Cooperative H2 Activation across a Metal‒Metal Multiple Bond and Hydrogenation Reactions Catalyzed by a Zr/Co Heterobimetallic Complex
Gramigna, Kathryn M.; Dickie, Diane A.; Foxman, Bruce M.; Thomas, Christine M.; ACS Catalysis 9 (2019) 3153–; doi:10.1021/acscatal.8b04390

data_4514745
_publ_section_title
;
 Cooperative H2 Activation across a Metal--Metal Multiple Bond and
 Hydrogenation Reactions Catalyzed by a Zr/Co Heterobimetallic Complex
;
_journal_issue                   4
_journal_name_full               'ACS Catalysis'
_journal_page_first              3153
_journal_paper_doi               10.1021/acscatal.8b04390
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C46 H64 Co I N2 O P2 Zr'
_chemical_formula_sum            'C46 H64 Co I N2 O P2 Zr'
_chemical_formula_weight         999.98
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-06-30
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                77.690(2)
_cell_angle_beta                 79.557(2)
_cell_angle_gamma                69.802(2)
_cell_formula_units_Z            2
_cell_length_a                   10.7474(4)
_cell_length_b                   11.7734(4)
_cell_length_c                   20.3607(7)
_cell_measurement_reflns_used    9905
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      29.281
_cell_measurement_theta_min      2.280
_cell_volume                     2345.95(15)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'Bruker Instrument Service v2012.12.0.3'
_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  'XL (Sheldrick, 2008)'
_computing.structure_refinement  'SHELXL--2016/6 (Sheldrick, 2016)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_computing.structure_solution    'SHELXT, VERSION 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      120.06
_diffrn.ambient_temp_esd         2.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement.device       'Bruker Kappa APEX II CCD'
_diffrn_measurement_device_type  'Bruker Kappa APEX II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation.monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation.type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0360
_diffrn_reflns_av_unetI/netI     0.0460
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            52875
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns.reduction_process narrow--frame
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.473
_diffrn_reflns_theta_min         1.868
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source.source            'fine--focus tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.336
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6534
_exptl_absorpt_correction_type   multi-scan
_exptl.absorpt_correction_type   Multi--Scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0635 before and 0.0428 after correction. The ratio of minimum to maximum transmission is 0.8758.'
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.416
_exptl_crystal_description       plate
_exptl_crystal_F_000             1024
_exptl_crystal_recrystallization_method
'The material was recrystallised from diethyl ether by slow evaporation'
_exptl_crystal_size_max          0.345
_exptl_crystal_size_mid          0.266
_exptl_crystal_size_min          0.088
_refine_diff_density_max         1.647
_refine_diff_density_min         -1.001
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     513
_refine_ls_number_reflns         14264
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0613
_refine_ls_R_factor_gt           0.0397
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0396P)^2^+1.6602P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0885
_refine_ls_wR_factor_ref         0.0971
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10759
_reflns_number_total             14264
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b04390_si_002.cif
_cod_data_source_block           6
_cod_database_code               4514745
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.891
_shelx_estimated_absorpt_t_min   0.656
_computing.bruker_data_scaling
'SADABS V2016/2 - Bruker AXS area detector scaling and absorption correction'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C46-C45
 1.53 with sigma of 0.02
 C45-C44
 1.53 with sigma of 0.02
 C44-C43
 1.53 with sigma of 0.02
 C45A-C46A
 1.53 with sigma of 0.02
 C45A-C44A
 1.53 with sigma of 0.02
 C43-C45A
 2.35 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(I1) = Uanis(I1A)
Uanis(C44) = Uanis(C44A)
Uanis(C45) = Uanis(C45A)
Uanis(C46) = Uanis(C46A)
4. Others
 Sof(I1A)=1-FVAR(1)
 Sof(I1)=FVAR(1)
 Sof(H43C)=Sof(H43D)=Sof(C44A)=Sof(H44C)=Sof(H44D)=Sof(C45A)=Sof(H45C)=
 Sof(H45D)=Sof(C46A)=Sof(H46C)=Sof(H46D)=1-FVAR(2)
 Sof(H43A)=Sof(H43B)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=
 Sof(C46)=Sof(H46A)=Sof(H46B)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C15(H15), C18(H18), C29(H29), C32(H32)
5.b Secondary CH2 refined with riding coordinates:
 C43(H43A,H43B), C43(H43C,H43D), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,
 H46B), C44A(H44C,H44D), C45A(H45C,H45D), C46A(H46C,H46D)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12),
 C13(H13), C14(H14), C22(H22), C24(H24), C26(H26), C36(H36), C38(H38), C40(H40)
5.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C41(H41A,H41B,H41C),
 C42(H42A,H42B,H42C)
;
_shelx_res_checksum              12290
_shelx_hkl_checksum              34255
_olex2_diffrn_ambient_temperature_device
'Oxford Cryosystems Cryostream 700Plus'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MiTeGen MicroMount using Paratone oil'
_olex2_submission_original_sample_id KG-751
_olex2_submission_special_instructions 'No special instructions were received'