Reversal of enantioselective Friedel-Crafts C3-alkylation of pyrrole by slightly tuning the amide units of N,N'-dioxide ligands
Yulong Zhang; Na Yang; Xiaohua Liu; Jing Guo; Xiying Zhang; Lili Lin; Changwei Hu; Xiaoming Feng; Chem.Commun. 51 (2015) 8432–; doi:10.1039/C4cc10055G

data_7117139
_publ_section_title
;
 Reversal of enantioselective Friedel-Crafts C3-alkylation of pyrrole by
 slightly tuning the amide units of N,N'-dioxide ligands
;
_journal_name_full               Chem.Commun.
_journal_page_first              8432
_journal_paper_doi               10.1039/C4cc10055G
_journal_volume                  51
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C44 H44 N4 Ni O6, 2(B F4), 0.5(O)'
_chemical_formula_sum            'C44 H71 B2 F8 N4 Ni O6.5'
_chemical_formula_weight         992.37
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-01-12
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.09 svn.r3130 for OlexSys, GUI svn.r4987)
;
_audit_update_record
;
2015-01-27 deposited with the CCDC.
2015-02-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.863(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.4359(8)
_cell_length_b                   15.6364(7)
_cell_length_c                   19.2398(14)
_cell_measurement_temperature    143.15
_cell_volume                     4938.4(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS-1997 (Sheldrick, 2008)'
_diffrn_ambient_temperature      143.15
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0724
_diffrn_reflns_av_unetI/netI     0.1711
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            25166
_diffrn_reflns_point_group_measured_fraction_full 0.799
_diffrn_reflns_point_group_measured_fraction_max 0.794
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.886
_exptl_absorpt_coefficient_mu    0.473
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.335
_exptl_crystal_description       prism
_exptl_crystal_F_000             2100
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.090
_refine_diff_density_min         -0.573
_refine_diff_density_rms         0.102
_refine_ls_abs_structure_details
;
 Flack x determined using 1867 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.995
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1191
_refine_ls_number_reflns         16033
_refine_ls_number_restraints     27
_refine_ls_restrained_S_all      0.997
_refine_ls_R_factor_all          0.1860
_refine_ls_R_factor_gt           0.1054
_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^)+(0.1762P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2645
_refine_ls_wR_factor_ref         0.3131
_reflns_Friedel_coverage         0.535
_reflns_Friedel_fraction_full    0.586
_reflns_Friedel_fraction_max     0.576
_reflns_number_gt                8096
_reflns_number_total             16033
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4cc10055g2.cif
_cod_data_source_block           1
_cod_database_code               7117139
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 O12-C88
 1.52 with sigma of 0.02
 O6-C87
 1.52 with sigma of 0.02
3. Rigid bond restraints
 C8, C9
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C82, C83
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C3, C4
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C37, C43
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C11, C12
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O12, C88
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
Uanis(C56) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C87) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5.a Rotating group:
 O7(H7A,H7B)
5.b Ternary CH refined with riding coordinates:
 C9(H9A), C12(H12), C14(H14), C16(H16), C20(H20), C24(H24), C28(H28), C30(H30),
  C40(H40), C43(H43), C52(H52), C55(H55), C57(H57), C63(H63), C67(H67),
 C71(H71), C73(H73), C83(H83), C86(H86)
5.c Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C25(H25A,H25B), C26(H26A,
 H26B), C27(H27A,H27B), C68(H68A,H68B), C69(H69A,H69B), C70(H70A,H70B),
 C72(H72A,H72B)
5.d Aromatic/amide H refined with riding coordinates:
 N4(H4), C34(H34), C35(H35), C36(H36), N9(H9), C45(H45), C46(H46), C47(H47),
 C77(H77), C78(H78), C79(H79)
5.e Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C42(H42A,H42B,
 H42C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C53(H53A,H53B,H53C), C54(H54A,
 H54B,H54C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C)
;
_shelx_res_checksum              43377
_shelx_hkl_checksum              49886
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'