# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_datam
_database_code_depnum_ccdc_archive 'CCDC 973778'
_audit_update_record             
;
2014-01-01 deposited with the CCDC.
2015-06-19 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C28 H18 F4 Ir N5 O2'
_chemical_formula_sum            'C28 H18 F4 Ir N5 O2'
_chemical_formula_weight         724.67

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ir Ir -1.4442 7.9887 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   'P b c a'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x, -y-1/2, z-1/2'
'-x-1/2, y-1/2, z'

_cell_length_a                   16.765(2)
_cell_length_b                   15.096(8)
_cell_length_c                   20.6420(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     5224(3)
_cell_formula_units_Z            8
_cell_measurement_temperature    301(2)
_cell_measurement_reflns_used    7438
_cell_measurement_theta_min      3.1
_cell_measurement_theta_max      27.5

_exptl_crystal_description       Block
_exptl_crystal_colour            Yellow
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.843
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2800
_exptl_absorpt_coefficient_mu    5.176
_exptl_absorpt_correction_type   Empirical
_exptl_absorpt_correction_T_min  0.4241
_exptl_absorpt_correction_T_max  0.4241
_exptl_absorpt_process_details   'Acta Crystallogr A. (1995) 51, 33'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      301(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  
;
Rigaku Saturn724+ (4x4 bin mode)
;
_diffrn_measurement_method       'profile data from ω-scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            31043
_diffrn_reflns_av_R_equivalents  0.1693
_diffrn_reflns_av_sigmaI/netI    0.0840
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         3.12
_diffrn_reflns_theta_max         26.50
_reflns_number_total             5260
_reflns_number_gt                4026
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       
;
CrystalClear-SM Expert 2.0 r14k (Rigaku, 2012)
;
_computing_cell_refinement       
;
CrystalClear-SM Expert 2.0 r14k (Rigaku, 2012)
;
_computing_data_reduction        
;
CrystalClear-SM Expert 2.0 r14k (Rigaku, 2012)
;
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.1443P)²+1.0246P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         5260
_refine_ls_number_parameters     363
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0900
_refine_ls_R_factor_gt           0.0772
_refine_ls_wR_factor_ref         0.2141
_refine_ls_wR_factor_gt          0.1937
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_restrained_S_all      1.048
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
C1S C 0.2031(7) 0.6606(7) 0.1001(5) 0.072(3) Uani 1 1 d . . .
H1SC H 0.1549 0.6918 0.0898 0.107 Uiso 1 1 calc R . .
H1SA H 0.2191 0.6252 0.0637 0.107 Uiso 1 1 calc R . .
H1SB H 0.2445 0.7025 0.1101 0.107 Uiso 1 1 calc R . .
C2S C 0.1559(6) 0.1043(7) 0.5528(9) 0.079(4) Uani 1 1 d . . .
H2SA H 0.1234 0.0536 0.5432 0.119 Uiso 1 1 calc R . .
H2SC H 0.1361 0.1331 0.5910 0.119 Uiso 1 1 calc R . .
H2SB H 0.2099 0.0856 0.5600 0.119 Uiso 1 1 calc R . .
C12 C 0.2379(5) 0.5177(5) 0.2494(4) 0.0435(18) Uani 1 1 d . . .
C13 C 0.2532(5) 0.5754(6) 0.1988(4) 0.051(2) Uani 1 1 d . . .
H13 H 0.3044 0.5969 0.1914 0.061 Uiso 1 1 calc R . .
C14 C 0.1889(6) 0.6009(6) 0.1584(5) 0.045(2) Uani 1 1 d . . .
C15 C 0.1134(6) 0.5687(6) 0.1708(4) 0.047(2) Uani 1 1 d . . .
H15 H 0.0700 0.5857 0.1457 0.057 Uiso 1 1 calc R . .
C16 C 0.1046(5) 0.5100(5) 0.2222(4) 0.0416(18) Uani 1 1 d . . .
H16 H 0.0539 0.4872 0.2302 0.050 Uiso 1 1 calc R . .
C17 C 0.2965(4) 0.4842(5) 0.2971(4) 0.0413(18) Uani 1 1 d . . .
C18 C 0.3766(6) 0.5084(6) 0.3024(5) 0.052(2) Uani 1 1 d . . .
C22 C 0.1725(5) 0.2058(6) 0.3901(5) 0.051(2) Uani 1 1 d . . .
