# Electronic Supplementary Material (ESI) for Dalton Transactions
# This journal is © The Royal Society of Chemistry 2011


data_global
_journal_name_full               'Dalton Trans.'

_journal_coden_Cambridge         0222
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Robert G. Bergman'
_publ_contact_author_address     
;695 Tan Hall
University of California, Berkeley
Berkeley, CA
94720
;
_publ_contact_author_email       rgbergman@berkeley.edu
loop_
_publ_author_address
;695 Tan Hall
University of California, Berkeley
Berkeley, CA
94720
;
;695 Tan Hall
University of California, Berkeley
Berkeley, CA
94720
;
;695 Tan Hall
University of California, Berkeley
Berkeley, CA
94720
;

_publ_section_title              
;
Preparation and Physical Properties
of Early-Late Heterobimetallic Compounds Featuring
Ir-M Bonds (M = Ti, Zr, Hf)
;
_publ_author_name                J.Curley

# Attachment '- curley_chemsci.cif'

#TrackingRef '- curley_chemsci.cif'

data_Ir-Ti
_database_code_depnum_ccdc_archive 'CCDC 838831'
#TrackingRef '- curley_chemsci.cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            Cp*Ir(mu-NtBu)TiCp2
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C24 H34 Ir N Ti'
_chemical_formula_weight         576.62

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'
Ti Ti 0.2776 0.4457 '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'

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

_cell_length_a                   10.309(5)
_cell_length_b                   15.143(7)
_cell_length_c                   14.512(7)
_cell_angle_alpha                90.00
_cell_angle_beta                 96.715(7)
_cell_angle_gamma                90.00
_cell_volume                     2250.0(18)
_cell_formula_units_Z            4

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   'P2(1)/n '
_cell_measurement_temperature    133(2)
_cell_measurement_reflns_used    3135
_cell_measurement_theta_min      2.69
_cell_measurement_theta_max      23.61
_exptl_crystal_description       block
_exptl_crystal_colour            orange
_exptl_crystal_size_min          0.10
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_max          0.25
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.702
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1136
_exptl_absorpt_coefficient_mu    6.272
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.3031
_exptl_absorpt_correction_T_max  0.5728
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      133(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  'Bruker Apex-I CCD'
_diffrn_measurement_method       '/f and /w scans'
_diffrn_detector_area_resol_mean 8.366
_diffrn_reflns_number            17399
_diffrn_reflns_av_R_equivalents  0.0778
_diffrn_reflns_av_sigmaI/netI    0.0781
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.30
_diffrn_reflns_theta_max         25.35
_reflns_number_total             4109
_reflns_number_gt                2961
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ 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/[\s^2^(Fo^2^)+(0.0471P)^2^+43.2616P] where P=(Fo^2^+2Fc^2^)/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         4109
_refine_ls_number_parameters     252
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0948
_refine_ls_R_factor_gt           0.0599
_refine_ls_wR_factor_ref         0.1475
_refine_ls_wR_factor_gt          0.1334
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_restrained_S_all      1.092
_refine_ls_shift/su_max          0.001
_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
Ir1 Ir 0.20111(5) 0.21756(3) 0.98528(3) 0.02207(17) Uani 1 1 d . . .
Ti1 Ti 0.0403(2) 0.28815(16) 1.08320(14) 0.0230(5) Uani 1 1 d . . .
N1 N 0.1449(10) 0.1780(7) 1.0960(7) 0.027(2) Uani 1 1 d . . .
C41 C 0.1790(14) 0.1049(9) 1.1587(9) 0.032(3) Uani 1 1 d . . .
C411 C 0.3202(15) 0.1189(12) 1.2020(11) 0.056(5) Uani 1 1 d . . .
H41A H 0.3769 0.1250 1.1527 0.084 Uiso 1 1 calc R . .
H41B H 0.3486 0.0681 1.2411 0.084 Uiso 1 1 calc R . .
H41C H 0.3255 0.1726 1.2400 0.084 Uiso 1 1 calc R . .
C412 C 0.0881(16) 0.1011(12) 1.2351(10) 0.052(4) Uani 1 1 d . . .
H41D H 0.0857 0.1591 1.2648 0.077 Uiso 1 1 calc R . .
H41E H 0.1206 0.0569 1.2815 0.077 Uiso 1 1 calc R . .
H41F H -0.0001 0.0848 1.2077 0.077 Uiso 1 1 calc R . .
C413 C 0.1647(17) 0.0192(9) 1.1031(10) 0.046(4) Uani 1 1 d . . .
H41G H 0.0738 0.0124 1.0757 0.068 Uiso 1 1 calc R . .
H41H H 0.1894 -0.0308 1.1443 0.068 Uiso 1 1 calc R . .
H41I H 0.2218 0.0211 1.0537 0.068 Uiso 1 1 calc R . .
C11 C 0.3628(13) 0.2773(10) 0.9198(9) 0.034(3) Uani 1 1 d . . .
C111 C 0.4520(16) 0.3463(13) 0.9616(11) 0.058(5) Uani 1 1 d . . .
H11A H 0.5237 0.3545 0.9237 0.087 Uiso 1 1 calc R . .
H11B H 0.4874 0.3284 1.0245 0.087 Uiso 1 1 calc R . .
H11C H 0.4040 0.4020 0.9645 0.087 Uiso 1 1 calc R . .
C12 C 0.3918(13) 0.1819(10) 0.9262(9) 0.035(3) Uani 1 1 d . . .
C121 C 0.5125(15) 0.1411(15) 0.9796(12) 0.071(6) Uani 1 1 d . . .
H12A H 0.4960 0.0786 0.9913 0.107 Uiso 1 1 calc R . .
H12B H 0.5331 0.1720 1.0388 0.107 Uiso 1 1 calc R . .
H12C H 0.5863 0.1463 0.9431 0.107 Uiso 1 1 calc R . .
C13 C 0.2910(13) 0.1375(9) 0.8751(9) 0.031(3) Uani 1 1 d . . .
C131 C 0.2772(19) 0.0378(10) 0.8612(12) 0.057(5) Uani 1 1 d . . .
H13A H 0.3453 0.0075 0.9022 0.086 Uiso 1 1 calc R . .
H13B H 0.2863 0.0230 0.7965 0.086 Uiso 1 1 calc R . .
H13C H 0.1910 0.0188 0.8759 0.086 Uiso 1 1 calc R . .
C14 C 0.1970(12) 0.2018(10) 0.8363(9) 0.031(3) Uani 1 1 d . . .
C141 C 0.0784(14) 0.1793(13) 0.7690(9) 0.050(4) Uani 1 1 d . . .
H14A H 0.0177 0.2293 0.7642 0.075 Uiso 1 1 calc R . .
H14B H 0.0350 0.1272 0.7913 0.075 Uiso 1 1 calc R . .
H14C H 0.1056 0.1667 0.7078 0.075 Uiso 1 1 calc R . .
C15 C 0.2472(13) 0.2833(10) 0.8572(9) 0.031(3) Uani 1 1 d . . .
C151 C 0.1884(18) 0.3720(11) 0.8226(11) 0.054(5) Uani 1 1 d . . .
H15A H 0.2274 0.3904 0.7672 0.080 Uiso 1 1 calc R . .
H15B H 0.2064 0.4166 0.8713 0.080 Uiso 1 1 calc R . .
H15C H 0.0938 0.3656 0.8071 0.080 Uiso 1 1 calc R . .
C21 C 0.0416(16) 0.3935(10) 1.2051(10) 0.045(4) Uani 1 1 d . . .
H21 H -0.0310 0.3926 1.2398 0.054 Uiso 1 1 calc R . .
C22 C 0.0528(15) 0.4419(9) 1.1249(10) 0.039(4) Uani 1 1 d . . .
H22 H -0.0101 0.4823 1.0964 0.047 Uiso 1 1 calc R . .
C23 C 0.1720(15) 0.4210(10) 1.0935(10) 0.041(4) Uani 1 1 d . . .
H23 H 0.2015 0.4423 1.0380 0.049 Uiso 1 1 calc R . .
C24 C 0.2397(15) 0.3646(10) 1.1556(10) 0.041(4) Uani 1 1 d . . .
H24 H 0.3253 0.3426 1.1520 0.049 Uiso 1 1 calc R . .
C25 C 0.1612(15) 0.3450(10) 1.2251(10) 0.043(4) Uani 1 1 d . . .
H25 H 0.1830 0.3066 1.2764 0.051 Uiso 1 1 calc R . .
C31 C -0.1790(14) 0.2473(13) 1.1063(11) 0.048(4) Uani 1 1 d . . .
H31 H -0.1945 0.2339 1.1680 0.058 Uiso 1 1 calc R . .
C32 C -0.1904(13) 0.3301(12) 1.0637(12) 0.048(4) Uani 1 1 d . . .
H32 H -0.2213 0.3822 1.0904 0.057 Uiso 1 1 calc R . .
C33 C -0.1496(13) 0.3243(11) 0.9770(11) 0.043(4) Uani 1 1 d . . .
H33 H -0.1428 0.3716 0.9348 0.052 Uiso 1 1 calc R . .
C34 C -0.1204(12) 0.2372(10) 0.9630(9) 0.036(4) Uani 1 1 d . . .
H34 H -0.0909 0.2144 0.9081 0.043 Uiso 1 1 calc R . .
C35 C -0.1402(12) 0.1873(11) 1.0401(10) 0.040(4) Uani 1 1 d . . .
H35 H -0.1297 0.1252 1.0471 0.048 Uiso 1 1 calc R . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Ir1 0.0225(3) 0.0225(3) 0.0213(2) 0.0008(2) 0.00254(16) 0.0014(3)
Ti1 0.0223(11) 0.0246(13) 0.0221(10) -0.0024(10) 0.0023(8) 0.0006(11)
N1 0.026(6) 0.026(6) 0.028(6) -0.007(5) 0.005(4) -0.004(5)
C41 0.045(9) 0.021(8) 0.030(7) -0.001(6) 0.007(6) -0.005(7)
C411 0.048(10) 0.059(12) 0.053(10) 0.025(9) -0.023(8) 0.004(9)
C412 0.063(11) 0.051(11) 0.040(9) 0.017(8) 0.002(8) -0.008(9)
C413 0.074(12) 0.020(8) 0.043(9) 0.008(7) 0.004(8) 0.001(8)
C11 0.031(7) 0.031(8) 0.041(8) -0.013(7) 0.008(6) 0.005(7)
C111 0.050(10) 0.070(13) 0.059(11) -0.007(10) 0.025(8) -0.014(10)
C12 0.022(7) 0.049(9) 0.035(8) -0.001(7) 0.008(6) 0.006(7)
C121 0.037(10) 0.113(18) 0.064(12) 0.011(12) 0.007(8) 0.024(11)
C13 0.036(8) 0.026(8) 0.034(7) -0.001(6) 0.010(6) -0.004(7)
C131 0.086(13) 0.030(9) 0.063(11) 0.000(8) 0.040(10) -0.001(9)
C14 0.025(7) 0.043(10) 0.027(7) 0.001(6) 0.014(5) -0.014(7)
C141 0.040(9) 0.085(13) 0.025(7) -0.004(8) 0.003(6) -0.015(9)
C15 0.035(7) 0.031(8) 0.031(7) 0.019(7) 0.016(6) 0.003(7)
C151 0.079(12) 0.042(10) 0.044(9) 0.020(8) 0.025(8) 0.018(9)
C21 0.056(10) 0.045(10) 0.036(8) -0.028(7) 0.011(7) 0.000(8)
C22 0.050(9) 0.020(8) 0.046(9) -0.018(6) -0.003(7) 0.011(7)
C23 0.053(10) 0.033(9) 0.039(8) -0.011(7) 0.016(7) -0.022(8)
C24 0.035(8) 0.032(9) 0.051(9) -0.016(7) -0.011(7) -0.005(7)
C25 0.061(10) 0.028(8) 0.034(8) -0.010(7) -0.014(7) -0.001(8)
C31 0.027(8) 0.077(13) 0.042(9) -0.001(8) 0.004(7) -0.001(8)
C32 0.020(7) 0.049(11) 0.071(11) -0.019(9) -0.009(7) -0.006(8)
C33 0.022(8) 0.048(11) 0.056(10) 0.011(8) -0.009(7) 0.004(7)
C34 0.014(6) 0.056(11) 0.035(7) -0.014(7) -0.003(5) -0.006(7)
C35 0.019(7) 0.044(9) 0.057(10) 0.002(7) -0.003(6) -0.015(7)

_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
Ir1 N1 1.869(10) . ?
Ir1 C14 2.171(12) . ?
Ir1 C11 2.207(14) . ?
Ir1 C15 2.209(11) . ?
Ir1 C13 2.287(13) . ?
Ir1 C12 2.299(13) . ?
Ir1 Ti1 2.542(2) . ?
Ti1 N1 1.982(11) . ?
Ti1 C21 2.381(13) . ?
Ti1 C34 2.389(13) . ?
Ti1 C31 2.405(15) . ?
Ti1 C22 2.405(14) . ?
Ti1 C33 2.408(14) . ?
Ti1 C23 2.422(14) . ?
Ti1 C35 2.431(14) . ?
Ti1 C25 2.437(13) . ?
Ti1 C32 2.445(15) . ?
Ti1 C24 2.483(14) . ?
N1 C41 1.451(17) . ?
C41 C413 1.525(19) . ?
C41 C411 1.53(2) . ?
C41 C412 1.533(19) . ?
C11 C15 1.415(19) . ?
C11 C111 1.48(2) . ?
C11 C12 1.48(2) . ?
C12 C13 1.379(19) . ?
C12 C121 1.52(2) . ?
C13 C14 1.440(19) . ?
C13 C131 1.53(2) . ?
C14 C15 1.358(19) . ?
C14 C141 1.512(18) . ?
C15 C151 1.533(19) . ?
C21 C22 1.39(2) . ?
C21 C25 1.44(2) . ?
C22 C23 1.40(2) . ?
C23 C24 1.37(2) . ?
C24 C25 1.40(2) . ?
C31 C32 1.40(2) . ?
C31 C35 1.41(2) . ?
C32 C33 1.38(2) . ?
C33 C34 1.37(2) . ?
C34 C35 1.39(2) . ?

