Pyridylpyrazole N^N ligands combined with sulfonyl-functionalised cyclometalating ligands for blue-emitting iridium(iii) complexes and solution-processable PhOLEDs
Benjamin, Helen; Fox, Mark A.; Batsanov, Andrei S.; Al-Attar, Hameed A.; Li, Chensen; Ren, Zhongjie; Monkman, Andrew P.; Bryce, Martin R.; Dalton Trans.  (2017) –; doi:10.1039/C7DT02289A

data_7043920
_publ_section_title
;
 Pyridylpyrazole N^N ligands combined with sulfonyl-functionalised
 cyclometalating ligands for blue-emitting iridium(iii) complexes and
 solution-processable PhOLEDs
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT02289A
_journal_year                    2017
_chemical_formula_moiety         'C74 H65 F5 Ir N5 O6 S2,3(C H2 Cl2)'
_chemical_formula_sum            'C77 H71 Cl6 F5 Ir N5 O6 S2'
_chemical_formula_weight         1726.40
_chemical_properties_physical    ', Air-sensitive'
_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_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-07-20
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2016.07.08 svn.r3312 for OlexSys, GUI svn.r5203)
;
_audit_update_record
;
2016-07-20 deposited with the CCDC.
2017-07-27 downloaded from the CCDC.
;
_cell_angle_alpha                67.984(2)
_cell_angle_beta                 86.202(2)
_cell_angle_gamma                69.653(2)
_cell_formula_units_Z            2
_cell_length_a                   14.2093(9)
_cell_length_b                   18.2151(11)
_cell_length_c                   18.7800(11)
_cell_measurement_reflns_used    9727
_cell_measurement_temperature    120
_cell_measurement_theta_max      24.64
_cell_measurement_theta_min      2.39
_cell_volume                     4213.6(5)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v.2013.4_1 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS 2013/1 (Sheldrick, 2008)'
_diffrn_ambient_temperature      120
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device       '3-circle area detector diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'focusing mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0479
_diffrn_reflns_av_unetI/netI     0.0547
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            57359
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.145
_diffrn_reflns_theta_max         25.145
_diffrn_reflns_theta_min         2.041
_diffrn_source                   'ImuS microsource'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.885
_exptl_absorpt_correction_T_max  0.8012
_exptl_absorpt_correction_T_min  0.6606
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1134 before and 0.0641 after correction.
The Ratio of minimum to maximum transmission is 0.8245.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.361
_exptl_crystal_description       trapetsoid
_exptl_crystal_F_000             1744
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane layered over DCM solution'
_exptl_crystal_size_max          0.329
_exptl_crystal_size_mid          0.212
_exptl_crystal_size_min          0.14
_refine_diff_density_max         3.822
_refine_diff_density_min         -2.201
_refine_diff_density_rms         0.143
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     899
_refine_ls_number_reflns         14940
_refine_ls_number_restraints     906
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0954
_refine_ls_R_factor_gt           0.0686
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0890P)^2^+33.7140P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1776
_refine_ls_wR_factor_ref         0.2012
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11521
_reflns_number_total             14940
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt02289a2.cif
_cod_data_source_block           16srv210
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_radiation_probe' value 'X-ray' changed to 'x-ray' according
to
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 
;
_cod_database_code               7043920
_shelx_estimated_absorpt_t_max   0.778
_shelx_estimated_absorpt_t_min   0.576
_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
 F1B-C1 = C1-F3B
 1.35 with sigma of 0.02
 S1-C43
 1.75 with sigma of 0.02
 F1B-F3B
 2.238 with sigma of 0.04
 Cl4-C76 \\sim Cl3-C76
 with sigma of 0.02
 C39-C42 \\sim C40-C35
 with sigma of 0.02
 F1-C1 \\sim F3B-C1 \\sim F2-C1 \\sim F3-C1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F2B) = Uanis(F2)
Uanis(F1) = Uanis(F1B)
Uanis(F3B) = Uanis(F3)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: F1(0.8) F2(0.8) F3(0.8) F1B(0.2) F2B(0.2) F3B(0.2) Cl3(0.8)
 Cl4(0.8) C76(0.8) H76A(0.8) H76B(0.8) Cl1(0.7) Cl2B(0.2) Cl2A(0.5) C75(0.7)
 H75A(0.7) H75B(0.7)
6.a Secondary CH2 refined with riding coordinates:
 C76(H76A,H76B), C75(H75A,H75B)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C8(H8), C9(H9), C11(H11), C17(H17), C19(H19), C20(H20),
 C23(H23), C29(H29), C31(H31), C32(H32), C52(H52), C54(H54), C60(H60), C61(H61),
  C63(H63), C64(H64), C68(H68), C70(H70), C36(H36), C38(H38), C48(H48),
 C47(H47), C45(H45), C44(H44)
6.c Fitted hexagon refined as free rotating group:
 C39(C34,C35,C36,C37,C38), C43(C48,C47,C46,C45,C44)
6.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C33(H33A,H33B,H33C), C56(H56A,H56B,H56C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C65(H65A,H65B,H65C), C72(H72A,H72B,H72C), C73(H73A,
 H73B,H73C), C74(H74A,H74B,H74C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C),
 C42(H42A,H42B,H42C), C49(H49A,H49B,H49C)
;
_shelx_fab_checksum              52866
_shelx_shelxl_version_number     2014/7
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_submission_special_instructions 'No special instructions were received'