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_1546350
_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         'C43 H3 F20 N4 Ni O2'
_chemical_formula_sum            'C43 H3 F20 N4 Ni O2'
_chemical_formula_weight         1046.20
_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_Hall           '-I 4ad'
_space_group_name_H-M_alt        'I 41/a'
_symmetry_space_group_name_Hall  '-I 4ad'
_symmetry_space_group_name_H-M   'I 41/a :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-06-06
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.25 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2017-06-06 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                   15.3093(2)
_cell_length_b                   15.3093(2)
_cell_length_c                   15.8346(4)
_cell_measurement_reflns_used    18724
_cell_measurement_temperature    180.0(2)
_cell_measurement_theta_max      30.1280
_cell_measurement_theta_min      3.7100
_cell_volume                     3711.23(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.16b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.16b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.16b (Rigaku OD, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      180.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -33.00  28.00   0.50    2.00    --   -1.70 -82.00  90.00  122
  2  \w    -73.00 -10.00   0.50    2.00    --   -1.70 -19.00  60.00  126
  3  \w    -80.00 -54.00   0.50    2.00    --   -1.70 -37.00-180.00   52
  4  \w    -33.00  30.00   0.50    2.00    --   -1.70 -82.00-120.00  126
  5  \w     -3.00  28.00   0.50    2.00    --   -1.70 -77.00 -30.00   62
  6  \w     -9.00  16.00   0.50    2.00    --   -1.70 -37.00-180.00   50
  7  \w     19.00  88.00   0.50    2.00    --   -1.70  37.00  30.00  138
  8  \w    -46.00  26.00   0.50    2.00    --    1.90 -77.00 -60.00  144
  9  \w    -85.00 -54.00   0.50    2.00    --    1.90 -57.00 -90.00   62
 10  \w    -32.00   9.00   0.50    2.00    --    1.90 -57.00   0.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0174669000
_diffrn_orient_matrix_UB_12      0.0301507000
_diffrn_orient_matrix_UB_13      0.0295089000
_diffrn_orient_matrix_UB_21      -0.0419913000
_diffrn_orient_matrix_UB_22      -0.0187450000
_diffrn_orient_matrix_UB_23      -0.0053444000
_diffrn_orient_matrix_UB_31      0.0087747000
_diffrn_orient_matrix_UB_32      -0.0298071000
_diffrn_orient_matrix_UB_33      0.0332593000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0241
_diffrn_reflns_av_unetI/netI     0.0088
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            34090
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.481
_diffrn_reflns_theta_min         3.702
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.673
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88781
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.16b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.872
_exptl_crystal_description       block
_exptl_crystal_F_000             2052
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.601
_refine_diff_density_min         -0.436
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     165
_refine_ls_number_reflns         2127
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0366
_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^)+(0.0622P)^2^+4.8393P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1056
_refine_ls_wR_factor_ref         0.1064
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2051
_reflns_number_total             2127
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc02073b2.cif
_cod_data_source_block           170604
_cod_original_cell_volume        3711.23(13)
_cod_database_code               1546350
_chemical_oxdiff_formula         'Ni1 F20 C20 N4 O3 Cl3 H20'
_reflns_odcompleteness_completeness 99.68
_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. Shared sites
{C00H, O0AA}
3. Uiso/Uaniso restraints and constraints
Uanis(C00H) = Uanis(O0AA)
4. Others
 Fixed Sof: C00H(0.75) H00H(0.75) O1(0.25) O0AA(0.25)
5.a Aromatic/amide H refined with riding coordinates:
 C00H(H00H)
;
_shelx_shelxl_version_number     2016/6
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.253
_oxdiff_exptl_absorpt_empirical_full_min 0.856