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 Ir1 C14 148.1(5) . . ?
N1 Ir1 C11 145.8(5) . . ?
C14 Ir1 C11 62.9(5) . . ?
N1 Ir1 C15 170.6(5) . . ?
C14 Ir1 C15 36.1(5) . . ?
C11 Ir1 C15 37.4(5) . . ?
N1 Ir1 C13 128.6(5) . . ?
C14 Ir1 C13 37.6(5) . . ?
C11 Ir1 C13 61.8(5) . . ?
C15 Ir1 C13 60.4(5) . . ?
N1 Ir1 C12 127.6(5) . . ?
C14 Ir1 C12 61.3(5) . . ?
C11 Ir1 C12 38.2(5) . . ?
C15 Ir1 C12 61.0(5) . . ?
C13 Ir1 C12 35.0(5) . . ?
N1 Ir1 Ti1 50.6(3) . . ?
C14 Ir1 Ti1 131.7(4) . . ?
C11 Ir1 Ti1 130.0(4) . . ?
C15 Ir1 Ti1 120.0(4) . . ?
C13 Ir1 Ti1 163.3(4) . . ?
C12 Ir1 Ti1 161.7(4) . . ?
N1 Ti1 C21 122.6(5) . . ?
N1 Ti1 C34 96.9(5) . . ?
C21 Ti1 C34 134.6(5) . . ?
N1 Ti1 C31 106.3(6) . . ?
C21 Ti1 C31 89.6(6) . . ?
C34 Ti1 C31 55.6(5) . . ?
N1 Ti1 C22 141.1(5) . . ?
C21 Ti1 C22 33.8(5) . . ?
C34 Ti1 C22 120.5(5) . . ?
C31 Ti1 C22 103.7(6) . . ?
N1 Ti1 C33 130.1(5) . . ?
C21 Ti1 C33 104.9(6) . . ?
C34 Ti1 C33 33.3(5) . . ?
C31 Ti1 C33 56.0(5) . . ?
C22 Ti1 C33 87.5(5) . . ?
N1 Ti1 C23 113.4(5) . . ?
C21 Ti1 C23 56.2(5) . . ?
C34 Ti1 C23 130.5(5) . . ?
C31 Ti1 C23 137.3(6) . . ?
C22 Ti1 C23 33.6(5) . . ?
C33 Ti1 C23 105.0(6) . . ?
N1 Ti1 C35 83.5(5) . . ?
C21 Ti1 C35 123.3(5) . . ?
C34 Ti1 C35 33.4(5) . . ?
C31 Ti1 C35 34.0(5) . . ?
C22 Ti1 C35 133.6(5) . . ?
C33 Ti1 C35 55.8(5) . . ?
C23 Ti1 C35 160.8(6) . . ?
N1 Ti1 C25 90.0(5) . . ?
C21 Ti1 C25 34.6(5) . . ?
C34 Ti1 C25 166.9(5) . . ?
C31 Ti1 C25 111.7(5) . . ?
C22 Ti1 C25 55.8(5) . . ?
C33 Ti1 C25 139.3(6) . . ?
C23 Ti1 C25 55.0(5) . . ?
C35 Ti1 C25 137.7(5) . . ?
N1 Ti1 C32 137.7(5) . . ?
C21 Ti1 C32 80.4(5) . . ?
C34 Ti1 C32 54.4(5) . . ?
C31 Ti1 C32 33.5(5) . . ?
C22 Ti1 C32 78.5(5) . . ?
C33 Ti1 C32 32.9(5) . . ?
C23 Ti1 C32 108.8(6) . . ?
C35 Ti1 C32 55.2(5) . . ?
C25 Ti1 C32 113.6(5) . . ?
N1 Ti1 C24 86.4(5) . . ?
C21 Ti1 C24 56.0(5) . . ?
C34 Ti1 C24 158.2(5) . . ?
C31 Ti1 C24 143.7(5) . . ?
C22 Ti1 C24 54.9(5) . . ?
C33 Ti1 C24 137.4(6) . . ?
C23 Ti1 C24 32.5(5) . . ?
C35 Ti1 C24 166.5(5) . . ?
C25 Ti1 C24 33.0(5) . . ?
C32 Ti1 C24 132.4(5) . . ?
N1 Ti1 Ir1 46.8(3) . . ?
C21 Ti1 Ir1 138.6(4) . . ?
C34 Ti1 Ir1 84.1(3) . . ?
C31 Ti1 Ir1 130.9(4) . . ?
C22 Ti1 Ir1 121.9(4) . . ?
C33 Ti1 Ir1 105.8(4) . . ?
C23 Ti1 Ir1 89.2(4) . . ?
C35 Ti1 Ir1 97.0(4) . . ?
C25 Ti1 Ir1 108.6(4) . . ?
C32 Ti1 Ir1 137.2(4) . . ?
C24 Ti1 Ir1 82.6(4) . . ?
C41 N1 Ir1 135.0(9) . . ?
C41 N1 Ti1 142.2(8) . . ?
Ir1 N1 Ti1 82.6(4) . . ?
N1 C41 C413 108.4(10) . . ?
N1 C41 C411 107.5(11) . . ?
C413 C41 C411 111.3(13) . . ?
N1 C41 C412 111.0(12) . . ?
C413 C41 C412 108.7(12) . . ?
C411 C41 C412 109.9(12) . . ?
C15 C11 C111 131.1(15) . . ?
C15 C11 C12 104.6(12) . . ?
C111 C11 C12 123.7(13) . . ?
C15 C11 Ir1 71.4(7) . . ?
C111 C11 Ir1 125.4(9) . . ?
C12 C11 Ir1 74.3(8) . . ?
C13 C12 C11 108.0(12) . . ?
C13 C12 C121 126.7(16) . . ?
C11 C12 C121 125.4(15) . . ?
C13 C12 Ir1 72.0(8) . . ?
C11 C12 Ir1 67.5(7) . . ?
C121 C12 Ir1 126.2(10) . . ?
C12 C13 C14 108.1(13) . . ?
C12 C13 C131 127.3(15) . . ?
C14 C13 C131 124.6(14) . . ?
C12 C13 Ir1 73.0(8) . . ?
C14 C13 Ir1 66.8(7) . . ?
C131 C13 Ir1 125.2(9) . . ?
C15 C14 C13 107.8(12) . . ?
C15 C14 C141 127.4(14) . . ?
C13 C14 C141 123.8(14) . . ?
C15 C14 Ir1 73.5(7) . . ?
C13 C14 Ir1 75.6(7) . . ?
C141 C14 Ir1 126.0(8) . . ?
C14 C15 C11 110.8(13) . . ?
C14 C15 C151 126.7(13) . . ?
C11 C15 C151 122.5(14) . . ?
C14 C15 Ir1 70.4(7) . . ?
C11 C15 Ir1 71.2(7) . . ?
C151 C15 Ir1 123.7(9) . . ?
C22 C21 C25 106.6(13) . . ?
C22 C21 Ti1 74.1(8) . . ?
C25 C21 Ti1 74.8(8) . . ?
C21 C22 C23 108.4(14) . . ?
C21 C22 Ti1 72.1(8) . . ?
C23 C22 Ti1 73.8(8) . . ?
C24 C23 C22 109.0(14) . . ?
C24 C23 Ti1 76.2(9) . . ?
C22 C23 Ti1 72.5(8) . . ?
C23 C24 C25 108.3(14) . . ?
C23 C24 Ti1 71.3(8) . . ?
C25 C24 Ti1 71.7(8) . . ?
C24 C25 C21 107.6(14) . . ?
C24 C25 Ti1 75.4(8) . . ?
C21 C25 Ti1 70.5(7) . . ?
C32 C31 C35 107.0(14) . . ?
C32 C31 Ti1 74.9(9) . . ?
C35 C31 Ti1 74.0(8) . . ?
C33 C32 C31 109.2(15) . . ?
C33 C32 Ti1 72.1(9) . . ?
C31 C32 Ti1 71.7(9) . . ?
C34 C33 C32 107.0(15) . . ?
C34 C33 Ti1 72.6(8) . . ?
C32 C33 Ti1 75.0(9) . . ?
C33 C34 C35 110.4(14) . . ?
C33 C34 Ti1 74.1(8) . . ?
C35 C34 Ti1 75.0(8) . . ?
C34 C35 C31 106.2(15) . . ?
C34 C35 Ti1 71.6(8) . . ?
C31 C35 Ti1 72.0(8) . . ?

_diffrn_measured_fraction_theta_max 0.996
_diffrn_reflns_theta_full        25.35
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         6.367
_refine_diff_density_min         -2.454
_refine_diff_density_rms         0.248

data_Ir-Hf
_database_code_depnum_ccdc_archive 'CCDC 838832'
#TrackingRef '- curley_chemsci.cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            Cp*Ir(mu-NtBu)HfCp2
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C24 H34 Hf Ir N'
_chemical_formula_weight         707.21

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'
Hf Hf -0.5830 6.1852 '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'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   Cc

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

_cell_length_a                   14.594(3)
_cell_length_b                   15.259(3)
_cell_length_c                   10.423(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 96.64(3)
_cell_angle_gamma                90.00
_cell_volume                     2305.5(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    153(2)
_cell_measurement_reflns_used    4539
_cell_measurement_theta_min      2.61
_cell_measurement_theta_max      25.53

