# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# 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_nb01
_database_code_depnum_ccdc_archive 'CCDC 1496571'
_audit_update_record             
;
2016-07-28 deposited with the CCDC.
2016-11-02 downloaded from the CCDC.
;
_audit_creation_date             2016-03-14
_audit_creation_method           
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_chemical_name_common            ?
_chemical_name_systematic        tris(cyclopentadienyl)titanium(tert-butoxide)
_chemical_formula_moiety         'C19 H24 O Ti'
_chemical_formula_sum            'C19 H24 O Ti'
_chemical_formula_weight         316.28
_chemical_melting_point          ?
_chemical_oxdiff_formula         C19Ti1O1H24
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      tetragonal
_space_group_IT_number           86
_space_group_name_H-M_alt        'P 42/n'
_space_group_name_Hall           '-P 4bc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y+1/2, z'
'-y, x+1/2, z+1/2'
'y+1/2, -x, z+1/2'
'-x, -y, -z'
'x-1/2, y-1/2, -z'
'y, -x-1/2, -z-1/2'
'-y-1/2, x, -z-1/2'

_cell_length_a                   19.4641(2)
_cell_length_b                   19.4641(2)
_cell_length_c                   8.58573(12)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3252.71(8)
_cell_formula_units_Z            8
_cell_measurement_reflns_used    8277
_cell_measurement_temperature    100
_cell_measurement_theta_max      72.3200
_cell_measurement_theta_min      4.5100
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    4.409
_exptl_absorpt_correction_T_max  0.864
_exptl_absorpt_correction_T_min  0.398
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.292
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             1344
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-13 1 0 0.0404
-1 -1 -6 0.2246
0 1 6 0.2951
-1 -13 -1 0.0336
1 13 1 0.0010
13 -1 0 0.0043

_exptl_crystal_size_max          0.546
_exptl_crystal_size_mid          0.045
_exptl_crystal_size_min          0.035
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-12.9847 0.9858 -0.0161 0.0367 0.0765 -1.0272
-0.9656 -0.9895 -6.0042 -0.6288 -0.8669 -0.1607
-0.0331 0.9885 6.0029 0.6264 0.8759 0.0822
-0.9746 -12.9836 -1.0077 -0.9738 0.3827 -0.0066
0.9746 12.9836 1.0077 0.9738 -0.3827 0.0066
12.9847 -0.9858 0.0161 -0.0367 -0.0765 1.0272

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0301
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            15228
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.503
_diffrn_reflns_theta_min         3.211
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω   -106.00 -20.00   1.00    5.00    --  -37.14 -38.00 -30.00   86
  2  ω   -104.00 -12.00   1.00    5.00    --  -37.14 -77.00 -90.00   92
  3  ω     22.00 103.00   1.00    5.00    --   37.14  57.00-180.00   81
  4  ω     92.00 174.00   1.00   15.00    --  108.59  61.00 -60.00   82
  5  ω     40.00 128.00   1.00   15.00    --  108.59 -30.00 -90.00   88
  6  ω     44.00 125.00   1.00   15.00    --  108.59 -61.00-150.00   81
  7  ω     89.00 177.00   1.00   15.00    --  108.59  30.00  90.00   88
  8  ω    -52.00  29.00   1.00    5.00    --  -37.14  57.00 -60.00   81
  9  ω    -62.00  29.00   1.00    5.00    --  -37.14  77.00  90.00   91
 10  ω     92.00 174.00   1.00   15.00    --  108.59  61.00   0.00   82
 11  ω     42.00 132.00   1.00   15.00    --  108.59 -77.00  30.00   90
 12  ω     83.00 140.00   1.00   15.00    --  108.59  77.00-120.00   57
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0021874000
_diffrn_orient_matrix_UB_12      0.0676022000
_diffrn_orient_matrix_UB_13      0.0932326000
_diffrn_orient_matrix_UB_21      -0.0091671000
_diffrn_orient_matrix_UB_22      -0.0406275000
_diffrn_orient_matrix_UB_23      0.1525464000
_diffrn_orient_matrix_UB_31      0.0785934000
_diffrn_orient_matrix_UB_32      -0.0065714000
_diffrn_orient_matrix_UB_33      0.0152015000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                2798
_reflns_number_total             3189
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.222
_refine_diff_density_min         -0.295
_refine_diff_density_rms         0.040
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     197
_refine_ls_number_reflns         3189
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0328
_refine_ls_R_factor_gt           0.0270
_refine_ls_restrained_S_all      1.029
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0320P)²+1.1430P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0651
_refine_ls_wR_factor_ref         0.0676
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C2(H2), C5(H5), C4(H4), C3(H3), C10(H10), C14(H14), C15(H15),
 C11(H11), C13(H13), C9(H9), C12(H12), C7(H7), C8(H8)
2.b Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C18(H18A,H18B,H18C)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   ?
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
Ti1 Ti 0.45546(2) 0.31793(2) 0.51643(3) 0.01174(8) Uani 1 1 d . . . . .
O1 O 0.53547(5) 0.29889(5) 0.61075(11) 0.0158(2) Uani 1 1 d . . . . .
C1 C 0.50415(7) 0.41347(7) 0.40270(15) 0.0136(3) Uani 1 1 d . . . . .
C16 C 0.59441(7) 0.29000(7) 0.70530(15) 0.0170(3) Uani 1 1 d . . . . .
C6 C 0.43093(8) 0.37742(8) 0.76261(16) 0.0199(3) Uani 1 1 d . . . . .
H6 H 0.4670 0.3906 0.8309 0.024 Uiso 1 1 calc R . . . .
C2 C 0.45534(7) 0.45140(7) 0.30676(16) 0.0151(3) Uani 1 1 d . . . . .
H2 H 0.4143 0.4724 0.3428 0.018 Uiso 1 1 calc R . . . .
C5 C 0.55981(7) 0.39546(7) 0.29800(15) 0.0149(3) Uani 1 1 d . . . . .
H5 H 0.6008 0.3722 0.3269 0.018 Uiso 1 1 calc R . . . .
C4 C 0.54382(7) 0.41731(7) 0.15124(16) 0.0177(3) Uani 1 1 d . . . . .
H4 H 0.5712 0.4109 0.0609 0.021 Uiso 1 1 calc R . . . .
C3 C 0.47836(7) 0.45178(7) 0.15669(16) 0.0173(3) Uani 1 1 d . . . . .
H3 H 0.4551 0.4715 0.0702 0.021 Uiso 1 1 calc R . . . .
C10 C 0.40223(7) 0.41816(7) 0.64559(17) 0.0195(3) Uani 1 1 d . . . . .
H10 H 0.4155 0.4638 0.6206 0.023 Uiso 1 1 calc R . . . .
C14 C 0.38048(8) 0.26486(7) 0.32696(17) 0.0206(3) Uani 1 1 d . . . . .
H14 H 0.3346 0.2806 0.3150 0.025 Uiso 1 1 calc R . . . .
C15 C 0.43772(8) 0.28901(7) 0.24548(16) 0.0198(3) Uani 1 1 d . . . . .
H15 H 0.4378 0.3248 0.1703 0.024 Uiso 1 1 calc R . . . .
C11 C 0.49564(8) 0.25062(7) 0.29471(17) 0.0209(3) Uani 1 1 d . . . . .
H11 H 0.5413 0.2560 0.2577 0.025 Uiso 1 1 calc R . . . .
C13 C 0.40294(8) 0.21276(7) 0.43072(18) 0.0217(3) Uani 1 1 d . . . . .
H13 H 0.3751 0.1885 0.5030 0.026 Uiso 1 1 calc R . . . .
C9 C 0.35013(8) 0.37988(8) 0.57067(18) 0.0215(3) Uani 1 1 d . . . . .
H9 H 0.3229 0.3947 0.4852 0.026 Uiso 1 1 calc R . . . .
C12 C 0.47388(8) 0.20352(7) 0.40726(18) 0.0219(3) Uani 1 1 d . . . . .
H12 H 0.5021 0.1709 0.4590 0.026 Uiso 1 1 calc R . . . .
C7 C 0.39703(8) 0.31330(8) 0.76174(17) 0.0226(3) Uani 1 1 d . . . . .
H7 H 0.4069 0.2753 0.8275 0.027 Uiso 1 1 calc R . . . .
C8 C 0.34597(8) 0.31575(8) 0.64591(18) 0.0234(3) Uani 1 1 d . . . . .
H8 H 0.3141 0.2802 0.6225 0.028 Uiso 1 1 calc R . . . .
C17 C 0.62814(8) 0.36036(8) 0.72639(17) 0.0229(3) Uani 1 1 d . . . . .
H17A H 0.6416 0.3786 0.6245 0.034 Uiso 1 1 calc GR . . . .
H17B H 0.6689 0.3557 0.7924 0.034 Uiso 1 1 calc GR . . . .
H17C H 0.5955 0.3919 0.7758 0.034 Uiso 1 1 calc GR . . . .
C19 C 0.57206(9) 0.26004(8) 0.86231(17) 0.0245(3) Uani 1 1 d . . . . .
H19A H 0.5411 0.2924 0.9146 0.037 Uiso 1 1 calc GR . . . .
H19B H 0.6126 0.2522 0.9275 0.037 Uiso 1 1 calc GR . . . .
H19C H 0.5481 0.2164 0.8452 0.037 Uiso 1 1 calc GR . . . .
C18 C 0.64310(8) 0.24092(8) 0.62192(18) 0.0248(3) Uani 1 1 d . . . . .
H18A H 0.6200 0.1968 0.6050 0.037 Uiso 1 1 calc GR . . . .
H18B H 0.6842 0.2338 0.6859 0.037 Uiso 1 1 calc GR . . . .
H18C H 0.6564 0.2606 0.5213 0.037 Uiso 1 1 calc GR . . . .
H1 H 0.5160(8) 0.4296(8) 0.5032(19) 0.016(4) Uiso 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
Ti1 O1 1.7939(10) . ?
Ti1 C1 2.3043(13) . ?
Ti1 C6 2.4568(14) . ?
Ti1 C10 2.4716(14) . ?
Ti1 C14 2.4174(14) . ?
Ti1 C15 2.4183(14) . ?
Ti1 C11 2.4397(14) . ?
Ti1 C13 2.4035(14) . ?
Ti1 C9 2.4236(14) . ?
Ti1 C12 2.4426(14) . ?
Ti1 C7 2.3952(14) . ?
Ti1 C8 2.4040(14) . ?
O1 C16 1.4160(16) . ?
C1 C2 1.4580(19) . ?
C1 C5 1.4508(18) . ?
C1 H1 0.946(16) . ?
C16 C17 1.5295(19) . ?
C16 C19 1.5318(19) . ?
C16 C18 1.524(2) . ?
C6 H6 0.9500 . ?
C6 C10 1.397(2) . ?
C6 C7 1.412(2) . ?
C2 H2 0.9500 . ?
C2 C3 1.3642(19) . ?
C5 H5 0.9500 . ?
C5 C4 1.3658(19) . ?
C4 H4 0.9500 . ?
C4 C3 1.4408(19) . ?
C3 H3 0.9500 . ?
C10 H10 0.9500 . ?
C10 C9 1.413(2) . ?
C14 H14 0.9500 . ?
C14 C15 1.397(2) . ?
C14 C13 1.419(2) . ?
C15 H15 0.9500 . ?
C15 C11 1.417(2) . ?
C11 H11 0.9500 . ?
C11 C12 1.398(2) . ?
C13 H13 0.9500 . ?
C13 C12 1.407(2) . ?
C9 H9 0.9500 . ?
C9 C8 1.408(2) . ?
C12 H12 0.9500 . ?
C7 H7 0.9500 . ?
C7 C8 1.407(2) . ?
C8 H8 0.9500 . ?
C17 H17A 0.9800 . ?
C17 H17B 0.9800 . ?
C17 H17C 0.9800 . ?
C19 H19A 0.9800 . ?
C19 H19B 0.9800 . ?
C19 H19C 0.9800 . ?
C18 H18A 0.9800 . ?
C18 H18B 0.9800 . ?
C18 H18C 0.9800 . ?

