Effects of geometrical isomerism on emissive behaviour of heteroleptic cyclometalated Ir(III) complexes.
Jinsenji, Yoshiki; Takimoto, Kazuyoshi; Yoshida, Jun; Mori, Shigeki; Watanabe, Yutaka; Sato, Hisako; Dalton transactions (Cambridge, England : 2003) 50 (2021) 8506–8511; doi:10.1039/d1dt00783a

data_7707490
_publ_section_title
;
 Effects of geometrical isomerism on emissive behaviour of heteroleptic
 cyclometalated Ir(III) complexes.
;
_journal_issue                   24
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              8506
_journal_page_last               8511
_journal_paper_doi               10.1039/d1dt00783a
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety         '3(C39 H24 Ir N3 O2), 1.5(C H2 Cl2)'
_chemical_formula_sum            'C118.5 H75 Cl3 Ir3 N9 O6'
_chemical_formula_weight         2403.82
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-03-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-03-01 deposited with the CCDC.	2021-05-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.6678(2)
_cell_length_b                   18.2211(4)
_cell_length_c                   46.7278(8)
_cell_measurement_reflns_used    42371
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.9910
_cell_measurement_theta_min      1.7120
_cell_volume                     9082.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection
'CrystalClear-SM Expert 2.1 b46 (Rigaku, 2016)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 7.111
_diffrn_detector_type            'Rigaku Saturn724+ area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -115.00  65.00   0.50    2.00    --  -25.00  45.00   0.00  360
  2  \w   -115.00  65.00   0.50    2.00    --  -25.00  45.00  90.00  360
  3  \w   -115.00  65.00   0.50    2.00    --  -25.00  45.00 180.00  360
  4  \w   -115.00  65.00   0.50    2.00    --  -25.00  45.00 270.00  360
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Rigaku Varimax with Saturn'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1618
_diffrn_reflns_av_unetI/netI     0.1061
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       58
_diffrn_reflns_limit_l_min       -58
_diffrn_reflns_number            117432
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.500
_diffrn_reflns_theta_min         1.720
_exptl_absorpt_coefficient_mu    4.541
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88192
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.758
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             4716
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.688
_refine_diff_density_min         -1.067
_refine_diff_density_rms         0.179
_refine_ls_abs_structure_details
;
 Flack x determined using 5236 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.018(7)
_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     1316
_refine_ls_number_reflns         18848
_refine_ls_number_restraints     2688
_refine_ls_restrained_S_all      0.973
_refine_ls_R_factor_all          0.0821
_refine_ls_R_factor_gt           0.0607
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0283P)^2^+23.8695P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1021
_refine_ls_wR_factor_ref         0.1098
_reflns_Friedel_coverage         0.820
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                15215
_reflns_number_total             18848
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt00783a2.cif
_cod_data_source_block           jinsenji
_cod_depositor_comments
'Adding full bibliography for 7707490--7707494.cif.'
_cod_original_formula_sum        'C118.50 H75 Cl3 Ir3 N9 O6'
_cod_database_code               7707490
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C118-Cl1 = C118-Cl2
 1.79 with sigma of 0.02
 C218-Cl21 = C218-Cl22
 1.79 with sigma of 0.02
 C119-Cl3 = C119-Cl4
 1.79 with sigma of 0.02
 C318-Cl31 = C318-Cl32
 1.79 with sigma of 0.02
 Cl31-Cl32
 2.85 with sigma of 0.04
 Cl3-Cl4
 2.85 with sigma of 0.04
 Cl1-Cl2
 2.85 with sigma of 0.04
 Cl21-Cl22
 2.85 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
N1 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8
\\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
N2 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26: within 2A with sigma of
0.03 and sigma for terminal atoms of 0.06
C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32: within 2A with sigma of
0.03 and sigma for terminal atoms of 0.06
O2 \\sim N3 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim
C39: within 2A with sigma of 0.03 and sigma for terminal atoms of 0.06
N4 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim
C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52: within 2A with sigma of
0.03 and sigma for terminal atoms of 0.06
N5 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim
C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65: within 2A with sigma of
0.03 and sigma for terminal atoms of 0.06
O4 \\sim N6 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim
C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04
N7 \\sim C79 \\sim C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim
C86 \\sim C87 \\sim C88 \\sim C89 \\sim C90 \\sim C91: within 2A with sigma of
0.03 and sigma for terminal atoms of 0.06
N8 \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96 \\sim C97 \\sim C98 \\sim
C99 \\sim C100 \\sim C101 \\sim C102 \\sim C103 \\sim C104: within 2A with
sigma of 0.03 and sigma for terminal atoms of 0.06
O6 \\sim N9 \\sim C111 \\sim C112 \\sim C113 \\sim C114 \\sim C115 \\sim C116
\\sim C117: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
Cl31 \\sim Cl32 \\sim C318: within 2A with sigma of 0.008 and sigma for
terminal atoms of 0.016
Cl1 \\sim Cl2 \\sim C118: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Cl21 \\sim Cl22 \\sim C218: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Cl3 \\sim Cl4 \\sim C119: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04
