
_olex2_submission_special_instructions 'No special instructions were received'