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
O1 Ti1 C1 90.06(5) . . ?
O1 Ti1 C6 82.97(5) . . ?
O1 Ti1 C10 108.93(5) . . ?
O1 Ti1 C14 137.70(5) . . ?
O1 Ti1 C15 120.67(5) . . ?
O1 Ti1 C11 87.88(5) . . ?
O1 Ti1 C13 109.36(5) . . ?
O1 Ti1 C9 138.62(5) . . ?
O1 Ti1 C12 81.80(5) . . ?
O1 Ti1 C7 90.43(5) . . ?
O1 Ti1 C8 123.86(5) . . ?
C1 Ti1 C6 93.68(5) . . ?
C1 Ti1 C10 74.07(5) . . ?
C1 Ti1 C14 107.94(5) . . ?
C1 Ti1 C15 80.73(5) . . ?
C1 Ti1 C11 88.33(5) . . ?
C1 Ti1 C13 137.10(5) . . ?
C1 Ti1 C9 91.59(5) . . ?
C1 Ti1 C12 120.85(5) . . ?
C1 Ti1 C7 126.74(5) . . ?
C1 Ti1 C8 125.08(5) . . ?
C6 Ti1 C10 32.92(5) . . ?
C14 Ti1 C6 131.53(5) . . ?
C14 Ti1 C10 112.72(5) . . ?
C14 Ti1 C15 33.59(5) . . ?
C14 Ti1 C11 55.87(5) . . ?
C14 Ti1 C9 80.28(5) . . ?
C14 Ti1 C12 56.00(5) . . ?
C15 Ti1 C6 155.45(5) . . ?
C15 Ti1 C10 123.75(5) . . ?
C15 Ti1 C11 33.91(5) . . ?
C15 Ti1 C9 100.36(5) . . ?
C15 Ti1 C12 55.91(5) . . ?
C11 Ti1 C6 170.64(5) . . ?
C11 Ti1 C10 155.27(5) . . ?
C11 Ti1 C12 33.27(5) . . ?
C13 Ti1 C6 125.60(5) . . ?
C13 Ti1 C10 129.15(5) . . ?
C13 Ti1 C14 34.23(5) . . ?
C13 Ti1 C15 56.39(5) . . ?
C13 Ti1 C11 55.95(5) . . ?
C13 Ti1 C9 97.05(5) . . ?
C13 Ti1 C12 33.74(5) . . ?
C13 Ti1 C8 75.49(5) . . ?
C9 Ti1 C6 55.66(5) . . ?
C9 Ti1 C10 33.54(5) . . ?
C9 Ti1 C11 133.49(5) . . ?
C9 Ti1 C12 130.66(5) . . ?
C12 Ti1 C6 142.03(5) . . ?
C12 Ti1 C10 162.42(5) . . ?
C7 Ti1 C6 33.80(5) . . ?
C7 Ti1 C10 55.68(5) . . ?
C7 Ti1 C14 106.80(5) . . ?
C7 Ti1 C15 140.29(5) . . ?
C7 Ti1 C11 144.89(5) . . ?
C7 Ti1 C13 92.02(5) . . ?
C7 Ti1 C9 56.51(5) . . ?
C7 Ti1 C12 111.89(5) . . ?
C7 Ti1 C8 34.09(5) . . ?
C8 Ti1 C6 55.82(5) . . ?
C8 Ti1 C10 55.59(5) . . ?
C8 Ti1 C14 76.61(5) . . ?
C8 Ti1 C15 108.31(5) . . ?
C8 Ti1 C11 129.46(5) . . ?
C8 Ti1 C9 33.91(5) . . ?
C8 Ti1 C12 106.95(5) . . ?
C16 O1 Ti1 170.88(9) . . ?
Ti1 C1 H1 88.9(10) . . ?
C2 C1 Ti1 112.33(9) . . ?
C2 C1 H1 120.4(10) . . ?
C5 C1 Ti1 112.00(9) . . ?
C5 C1 C2 105.00(11) . . ?
C5 C1 H1 117.5(10) . . ?
O1 C16 C17 107.82(11) . . ?
O1 C16 C19 108.72(12) . . ?
O1 C16 C18 108.13(11) . . ?
C17 C16 C19 111.01(12) . . ?
C18 C16 C17 110.48(12) . . ?
C18 C16 C19 110.57(12) . . ?
Ti1 C6 H6 121.0 . . ?
C10 C6 Ti1 74.12(8) . . ?
C10 C6 H6 125.9 . . ?
C10 C6 C7 108.13(14) . . ?
C7 C6 Ti1 70.71(8) . . ?
C7 C6 H6 125.9 . . ?
C1 C2 H2 125.6 . . ?
C3 C2 C1 108.81(12) . . ?
C3 C2 H2 125.6 . . ?
C1 C5 H5 125.5 . . ?
C4 C5 C1 109.04(12) . . ?
C4 C5 H5 125.5 . . ?
C5 C4 H4 125.8 . . ?
C5 C4 C3 108.46(12) . . ?
C3 C4 H4 125.8 . . ?
C2 C3 C4 108.57(12) . . ?
C2 C3 H3 125.7 . . ?
C4 C3 H3 125.7 . . ?
Ti1 C10 H10 121.6 . . ?
C6 C10 Ti1 72.96(8) . . ?
C6 C10 H10 125.8 . . ?
C6 C10 C9 108.37(13) . . ?
C9 C10 Ti1 71.36(8) . . ?
C9 C10 H10 125.8 . . ?
Ti1 C14 H14 120.2 . . ?
C15 C14 Ti1 73.24(8) . . ?
C15 C14 H14 126.0 . . ?
C15 C14 C13 108.00(13) . . ?
C13 C14 Ti1 72.35(8) . . ?
C13 C14 H14 126.0 . . ?
Ti1 C15 H15 118.8 . . ?
C14 C15 Ti1 73.17(8) . . ?
C14 C15 H15 126.0 . . ?
C14 C15 C11 107.92(13) . . ?
C11 C15 Ti1 73.87(8) . . ?
C11 C15 H15 126.0 . . ?
Ti1 C11 H11 120.2 . . ?
C15 C11 Ti1 72.22(8) . . ?
C15 C11 H11 125.9 . . ?
C12 C11 Ti1 73.48(8) . . ?
C12 C11 C15 108.13(13) . . ?
C12 C11 H11 125.9 . . ?
Ti1 C13 H13 117.8 . . ?
C14 C13 Ti1 73.42(8) . . ?
C14 C13 H13 126.2 . . ?
C12 C13 Ti1 74.65(8) . . ?
C12 C13 C14 107.69(14) . . ?
C12 C13 H13 126.2 . . ?
Ti1 C9 H9 118.3 . . ?
C10 C9 Ti1 75.09(8) . . ?
C10 C9 H9 126.3 . . ?
C8 C9 Ti1 72.28(8) . . ?
C8 C9 C10 107.45(14) . . ?
C8 C9 H9 126.3 . . ?
Ti1 C12 H12 121.0 . . ?
C11 C12 Ti1 73.25(8) . . ?
C11 C12 C13 108.21(13) . . ?
C11 C12 H12 125.9 . . ?
C13 C12 Ti1 71.61(8) . . ?
C13 C12 H12 125.9 . . ?
Ti1 C7 H7 117.1 . . ?
C6 C7 Ti1 75.49(8) . . ?
C6 C7 H7 126.2 . . ?
C8 C7 Ti1 73.30(8) . . ?
C8 C7 C6 107.69(14) . . ?
C8 C7 H7 126.2 . . ?
Ti1 C8 H8 119.5 . . ?
C9 C8 Ti1 73.81(8) . . ?
C9 C8 H8 125.9 . . ?
C7 C8 Ti1 72.62(8) . . ?
C7 C8 C9 108.29(14) . . ?
C7 C8 H8 125.9 . . ?
C16 C17 H17A 109.5 . . ?
C16 C17 H17B 109.5 . . ?
C16 C17 H17C 109.5 . . ?
H17A C17 H17B 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
C16 C19 H19A 109.5 . . ?
C16 C19 H19B 109.5 . . ?
C16 C19 H19C 109.5 . . ?
H19A C19 H19B 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C16 C18 H18A 109.5 . . ?
C16 C18 H18B 109.5 . . ?
C16 C18 H18C 109.5 . . ?
H18A C18 H18B 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Ti1 C1 C2 C3 -118.46(11) . . . . ?
Ti1 C1 C5 C4 119.11(11) . . . . ?
Ti1 C6 C10 C9 63.00(10) . . . . ?
Ti1 C6 C7 C8 -66.78(10) . . . . ?
Ti1 C10 C9 C8 65.56(10) . . . . ?
Ti1 C14 C15 C11 66.24(10) . . . . ?
Ti1 C14 C13 C12 -67.36(10) . . . . ?
Ti1 C15 C11 C12 65.21(10) . . . . ?
Ti1 C11 C12 C13 63.52(10) . . . . ?
Ti1 C13 C12 C11 -64.59(10) . . . . ?
Ti1 C9 C8 C7 64.93(10) . . . . ?
Ti1 C7 C8 C9 -65.72(10) . . . . ?
C1 C2 C3 C4 -2.66(16) . . . . ?
C1 C5 C4 C3 1.56(16) . . . . ?
C6 C10 C9 Ti1 -64.03(10) . . . . ?
C6 C10 C9 C8 1.53(16) . . . . ?
C6 C7 C8 Ti1 68.27(10) . . . . ?
C6 C7 C8 C9 2.55(16) . . . . ?
C2 C1 C5 C4 -3.07(15) . . . . ?
C5 C1 C2 C3 3.50(15) . . . . ?
C5 C4 C3 C2 0.70(16) . . . . ?
C10 C6 C7 Ti1 65.19(10) . . . . ?
C10 C6 C7 C8 -1.60(16) . . . . ?
C10 C9 C8 Ti1 -67.45(10) . . . . ?
C10 C9 C8 C7 -2.52(16) . . . . ?
C14 C15 C11 Ti1 -65.78(10) . . . . ?
C14 C15 C11 C12 -0.56(16) . . . . ?
C14 C13 C12 Ti1 66.54(10) . . . . ?
C14 C13 C12 C11 1.95(16) . . . . ?
C15 C14 C13 Ti1 65.07(10) . . . . ?
C15 C14 C13 C12 -2.30(16) . . . . ?
C15 C11 C12 Ti1 -64.39(10) . . . . ?
C15 C11 C12 C13 -0.87(16) . . . . ?
C13 C14 C15 Ti1 -64.48(10) . . . . ?
C13 C14 C15 C11 1.76(16) . . . . ?
C7 C6 C10 Ti1 -62.96(10) . . . . ?
C7 C6 C10 C9 0.04(16) . . . . ?