H22 H 0.1834 0.1872 0.3480 0.061 Uiso 1 1 calc R . .
C23 C 0.1764(6) 0.1445(6) 0.4393(5) 0.052(2) Uani 1 1 d . . .
H23 H 0.1954 0.0880 0.4300 0.063 Uiso 1 1 calc R . .
C24 C 0.1536(4) 0.1630(11) 0.5011(5) 0.070(4) Uani 1 1 d . . .
C25 C 0.1307(6) 0.2560(6) 0.5106(4) 0.052(2) Uani 1 1 d . . .
H25 H 0.1137 0.2744 0.5513 0.062 Uiso 1 1 calc R . .
C26 C 0.1338(5) 0.3168(6) 0.4611(4) 0.0467(19) Uani 1 1 d . . .
C27 C 0.1193(5) 0.4156(6) 0.4643(4) 0.0444(18) Uani 1 1 d . . .
C28 C 0.1022(5) 0.4642(7) 0.5188(4) 0.057(2) Uani 1 1 d . . .
C32 C 0.0329(4) 0.2921(5) 0.2495(4) 0.0388(16) Uani 1 1 d . . .
C33 C -0.0391(6) 0.2615(5) 0.2248(5) 0.058(2) Uani 1 1 d . . .
H33A H -0.0404 0.2265 0.1877 0.070 Uiso 1 1 calc R . .
C34 C -0.1085(6) 0.2840(8) 0.2564(6) 0.071(3) Uani 1 1 d . . .
H52A H -0.1570 0.2616 0.2419 0.086 Uiso 1 1 calc R . .
C35 C -0.1064(5) 0.3401(7) 0.3100(5) 0.063(3) Uani 1 1 d . . .
H42A H -0.1534 0.3563 0.3307 0.075 Uiso 1 1 calc R . .
C36 C -0.0335(6) 0.3716(7) 0.3321(4) 0.053(3) Uani 1 1 d . . .
H38A H -0.0315 0.4099 0.3673 0.064 Uiso 1 1 calc R . .
C37 C 0.1127(5) 0.2708(5) 0.2187(4) 0.0444(18) Uani 1 1 d . . .
C110 C 0.3980(5) 0.4222(7) 0.3883(5) 0.057(2) Uani 1 1 d . . .
C111 C 0.3217(6) 0.3887(5) 0.3894(5) 0.048(2) Uani 1 1 d . . .
H111 H 0.3062 0.3472 0.4202 0.058 Uiso 1 1 calc R . .
C112 C 0.2678(4) 0.4194(6) 0.3421(4) 0.0389(17) Uani 1 1 d . . .
C210 C 0.1019(7) 0.5924(7) 0.4648(6) 0.068(3) Uani 1 1 d . . .
C211 C 0.1174(6) 0.5535(6) 0.4070(5) 0.057(2) Uani 1 1 d . . .
H211 H 0.1214 0.5875 0.3696 0.068 Uiso 1 1 calc R . .
C212 C 0.1274(5) 0.4621(5) 0.4045(4) 0.0455(19) Uani 1 1 d . . .
N11 N 0.1640(3) 0.4842(5) 0.2607(4) 0.0389(16) Uani 1 1 d . . .
N19 N 0.4271(5) 0.4781(6) 0.3465(5) 0.064(2) Uani 1 1 d . . .
N21 N 0.1537(3) 0.2915(5) 0.4000(4) 0.0402(17) Uani 1 1 d . . .
N29 N 0.0938(5) 0.5504(6) 0.5215(4) 0.067(2) Uani 1 1 d . . .
N31 N 0.0352(3) 0.3460(4) 0.3018(3) 0.0376(13) Uani 1 1 d . . .
O37A O 0.1752(3) 0.2955(4) 0.2503(3) 0.0449(13) Uani 1 1 d . . .
O37B O 0.1127(5) 0.2281(5) 0.1679(3) 0.065(2) Uani 1 1 d . . .
F18 F 0.4067(3) 0.5680(5) 0.2610(3) 0.0719(17) Uani 1 1 d . . .
F28 F 0.0950(4) 0.4246(4) 0.5773(3) 0.0804(18) Uani 1 1 d . . .
F110 F 0.4512(4) 0.3923(4) 0.4325(4) 0.095(2) Uani 1 1 d . . .
F210 F 0.0917(5) 0.6806(4) 0.4691(4) 0.107(3) Uani 1 1 d . . .
