# Supplementary Material (ESI) for Organic & Biomolecular Chemistry
# This journal is © The Royal Society of Chemistry 2005

data_global
_journal_name_full               Org.Biomol.Chem.

_journal_coden_Cambridge         0177

_publ_contact_author_name        'ProfD Koichiro Oshima'
_publ_contact_author_address     
;
Department of Material Chemistry
Kyoto University
Kyoto-daigaku Katsura
Nishikyo
Kyoto
615-8510
JAPAN
;

_publ_contact_author_email       OSHIMA@ORGRXN.MBOX.MEDIA.KYOTO-U.AC.JP

_publ_section_title              
;
A new method for the synthesis of acyltitanium complexes and
their application to copper-mediated acylmetallation of carbon-carbon multiple
bonds in aqueous media
;
loop_
_publ_author_name
'Koichiro Oshima'
'Takuma Fujioka'
'Zhenfu Han'
'Hiroshi Shinokubo'
'Shin-ichi Usugi'
'Hideki Yorimitsu'

data_k:\crystals\obc\proper\b503117f
_database_code_depnum_ccdc_archive 'CCDC 265208'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            
'bis(cyclopentadienyl)-p-toluoyltitanium bromide'
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H17 Br O Ti'
_chemical_formula_sum            'C18 H17 Br O Ti'
_chemical_formula_weight         377.13

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'
Br Br -0.2901 2.4595 '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'

_symmetry_cell_setting           Triclinic
_symmetry_space_group_name_H-M   P-1

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   7.7237(7)
_cell_length_b                   9.8885(9)
_cell_length_c                   11.0929(10)
_cell_angle_alpha                81.444(2)
_cell_angle_beta                 70.937(2)
_cell_angle_gamma                89.529(2)
_cell_volume                     791.12(12)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       block
_exptl_crystal_colour            orange
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.2
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.583
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             380
_exptl_absorpt_coefficient_mu    3.062
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(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  ?
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean 8.366
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            4848
_diffrn_reflns_av_R_equivalents  0.0125
_diffrn_reflns_av_sigmaI/netI    0.0180
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         1.97
_diffrn_reflns_theta_max         28.36
_reflns_number_total             3431
_reflns_number_gt                2791
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