_shelx_SHELXL_version_number     2014/7
_olex2_date_sample_data_collection 2016-03-11
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.754
_oxdiff_exptl_absorpt_empirical_full_min 0.485
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: hexanes'
_chemical_properties_physical    ', Air-sensitive,Moisture-sensitive'
####################################################################### 
# 
# 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_haneb03
_database_code_depnum_ccdc_archive 'CCDC 1496572'
_audit_update_record             
;
2016-07-28 deposited with the CCDC.
2016-11-02 downloaded from the CCDC.
;

_vrf_PLAT301_haneb03             
; 
PROBLEM: _G Note: Main Residue Disorder ................... 86 Perc. 
RESPONSE: The cyclopentadienyl ligand and tert-butyl group are modeled as 
disordered over crystallographic mirror planes (50:50). 
;

_vrf_PLAT860_haneb03             
; 
PROBLEM: _G Note: Number of Least-Squares Restraints ....... 28 
RESPONSE: Bond lengths and angles around the cyclopentadienyl ligand were 
restrained to be similar and the ligand was restrained to be flat. In the 
tert-butyl group, both C--C bond lengths and C...C through-space distances 
were restrained to be similar, respectively. Anisotropic displacement 
parameters for spatially close symmetry-related atom pairs were constrained 
to be equivalent. 
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
bis(cyclopentadienyl)zirconium(bis(tert-butoxide))
_chemical_name_common            haneb03
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H28 O2 Zr'
_chemical_formula_sum            'C18 H28 O2 Zr'
_chemical_formula_weight         367.62

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'
O O 0.0106 0.0060 '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'

_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_H-M   'P -4 21 m'

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

_cell_length_a                   8.5606(8)
_cell_length_b                   8.5606(8)
_cell_length_c                   12.9538(12)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     949.30(15)
_cell_formula_units_Z            2
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    4002
_cell_measurement_theta_min      2.85
_cell_measurement_theta_max      29.15

_exptl_crystal_description       plate
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             384
_exptl_absorpt_coefficient_mu    0.581
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8358
_exptl_absorpt_correction_T_max  0.9442
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2008)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      173(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 SMART APEX II CCD Platform'
_diffrn_measurement_method       'area detector, ω scans per φ'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            35496
_diffrn_reflns_av_R_equivalents  0.0472
_diffrn_reflns_av_sigmaI/netI    0.0213
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         2.85
_diffrn_reflns_theta_max         37.78
_reflns_number_total             2737
_reflns_number_gt                2258
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'APEX2 (Bruker, 2012)'
_computing_cell_refinement       'SAINT (Bruker, 2009)'
_computing_data_reduction        'SAINT (Bruker, 2009)'
_computing_structure_solution    'SIR97 (Altomare et al., 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2008)'
_computing_publication_material  'SHELXTL (Sheldrick, 2008)'

_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. 
  
 The cyclopentadienyl ligand and tert-butyl group are modeled as 
 disordered over crystallographic mirror planes (50:50). Bond lengths and 
 angles around the cyclopentadienyl ligand wererestrained to be similar and 
 the ligand was restrained to be flat. In the tert-butyl group, both C--C 
 bond lengths and C...C through-space distances were restrained to be 
 similar, respectively. Anisotropic displacement parameters for spatially 
 close symmetry-related atom pairs were constrained to be equivalent. 
;

_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)+(0.0420P)²+0.1045P] 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_abs_structure_details 
'Flack H D (1983), 1193 Friedel pairs, Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.08(8)
_refine_ls_number_reflns         2737
_refine_ls_number_parameters     83
_refine_ls_number_restraints     28
_refine_ls_R_factor_all          0.0449
_refine_ls_R_factor_gt           0.0330
_refine_ls_wR_factor_ref         0.0808
_refine_ls_wR_factor_gt          0.0758
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_restrained_S_all      1.043
_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
Zr1 Zr 0.5000 0.0000 0.330591(16) 0.03166(7) Uani 1 4 d S . .
C1 C 0.7318(9) 0.1888(9) 0.3312(4) 0.072(3) Uani 0.50 1 d PD A -1
H1 H 0.7794 0.2112 0.2666 0.086 Uiso 0.50 1 calc PR A -1
C2 C 0.6067(6) 0.2694(8) 0.3796(5) 0.0565(10) Uani 0.50 1 d PD A -1
H2 H 0.5556 0.3584 0.3517 0.068 Uiso 0.50 1 calc PR A -1
C3 C 0.5709(8) 0.2029(8) 0.4700(5) 0.0619(9) Uani 0.50 1 d PD A -1
H3 H 0.4906 0.2363 0.5155 0.074 Uiso 0.50 1 calc PR A -1
C4 C 0.6716(6) 0.0754(10) 0.4864(6) 0.0619(9) Uani 0.50 1 d PD A -1
H4 H 0.6720 0.0083 0.5448 0.074 Uiso 0.50 1 calc PR A -1
C5 C 0.7700(8) 0.0657(6) 0.4020(5) 0.0565(10) Uani 0.50 1 d PD A -1
H5 H 0.8497 -0.0101 0.3924 0.068 Uiso 0.50 1 calc PR A -1
O1 O 0.37819(18) 0.12181(18) 0.23511(15) 0.0510(5) Uani 1 2 d S A .
C6 C 0.3124(4) 0.2293(4) 0.1637(3) 0.0471(11) Uani 0.50 1 d PD A -1
C7 C 0.1621(13) 0.2856(15) 0.2115(6) 0.121(6) Uani 0.50 1 d PD A -1
H7A H 0.0934 0.1962 0.2245 0.182 Uiso 0.50 1 calc PR A -1
H7B H 0.1102 0.3584 0.1642 0.182 Uiso 0.50 1 calc PR A -1
H7C H 0.1848 0.3389 0.2767 0.182 Uiso 0.50 1 calc PR A -1
C8 C 0.4190(9) 0.3652(7) 0.1411(5) 0.099(3) Uani 0.50 1 d PD A -1
H8A H 0.4310 0.4290 0.2034 0.149 Uiso 0.50 1 calc PR A -1
H8B H 0.3738 0.4289 0.0857 0.149 Uiso 0.50 1 calc PR A -1
H8C H 0.5214 0.3260 0.1193 0.149 Uiso 0.50 1 calc PR A -1
C9 C 0.2798(9) 0.1323(7) 0.0678(4) 0.100(3) Uani 0.50 1 d PD A -1
H9A H 0.3786 0.0932 0.0395 0.150 Uiso 0.50 1 calc PR A -1
H9B H 0.2273 0.1972 0.0160 0.150 Uiso 0.50 1 calc PR A -1
H9C H 0.2125 0.0438 0.0859 0.150 Uiso 0.50 1 calc PR A -1


_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
Zr1 O1 1.9247(19) 2_655 ?
Zr1 O1 1.9247(19) . ?
Zr1 C5 2.552(6) . ?
Zr1 C5 2.552(6) 2_655 ?
Zr1 C5 2.552(6) 7 ?
Zr1 C5 2.552(6) 8_545 ?
Zr1 C1 2.559(3) 8_545 ?
Zr1 C1 2.559(3) . ?
Zr1 C1 2.559(3) 2_655 ?
Zr1 C1 2.559(3) 7 ?
Zr1 C2 2.561(6) . ?
Zr1 C2 2.561(6) 7 ?
C1 C2 1.420(10) . ?
C1 C5 1.435(8) . ?
C1 H1 0.9500 . ?
C2 C3 1.337(9) . ?
C2 H2 0.9500 . ?
C3 C4 1.408(7) . ?
C3 H3 0.9500 . ?
C4 C5 1.383(9) . ?
C4 H4 0.9500 . ?
C5 H5 0.9500 . ?
O1 C6 1.421(4) 7 ?
O1 C6 1.421(4) . ?
C6 C7 1.507(7) . ?
C6 C8 1.507(5) . ?
C6 C9 1.521(5) . ?
C7 H7A 0.9800 . ?
C7 H7B 0.9800 . ?
C7 H7C 0.9800 . ?
C8 H8A 0.9800 . ?
C8 H8B 0.9800 . ?
C8 H8C 0.9800 . ?
C9 H9A 0.9800 . ?
C9 H9B 0.9800 . ?
C9 H9C 0.9800 . ?

