Bis[cyclic (alkyl)(amino)carbene] isomers: Stable trans-bis(CAAC) versus facile olefin formation for cis-bis(CAAC)
Puerta Lombardi, Braulio M.; Pezoulas, Ethan R.; Suvinen, Roope A.; Harrison, Alexander; Dubrawski, Zachary S.; Gelfand, Benjamin S.; Tuononen, Heikki M.; Roesler, Roland; Chemical Communications  (2022) –; doi:10.1039/D2CC01476A

data_7130115
_publ_section_title
;
 Bis[cyclic (alkyl)(amino)carbene] isomers: Stable trans-bis(CAAC) versus
 facile olefin formation for cis-bis(CAAC)
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC01476A
_journal_year                    2022
_chemical_formula_moiety         'C78 H88 Cl2 Ir2 N2 O2 P2, 3(C6 H6)'
_chemical_formula_sum            'C96 H106 Cl2 Ir2 N2 O2 P2'
_chemical_formula_weight         1837.06
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-04
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-12-27 deposited with the CCDC.	2022-04-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 117.1090(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   19.478(2)
_cell_length_b                   12.9125(16)
_cell_length_c                   18.832(2)
_cell_measurement_reflns_used    9271
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      28.869
_cell_measurement_theta_min      2.430
_cell_volume                     4216.1(8)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.0617
_diffrn_reflns_av_unetI/netI     0.0325
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            98144
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.281
_diffrn_reflns_theta_min         1.966
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.304
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6090
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0925 before and 0.0504 after correction.
The Ratio of minimum to maximum transmission is 0.8166.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.447
_exptl_crystal_description       block
_exptl_crystal_F_000             1860
_exptl_crystal_preparation
'Stirred a solution of ligand and Vaska's complex in benzene for 24h. Product precipitated'
_exptl_crystal_recrystallization_method
'Product crystallized as large blocks when the reaction was carried out in an NMR tube'
_exptl_crystal_size_max          0.288
_exptl_crystal_size_mid          0.267
_exptl_crystal_size_min          0.233
_refine_diff_density_max         1.187
_refine_diff_density_min         -0.684
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     484
_refine_ls_number_reflns         10460
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0380
_refine_ls_R_factor_gt           0.0244
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0176P)^2^+5.0896P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0487
_refine_ls_wR_factor_ref         0.0538
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8530
_reflns_number_total             10460
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01476a2.cif
_cod_data_source_block           transbiscaac
_cod_original_cell_volume        4216.1(9)
_cod_database_code               7130115
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.513
_shelx_estimated_absorpt_t_min   0.450
_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.a Ternary CH refined with riding coordinates:
 C14(H14), C17(H17)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C19(H19A,H19B), C20(H20A,H20B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26),
 C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C34(H34), C35(H35), C36(H36),
  C37(H37), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C43(H43),
 C44(H44), C45(H45), C46(H46), C47(H47)
2.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C),
 C16(H16A,H16B,H16C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              37772
_olex2_submission_special_instructions 'No special instructions were received'