2-(Thienyl)quinoxaline derivatives and their application in Ir(III) complexes yielding tuneable deep red emitters.
Fitzgerald, Sophie A.; Payce, Ellie N.; Horton, Peter N.; Coles, Simon J.; Pope, Simon J. A.; Dalton transactions (Cambridge, England : 2003)  (2023) –; doi:10.1039/d3dt02193a

data_7714307
_publ_section_title
;
 2-(Thienyl)quinoxaline derivatives and their application in Ir(III)
 complexes yielding tuneable deep red emitters.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d3dt02193a
_journal_year                    2023
_chemical_formula_moiety         'C38 H30 Ir N6 S2, F6 P'
_chemical_formula_sum            'C38 H30 F6 Ir N6 P S2'
_chemical_formula_weight         972.014
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     dual
_audit_creation_date             2023-01-11
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-06-16 deposited with the CCDC.	2023-10-19 downloaded from the CCDC.
;
_cell_angle_alpha                84.601(3)
_cell_angle_beta                 75.930(3)
_cell_angle_gamma                70.807(3)
_cell_formula_units_Z            2
_cell_length_a                   11.7348(5)
_cell_length_b                   12.2893(4)
_cell_length_c                   13.6241(4)
_cell_measurement_reflns_used    12402
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.2060
_cell_measurement_theta_min      2.2980
_cell_volume                     1799.67(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.70a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.70a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.70a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'hybrid pixel array detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000HE'
_diffrn_measured_fraction_theta_full 0.9983
_diffrn_measured_fraction_theta_max 0.9974
_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    -55.00   0.00   0.50   80.00    --  -10.36 -58.00 -18.00  110
  2  \w    -22.00  62.00   0.50   80.00    --  -10.36  58.00 121.00  168
  3  \w    -56.00  26.00   0.50   80.00    --   13.80 -58.00 -18.00  164
  4  \w      3.00  61.00   0.50   80.00    --   13.80  58.00 121.00  116
  5  \w    -30.00  24.00   0.50   80.00    --  -10.36  77.00-180.00  108
  6  \w    -87.00 -17.00   0.50   80.00    --  -10.36 -19.00-150.00  140
  7  \w    -18.00  34.00   0.50   80.00    --   13.80 -77.00-150.00  104
  8  \w    -64.00 -17.00   0.50   80.00    --   13.80 -19.00  60.00   94
  9  \w      2.00  62.00   0.50   80.00    --   13.80  57.00-180.00  120
 10  \w      2.00  62.00   0.50   80.00    --   13.80  57.00 -30.00  120
 11  \w      2.00  62.00   0.50   80.00    --   13.80  57.00  30.00  120
 12  \w    -18.00  34.00   0.50   80.00    --   13.80 -77.00 120.00  104
 13  \w      2.00  62.00   0.50   80.00    --   13.80  57.00 -90.00  120
 14  \w    -18.00  34.00   0.50   80.00    --   13.80 -77.00 -60.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, UG2 \k goniometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0570447000
_diffrn_orient_matrix_UB_12      -0.0093104000
_diffrn_orient_matrix_UB_13      0.0235346000
_diffrn_orient_matrix_UB_21      -0.0177364000
_diffrn_orient_matrix_UB_22      0.0504545000
_diffrn_orient_matrix_UB_23      0.0288130000
_diffrn_orient_matrix_UB_31      -0.0273361000
_diffrn_orient_matrix_UB_32      0.0332181000
_diffrn_orient_matrix_UB_33      -0.0386953000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, Arc)Sec VHF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0810