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
O1 Zr1 O1 100.03(14) 2_655 . ?
O1 Zr1 C5 82.04(17) 2_655 . ?
O1 Zr1 C5 127.16(11) . . ?
O1 Zr1 C5 127.16(11) 2_655 2_655 ?
O1 Zr1 C5 82.04(17) . 2_655 ?
C5 Zr1 C5 137.5(3) . 2_655 ?
O1 Zr1 C5 82.03(17) 2_655 7 ?
O1 Zr1 C5 127.16(11) . 7 ?
C5 Zr1 C5 105.5(2) . 7 ?
C5 Zr1 C5 58.0(3) 2_655 7 ?
O1 Zr1 C5 127.17(11) 2_655 8_545 ?
O1 Zr1 C5 82.04(17) . 8_545 ?
C5 Zr1 C5 58.0(3) . 8_545 ?
C5 Zr1 C5 105.5(2) 2_655 8_545 ?
C5 Zr1 C5 137.5(3) 7 8_545 ?
O1 Zr1 C1 94.58(19) 2_655 8_545 ?
O1 Zr1 C1 85.63(19) . 8_545 ?
C5 Zr1 C1 41.9(2) . 8_545 ?
C5 Zr1 C1 137.9(2) 2_655 8_545 ?
C5 Zr1 C1 147.2(2) 7 8_545 ?
C5 Zr1 C1 32.6(2) 8_545 8_545 ?
O1 Zr1 C1 85.63(19) 2_655 . ?
O1 Zr1 C1 94.58(19) . . ?
C5 Zr1 C1 32.6(2) . . ?
C5 Zr1 C1 147.2(2) 2_655 . ?
C5 Zr1 C1 137.9(2) 7 . ?
C5 Zr1 C1 41.9(2) 8_545 . ?
C1 Zr1 C1 11.7(5) 8_545 . ?
O1 Zr1 C1 94.58(19) 2_655 2_655 ?
O1 Zr1 C1 85.63(19) . 2_655 ?
C5 Zr1 C1 147.2(2) . 2_655 ?
C5 Zr1 C1 32.6(2) 2_655 2_655 ?
C5 Zr1 C1 41.9(2) 7 2_655 ?
C5 Zr1 C1 137.9(2) 8_545 2_655 ?
C1 Zr1 C1 168.3(5) 8_545 2_655 ?
C1 Zr1 C1 179.7(2) . 2_655 ?
O1 Zr1 C1 85.63(19) 2_655 7 ?
O1 Zr1 C1 94.58(19) . 7 ?
C5 Zr1 C1 137.9(2) . 7 ?
C5 Zr1 C1 41.9(2) 2_655 7 ?
C5 Zr1 C1 32.6(2) 7 7 ?
C5 Zr1 C1 147.2(2) 8_545 7 ?
C1 Zr1 C1 179.7(2) 8_545 7 ?
C1 Zr1 C1 168.3(5) . 7 ?
C1 Zr1 C1 11.7(5) 2_655 7 ?
O1 Zr1 C2 117.00(14) 2_655 . ?
O1 Zr1 C2 82.23(14) . . ?
C5 Zr1 C2 52.31(13) . . ?
C5 Zr1 C2 115.58(17) 2_655 . ?
C5 Zr1 C2 143.56(15) 7 . ?
C5 Zr1 C2 10.21(19) 8_545 . ?
C1 Zr1 C2 22.4(2) 8_545 . ?
C1 Zr1 C2 32.2(2) . . ?
C1 Zr1 C2 147.6(2) 2_655 . ?
C1 Zr1 C2 157.4(3) 7 . ?
O1 Zr1 C2 117.00(14) 2_655 7 ?
O1 Zr1 C2 82.23(14) . 7 ?
C5 Zr1 C2 143.55(15) . 7 ?
C5 Zr1 C2 10.21(19) 2_655 7 ?
C5 Zr1 C2 52.31(13) 7 7 ?
C5 Zr1 C2 115.58(17) 8_545 7 ?
C1 Zr1 C2 147.6(2) 8_545 7 ?
C1 Zr1 C2 157.4(3) . 7 ?
C1 Zr1 C2 22.4(2) 2_655 7 ?
C1 Zr1 C2 32.2(2) 7 7 ?
C2 Zr1 C2 125.5(3) . 7 ?
C2 C1 C5 104.2(4) . . ?
C2 C1 Zr1 74.0(3) . . ?
C5 C1 Zr1 73.4(3) . . ?
C2 C1 H1 127.9 . . ?
C5 C1 H1 127.9 . . ?
Zr1 C1 H1 117.2 . . ?
C3 C2 C1 110.7(6) . . ?
C3 C2 Zr1 75.6(3) . . ?
C1 C2 Zr1 73.8(3) . . ?
C3 C2 H2 124.7 . . ?
C1 C2 H2 124.7 . . ?
Zr1 C2 H2 117.6 . . ?
C2 C3 C4 108.8(9) . . ?
C2 C3 Zr1 74.2(3) . . ?
C4 C3 Zr1 74.2(4) . . ?
C2 C3 H3 125.6 . . ?
C4 C3 H3 125.6 . . ?
Zr1 C3 H3 117.9 . . ?
C5 C4 C3 107.4(10) . . ?
C5 C4 Zr1 73.3(3) . . ?
C3 C4 Zr1 74.1(4) . . ?
C5 C4 H4 126.3 . . ?
C3 C4 H4 126.3 . . ?
Zr1 C4 H4 118.3 . . ?
C4 C5 C1 108.8(7) . . ?
C4 C5 Zr1 75.4(3) . . ?
C1 C5 Zr1 74.0(3) . . ?
C4 C5 H5 125.6 . . ?
C1 C5 H5 125.6 . . ?
Zr1 C5 H5 117.0 . . ?
C6 O1 Zr1 169.68(14) 7 . ?
C6 O1 Zr1 169.68(14) . . ?
O1 C6 C7 106.2(4) . . ?
O1 C6 C8 112.7(3) . . ?
C7 C6 C8 110.5(7) . . ?
O1 C6 C9 104.5(3) . . ?
C7 C6 C9 110.7(5) . . ?
C8 C6 C9 111.9(4) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 Zr1 C1 C2 167.3(4) 2_655 . . . ?
O1 Zr1 C1 C2 67.6(3) . . . . ?
C5 Zr1 C1 C2 -110.7(3) . . . . ?
C5 Zr1 C1 C2 -14.8(7) 2_655 . . . ?
C5 Zr1 C1 C2 -119.7(4) 7 . . . ?
C5 Zr1 C1 C2 -5.2(5) 8_545 . . . ?
C1 Zr1 C1 C2 27.4(3) 8_545 . . . ?
C1 Zr1 C1 C2 -62.6(3) 2_655 . . . ?
C1 Zr1 C1 C2 -150.9(10) 7 . . . ?
C2 Zr1 C1 C2 -13.2(6) 7 . . . ?
O1 Zr1 C1 C5 -82.0(4) 2_655 . . . ?
O1 Zr1 C1 C5 178.2(4) . . . . ?
C5 Zr1 C1 C5 95.8(8) 2_655 . . . ?
C5 Zr1 C1 C5 -9.0(4) 7 . . . ?
C5 Zr1 C1 C5 105.5(6) 8_545 . . . ?
C1 Zr1 C1 C5 138.1(4) 8_545 . . . ?
C1 Zr1 C1 C5 48.0(4) 2_655 . . . ?
C1 Zr1 C1 C5 -40.3(12) 7 . . . ?
C2 Zr1 C1 C5 110.7(3) . . . . ?
C2 Zr1 C1 C5 97.4(7) 7 . . . ?
C5 C1 C2 C3 -0.38(19) . . . . ?
Zr1 C1 C2 C3 67.3(2) . . . . ?
C5 C1 C2 Zr1 -67.7(2) . . . . ?
O1 Zr1 C2 C3 -131.2(4) 2_655 . . . ?
O1 Zr1 C2 C3 131.4(4) . . . . ?
C5 Zr1 C2 C3 -77.4(5) . . . . ?
C5 Zr1 C2 C3 54.2(4) 2_655 . . . ?
C5 Zr1 C2 C3 -15.9(6) 7 . . . ?
C5 Zr1 C2 C3 43.2(15) 8_545 . . . ?
C1 Zr1 C2 C3 -131.2(7) 8_545 . . . ?
C1 Zr1 C2 C3 -117.0(5) . . . . ?
C1 Zr1 C2 C3 62.5(5) 2_655 . . . ?
C1 Zr1 C2 C3 48.2(7) 7 . . . ?
C2 Zr1 C2 C3 56.8(5) 7 . . . ?
O1 Zr1 C2 C1 -14.2(4) 2_655 . . . ?
O1 Zr1 C2 C1 -111.6(4) . . . . ?
C5 Zr1 C2 C1 39.6(3) . . . . ?
C5 Zr1 C2 C1 171.1(4) 2_655 . . . ?
C5 Zr1 C2 C1 101.1(4) 7 . . . ?
C5 Zr1 C2 C1 160.2(18) 8_545 . . . ?
C1 Zr1 C2 C1 -14.2(6) 8_545 . . . ?
C1 Zr1 C2 C1 179.4(4) 2_655 . . . ?
C1 Zr1 C2 C1 165.2(7) 7 . . . ?
C2 Zr1 C2 C1 173.8(3) 7 . . . ?
C1 C2 C3 C4 0.5(2) . . . . ?
Zr1 C2 C3 C4 66.7(3) . . . . ?
C1 C2 C3 Zr1 -66.2(3) . . . . ?
O1 Zr1 C3 C2 67.3(4) 2_655 . . . ?
O1 Zr1 C3 C2 -49.5(4) . . . . ?
C5 Zr1 C3 C2 78.4(4) . . . . ?
C5 Zr1 C3 C2 -132.7(4) 2_655 . . . ?
C5 Zr1 C3 C2 169.7(4) 7 . . . ?
C5 Zr1 C3 C2 -17.6(4) 8_545 . . . ?
C1 Zr1 C3 C2 22.9(4) 8_545 . . . ?
C1 Zr1 C3 C2 36.8(4) . . . . ?
C1 Zr1 C3 C2 -143.4(4) 2_655 . . . ?
C1 Zr1 C3 C2 -157.3(4) 7 . . . ?
C2 Zr1 C3 C2 -134.8(4) 7 . . . ?
O1 Zr1 C3 C4 -48.0(6) 2_655 . . . ?
O1 Zr1 C3 C4 -164.8(5) . . . . ?
C5 Zr1 C3 C4 -36.9(5) . . . . ?
C5 Zr1 C3 C4 112.0(6) 2_655 . . . ?
C5 Zr1 C3 C4 54.4(6) 7 . . . ?
C5 Zr1 C3 C4 -132.9(10) 8_545 . . . ?
C1 Zr1 C3 C4 -92.5(7) 8_545 . . . ?
C1 Zr1 C3 C4 -78.5(6) . . . . ?
C1 Zr1 C3 C4 101.3(6) 2_655 . . . ?
C1 Zr1 C3 C4 87.4(7) 7 . . . ?
C2 Zr1 C3 C4 -115.3(8) . . . . ?
C2 Zr1 C3 C4 109.8(5) 7 . . . ?
C2 C3 C4 C5 -0.5(4) . . . . ?
Zr1 C3 C4 C5 66.3(3) . . . . ?
C2 C3 C4 Zr1 -66.74(19) . . . . ?
O1 Zr1 C4 C5 30.9(5) 2_655 . . . ?
O1 Zr1 C4 C5 -93.9(4) . . . . ?
C5 Zr1 C4 C5 171.5(3) 2_655 . . . ?
C5 Zr1 C4 C5 113.8(5) 7 . . . ?
C5 Zr1 C4 C5 -91.9(5) 8_545 . . . ?
C1 Zr1 C4 C5 -51.5(5) 8_545 . . . ?
C1 Zr1 C4 C5 -37.7(4) . . . . ?
C1 Zr1 C4 C5 142.4(4) 2_655 . . . ?
C1 Zr1 C4 C5 128.6(5) 7 . . . ?
C2 Zr1 C4 C5 -78.8(5) . . . . ?
C2 Zr1 C4 C5 164.0(4) 7 . . . ?
O1 Zr1 C4 C3 145.1(5) 2_655 . . . ?
O1 Zr1 C4 C3 20.3(6) . . . . ?
C5 Zr1 C4 C3 114.3(9) . . . . ?
C5 Zr1 C4 C3 -74.2(6) 2_655 . . . ?
C5 Zr1 C4 C3 -131.9(5) 7 . . . ?
C5 Zr1 C4 C3 22.4(5) 8_545 . . . ?
C1 Zr1 C4 C3 62.7(6) 8_545 . . . ?
C1 Zr1 C4 C3 76.5(7) . . . . ?
C1 Zr1 C4 C3 -103.4(7) 2_655 . . . ?
C1 Zr1 C4 C3 -117.1(7) 7 . . . ?
C2 Zr1 C4 C3 35.5(5) . . . . ?
C2 Zr1 C4 C3 -81.8(6) 7 . . . ?
C3 C4 C5 C1 0.2(4) . . . . ?
Zr1 C4 C5 C1 67.1(3) . . . . ?
C3 C4 C5 Zr1 -66.8(3) . . . . ?
C2 C1 C5 C4 0.1(3) . . . . ?
Zr1 C1 C5 C4 -68.0(3) . . . . ?
C2 C1 C5 Zr1 68.1(2) . . . . ?
O1 Zr1 C5 C4 -150.7(5) 2_655 . . . ?
O1 Zr1 C5 C4 112.7(4) . . . . ?
C5 Zr1 C5 C4 -12.1(4) 2_655 . . . ?
C5 Zr1 C5 C4 -71.3(5) 7 . . . ?
C5 Zr1 C5 C4 65.5(5) 8_545 . . . ?
C1 Zr1 C5 C4 103.3(6) 8_545 . . . ?
C1 Zr1 C5 C4 114.9(6) . . . . ?
C1 Zr1 C5 C4 -64.6(6) 2_655 . . . ?
C1 Zr1 C5 C4 -76.3(6) 7 . . . ?
C2 Zr1 C5 C4 75.9(5) . . . . ?
C2 Zr1 C5 C4 -25.1(6) 7 . . . ?
O1 Zr1 C5 C1 94.4(4) 2_655 . . . ?
O1 Zr1 C5 C1 -2.2(5) . . . . ?
C5 Zr1 C5 C1 -127.0(4) 2_655 . . . ?
C5 Zr1 C5 C1 173.8(3) 7 . . . ?
C5 Zr1 C5 C1 -49.4(5) 8_545 . . . ?
C1 Zr1 C5 C1 -11.7(5) 8_545 . . . ?
C1 Zr1 C5 C1 -179.5(3) 2_655 . . . ?
C1 Zr1 C5 C1 168.7(6) 7 . . . ?
C2 Zr1 C5 C1 -39.1(3) . . . . ?
C2 Zr1 C5 C1 -140.0(5) 7 . . . ?
O1 Zr1 O1 C6 82.3(12) 2_655 . . 7 ?
C5 Zr1 O1 C6 169.8(12) . . . 7 ?
C5 Zr1 O1 C6 -44.2(12) 2_655 . . 7 ?
C5 Zr1 O1 C6 -5.3(13) 7 . . 7 ?
C5 Zr1 O1 C6 -151.2(12) 8_545 . . 7 ?
C1 Zr1 O1 C6 176.2(12) 8_545 . . 7 ?
C1 Zr1 O1 C6 168.6(12) . . . 7 ?
C1 Zr1 O1 C6 -11.6(12) 2_655 . . 7 ?
C1 Zr1 O1 C6 -4.1(12) 7 . . 7 ?
C2 Zr1 O1 C6 -161.6(12) . . . 7 ?
C2 Zr1 O1 C6 -33.9(12) 7 . . 7 ?
O1 Zr1 O1 C6 -82.3(12) 2_655 . . . ?
C5 Zr1 O1 C6 5.3(13) . . . . ?
C5 Zr1 O1 C6 151.2(12) 2_655 . . . ?
C5 Zr1 O1 C6 -169.8(12) 7 . . . ?
C5 Zr1 O1 C6 44.2(12) 8_545 . . . ?
C1 Zr1 O1 C6 11.6(12) 8_545 . . . ?
C1 Zr1 O1 C6 4.1(12) . . . . ?
C1 Zr1 O1 C6 -176.2(12) 2_655 . . . ?
C1 Zr1 O1 C6 -168.6(12) 7 . . . ?
C2 Zr1 O1 C6 33.9(12) . . . . ?
C2 Zr1 O1 C6 161.5(12) 7 . . . ?
Zr1 O1 C6 C7 -124.7(12) . . . . ?
Zr1 O1 C6 C8 -3.6(14) . . . . ?
Zr1 O1 C6 C9 118.2(12) . . . . ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        37.78
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.341
_refine_diff_density_min         -0.445
_refine_diff_density_rms         0.055
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: hexanes'
_chemical_properties_physical    ', Air-sensitive,Moisture-sensitive'
####################################################################### 
# 
# 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_haneb04
_database_code_depnum_ccdc_archive 'CCDC 1496573'
_audit_update_record             
;
2016-07-28 deposited with the CCDC.
2016-11-02 downloaded from the CCDC.
;