Ir1 Ir 0.153893(16) 0.38607(2) 0.329050(16) 0.0330(2) Uani 1 1 d . . .


_geom_special_details            
; 
 All esds (except the esd in the dihedral angle between two l.s. planes) 
 are estimated using the full covariance matrix.  The cell esds are taken 
 into account individually in the estimation of esds in distances, angles 
 and torsion angles; correlations between esds in cell parameters are only 
 used when they are defined by crystal symmetry.  An approximate (isotropic) 
 treatment of cell esds is used for estimating esds involving l.s. planes. 
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1S C14 1.522(12) . ?
C2S C24 1.39(2) . ?
C12 N11 1.359(10) . ?
C12 C13 1.385(11) . ?
C12 C17 1.478(11) . ?
C13 C14 1.416(13) . ?
C14 C15 1.379(15) . ?
C15 C16 1.390(11) . ?
C16 N11 1.333(10) . ?
C17 C18 1.396(12) . ?
C17 C112 1.432(12) . ?
C18 N19 1.325(13) . ?
C18 F18 1.341(10) . ?
C22 N21 1.348(12) . ?
C22 C23 1.376(13) . ?
C23 C24 1.360(13) . ?
C24 C25 1.469(18) . ?
C25 C26 1.373(12) . ?
C26 N21 1.359(11) . ?
C26 C27 1.513(12) . ?
C27 C28 1.373(11) . ?
C27 C212 1.428(12) . ?
C28 N29 1.310(12) . ?
C28 F28 1.354(11) . ?
C32 N31 1.351(9) . ?
C32 C33 1.390(11) . ?
C32 C37 1.517(11) . ?
C33 C34 1.375(14) . ?
C34 C35 1.394(15) . ?
C35 C36 1.388(14) . ?
C36 N31 1.367(11) . ?
C37 O37B 1.232(10) . ?
C37 O37A 1.288(10) . ?
C110 N19 1.302(13) . ?
C110 F110 1.354(11) . ?
C110 C111 1.376(13) . ?
C111 C112 1.409(11) . ?
C112 Ir1 1.993(7) . ?
C210 N29 1.337(14) . ?
C210 F210 1.345(11) . ?
C210 C211 1.355(14) . ?
C211 C212 1.391(12) . ?
C212 Ir1 1.984(9) . ?
N11 Ir1 2.052(7) . ?
N21 Ir1 2.046(8) . ?
N31 Ir1 2.155(6) . ?
O37A Ir1 2.154(6) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N11 C12 C13 122.1(8) . . ?
N11 C12 C17 111.3(7) . . ?
C13 C12 C17 126.5(7) . . ?
C12 C13 C14 118.4(8) . . ?
C15 C14 C13 119.5(8) . . ?
C15 C14 C1S 120.0(9) . . ?
C13 C14 C1S 120.4(8) . . ?
C14 C15 C16 117.7(9) . . ?
N11 C16 C15 124.1(8) . . ?
C18 C17 C112 116.8(7) . . ?
C18 C17 C12 127.0(7) . . ?
C112 C17 C12 116.3(6) . . ?
N19 C18 F18 115.4(8) . . ?
N19 C18 C17 125.4(8) . . ?
F18 C18 C17 119.2(8) . . ?
N21 C22 C23 122.9(9) . . ?
C24 C23 C22 122.8(11) . . ?
C23 C24 C2S 125.6(14) . . ?
C23 C24 C25 113.2(11) . . ?
C2S C24 C25 121.0(10) . . ?
C26 C25 C24 122.0(9) . . ?
N21 C26 C25 120.8(8) . . ?
N21 C26 C27 110.9(7) . . ?
C25 C26 C27 128.3(8) . . ?
C28 C27 C212 117.7(8) . . ?
C28 C27 C26 126.6(8) . . ?
C212 C27 C26 115.6(7) . . ?
N29 C28 F28 113.0(8) . . ?
N29 C28 C27 126.1(9) . . ?
F28 C28 C27 120.9(9) . . ?
N31 C32 C33 121.2(8) . . ?
N31 C32 C37 116.0(7) . . ?
C33 C32 C37 122.8(8) . . ?
C34 C33 C32 118.6(9) . . ?
C33 C34 C35 120.3(9) . . ?
C36 C35 C34 119.4(9) . . ?
N31 C36 C35 119.6(9) . . ?