_diffrn_reflns_av_unetI/netI     0.0735
_diffrn_reflns_Laue_measured_fraction_full 0.9983
_diffrn_reflns_Laue_measured_fraction_max 0.9974
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            41819
_diffrn_reflns_point_group_measured_fraction_full 0.9983
_diffrn_reflns_point_group_measured_fraction_max 0.9974
_diffrn_reflns_theta_full        25.2425
_diffrn_reflns_theta_max         28.70
_diffrn_reflns_theta_min         2.13
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku FRE+'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    3.940
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73698
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.70a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.794
_exptl_crystal_description       block
_exptl_crystal_F_000             955.495
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and ether'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.1841
_refine_diff_density_min         -0.9983
_refine_diff_density_rms         0.2548
_refine_ls_d_res_high            0.7400
_refine_ls_d_res_low             9.5572
_refine_ls_goodness_of_fit_ref   1.0674
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    90
_refine_ls_number_parameters     828
_refine_ls_number_reflns         9285
_refine_ls_number_restraints     2473
_refine_ls_restrained_S_all      0.9390
_refine_ls_R_factor_all          0.0913
_refine_ls_R_factor_gt           0.0430
_refine_ls_shift/su_max          -0.0008
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0422P)^2^+0.8148P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0870
_refine_ls_wR_factor_ref         0.1020
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              15
_reflns_limit_h_min              -15
_reflns_limit_k_max              16
_reflns_limit_k_min              -16
_reflns_limit_l_max              18
_reflns_limit_l_min              0
_reflns_number_gt                5963
_reflns_number_total             9285
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d3dt02193a2.cif
_cod_data_source_block           Ir_L6
_cod_database_code               7714307
_chemical_oxdiff_formula         'C38 H30 Ir N6 S2 P F6'
_chemical_oxdiff_usercomment     SAF063
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N21-C24 \\sim N21A-C24A
 with sigma of 0.04
 Ir1-N21 \\sim Ir1-N21A
 with sigma of 0.02
 Ir1-C23 \\sim Ir1-C23A
 with sigma of 0.02
 C21-C24 \\sim C21A-C24A
 with sigma of 0.04
 S21-C21 \\sim S21A-C21A
 with sigma of 0.02
 S21-C24 \\sim S21A-C24A
 with sigma of 0.02
 N22-C25 \\sim N22A-C25A
 with sigma of 0.04
 C29-C31 \\sim C29A-C31A
 with sigma of 0.04
 C23-C25 \\sim C23A-C25A
 with sigma of 0.04
 N21-C28 \\sim N21A-C28A
 with sigma of 0.02
 C27-C29 \\sim C27A-C29A
 with sigma of 0.04
 N22-C26 \\sim N22A-C26A
 with sigma of 0.02
 N21-C25 \\sim N21A-C25A
 with sigma of 0.02
 N22-C27 \\sim N22A-C27A
 with sigma of 0.02
 N21-C27 \\sim N21A-C27A
 with sigma of 0.04
 C31-C33 \\sim C31A-C33A
 with sigma of 0.04
 N22-C32 \\sim N22A-C32A
 with sigma of 0.04
 C22-C23 \\sim C22A-C23A
 with sigma of 0.02
 C23-C24 \\sim C23A-C24A
 with sigma of 0.02
 C24-C26 \\sim C24A-C26A
 with sigma of 0.04
 C28-C30 \\sim C28A-C30A
 with sigma of 0.04
 C24-C25 \\sim C24A-C25A
 with sigma of 0.02
 C30-C32 \\sim C30A-C32A
 with sigma of 0.04
 C21-C22 \\sim C21A-C22A
 with sigma of 0.02
 C25-C26 \\sim C25A-C26A
 with sigma of 0.02
 N21-C26 \\sim N21A-C26A