_vrf_DIFMX01_haneb04             
; 
PROBLEM: _C  The maximum difference density is > 0.1*ZMAX*0.75 
             _refine_diff_density_max given =      5.421 
             Test value =      5.400 
RESPONSE: The largest residual peak of 5.42 electrons per \%A^3^ is 
located 0.65 \%A from atom HF1. It may be due to residual absorption 
errors, or to a minor component of disorder, or to something else that 
is minor, but systematic. 
;

_vrf_DIFMX02_haneb04             
; 
PROBLEM: _C  The maximum difference density is > 0.1*ZMAX*0.75 
             The relevant atom site should be identified. 
RESPONSE: See above. 
;

_vrf_PLAT094_haneb04             
; 
PROBLEM: _C Ratio of Maximum / Minimum Residual Density .... 2.39 
RESPONSE: See above. 
;

_vrf_PLAT301_haneb04             
; 
PROBLEM: _G Note: Main Residue Disorder ................... 86 % 
RESPONSE: The cyclopentadienyl ligand and tert-butyl group are modeled as 
disordered over crystallographic mirror planes (50:50). 
;

_vrf_PLAT860_haneb04             
; 
PROBLEM: _G Note: Number of Least-Squares Restraints ....... 28 
RESPONSE: Bond lengths and angles around the cyclopentadienyl ligand were 
restrained to be similar and the ligand was restrained to be flat. In the 
tert-butyl group, both C--C bond lengths and C...C through-space distances 
were restrained to be similar, respectively. Anisotropic displacement 
parameters for spatially close symmetry-related atom pairs were constrained 
to be equivalent. 
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
bis(cyclopentadienyl)hafnium(bis(tert-butoxide))
_chemical_name_common            haneb04
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H28 Hf O2'
_chemical_formula_sum            'C18 H28 Hf O2'
_chemical_formula_weight         454.89

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'
Hf Hf -0.5830 6.1852 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           113
_space_group_name_H-M_alt        'P -4 21 m'
_space_group_name_Hall           'P -4 2ab'

_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, z'
'y, -x, -z'
'-y, x, -z'
'-x+1/2, y+1/2, -z'
'x+1/2, -y+1/2, -z'
'-y+1/2, -x+1/2, z'
'y+1/2, x+1/2, z'

_cell_length_a                   8.4676(7)
_cell_length_b                   8.4676(7)
_cell_length_c                   12.8196(11)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     919.17(17)
_cell_formula_units_Z            2
_cell_measurement_temperature    100.0(5)
_cell_measurement_reflns_used    4002
_cell_measurement_theta_min      2.88
_cell_measurement_theta_max      35.20

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.644
_exptl_crystal_F_000             448
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_exptl_absorpt_coefficient_mu    5.677
_shelx_estimated_absorpt_T_min   0.428
_shelx_estimated_absorpt_T_max   0.549
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.3290
_exptl_absorpt_correction_T_max  0.4405
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2012)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      100.0(5)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker SMART APEX II CCD platform'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            34629
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_av_R_equivalents  0.0345
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         1.588
_diffrn_reflns_theta_max         38.697
_diffrn_reflns_theta_full        37.785
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             2761
_reflns_number_gt                2491
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.765
_reflns_Friedel_fraction_max     0.977
_reflns_Friedel_fraction_full    1.000