O37B C37 O37A 125.7(8) . . ?
O37B C37 C32 117.9(8) . . ?
O37A C37 C32 116.3(7) . . ?
N19 C110 F110 114.5(8) . . ?
N19 C110 C111 126.7(9) . . ?
F110 C110 C111 118.7(10) . . ?
C110 C111 C112 117.6(8) . . ?
C111 C112 C17 117.4(7) . . ?
C111 C112 Ir1 128.6(7) . . ?
C17 C112 Ir1 114.0(6) . . ?
N29 C210 F210 113.6(9) . . ?
N29 C210 C211 125.7(10) . . ?
F210 C210 C211 120.7(11) . . ?
C210 C211 C212 119.1(10) . . ?
C211 C212 C27 116.3(8) . . ?
C211 C212 Ir1 129.1(7) . . ?
C27 C212 Ir1 114.6(6) . . ?
C16 N11 C12 118.1(7) . . ?
C16 N11 Ir1 124.0(5) . . ?
C12 N11 Ir1 117.5(5) . . ?
C110 N19 C18 116.1(8) . . ?
C22 N21 C26 118.0(8) . . ?
C22 N21 Ir1 124.1(7) . . ?
C26 N21 Ir1 117.9(6) . . ?
C28 N29 C210 115.0(9) . . ?
C32 N31 C36 120.8(7) . . ?
C32 N31 Ir1 113.8(5) . . ?
C36 N31 Ir1 125.4(6) . . ?
C37 O37A Ir1 115.5(5) . . ?
C212 Ir1 C112 87.8(3) . . ?
C212 Ir1 N21 80.9(3) . . ?
C112 Ir1 N21 94.6(3) . . ?
C212 Ir1 N11 98.0(3) . . ?
C112 Ir1 N11 80.3(3) . . ?
N21 Ir1 N11 174.9(2) . . ?
C212 Ir1 O37A 175.1(3) . . ?
C112 Ir1 O37A 96.0(3) . . ?
N21 Ir1 O37A 95.6(3) . . ?
N11 Ir1 O37A 85.8(3) . . ?
C212 Ir1 N31 99.3(3) . . ?
C112 Ir1 N31 172.3(3) . . ?
N21 Ir1 N31 89.4(2) . . ?
N11 Ir1 N31 95.7(2) . . ?
O37A Ir1 N31 77.1(2) . . ?

_diffrn_measured_fraction_theta_max 0.973
_diffrn_reflns_theta_full        26.50
_diffrn_measured_fraction_theta_full 0.973
_refine_diff_density_max         6.686
_refine_diff_density_min         -2.401
_refine_diff_density_rms         0.299

# start Validation Reply Form
_vrf_PLAT230_datam               
;
RESPONSE: caused by vibration of -CH3 substituent
on phenyl ring
;

#END of validation reply form
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_shelx
_database_code_depnum_ccdc_archive 'CCDC 1005716'
_audit_update_record             
;
2014-05-28 deposited with the CCDC.
2015-06-19 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         
;
C28 H18 F4 Ir N5 O4, C H2 Cl2
;
_chemical_formula_sum            'C29 H20 Cl2 F4 Ir N5 O4'
_chemical_formula_weight         841.60

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ir Ir -1.4442 7.9887 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   12.069(3)
_cell_length_b                   12.029(3)
_cell_length_c                   19.562(5)
_cell_angle_alpha                90
_cell_angle_beta                 92.189(4)
_cell_angle_gamma                90
_cell_volume                     2837.8(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    5343
_cell_measurement_theta_min      3.1
_cell_measurement_theta_max      27.5

_exptl_crystal_description       Block
_exptl_crystal_colour            Yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.970
_exptl_crystal_F_000             1632
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.500
_exptl_crystal_size_mid          0.400
_exptl_crystal_size_min          0.300
_exptl_absorpt_coefficient_mu    4.967
_shelx_estimated_absorpt_T_min   0.190
_shelx_estimated_absorpt_T_max   0.317
_exptl_absorpt_correction_type   Empirical
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.723
_exptl_absorpt_process_details   
;
R. H. Blessing Acta Crystallogr., Sect. A, 1995, 51, 33-38
;

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  ?
