Asymmetric Synthesis of Enantiomerically Pure Mono- and Binuclear Bis(cyclometalated) Iridium(III) Complexes.
Yao, Su-Yang; Ou, Yan-Ling; Ye, Bao-Hui; Inorganic chemistry 55 (2016) 6018–6026; doi:10.1021/acs.inorgchem.6b00527

data_4347725
_publ_section_title
;
 Asymmetric Synthesis of Enantiomerically Pure Mono- and Binuclear
 Bis(cyclometalated) Iridium(III) Complexes.
;
_journal_issue                   12
_journal_name_full               'Inorganic chemistry'
_journal_page_first              6018
_journal_page_last               6026
_journal_paper_doi               10.1021/acs.inorgchem.6b00527
_journal_volume                  55
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         '6(C0.5 H Cl), 2(C30 H22 Ir N6), 2(F6 P)'
_chemical_formula_sum            'C63 H50 Cl6 F12 Ir2 N12 P2'
_chemical_formula_weight         1862.19
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-02-03
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 97.851(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   23.7369(4)
_cell_length_b                   14.0057(2)
_cell_length_c                   20.0866(3)
_cell_measurement_reflns_used    14449
_cell_measurement_temperature    156(3)
_cell_measurement_theta_max      62.2938
_cell_measurement_theta_min      3.6703
_cell_volume                     6615.23(18)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      156(3)
_diffrn_detector_area_resol_mean 16.0855
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -21.00   16.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000   90.0000 37

  2 omega   20.00   49.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000   90.0000 29

  3 omega   35.00   83.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000    0.0000 48

  4 omega   27.00   78.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000 -120.0000 51

  5 omega  -31.00   11.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000 -120.0000 42

  6 omega  -95.00  -19.00   1.0000    5.1200
omega____ theta____ kappa____ phi______ frames
    -      -48.7500  125.0000    0.0000 76

  7 omega   99.00  125.00   1.0000    5.1200
omega____ theta____ kappa____ phi______ frames
    -       48.7500   45.0000    0.0000 26

  8 omega   32.00   58.00   1.0000    5.1200
omega____ theta____ kappa____ phi______ frames
    -       48.7500  -30.0000   30.0000 26

  9 omega   45.00   79.00   1.0000    5.1200
omega____ theta____ kappa____ phi______ frames
    -       48.7500 -125.0000 -150.0000 34

 10 omega   91.00  127.00   1.0000    5.1200
omega____ theta____ kappa____ phi______ frames
    -       48.7500  125.0000   60.0000 36

 11 omega  -19.00    7.00   1.0000    5.1200
omega____ theta____ kappa____ phi______ frames
    -       48.7500  -30.0000   30.0000 26

 12 omega    9.00   59.00   1.0000    5.1200
omega____ theta____ kappa____ phi______ frames
    -       48.7500   45.0000    0.0000 50

 13 omega   74.00  127.00   1.0000    5.1200
omega____ theta____ kappa____ phi______ frames
    -       48.7500  125.0000  -30.0000 53

 14 omega   16.00  120.00   1.0000    5.1200
omega____ theta____ kappa____ phi______ frames
    -       48.7500   61.0000 -150.0000 104

 15 omega   16.00   76.00   1.0000    5.1200
omega____ theta____ kappa____ phi______ frames
    -       48.7500   52.0000  176.0000 60

 16 omega   74.00  127.00   1.0000    5.1200
omega____ theta____ kappa____ phi______ frames
    -       48.7500  125.0000 -150.0000 53

 17 omega   74.00  121.00   1.0000    5.1200
omega____ theta____ kappa____ phi______ frames
    -       48.7500  125.0000    0.0000 47

 18 omega   39.00  114.00   1.0000    5.1200
omega____ theta____ kappa____ phi______ frames
    -       48.7500   61.0000  -90.0000 75

 19 omega  -79.00  -53.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      -92.0000  -77.0000  -90.0000 26

