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_7130116
_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         'C H2 Cl2, C40 H60 N2, 2(B F4)'
_chemical_formula_sum            'C41 H62 B2 Cl2 F8 N2'
_chemical_formula_weight         827.44
_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             2021-07-13
_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                102.6880(10)
_cell_angle_beta                 91.3310(10)
_cell_angle_gamma                94.5830(10)
_cell_formula_units_Z            2
_cell_length_a                   9.5425(8)
_cell_length_b                   10.9809(9)
_cell_length_c                   22.1072(19)
_cell_measurement_reflns_used    9928
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      27.436
_cell_measurement_theta_min      2.305
_cell_volume                     2250.7(3)
_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 1.000
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0388
_diffrn_reflns_av_unetI/netI     0.0387
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            41966
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.454
_diffrn_reflns_theta_min         1.890
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.207
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.7209
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0538 before and 0.0405 after correction. The Ratio of minimum to maximum transmission is 0.9669. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.221
_exptl_crystal_description       plank
_exptl_crystal_F_000             876
_exptl_crystal_size_max          0.449
_exptl_crystal_size_mid          0.341
_exptl_crystal_size_min          0.256
_refine_diff_density_max         0.768
_refine_diff_density_min         -0.682
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     657
_refine_ls_number_reflns         10286
_refine_ls_number_restraints     1526
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0935
_refine_ls_R_factor_gt           0.0546
_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^)+(0.0594P)^2^+1.1661P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1283
_refine_ls_wR_factor_ref         0.1497
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6661
_reflns_number_total             10286
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01476a2.cif
_cod_data_source_block           mo_20210516_biscaacbf4_0m
_cod_database_code               7130116
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.913
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 B1_1-F1_1 \\sim B1_1-F2_1 \\sim B1_1-F3_1 \\sim B1_1-F4_1
 B1_2-F1_2 \\sim B1_2-F2_2 \\sim B1_2-F3_2 \\sim B1_2-F4_2
 B1_3-F1_3 \\sim B1_3-F2_3 \\sim B1_3-F3_3 \\sim B1_3-F4_3
 B1_4-F1_4 \\sim B1_4-F2_4 \\sim B1_4-F3_4 \\sim B1_4-F4_4
 B1_5-F1_5 \\sim B1_5-F2_5 \\sim B1_5-F3_5 \\sim B1_5-F4_5
 with sigma of 0.02
 F1_1-F2_1 \\sim F1_1-F3_1 \\sim F1_1-F4_1 \\sim F2_1-F3_1 \\sim F2_1-F4_1
\\sim F3_1-F4_1
 F1_2-F2_2 \\sim F1_2-F3_2 \\sim F1_2-F4_2 \\sim F2_2-F3_2 \\sim F2_2-F4_2
\\sim F3_2-F4_2
 F1_3-F2_3 \\sim F1_3-F3_3 \\sim F1_3-F4_3 \\sim F2_3-F3_3 \\sim F2_3-F4_3
\\sim F3_3-F4_3
 F1_4-F2_4 \\sim F1_4-F3_4 \\sim F1_4-F4_4 \\sim F2_4-F3_4 \\sim F2_4-F4_4
\\sim F3_4-F4_4
 F1_5-F2_5 \\sim F1_5-F3_5 \\sim F1_5-F4_5 \\sim F2_5-F3_5 \\sim F2_5-F4_5
\\sim F3_5-F4_5
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 1*[Sof(F1)+Sof(F2)+Sof(F3)+Sof(F4)+Sof(B1)]+1*[Sof(F1)+Sof(F2)+Sof(F3)+
 Sof(F4)+Sof(B1)]+1*[Sof(F1)+Sof(F2)+Sof(F3)+Sof(F4)+Sof(B1)]=1 with esd of 0
 Sof(Cl1B)=Sof(H41C)=Sof(H41D)=1-FVAR(1)
 Sof(Cl1A)=Sof(H41A)=Sof(H41B)=FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(B1)=FVAR(2)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(B1)=FVAR(3)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(B1)=FVAR(4)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(B1)=1-FVAR(5)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(B1)=FVAR(5)
5.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C36(H36), C39(H39)
5.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), C41(H41C,H41D), C41(H41A,H41B)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C7(H7), C19(H19), C20(H20), C21(H21), C31(H31), C32(H32), C33(H33)
5.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,
 H28C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C40(H40A,
 H40B,H40C)
;
_shelx_res_checksum              64106
_shelx_fab_checksum              34850
_olex2_submission_special_instructions 'No special instructions were received'