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_7130114
_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         'C40 H58 N2'
_chemical_formula_sum            'C40 H58 N2'
_chemical_formula_weight         566.88
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-12-27 deposited with the CCDC.	2022-04-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.3426(7)
_cell_length_b                   13.8099(5)
_cell_length_c                   11.6460(3)
_cell_measurement_reflns_used    2904
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      66.551
_cell_measurement_theta_min      4.143
_cell_volume                     3432.53(19)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.998
_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           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0277
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            11119
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.588
_diffrn_reflns_theta_max         66.588
_diffrn_reflns_theta_min         4.143
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.464
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.7023
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0691 before and 0.0344 after correction. The Ratio of minimum to maximum transmission is 0.9329. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.097
_exptl_crystal_description       block
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.264
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.192
_refine_diff_density_min         -0.141
_refine_diff_density_rms         0.033
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     391
_refine_ls_number_reflns         3161
_refine_ls_number_restraints     375
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.1194
_refine_ls_R_factor_gt           0.0867
_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^)+(0.1073P)^2^+2.2290P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2422
_refine_ls_wR_factor_ref         0.2676
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1889
_reflns_number_total             3161
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01476a2.cif
_cod_data_source_block           dippcaacdimer
_cod_database_code               7130114
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.887
_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. Rigid body (RIGU) restrains
 N1, N2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16,
  C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31,
 C32, C33, C34, C35, C36, C37, C38, C39, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Fixed Sof: N1(0.5) N2(0.5) C1(0.5) C2(0.5) C3(0.5) H3A(0.5) H3B(0.5) C4(0.5)
 C5(0.5) H5A(0.5) H5B(0.5) H5C(0.5) C6(0.5) H6A(0.5) H6B(0.5) H6C(0.5) C7(0.5)
 C8(0.5) C9(0.5) H9A(0.5) H9B(0.5) C10(0.5) C11(0.5) H11A(0.5) H11B(0.5)
 H11C(0.5) C12(0.5) H12A(0.5) H12B(0.5) H12C(0.5) C13(0.5) H13A(0.5) H13B(0.5)
 C14(0.5) H14A(0.5) H14B(0.5) C15(0.5) H15A(0.5) H15B(0.5) C16(0.5) H16A(0.5)
 H16B(0.5) C17(0.5) C18(0.5) C19(0.5) H19(0.5) C20(0.5) H20(0.5) C21(0.5)
 H21(0.5) C22(0.5) C23(0.5) H23(0.5) C24(0.5) H24A(0.5) H24B(0.5) H24C(0.5)
 C25(0.5) H25A(0.5) H25B(0.5) H25C(0.5) C26(0.5) H26(0.5) C27(0.5) H27A(0.5)
 H27B(0.5) H27C(0.5) C28(0.5) H28A(0.5) H28B(0.5) H28C(0.5) C29(0.5) C30(0.5)
 C31(0.5) H31(0.5) C32(0.5) H32(0.5) C33(0.5) H33(0.5) C34(0.5) C35(0.5)
 H35(0.5) C36(0.5) H36A(0.5) H36B(0.5) H36C(0.5) C37(0.5) H37A(0.5) H37B(0.5)
 H37C(0.5) C38(0.5) H38(0.5) C39(0.5) H39A(0.5) H39B(0.5) H39C(0.5) C40(0.5)
 H40A(0.5) H40B(0.5) H40C(0.5)
4.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C35(H35), C38(H38)
4.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C9(H9A,H9B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B),
 C16(H16A,H16B)
4.c Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C21(H21), C31(H31), C32(H32), C33(H33)
4.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C39(H39A,H39B,H39C), C40(H40A,
 H40B,H40C)
;
_shelx_res_checksum              52998
_olex2_submission_special_instructions 'No special instructions were received'