CO Coupling Chemistry of a Terminal Mo Carbide: Sequential Addition of Proton, Hydride, and CO Releases Ethenone.
Buss, Joshua A.; Bailey, Gwendolyn A.; Oppenheim, Julius; VanderVelde, David G.; Goddard, 3rd, William A; Agapie, Theodor; Journal of the American Chemical Society 141 (2019) 15664–15674; doi:10.1021/jacs.9b07743

data_4127991
_publ_section_title
;
 CO Coupling Chemistry of a Terminal Mo Carbide: Sequential Addition of
 Proton, Hydride, and CO Releases Ethenone.
;
_journal_issue                   39
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15664
_journal_page_last               15674
_journal_paper_doi               10.1021/jacs.9b07743
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         '2(C32 H41 Cl Mo O P2), C5 H12'
_chemical_formula_sum            'C69 H94 Cl2 Mo2 O2 P4'
_chemical_formula_weight         1342.10
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-02-12
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155),
SHELXL-2014,
and manual edit
;
_cell_angle_alpha                90
_cell_angle_beta                 95.462(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.1011(8)
_cell_length_b                   13.0037(8)
_cell_length_c                   19.0467(12)
_cell_measurement_reflns_used    9308
_cell_measurement_temperature    100
_cell_measurement_theta_max      36.78
_cell_measurement_theta_min      2.21
_cell_volume                     3230.1(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2014.11-0 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'XT-2014/4 (Sheldrick, 2012)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'CCD Area Detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'Bruker APEXII CCD'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker KAPPA 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  0.0489
_diffrn_reflns_av_unetI/netI     0.0267
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            197361
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         37.783
_diffrn_reflns_theta_min         1.809
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_current           30
_diffrn_source_power             1.5
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.614
_exptl_absorpt_correction_T_max  0.7474
_exptl_absorpt_correction_T_min  0.6860
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0633 before and 0.0520 after correction. The Ratio of minimum to maximum transmission is 0.9178. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1404
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.936
_refine_diff_density_min         -0.546
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     434
_refine_ls_number_reflns         16939
_refine_ls_number_restraints     45
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0492
_refine_ls_R_factor_gt           0.0339
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0254P)^2^+1.7167P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0730
_refine_ls_wR_factor_ref         0.0774
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13708
_reflns_number_total             16939
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07743_si_002.cif
_cod_data_source_block           4
_cod_database_code               4127991
_shelxl_version_number           2014-7
_shelx_estimated_absorpt_t_max   0.877
_shelx_estimated_absorpt_t_min   0.818
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C37-C36 \\sim C38-C37 \\sim C38-C38_$1 \\sim C38_$1-C37_$1 \\sim C34-C33 \\sim
C35-C34 \\sim C35-
 C35_$1 \\sim C35_$1-C34_$1 \\sim C34_$1-C33_$1 \\sim C37_$1-C36_$1
 with sigma of 0.02
3. Others
 Sof(C31B)=Sof(H31B)=Sof(Cl1B)=Sof(O1B)=Sof(C32B)=1-FVAR(1)
 Sof(Cl1A)=Sof(O1A)=Sof(C32A)=Sof(C31A)=Sof(H31A)=FVAR(1)
 Sof(C37)=Sof(C38)=Sof(H38A)=Sof(H38B)=1-FVAR(2)
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(H36D)=Sof(H37A)=Sof(H37B)=
 Sof(H37C)=Sof(H37D)=0.5*(1-FVAR(3))
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(H34A)=Sof(H34B)=Sof(H34C)=
 Sof(H34D)=Sof(H33D)=0.5*FVAR(3)
 Sof(C34)=Sof(C35)=Sof(H35A)=Sof(H35B)=FVAR(2)
4.a Riding coordinates:
 C34(H34A,H34B,H34C,H34D,H33D), C37(H36D,H37A,H37B,H37C,H37D)
4.b Ternary CH refined with riding coordinates:
 C19(H19), C22(H22), C25(H25), C28(H28)
4.c Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C38(H38A,H38B)
4.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C15(H15), C16(H16), C17(H17), C18(H18)
4.e Idealised Me refined with riding coordinates:
 C33(H33A,H33B,H33C), C36(H36A,H36B,H36C)
4.f Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C)
4.g :
 C31B(H31B), C31A(H31A)
;
_olex2_submission_special_instructions 'No special instructions were received'