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

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
; calc
[1.00000+0.00000exp(0.00(sinθ/λ)²)]/
[σ²(Fo²)+0.0000+0.1377*P+(0.0626P)²+0.0000sinθ/λ]
where P = 0.00000Fo² + 1.00000Fc²
;
_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         3431
_refine_ls_number_parameters     191
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0417
_refine_ls_R_factor_gt           0.0335
_refine_ls_wR_factor_ref         0.0926
_refine_ls_wR_factor_gt          0.0892
_refine_ls_goodness_of_fit_ref   0.980
_refine_ls_restrained_S_all      0.980
_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
Br1 Br 0.73802(3) 0.30384(3) 0.86598(3) 0.06638(13) Uani 1 1 d . . .
Ti1 Ti 0.40126(5) 0.28262(4) 0.84665(4) 0.03817(11) Uani 1 1 d . . .
O1 O 0.5332(2) 0.11204(19) 0.75489(18) 0.0582(4) Uani 1 1 d . . .
C1 C 0.1028(4) 0.0500(3) 0.7083(2) 0.0522(6) Uani 1 1 d . . .
H1 H 0.0452 0.1272 0.7383 0.063 Uiso 1 1 calc R . .
C2 C 0.0114(4) -0.0406(3) 0.6645(2) 0.0575(6) Uani 1 1 d . . .
H2 H -0.1068 -0.0231 0.6639 0.069 Uiso 1 1 calc R . .
C3 C 0.0939(4) -0.1576(3) 0.6214(2) 0.0581(6) Uani 1 1 d . . .
C4 C 0.2683(5) -0.1800(3) 0.6221(3) 0.0637(7) Uani 1 1 d . . .
H4 H 0.3242 -0.2584 0.5940 0.076 Uiso 1 1 calc R . .
C5 C 0.3639(4) -0.0900(3) 0.6632(3) 0.0577(6) Uani 1 1 d . . .
H5 H 0.4834 -0.1068 0.6612 0.069 Uiso 1 1 calc R . .
C6 C 0.2795(3) 0.0264(2) 0.7077(2) 0.0463(5) Uani 1 1 d . . .
C7 C 0.3740(3) 0.1208(2) 0.7569(2) 0.0452(5) Uani 1 1 d . . .
C24 C 0.5163(4) 0.5052(3) 0.7298(3) 0.0626(7) Uani 1 1 d . . .
H24 H 0.6132 0.5499 0.7422 0.075 Uiso 1 1 calc R . .
C25 C 0.5333(5) 0.4172(3) 0.6418(3) 0.0675(7) Uani 1 1 d . . .
H25 H 0.6428 0.3906 0.5867 0.081 Uiso 1 1 calc R . .
C26 C 0.3608(6) 0.3758(3) 0.6495(3) 0.0774(10) Uani 1 1 d . . .
H26 H 0.3324 0.3184 0.5988 0.093 Uiso 1 1 calc R . .
C27 C 0.3351(5) 0.5165(3) 0.7962(3) 0.0730(8) Uani 1 1 d . . .
H27 H 0.2865 0.5686 0.8618 0.088 Uiso 1 1 calc R . .
C28 C 0.2361(5) 0.4345(4) 0.7461(4) 0.0855(12) Uani 1 1 d . . .
H28 H 0.1092 0.4218 0.7732 0.103 Uiso 1 1 calc R . .
C29 C -0.0096(6) -0.2574(4) 0.5775(3) 0.0848(10) Uani 1 1 d . . .
H29A H 0.0526 -0.2630 0.4882 0.127 Uiso 1 1 calc R . .
H29B H -0.1313 -0.2268 0.5882 0.127 Uiso 1 1 calc R . .
H29C H -0.0164 -0.3460 0.6282 0.127 Uiso 1 1 calc R . .
C32 C 0.2686(7) 0.1085(3) 1.0268(3) 0.0975(16) Uani 1 1 d . . .
H32 H 0.2992 0.0179 1.0216 0.117 Uiso 1 1 calc R . .
C34 C 0.1301(5) 0.2973(5) 1.0160(3) 0.0894(12) Uani 1 1 d . . .
H34 H 0.0458 0.3606 1.0029 0.107 Uiso 1 1 calc R . .
C35 C 0.1296(5) 0.1721(5) 0.9959(3) 0.0862(12) Uani 1 1 d . . .
H35 H 0.0470 0.1320 0.9653 0.103 Uiso 1 1 calc R . .
C36 C 0.2648(7) 0.3232(4) 1.0572(3) 0.0958(14) Uani 1 1 d . . .
H36 H 0.2936 0.4070 1.0761 0.115 Uiso 1 1 calc R . .
C37 C 0.3560(5) 0.2050(7) 1.0675(3) 0.1063(17) Uani 1 1 d . . .
H37 H 0.4564 0.1923 1.0960 0.128 Uiso 1 1 calc R . .


_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
Br1 Ti1 2.6911(5) . ?
Ti1 C7 2.052(2) . ?
Ti1 O1 2.1735(17) . ?
Ti1 C36 2.322(3) . ?
Ti1 C34 2.333(3) . ?
Ti1 C28 2.351(3) . ?
Ti1 C35 2.360(3) . ?
Ti1 C26 2.360(3) . ?
Ti1 C25 2.363(3) . ?
Ti1 C37 2.366(3) . ?
Ti1 C32 2.382(3) . ?
Ti1 C27 2.389(3) . ?
Ti1 C24 2.397(3) . ?
O1 C7 1.225(3) . ?
C1 C2 1.378(4) . ?
C1 C6 1.381(4) . ?
C1 H1 0.9300 . ?
C2 C3 1.389(4) . ?
C2 H2 0.9300 . ?
C3 C4 1.365(4) . ?
C3 C29 1.503(4) . ?
C4 C5 1.377(4) . ?
C4 H4 0.9300 . ?
C5 C6 1.394(3) . ?
C5 H5 0.9300 . ?
C6 C7 1.457(3) . ?
C24 C27 1.365(4) . ?
C24 C25 1.376(4) . ?
C24 H24 0.9300 . ?
C25 C26 1.369(5) . ?
C25 H25 0.9300 . ?
C26 C28 1.384(5) . ?
C26 H26 0.9300 . ?
C27 C28 1.405(5) . ?
C27 H27 0.9300 . ?
C28 H28 0.9300 . ?
C29 H29A 0.9600 . ?
C29 H29B 0.9600 . ?
C29 H29C 0.9600 . ?
C32 C35 1.353(6) . ?
C32 C37 1.381(6) . ?
C32 H32 0.9300 . ?
C34 C35 1.290(6) . ?
C34 C36 1.307(6) . ?
C34 H34 0.9300 . ?
C35 H35 0.9300 . ?
C36 C37 1.370(7) . ?
C36 H36 0.9300 . ?
C37 H37 0.9300 . ?

