#------------------------------------------------------------------------------
#$Date: 2016-03-23 21:03:00 +0200 (Wed, 23 Mar 2016) $
#$Revision: 179437 $
#$URL: svn://www.crystallography.net/cod/cif/4/33/34/4333402.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4333402
loop_
_publ_author_name
'Caruso, Francesco'
'Pettinari, Claudio'
'Marchetti, Fabio'
'Natanti, Paolo'
'Phillips, Christine'
'Tanski, Joseph'
'Rossi, Miriam'
_publ_section_title
;
 Synthesis, molecular structure (X-ray and DFT), and solution behavior of
 titanium 4-Acyl-5-pyrazolonates. Correlations with related antitumor
 beta-diketonato derivatives.
;
_journal_issue                   18
_journal_name_full               'Inorganic chemistry'
_journal_page_first              7553
_journal_page_last               7560
_journal_paper_doi               10.1021/ic700935x
_journal_volume                  46
_journal_year                    2007
_chemical_formula_moiety         'C68 H86 N8 O11 Ti2'
_chemical_formula_sum            'C68 H86 N8 O11 Ti2'
_chemical_formula_weight         1287.19
_chemical_name_systematic
;
di-mu-Oxo-bis(4-(3,3-dimethylbutanoyl-3-methyl-1-phenyl)pyrazolon-
5-ato-O,O')-ethoxy-titanium(iv)
;
_space_group_IT_number           15
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2007-03-11
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 108.744(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   25.298(3)
_cell_length_b                   13.1985(14)
_cell_length_c                   22.0359(19)
_cell_measurement_temperature    243(2)
_cell_volume                     6967.5(13)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      243(2)
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0395
_diffrn_reflns_av_sigmaI/netI    0.0688
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            15115
_diffrn_reflns_theta_full        27.50
_diffrn_reflns_theta_max         27.50
_diffrn_reflns_theta_min         1.70
_exptl_absorpt_coefficient_mu    0.291
_exptl_absorpt_correction_T_max  0.9715
_exptl_absorpt_correction_T_min  0.9576
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.227
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2728
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.406
_refine_diff_density_min         -0.297
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     411
_refine_ls_number_reflns         7945
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.1461
_refine_ls_R_factor_gt           0.0641
_refine_ls_shift/su_max          0.022
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0910P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1597
_refine_ls_wR_factor_ref         0.1911
_reflns_number_gt                4140
_reflns_number_total             7945
_reflns_threshold_expression     >1.5sigma(I)
_cod_data_source_file            ic700935xsup2.cif
_cod_data_source_block           Ti-dinuclear
_cod_depositor_comments
'Adding full bibliography for 4333401--4333402.cif.'
_cod_original_cell_volume        6967.6(12)
_cod_original_sg_symbol_H-M      C2/c
_cod_database_code               4333402
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'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'
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
Ti Ti 0.07238(2) 0.11676(4) 0.26005(3) 0.0583(2) Uani 1 1 d .
O3 O 0.08160(12) 0.19519(19) 0.20041(14) 0.0812(8) Uani 1 1 d .
O4 O 0.0000 0.1393(2) 0.2500 0.0553(8) Uani 1 2 d S
O11 O 0.09903(9) 0.21905(17) 0.32972(12) 0.0712(7) Uani 1 1 d .
O12 O 0.15687(10) 0.0766(2) 0.28691(13) 0.0843(8) Uani 1 1 d .
O21 O 0.06275(9) -0.00476(16) 0.20445(10) 0.0575(6) Uani 1 1 d .
O22 O 0.07655(9) 0.01046(18) 0.33180(10) 0.0635(7) Uani 1 1 d .
N11 N 0.16203(13) 0.3331(2) 0.39371(14) 0.0705(9) Uani 1 1 d .
N12 N 0.22007(15) 0.3476(3) 0.41716(18) 0.0938(11) Uani 1 1 d .
N21 N 0.06156(11) -0.17528(19) 0.17771(13) 0.0546(7) Uani 1 1 d .
N22 N 0.06545(14) -0.2695(2) 0.20806(15) 0.0706(9) Uani 1 1 d .
C11 C 0.14918(15) 0.2507(2) 0.35475(17) 0.0611(9) Uani 1 1 d .
C12 C 0.20014(14) 0.2107(3) 0.35128(18) 0.0640(9) Uani 1 1 d .
C13 C 0.24204(16) 0.2759(3) 0.3922(2) 0.0847(12) Uani 1 1 d .
C14 C 0.20193(15) 0.1239(3) 0.31693(19) 0.0687(10) Uani 1 1 d .
C15 C 0.25484(17) 0.0762(4) 0.3115(2) 0.1020(15) Uani 1 1 d .
H15A H 0.2864 0.1176 0.3369 0.122 Uiso 1 1 calc R
H15B H 0.2589 0.0095 0.3320 0.122 Uiso 1 1 calc R
C16 C 0.2608(2) 0.0621(4) 0.2462(3) 0.1154(18) Uani 1 1 d .
C17 C 0.2164(3) -0.0015(7) 0.2039(5) 0.273(6) Uani 1 1 d .
