Fluorescence in rhoda- and iridacyclopentadienes neglecting the spin-orbit coupling of the heavy atom: the ligand dominates.
Steffen, Andreas; Costuas, Karine; Boucekkine, Abdou; Thibault, Marie-Hélène; Beeby, Andrew; Batsanov, Andrei S.; Charaf-Eddin, Azzam; Jacquemin, Denis; Halet, Jean-François; Marder, Todd B.; Inorganic chemistry 53 (2014) 7055–7069; doi:10.1021/ic501115k

data_4338824
_publ_section_title
;
 Fluorescence in rhoda- and iridacyclopentadienes neglecting the
 spin-orbit coupling of the heavy atom: the ligand dominates.
;
_journal_issue                   13
_journal_name_full               'Inorganic chemistry'
_journal_page_first              7055
_journal_page_last               7069
_journal_paper_doi               10.1021/ic501115k
_journal_volume                  53
_journal_year                    2014
_chemical_formula_moiety         'C46 H67 Cl Ir O4 P3'
_chemical_formula_sum            'C46 H67 Cl Ir O4 P3'
_chemical_formula_weight         1004.55
_chemical_name_systematic
; mer,cis-[tris(triethylphosphine)chlorido-2,5-bis(p-carbomethoxy-phenylethynyl)-
cyclohexa[1',2':3,4]iridacyclopenta-2,4-diene]
;
_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   mixed
_audit_creation_date             2013-07-24
_audit_creation_method
;
Olex2 1.2-alpha (compiled 2013.07.19 svn.r0, GUI svn.r4539)
;
_cell_angle_alpha                91.51(4)
_cell_angle_beta                 99.28(4)
_cell_angle_gamma                107.89(4)
_cell_formula_units_Z            2
_cell_length_a                   10.657(3)
_cell_length_b                   12.944(3)
_cell_length_c                   17.831(5)
_cell_measurement_reflns_used    5508
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      26.47
_cell_measurement_theta_min      2.16
_cell_volume                     2302.6(12)
_computing_cell_refinement       'SAINT version 7.46A (Bruker, 2007)'
_computing_data_collection       'SMART version 5.625 (Bruker, 2001)'
_computing_data_reduction        'SAINT version 7.46A (Bruker, 2007)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXTL-2013/2 miulti-CPU version, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
'SHELXS, G.M. Sheldrick, Acta Cryst. (2008). A64, 112-122'
_diffrn_ambient_temperature      120.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0860
_diffrn_reflns_av_unetI/netI     0.0815
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            40930
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.072
_diffrn_reflns_theta_min         1.659
_exptl_absorpt_coefficient_mu    3.102
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.5922
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2009/1 (Bruker,2010) was used for absorption correction.
wR2(int) was 0.0666 before and 0.0519 after correction.
The Ratio of minimum to maximum transmission is 0.7938.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_density_diffrn    1.449
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1028
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.230
_refine_diff_density_min         -1.438
_refine_diff_density_rms         0.136
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.977
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     506
_refine_ls_number_reflns         13468
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      0.986
_refine_ls_R_factor_all          0.0607
_refine_ls_R_factor_gt           0.0422
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0430P)^2^] where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0940
_refine_ls_wR_factor_ref         0.0997
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10430
_reflns_number_total             13468
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic501115k_si_003.cif
_cod_data_source_block           3
_cod_depositor_comments          'Adding full bibliography for 4338824.cif.'
_cod_original_cell_volume        2302.5(11)
_cod_database_code               4338824
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 P3-C17 \\sim P3-C17' \\sim P3-C15' \\sim P3-C15 \\sim P1-C5' \\sim P1-C5
 with sigma of 0.005
 C24-C23' \\sim C23'-C22 \\sim C24-C23 \\sim C23-C22
 with sigma of 0.02
 C18'-C17' \\sim C18-C17 \\sim C16'-C15' \\sim C16-C15 \\sim C6-C5 \\sim C6'-C5'
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(C15') = Uiso(C15)
Uiso(C16) = Uiso(C16')
Uiso(C23) = Uiso(C23')
Uiso(C18) = Uiso(C18')
Uiso(C17) = Uiso(C17')
4. Others
 Uiso(H2A)=Uiso(H2B)=Uiso(H2C)=FVAR(1)
 Uiso(H4A)=Uiso(H4B)=Uiso(H4C)=FVAR(2)
 Uiso(H46A)=Uiso(H46B)=Uiso(H46C)=FVAR(3)
 Uiso(H8A)=Uiso(H8B)=Uiso(H8C)=FVAR(4)
 Uiso(H10A)=Uiso(H10B)=Uiso(H10C)=FVAR(5)
 Uiso(H12A)=Uiso(H12B)=Uiso(H12C)=FVAR(6)
 Uiso(H14A)=Uiso(H14B)=Uiso(H14C)=FVAR(7)
 Uiso(H36A)=Uiso(H36B)=Uiso(H36C)=FVAR(8)
 Sof(C15')=Sof(H15C)=Sof(H15D)=Sof(C16')=Sof(H16D)=Sof(H16E)=Sof(H16F)=
 Sof(C17')=Sof(H17C)=Sof(H17D)=Sof(C18')=Sof(H18D)=Sof(H18E)=Sof(H18F)=
 Sof(H22C)=Sof(H22D)=Sof(C23')=Sof(H23C)=Sof(H23D)=Sof(H24C)=Sof(H24D)=1-FVAR(9)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=
 Sof(H17A)=Sof(H17B)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(H22A)=Sof(H22B)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H24A)=Sof(H24B)=FVAR(9)
 Fixed Sof: C5(0.67) H5A(0.67) H5B(0.67) C6(0.67) H6A(0.67) H6B(0.67)
 H6C(0.67) C5'(0.33) H5'A(0.33) H5'B(0.33) C6'(0.33) H6'A(0.33) H6'B(0.33)
 H6'C(0.33)
5.a Riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C7(H7A,H7B), C9(H9A,H9B), C11(H11A,H11B), C13(H13A,
 H13B), C16(H16A,H16B,H16C), C17(H17A,H17B), C18(H18A,H18B,H18C), C16'(H16D,
 H16E,H16F), C17'(H17C,H17D), C18'(H18D,H18E,H18F), C21(H21A,H21B), C23(H23A,
 H23B), C23'(H23C,H23D), C30(H30), C31(H31), C33(H33), C34(H34), C40(H40),
 C41(H41), C43(H43), C44(H44)
5.b Rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C),
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C36(H36A,H36B,H36C), C46(H46A,H46B,
 H46C)
5.c Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C5'(H5'A,H5'B), C15(H15A,H15B), C15'(H15C,H15D), C22(H22A,H22B),
 C22(H22C,H22D), C24(H24A,H24B), C24(H24C,H24D)
5.d Me refined with riding coordinates:
 C6(H6A,H6B,H6C), C6'(H6'A,H6'B,H6'C)
;
_shelxl_version_number           2013-2