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
C7 Ti1 O1 33.54(8) . . ?
C7 Ti1 C36 131.64(11) . . ?
O1 Ti1 C36 136.00(13) . . ?
C7 Ti1 C34 108.90(15) . . ?
O1 Ti1 C34 132.60(13) . . ?
C36 Ti1 C34 32.60(16) . . ?
C7 Ti1 C28 95.65(13) . . ?
O1 Ti1 C28 120.10(13) . . ?
C36 Ti1 C28 98.50(18) . . ?
C34 Ti1 C28 77.95(14) . . ?
C7 Ti1 C35 79.20(12) . . ?
O1 Ti1 C35 100.80(13) . . ?
C36 Ti1 C35 54.38(13) . . ?
C34 Ti1 C35 31.91(14) . . ?
C28 Ti1 C35 92.06(15) . . ?
C7 Ti1 C26 73.11(10) . . ?
O1 Ti1 C26 88.32(11) . . ?
C36 Ti1 C26 132.64(17) . . ?
C34 Ti1 C26 109.30(15) . . ?
C28 Ti1 C26 34.16(13) . . ?
C35 Ti1 C26 111.85(13) . . ?
C7 Ti1 C25 89.16(10) . . ?
O1 Ti1 C25 85.79(10) . . ?
C36 Ti1 C25 136.33(12) . . ?
C34 Ti1 C25 132.58(12) . . ?
C28 Ti1 C25 56.37(12) . . ?
C35 Ti1 C25 145.28(13) . . ?
C26 Ti1 C25 33.70(11) . . ?
C7 Ti1 C37 109.94(18) . . ?
O1 Ti1 C37 102.62(17) . . ?
C36 Ti1 C37 33.96(17) . . ?
C34 Ti1 C37 54.79(14) . . ?
C28 Ti1 C37 131.06(17) . . ?
C35 Ti1 C37 55.16(12) . . ?
C26 Ti1 C37 164.09(15) . . ?
C25 Ti1 C37 156.70(15) . . ?
C7 Ti1 C32 78.54(12) . . ?
O1 Ti1 C32 83.45(9) . . ?
C36 Ti1 C32 55.67(13) . . ?
C34 Ti1 C32 54.28(13) . . ?
C28 Ti1 C32 125.20(16) . . ?
C35 Ti1 C32 33.14(15) . . ?
C26 Ti1 C32 139.53(17) . . ?
C25 Ti1 C32 167.67(13) . . ?
C37 Ti1 C32 33.81(16) . . ?
C7 Ti1 C27 128.27(11) . . ?
O1 Ti1 C27 141.29(10) . . ?
C36 Ti1 C27 82.63(14) . . ?
C34 Ti1 C27 79.48(13) . . ?
C28 Ti1 C27 34.46(13) . . ?
C35 Ti1 C27 107.02(16) . . ?
C26 Ti1 C27 56.65(13) . . ?
C25 Ti1 C27 56.16(11) . . ?
C37 Ti1 C27 115.24(19) . . ?
C32 Ti1 C27 133.32(11) . . ?
C7 Ti1 C24 122.61(9) . . ?
O1 Ti1 C24 115.18(9) . . ?
C36 Ti1 C24 103.34(12) . . ?
C34 Ti1 C24 110.90(13) . . ?
C28 Ti1 C24 55.82(11) . . ?
C35 Ti1 C24 140.13(15) . . ?
C26 Ti1 C24 55.68(10) . . ?
C25 Ti1 C24 33.60(10) . . ?
C37 Ti1 C24 126.56(17) . . ?
C32 Ti1 C24 158.72(12) . . ?
C27 Ti1 C24 33.14(10) . . ?
C7 O1 Ti1 67.80(13) . . ?
C2 C1 C6 120.2(2) . . ?
C2 C1 H1 119.9 . . ?
C6 C1 H1 119.9 . . ?
C1 C2 C3 120.7(3) . . ?
C1 C2 H2 119.7 . . ?
C3 C2 H2 119.7 . . ?
C4 C3 C2 118.4(2) . . ?
C4 C3 C29 121.5(3) . . ?
C2 C3 C29 120.0(3) . . ?
C3 C4 C5 122.1(3) . . ?
C3 C4 H4 119.0 . . ?
