Insights into the Structure‒Activity Relationships in Metal‒Organic Framework-Supported Nickel Catalysts for Ethylene Hydrogenation
Wang, Xingjie; Zhang, Xuan; Pandharkar, Riddhish; Lyu, Jiafei; Ray, Debmalya; Yang, Ying; Kato, Satoshi; Liu, Jian; Wasson, Megan C.; Islamoglu, Timur; Li, Zhong; Hupp, Joseph T.; Cramer, Christopher J.; Gagliardi, Laura; Farha, Omar K.; ACS Catalysis  (2020) 8995–9005; doi:10.1021/acscatal.0c01844

data_4517883
_publ_section_title
;
 Insights into the Structure--Activity Relationships in Metal--Organic
 Framework-Supported Nickel Catalysts for Ethylene Hydrogenation
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              8995
_journal_page_last               9005
_journal_paper_doi               10.1021/acscatal.0c01844
_journal_year                    2020
_chemical_formula_moiety
'0.17(C208.8 H96 Br12 Hf18 Ni1.2 O96), 0.24(Ni)'
_chemical_formula_sum            'C34.8 H16 Br2 Hf3 Ni0.44 O16'
_chemical_formula_weight         1411.20
_space_group_crystal_system      hexagonal
_space_group_IT_number           191
_space_group_name_Hall           '-P 6 2'
_space_group_name_H-M_alt        'P 6/m m m'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-03-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   40.4333(11)
_cell_length_b                   40.4333(11)
_cell_length_c                   11.4682(5)
_cell_measurement_reflns_used    9758
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      50.64
_cell_measurement_theta_min      3.34
_cell_volume                     16236.9(9)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      200.02
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.596
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0545
_diffrn_reflns_av_unetI/netI     0.0229
_diffrn_reflns_Laue_measured_fraction_full 0.596
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            62553
_diffrn_reflns_point_group_measured_fraction_full 0.596
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         50.636
_diffrn_reflns_theta_min         2.185
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.345
_exptl_absorpt_correction_T_max  0.7500
_exptl_absorpt_correction_T_min  0.6258
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0775 before and 0.0578 after correction. The Ratio of minimum to maximum transmission is 0.8344. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    0.866
_exptl_crystal_description       rod
_exptl_crystal_F_000             3907
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.798
_refine_diff_density_min         -2.268
_refine_diff_density_rms         0.196
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     166
_refine_ls_number_reflns         3306
_refine_ls_number_restraints     187
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0883
_refine_ls_R_factor_gt           0.0865
_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^)+(0.1458P)^2^+261.7598P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2509
_refine_ls_wR_factor_ref         0.2529
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3143
_reflns_number_total             3306
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01844_si_003.cif
_cod_data_source_block           p6mmm_a
_cod_depositor_comments
'Adding full bibliography for 4517880--4517884.cif.'
_cod_original_cell_volume        16236.9(11)
_cod_original_formula_sum        'C34.80 H16 Br2 Hf3 Ni0.44 O16'
_cod_database_code               4517883
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.884
_shelx_estimated_absorpt_t_min   0.665
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 O5A-Ni2
 2.95 with sigma of 0.02
 O5A-Ni2A
 3.31 with sigma of 0.02
 C10-C11
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Ni2A \\sim Ni2: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O6A)=0.5*(1-FVAR(2))
 Sof(O6)=0.5*FVAR(2)
 Sof(O5A)=0.5*(1-FVAR(3))
 Sof(O5)=0.5*FVAR(3)
 Fixed Sof: Ni1(0.05) C11(0.125) C10(0.075) Ni2A(0.02) Ni2(0.04)
6.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7)
;
_olex2_submission_special_instructions 'No special instructions were received'