Flexible Steric Bulky Bis(Imino)acenaphthene (BIAN)-Supported N-Heterocyclic Carbene Palladium Precatalysts: Catalytic Application in Buchwald-Hartwig Amination in Air.
Lan, Xiao-Bing; Li, Yinwu; Li, Yan-Fang; Shen, Dong-Sheng; Ke, Zhuofeng; Liu, Feng-Shou; The Journal of organic chemistry 82 (2017) 2914–2925; doi:10.1021/acs.joc.6b02867

data_4032422
_publ_section_title
;
 Flexible Steric Bulky Bis(Imino)acenaphthene (BIAN)-Supported
 N-Heterocyclic Carbene Palladium Precatalysts: Catalytic Application in
 Buchwald-Hartwig Amination in Air.
;
_journal_issue                   6
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              2914
_journal_page_last               2925
_journal_paper_doi               10.1021/acs.joc.6b02867
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C63 H55 Cl2 N3 O Pd, 3(O), 0.88(C H2 Cl2)'
_chemical_formula_sum            'C63.88 H56.76 Cl3.76 N3 O4 Pd'
_chemical_formula_weight         1170.13
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-05-12
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 96.512(5)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   19.6310(15)
_cell_length_b                   12.8061(10)
_cell_length_c                   23.818(2)
_cell_measurement_reflns_used    9914
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      23.50
_cell_measurement_theta_min      2.34
_cell_volume                     5949.1(8)
_computing_cell_refinement       'SAINT v7.34A (Bruker, 200?)'
_computing_data_reduction        'SAINT v7.34A (Bruker, 200?)'
_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    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'CCD area detector'
_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  0.0729
_diffrn_reflns_av_unetI/netI     0.0558
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            90984
_diffrn_reflns_theta_full        27.62
_diffrn_reflns_theta_max         27.62
_diffrn_reflns_theta_min         1.72
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.529
_exptl_absorpt_correction_T_max  0.9487
_exptl_absorpt_correction_T_min  0.810891
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2004/1 (Bruker,2004) was used for absorption correction.
R(int) was 0.0734 before and 0.0437 after correction.
The Ratio of minimum to maximum transmission is 0.8109.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2412
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.877
_refine_diff_density_min         -0.522
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     718
_refine_ls_number_reflns         13614
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.1078
_refine_ls_R_factor_gt           0.0584
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0880P)^2^+4.5678P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1492
_refine_ls_wR_factor_ref         0.1790
_reflns_number_gt                8316
_reflns_number_total             13614
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo6b02867_si_002.cif
_cod_data_source_block           C4
_cod_original_cell_volume        5949.2(8)
_cod_database_code               4032422
_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
 C64B-Cl3B = C64A-Cl4B
 1.8 with sigma of 0.005
 Cl3B-Cl4B
 2.9 with sigma of 0.005
 C64A-Cl3A = C64A-Cl4A
 1.8 with sigma of 0.005
 Cl3A-Cl4A
 2.9 with sigma of 0.005
3. Rigid bond restraints
 O3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O3: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(O3) \\sim Ueq: with sigma of 5 and sigma for terminal atoms of 10
Uanis(O3) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
5. Others
 Sof(C64A)=Sof(H64A)=Sof(H64B)=Sof(Cl3A)=Sof(Cl4A)=Sof(C64B)=Sof(H64C)=
 Sof(H64D)=Sof(Cl3B)=Sof(Cl4B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C34(H34), C16(H16), C49(H49), C56(H56)
6.b Secondary CH2 refined with riding coordinates:
 C64A(H64A,H64B), C64B(H64C,H64D)
6.c Aromatic/amide H refined with riding coordinates:
 C32(H32), C29(H29), C10(H10), C36(H36), C42(H42), C28(H28), C40(H40),
 C18(H18), C4(H4), C43(H43), C9(H9), C27(H27), C53(H53), C6(H6), C22(H22),
 C52(H52), C24(H24), C8(H8), C5(H5), C39(H39), C54(H54), C26(H26), C25(H25),
 C62(H62), C45(H45), C63(H63), C38(H38), C37(H37), C59(H59), C46(H46), C44(H44),
  C19(H19), C20(H20), C21(H21), C60(H60), C61(H61)
6.d Idealised Me refined as rotating group:
 C51(H51A,H51B,H51C), C50(H50A,H50B,H50C), C57(H57A,H57B,H57C), C58(H58A,H58B,
 H58C), C31(H31A,H31B,H31C)
;
_olex2_submission_special_instructions 'No special instructions were received'