Cobalt-Bridged Secondary Building Units in a Titanium Metal-Organic Framework Catalyze Cascade Reduction of N-Heteroarenes
Feng, Xuanyu; Song, Yang; Chen, Justin S.; Li, Zhe; Chen, Emily Y.; Kaufmann, Michael; Wang, Cheng; Lin, Wenbin; Chemical Science  (2019) –; doi:10.1039/C8SC04610G

data_1550380
_publ_section_title
;
 Cobalt-Bridged Secondary Building Units in a Titanium Metal-Organic
 Framework Catalyze Cascade Reduction of N-Heteroarenes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC04610G
_journal_year                    2019
_chemical_compound_source        No
_chemical_formula_moiety         '0.67(C63 H37.5 O21 Ti4.5)'
_chemical_formula_sum            'C42 H30 O14 Ti3'
_chemical_formula_weight         902.36
_chemical_name_common            Ti3-BPDC
_chemical_name_systematic        Ti3-BPDC
_space_group_crystal_system      trigonal
_space_group_IT_number           166
_space_group_name_Hall           '-R 3 2"'
_space_group_name_H-M_alt        'R -3 m'
_symmetry_space_group_name_Hall  '-R 3 2"'
_symmetry_space_group_name_H-M   'R -3 m :H'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-07-29 deposited with the CCDC.
2018-12-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   25.8366(16)
_cell_length_b                   25.8366(16)
_cell_length_c                   13.6675(9)
_cell_measurement_reflns_used    8282
_cell_measurement_temperature    297(2)
_cell_measurement_theta_max      49.454
_cell_measurement_theta_min      4.706
_cell_volume                     7901.2(9)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'SAINT v8.34A (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)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.96
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_av_unetI/netI     0.0157
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            16826
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        24.727
_diffrn_reflns_theta_max         24.727
_diffrn_reflns_theta_min         2.353
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.248
_exptl_absorpt_correction_T_max  0.7451
_exptl_absorpt_correction_T_min  0.5804
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0802 before and 0.0448 after correction.
The Ratio of minimum to maximum transmission is 0.7790.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    0.569
_exptl_crystal_description       Cubic
_exptl_crystal_F_000             1380
_exptl_crystal_preparation       Catalysis
_exptl_crystal_recrystallization_method Solvothermal
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.976
_refine_diff_density_min         -1.412
_refine_diff_density_rms         0.095
_refine_ls_extinction_coef       0.0018(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.607
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     64
_refine_ls_number_reflns         1614
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.604
_refine_ls_R_factor_all          0.1213
_refine_ls_R_factor_gt           0.1129
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3430
_refine_ls_wR_factor_ref         0.3547
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1332
_reflns_number_total             1614
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc04610g2.cif
_cod_data_source_block           trial2_a
_cod_original_cell_volume        7901.1(11)
_cod_database_code               1550380
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 O3-H3A
 1 with sigma of 0.96
3. Uiso/Uaniso restraints and constraints
Uanis(O3) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4.a Riding coordinates:
 C6(H3A)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C3(H3), C7(H7), C6(H6)
;
_shelx_res_checksum              30291
_olex2_submission_special_instructions 'No special instructions were received'