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            24916
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_av_R_equivalents  0.0251
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         3.130
_diffrn_reflns_theta_max         27.503
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measured_fraction_theta_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_point_group_measured_fraction_full 0.989
_reflns_number_total             6465
_reflns_number_gt                5826
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       
;
CrystalClear-SM Expert 2.0 r14k (Rigaku, 2012)
;
_computing_cell_refinement       
;
CrystalClear-SM Expert 2.0 r14k (Rigaku, 2012)
;
_computing_data_reduction        
;
CrystalClear-SM Expert 2.0 r14k (Rigaku, 2012)
;
_computing_structure_solution    'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0295P)²+1.0336P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         6465
_refine_ls_number_parameters     406
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0250
_refine_ls_R_factor_gt           0.0214
_refine_ls_wR_factor_ref         0.0530
_refine_ls_wR_factor_gt          0.0517
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_restrained_S_all      1.047
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C2 C 0.5003(2) 0.8054(2) 0.53019(14) 0.0183(5) Uani 1 1 d . . . . .
H2 H 0.5024 0.8770 0.5097 0.022 Uiso 1 1 calc R U . . .
C3 C 0.4123(2) 0.7799(2) 0.56979(15) 0.0196(6) Uani 1 1 d . . . . .
H3 H 0.3535 0.8313 0.5752 0.023 Uiso 1 1 calc R U . . .
C4 C 0.4118(2) 0.6762(2) 0.60178(14) 0.0188(5) Uani 1 1 d . . . . .
C5 C 0.4975(2) 0.6020(2) 0.59067(15) 0.0196(6) Uani 1 1 d . . . . .
H5 H 0.4980 0.5310 0.6120 0.024 Uiso 1 1 calc R U . . .
C6 C 0.5819(2) 0.6315(2) 0.54864(14) 0.0168(5) Uani 1 1 d . . . . .
C7 C 0.6771(2) 0.5629(2) 0.53063(14) 0.0171(5) Uani 1 1 d . . . . .
C8 C 0.6921(2) 0.4512(2) 0.54576(15) 0.0208(6) Uani 1 1 d . . . . .
C10 C 0.8462(2) 0.4390(2) 0.48960(15) 0.0214(6) Uani 1 1 d . . . . .
C11 C 0.8456(2) 0.5494(2) 0.46978(15) 0.0201(6) Uani 1 1 d . . . . .
H11 H 0.9025 0.5792 0.4430 0.024 Uiso 1 1 calc R U . . .
C12 C 0.7576(2) 0.6154(2) 0.49089(14) 0.0159(5) Uani 1 1 d . . . . .
C13 C 0.2462(3) 0.7156(3) 0.6617(2) 0.0353(8) Uani 1 1 d . . . . .
H13B H 0.1973 0.6792 0.6937 0.053 Uiso 1 1 calc R U . . .
H13C H 0.2037 0.7346 0.6196 0.053 Uiso 1 1 calc R U . . .
H13A H 0.2770 0.7835 0.6826 0.053 Uiso 1 1 calc R U . . .
C15 C 0.8901(2) 0.7961(2) 0.35520(16) 0.0240(6) Uani 1 1 d . . . . .
H15 H 0.8303 0.7762 0.3247 0.029 Uiso 1 1 calc R U . . .
C16 C 0.9921(2) 0.8133(3) 0.32896(16) 0.0271(6) Uani 1 1 d . . . . .
H16 H 1.0026 0.8066 0.2813 0.033 Uiso 1 1 calc R U . . .
C17 C 1.0807(2) 0.8410(2) 0.37399(17) 0.0259(6) Uani 1 1 d . . . . .
C18 C 1.0614(2) 0.8541(2) 0.44249(16) 0.0228(6) Uani 1 1 d . . . . .
H18 H 1.1203 0.8751 0.4734 0.027 Uiso 1 1 calc R U . . .
C19 C 0.9561(2) 0.8367(2) 0.46626(15) 0.0182(5) Uani 1 1 d . . . . .
C20 C 1.2746(2) 0.8774(3) 0.3900(2) 0.0380(8) Uani 1 1 d . . . . .
H20A H 1.3414 0.8839 0.3633 0.057 Uiso 1 1 calc R U . . .
H20B H 1.2845 0.8172 0.4235 0.057 Uiso 1 1 calc R U . . .
H20C H 1.2619 0.9475 0.4140 0.057 Uiso 1 1 calc R U . . .
C21 C 0.9228(2) 0.8463(2) 0.53672(15) 0.0178(5) Uani 1 1 d . . . . .