_exptl_crystal_description       block
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.037
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1336
_exptl_absorpt_coefficient_mu    10.274
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.1486
_exptl_absorpt_correction_T_max  0.2331
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      153(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  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_detector_area_resol_mean 8.366
_diffrn_reflns_number            10601
_diffrn_reflns_av_R_equivalents  0.0664
_diffrn_reflns_av_sigmaI/netI    0.0730
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         3.32
_diffrn_reflns_theta_max         25.02
_reflns_number_total             11090
_reflns_number_gt                3272
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ 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/[\s^2^(Fo^2^)+(0.0204P)^2^+18.4648P] where P=(Fo^2^+2Fc^2^)/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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.56(2)
_refine_ls_number_reflns         3628
_refine_ls_number_parameters     232
_refine_ls_number_restraints     108
_refine_ls_R_factor_all          0.0465
_refine_ls_R_factor_gt           0.0375
_refine_ls_wR_factor_ref         0.0833
_refine_ls_wR_factor_gt          0.0759
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_restrained_S_all      1.059
_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
Ir1 Ir 0.45317(4) 0.27586(3) 0.08191(5) 0.03137(13) Uani 1 1 d . . .
Hf1 Hf 0.35625(5) 0.20138(4) 0.24139(5) 0.03560(16) Uani 1 1 d . . .
N4 N 0.3386(8) 0.3125(7) 0.1350(11) 0.038(3) Uani 1 1 d . . .
C41 C 0.2818(10) 0.3893(9) 0.1028(16) 0.050(4) Uani 1 1 d . . .
C411 C 0.2462(17) 0.3830(19) -0.040(2) 0.133(11) Uani 1 1 d . . .
H41A H 0.2981 0.3879 -0.0912 0.200 Uiso 1 1 calc R . .
H41B H 0.2023 0.4305 -0.0628 0.200 Uiso 1 1 calc R . .
H41C H 0.2154 0.3264 -0.0570 0.200 Uiso 1 1 calc R . .
C412 C 0.3381(13) 0.4703(12) 0.124(3) 0.124(10) Uani 1 1 d . . .
H41D H 0.3591 0.4764 0.2168 0.185 Uiso 1 1 calc R . .
H41E H 0.3006 0.5213 0.0950 0.185 Uiso 1 1 calc R . .
H41F H 0.3916 0.4666 0.0760 0.185 Uiso 1 1 calc R . .
C413 C 0.2000(14) 0.3892(14) 0.173(3) 0.106(9) Uani 1 1 d . . .
H41G H 0.1678 0.3330 0.1594 0.159 Uiso 1 1 calc R . .
H41H H 0.1585 0.4368 0.1404 0.159 Uiso 1 1 calc R . .
H41I H 0.2190 0.3978 0.2652 0.159 Uiso 1 1 calc R . .
C11 C 0.5147(10) 0.3115(10) -0.1094(15) 0.048(4) Uani 1 1 d . . .
C12 C 0.5618(10) 0.3616(9) -0.0106(17) 0.049(4) Uani 1 1 d . . .
C13 C 0.5986(10) 0.3011(12) 0.0889(15) 0.052(4) Uani 1 1 d . . .
C14 C 0.5826(10) 0.2153(10) 0.0466(16) 0.049(4) Uani 1 1 d . . .
C15 C 0.5225(12) 0.2199(11) -0.0734(17) 0.057(5) Uani 1 1 d . . .
C111 C 0.4651(15) 0.3439(17) -0.2311(18) 0.102(8) Uani 1 1 d . . .
H11A H 0.4799 0.4059 -0.2423 0.153 Uiso 1 1 calc R . .
H11B H 0.3985 0.3375 -0.2284 0.153 Uiso 1 1 calc R . .
H11C H 0.4837 0.3100 -0.3035 0.153 Uiso 1 1 calc R . .
C121 C 0.5723(12) 0.4561(11) -0.0049(19) 0.078(6) Uani 1 1 d . . .
H12A H 0.6336 0.4721 -0.0268 0.117 Uiso 1 1 calc R . .
H12B H 0.5652 0.4766 0.0825 0.117 Uiso 1 1 calc R . .
H12C H 0.5250 0.4834 -0.0667 0.117 Uiso 1 1 calc R . .
C131 C 0.6602(10) 0.3286(15) 0.2058(17) 0.083(7) Uani 1 1 d . . .
H13A H 0.6679 0.2799 0.2673 0.125 Uiso 1 1 calc R . .
H13B H 0.6327 0.3787 0.2461 0.125 Uiso 1 1 calc R . .
H13C H 0.7205 0.3455 0.1810 0.125 Uiso 1 1 calc R . .
C141 C 0.6206(16) 0.1344(14) 0.105(3) 0.101(8) Uani 1 1 d . . .
H14A H 0.6745 0.1169 0.0629 0.151 Uiso 1 1 calc R . .
H14B H 0.5738 0.0882 0.0930 0.151 Uiso 1 1 calc R . .
H14C H 0.6389 0.1437 0.1971 0.151 Uiso 1 1 calc R . .
C151 C 0.4860(9) 0.1423(7) -0.1575(9) 0.083(6) Uani 1 1 d . . .
H15A H 0.4310 0.1604 -0.2142 0.124 Uiso 1 1 calc R . .
H15B H 0.4700 0.0941 -0.1020 0.124 Uiso 1 1 calc R . .
H15C H 0.5336 0.1227 -0.2100 0.124 Uiso 1 1 calc R . .
C21 C 0.3417(5) 0.0552(4) 0.1313(5) 0.084(4) Uani 1 1 d RDU . .
H21 H 0.3961 0.0245 0.1162 0.101 Uiso 1 1 calc R . .
C22 C 0.2957(5) 0.0490(4) 0.2437(5) 0.083(4) Uani 1 1 d RDU . .
H22 H 0.3139 0.0134 0.3171 0.100 Uiso 1 1 calc R . .
C23 C 0.2177(4) 0.1053(4) 0.2274(6) 0.076(4) Uani 1 1 d RDU . .
H23 H 0.1746 0.1139 0.2878 0.092 Uiso 1 1 calc R . .
C24 C 0.2155(5) 0.1462(4) 0.1048(7) 0.079(4) Uani 1 1 d RDU . .
H24 H 0.1706 0.1872 0.0688 0.095 Uiso 1 1 calc R . .
C25 C 0.2922(4) 0.1153(4) 0.0455(6) 0.075(4) Uani 1 1 d RDU . .
H25 H 0.3076 0.1319 -0.0372 0.090 Uiso 1 1 calc R . .
C31 C 0.4524(5) 0.1605(4) 0.4503(7) 0.095(5) Uani 1 1 d RDU . .
H31 H 0.4888 0.1088 0.4525 0.114 Uiso 1 1 calc R . .
C32 C 0.3600(5) 0.1663(4) 0.4799(5) 0.086(4) Uani 1 1 d RDU . .
H32 H 0.3237 0.1190 0.5054 0.104 Uiso 1 1 calc R . .
C33 C 0.3314(4) 0.2550(4) 0.4648(5) 0.085(4) Uani 1 1 d RDU . .
H33 H 0.2726 0.2775 0.4783 0.103 Uiso 1 1 calc R . .
C34 C 0.4061(5) 0.3040(4) 0.4259(5) 0.084(4) Uani 1 1 d RDU . .
H34 H 0.4061 0.3652 0.4088 0.101 Uiso 1 1 calc R . .
C35 C 0.4809(5) 0.2457(4) 0.4169(6) 0.096(5) Uani 1 1 d RDU . .
H35 H 0.5397 0.2609 0.3928 0.115 Uiso 1 1 calc R . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Ir1 0.0328(3) 0.0314(2) 0.0307(3) -0.0014(2) 0.0072(2) 0.0004(2)
Hf1 0.0387(3) 0.0368(3) 0.0324(3) 0.0000(3) 0.0088(2) -0.0023(3)
N4 0.051(7) 0.031(6) 0.033(6) -0.005(5) 0.003(5) -0.002(5)
C41 0.049(9) 0.032(7) 0.069(11) 0.007(7) 0.008(8) 0.006(7)
C411 0.13(2) 0.18(3) 0.091(17) 0.041(17) -0.006(15) 0.09(2)
C412 0.066(13) 0.042(10) 0.26(3) -0.016(15) -0.012(17) 0.008(10)
C413 0.067(13) 0.070(13) 0.19(3) 0.012(15) 0.039(16) 0.029(11)
C11 0.046(8) 0.058(9) 0.046(9) 0.007(8) 0.027(7) 0.005(7)
C12 0.048(8) 0.031(7) 0.074(12) 0.008(8) 0.033(8) -0.006(7)
C13 0.036(8) 0.077(12) 0.044(9) -0.009(9) 0.007(7) -0.006(8)
C14 0.038(8) 0.057(10) 0.054(10) 0.016(8) 0.013(7) 0.023(7)
C15 0.076(12) 0.062(11) 0.040(9) -0.017(8) 0.032(9) -0.019(9)
C111 0.125(19) 0.14(2) 0.038(11) 0.019(12) -0.001(11) -0.011(16)
C121 0.065(11) 0.054(10) 0.121(18) -0.008(11) 0.034(11) -0.014(9)
C131 0.027(8) 0.15(2) 0.071(12) -0.021(13) -0.005(8) -0.027(10)
C141 0.079(14) 0.093(16) 0.14(2) 0.047(15) 0.052(15) 0.044(12)
C151 0.092(13) 0.095(14) 0.068(12) -0.051(11) 0.041(11) -0.014(11)
C21 0.091(10) 0.052(9) 0.111(11) -0.032(8) 0.013(8) -0.014(7)
C22 0.097(10) 0.047(8) 0.103(10) 0.015(7) 0.002(8) -0.033(7)
C23 0.067(8) 0.072(9) 0.092(9) -0.006(7) 0.016(7) -0.041(6)
C24 0.063(8) 0.070(9) 0.101(10) 0.007(7) -0.008(7) -0.028(6)
C25 0.093(10) 0.065(9) 0.067(8) -0.022(7) 0.006(7) -0.045(8)
C31 0.085(9) 0.138(10) 0.053(9) 0.012(9) -0.028(8) 0.024(8)
C32 0.097(9) 0.108(9) 0.051(9) -0.001(9) -0.004(9) -0.011(8)
C33 0.098(9) 0.112(10) 0.047(9) -0.027(9) 0.012(8) 0.002(8)
C34 0.105(10) 0.103(9) 0.034(8) -0.013(8) -0.038(8) -0.026(8)
C35 0.068(8) 0.169(13) 0.043(9) 0.009(10) -0.026(7) -0.019(8)

_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
Ir1 N4 1.905(11) . ?
Ir1 C13 2.150(14) . ?
Ir1 C14 2.172(13) . ?
Ir1 C15 2.179(14) . ?
Ir1 C11 2.344(14) . ?
Ir1 C12 2.346(13) . ?
Ir1 Hf1 2.5689(9) . ?
Hf1 N4 2.026(11) . ?
Hf1 C22 2.489(6) . ?
Hf1 C23 2.489(6) . ?
Hf1 C24 2.506(5) . ?
Hf1 C21 2.506(6) . ?
Hf1 C25 2.516(5) . ?
Hf1 C35 2.519(6) . ?
Hf1 C34 2.521(5) . ?
Hf1 C31 2.529(6) . ?
Hf1 C33 2.533(5) . ?
Hf1 C32 2.538(6) . ?
N4 C41 1.452(18) . ?
C41 C413 1.47(2) . ?
C41 C412 1.49(2) . ?
C41 C411 1.52(3) . ?
C11 C12 1.40(2) . ?
C11 C15 1.45(2) . ?
C11 C111 1.47(2) . ?
C12 C13 1.44(2) . ?
C12 C121 1.45(2) . ?
C13 C14 1.39(2) . ?
C13 C131 1.49(2) . ?
C14 C15 1.44(2) . ?
C14 C141 1.46(2) . ?
C15 C151 1.533(17) . ?
C21 C25 1.4195(15) . ?
C21 C22 1.4201 . ?
C22 C23 1.4205(13) . ?
C23 C24 1.419(2) . ?
C24 C25 1.4206(16) . ?
C31 C35 1.4198 . ?
C31 C32 1.421(2) . ?
C32 C33 1.4198 . ?
C33 C34 1.4202 . ?
C34 C35 1.4205(14) . ?