 with sigma of 0.04
 C27-C28 \\sim C27A-C28A
 with sigma of 0.02
 N21-C29 \\sim N21A-C29A
 with sigma of 0.04
 C27-C32 \\sim C27A-C32A
 with sigma of 0.02
 N22-C28 \\sim N22A-C28A
 with sigma of 0.04
 C28-C29 \\sim C28A-C29A
 with sigma of 0.02
 C21-C23 \\sim C21A-C23A
 with sigma of 0.04
 C29-C30 \\sim C29A-C30A
 with sigma of 0.02
 C22-C24 \\sim C22A-C24A
 with sigma of 0.04
 C30-C31 \\sim C30A-C31A
 with sigma of 0.02
 C30-C33 \\sim C30A-C33A
 with sigma of 0.02
 C31-C32 \\sim C31A-C32A
 with sigma of 0.02
 C31-C34 \\sim C31A-C34A
 with sigma of 0.02
 C25-C28 \\sim C25A-C28A
 with sigma of 0.04
 Ir1-C22 \\sim Ir1-C22A
 with sigma of 0.04
 C26-C27 \\sim C26A-C27A
 with sigma of 0.04
 Ir1-C24 \\sim Ir1-C24A
 with sigma of 0.04
 C27-C31 \\sim C27A-C31A
 with sigma of 0.04
 Ir1-C25 \\sim Ir1-C25A
 with sigma of 0.04
 C28-C32 \\sim C28A-C32A
 with sigma of 0.04
 Ir1-C28 \\sim Ir1-C28A
 with sigma of 0.04
 C29-C33 \\sim C29A-C33A
 with sigma of 0.04
 S21-C22 \\sim S21A-C22A
 with sigma of 0.04
 C30-C34 \\sim C30A-C34A
 with sigma of 0.04
 S21-C23 \\sim S21A-C23A
 with sigma of 0.04
 C32-C34 \\sim C32A-C34A
 with sigma of 0.04
 S21-C25 \\sim S21A-C25A
 with sigma of 0.04
 C7-C11 \\sim C7A-C11A
 with sigma of 0.04
 C8-C12 \\sim C8A-C12A
 with sigma of 0.04
 C2-C4 \\sim C2A-C4A
 with sigma of 0.04
 C9-C11 \\sim C9A-C11A
 with sigma of 0.04
 S1-C2 \\sim S1A-C2A
 with sigma of 0.04
 C10-C12 \\sim C10A-C12A
 with sigma of 0.04
 N2-C8 \\sim N2A-C8A
 with sigma of 0.04
 N1-C6 \\sim N1A-C6A
 with sigma of 0.04
 C3-C5 \\sim C3A-C5A
 with sigma of 0.04
 Ir1-C5 \\sim Ir1-C5A
 with sigma of 0.04
 N2-C6 \\sim N2A-C6A
 with sigma of 0.02
 S1-C5 \\sim S1A-C5A
 with sigma of 0.04
 N2-C7 \\sim N2A-C7A
 with sigma of 0.02
 C11-C13 \\sim C11A-C13A
 with sigma of 0.04
 C1-C2 \\sim C1A-C2A
 with sigma of 0.02
 C1-C3 \\sim C1A-C3A
 with sigma of 0.04
 C2-C3 \\sim C2A-C3A
 with sigma of 0.02
 C3-C4 \\sim C3A-C4A
 with sigma of 0.02
 C6-C7 \\sim C6A-C7A
 with sigma of 0.04
 Ir1-C8 \\sim Ir1-C8A
 with sigma of 0.04
 S1-C3 \\sim S1A-C3A
 with sigma of 0.04
 C4-C5 \\sim C4A-C5A
 with sigma of 0.02
 N1-C4 \\sim N1A-C4A
 with sigma of 0.04
 C5-C6 \\sim C5A-C6A
 with sigma of 0.02
 N1-C7 \\sim N1A-C7A
 with sigma of 0.04
 C7-C8 \\sim C7A-C8A
 with sigma of 0.02
 N2-C5 \\sim N2A-C5A
 with sigma of 0.04
 C7-C12 \\sim C7A-C12A
 with sigma of 0.02
 N2-C12 \\sim N2A-C12A
 with sigma of 0.04
 C8-C9 \\sim C8A-C9A
 with sigma of 0.02
 C1-C4 \\sim C1A-C4A
 with sigma of 0.04
 C9-C10 \\sim C9A-C10A
 with sigma of 0.02
 C10-C11 \\sim C10A-C11A
 with sigma of 0.02
 C10-C13 \\sim C10A-C13A
 with sigma of 0.02
 C4-C6 \\sim C4A-C6A
 with sigma of 0.04
 C11-C12 \\sim C11A-C12A
 with sigma of 0.02
 C11-C14 \\sim C11A-C14A
 with sigma of 0.02
 C5-C8 \\sim C5A-C8A
 with sigma of 0.04
 Ir1-C2 \\sim Ir1-C2A
 with sigma of 0.04
 Ir1-C4 \\sim Ir1-C4A
 with sigma of 0.04
 C7-C9 \\sim C7A-C9A
 with sigma of 0.04
 Ir1-N1 \\sim Ir1-N1A
 with sigma of 0.02
 C8-C10 \\sim C8A-C10A
 with sigma of 0.04
 Ir1-C3 \\sim Ir1-C3A
 with sigma of 0.02
 S1-C1 \\sim S1A-C1A
 with sigma of 0.02
 C9-C13 \\sim C9A-C13A
 with sigma of 0.04
 S1-C4 \\sim S1A-C4A
 with sigma of 0.02
 C10-C14 \\sim C10A-C14A
 with sigma of 0.04
 N1-C5 \\sim N1A-C5A
 with sigma of 0.02
 C12-C14 \\sim C12A-C14A
 with sigma of 0.04
 N1-C8 \\sim N1A-C8A
 with sigma of 0.02
 N1-C9 \\sim N1A-C9A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Ir1 \\sim C23A \\sim C3 \\sim N1 \\sim C23 \\sim N21A \\sim C3A \\sim N1A \\sim