C22 C 0.9898(2) 0.8774(2) 0.59260(16) 0.0230(6) Uani 1 1 d . . . . .
C24 C 0.8558(3) 0.8584(3) 0.66597(16) 0.0271(6) Uani 1 1 d . . . . .
C25 C 0.7775(2) 0.8270(2) 0.61675(15) 0.0227(6) Uani 1 1 d . . . . .
H25 H 0.7035 0.8108 0.6283 0.027 Uiso 1 1 calc R U . . .
C26 C 0.8106(2) 0.8197(2) 0.54902(14) 0.0167(5) Uani 1 1 d . . . . .
C28 C 0.6406(2) 0.6296(2) 0.34086(14) 0.0191(6) Uani 1 1 d . . . . .
H28 H 0.6821 0.5710 0.3620 0.023 Uiso 1 1 calc R U . . .
C29 C 0.5846(2) 0.6097(2) 0.27923(15) 0.0219(6) Uani 1 1 d . . . . .
H29 H 0.5871 0.5385 0.2584 0.026 Uiso 1 1 calc R U . . .
C30 C 0.5251(3) 0.6945(3) 0.24852(16) 0.0273(6) Uani 1 1 d . . . . .
H30 H 0.4853 0.6826 0.2063 0.033 Uiso 1 1 calc R U . . .
C31 C 0.5239(2) 0.7981(2) 0.27996(16) 0.0257(6) Uani 1 1 d . . . . .
H31 H 0.4835 0.8579 0.2593 0.031 Uiso 1 1 calc R U . . .
C32 C 0.5817(2) 0.8136(2) 0.34141(14) 0.0178(5) Uani 1 1 d . . . . .
C33 C 0.5881(2) 0.9239(2) 0.37831(15) 0.0189(6) Uani 1 1 d . . . . .
N1 N 0.58394(18) 0.73450(17) 0.51877(12) 0.0159(4) Uani 1 1 d . . . . .
N9 N 0.77437(18) 0.38763(19) 0.52637(12) 0.0214(5) Uani 1 1 d . . . . .
N14 N 0.87025(18) 0.80604(18) 0.42229(12) 0.0177(5) Uani 1 1 d . . . . .
N23 N 0.9605(2) 0.8836(2) 0.65637(13) 0.0267(6) Uani 1 1 d . . . . .
N27 N 0.63835(18) 0.72896(17) 0.37180(12) 0.0154(4) Uani 1 1 d . . . . .
O4 O 0.33517(16) 0.64127(16) 0.64574(11) 0.0265(5) Uani 1 1 d . . . . .
O17 O 1.18069(17) 0.8533(2) 0.34491(13) 0.0372(6) Uani 1 1 d . . . . .
O33A O 0.65403(15) 0.92856(14) 0.43142(10) 0.0199(4) Uani 1 1 d . . . . .
O33B O 0.53035(18) 1.00046(16) 0.35504(11) 0.0299(5) Uani 1 1 d . . . . .
F8 F 0.61651(13) 0.39605(13) 0.58257(10) 0.0282(4) Uani 1 1 d . . . . .
F10 F 0.92884(13) 0.37293(13) 0.46801(10) 0.0298(4) Uani 1 1 d . . . . .
F22 F 1.09678(13) 0.90667(14) 0.58421(10) 0.0309(4) Uani 1 1 d . . . . .
F24 F 0.82645(16) 0.86571(18) 0.73170(10) 0.0422(5) Uani 1 1 d . . . . .
Ir1 Ir 0.72220(2) 0.77145(2) 0.46565(2) 0.01451(4) Uani 1 1 d . . . . .
C90 C 0.8619(3) 0.4540(3) 0.70834(19) 0.0421(9) Uani 1 1 d . . . . .
H90A H 0.9067 0.4368 0.7504 0.051 Uiso 1 1 calc R U . . .
H90B H 0.8465 0.3832 0.6840 0.051 Uiso 1 1 calc R U . . .
Cl90 Cl 0.73611(8) 0.51439(10) 0.73085(6) 0.0630(3) Uani 1 1 d . . . . .
Cl91 Cl 0.93807(8) 0.54140(9) 0.65610(5) 0.0519(2) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C2 N1 1.346(3) . ?
C2 C3 1.374(4) . ?
C2 H2 0.9500 . ?
C3 C4 1.396(4) . ?
C3 H3 0.9500 . ?