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
N4 Ir1 C13 146.5(6) . . ?
N4 Ir1 C14 169.7(5) . . ?
C13 Ir1 C14 37.6(6) . . ?
N4 Ir1 C15 146.0(6) . . ?
C13 Ir1 C15 63.5(6) . . ?
C14 Ir1 C15 38.8(6) . . ?
N4 Ir1 C11 127.9(5) . . ?
C13 Ir1 C11 60.9(6) . . ?
C14 Ir1 C11 61.9(5) . . ?
C15 Ir1 C11 37.1(5) . . ?
N4 Ir1 C12 127.8(5) . . ?
C13 Ir1 C12 37.2(6) . . ?
C14 Ir1 C12 61.7(5) . . ?
C15 Ir1 C12 61.3(5) . . ?
C11 Ir1 C12 34.7(5) . . ?
N4 Ir1 Hf1 51.3(3) . . ?
C13 Ir1 Hf1 132.3(5) . . ?
C14 Ir1 Hf1 118.4(4) . . ?
C15 Ir1 Hf1 130.1(4) . . ?
C11 Ir1 Hf1 161.3(4) . . ?
C12 Ir1 Hf1 164.0(4) . . ?
N4 Hf1 C22 139.9(3) . . ?
N4 Hf1 C23 114.2(4) . . ?
C22 Hf1 C23 33.16(8) . . ?
N4 Hf1 C24 85.8(4) . . ?
C22 Hf1 C24 54.77(12) . . ?
C23 Hf1 C24 33.02(9) . . ?
N4 Hf1 C21 119.7(3) . . ?
C22 Hf1 C21 33.03(8) . . ?
C23 Hf1 C21 54.80(14) . . ?
C24 Hf1 C21 54.60(13) . . ?
N4 Hf1 C25 88.9(3) . . ?
C22 Hf1 C25 54.62(14) . . ?
C23 Hf1 C25 54.64(12) . . ?
C24 Hf1 C25 32.87(8) . . ?
C21 Hf1 C25 32.83(7) . . ?
N4 Hf1 C35 102.0(3) . . ?
C22 Hf1 C35 118.1(3) . . ?
C23 Hf1 C35 135.6(3) . . ?
C24 Hf1 C35 168.1(3) . . ?
C21 Hf1 C35 126.0(3) . . ?
C25 Hf1 C35 154.1(3) . . ?
N4 Hf1 C34 84.5(3) . . ?
C22 Hf1 C34 130.1(2) . . ?
C23 Hf1 C34 124.9(2) . . ?
C24 Hf1 C34 141.9(3) . . ?
C21 Hf1 C34 154.7(3) . . ?
C25 Hf1 C34 172.3(3) . . ?
C35 Hf1 C34 32.74(7) . . ?
N4 Hf1 C31 134.5(3) . . ?
C22 Hf1 C31 85.6(2) . . ?
C23 Hf1 C31 105.8(2) . . ?
C24 Hf1 C31 138.0(3) . . ?
C21 Hf1 C31 100.6(2) . . ?
C25 Hf1 C31 133.4(3) . . ?
C35 Hf1 C31 32.67(8) . . ?
C34 Hf1 C31 54.11(11) . . ?
N4 Hf1 C33 102.1(3) . . ?
C22 Hf1 C33 101.8(2) . . ?
C23 Hf1 C33 92.4(2) . . ?
C24 Hf1 C33 115.8(3) . . ?
C21 Hf1 C33 134.0(3) . . ?
C25 Hf1 C33 146.6(3) . . ?
C35 Hf1 C33 54.13(14) . . ?
C34 Hf1 C33 32.63(7) . . ?
C31 Hf1 C33 54.00(13) . . ?
N4 Hf1 C32 134.4(3) . . ?
C22 Hf1 C32 76.15(18) . . ?
C23 Hf1 C32 81.87(18) . . ?
C24 Hf1 C32 114.2(2) . . ?
C21 Hf1 C32 104.6(2) . . ?
C25 Hf1 C32 130.5(3) . . ?
C35 Hf1 C32 54.06(13) . . ?
C34 Hf1 C32 54.01(11) . . ?
C31 Hf1 C32 32.57(10) . . ?
C33 Hf1 C32 32.52(7) . . ?
N4 Hf1 Ir1 47.2(3) . . ?
C22 Hf1 Ir1 129.98(14) . . ?
C23 Hf1 Ir1 136.65(14) . . ?
C24 Hf1 Ir1 104.93(18) . . ?
C21 Hf1 Ir1 96.96(15) . . ?
C25 Hf1 Ir1 83.49(16) . . ?
C35 Hf1 Ir1 86.88(18) . . ?
C34 Hf1 Ir1 94.97(14) . . ?
C31 Hf1 Ir1 112.0(2) . . ?
C33 Hf1 Ir1 126.88(13) . . ?
C32 Hf1 Ir1 140.91(15) . . ?
C41 N4 Ir1 131.8(9) . . ?
C41 N4 Hf1 146.6(9) . . ?
Ir1 N4 Hf1 81.5(4) . . ?
N4 C41 C413 111.0(14) . . ?
N4 C41 C412 110.2(13) . . ?
C413 C41 C412 113.1(18) . . ?
N4 C41 C411 107.2(14) . . ?
C413 C41 C411 106.3(17) . . ?
C412 C41 C411 108.8(19) . . ?
C12 C11 C15 108.6(14) . . ?
C12 C11 C111 127.0(16) . . ?
C15 C11 C111 124.3(18) . . ?
C12 C11 Ir1 72.8(8) . . ?
C15 C11 Ir1 65.3(7) . . ?
C111 C11 Ir1 127.7(12) . . ?
C11 C12 C13 106.8(13) . . ?
C11 C12 C121 127.9(17) . . ?
C13 C12 C121 125.3(17) . . ?
C11 C12 Ir1 72.6(8) . . ?
C13 C12 Ir1 64.0(7) . . ?
C121 C12 Ir1 127.6(10) . . ?
C14 C13 C12 109.8(13) . . ?
C14 C13 C131 126.0(17) . . ?
C12 C13 C131 123.1(17) . . ?
C14 C13 Ir1 72.1(8) . . ?
C12 C13 Ir1 78.8(8) . . ?
C131 C13 Ir1 125.3(10) . . ?
C13 C14 C15 107.0(13) . . ?
C13 C14 C141 129(2) . . ?
C15 C14 C141 124.4(19) . . ?
C13 C14 Ir1 70.4(8) . . ?
C15 C14 Ir1 70.9(8) . . ?
C141 C14 Ir1 125.9(12) . . ?
C14 C15 C11 107.0(14) . . ?
C14 C15 C151 126.5(16) . . ?
C11 C15 C151 125.9(16) . . ?
C14 C15 Ir1 70.3(8) . . ?
C11 C15 Ir1 77.6(8) . . ?
C151 C15 Ir1 124.5(9) . . ?
C25 C21 C22 107.9(2) . . ?
C25 C21 Hf1 73.95(16) . . ?
C22 C21 Hf1 72.80(15) . . ?
C21 C22 C23 108.05(15) . . ?
C21 C22 Hf1 74.17(14) . . ?
C23 C22 Hf1 73.42(16) . . ?
C24 C23 C22 108.0 . . ?
C24 C23 Hf1 74.15(14) . . ?
C22 C23 Hf1 73.42(17) . . ?
C23 C24 C25 107.97(8) . . ?
C23 C24 Hf1 72.84(15) . . ?
C25 C24 Hf1 73.96(17) . . ?
C21 C25 C24 108.1(2) . . ?
C21 C25 Hf1 73.22(18) . . ?
C24 C25 Hf1 73.17(16) . . ?
C35 C31 C32 108.02(6) . . ?
C35 C31 Hf1 73.29(16) . . ?
C32 C31 Hf1 74.06(15) . . ?
C33 C32 C31 108.0 . . ?
C33 C32 Hf1 73.58(16) . . ?
C31 C32 Hf1 73.37(15) . . ?
C32 C33 C34 107.96(11) . . ?
C32 C33 Hf1 73.91(17) . . ?
C34 C33 Hf1 73.22(13) . . ?
C33 C34 C35 108.05(16) . . ?
C33 C34 Hf1 74.15(14) . . ?
C35 C34 Hf1 73.54(16) . . ?
C31 C35 C34 107.95(14) . . ?
C31 C35 Hf1 74.04(17) . . ?
C34 C35 Hf1 73.72(16) . . ?

_diffrn_measured_fraction_theta_max 0.980
_diffrn_reflns_theta_full        25.02
_diffrn_measured_fraction_theta_full 0.980
_refine_diff_density_max         1.038
_refine_diff_density_min         -1.112
_refine_diff_density_rms         0.184

data_Ir-Zr-muH
_database_code_depnum_ccdc_archive 'CCDC 838833'
#TrackingRef '- curley_chemsci.cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            Cp*Ir(mu-NtBu)(mu-H)ZrCp2OTf
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C25 H35 F3 Ir1 N1 O3 S1 Zr1'
_chemical_formula_weight         770.02

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'
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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zr Zr -2.9673 0.5597 '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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P2(1)/c

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

_cell_length_a                   9.1580(3)
_cell_length_b                   19.2669(6)
_cell_length_c                   15.2292(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 100.551(2)
_cell_angle_gamma                90.00
_cell_volume                     2641.70(15)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9912
_cell_measurement_theta_min      2.50
_cell_measurement_theta_max      28.32