 20 omega -155.00 -129.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      -92.0000  -63.0000  -90.0000 26

 21 omega  -84.00  -59.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      -92.0000  -63.0000  -90.0000 25

 22 omega  -78.00  -52.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      -92.0000  -77.0000  -60.0000 26

 23 omega   59.00   85.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   77.0000 -150.0000 26

 24 omega   64.00  125.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   63.0000   90.0000 61

 25 omega   65.00  171.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   63.0000 -120.0000 106

 26 omega   18.00   59.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -37.0000  150.0000 41

 27 omega   65.00   92.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  138.0000   60.0000 27

 28 omega   17.00   50.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000 -104.0000  -60.0000 33

 29 omega   30.00   56.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -91.0000  -60.0000 26

 30 omega  104.00  161.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   77.0000 -150.0000 57

 31 omega   14.00  121.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -12.0000 -120.0000 107

 32 omega   43.00   75.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000 -104.0000  120.0000 32

 33 omega   38.00   63.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -37.0000   90.0000 25

 34 omega   35.00   61.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000 -104.0000  150.0000 26

 35 omega   35.00   68.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -37.0000  -60.0000 33

 36 omega   49.00   93.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -15.0000   75.0269 44

 37 omega   85.00  133.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  138.0000 -180.0000 48

 38 omega   29.00   61.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -37.0000 -180.0000 32

 39 omega   93.00  118.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -77.0000  150.0000 25

 40 omega   18.00   65.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -77.0000  150.0000 47

 41 omega   58.00  148.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   77.0000  -90.0000 90

 42 omega   28.00  146.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   25.0000   90.0000 118

 43 omega   64.00  137.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   63.0000  -90.0000 73

 44 omega   94.00  120.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -63.0000  120.0000 26

 45 omega   45.00   70.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -37.0000   30.0000 25

 46 omega   43.00   80.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000 -104.0000   30.0000 37

 47 omega   96.00  121.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   77.0000 -120.0000 25

 48 omega   58.00   84.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   77.0000 -120.0000 26

 49 omega   58.00  176.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   77.0000  -60.0000 118

 50 omega   26.00   51.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -63.0000  120.0000 25

 51 omega  131.00  157.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  104.0000 -180.0000 26

 52 omega   58.00   83.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -50.0000 -180.0000 25

 53 omega   75.00  136.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -91.0000 -180.0000 61

 54 omega   66.00   97.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   12.0000   60.0000 31

 55 omega  120.00  167.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -15.0000   75.0269 47

 56 omega   97.00  122.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  104.0000  150.0000 25

 57 omega   91.00  116.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   63.0000  150.0000 25

 58 omega   80.00  105.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   50.0000  -90.0000 25

 59 omega  133.00  159.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   14.0000   39.6018 26

 60 omega   92.00  118.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -91.0000  -60.0000 26

 61 omega   79.00  105.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000  -12.0000  -30.0000 26