_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       'APEX2 (Bruker, 2013)'
_computing_cell_refinement       'SAINT (Bruker, 2013)'
_computing_data_reduction        'SAINT (Bruker, 2013)'
_computing_structure_solution    'SIR97 (Altomare et al., 1999)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2008)'
_computing_publication_material  'SHELXTL (Sheldrick, 2008)'

_refine_special_details          
; 
 The cyclopentadienyl ligand and tert-butyl group are modeled as 
 disordered over crystallographic mirror planes (50:50). Bond lengths and 
 angles around the cyclopentadienyl ligand wererestrained to be similar and 
 the ligand was restrained to be flat. In the tert-butyl group, both C--C 
 bond lengths and C...C through-space distances were restrained to be 
 similar, respectively. Anisotropic displacement parameters for spatially 
 close symmetry-related atom pairs were constrained to be equivalent. 
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
; 
 w=1/[σ²(Fo²)+(0.0286P)²+3.1716P] 
 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_abs_structure_details 
; 
 Flack x determined using 1022 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   -0.023(6)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         2761
_refine_ls_number_parameters     83
_refine_ls_number_restraints     28
_refine_ls_R_factor_all          0.0440
_refine_ls_R_factor_gt           0.0391
_refine_ls_wR_factor_ref         0.0927
_refine_ls_wR_factor_gt          0.0908
_refine_ls_goodness_of_fit_ref   1.170
_refine_ls_restrained_S_all      1.167
_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_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
Hf1 Hf 0.5000 0.0000 0.32900(2) 0.02548(9) Uani 1 4 d S T P . .
C1 C 0.7336(18) 0.1874(18) 0.3291(10) 0.062(9) Uani 0.5 1 d D . P A -1
H1 H 0.7817 0.2097 0.2638 0.075 Uiso 0.5 1 calc R U P A -1
C2 C 0.6077(16) 0.271(2) 0.3763(14) 0.047(3) Uani 0.5 1 d D . P A -1
H2 H 0.5564 0.3605 0.3474 0.056 Uiso 0.5 1 calc R U P A -1
C3 C 0.571(2) 0.202(2) 0.4711(12) 0.049(3) Uani 0.5 1 d D . P A -1
H3 H 0.4908 0.2352 0.5182 0.059 Uiso 0.5 1 calc R U P A -1
C4 C 0.673(2) 0.074(2) 0.4846(12) 0.049(3) Uani 0.5 1 d D . P A -1
H4 H 0.6744 0.0052 0.5430 0.059 Uiso 0.5 1 calc R U P A -1
C5 C 0.773(2) 0.0640(18) 0.3985(13) 0.047(3) Uani 0.5 1 d D . P A -1
H5 H 0.8540 -0.0124 0.3883 0.056 Uiso 0.5 1 calc R U P A -1
O1 O 0.3782(7) 0.1218(7) 0.2323(6) 0.0457(17) Uani 1 2 d S T P A .
C6 C 0.3169(12) 0.2390(12) 0.1615(7) 0.031(2) Uani 0.5 1 d D . P A -1
C7 C 0.163(2) 0.295(2) 0.2095(13) 0.058(7) Uani 0.5 1 d D . P A -1
H7A H 0.0911 0.2050 0.2168 0.086 Uiso 0.5 1 calc R U P A -1
H7B H 0.1151 0.3748 0.1643 0.086 Uiso 0.5 1 calc R U P A -1
H7C H 0.1843 0.3406 0.2783 0.086 Uiso 0.5 1 calc R U P A -1
C8 C 0.425(2) 0.3778(19) 0.1416(12) 0.058(5) Uani 0.5 1 d D . P A -1
H8A H 0.4496 0.4302 0.2079 0.087 Uiso 0.5 1 calc R U P A -1
H8B H 0.3732 0.4528 0.0947 0.087 Uiso 0.5 1 calc R U P A -1
H8C H 0.5234 0.3403 0.1095 0.087 Uiso 0.5 1 calc R U P A -1
C9 C 0.287(2) 0.1479(18) 0.0621(9) 0.053(4) Uani 0.5 1 d D . P A -1
H9A H 0.3886 0.1216 0.0293 0.080 Uiso 0.5 1 calc R U P A -1
H9B H 0.2244 0.2125 0.0142 0.080 Uiso 0.5 1 calc R U P A -1
H9C H 0.2300 0.0504 0.0783 0.080 Uiso 0.5 1 calc R U P A -1


_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
Hf1 O1 1.915(7) . ?
Hf1 O1 1.915(7) 2_655 ?
Hf1 C1 2.535(11) . ?
Hf1 C5 2.538(16) . ?
Hf1 C2 2.542(17) . ?
Hf1 C4 2.554(14) . ?
Hf1 C3 2.569(14) . ?
C1 C5 1.413(15) . ?
C1 C2 1.416(17) . ?
C1 H1 0.9500 . ?
C2 C3 1.384(16) . ?
C2 H2 0.9500 . ?
C3 C4 1.398(15) . ?
C3 H3 0.9500 . ?
C4 C5 1.394(17) . ?
C4 H4 0.9500 . ?
C5 H5 0.9500 . ?
O1 C6 1.441(13) . ?
C6 C9 1.510(11) . ?
C6 C8 1.514(12) . ?
C6 C7 1.514(12) . ?
C7 H7A 0.9800 . ?
C7 H7B 0.9800 . ?
C7 H7C 0.9800 . ?
C8 H8A 0.9800 . ?
C8 H8B 0.9800 . ?
C8 H8C 0.9800 . ?
C9 H9A 0.9800 . ?
C9 H9B 0.9800 . ?
C9 H9C 0.9800 . ?

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
O1 Hf1 O1 99.3(5) . 2_655 ?
O1 Hf1 C1 94.8(4) . . ?
O1 Hf1 C1 85.2(4) 2_655 . ?
O1 Hf1 C5 127.1(3) . . ?
O1 Hf1 C5 81.4(4) 2_655 . ?
C1 Hf1 C5 32.3(4) . . ?
O1 Hf1 C2 82.0(4) . . ?
O1 Hf1 C2 116.6(4) 2_655 . ?
C1 Hf1 C2 32.4(4) . . ?
C5 Hf1 C2 52.9(4) . . ?
O1 Hf1 C4 133.1(5) . . ?
O1 Hf1 C4 109.2(5) 2_655 . ?
C1 Hf1 C4 53.0(5) . . ?
C5 Hf1 C4 31.8(4) . . ?
C2 Hf1 C4 52.1(5) . . ?
O1 Hf1 C3 103.1(5) . . ?
O1 Hf1 C3 133.8(4) 2_655 . ?
C1 Hf1 C3 53.2(4) . . ?
C5 Hf1 C3 52.9(5) . . ?
C2 Hf1 C3 31.4(4) . . ?
C4 Hf1 C3 31.7(3) . . ?
C5 C1 C2 106.2(10) . . ?
C5 C1 Hf1 73.9(7) . . ?
C2 C1 Hf1 74.1(8) . . ?
C5 C1 H1 126.9 . . ?
C2 C1 H1 126.9 . . ?
Hf1 C1 H1 117.3 . . ?
C3 C2 C1 109.6(12) . . ?
C3 C2 Hf1 75.4(6) . . ?
C1 C2 Hf1 73.6(7) . . ?
C3 C2 H2 125.2 . . ?
C1 C2 H2 125.2 . . ?
Hf1 C2 H2 117.6 . . ?
C2 C3 C4 107.2(15) . . ?
C2 C3 Hf1 73.2(6) . . ?
C4 C3 Hf1 73.6(9) . . ?
C2 C3 H3 126.4 . . ?
C4 C3 H3 126.4 . . ?
Hf1 C3 H3 118.8 . . ?
C5 C4 C3 109.1(16) . . ?
C5 C4 Hf1 73.5(6) . . ?
C3 C4 Hf1 74.8(10) . . ?
C5 C4 H4 125.4 . . ?
C3 C4 H4 125.4 . . ?
Hf1 C4 H4 118.1 . . ?
C4 C5 C1 108.0(13) . . ?
C4 C5 Hf1 74.7(6) . . ?
C1 C5 Hf1 73.7(7) . . ?
C4 C5 H5 126.0 . . ?
C1 C5 H5 126.0 . . ?
Hf1 C5 H5 117.5 . . ?
C6 O1 Hf1 166.6(4) . . ?
O1 C6 C9 103.9(9) . . ?
O1 C6 C8 114.9(10) . . ?
C9 C6 C8 110.8(9) . . ?
O1 C6 C7 105.5(9) . . ?
C9 C6 C7 111.1(10) . . ?
C8 C6 C7 110.3(11) . . ?
C6 C7 H7A 109.5 . . ?
C6 C7 H7B 109.5 . . ?
H7A C7 H7B 109.5 . . ?
C6 C7 H7C 109.5 . . ?
H7A C7 H7C 109.5 . . ?
H7B C7 H7C 109.5 . . ?
C6 C8 H8A 109.5 . . ?
C6 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
C6 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
C6 C9 H9A 109.5 . . ?
C6 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
C6 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C5 C1 C2 C3 -0.1(3) . . . . ?
Hf1 C1 C2 C3 67.4(6) . . . . ?
C5 C1 C2 Hf1 -67.5(6) . . . . ?
C1 C2 C3 C4 0.0(3) . . . . ?
Hf1 C2 C3 C4 66.3(8) . . . . ?
C1 C2 C3 Hf1 -66.2(7) . . . . ?
C2 C3 C4 C5 0.0(6) . . . . ?
Hf1 C3 C4 C5 66.1(5) . . . . ?
C2 C3 C4 Hf1 -66.0(4) . . . . ?
C3 C4 C5 C1 -0.1(7) . . . . ?
Hf1 C4 C5 C1 66.8(8) . . . . ?
C3 C4 C5 Hf1 -66.9(8) . . . . ?
C2 C1 C5 C4 0.1(6) . . . . ?
Hf1 C1 C5 C4 -67.5(6) . . . . ?
C2 C1 C5 Hf1 67.6(6) . . . . ?
Hf1 O1 C6 C9 124(3) . . . . ?
Hf1 O1 C6 C8 3(3) . . . . ?
Hf1 O1 C6 C7 -119(3) . . . . ?