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.035
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.936
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1504
_exptl_absorpt_coefficient_mu    5.55
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.5514
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      100(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  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            84903
_diffrn_reflns_av_R_equivalents  0.0384
_diffrn_reflns_av_sigmaI/netI    0.0175
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         1.72
_diffrn_reflns_theta_max         27.10
_reflns_number_total             5831
_reflns_number_gt                5314
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ 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/[\s^2^(Fo^2^)+(0.0064P)^2^+4.0238P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         5831
_refine_ls_number_parameters     327
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0200
_refine_ls_R_factor_gt           0.0157
_refine_ls_wR_factor_ref         0.0320
_refine_ls_wR_factor_gt          0.0304
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ir1 Ir 0.283682(9) 0.548285(4) 0.230305(5) 0.01060(3) Uani 1 1 d D . .
Zr1 Zr 0.30455(2) 0.670269(11) 0.113532(13) 0.01005(5) Uani 1 1 d D . .
H1 H 0.3942(19) 0.5918(9) 0.1924(13) 0.012 Uiso 1 1 d D . .
N1 N 0.1420(2) 0.60482(10) 0.15596(12) 0.0132(4) Uani 1 1 d . . .
C4 C -0.0223(2) 0.60203(12) 0.14120(15) 0.0158(5) Uani 1 1 d . . .
C41 C -0.0776(3) 0.53813(14) 0.18291(18) 0.0281(6) Uani 1 1 d . . .
H41A H -0.0358 0.4965 0.1600 0.042 Uiso 1 1 calc R . .
H41B H -0.1863 0.5363 0.1678 0.042 Uiso 1 1 calc R . .
H41C H -0.0466 0.5402 0.2479 0.042 Uiso 1 1 calc R . .
C42 C -0.0775(3) 0.66654(13) 0.18437(16) 0.0222(5) Uani 1 1 d . . .
H42A H -0.0335 0.6677 0.2480 0.033 Uiso 1 1 calc R . .
H42B H -0.1860 0.6648 0.1774 0.033 Uiso 1 1 calc R . .
H42C H -0.0483 0.7084 0.1552 0.033 Uiso 1 1 calc R . .
C43 C -0.0824(3) 0.59821(12) 0.04034(15) 0.0176(5) Uani 1 1 d . . .
H43A H -0.0505 0.6394 0.0111 0.026 Uiso 1 1 calc R . .
H43B H -0.1911 0.5963 0.0298 0.026 Uiso 1 1 calc R . .
H43C H -0.0439 0.5564 0.0157 0.026 Uiso 1 1 calc R . .
C11 C 0.3737(3) 0.44347(11) 0.25305(14) 0.0149(5) Uani 1 1 d . . .
C12 C 0.4702(3) 0.48927(12) 0.31025(14) 0.0150(5) Uani 1 1 d . . .
C13 C 0.3844(3) 0.52319(12) 0.36716(14) 0.0149(5) Uani 1 1 d . . .
C14 C 0.2368(3) 0.49238(11) 0.35179(14) 0.0141(5) Uani 1 1 d . . .
C15 C 0.2310(3) 0.44297(11) 0.28186(14) 0.0144(5) Uani 1 1 d . . .
C111 C 0.4125(3) 0.39929(12) 0.17985(15) 0.0184(5) Uani 1 1 d . . .
H11A H 0.4969 0.4199 0.1579 0.028 Uiso 1 1 calc R . .
H11B H 0.3269 0.3965 0.1308 0.028 Uiso 1 1 calc R . .
H11C H 0.4391 0.3526 0.2029 0.028 Uiso 1 1 calc R . .
C121 C 0.6318(3) 0.50013(13) 0.30983(17) 0.0211(5) Uani 1 1 d . . .
H12A H 0.6908 0.4708 0.3556 0.032 Uiso 1 1 calc R . .
H12B H 0.6573 0.5490 0.3226 0.032 Uiso 1 1 calc R . .
H12C H 0.6532 0.4878 0.2510 0.032 Uiso 1 1 calc R . .
C131 C 0.4375(3) 0.57758(12) 0.43668(15) 0.0198(5) Uani 1 1 d . . .
H13A H 0.4642 0.5555 0.4954 0.030 Uiso 1 1 calc R . .
H13B H 0.3583 0.6115 0.4380 0.030 Uiso 1 1 calc R . .
H13C H 0.5248 0.6011 0.4219 0.030 Uiso 1 1 calc R . .
C141 C 0.1228(3) 0.50546(13) 0.40898(16) 0.0205(5) Uani 1 1 d . . .
H14A H 0.0287 0.4836 0.3817 0.031 Uiso 1 1 calc R . .
H14B H 0.1080 0.5556 0.4141 0.031 Uiso 1 1 calc R . .
H14C H 0.1570 0.4858 0.4685 0.031 Uiso 1 1 calc R . .
C151 C 0.1101(3) 0.39136(12) 0.25045(16) 0.0205(5) Uani 1 1 d . . .
H15A H 0.1399 0.3457 0.2759 0.031 Uiso 1 1 calc R . .
H15B H 0.0928 0.3885 0.1851 0.031 Uiso 1 1 calc R . .
H15C H 0.0186 0.4061 0.2698 0.031 Uiso 1 1 calc R . .
C21 C 0.4037(3) 0.68906(13) -0.02881(16) 0.0237(6) Uani 1 1 d . . .
H21 H 0.4166 0.7359 -0.0455 0.028 Uiso 1 1 calc R . .
C22 C 0.2773(3) 0.64953(15) -0.05462(16) 0.0274(6) Uani 1 1 d . . .
H22 H 0.1891 0.6643 -0.0930 0.033 Uiso 1 1 calc R . .
C23 C 0.3011(3) 0.58417(15) -0.01464(18) 0.0312(7) Uani 1 1 d . . .
H23 H 0.2321 0.5469 -0.0202 0.037 Uiso 1 1 calc R . .
C24 C 0.4467(3) 0.58398(14) 0.03543(17) 0.0303(7) Uani 1 1 d . . .
H24 H 0.4940 0.5464 0.0697 0.036 Uiso 1 1 calc R . .
C25 C 0.5084(3) 0.64867(14) 0.02554(16) 0.0244(6) Uani 1 1 d . . .
H25 H 0.6061 0.6629 0.0517 0.029 Uiso 1 1 calc R . .
C31 C 0.5170(3) 0.75670(12) 0.17120(16) 0.0197(5) Uani 1 1 d . . .
H31 H 0.6015 0.7596 0.1433 0.024 Uiso 1 1 calc R . .
C32 C 0.3873(3) 0.79582(12) 0.14883(15) 0.0190(5) Uani 1 1 d . . .
H32 H 0.3660 0.8284 0.1014 0.023 Uiso 1 1 calc R . .
C33 C 0.2930(3) 0.77819(12) 0.20974(15) 0.0188(5) Uani 1 1 d . . .
H33 H 0.1985 0.7979 0.2114 0.023 Uiso 1 1 calc R . .
C34 C 0.3636(3) 0.72680(12) 0.26672(15) 0.0193(5) Uani 1 1 d . . .
H34 H 0.3254 0.7054 0.3139 0.023 Uiso 1 1 calc R . .
C35 C 0.5012(3) 0.71226(12) 0.24208(16) 0.0211(5) Uani 1 1 d . . .
H35 H 0.5709 0.6784 0.2686 0.025 Uiso 1 1 calc R . .
O1 O 0.10154(17) 0.73291(8) 0.04446(10) 0.0144(3) Uani 1 1 d . . .
O2 O 0.0714(2) 0.85780(9) 0.05867(12) 0.0287(4) Uani 1 1 d . . .
O3 O 0.13441(19) 0.80901(9) -0.07724(12) 0.0256(4) Uani 1 1 d . . .
S1 S 0.06704(6) 0.80003(3) -0.00077(4) 0.01625(12) Uani 1 1 d . . .
C5 C -0.1303(3) 0.79055(13) -0.04749(17) 0.0239(6) Uani 1 1 d . . .
F1 F -0.15446(18) 0.73883(8) -0.10631(11) 0.0400(4) Uani 1 1 d . . .
F2 F -0.21069(17) 0.77898(10) 0.01488(12) 0.0446(5) Uani 1 1 d . . .
F3 F -0.18066(16) 0.84897(8) -0.09032(10) 0.0303(4) Uani 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Ir1 0.01279(4) 0.00903(4) 0.00986(4) 0.00132(3) 0.00178(3) 0.00036(3)
Zr1 0.01206(10) 0.00862(10) 0.00948(10) 0.00013(8) 0.00201(8) 0.00071(8)
N1 0.0127(9) 0.0135(10) 0.0128(9) -0.0004(7) 0.0009(7) -0.0001(8)
C4 0.0122(11) 0.0185(12) 0.0166(11) 0.0037(9) 0.0024(9) 0.0005(9)
C41 0.0163(13) 0.0327(16) 0.0338(15) 0.0145(12) 0.0006(11) -0.0053(11)
C42 0.0171(12) 0.0317(15) 0.0186(12) -0.0007(10) 0.0049(10) 0.0061(11)
C43 0.0140(12) 0.0163(12) 0.0217(12) -0.0002(9) 0.0015(9) 0.0004(9)
C11 0.0217(12) 0.0103(11) 0.0124(11) 0.0035(8) 0.0026(9) 0.0030(9)
C12 0.0185(12) 0.0135(11) 0.0125(11) 0.0047(9) 0.0014(9) 0.0024(9)
C13 0.0214(12) 0.0108(11) 0.0114(10) 0.0031(8) -0.0001(9) 0.0021(9)
C14 0.0209(12) 0.0107(11) 0.0111(10) 0.0016(8) 0.0043(9) 0.0002(9)
C15 0.0201(12) 0.0091(11) 0.0138(11) 0.0035(8) 0.0027(9) 0.0015(9)
C111 0.0254(13) 0.0144(12) 0.0154(11) 0.0008(9) 0.0040(10) 0.0038(10)
C121 0.0173(12) 0.0206(13) 0.0240(13) 0.0033(10) 0.0004(10) 0.0018(10)
C131 0.0287(14) 0.0148(12) 0.0140(11) -0.0004(9) -0.0009(10) 0.0001(10)
C141 0.0275(14) 0.0188(13) 0.0173(12) 0.0003(9) 0.0099(10) -0.0004(11)
C151 0.0248(13) 0.0133(12) 0.0238(13) -0.0005(9) 0.0058(10) -0.0045(10)
C21 0.0383(16) 0.0192(13) 0.0184(12) 0.0006(10) 0.0173(11) 0.0020(11)
C22 0.0244(14) 0.0449(17) 0.0118(12) -0.0081(11) 0.0004(10) 0.0141(13)
C23 0.0397(17) 0.0302(16) 0.0316(15) -0.0215(12) 0.0274(13) -0.0205(13)
C24 0.0531(19) 0.0247(15) 0.0181(13) 0.0058(10) 0.0198(12) 0.0236(13)
C25 0.0165(12) 0.0386(16) 0.0202(13) -0.0106(11) 0.0086(10) 0.0008(11)
C31 0.0184(12) 0.0180(12) 0.0227(12) -0.0064(10) 0.0035(10) -0.0063(10)
C32 0.0278(13) 0.0105(11) 0.0170(12) 0.0001(9) -0.0007(10) -0.0044(10)
C33 0.0199(12) 0.0164(12) 0.0192(12) -0.0099(9) 0.0014(10) -0.0013(10)
C34 0.0296(14) 0.0176(12) 0.0101(11) -0.0055(9) 0.0021(9) -0.0067(10)
C35 0.0220(13) 0.0157(12) 0.0213(12) -0.0040(10) -0.0073(10) 0.0000(10)
O1 0.0148(8) 0.0112(8) 0.0168(8) 0.0030(6) 0.0016(6) 0.0010(6)
O2 0.0400(11) 0.0148(9) 0.0277(10) -0.0029(7) -0.0029(8) 0.0079(8)
O3 0.0258(10) 0.0259(10) 0.0270(10) 0.0108(8) 0.0099(8) 0.0061(8)
S1 0.0172(3) 0.0127(3) 0.0182(3) 0.0030(2) 0.0013(2) 0.0025(2)
C5 0.0176(13) 0.0232(14) 0.0294(14) 0.0104(11) 0.0002(11) 0.0057(11)
F1 0.0395(10) 0.0249(9) 0.0455(10) -0.0010(7) -0.0186(8) -0.0024(7)
F2 0.0216(8) 0.0607(12) 0.0546(11) 0.0298(9) 0.0154(8) 0.0101(8)
F3 0.0258(8) 0.0252(8) 0.0368(9) 0.0135(7) -0.0026(7) 0.0097(7)

_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
Ir1 N1 1.9013(18) . ?
Ir1 C13 2.174(2) . ?
Ir1 C11 2.185(2) . ?
Ir1 C12 2.220(2) . ?
Ir1 C14 2.249(2) . ?
Ir1 C15 2.260(2) . ?
Ir1 Zr1 2.9744(2) . ?
Ir1 H1 1.5076(15) . ?
Zr1 H1 2.0106(15) . ?
Zr1 N1 2.1394(19) . ?
Zr1 O1 2.3028(15) . ?
Zr1 C25 2.524(2) . ?
Zr1 C21 2.525(2) . ?
Zr1 C35 2.537(2) . ?
Zr1 C24 2.538(2) . ?
Zr1 C34 2.542(2) . ?
Zr1 C33 2.557(2) . ?
Zr1 C23 2.557(2) . ?
Zr1 C22 2.558(2) . ?
Zr1 C32 2.562(2) . ?
Zr1 C31 2.589(2) . ?
N1 C4 1.481(3) . ?
C4 C41 1.515(3) . ?
C4 C42 1.534(3) . ?
C4 C43 1.536(3) . ?
C11 C12 1.427(3) . ?
C11 C15 1.453(3) . ?
C11 C111 1.496(3) . ?
C12 C13 1.430(3) . ?
C12 C121 1.496(3) . ?
C13 C14 1.455(3) . ?
C13 C131 1.506(3) . ?
C14 C15 1.422(3) . ?
C14 C141 1.499(3) . ?
C15 C151 1.499(3) . ?
C21 C22 1.382(4) . ?
C21 C25 1.386(4) . ?
C22 C23 1.398(4) . ?
C23 C24 1.410(4) . ?
C24 C25 1.388(4) . ?
C31 C32 1.395(3) . ?
C31 C35 1.406(3) . ?
C32 C33 1.420(3) . ?
C33 C34 1.395(3) . ?
C34 C35 1.407(4) . ?
O1 S1 1.4721(16) . ?
O2 S1 1.4307(18) . ?
O3 S1 1.4248(18) . ?
S1 C5 1.826(3) . ?
C5 F2 1.323(3) . ?
C5 F1 1.331(3) . ?
C5 F3 1.340(3) . ?

