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_7130110
_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 H60 N2, 2(B F4)'
_chemical_formula_sum            'C40 H60 B2 F8 N2'
_chemical_formula_weight         742.52
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-06
_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                101.896(2)
_cell_angle_beta                 110.7630(10)
_cell_angle_gamma                111.6370(10)
_cell_formula_units_Z            2
_cell_length_a                   11.0116(3)
_cell_length_b                   14.7548(4)
_cell_length_c                   15.4039(4)
_cell_measurement_reflns_used    9468
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      72.47
_cell_measurement_theta_min      3.33
_cell_volume                     2005.29(10)
_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 0.965
_diffrn_measured_fraction_theta_max 0.963
_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  0.0324
_diffrn_reflns_av_unetI/netI     0.0318
_diffrn_reflns_Laue_measured_fraction_full 0.965
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            30428
_diffrn_reflns_point_group_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.059
_diffrn_reflns_theta_min         3.328
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.803
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6608
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0780 before and 0.0461 after correction. The Ratio of minimum to maximum transmission is 0.8769. 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    1.230
_exptl_crystal_description       plate
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.475
_exptl_crystal_size_mid          0.337
_exptl_crystal_size_min          0.066
_refine_diff_density_max         0.558
_refine_diff_density_min         -0.456
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     621
_refine_ls_number_reflns         7319
_refine_ls_number_restraints     1466
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0881
_refine_ls_R_factor_gt           0.0839
_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^)+(0.0563P)^2^+3.7154P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2070
_refine_ls_wR_factor_ref         0.2092
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6716
_reflns_number_total             7319
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01476a2.cif
_cod_data_source_block           transbiscaacbf4
_cod_database_code               7130110
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.702
_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
 B1-F1 \\sim B1-F2 \\sim B1-F3 \\sim B1-F4 \\sim B1A-F1A \\sim B1A-F2A \\sim
B1A-F3A \\sim B1A-F4A \\sim B1B-
 F1B \\sim B1B-F2B \\sim B1B-F3B \\sim B1B-F4B \\sim B2-F5 \\sim B2-F6 \\sim
B2-F7 \\sim B2-F8 \\sim B2-F5A ~
 B2-F6A \\sim B2-F7A \\sim B2-F8A
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F1-F4 \\sim F2-F3 \\sim F2-F4 \\sim F3-F4 \\sim
F1A-F2A \\sim F1A-F3A \\sim F1A-F4A ~
 F2A-F3A \\sim F2A-F4A \\sim F3A-F4A \\sim F1B-F2B \\sim F1B-F3B \\sim F1B-F4B
\\sim F2B-F3B \\sim F2B-F4B
 \\sim F3B-F4B \\sim F5-F6 \\sim F5-F7 \\sim F5-F8 \\sim F6-F7 \\sim F6-F8
\\sim F7-F8 \\sim F5A-F6A \\sim F5A-F7A
 \\sim F5A-F8A \\sim F6A-F7A \\sim F6A-F8A \\sim F7A-F8A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
B1 \\sim F2 \\sim F3 \\sim F4 \\sim F1 \\sim B1A \\sim F1A \\sim F3A \\sim F4A
\\sim F2A \\sim B1B \\sim F3B \\sim F1B \\sim F4B \\sim F2B: within 3A with
sigma of 0.02 and sigma for terminal atoms of 0.04
B2 \\sim F6 \\sim F8A \\sim F7A \\sim F5A \\sim F7 \\sim F5 \\sim F8 \\sim F6A:
within 3A with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Others
 1*[Sof(F2)+Sof(F3)+Sof(F4)+Sof(B1)+Sof(F1)]+1*[Sof(F1A)+Sof(B1A)+Sof(F3A)+
 Sof(F4A)+Sof(F2A)]+1*[Sof(F1B)+Sof(B1B)+Sof(F3B)+Sof(F4B)+Sof(F2B)]=1 with esd
 of 0
 Sof(F5A)=Sof(F7A)=Sof(F8A)=Sof(F6A)=1-FVAR(1)
 Sof(F6)=Sof(F8)=Sof(F5)=Sof(F7)=FVAR(1)
 Sof(C0AA)=Sof(H0AA)=Sof(H0AB)=1-FVAR(2)
 Sof(C3)=Sof(H3A)=Sof(H3B)=FVAR(2)
 Sof(F2)=Sof(F3)=Sof(F4)=Sof(B1)=Sof(F1)=FVAR(3)
 Sof(F1A)=Sof(B1A)=Sof(F3A)=Sof(F4A)=Sof(F2A)=FVAR(4)
 Sof(F1B)=Sof(B1B)=Sof(F3B)=Sof(F4B)=Sof(F2B)=FVAR(5)
5.a Ternary CH refined with riding coordinates:
 C17(H17), C37(H37), C34(H34), C14(H14)
5.b Secondary CH2 refined with riding coordinates:
 C39(H39A,H39B), C40(H40A,H40B), C23(H23A,H23B), C19(H19A,H19B), C20(H20A,
 H20B), C3(H3A,H3B), C0AA(H0AA,H0AB)
5.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C1(H1), C11(H11), C31(H31), C9(H9), C29(H29), C10(H10), C30(H30)
5.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C25(H25A,H25B,H25C), C18(H18A,H18B,H18C), C38(H38A,H38B,
 H38C), C16(H16A,H16B,H16C), C6(H6A,H6B,H6C), C5(H5A,H5B,H5C), C36(H36A,H36B,
 H36C), C33(H33A,H33B,H33C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C35(H35A,
 H35B,H35C)
;
_shelx_res_checksum              46180
_olex2_submission_original_sample_id 'trans-Dippiminium BF4'
_olex2_submission_special_instructions 'No special instructions were received'