Uanis(N1) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim
Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7)
\\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(N2) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq,
Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq:
with sigma of 0.03 and sigma for terminal atoms of 0.06
Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq: with sigma of 0.03 and
sigma for terminal atoms of 0.06
Uanis(N3) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(C34)
\\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq,
Uanis(C38) \\sim Ueq, Uanis(C39) \\sim Ueq: with sigma of 0.03 and sigma for
terminal atoms of 0.06
Uanis(N4) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42)
\\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq,
Uanis(C46) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C49)
\\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq:
with sigma of 0.03 and sigma for terminal atoms of 0.06
Uanis(N5) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C55)
\\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq,
Uanis(C59) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C62)
\\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C65) \\sim Ueq:
with sigma of 0.03 and sigma for terminal atoms of 0.06
Uanis(C66) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C69)
\\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(N6) \\sim Ueq,
Uanis(C72) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C74)
\\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C77) \\sim Ueq,
Uanis(C78) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(N7) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C81)
\\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C84) \\sim Ueq,
Uanis(C85) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C88)
\\sim Ueq, Uanis(C89) \\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C91) \\sim Ueq:
with sigma of 0.03 and sigma for terminal atoms of 0.06
Uanis(N8) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C94)
\\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C96) \\sim Ueq, Uanis(C97) \\sim Ueq,
Uanis(C98) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C100) \\sim Ueq, Uanis(C101)
\\sim Ueq, Uanis(C102) \\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C104) \\sim Ueq:
with sigma of 0.03 and sigma for terminal atoms of 0.06
Uanis(N9) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(C112)
\\sim Ueq, Uanis(C113) \\sim Ueq, Uanis(C114) \\sim Ueq, Uanis(C115) \\sim Ueq,
Uanis(C116) \\sim Ueq, Uanis(C117) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C318) \\sim Ueq, Uanis(Cl31) \\sim Ueq, Uanis(Cl32) \\sim Ueq: with sigma
of 0.008 and sigma for terminal atoms of 0.016
Uanis(C118) \\sim Ueq, Uanis(Cl1) \\sim Ueq, : with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C218) \\sim Ueq, Uanis(Cl21) \\sim Ueq, Uanis(Cl22) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl3) \\sim Ueq, Uanis(C119) \\sim Ueq, Uanis(Cl4) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(C118) = Uanis(C218)
4. Rigid body (RIGU) restrains
 N1, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N2, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27, C28, C29, C30, C31, C32
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2, N3, C33, C34, C35, C36, C37, C38, C39
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, C40, C41, C42, C43, C44, C45, C46, C47, C48, C49, C50, C51, C52
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N5, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, C64, C65
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O4, N6, C66, C67, C68, C69, C70, C71, C72, C73, C74, C75, C76, C77, C78
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N7, C79, C80, C81, C82, C83, C84, C85, C86, C87, C88, C89, C90, C91
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N8, C92, C93, C94, C95, C96, C97, C98, C99, C100, C101, C102, C103, C104
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O6, N9, C111, C112, C113, C114, C115, C116, C117
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl31, Cl32, C318
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1, Cl2, C118
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl21, Cl22, C218
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl3, Cl4, C119
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(Cl1)+Sof(Cl2)+Sof(C118)+Sof(H11A)+Sof(H11B)]+1*[Sof(Cl21)+Sof(Cl22)+
 Sof(C218)+Sof(H21A)+Sof(H21B)]+1*[Sof(Cl31)+Sof(Cl32)+Sof(C318)+Sof(H31A)+
 Sof(H31B)]=1 with esd of 0.0005
 Sof(Cl1)=Sof(Cl2)=Sof(C118)=Sof(H11A)=Sof(H11B)=FVAR(1)
 Sof(Cl21)=Sof(Cl22)=Sof(C218)=Sof(H21A)=Sof(H21B)=FVAR(2)
 Sof(Cl31)=Sof(Cl32)=Sof(C318)=Sof(H31A)=Sof(H31B)=FVAR(3)
 Fixed Sof: Cl3(0.5) Cl4(0.5) C119(0.5) H11C(0.5) H11D(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C118(H11A,H11B), C218(H21A,H21B), C318(H31A,H31B), C119(H11C,H11D)
6.b Aromatic/amide H refined with riding coordinates:
 C40(H40), C41(H41), C42(H42), C44(H44), C45(H45), C47(H47), C48(H48),
 C49(H49), C53(H53), C54(H54), C55(H55), C57(H57), C58(H58), C60(H60), C61(H61),
  C62(H62), C67(H67), C68(H68), C69(H69), C70(H70), C74(H74), C75(H75),
 C76(H76), C77(H77), C1(H1), C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9),
 C10(H10), C14(H14), C15(H15), C16(H16), C18(H18), C19(H19), C21(H21), C22(H22),
  C23(H23), C28(H28), C29(H29), C30(H30), C31(H31), C35(H35), C36(H36),
 C37(H37), C38(H38), C79(H79), C80(H80), C81(H81), C83(H83), C84(H84), C86(H86),
  C87(H87), C88(H88), C92(H92), C93(H93), C94(H94), C96(H96), C97(H97),
 C99(H99), C100(H100), C101(H101), C106(H106), C107(H107), C108(H108),
 C109(H109), C113(H113), C114(H114), C115(H115), C116(H116)
;
_shelx_res_checksum              5721
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;