Bicyclic (Alkyl)(amino)carbenes (BICAACs): Stable Carbenes more Ambiphilic than CAACs.
Tomás-Mendivil, Eder; Hansmann, Max M.; Weinstein, Cory M.; Jazzar, Rodolphe; Melaimi, Mohand; Bertrand, Guy; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b04640

data_4126085
_publ_section_title
;
 Bicyclic (Alkyl)(amino)carbenes (BICAACs): Stable Carbenes more
 Ambiphilic than CAACs.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b04640
_journal_year                    2017
_chemical_formula_moiety         'C22 H33 N'
_chemical_formula_sum            'C22 H33 N'
_chemical_formula_weight         311.49
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-03-28
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5332)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.7958(10)
_cell_length_b                   16.9330(9)
_cell_length_c                   6.5073(3)
_cell_measurement_reflns_used    5726
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.26
_cell_measurement_theta_min      2.29
_cell_volume                     1960.89(18)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker X8 APEX II'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0286
_diffrn_reflns_av_unetI/netI     0.0283
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -5
_diffrn_reflns_number            12923
_diffrn_reflns_point_group_measured_fraction_full 0.879
_diffrn_reflns_point_group_measured_fraction_max 0.875
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.354
_diffrn_reflns_theta_min         2.289
_exptl_absorpt_coefficient_mu    0.060
_exptl_absorpt_correction_T_max  0.2590
_exptl_absorpt_correction_T_min  0.2193
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0587 before and 0.0432 after correction. The Ratio of minimum to maximum transmission is 0.8467. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.055
_exptl_crystal_description       block
_exptl_crystal_F_000             688
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.125
_refine_diff_density_min         -0.124
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 868 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.2(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     290
_refine_ls_number_reflns         3139
_refine_ls_number_restraints     97
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0497
_refine_ls_R_factor_gt           0.0371
_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^)+(0.0421P)^2^+0.2986P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0832
_refine_ls_wR_factor_ref         0.0893
_reflns_Friedel_coverage         0.599
_reflns_Friedel_fraction_full    0.734
_reflns_Friedel_fraction_max     0.725
_reflns_number_gt                2675
_reflns_number_total             3139
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b04640_si_002.cif
_cod_data_source_block           5a
_cod_database_code               4126085
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.987
_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
 C4-C5 \\sim C6A-C5 \\sim C4A-C5 \\sim C6-C5
 with sigma of 0.01
 C2-C7 \\sim C3-C2 \\sim C2A-C3A \\sim C2A-C7A
 with sigma of 0.01
3. Rigid body (RIGU) restrains
 N1, C5, C6A, C7A, C2A, C22A, C1A, C3A, C9A, C4A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(C3A)=Sof(H3A)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=
 Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=
 Sof(C2A)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(C1A)=1-FVAR(1)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C1)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C7)=Sof(H7A)=
 Sof(H7B)=Sof(C2)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C3)=Sof(H3)=
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C19(H19), C16(H16), C3(H3), C3A(H3A)
5.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C4(H4A,H4B), C7(H7A,H7B), C6A(H6AA,H6AB), C7A(H7AA,H7AB),
 C4A(H4AA,H4AB)
5.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14)
5.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C21(H21A,H21B,H21C), C20(H20A,H20B,H20C), C18(H18A,H18B,
 H18C), C22(H22A,H22B,H22C), C17(H17A,H17B,H17C), C9(H9A,H9B,H9C), C22A(H22D,
 H22E,H22F), C9A(H9AA,H9AB,H9AC)
;
_shelx_res_checksum              26496
_shelx_hkl_checksum              15763
_olex2_submission_special_instructions 'No special instructions were received'