Understanding the Relationship Between Kinetics and Thermodynamics in CO2 Hydrogenation Catalysis
Jeletic, Matthew S.; Hulley, Elliott B.; Helm, Monte L.; Mock, Michael T.; Appel, Aaron M.; Wiedner, Eric S.; Linehan, John C.; ACS Catalysis 7 (2017) 6008–; doi:10.1021/acscatal.7b01673

data_4516741
_publ_section_title
;
 Understanding the Relationship Between Kinetics and Thermodynamics in CO2
 Hydrogenation Catalysis
;
_journal_issue                   9
_journal_name_full               'ACS Catalysis'
_journal_page_first              6008
_journal_paper_doi               10.1021/acscatal.7b01673
_journal_volume                  7
_journal_year                    2017
_chemical_formula_moiety         'C20 H32 Co P4'
_chemical_formula_sum            'C20 H32 Co P4'
_chemical_formula_weight         455.26
_chemical_name_systematic        CoH(dmpbz)
_space_group_crystal_system      orthorhombic
_space_group_IT_number           41
_space_group_name_Hall           'A 2 -2ab'
_space_group_name_H-M_alt        'A e a 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-08-09
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.7643(5)
_cell_length_b                   16.3813(5)
_cell_length_c                   8.9459(2)
_cell_measurement_reflns_used    3716
_cell_measurement_temperature    140
_cell_measurement_theta_max      27.654
_cell_measurement_theta_min      2.486
_cell_volume                     2310.19(11)
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      140.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0311
_diffrn_reflns_av_unetI/netI     0.0387
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            12882
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.081
_diffrn_reflns_theta_min         2.487
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.022
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9101
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0551 before and 0.0501 after correction.
The Ratio of minimum to maximum transmission is 0.9101.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.309
_exptl_crystal_description       prism
_exptl_crystal_F_000             956
_exptl_crystal_preparation
'Selected from crystals of similar habit under a microscope.'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.320
_refine_diff_density_min         -0.271
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     185
_refine_ls_number_reflns         3192
_refine_ls_number_restraints     179
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.0451
_refine_ls_R_factor_gt           0.0321
_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^)+(0.0307P)^2^+0.4074P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0655
_refine_ls_wR_factor_ref         0.0700
_reflns_Friedel_coverage         0.779
_reflns_Friedel_fraction_full    0.962
_reflns_Friedel_fraction_max     0.876
_reflns_number_gt                2624
_reflns_number_total             3192
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs7b01673_si_001.cif
_cod_data_source_block           Co(dmpbz)2H
_cod_original_sg_symbol_Hall     'A 2 -2ac'
_cod_original_sg_symbol_H-M      'A b a 2'
_cod_database_code               4516741
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 P3-C13 \\sim P4-C18 \\sim P2-C8 \\sim P1-C3
 with sigma of 0.02
 P3-C11 \\sim P3-C12 \\sim P1-C2 \\sim P1-C1 \\sim P2-C9 \\sim P2-C10 \\sim P4-C19 \\sim P4-C20
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C8) = Uanis(C3)
Uanis(C13) = Uanis(C18)
Uanis(C11) = Uanis(C10)
Uanis(C1) = Uanis(C20)
4. Others
 Fixed Sof: C17(0.5) H17(0.5) C18(0.5) C13(0.5) C14(0.5) H14(0.5) C15(0.5)
 H15(0.5) C16(0.5) H16(0.5) C4(0.5) H4(0.5) C5(0.5) H5(0.5) C6(0.5) H6(0.5)
 C7(0.5) H7(0.5) C8(0.5) C3(0.5) C11(0.5) H11A(0.5) H11B(0.5) H11C(0.5)
 C10(0.5) H10A(0.5) H10B(0.5) H10C(0.5) C12(0.5) H12A(0.5) H12B(0.5) H12C(0.5)
 C9(0.5) H9A(0.5) H9B(0.5) H9C(0.5) C20(0.5) H20A(0.5) H20B(0.5) H20C(0.5)
 C1(0.5) H1A(0.5) H1B(0.5) H1C(0.5) C19(0.5) H19A(0.5) H19B(0.5) H19C(0.5)
 C2(0.5) H2A(0.5) H2B(0.5) H2C(0.5) P3(0.5) P2(0.5) P4(0.5) P1(0.5) Co1(0.5)
5.a Me refined with riding coordinates:
 C1(H1A,H1B,H1C)
5.b Aromatic/amide H refined with riding coordinates:
 C17(H17), C14(H14), C15(H15), C16(H16), C4(H4), C5(H5), C6(H6), C7(H7)
5.c Fitted hexagon refined as free rotating group:
 C17(C18,C13,C14,C15,C16), C4(C5,C6,C7,C8,C3)
5.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C9(H9A,H9B,
 H9C), C20(H20A,H20B,H20C), C19(H19A,H19B,H19C), C2(H2A,H2B,H2C)
;
_shelxl_version_number           2013-2