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_7130117
_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 H61 N3'
_chemical_formula_sum            'C40 H61 N3'
_chemical_formula_weight         583.91
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-03
_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                108.7680(10)
_cell_angle_beta                 96.6350(10)
_cell_angle_gamma                99.3050(10)
_cell_formula_units_Z            4
_cell_length_a                   9.9563(10)
_cell_length_b                   16.8762(17)
_cell_length_c                   22.908(2)
_cell_measurement_reflns_used    9960
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      27.488
_cell_measurement_theta_min      2.397
_cell_volume                     3538.2(6)
_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 0.999
_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  0.0653
_diffrn_reflns_av_unetI/netI     0.0668
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            65921
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.537
_diffrn_reflns_theta_min         0.954
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.063
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.7166
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0704 before and 0.0487 after correction.
The Ratio of minimum to maximum transmission is 0.9611.
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    1.096
_exptl_crystal_description       block
_exptl_crystal_F_000             1288
_exptl_crystal_size_max          0.498
_exptl_crystal_size_mid          0.276
_exptl_crystal_size_min          0.142
_refine_diff_density_max         1.530
_refine_diff_density_min         -0.627
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     889
_refine_ls_number_reflns         16272
_refine_ls_number_restraints     173
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.1318
_refine_ls_R_factor_gt           0.0755
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0749P)^2^+3.2806P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1730
_refine_ls_wR_factor_ref         0.2041
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9770
_reflns_number_total             16272
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01476a2.cif
_cod_data_source_block           mo_20210814_newmecnactivation_
_cod_database_code               7130117
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.969
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2-C7B \\sim N2-C7A \\sim N1-C1A \\sim N1-C1B
 with sigma of 0.02
 N3-C1A \\sim N3-C1B \\sim N3-C7B \\sim N3-C7A
 with sigma of 0.02
 C4-C3A \\sim C4-C3B
 with sigma of 0.02
 C3A-C2 \\sim C3B-C2
 with sigma of 0.02
 N2-C10A \\sim N2-C10B
 with sigma of 0.02
 C9-C10A \\sim C9-C10B
 with sigma of 0.02
 C11B-C10B \\sim C11A-C10A \\sim C12B-C10B \\sim C12A-C10A
 with sigma of 0.02
 C32B-C31B \\sim C32A-C31A \\sim C33B-C32B \\sim C33A-C32A
 with sigma of 0.02
 C32B-C30 \\sim C32A-C30
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C7A \\sim C7B \\sim C1A \\sim C1B: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
C3A \\sim C3B: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
C12A \\sim C12B \\sim C11B \\sim C11A \\sim C10B \\sim C10A: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C32B \\sim C32A \\sim C33A \\sim C33B \\sim C31A \\sim C31B: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
4. Others
 Sof(C1B)=Sof(H1B)=1-FVAR(1)
 Sof(C1A)=Sof(H1A)=FVAR(1)
 Sof(C7B)=Sof(H7B)=1-FVAR(2)
 Sof(C7A)=Sof(H7A)=FVAR(2)
 Sof(C3B)=Sof(H3BA)=Sof(H3BB)=1-FVAR(3)
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=FVAR(3)
 Sof(H9BC)=Sof(H9BD)=Sof(C10B)=Sof(C11B)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C12B)=Sof(H12A)=Sof(H12B)=Sof(H12C)=1-FVAR(4)
 Sof(H9AA)=Sof(H9AB)=Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C10A)=
 Sof(C11A)=Sof(H11D)=Sof(H11E)=Sof(H11F)=FVAR(4)
 Sof(C32B)=Sof(H32B)=Sof(C31B)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C33B)=
 Sof(H33A)=Sof(H33B)=Sof(H33C)=1-FVAR(5)
 Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(C32A)=Sof(H32A)=Sof(C33A)=
 Sof(H33D)=Sof(H33E)=Sof(H33F)=FVAR(5)
5.a Riding coordinates:
 N6(H6)
5.b Ternary CH refined with riding coordinates:
 C47(H47), C41(H41), C75(H75), C23(H23), C63(H63), C20(H20), C72(H72),
 C60(H60), C35(H35), C32B(H32B), C7B(H7B), C1B(H1B), C1A(H1A), C7A(H7A),
 C32A(H32A)
5.c Secondary CH2 refined with riding coordinates:
 C80(H80A,H80B), C78(H78A,H78B), C43(H43A,H43B), C79(H79A,H79B), C77(H77A,
 H77B), C49(H49A,H49B), C37(H37A,H37B), C9(H9BC,H9BD), C9(H9AA,H9AB), C38(H38A,
 H38B), C39(H39A,H39B), C40(H40A,H40B), C3B(H3BA,H3BB), C3A(H3AA,H3AB)
5.d Aromatic/amide H refined with riding coordinates:
 N3(H3), C67(H67), C68(H68), C69(H69), C17(H17), C15(H15), C57(H57), C16(H16),
 C27(H27), C29(H29), C28(H28), C56(H56), C55(H55)
5.e Idealised Me refined as rotating group:
 C46(H46A,H46B,H46C), C45(H45A,H45B,H45C), C74(H74A,H74B,H74C), C52(H52A,H52B,
 H52C), C51(H51A,H51B,H51C), C73(H73A,H73B,H73C), C76(H76A,H76B,H76C), C64(H64A,
 H64B,H64C), C59(H59A,H59B,H59C), C71(H71A,H71B,H71C), C24(H24A,H24B,H24C),
 C22(H22A,H22B,H22C), C21(H21A,H21B,H21C), C61(H61A,H61B,H61C), C19(H19A,H19B,
 H19C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C62(H62A,H62B,H62C),
 C31B(H31A,H31B,H31C), C6(H6A,H6B,H6C), C5(H5A,H5B,H5C), C33B(H33A,H33B,H33C),
 C11B(H11A,H11B,H11C), C12B(H12A,H12B,H12C), C12A(H12D,H12E,H12F), C11A(H11D,
 H11E,H11F), C31A(H31D,H31E,H31F), C33A(H33D,H33E,H33F)
;
_shelx_res_checksum              18599
_olex2_submission_special_instructions 'No special instructions were received'