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

Ir1 H1 Zr1 114.69(97) . . ?
N1 Ir1 C13 145.29(8) . . ?
N1 Ir1 C11 145.15(8) . . ?
C13 Ir1 C11 63.94(8) . . ?
N1 Ir1 C12 173.00(8) . . ?
C13 Ir1 C12 37.96(8) . . ?
C11 Ir1 C12 37.78(8) . . ?
N1 Ir1 C14 123.51(8) . . ?
C13 Ir1 C14 38.38(8) . . ?
C11 Ir1 C14 63.27(8) . . ?
C12 Ir1 C14 63.07(8) . . ?
N1 Ir1 C15 123.74(8) . . ?
C13 Ir1 C15 63.08(8) . . ?
C11 Ir1 C15 38.12(8) . . ?
C12 Ir1 C15 62.70(8) . . ?
C14 Ir1 C15 36.77(8) . . ?
N1 Ir1 Zr1 45.80(6) . . ?
C13 Ir1 Zr1 133.36(6) . . ?
C11 Ir1 Zr1 139.59(6) . . ?
C12 Ir1 Zr1 127.25(6) . . ?
C14 Ir1 Zr1 155.94(6) . . ?
C15 Ir1 Zr1 163.44(6) . . ?
N1 Zr1 O1 84.18(6) . . ?
N1 Zr1 C25 133.36(8) . . ?
O1 Zr1 C25 117.24(7) . . ?
N1 Zr1 C21 136.34(8) . . ?
O1 Zr1 C21 85.41(7) . . ?
C25 Zr1 C21 31.85(8) . . ?
N1 Zr1 C35 112.94(8) . . ?
O1 Zr1 C35 125.79(7) . . ?
C25 Zr1 C35 88.44(8) . . ?
C21 Zr1 C35 107.50(9) . . ?
N1 Zr1 C24 101.57(8) . . ?
O1 Zr1 C24 124.73(7) . . ?
C25 Zr1 C24 31.83(9) . . ?
C21 Zr1 C24 52.81(8) . . ?
C35 Zr1 C24 102.59(9) . . ?
N1 Zr1 C34 91.04(7) . . ?
O1 Zr1 C34 102.29(7) . . ?
C25 Zr1 C34 120.28(8) . . ?
C21 Zr1 C34 132.61(8) . . ?
C35 Zr1 C34 32.17(8) . . ?
C24 Zr1 C34 132.05(9) . . ?
N1 Zr1 C33 101.67(7) . . ?
O1 Zr1 C33 73.80(7) . . ?
C25 Zr1 C33 123.39(8) . . ?
C21 Zr1 C33 115.75(8) . . ?
C35 Zr1 C33 52.88(8) . . ?
C24 Zr1 C33 151.62(9) . . ?
C34 Zr1 C33 31.75(8) . . ?
N1 Zr1 C23 86.34(8) . . ?
O1 Zr1 C23 95.46(8) . . ?
C25 Zr1 C23 52.76(8) . . ?
C21 Zr1 C23 52.69(8) . . ?
C35 Zr1 C23 134.71(9) . . ?
C24 Zr1 C23 32.12(9) . . ?
C34 Zr1 C23 161.70(9) . . ?
C33 Zr1 C23 165.65(9) . . ?
N1 Zr1 C22 105.34(8) . . ?
O1 Zr1 C22 72.66(7) . . ?
C25 Zr1 C22 52.34(8) . . ?
C21 Zr1 C22 31.53(9) . . ?
C35 Zr1 C22 138.37(9) . . ?
C24 Zr1 C22 52.63(8) . . ?
C34 Zr1 C22 162.00(9) . . ?
C33 Zr1 C22 133.93(8) . . ?
C23 Zr1 C22 31.73(9) . . ?
N1 Zr1 C32 133.52(8) . . ?
O1 Zr1 C32 77.54(7) . . ?
C25 Zr1 C32 92.74(8) . . ?
C21 Zr1 C32 84.58(8) . . ?
C35 Zr1 C32 52.86(8) . . ?
C24 Zr1 C32 124.00(9) . . ?
C34 Zr1 C32 52.97(8) . . ?
C33 Zr1 C32 32.20(8) . . ?
C23 Zr1 C32 137.25(8) . . ?
C22 Zr1 C32 109.17(9) . . ?
N1 Zr1 C31 142.94(7) . . ?
O1 Zr1 C31 108.15(7) . . ?
C25 Zr1 C31 72.73(8) . . ?
C21 Zr1 C31 80.38(8) . . ?
C35 Zr1 C31 31.82(8) . . ?
C24 Zr1 C31 99.33(9) . . ?
C34 Zr1 C31 52.61(8) . . ?
C33 Zr1 C31 52.40(8) . . ?
C23 Zr1 C31 125.42(8) . . ?
C22 Zr1 C31 111.68(9) . . ?
C32 Zr1 C31 31.41(8) . . ?
C4 N1 Ir1 129.30(14) . . ?
C4 N1 Zr1 136.01(14) . . ?
Ir1 N1 Zr1 94.62(8) . . ?
N1 C4 C41 112.00(19) . . ?
N1 C4 C42 108.11(19) . . ?
C41 C4 C42 108.5(2) . . ?
N1 C4 C43 108.77(18) . . ?
C41 C4 C43 107.1(2) . . ?
C42 C4 C43 112.42(19) . . ?
C12 C11 C15 108.08(19) . . ?
C12 C11 C111 127.0(2) . . ?
C15 C11 C111 124.8(2) . . ?
C12 C11 Ir1 72.46(13) . . ?
C15 C11 Ir1 73.73(12) . . ?
C111 C11 Ir1 122.81(15) . . ?
C11 C12 C13 107.8(2) . . ?
C11 C12 C121 125.9(2) . . ?
C13 C12 C121 126.3(2) . . ?
C11 C12 Ir1 69.76(12) . . ?
C13 C12 Ir1 69.25(12) . . ?
C121 C12 Ir1 126.04(16) . . ?
C12 C13 C14 108.24(19) . . ?
C12 C13 C131 127.0(2) . . ?
C14 C13 C131 124.6(2) . . ?
C12 C13 Ir1 72.79(12) . . ?
C14 C13 Ir1 73.61(12) . . ?
C131 C13 Ir1 123.03(15) . . ?
C15 C14 C13 107.5(2) . . ?
C15 C14 C141 127.8(2) . . ?
C13 C14 C141 124.3(2) . . ?
C15 C14 Ir1 72.02(12) . . ?
C13 C14 Ir1 68.01(12) . . ?
C141 C14 Ir1 130.98(16) . . ?
C14 C15 C11 107.99(19) . . ?
C14 C15 C151 127.4(2) . . ?
C11 C15 C151 124.1(2) . . ?
C14 C15 Ir1 71.21(12) . . ?
C11 C15 Ir1 68.15(12) . . ?
C151 C15 Ir1 132.59(16) . . ?
C22 C21 C25 108.2(2) . . ?
C22 C21 Zr1 75.57(14) . . ?
C25 C21 Zr1 74.04(14) . . ?
C21 C22 C23 108.5(2) . . ?
C21 C22 Zr1 72.90(14) . . ?
C23 C22 Zr1 74.10(14) . . ?
C22 C23 C24 107.1(2) . . ?
C22 C23 Zr1 74.18(14) . . ?
C24 C23 Zr1 73.18(14) . . ?
C25 C24 C23 107.6(2) . . ?
C25 C24 Zr1 73.54(14) . . ?
C23 C24 Zr1 74.70(14) . . ?
C21 C25 C24 108.5(2) . . ?
C21 C25 Zr1 74.11(14) . . ?
C24 C25 Zr1 74.63(14) . . ?
C32 C31 C35 108.3(2) . . ?
C32 C31 Zr1 73.23(13) . . ?
C35 C31 Zr1 72.06(13) . . ?
C31 C32 C33 107.7(2) . . ?
C31 C32 Zr1 75.35(13) . . ?
C33 C32 Zr1 73.69(13) . . ?
C34 C33 C32 108.0(2) . . ?
C34 C33 Zr1 73.51(13) . . ?
C32 C33 Zr1 74.11(13) . . ?
C33 C34 C35 108.1(2) . . ?
C33 C34 Zr1 74.74(13) . . ?
C35 C34 Zr1 73.75(13) . . ?
C31 C35 C34 107.9(2) . . ?
C31 C35 Zr1 76.13(13) . . ?
C34 C35 Zr1 74.08(13) . . ?
S1 O1 Zr1 139.49(9) . . ?
O3 S1 O2 117.18(11) . . ?
O3 S1 O1 113.65(10) . . ?
O2 S1 O1 114.12(10) . . ?
O3 S1 C5 103.86(11) . . ?
O2 S1 C5 103.60(12) . . ?
O1 S1 C5 101.93(10) . . ?
F2 C5 F1 108.1(2) . . ?
F2 C5 F3 107.7(2) . . ?
F1 C5 F3 107.5(2) . . ?
F2 C5 S1 112.22(18) . . ?
F1 C5 S1 111.56(17) . . ?
F3 C5 S1 109.47(17) . . ?

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        27.10
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         0.853
_refine_diff_density_min         -0.424
_refine_diff_density_rms         0.084

data_Ir-Hf-N3Ph
_database_code_depnum_ccdc_archive 'CCDC 838834'
#TrackingRef '- curley_chemsci.cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            Cp*Ir(mu-NtBu)(mu-N3Ph)HfCp2
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C23.25 H30 Hf0.75 Ir0.75 N3'
_chemical_formula_weight         629.52

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'
Hf Hf -0.5830 6.1852 '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'

_symmetry_cell_setting           Rhombohedral
_symmetry_space_group_name_H-M   R-3

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'

_cell_length_a                   32.6021(11)
_cell_length_b                   32.6021(11)
_cell_length_c                   14.0691(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     12950.5(8)
_cell_formula_units_Z            24
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9681
_cell_measurement_theta_min      2.40
_cell_measurement_theta_max      36.59

