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_1546351
_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 H5 F20 N4 Ni O2'
_chemical_formula_sum            'C43 H5 F20 N4 Ni O2'
_chemical_formula_weight         1048.22
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3'
_symmetry_space_group_name_Hall  '-R 3'
_symmetry_space_group_name_H-M   'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-06-04
_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                120
_cell_formula_units_Z            9
_cell_length_a                   20.0377(5)
_cell_length_b                   20.0377(5)
_cell_length_c                   24.6135(9)
_cell_measurement_reflns_used    11621
_cell_measurement_temperature    179.9(4)
_cell_measurement_theta_max      28.8500
_cell_measurement_theta_min      4.0650
_cell_volume                     8558.5(4)
_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      179.9(4)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.997
_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    -31.00  27.00   0.50    2.00    --   -2.00 -82.00 -30.00  116
  2  \w    -17.00  38.00   0.50    2.00    --   -2.00  37.00 150.00  110
  3  \w     54.00  81.00   0.50    2.00    --   -2.00  37.00 150.00   54
  4  \w    -19.00   7.00   0.50    2.00    --   -2.00  37.00   0.00   52
  5  \w     45.00  72.00   0.50    2.00    --   -2.00  37.00   0.00   54
  6  \w    -56.00 -29.00   0.50    2.00    --    2.20 -37.00   0.00   54
  7  \w    -15.00  55.00   0.50    2.00    --    2.20  37.00 -60.00  140
;
_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      0.0338485333
_diffrn_orient_matrix_UB_12      0.0304469667
_diffrn_orient_matrix_UB_13      -0.0118178333
_diffrn_orient_matrix_UB_21      -0.0193539333
_diffrn_orient_matrix_UB_22      0.0210500333
_diffrn_orient_matrix_UB_23      -0.0042212667
_diffrn_orient_matrix_UB_31      0.0122425333
_diffrn_orient_matrix_UB_32      0.0172917667
_diffrn_orient_matrix_UB_33      0.0259623667
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0319
_diffrn_reflns_av_unetI/netI     0.0180
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            30789
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.478
_diffrn_reflns_theta_min         3.520
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.656
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94302
_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    1.830
_exptl_crystal_description       block
_exptl_crystal_F_000             4635
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.360
_refine_diff_density_min         -0.393
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.161
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     332
_refine_ls_number_reflns         4340
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.162
_refine_ls_R_factor_all          0.0756
_refine_ls_R_factor_gt           0.0634
_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^)+(0.0257P)^2^+49.0360P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1342
_refine_ls_wR_factor_ref         0.1418
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3677
_reflns_number_total             4340
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc02073b2.cif
_cod_data_source_block           170604
_cod_original_cell_volume        8558.5(5)
_cod_database_code               1546351
_chemical_oxdiff_formula         'Ni1 C20 F20 O3 N4 H10 Cl3'
_reflns_odcompleteness_completeness 99.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2. Shared sites
{C1, O1A}
{C2, O2A}
3. Restrained distances
 O2-C2
 1.32 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(O2) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(C1) = Uanis(O1A)
Uanis(C2) = Uanis(O2A)
5. Others
 Fixed Sof: C1(0.75) O2A(0.25) O1(0.25) H1(0.25) O1A(0.25) C2(0.75) O2(0.25)
 H2(0.25)
6.a Aromatic/amide H refined with riding coordinates:
 C00H(H00H), C00U(H00U)
6.b Tetrahedral OH refined with riding coordinates:
 O2(H2)
6.c Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_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 1.150
_oxdiff_exptl_absorpt_empirical_full_min 0.914