C5 C4 H4 119.0 . . ?
C4 C5 C6 119.2(3) . . ?
C4 C5 H5 120.4 . . ?
C6 C5 H5 120.4 . . ?
C1 C6 C5 119.3(2) . . ?
C1 C6 C7 120.0(2) . . ?
C5 C6 C7 120.6(2) . . ?
O1 C7 C6 124.7(2) . . ?
O1 C7 Ti1 78.66(14) . . ?
C6 C7 Ti1 156.56(18) . . ?
C27 C24 C25 109.4(3) . . ?
C27 C24 Ti1 73.12(15) . . ?
C25 C24 Ti1 71.86(15) . . ?
C27 C24 H24 125.3 . . ?
C25 C24 H24 125.3 . . ?
Ti1 C24 H24 121.4 . . ?
C26 C25 C24 108.0(3) . . ?
C26 C25 Ti1 73.02(16) . . ?
C24 C25 Ti1 74.53(15) . . ?
C26 C25 H25 126.0 . . ?
C24 C25 H25 126.0 . . ?
Ti1 C25 H25 118.4 . . ?
C25 C26 C28 108.0(3) . . ?
C25 C26 Ti1 73.28(16) . . ?
C28 C26 Ti1 72.55(17) . . ?
C25 C26 H26 126.0 . . ?
C28 C26 H26 126.0 . . ?
Ti1 C26 H26 120.0 . . ?
C24 C27 C28 106.7(3) . . ?
C24 C27 Ti1 73.74(16) . . ?
C28 C27 Ti1 71.27(16) . . ?
C24 C27 H27 126.6 . . ?
C28 C27 H27 126.6 . . ?
Ti1 C27 H27 120.2 . . ?
C26 C28 C27 107.9(3) . . ?
C26 C28 Ti1 73.29(17) . . ?
C27 C28 Ti1 74.26(17) . . ?
C26 C28 H28 126.1 . . ?
C27 C28 H28 126.1 . . ?
Ti1 C28 H28 118.3 . . ?
C3 C29 H29A 109.5 . . ?
C3 C29 H29B 109.5 . . ?
H29A C29 H29B 109.5 . . ?
C3 C29 H29C 109.5 . . ?
H29A C29 H29C 109.5 . . ?
H29B C29 H29C 109.5 . . ?
C35 C32 C37 106.3(3) . . ?
C35 C32 Ti1 72.54(18) . . ?
C37 C32 Ti1 72.44(19) . . ?
C35 C32 H32 126.8 . . ?
C37 C32 H32 126.8 . . ?
Ti1 C32 H32 120.1 . . ?
C35 C34 C36 110.9(4) . . ?
C35 C34 Ti1 75.2(2) . . ?
C36 C34 Ti1 73.2(2) . . ?
C35 C34 H34 124.5 . . ?
C36 C34 H34 124.5 . . ?
Ti1 C34 H34 118.7 . . ?
C34 C35 C32 108.9(4) . . ?
C34 C35 Ti1 72.9(2) . . ?
C32 C35 Ti1 74.3(2) . . ?
C34 C35 H35 125.5 . . ?
C32 C35 H35 125.5 . . ?
Ti1 C35 H35 119.1 . . ?
C34 C36 C37 107.7(4) . . ?
C34 C36 Ti1 74.18(19) . . ?
C37 C36 Ti1 74.8(2) . . ?
C34 C36 H36 126.1 . . ?
C37 C36 H36 126.1 . . ?
Ti1 C36 H36 117.0 . . ?
C36 C37 C32 106.0(3) . . ?
C36 C37 Ti1 71.25(18) . . ?
C32 C37 Ti1 73.75(18) . . ?
C36 C37 H37 127.0 . . ?
C32 C37 H37 127.0 . . ?
Ti1 C37 H37 120.0 . . ?

_diffrn_measured_fraction_theta_max 0.867
_diffrn_reflns_theta_full        28.36
_diffrn_measured_fraction_theta_full 0.867
_refine_diff_density_max         0.425
_refine_diff_density_min         -0.408
_refine_diff_density_rms         0.063