_exptl_crystal_description       block
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             7254
_exptl_absorpt_coefficient_mu    8.250
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.6831
_exptl_absorpt_correction_T_max  0.6831
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      100(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  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_detector_area_resol_mean 8.366
_diffrn_reflns_number            90843
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_sigmaI/netI    0.0362
_diffrn_reflns_limit_h_min       -47
_diffrn_reflns_limit_h_max       47
_diffrn_reflns_limit_k_min       -46
_diffrn_reflns_limit_k_max       47
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         1.25
_diffrn_reflns_theta_max         31.50
_reflns_number_total             9595
_reflns_number_gt                7741
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ 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/[\s^2^(Fo^2^)+(0.0096P)^2^+48.0149P] where P=(Fo^2^+2Fc^2^)/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         9595
_refine_ls_number_parameters     414
_refine_ls_number_restraints     198
_refine_ls_R_factor_all          0.0391
_refine_ls_R_factor_gt           0.0242
_refine_ls_wR_factor_ref         0.0408
_refine_ls_wR_factor_gt          0.0375
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_restrained_S_all      1.026
_refine_ls_shift/su_max          0.007
_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
Ir1 Ir 0.609980(4) 0.145060(4) 0.056291(7) 0.01176(3) Uani 1 1 d . . .
Hf1 Hf 0.633624(4) 0.098567(4) 0.214239(7) 0.01313(3) Uani 1 1 d . A .
N2 N 0.57399(8) 0.09345(8) 0.15687(15) 0.0157(5) Uani 1 1 d . A .
N3 N 0.52781(8) 0.06896(8) 0.16190(15) 0.0158(5) Uani 1 1 d . . .
N4 N 0.51342(8) 0.03925(8) 0.23346(16) 0.0183(5) Uani 1 1 d . A .
C51 C 0.46368(10) 0.01181(10) 0.2412(2) 0.0178(6) Uani 1 1 d . . .
C52 C 0.43049(11) 0.00868(11) 0.1742(2) 0.0240(7) Uani 1 1 d . A .
H52 H 0.4408 0.0256 0.1160 0.029 Uiso 1 1 calc R . .
C53 C 0.38239(11) -0.01918(11) 0.1930(3) 0.0315(8) Uani 1 1 d . . .
H53 H 0.3600 -0.0208 0.1477 0.038 Uiso 1 1 calc R A .
C54 C 0.36647(11) -0.04472(11) 0.2768(3) 0.0321(8) Uani 1 1 d . A .
H54 H 0.3335 -0.0635 0.2889 0.038 Uiso 1 1 calc R . .
C55 C 0.39869(12) -0.04262(11) 0.3422(2) 0.0298(8) Uani 1 1 d . . .
H55 H 0.3881 -0.0602 0.3996 0.036 Uiso 1 1 calc R A .
C56 C 0.44691(11) -0.01470(10) 0.3244(2) 0.0224(6) Uani 1 1 d . A .
H56 H 0.4689 -0.0137 0.3700 0.027 Uiso 1 1 calc R . .
N1 N 0.66756(8) 0.14934(8) 0.11136(15) 0.0144(5) Uani 1 1 d . A .
C41 C 0.71695(9) 0.18089(10) 0.08039(19) 0.0183(6) Uani 1 1 d . . .
C411 C 0.75063(11) 0.16958(13) 0.1350(2) 0.0352(8) Uani 1 1 d . A .
H41A H 0.7444 0.1689 0.2033 0.053 Uiso 1 1 calc R . .
H41B H 0.7834 0.1940 0.1218 0.053 Uiso 1 1 calc R . .
H41C H 0.7456 0.1386 0.1148 0.053 Uiso 1 1 calc R . .
C412 C 0.73065(11) 0.23235(11) 0.1004(2) 0.0265(7) Uani 1 1 d . A .
H41D H 0.7068 0.2388 0.0728 0.040 Uiso 1 1 calc R . .
H41E H 0.7616 0.2536 0.0720 0.040 Uiso 1 1 calc R . .
H41F H 0.7323 0.2376 0.1692 0.040 Uiso 1 1 calc R . .
C413 C 0.72239(10) 0.17334(11) -0.0252(2) 0.0234(6) Uani 1 1 d . A .
H41G H 0.7103 0.1396 -0.0372 0.035 Uiso 1 1 calc R . .
H41H H 0.7559 0.1914 -0.0429 0.035 Uiso 1 1 calc R . .
H41I H 0.7044 0.1842 -0.0632 0.035 Uiso 1 1 calc R . .
C11 C 0.59676(10) 0.20168(10) 0.01405(19) 0.0179(6) Uani 1 1 d . . .
C111 C 0.60941(12) 0.24551(11) 0.0702(2) 0.0278(7) Uani 1 1 d . . .
H11A H 0.6433 0.2620 0.0850 0.042 Uiso 1 1 calc R . .
H11B H 0.5912 0.2368 0.1295 0.042 Uiso 1 1 calc R . .
H11C H 0.6020 0.2664 0.0329 0.042 Uiso 1 1 calc R . .
C12 C 0.62585(10) 0.19807(10) -0.05925(19) 0.0176(6) Uani 1 1 d . . .
C121 C 0.66856(11) 0.23885(11) -0.1031(2) 0.0254(7) Uani 1 1 d . . .
H12A H 0.6589 0.2579 -0.1405 0.038 Uiso 1 1 calc R . .
H12B H 0.6844 0.2269 -0.1447 0.038 Uiso 1 1 calc R . .
H12C H 0.6905 0.2585 -0.0529 0.038 Uiso 1 1 calc R . .
C13 C 0.60018(10) 0.15099(10) -0.09565(18) 0.0178(6) Uani 1 1 d . . .
C131 C 0.61556(11) 0.13131(12) -0.17568(19) 0.0261(7) Uani 1 1 d . . .
H13A H 0.6046 0.1373 -0.2362 0.039 Uiso 1 1 calc R . .
H13B H 0.6019 0.0971 -0.1669 0.039 Uiso 1 1 calc R . .
H13C H 0.6502 0.1466 -0.1762 0.039 Uiso 1 1 calc R . .
C14 C 0.55417(10) 0.12624(10) -0.04992(18) 0.0159(6) Uani 1 1 d . . .
C141 C 0.51536(10) 0.07718(10) -0.0694(2) 0.0231(6) Uani 1 1 d . . .
H14A H 0.5015 0.0611 -0.0092 0.035 Uiso 1 1 calc R . .
H14B H 0.5281 0.0599 -0.1039 0.035 Uiso 1 1 calc R . .
H14C H 0.4909 0.0783 -0.1081 0.035 Uiso 1 1 calc R . .
C15 C 0.55187(10) 0.15818(10) 0.01709(18) 0.0151(5) Uani 1 1 d . . .
C151 C 0.51012(10) 0.14865(11) 0.0761(2) 0.0215(6) Uani 1 1 d . . .
H15A H 0.4888 0.1555 0.0390 0.032 Uiso 1 1 calc R . .
H15B H 0.5208 0.1688 0.1327 0.032 Uiso 1 1 calc R . .
H15C H 0.4933 0.1153 0.0954 0.032 Uiso 1 1 calc R . .
C21 C 0.63962(16) 0.02632(13) 0.2563(3) 0.0434(10) Uani 1 1 d . A .
H21 H 0.6457 0.0220 0.3205 0.052 Uiso 1 1 calc R . .
C22 C 0.67341(13) 0.05076(12) 0.1878(3) 0.0407(10) Uani 1 1 d . A .
H22 H 0.7067 0.0667 0.1968 0.049 Uiso 1 1 calc R . .
C23 C 0.65004(14) 0.04796(11) 0.1027(2) 0.0355(9) Uani 1 1 d . A .
H23 H 0.6645 0.0610 0.0432 0.043 Uiso 1 1 calc R . .
C24 C 0.60168(12) 0.02258(11) 0.1214(2) 0.0325(8) Uani 1 1 d . A .
H24 H 0.5771 0.0156 0.0769 0.039 Uiso 1 1 calc R . .
C25 C 0.59567(13) 0.00930(11) 0.2160(3) 0.0377(9) Uani 1 1 d . . .
H25 H 0.5662 -0.0085 0.2477 0.045 Uiso 1 1 calc R A .
C31 C 0.65065(15) 0.10179(16) 0.3900(3) 0.045(3) Uani 0.555(19) 1 d PGDU A 1
H31 H 0.6566 0.0782 0.4152 0.054 Uiso 0.555(19) 1 calc PR A 1
C32 C 0.68426(15) 0.14549(16) 0.3557(3) 0.043(4) Uani 0.555(19) 1 d PRDU A 1
H32 H 0.7174 0.1573 0.3533 0.052 Uiso 0.555(19) 1 calc PR A 1
C33 C 0.66126(15) 0.16898(16) 0.3257(3) 0.039(3) Uani 0.555(19) 1 d PRDU A 1
H33 H 0.6758 0.1998 0.2989 0.046 Uiso 0.555(19) 1 calc PR A 1
C34 C 0.61344(15) 0.13980(16) 0.3413(3) 0.030(3) Uani 0.555(19) 1 d PRDU A 1
H34 H 0.5893 0.1470 0.3272 0.036 Uiso 0.555(19) 1 calc PR A 1
C35 C 0.60688(15) 0.09827(16) 0.3811(3) 0.033(3) Uani 0.555(19) 1 d PRDU A 1
H35 H 0.5774 0.0719 0.3991 0.039 Uiso 0.555(19) 1 calc PR A 1
C31A C 0.6716(4) 0.1233(4) 0.3734(12) 0.047(4) Uani 0.445(19) 1 d PDU A 2
H31A H 0.6960 0.1163 0.3862 0.056 Uiso 0.445(19) 1 calc PR A 2
C32A C 0.6769(4) 0.1642(4) 0.3317(11) 0.041(4) Uani 0.445(19) 1 d PDU A 2
H32A H 0.7061 0.1903 0.3113 0.049 Uiso 0.445(19) 1 calc PR A 2
C33A C 0.6329(4) 0.1608(4) 0.3244(9) 0.036(4) Uani 0.445(19) 1 d PDU A 2
H33A H 0.6266 0.1842 0.2998 0.044 Uiso 0.445(19) 1 calc PR A 2
C34A C 0.5999(3) 0.1167(4) 0.3601(9) 0.040(4) Uani 0.445(19) 1 d PDU A 2
H34A H 0.5666 0.1040 0.3617 0.047 Uiso 0.445(19) 1 calc PR A 2
C35A C 0.6237(4) 0.0945(4) 0.3929(9) 0.042(4) Uani 0.445(19) 1 d PDU A 2
H35A H 0.6097 0.0645 0.4237 0.050 Uiso 0.445(19) 1 calc PR A 2
C61 C 0.638(3) 0.2739(10) 0.339(7) 0.086(11) Uani 0.17 1 d PGDU B -1
H61 H 0.6204 0.2404 0.3339 0.103 Uiso 0.17 1 calc PR B -1
C62 C 0.616(3) 0.2990(12) 0.348(6) 0.094(12) Uani 0.17 1 d PGDU B -1
H62 H 0.5821 0.2831 0.3504 0.113 Uiso 0.17 1 calc PR B -1
C63 C 0.641(3) 0.3466(11) 0.355(4) 0.089(11) Uani 0.17 1 d PGDU B -1
H63 H 0.6252 0.3642 0.3618 0.107 Uiso 0.17 1 calc PR B -1
C64 C 0.689(3) 0.3692(10) 0.352(3) 0.087(11) Uani 0.17 1 d PGDU B -1
H64 H 0.7065 0.4027 0.3567 0.104 Uiso 0.17 1 calc PR B -1
C65 C 0.711(3) 0.3442(11) 0.342(6) 0.078(10) Uani 0.17 1 d PGDU B -1
H65 H 0.7448 0.3601 0.3402 0.094 Uiso 0.17 1 calc PR B -1
C66 C 0.686(3) 0.2965(11) 0.336(7) 0.085(11) Uani 0.17 1 d PGDU B -1
H66 H 0.7018 0.2789 0.3288 0.102 Uiso 0.17 1 calc PR B -1

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Ir1 0.01173(5) 0.01245(5) 0.01088(5) 0.00028(4) 0.00014(4) 0.00587(4)
Hf1 0.01327(6) 0.01490(6) 0.01134(5) 0.00012(4) -0.00077(4) 0.00714(5)
N2 0.0167(12) 0.0175(12) 0.0130(11) 0.0027(9) 0.0022(9) 0.0085(10)
N3 0.0158(12) 0.0168(12) 0.0149(11) 0.0009(9) 0.0018(9) 0.0082(10)
N4 0.0159(12) 0.0195(13) 0.0169(11) 0.0053(9) 0.0027(9) 0.0070(11)
C51 0.0148(14) 0.0133(14) 0.0242(14) -0.0025(11) 0.0031(11) 0.0063(12)
C52 0.0212(16) 0.0212(16) 0.0309(16) -0.0005(13) -0.0012(13) 0.0114(14)
C53 0.0205(17) 0.0254(18) 0.050(2) -0.0074(15) -0.0081(15) 0.0126(15)
C54 0.0166(16) 0.0190(16) 0.055(2) -0.0073(15) 0.0114(15) 0.0050(14)
C55 0.0325(19) 0.0163(16) 0.0327(17) 0.0005(13) 0.0170(15) 0.0062(14)
C56 0.0255(17) 0.0156(15) 0.0223(15) 0.0006(11) 0.0027(12) 0.0073(13)
N1 0.0117(11) 0.0159(12) 0.0147(11) -0.0008(9) -0.0002(9) 0.0062(10)
C41 0.0091(13) 0.0187(15) 0.0223(14) 0.0033(11) -0.0002(10) 0.0034(12)
C411 0.0133(16) 0.047(2) 0.0394(19) 0.0148(16) 0.0027(13) 0.0106(16)
C412 0.0156(15) 0.0212(16) 0.0309(17) -0.0024(13) 0.0006(12) 0.0002(13)
C413 0.0160(15) 0.0246(16) 0.0273(15) 0.0026(12) 0.0069(12) 0.0085(13)
C11 0.0209(15) 0.0171(15) 0.0182(13) 0.0008(11) -0.0015(11) 0.0113(13)
C111 0.0354(19) 0.0194(16) 0.0345(18) -0.0064(13) -0.0031(14) 0.0180(15)
C12 0.0160(14) 0.0221(15) 0.0157(13) 0.0062(11) -0.0001(10) 0.0103(13)
C121 0.0209(16) 0.0244(17) 0.0259(16) 0.0114(13) 0.0025(12) 0.0075(14)
C13 0.0201(15) 0.0258(16) 0.0105(12) 0.0023(11) 0.0000(10) 0.0138(13)
C131 0.0260(17) 0.0391(19) 0.0143(13) -0.0040(13) 0.0022(12) 0.0171(15)
C14 0.0147(14) 0.0198(15) 0.0135(12) 0.0013(10) -0.0015(10) 0.0088(12)
C141 0.0199(16) 0.0224(16) 0.0190(14) -0.0003(12) -0.0033(11) 0.0047(13)
C15 0.0159(14) 0.0192(14) 0.0133(12) 0.0027(10) -0.0014(10) 0.0110(12)
C151 0.0192(15) 0.0285(17) 0.0205(14) 0.0034(12) 0.0031(11) 0.0145(14)
C21 0.075(3) 0.029(2) 0.037(2) -0.0026(16) -0.018(2) 0.035(2)
C22 0.0253(19) 0.0229(18) 0.081(3) -0.0122(19) -0.0131(19) 0.0172(16)
C23 0.057(2) 0.0219(17) 0.0367(19) 0.0035(14) 0.0197(17) 0.0260(18)
C24 0.037(2) 0.0191(17) 0.046(2) -0.0161(15) -0.0220(16) 0.0174(16)
C25 0.041(2) 0.0130(16) 0.054(2) 0.0057(15) 0.0169(18) 0.0098(16)
C31 0.075(10) 0.071(8) 0.016(4) -0.010(5) -0.017(7) 0.056(8)
C32 0.025(4) 0.075(10) 0.029(6) -0.039(6) -0.015(3) 0.024(5)
C33 0.051(8) 0.031(4) 0.024(4) -0.017(3) 0.005(6) 0.012(5)
C34 0.037(6) 0.040(8) 0.024(6) -0.015(6) -0.010(5) 0.026(6)
C35 0.034(5) 0.050(6) 0.012(5) -0.004(4) 0.006(4) 0.019(4)
C31A 0.050(8) 0.061(11) 0.052(8) -0.043(6) -0.046(6) 0.045(8)
C32A 0.038(6) 0.042(6) 0.024(6) -0.012(4) 0.014(5) 0.005(5)
C33A 0.073(11) 0.037(8) 0.020(5) -0.013(6) -0.019(8) 0.043(8)
C34A 0.022(4) 0.058(10) 0.036(8) -0.029(7) 0.001(4) 0.018(6)
C35A 0.077(11) 0.034(5) 0.007(4) 0.006(3) -0.002(7) 0.022(6)
C61 0.12(3) 0.043(15) 0.07(2) -0.001(15) -0.06(2) 0.025(17)
C62 0.13(2) 0.053(15) 0.08(2) -0.031(15) -0.02(2) 0.028(17)
C63 0.12(2) 0.050(15) 0.08(2) 0.000(15) -0.03(2) 0.031(18)
C64 0.12(2) 0.044(15) 0.08(2) -0.019(14) -0.04(2) 0.035(17)
C65 0.13(2) 0.026(13) 0.07(2) -0.002(14) -0.04(2) 0.029(18)
C66 0.12(3) 0.029(13) 0.08(2) -0.017(15) -0.03(2) 0.018(18)

