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_7130109
_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         'C32 H46 N2'
_chemical_formula_sum            'C32 H46 N2'
_chemical_formula_weight         458.71
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-22
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.8016(2)
_cell_length_b                   17.7157(4)
_cell_length_c                   20.7203(4)
_cell_measurement_reflns_used    9978
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      68.297
_cell_measurement_theta_min      4.268
_cell_volume                     2863.77(11)
_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           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0313
_diffrn_reflns_av_unetI/netI     0.0217
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            18261
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.383
_diffrn_reflns_theta_min         4.267
_diffrn_source_current           0.64
_diffrn_source_power             0.0285952
_diffrn_source_voltage           44.68
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.454
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.7124
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0623 before and 0.0429 after correction.
The Ratio of minimum to maximum transmission is 0.9460.
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    1.064
_exptl_crystal_description       block
_exptl_crystal_F_000             1008
_exptl_crystal_size_max          0.307
_exptl_crystal_size_mid          0.168
_exptl_crystal_size_min          0.118
_refine_diff_density_max         0.279
_refine_diff_density_min         -0.220
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     169
_refine_ls_number_reflns         2631
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0597
_refine_ls_R_factor_gt           0.0544
_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^)+(0.0948P)^2^+0.8896P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1606
_refine_ls_wR_factor_ref         0.1683
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2316
_reflns_number_total             2631
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01476a2.cif
_cod_data_source_block           20201023bp
_cod_database_code               7130109
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.873
_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. Restrained distances
 C13-C12 \\sim C13A-C12
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C13 \\sim C13A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
4. Others
 Sof(H12A)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=1-FVAR(1)
 Sof(H12)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C15(H15), C12(H12), C12(H12A)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C7(H7), C9(H9), C8(H8)
5.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C11(H11A,H11B,H11C), C13(H13A,H13B,
 H13C), C13A(H13D,H13E,H13F)
;
_shelx_res_checksum              39361
_olex2_submission_special_instructions 'No special instructions were received'