N41 \\sim N42 \\sim N21 \\sim C22A \\sim C24A \\sim C2 \\sim C4 \\sim C5 \\sim
C8 \\sim C22 \\sim C24 \\sim C25A \\sim C28A \\sim C2A \\sim C4A \\sim C5A
\\sim C8A \\sim C41 \\sim C45 \\sim C46 \\sim C50 \\sim C25 \\sim C28 \\sim
C21A \\sim S21A \\sim C1 \\sim S1 \\sim C6 \\sim C9 \\sim C7 \\sim C21 \\sim
S21 \\sim C26A \\sim C27A \\sim C29A \\sim C1A \\sim S1A \\sim C6A \\sim C7A
\\sim C9A \\sim C42 \\sim C44 \\sim C47 \\sim C49 \\sim C26 \\sim C27 \\sim C29
\\sim N2 \\sim C10 \\sim C12 \\sim N22A \\sim C32A \\sim C30A \\sim N2A \\sim
C12A \\sim C10A \\sim C43 \\sim C48 \\sim N22 \\sim C32 \\sim C30 \\sim C11
\\sim C13 \\sim C31A \\sim C33A \\sim C11A \\sim C13A \\sim C31 \\sim C33 \\sim
C14 \\sim C34A \\sim C14A \\sim C34 \\sim P51 \\sim F51 \\sim F52 \\sim F53
\\sim F54 \\sim F55 \\sim F56: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 Ir1, C23A, C3, N1, C23, N21A, C3A, N1A, N41, N42, N21, C22A, C24A, C2, C4, C5,
  C8, C22, C24, C25A, C28A, C2A, C4A, C5A, C8A, C41, C45, C46, C50, C25, C28,
 C21A, S21A, C1, S1, C6, C9, C7, C21, S21, C26A, C27A, C29A, C1A, S1A, C6A, C7A,
  C9A, C42, C44, C47, C49, C26, C27, C29, N2, C10, C12, N22A, C32A, C30A, N2A,
 C12A, C10A, C43, C48, N22, C32, C30, C11, C13, C31A, C33A, C11A, C13A, C31,
 C33, C14, C34A, C14A, C34, F52, P51, F51, F53, F54, F55, F56
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(S21A)=Sof(N21A)=Sof(N22A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=
 Sof(C23A)=Sof(C24A)=Sof(C25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(C28A)=
 Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(C31A)=Sof(C32A)=Sof(H32A)=Sof(C34A)=
 Sof(H34d)=Sof(H34e)=Sof(H34f)=Sof(C33A)=Sof(H33d)=Sof(H33e)=Sof(H33f)=1-FVAR(1)
 Sof(S21)=Sof(N21)=Sof(N22)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=Sof(C23)=
 Sof(C24)=Sof(C25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(C28)=Sof(C29)=Sof(H29)=
 Sof(C30)=Sof(C31)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33a)=Sof(H33b)=Sof(H33c)=
 Sof(C34)=Sof(H34a)=Sof(H34b)=Sof(H34c)=FVAR(1)
 Sof(S1A)=Sof(N1A)=Sof(N2A)=Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=
 Sof(C4A)=Sof(C5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(C8A)=Sof(C9A)=Sof(H9A)=
 Sof(C10A)=Sof(C11A)=Sof(C12A)=Sof(H12A)=Sof(C14A)=Sof(H14d)=Sof(H14e)=
 Sof(H14f)=Sof(C13A)=Sof(H13d)=Sof(H13e)=Sof(H13f)=1-FVAR(2)
 Sof(S1)=Sof(N1)=Sof(N2)=Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(C4)=
 Sof(C5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(C8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(C11)=
 Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13a)=Sof(H13b)=Sof(H13c)=Sof(C14)=Sof(H14a)=
 Sof(H14b)=Sof(H14c)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C6(H6), C9(H9), C12(H12), C21(H21), C22(H22), C26(H26),
 C29(H29), C32(H32), C41(H41), C42(H42), C43(H43), C44(H44), C47(H47), C48(H48),
  C49(H49), C50(H50), C21A(H21A), C22A(H22A), C26A(H26A), C29A(H29A),
 C32A(H32A), C1A(H1A), C2A(H2A), C6A(H6A), C9A(H9A), C12A(H12A)
6.b Idealised Me refined as rotating group:
 C13(H13a,H13b,H13c), C14(H14a,H14b,H14c), C33(H33a,H33b,H33c), C34(H34a,H34b,
 H34c), C34A(H34d,H34e,H34f), C33A(H33d,H33e,H33f), C14A(H14d,H14e,H14f),
 C13A(H13d,H13e,H13f)
;
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in oil'
_olex2_submission_original_sample_id SAF063
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 3.779
_oxdiff_exptl_absorpt_empirical_full_min 0.227