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_4127992
_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
'C32 H41 Cl Mo O P2, 0.5(C4 H8 O), 0.25(C7 H16 O2)'
_chemical_formula_sum            'C35.75 H45 Cl Mo O2 P2'
_chemical_formula_weight         700.04
_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   mixed
_audit_creation_date             2019-09-02
_audit_creation_method
;
Olex2 1.2
(compiled Apr  3 2018 11:26:26 for OlexSys, GUI svn.r5486)
;
_cell_angle_alpha                91.78(3)
_cell_angle_beta                 104.66(2)
_cell_angle_gamma                102.92(3)
_cell_formula_units_Z            4
_cell_length_a                   12.469(6)
_cell_length_b                   12.592(5)
_cell_length_c                   23.363(11)
_cell_measurement_reflns_used    9685
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      38.67
_cell_measurement_theta_min      2.41
_cell_volume                     3444(3)
_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      100.03
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.954
_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  0.0348
_diffrn_reflns_av_unetI/netI     0.0353
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            138567
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         39.299
_diffrn_reflns_theta_min         1.666
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.581
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9410
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0470 before and 0.0427 after correction. The Ratio of minimum to maximum transmission is 0.9410. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.350
_exptl_crystal_description       block
_exptl_crystal_F_000             1458
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.25
_refine_diff_density_max         1.678
_refine_diff_density_min         -1.877
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     753
_refine_ls_number_reflns         38955
_refine_ls_number_restraints     87
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0598
_refine_ls_R_factor_gt           0.0399
_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^)+(0.0397P)^2^+3.6612P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0947
_refine_ls_wR_factor_ref         0.1040
_reflns_Friedel_coverage         0.000
_reflns_number_gt                30480
_reflns_number_total             38955
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07743_si_002.cif
_cod_data_source_block           4prime
_cod_database_code               4127992
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.868
_shelx_estimated_absorpt_t_min   0.788
_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
 C7S-C8S \\sim C5S-C6S \\sim C8S'-C7S' \\sim C5S-C6S' \\sim C1S-C3S \\sim
C3S'-C1S \\sim C2S-C4S' ~
 C4S-C2S
 with sigma of 0.02
 C3S-C4S \\sim C3S'-C4S' \\sim C7S'-C6S' \\sim C6S-C7S
 with sigma of 0.02
 O1S-C2S \\sim O1S-C1S \\sim O2S'-C8S' \\sim O2S'-C5S \\sim O2S-C8S \\sim
O2S-C5S
 with sigma of 0.02
 O2S-C6S \\sim O2S'-C7S'
 with sigma of 0.02
 O2S-C7S \\sim C6S'-O2S'
 with sigma of 0.02
 O2S-C6S \\sim O2S'-C6S'
 with sigma of 0.02
 O2S-C6S \\sim O1S-C3S'
 with sigma of 0.02
 O1S-C4S' \\sim O2S'-C7S'
 with sigma of 0.02
 O1S-C3S \\sim C6S-O2S
 with sigma of 0.02
 C8S'-C6S' \\sim C5S-C7S \\sim C4S'-C1S \\sim C2S-C3S'
 with sigma of 0.02
 C5S-C7S' \\sim C8S-C6S \\sim C1S-C4S \\sim C3S-C2S
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O2S' \\sim C8S \\sim C3S \\sim C1S \\sim C4S \\sim C2S \\sim O1S: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 O2S', C8S, C3S, C1S, C4S, C2S, O1S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: H2SA(0.5) H2SB(0.5) H2SC(0.5) H2SD(0.5) C4S(0.5) H4SA(0.5)
 H4SB(0.5) C3S(0.5) H3SA(0.5) H3SB(0.5) H1SB(0.5) H1SA(0.5) H1SD(0.5) H1SC(0.5)
 O2S'(0.5) C8S(0.5) H8SA(0.5) H8SB(0.5) C6S'(0.5) H6SA(0.5) H6SB(0.5) C7S'(0.5)
 H7SA(0.5) H7SB(0.5) O2S(0.5) C7S(0.5) H7SC(0.5) H7SD(0.5) C5S(0.5) H5SB(0.5)
 H5SA(0.5) H5SC(0.5) H5SD(0.5) C6S(0.5) H6SC(0.5) H6SD(0.5) C3S'(0.5) H3SC(0.5)
 H3SD(0.5) C8S'(0.5) H8SC(0.5) H8SD(0.5) C4S'(0.5) H4SC(0.5) H4SD(0.5)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C4(H4), C25(H25), C28(H28), C1B(H1B), C4B(H4B), C25B(H25B), C28B(H28B)
6.b Secondary CH2 refined with riding coordinates:
 C2S(H2SA,H2SB), C2S(H2SC,H2SD), C4S(H4SA,H4SB), C3S(H3SA,H3SB), C1S(H1SB,
 H1SA), C1S(H1SD,H1SC), C8S(H8SA,H8SB), C6S'(H6SA,H6SB), C7S'(H7SA,H7SB),
 C7S(H7SC,H7SD), C5S(H5SB,H5SA), C5S(H5SC,H5SD), C6S(H6SC,H6SD), C3S'(H3SC,
 H3SD), C8S'(H8SC,H8SD), C4S'(H4SC,H4SD)
6.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C14(H14), C15(H15), C17(H17), C18(H18),
 C20(H20), C21(H21), C22(H22), C23(H23), C8B(H8B), C9B(H9B), C10B(H10B),
 C11B(H11B), C14B(H14B), C15B(H15B), C17B(H17B), C18B(H18B), C20B(H20B),
 C21B(H21B), C22B(H22B), C23B(H23B)
6.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C26(H26A,
 H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C2B(H2BA,H2BB,H2BC), C3B(H3BA,H3BB,H3BC), C5B(H5BA,H5BB,H5BC), C6B(H6BA,H6BB,
 H6BC), C26B(H26D,H26E,H26F), C27B(H27D,H27E,H27F), C29B(H29D,H29E,H29F),
 C30B(H30D,H30E,H30F)
;
_shelx_res_checksum              57551
_shelx_hkl_checksum              26888
_olex2_submission_special_instructions 'No special instructions were received'