C4 O4 1.353(3) . ?
C4 C5 1.390(4) . ?
C5 C6 1.380(4) . ?
C5 H5 0.9500 . ?
C6 N1 1.370(3) . ?
C6 C7 1.468(3) . ?
C7 C8 1.386(4) . ?
C7 C12 1.417(4) . ?
C8 N9 1.320(4) . ?
C8 F8 1.357(3) . ?
C10 N9 1.303(4) . ?
C10 F10 1.356(3) . ?
C10 C11 1.383(4) . ?
C11 C12 1.400(4) . ?
C11 H11 0.9500 . ?
C12 Ir1 1.984(2) . ?
C13 O4 1.441(3) . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?
C13 H13A 0.9800 . ?
C15 N14 1.348(4) . ?
C15 C16 1.368(4) . ?
C15 H15 0.9500 . ?
C16 C17 1.399(4) . ?
C16 H16 0.9500 . ?
C17 O17 1.361(3) . ?
C17 C18 1.378(4) . ?
C18 C19 1.386(4) . ?
C18 H18 0.9500 . ?
C19 N14 1.371(3) . ?
C19 C21 1.455(4) . ?
C20 O17 1.439(4) . ?
C20 H20A 0.9800 . ?
C20 H20B 0.9800 . ?
C20 H20C 0.9800 . ?
C21 C22 1.386(4) . ?
C21 C26 1.421(4) . ?
C22 N23 1.312(4) . ?
C22 F22 1.355(3) . ?
C24 N23 1.320(4) . ?
C24 F24 1.350(4) . ?
C24 C25 1.376(4) . ?
C25 C26 1.401(4) . ?
C25 H25 0.9500 . ?
C26 Ir1 2.000(3) . ?
C28 N27 1.341(3) . ?
C28 C29 1.380(4) . ?
C28 H28 0.9500 . ?
C29 C30 1.372(4) . ?
C29 H29 0.9500 . ?
C30 C31 1.390(4) . ?
C30 H30 0.9500 . ?
C31 C32 1.379(4) . ?
C31 H31 0.9500 . ?
C32 N27 1.351(3) . ?
C32 C33 1.511(4) . ?
C33 O33B 1.232(3) . ?
C33 O33A 1.286(3) . ?
N1 Ir1 2.048(2) . ?
N14 Ir1 2.050(2) . ?
N27 Ir1 2.125(2) . ?
O33A Ir1 2.1574(18) . ?
C90 Cl91 1.751(4) . ?
C90 Cl90 1.754(4) . ?
C90 H90A 0.9900 . ?
C90 H90B 0.9900 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 C2 C3 123.6(3) . . ?
N1 C2 H2 118.2 . . ?
C3 C2 H2 118.2 . . ?
C2 C3 C4 118.0(2) . . ?
C2 C3 H3 121.0 . . ?
C4 C3 H3 121.0 . . ?
O4 C4 C5 115.5(2) . . ?
O4 C4 C3 125.2(2) . . ?
C5 C4 C3 119.2(2) . . ?
C6 C5 C4 119.9(2) . . ?
C6 C5 H5 120.0 . . ?
C4 C5 H5 120.0 . . ?
N1 C6 C5 120.8(2) . . ?
N1 C6 C7 112.3(2) . . ?
C5 C6 C7 126.9(2) . . ?
C8 C7 C12 117.5(2) . . ?
C8 C7 C6 126.3(2) . . ?
C12 C7 C6 116.1(2) . . ?
N9 C8 F8 113.4(2) . . ?
N9 C8 C7 126.4(3) . . ?
F8 C8 C7 120.1(2) . . ?
N9 C10 F10 114.0(2) . . ?
N9 C10 C11 127.9(3) . . ?
F10 C10 C11 118.1(3) . . ?
C10 C11 C12 117.2(3) . . ?
C10 C11 H11 121.4 . . ?
C12 C11 H11 121.4 . . ?
C11 C12 C7 116.9(2) . . ?
C11 C12 Ir1 128.5(2) . . ?
C7 C12 Ir1 114.37(18) . . ?
O4 C13 H13B 109.5 . . ?
O4 C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
O4 C13 H13A 109.5 . . ?
H13B C13 H13A 109.5 . . ?
H13C C13 H13A 109.5 . . ?
N14 C15 C16 123.2(3) . . ?
N14 C15 H15 118.4 . . ?