_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
Ir1 N1 1.970(2) . ?
Ir1 N2 2.058(2) . ?
Ir1 C11 2.178(3) . ?
Ir1 C13 2.184(3) . ?
Ir1 C14 2.192(3) . ?
Ir1 C15 2.211(3) . ?
Ir1 C12 2.237(3) . ?
Ir1 Hf1 2.99974(16) . ?
Hf1 N2 2.033(2) . ?
Hf1 N1 2.056(2) . ?
Hf1 C31A 2.490(16) . ?
Hf1 C35 2.502(4) . ?
Hf1 C22 2.504(3) . ?
Hf1 C32A 2.506(15) . ?
Hf1 C34 2.514(4) . ?
Hf1 C24 2.520(3) . ?
Hf1 C23 2.520(3) . ?
Hf1 C31 2.524(4) . ?
Hf1 C21 2.529(3) . ?
Hf1 C35A 2.530(12) . ?
N2 N3 1.307(3) . ?
N3 N4 1.311(3) . ?
N4 C51 1.411(3) . ?
C51 C56 1.394(4) . ?
C51 C52 1.400(4) . ?
C52 C53 1.389(4) . ?
C53 C54 1.386(5) . ?
C54 C55 1.372(5) . ?
C55 C56 1.390(4) . ?
N1 C41 1.478(3) . ?
C41 C411 1.529(4) . ?
C41 C413 1.531(4) . ?
C41 C412 1.531(4) . ?
C11 C15 1.442(4) . ?
C11 C12 1.445(4) . ?
C11 C111 1.499(4) . ?
C12 C13 1.426(4) . ?
C12 C121 1.495(4) . ?
C13 C14 1.451(4) . ?
C13 C131 1.501(4) . ?
C14 C15 1.434(4) . ?
C14 C141 1.487(4) . ?
C15 C151 1.488(4) . ?
C21 C25 1.374(5) . ?
C21 C22 1.378(5) . ?
C22 C23 1.397(5) . ?
C23 C24 1.391(5) . ?
C24 C25 1.383(5) . ?
C31 C32 1.3788 . ?
C31 C35 1.3788 . ?
C32 C33 1.3789 . ?
C33 C34 1.3788 . ?
C34 C35 1.3788 . ?
C31A C32A 1.386(12) . ?
C31A C35A 1.389(12) . ?
C32A C33A 1.387(11) . ?
C33A C34A 1.389(12) . ?
C34A C35A 1.379(11) . ?
C61 C62 1.349(8) . ?
C61 C66 1.349(8) . ?
C62 C63 1.349(8) . ?
C63 C64 1.349(8) . ?
C64 C65 1.349(8) . ?
C65 C66 1.349(8) . ?

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 Ir1 N2 85.47(9) . . ?
N1 Ir1 C11 129.25(10) . . ?
N2 Ir1 C11 127.38(10) . . ?
N1 Ir1 C13 123.71(10) . . ?
N2 Ir1 C13 134.14(10) . . ?
C11 Ir1 C13 63.78(10) . . ?
N1 Ir1 C14 156.37(10) . . ?
N2 Ir1 C14 100.71(9) . . ?
C11 Ir1 C14 64.08(10) . . ?
C13 Ir1 C14 38.72(10) . . ?
N1 Ir1 C15 164.32(10) . . ?
N2 Ir1 C15 97.84(9) . . ?
C11 Ir1 C15 38.36(10) . . ?
C13 Ir1 C15 63.98(10) . . ?
C14 Ir1 C15 38.03(10) . . ?
N1 Ir1 C12 112.76(9) . . ?
N2 Ir1 C12 161.52(9) . . ?
C11 Ir1 C12 38.19(10) . . ?
C13 Ir1 C12 37.62(10) . . ?
C14 Ir1 C12 63.88(10) . . ?
C15 Ir1 C12 63.81(10) . . ?
N1 Ir1 Hf1 42.95(6) . . ?
N2 Ir1 Hf1 42.53(6) . . ?
C11 Ir1 Hf1 147.17(7) . . ?
C13 Ir1 Hf1 148.83(8) . . ?
C14 Ir1 Hf1 138.65(7) . . ?
C15 Ir1 Hf1 138.09(7) . . ?
C12 Ir1 Hf1 155.53(7) . . ?
N2 Hf1 N1 83.92(9) . . ?
N2 Hf1 C31A 133.1(3) . . ?
N1 Hf1 C31A 113.1(3) . . ?
N2 Hf1 C35 93.15(12) . . ?
N1 Hf1 C35 135.20(12) . . ?
C31A Hf1 C35 43.4(3) . . ?
N2 Hf1 C22 131.41(11) . . ?
N1 Hf1 C22 99.14(11) . . ?
C31A Hf1 C22 90.4(3) . . ?
C35 Hf1 C22 115.15(15) . . ?
N2 Hf1 C32A 116.1(3) . . ?
N1 Hf1 C32A 86.0(3) . . ?
C31A Hf1 C32A 32.2(3) . . ?
C35 Hf1 C32A 55.3(3) . . ?
C22 Hf1 C32A 112.5(3) . . ?
N2 Hf1 C34 80.28(12) . . ?
N1 Hf1 C34 104.45(12) . . ?
C31A Hf1 C34 53.7(3) . . ?
C35 Hf1 C34 31.90(6) . . ?
C22 Hf1 C34 142.54(14) . . ?
C32A Hf1 C34 42.4(3) . . ?
N2 Hf1 C24 78.77(10) . . ?
N1 Hf1 C24 102.59(10) . . ?
C31A Hf1 C24 132.7(3) . . ?
C35 Hf1 C24 120.71(13) . . ?
C22 Hf1 C24 53.06(11) . . ?
C32A Hf1 C24 163.9(3) . . ?
C34 Hf1 C24 143.55(13) . . ?
N2 Hf1 C23 101.91(11) . . ?
N1 Hf1 C23 83.34(10) . . ?
C31A Hf1 C23 122.5(3) . . ?
C35 Hf1 C23 140.27(13) . . ?
C22 Hf1 C23 32.28(12) . . ?
C32A Hf1 C23 139.1(3) . . ?
C34 Hf1 C23 172.14(13) . . ?
C24 Hf1 C23 32.04(11) . . ?
N2 Hf1 C31 124.99(12) . . ?
N1 Hf1 C31 129.59(11) . . ?
C31A Hf1 C31 16.7(3) . . ?
C35 Hf1 C31 31.84(5) . . ?
C22 Hf1 C31 90.00(14) . . ?
C32A Hf1 C31 45.6(3) . . ?
C34 Hf1 C31 52.56(9) . . ?
C24 Hf1 C31 121.53(13) . . ?
C23 Hf1 C31 121.51(14) . . ?
N2 Hf1 C21 122.16(11) . . ?
N1 Hf1 C21 130.80(12) . . ?
C31A Hf1 C21 80.4(3) . . ?
C35 Hf1 C21 88.06(14) . . ?
C22 Hf1 C21 31.77(13) . . ?
C32A Hf1 C21 111.6(3) . . ?
C34 Hf1 C21 119.62(14) . . ?
C24 Hf1 C21 52.56(11) . . ?
C23 Hf1 C21 52.80(12) . . ?
C31 Hf1 C21 72.06(13) . . ?
N2 Hf1 C35A 107.3(3) . . ?
N1 Hf1 C35A 138.2(3) . . ?
C31A Hf1 C35A 32.1(3) . . ?
C35 Hf1 C35A 14.6(2) . . ?
C22 Hf1 C35A 102.0(3) . . ?
C32A Hf1 C35A 52.6(4) . . ?
C34 Hf1 C35A 42.3(3) . . ?
C24 Hf1 C35A 119.0(3) . . ?
C23 Hf1 C35A 130.4(3) . . ?
C31 Hf1 C35A 18.0(3) . . ?
C21 Hf1 C35A 77.6(3) . . ?
N3 N2 Hf1 142.28(18) . . ?
N3 N2 Ir1 123.26(17) . . ?
Hf1 N2 Ir1 94.30(9) . . ?
N2 N3 N4 111.7(2) . . ?
N3 N4 C51 113.6(2) . . ?
C56 C51 C52 118.1(3) . . ?
C56 C51 N4 115.3(3) . . ?
C52 C51 N4 126.6(3) . . ?
C53 C52 C51 119.9(3) . . ?
C54 C53 C52 121.1(3) . . ?
C55 C54 C53 119.5(3) . . ?
C54 C55 C56 119.9(3) . . ?
C55 C56 C51 121.5(3) . . ?
C41 N1 Ir1 126.97(17) . . ?
C41 N1 Hf1 136.73(17) . . ?
Ir1 N1 Hf1 96.30(9) . . ?
N1 C41 C411 110.4(2) . . ?
N1 C41 C413 110.4(2) . . ?
C411 C41 C413 107.1(2) . . ?
N1 C41 C412 109.1(2) . . ?
C411 C41 C412 108.7(3) . . ?
C413 C41 C412 111.2(2) . . ?
C15 C11 C12 109.0(2) . . ?
C15 C11 C111 125.6(3) . . ?
C12 C11 C111 125.1(3) . . ?
C15 C11 Ir1 72.06(15) . . ?
C12 C11 Ir1 73.12(16) . . ?
C111 C11 Ir1 126.0(2) . . ?
C13 C12 C11 106.7(2) . . ?
C13 C12 C121 126.4(3) . . ?
C11 C12 C121 125.4(3) . . ?
C13 C12 Ir1 69.20(15) . . ?
C11 C12 Ir1 68.69(15) . . ?
C121 C12 Ir1 137.7(2) . . ?
C12 C13 C14 109.1(2) . . ?
C12 C13 C131 126.0(3) . . ?
C14 C13 C131 124.6(3) . . ?
C12 C13 Ir1 73.19(15) . . ?
C14 C13 Ir1 70.92(14) . . ?
C131 C13 Ir1 127.0(2) . . ?
C15 C14 C13 107.6(2) . . ?
C15 C14 C141 125.2(2) . . ?
C13 C14 C141 127.1(3) . . ?
C15 C14 Ir1 71.71(15) . . ?
C13 C14 Ir1 70.36(15) . . ?
C141 C14 Ir1 124.60(19) . . ?
C14 C15 C11 107.4(2) . . ?
C14 C15 C151 126.1(3) . . ?
C11 C15 C151 126.5(2) . . ?
C14 C15 Ir1 70.27(15) . . ?
C11 C15 Ir1 69.58(15) . . ?
C151 C15 Ir1 127.09(18) . . ?
C25 C21 C22 108.4(3) . . ?
C25 C21 Hf1 74.3(2) . . ?
C22 C21 Hf1 73.13(19) . . ?
C21 C22 C23 108.0(3) . . ?
C21 C22 Hf1 75.1(2) . . ?
C23 C22 Hf1 74.49(19) . . ?
C24 C23 C22 107.2(3) . . ?
C24 C23 Hf1 73.96(18) . . ?
C22 C23 Hf1 73.23(19) . . ?
C25 C24 C23 108.0(3) . . ?
C25 C24 Hf1 74.50(18) . . ?
C23 C24 Hf1 74.01(18) . . ?
C21 C25 C24 108.4(3) . . ?
C21 C25 Hf1 74.2(2) . . ?
C24 C25 Hf1 73.70(18) . . ?
C32 C31 C35 108.0 . . ?
C32 C31 Hf1 75.26(10) . . ?
C35 C31 Hf1 73.20(10) . . ?
C31 C32 C33 108.0 . . ?
C31 C32 Hf1 73.21(10) . . ?
C33 C32 Hf1 74.05(10) . . ?
C34 C33 C32 108.0 . . ?
C34 C33 Hf1 73.00(10) . . ?
C32 C33 Hf1 74.54(10) . . ?
C33 C34 C35 108.0 . . ?
C33 C34 Hf1 75.37(10) . . ?
C35 C34 Hf1 73.56(10) . . ?
C34 C35 C31 108.0 . . ?
C34 C35 Hf1 74.53(11) . . ?
C31 C35 Hf1 74.97(10) . . ?
C32A C31A C35A 107.0(9) . . ?
C32A C31A Hf1 74.5(9) . . ?
C35A C31A Hf1 75.5(8) . . ?
C31A C32A C33A 109.1(9) . . ?
C31A C32A Hf1 73.3(9) . . ?
C33A C32A Hf1 76.4(8) . . ?
C32A C33A C34A 106.9(9) . . ?
C32A C33A Hf1 71.9(8) . . ?
C34A C33A Hf1 73.0(8) . . ?
C35A C34A C33A 108.5(9) . . ?
C35A C34A Hf1 74.0(8) . . ?
C33A C34A Hf1 75.3(8) . . ?
C34A C35A C31A 108.4(9) . . ?
C34A C35A Hf1 74.4(8) . . ?
C31A C35A Hf1 72.4(8) . . ?
C62 C61 C66 120.0 . . ?
C61 C62 C63 120.0 . . ?
C64 C63 C62 120.0 . . ?
C63 C64 C65 120.0 . . ?
C66 C65 C64 120.0 . . ?
C65 C66 C61 120.0 . . ?

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        31.50
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         0.810
_refine_diff_density_min         -0.752
_refine_diff_density_rms         0.169