 62 omega   42.00   67.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       97.5000   14.0000   39.6018 25
;
_diffrn_measurement_device_type  'multiwire proportional'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0442989000
_diffrn_orient_matrix_UB_12      -0.0163060000
_diffrn_orient_matrix_UB_13      -0.0624670000
_diffrn_orient_matrix_UB_21      0.0332376000
_diffrn_orient_matrix_UB_22      0.0678108000
_diffrn_orient_matrix_UB_23      -0.0408473000
_diffrn_orient_matrix_UB_31      0.0349989000
_diffrn_orient_matrix_UB_32      -0.0850420000
_diffrn_orient_matrix_UB_33      -0.0205889000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0573
_diffrn_reflns_av_unetI/netI     0.0587
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            27745
_diffrn_reflns_theta_full        62.38
_diffrn_reflns_theta_max         62.38
_diffrn_reflns_theta_min         3.67
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.111
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.02872
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.870
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3624
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         2.955
_refine_diff_density_min         -2.503
_refine_diff_density_rms         0.215
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.003(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     936
_refine_ls_number_reflns         10424
_refine_ls_number_restraints     183
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0774
_refine_ls_R_factor_gt           0.0764
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1711P)^2^+6.5433P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1957
_refine_ls_wR_factor_ref         0.1986
_reflns_number_gt                10095
_reflns_number_total             10424
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic6b00527_si_003.cif
_cod_data_source_block           l-dpm
_cod_original_sg_symbol_H-M      'C 2'
_cod_database_code               4347725
_chemical_oxdiff_formula         'C11 H10 S O2'
_reflns_odcompleteness_completeness 88.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Cl2-Cl3 = Cl2'-Cl3' = Cl4-Cl5 = Cl4'-Cl5' = Cl6-Cl7
 2.9 with sigma of 0.002
 C63-Cl4 = C63-Cl5 = C63'-Cl4' = C63'-Cl5' = C64-Cl6 = C64-Cl7
 1.75 with sigma of 0.002
 C61-Cl1 = C62-Cl2 = C62-Cl3 = C62'-Cl2' = C62'-Cl3'
 1.75 with sigma of 0.002
3. Rigid bond restraints
 C64, Cl6, Cl7
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C61, C62, C62', C63, C63', Cl1, Cl2, Cl3, Cl2', Cl3', Cl4, Cl5, Cl4', Cl5'
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
C64 \\sim Cl6 \\sim Cl7: within 1.7A with sigma of 0.005 and sigma for terminal
atoms of 0.01
C61 \\sim C62 \\sim C62' \\sim C63 \\sim C63' \\sim Cl1 \\sim Cl2 \\sim Cl3
\\sim Cl2' \\sim Cl3' \\sim Cl4 \\sim Cl5 \\sim Cl4' \\sim Cl5': within 1.7A
with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C64) \\sim Ueq, Uanis(Cl6) \\sim Ueq, Uanis(Cl7) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C61) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C62') \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C63') \\sim Ueq, Uanis(Cl1) \\sim Ueq, Uanis(Cl2) \\sim Ueq,
Uanis(Cl3) \\sim Ueq, Uanis(Cl2') \\sim Ueq, Uanis(Cl3') \\sim Ueq, Uanis(Cl4)
\\sim Ueq, Uanis(Cl5) \\sim Ueq, Uanis(Cl4') \\sim Ueq, Uanis(Cl5') \\sim Ueq:
with sigma of 0.005 and sigma for terminal atoms of 0.01
5. Others
 Sof(C62')=Sof(H62C)=Sof(H62D)=Sof(Cl2')=Sof(Cl3')=1-FVAR(1)
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(Cl2)=Sof(Cl3)=FVAR(1)
 Sof(C63')=Sof(H63C)=Sof(H63D)=Sof(Cl4')=Sof(Cl5')=1-FVAR(2)
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(Cl4)=Sof(Cl5)=FVAR(2)
 Fixed Sof: H61A(0.5) H61B(0.5) Cl6(0.5) Cl7(0.5) C64(0.5) H64A(0.5) H64B(0.5)
6.a Riding coordinates:
 C62(H62A,H62B), C62'(H62C,H62D), C63(H63A,H63B), C63'(H63C,H63D)
6.b Secondary CH2 refined with riding coordinates:
 C61(H61A,H61B), C64(H64A,H64B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C6(H6), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12),
 C13(H13), C16(H16), C17(H17), C18(H18), C19(H19), C21(H21), C22(H22), C23(H23),
  C24(H24), C27(H27), C28(H28), C29(H29), C30(H30), C32(H32), C33(H33),
 C34(H34), C36(H36), C37(H37), C38(H38), C40(H40), C41(H41), C42(H42), C43(H43),
  C46(H46), C47(H47), C48(H48), C49(H49), C51(H51), C52(H52), C53(H53),
 C54(H54), C57(H57), C58(H58), C59(H59), C60(H60)
;
_olex2_submission_special_instructions 'No special instructions were received'