C16 C15 H15 118.4 . . ?
C15 C16 C17 118.5(3) . . ?
C15 C16 H16 120.8 . . ?
C17 C16 H16 120.8 . . ?
O17 C17 C18 125.4(3) . . ?
O17 C17 C16 115.5(3) . . ?
C18 C17 C16 119.1(3) . . ?
C17 C18 C19 120.0(3) . . ?
C17 C18 H18 120.0 . . ?
C19 C18 H18 120.0 . . ?
N14 C19 C18 120.7(3) . . ?
N14 C19 C21 112.7(2) . . ?
C18 C19 C21 126.6(3) . . ?
O17 C20 H20A 109.5 . . ?
O17 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
O17 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C22 C21 C26 117.3(3) . . ?
C22 C21 C19 126.5(3) . . ?
C26 C21 C19 116.3(2) . . ?
N23 C22 F22 113.1(2) . . ?
N23 C22 C21 126.6(3) . . ?
F22 C22 C21 120.3(3) . . ?
N23 C24 F24 114.1(2) . . ?
N23 C24 C25 126.8(3) . . ?
F24 C24 C25 119.1(3) . . ?
C24 C25 C26 117.8(3) . . ?
C24 C25 H25 121.1 . . ?
C26 C25 H25 121.1 . . ?
C25 C26 C21 117.0(2) . . ?
C25 C26 Ir1 128.8(2) . . ?
C21 C26 Ir1 114.2(2) . . ?
N27 C28 C29 122.1(2) . . ?
N27 C28 H28 119.0 . . ?
C29 C28 H28 119.0 . . ?
C30 C29 C28 119.0(3) . . ?
C30 C29 H29 120.5 . . ?
C28 C29 H29 120.5 . . ?
C29 C30 C31 119.1(3) . . ?
C29 C30 H30 120.4 . . ?
C31 C30 H30 120.4 . . ?
C32 C31 C30 119.5(3) . . ?
C32 C31 H31 120.2 . . ?
C30 C31 H31 120.2 . . ?
N27 C32 C31 120.8(3) . . ?
N27 C32 C33 115.8(2) . . ?
C31 C32 C33 123.3(2) . . ?
O33B C33 O33A 126.2(2) . . ?
O33B C33 C32 117.5(2) . . ?
O33A C33 C32 116.3(2) . . ?
C2 N1 C6 118.4(2) . . ?
C2 N1 Ir1 125.24(18) . . ?
C6 N1 Ir1 116.15(17) . . ?
C10 N9 C8 114.0(2) . . ?
C15 N14 C19 118.4(2) . . ?
C15 N14 Ir1 125.11(18) . . ?
C19 N14 Ir1 116.40(19) . . ?
C22 N23 C24 114.6(2) . . ?
C28 N27 C32 119.5(2) . . ?
C28 N27 Ir1 125.97(18) . . ?
C32 N27 Ir1 114.53(17) . . ?
C4 O4 C13 118.6(2) . . ?
C17 O17 C20 117.1(3) . . ?
C33 O33A Ir1 115.45(16) . . ?
C12 Ir1 C26 88.18(10) . . ?
C12 Ir1 N1 80.82(10) . . ?
C26 Ir1 N1 93.95(10) . . ?
C12 Ir1 N14 96.43(10) . . ?
C26 Ir1 N14 80.35(10) . . ?
N1 Ir1 N14 173.78(9) . . ?
C12 Ir1 N27 94.50(9) . . ?
C26 Ir1 N27 174.78(10) . . ?
N1 Ir1 N27 90.91(9) . . ?
N14 Ir1 N27 94.88(9) . . ?
C12 Ir1 O33A 169.20(9) . . ?
C26 Ir1 O33A 100.62(9) . . ?
N1 Ir1 O33A 92.25(8) . . ?
N14 Ir1 O33A 91.25(8) . . ?
N27 Ir1 O33A 77.24(8) . . ?
Cl91 C90 Cl90 112.1(2) . . ?
Cl91 C90 H90A 109.2 . . ?
Cl90 C90 H90A 109.2 . . ?
Cl91 C90 H90B 109.2 . . ?
Cl90 C90 H90B 109.2 . . ?
H90A C90 H90B 107.9 . . ?

_refine_diff_density_max         1.327
_refine_diff_density_min         -0.979
_refine_diff_density_rms         0.091

_shelxl_version_number           2013-4