_refine_diff_density_max         5.421
_refine_diff_density_min         -2.269
_refine_diff_density_rms         0.170

_shelxl_version_number           2013-2


_chemical_properties_physical    ', Air-sensitive,Moisture-sensitive'
####################################################################### 
# 
# 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_nb04
_database_code_depnum_ccdc_archive 'CCDC 1496574'
_audit_update_record             
;
2016-07-28 deposited with the CCDC.
2016-11-02 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT972_nb04                
;
PROBLEM: Check Calcd Residual Density  0.90A From     Hf1      -1.61 eA-3
RESPONSE: The largest residual peak of -1.61 electrons per \%A^3^ is located 0.90 \%A from atom Hf1. It may be due to residual absorption errors.
;
# Added during the CSD deposition process: Thursday 28 July 2016 03:58 PM
# end Validation Reply Form

_audit_creation_date             2016-06-16
_audit_creation_method           
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_chemical_name_common            ?
_chemical_name_systematic        
bis(cyclopentadienyl)hafnium(cloro)(tert-butoxide)
_chemical_formula_moiety         'C14 H19 Cl Hf O'
_chemical_formula_sum            'C14 H19 Cl Hf O'
_chemical_formula_weight         417.23
_chemical_melting_point          ?
_chemical_oxdiff_formula         C14H19Cl1Hf1O1
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'
Cl Cl 0.1484 0.1585 '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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'
loop_
_space_group_symop_operation_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                   15.2640(3)
_cell_length_b                   12.0177(3)
_cell_length_c                   15.8499(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2907.49(13)
_cell_formula_units_Z            8
_cell_measurement_reflns_used    11579
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.5270
_cell_measurement_theta_min      3.6250
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    7.342
_exptl_absorpt_correction_T_max  0.616
_exptl_absorpt_correction_T_min  0.498
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.906
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1600
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-4 -17 -1 0.0380
-7 14 11 0.0495
14 11 -9 0.0538
4 -14 11 0.0356
6 -15 -9 0.0500
2 1 -22 0.0793
-5 15 -1 0.0493
-6 11 16 0.0544
0 -7 27 0.0408
-20 6 -2 0.0401
18 0 12 0.0475
-16 -8 10 0.0475
-14 -8 -12 0.0590

_exptl_crystal_preparation       ?
_exptl_crystal_recrystallization_method ?
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.121
_exptl_crystal_size_min          0.1
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-4.4328 -16.5507 -1.1417 -0.0500 0.6148 0.7871
-7.0460 13.6438 11.0227 -0.0036 0.0648 -0.9979
13.7801 10.8454 -9.4983 0.0784 -0.9838 -0.1610
3.6801 -14.2691 11.4235 0.5871 0.6185 0.5223
6.1633 -14.6708 -9.1339 0.0406 0.0407 0.9983
2.1391 1.1198 -22.2003 -0.6206 -0.6558 0.4298
-5.3357 14.5510 -1.2612 -0.3318 -0.3227 -0.7674
-5.5736 10.5962 16.4430 0.2362 0.2513 -0.9386
0.1159 -6.8077 27.0880 0.8911 0.8873 -0.2181
-20.0488 6.0129 -1.9875 -0.7739 0.3608 -0.5229
18.0258 -0.0230 12.0443 0.9683 -0.2332 -0.0085
-16.0082 -8.0658 9.9673 -0.1600 0.9760 -0.0162
-14.0024 -7.9814 -12.0099 -0.7699 0.3617 0.4586

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0475
_diffrn_reflns_av_unetI/netI     0.0253
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.935
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            37885
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.935
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.829
_diffrn_reflns_theta_min         3.162
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.935
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     -1.00  87.00   1.00   10.00    --   17.57  38.00  90.00   88
  2  ω      1.00  85.00   1.00   10.00    --   17.57  57.00-150.00   84
  3  ω      1.00  85.00   1.00   10.00    --   17.57  57.00 -30.00   84
  4  ω      1.00  85.00   1.00   10.00    --   17.57  57.00 150.00   84
  5  ω    -50.00  44.00   1.00   10.00    --   17.57 -77.00  60.00   94
  6  ω    -50.00  34.00   1.00   10.00    --   17.57 -57.00 -60.00   84
  7  ω    -50.00  44.00   1.00   10.00    --   17.57 -77.00-180.00   94
  8  ω    -52.00 -23.00   1.00   10.00    --   17.57 -38.00  60.00   29
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0331609000
_diffrn_orient_matrix_UB_12      -0.0079787000
_diffrn_orient_matrix_UB_13      0.0307485000
_diffrn_orient_matrix_UB_21      -0.0297566000
_diffrn_orient_matrix_UB_22      -0.0309111000
_diffrn_orient_matrix_UB_23      0.0251151000
_diffrn_orient_matrix_UB_31      0.0132220000
_diffrn_orient_matrix_UB_32      -0.0496758000
_diffrn_orient_matrix_UB_33      -0.0205909000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_diffrn_special_details          ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3356
_reflns_number_total             3899
_reflns_odcompleteness_completeness 99.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.04
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         1.312
_refine_diff_density_min         -1.744
_refine_diff_density_rms         0.157
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     157
_refine_ls_number_reflns         3899
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0320
_refine_ls_R_factor_gt           0.0243
_refine_ls_restrained_S_all      1.042
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0170P)²+9.0550P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0478
_refine_ls_wR_factor_ref         0.0509
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9),
 C10(H10)
2.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   ?
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
Hf1 Hf 0.38609(2) 0.34365(2) 0.68544(2) 0.00886(5) Uani 1 1 d . . . . .
Cl1 Cl 0.40318(5) 0.54242(7) 0.71962(5) 0.01999(17) Uani 1 1 d . . . . .
O1 O 0.28320(14) 0.35964(18) 0.61717(14) 0.0142(5) Uani 1 1 d . . . . .
C1 C 0.4719(2) 0.3673(3) 0.5501(2) 0.0183(7) Uani 1 1 d . . . . .
H1 H 0.4505 0.4190 0.5097 0.022 Uiso 1 1 calc R . . . .
C2 C 0.4487(2) 0.2534(3) 0.5555(2) 0.0168(7) Uani 1 1 d . . . . .
H2 H 0.4095 0.2151 0.5191 0.020 Uiso 1 1 calc R . . . .
C3 C 0.4945(2) 0.2068(3) 0.6247(2) 0.0165(7) Uani 1 1 d . . . . .
H3 H 0.4912 0.1317 0.6431 0.020 Uiso 1 1 calc R . . . .
C4 C 0.5460(2) 0.2920(3) 0.6616(2) 0.0176(7) Uani 1 1 d . . . . .
H4 H 0.5833 0.2842 0.7093 0.021 Uiso 1 1 calc R . . . .
C5 C 0.5320(2) 0.3908(3) 0.6149(2) 0.0188(7) Uani 1 1 d . . . . .
H5 H 0.5585 0.4608 0.6255 0.023 Uiso 1 1 calc R . . . .
C6 C 0.3788(2) 0.3406(3) 0.8466(2) 0.0185(7) Uani 1 1 d . . . . .
H6 H 0.4024 0.4010 0.8778 0.022 Uiso 1 1 calc R . . . .
C7 C 0.4246(2) 0.2440(3) 0.8228(2) 0.0182(7) Uani 1 1 d . . . . .
H7 H 0.4842 0.2279 0.8350 0.022 Uiso 1 1 calc R . . . .
C8 C 0.3659(2) 0.1748(3) 0.7772(2) 0.0195(7) Uani 1 1 d . . . . .
H8 H 0.3796 0.1048 0.7525 0.023 Uiso 1 1 calc R . . . .
C9 C 0.2829(2) 0.2289(3) 0.7748(2) 0.0210(7) Uani 1 1 d . . . . .
H9 H 0.2310 0.2003 0.7499 0.025 Uiso 1 1 calc R . . . .
C10 C 0.2914(2) 0.3327(3) 0.8163(2) 0.0181(7) Uani 1 1 d . . . . .
H10 H 0.2468 0.3872 0.8227 0.022 Uiso 1 1 calc R . . . .
C11 C 0.2142(2) 0.3621(3) 0.5568(2) 0.0147(6) Uani 1 1 d . . . . .
C12 C 0.2486(2) 0.4139(3) 0.4749(2) 0.0203(7) Uani 1 1 d . . . . .
H12A H 0.2697 0.4894 0.4862 0.030 Uiso 1 1 calc GR . . . .
H12B H 0.2012 0.4169 0.4332 0.030 Uiso 1 1 calc GR . . . .
H12C H 0.2967 0.3685 0.4528 0.030 Uiso 1 1 calc GR . . . .
C13 C 0.1409(2) 0.4352(4) 0.5937(2) 0.0305(9) Uani 1 1 d . . . . .
H13A H 0.1212 0.4037 0.6474 0.046 Uiso 1 1 calc GR . . . .
H13B H 0.0916 0.4378 0.5541 0.046 Uiso 1 1 calc GR . . . .
H13C H 0.1632 0.5107 0.6030 0.046 Uiso 1 1 calc GR . . . .
C14 C 0.1827(3) 0.2437(3) 0.5416(2) 0.0272(8) Uani 1 1 d . . . . .
H14A H 0.2317 0.1982 0.5214 0.041 Uiso 1 1 calc GR . . . .
H14B H 0.1360 0.2441 0.4992 0.041 Uiso 1 1 calc GR . . . .
H14C H 0.1603 0.2124 0.5945 0.041 Uiso 1 1 calc GR . . . .


_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
Hf1 Cl1 2.4633(8) . ?
Hf1 O1 1.917(2) . ?
Hf1 C1 2.529(3) . ?
Hf1 C2 2.517(3) . ?
Hf1 C3 2.524(3) . ?
Hf1 C4 2.546(3) . ?
Hf1 C5 2.555(3) . ?
Hf1 C6 2.557(3) . ?
Hf1 C7 2.553(3) . ?
Hf1 C8 2.515(3) . ?
Hf1 C9 2.528(3) . ?
Hf1 C10 2.532(3) . ?
O1 C11 1.423(4) . ?
C1 H1 0.9500 . ?
C1 C2 1.416(5) . ?
C1 C5 1.405(5) . ?
C2 H2 0.9500 . ?
C2 C3 1.416(5) . ?
C3 H3 0.9500 . ?
C3 C4 1.418(5) . ?
C4 H4 0.9500 . ?
C4 C5 1.415(5) . ?
C5 H5 0.9500 . ?
C6 H6 0.9500 . ?
C6 C7 1.407(5) . ?
C6 C10 1.421(5) . ?
C7 H7 0.9500 . ?
C7 C8 1.420(5) . ?
C8 H8 0.9500 . ?
C8 C9 1.425(5) . ?
C9 H9 0.9500 . ?
C9 C10 1.417(5) . ?
C10 H10 0.9500 . ?
C11 C12 1.532(5) . ?
C11 C13 1.538(5) . ?
C11 C14 1.522(5) . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?

