Carbon Monoxide Insertion at a Heavy p-Block Element: Unprecedented Formation of a Cationic Bismuth Carbamoyl
Ramler, Jacqueline; Poater, Jordi; Hrisch, Florian; Ritschel, Benedikt; Fischer, Ingo; Bickelhaupt, F. Matthias; Lichtenberg, Crispin; Chemical Science  (2019) –; doi:10.1039/C9SC00278B

data_1550682
_publ_section_title
;
 Carbon Monoxide Insertion at a Heavy p-Block Element: Unprecedented
 Formation of a Cationic Bismuth Carbamoyl
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC00278B
_journal_year                    2019
_chemical_formula_moiety         'C34.2 H30.2 Bi F3 N4.44 O3 S, 0.56(C5 H5 N)'
_chemical_formula_sum            'C37 H33 Bi F3 N5 O3 S'
_chemical_formula_weight         893.72
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
;
_audit_update_record
;
2019-01-17 deposited with the CCDC.    2019-02-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.575(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.2452(6)
_cell_length_b                   16.0336(7)
_cell_length_c                   19.9108(11)
_cell_measurement_reflns_used    9882
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      26.75
_cell_measurement_theta_min      2.36
_cell_volume                     3566.3(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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  0.0374
_diffrn_reflns_av_unetI/netI     0.0214
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            51137
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.781
_diffrn_reflns_theta_min         2.222
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.062
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5774
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0687 before and 0.0450 after correction. The Ratio of minimum to maximum transmission is 0.7746. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.665
_exptl_crystal_description       block
_exptl_crystal_F_000             1760
_exptl_crystal_size_max          0.316
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.162
_refine_diff_density_max         1.202
_refine_diff_density_min         -0.902
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.221
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     616
_refine_ls_number_reflns         7585
_refine_ls_number_restraints     213
_refine_ls_restrained_S_all      1.215
_refine_ls_R_factor_all          0.0361
_refine_ls_R_factor_gt           0.0316
_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^)+(0.0032P)^2^+17.1504P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0673
_refine_ls_wR_factor_ref         0.0687
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6971
_reflns_number_total             7585
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc00278b2.cif
_cod_data_source_block           Compound_5
_cod_database_code               1550682
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.494
_shelx_estimated_absorpt_t_min   0.298
_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
 S1A-C32
 1.84 with sigma of 0.02
 F3-C32
 1.3 with sigma of 0.02
 F1-C32
 1.3 with sigma of 0.02
 H22_$9-H33A
 2.02 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C7) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F1) \\sim Ueq, Uanis(F3) \\sim Ueq: with sigma of 0.004 and sigma for
terminal atoms of 0.008
Uanis(C32) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C10) \\sim Ueq: with sigma of 0.008 and sigma for terminal atoms of 0.016
Uanis(N1A) = Uanis(N1)
4. Rigid body (RIGU) restrains
 C36, C35, C34, C33, C37, N5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7, C12, C11, C10, C9, C8, N1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1A, C7A, C8A, C9A, C10A, C11A, C12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1A, F2A, F3A, C32A, S1, O3A, O2A, O1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C37A, C36A, C35A, C34A, C33A, N5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C7)=Sof(C12)=Sof(H12)=Sof(C11)=Sof(H11)=Sof(C10)=Sof(H10)=Sof(C9)=Sof(H9)=
 Sof(C8)=Sof(H8)=Sof(N1)=1-FVAR(1)
 Sof(N1A)=Sof(C7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=
 Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=FVAR(1)
 Sof(C36)=Sof(H36)=Sof(C35)=Sof(H35)=Sof(C34)=Sof(H34)=Sof(C33)=Sof(H33)=
 Sof(C37)=Sof(H37)=Sof(N5)=1-FVAR(2)
 Sof(C37A)=Sof(H37A)=Sof(C36A)=Sof(H36A)=Sof(C35A)=Sof(H35A)=Sof(C34A)=
 Sof(H34A)=Sof(C33A)=Sof(H33A)=Sof(N5A)=FVAR(2)
 Sof(O3)=Sof(S1A)=Sof(O2)=Sof(O1)=1-FVAR(3)
 Sof(S1)=Sof(O3A)=Sof(O2A)=Sof(O1A)=FVAR(3)
 Sof(C32)=Sof(F3)=Sof(F1)=Sof(F2)=1-FVAR(4)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(C32A)=FVAR(4)
6.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6), C18(H18), C27(H27), C4(H4), C22(H22), C26(H26),
 C28(H28), C31(H31), C23(H23), C16(H16), C24(H24), C17(H17), C29(H29), C30(H30),
  C25(H25), C8A(H8A), C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A), C12(H12),
 C11(H11), C10(H10), C9(H9), C8(H8), C37A(H37A), C36A(H36A), C35A(H35A),
 C34A(H34A), C33A(H33A), C36(H36), C35(H35), C34(H34), C33(H33), C37(H37)
6.b Fitted hexagon refined as free rotating group:
 C7A(C8A,C9A,C10A,C11A,C12A), C37A(C36A,C35A,C34A,C33A,N5A)
6.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C20(H20A,H20B,H20C)
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_olex2_submission_special_instructions 'No special instructions were received'