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
Cl1 Hf1 C1 91.30(8) . . ?
Cl1 Hf1 C2 123.90(8) . . ?
Cl1 Hf1 C3 130.28(8) . . ?
Cl1 Hf1 C4 99.65(8) . . ?
Cl1 Hf1 C5 77.82(8) . . ?
Cl1 Hf1 C6 78.41(8) . . ?
Cl1 Hf1 C7 104.07(9) . . ?
Cl1 Hf1 C8 131.93(8) . . ?
Cl1 Hf1 C9 118.15(9) . . ?
Cl1 Hf1 C10 86.01(8) . . ?
O1 Hf1 Cl1 96.53(7) . . ?
O1 Hf1 C1 86.24(10) . . ?
O1 Hf1 C2 83.81(10) . . ?
O1 Hf1 C3 112.77(10) . . ?
O1 Hf1 C4 136.56(10) . . ?
O1 Hf1 C5 116.42(10) . . ?
O1 Hf1 C6 121.98(10) . . ?
O1 Hf1 C7 135.81(10) . . ?
O1 Hf1 C8 107.88(11) . . ?
O1 Hf1 C9 81.99(10) . . ?
O1 Hf1 C10 89.99(10) . . ?
C1 Hf1 C4 53.52(11) . . ?
C1 Hf1 C5 32.09(11) . . ?
C1 Hf1 C6 150.62(11) . . ?
C1 Hf1 C7 131.02(11) . . ?
C1 Hf1 C10 175.10(11) . . ?
C2 Hf1 C1 32.60(11) . . ?
C2 Hf1 C3 32.63(10) . . ?
C2 Hf1 C4 53.83(11) . . ?
C2 Hf1 C5 53.59(11) . . ?
C2 Hf1 C6 145.90(11) . . ?
C2 Hf1 C7 114.09(11) . . ?
C2 Hf1 C9 117.41(11) . . ?
C2 Hf1 C10 149.90(11) . . ?
C3 Hf1 C1 53.86(11) . . ?
C3 Hf1 C4 32.47(11) . . ?
C3 Hf1 C5 53.58(11) . . ?
C3 Hf1 C6 113.60(11) . . ?
C3 Hf1 C7 82.45(11) . . ?
C3 Hf1 C9 105.46(12) . . ?
C3 Hf1 C10 130.78(11) . . ?
C4 Hf1 C5 32.22(11) . . ?
C4 Hf1 C6 100.73(11) . . ?
C4 Hf1 C7 77.94(10) . . ?
C5 Hf1 C6 118.57(11) . . ?
C7 Hf1 C5 106.03(11) . . ?
C7 Hf1 C6 31.96(11) . . ?
C8 Hf1 C1 130.10(11) . . ?
C8 Hf1 C2 99.90(11) . . ?
C8 Hf1 C3 76.99(11) . . ?
C8 Hf1 C4 90.35(11) . . ?
C8 Hf1 C5 122.56(12) . . ?
C8 Hf1 C6 53.52(11) . . ?
C8 Hf1 C7 32.53(12) . . ?
C8 Hf1 C9 32.82(11) . . ?
C8 Hf1 C10 54.18(11) . . ?
C9 Hf1 C1 149.24(12) . . ?
C9 Hf1 C4 123.16(11) . . ?
C9 Hf1 C5 155.37(12) . . ?
C9 Hf1 C6 53.48(11) . . ?
C9 Hf1 C7 53.82(11) . . ?
C9 Hf1 C10 32.52(11) . . ?
C10 Hf1 C4 130.99(11) . . ?
C10 Hf1 C5 150.18(11) . . ?
C10 Hf1 C6 32.42(11) . . ?
C10 Hf1 C7 53.76(11) . . ?
C11 O1 Hf1 171.1(2) . . ?
Hf1 C1 H1 117.9 . . ?
C2 C1 Hf1 73.21(18) . . ?
C2 C1 H1 125.9 . . ?
C5 C1 Hf1 74.96(19) . . ?
C5 C1 H1 125.9 . . ?
C5 C1 C2 108.3(3) . . ?
Hf1 C2 H2 117.8 . . ?
C1 C2 Hf1 74.19(19) . . ?
C1 C2 H2 126.1 . . ?
C3 C2 Hf1 73.96(18) . . ?
C3 C2 C1 107.8(3) . . ?
C3 C2 H2 126.1 . . ?
Hf1 C3 H3 117.9 . . ?
C2 C3 Hf1 73.41(18) . . ?
C2 C3 H3 126.0 . . ?
C2 C3 C4 107.9(3) . . ?
C4 C3 Hf1 74.65(18) . . ?
C4 C3 H3 126.0 . . ?
Hf1 C4 H4 118.7 . . ?
C3 C4 Hf1 72.88(18) . . ?
C3 C4 H4 126.1 . . ?
C5 C4 Hf1 74.21(18) . . ?
C5 C4 C3 107.8(3) . . ?
C5 C4 H4 126.1 . . ?
Hf1 C5 H5 119.4 . . ?
C1 C5 Hf1 72.96(19) . . ?
C1 C5 C4 108.2(3) . . ?
C1 C5 H5 125.9 . . ?
C4 C5 Hf1 73.57(18) . . ?
C4 C5 H5 125.9 . . ?
Hf1 C6 H6 119.5 . . ?
C7 C6 Hf1 73.89(19) . . ?
C7 C6 H6 125.6 . . ?
C7 C6 C10 108.8(3) . . ?
C10 C6 Hf1 72.82(18) . . ?
C10 C6 H6 125.6 . . ?
Hf1 C7 H7 119.4 . . ?
C6 C7 Hf1 74.15(19) . . ?
C6 C7 H7 126.1 . . ?
C6 C7 C8 107.8(3) . . ?
C8 C7 Hf1 72.25(19) . . ?
C8 C7 H7 126.1 . . ?
Hf1 C8 H8 116.7 . . ?
C7 C8 Hf1 75.22(19) . . ?
C7 C8 H8 126.1 . . ?
C7 C8 C9 107.9(3) . . ?
C9 C8 Hf1 74.09(19) . . ?
C9 C8 H8 126.1 . . ?
Hf1 C9 H9 118.9 . . ?
C8 C9 Hf1 73.09(19) . . ?
C8 C9 H9 126.0 . . ?
C10 C9 Hf1 73.89(19) . . ?
C10 C9 C8 108.0(3) . . ?
C10 C9 H9 126.0 . . ?
Hf1 C10 H10 117.5 . . ?
C6 C10 Hf1 74.75(19) . . ?
C6 C10 H10 126.3 . . ?
C9 C10 Hf1 73.59(18) . . ?
C9 C10 C6 107.5(3) . . ?
C9 C10 H10 126.3 . . ?
O1 C11 C12 109.0(3) . . ?
O1 C11 C13 107.2(3) . . ?
O1 C11 C14 108.7(3) . . ?
C12 C11 C13 109.8(3) . . ?
C14 C11 C12 110.7(3) . . ?
C14 C11 C13 111.4(3) . . ?
C11 C12 H12A 109.5 . . ?
C11 C12 H12B 109.5 . . ?
C11 C12 H12C 109.5 . . ?
H12A C12 H12B 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
C11 C13 H13A 109.5 . . ?
C11 C13 H13B 109.5 . . ?
C11 C13 H13C 109.5 . . ?
H13A C13 H13B 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
C11 C14 H14A 109.5 . . ?
C11 C14 H14B 109.5 . . ?
C11 C14 H14C 109.5 . . ?
H14A C14 H14B 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Hf1 C1 C2 C3 -66.9(2) . . . . ?
Hf1 C1 C5 C4 65.6(2) . . . . ?
Hf1 C2 C3 C4 -67.2(2) . . . . ?
Hf1 C3 C4 C5 -66.6(2) . . . . ?
Hf1 C4 C5 C1 -65.2(2) . . . . ?
Hf1 C6 C7 C8 -64.9(2) . . . . ?
Hf1 C6 C10 C9 66.9(2) . . . . ?
Hf1 C7 C8 C9 -67.5(2) . . . . ?
Hf1 C8 C9 C10 -66.2(2) . . . . ?
Hf1 C9 C10 C6 -67.7(2) . . . . ?
C1 C2 C3 Hf1 67.0(2) . . . . ?
C1 C2 C3 C4 -0.2(4) . . . . ?
C2 C1 C5 Hf1 -66.2(2) . . . . ?
C2 C1 C5 C4 -0.6(4) . . . . ?
C2 C3 C4 Hf1 66.4(2) . . . . ?
C2 C3 C4 C5 -0.1(4) . . . . ?
C3 C4 C5 Hf1 65.7(2) . . . . ?
C3 C4 C5 C1 0.4(4) . . . . ?
C5 C1 C2 Hf1 67.4(2) . . . . ?
C5 C1 C2 C3 0.5(4) . . . . ?
C6 C7 C8 Hf1 66.2(2) . . . . ?
C6 C7 C8 C9 -1.3(4) . . . . ?
C7 C6 C10 Hf1 -65.7(2) . . . . ?
C7 C6 C10 C9 1.2(4) . . . . ?
C7 C8 C9 Hf1 68.2(2) . . . . ?
C7 C8 C9 C10 2.0(4) . . . . ?
C8 C9 C10 Hf1 65.7(2) . . . . ?
C8 C9 C10 C6 -2.0(4) . . . . ?
C10 C6 C7 Hf1 65.0(2) . . . . ?
C10 C6 C7 C8 0.1(4) . . . . ?

_shelx_SHELXL_version_number     2014/7
_olex2_date_sample_data_collection 2016-06-16
_olex2_exptl_crystal_mounting_method 'mounted in a polyimide loop'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.421
_oxdiff_exptl_absorpt_empirical_full_min 0.814
_chemical_properties_physical    ', Air-sensitive,Moisture-sensitive'