H17A H 0.1809 0.0334 0.1942 0.410 Uiso 1 1 calc R
H17B H 0.2145 -0.0651 0.2252 0.410 Uiso 1 1 calc R
H17C H 0.2244 -0.0148 0.1645 0.410 Uiso 1 1 calc R
C18 C 0.2595(3) 0.1685(7) 0.2197(4) 0.212(4) Uani 1 1 d .
H18A H 0.2234 0.1990 0.2144 0.318 Uiso 1 1 calc R
H18B H 0.2657 0.1656 0.1785 0.318 Uiso 1 1 calc R
H18C H 0.2885 0.2089 0.2492 0.318 Uiso 1 1 calc R
C19 C 0.3191(3) 0.0201(5) 0.2552(4) 0.184(3) Uani 1 1 d .
H19A H 0.3238 -0.0435 0.2785 0.276 Uiso 1 1 calc R
H19B H 0.3469 0.0683 0.2793 0.276 Uiso 1 1 calc R
H19C H 0.3236 0.0088 0.2137 0.276 Uiso 1 1 calc R
C21 C 0.06585(12) -0.0982(2) 0.22030(15) 0.0500(8) Uani 1 1 d .
C22 C 0.07382(13) -0.1435(2) 0.28089(15) 0.0540(8) Uani 1 1 d .
C23 C 0.07229(16) -0.2508(3) 0.26808(18) 0.0660(10) Uani 1 1 d .
C24 C 0.08031(13) -0.0851(3) 0.33640(16) 0.0549(9) Uani 1 1 d .
C25 C 0.09343(14) -0.1295(3) 0.40171(15) 0.0634(9) Uani 1 1 d .
H25A H 0.0837 -0.2016 0.3974 0.076 Uiso 1 1 calc R
H25B H 0.0697 -0.0968 0.4235 0.076 Uiso 1 1 calc R
C26 C 0.15497(17) -0.1192(3) 0.44443(18) 0.0761(11) Uani 1 1 d .
C27 C 0.1942(2) -0.1675(4) 0.4129(2) 0.1274(19) Uani 1 1 d .
H27A H 0.2325 -0.1513 0.4375 0.191 Uiso 1 1 calc R
H27B H 0.1859 -0.1416 0.3697 0.191 Uiso 1 1 calc R
H27C H 0.1893 -0.2404 0.4115 0.191 Uiso 1 1 calc R
C28 C 0.17123(17) -0.0090(4) 0.4582(2) 0.0998(15) Uani 1 1 d .
H28A H 0.2095 -0.0049 0.4864 0.150 Uiso 1 1 calc R
H28B H 0.1468 0.0226 0.4787 0.150 Uiso 1 1 calc R
H28C H 0.1678 0.0258 0.4184 0.150 Uiso 1 1 calc R
C29 C 0.1598(2) -0.1717(4) 0.5078(2) 0.1248(19) Uani 1 1 d .
H29A H 0.1965 -0.1590 0.5383 0.187 Uiso 1 1 calc R
H29B H 0.1544 -0.2440 0.5007 0.187 Uiso 1 1 calc R
H29C H 0.1315 -0.1453 0.5245 0.187 Uiso 1 1 calc R
C31 C 0.0702(4) 0.2557(9) 0.1599(5) 0.309(7) Uani 1 1 d .
H31A H 0.0568 0.3125 0.1797 0.371 Uiso 1 1 calc R
H31B H 0.0366 0.2273 0.1287 0.371 Uiso 1 1 calc R
C32 C 0.0945(4) 0.3010(7) 0.1237(4) 0.221(4) Uani 1 1 d .
H32A H 0.0815 0.3704 0.1164 0.331 Uiso 1 1 calc R
H32B H 0.0856 0.2658 0.0830 0.331 Uiso 1 1 calc R
H32C H 0.1346 0.3004 0.1447 0.331 Uiso 1 1 calc R
C110 C 0.30439(17) 0.2729(4) 0.4098(3) 0.138(2) Uani 1 1 d .
H11A H 0.3200 0.3354 0.4313 0.207 Uiso 1 1 calc R
H11B H 0.3147 0.2654 0.3713 0.207 Uiso 1 1 calc R
H11C H 0.3188 0.2161 0.4382 0.207 Uiso 1 1 calc R
C111 C 0.12716(19) 0.4000(3) 0.41398(18) 0.0677(10) Uani 1 1 d .
C112 C 0.1509(2) 0.4564(3) 0.4691(2) 0.0995(14) Uani 1 1 d .
H11D H 0.1891 0.4496 0.4919 0.119 Uiso 1 1 calc R
C113 C 0.1187(3) 0.5223(4) 0.4903(3) 0.1178(18) Uani 1 1 d .
H11E H 0.1347 0.5594 0.5282 0.141 Uiso 1 1 calc R
C114 C 0.0642(3) 0.5338(3) 0.4571(3) 0.1058(17) Uani 1 1 d .
H11F H 0.0424 0.5793 0.4719 0.127 Uiso 1 1 calc R
C115 C 0.0399(2) 0.4794(3) 0.4014(2) 0.0910(13) Uani 1 1 d .
H11G H 0.0019 0.4884 0.3781 0.109 Uiso 1 1 calc R
C116 C 0.07217(18) 0.4111(3) 0.38018(19) 0.0703(11) Uani 1 1 d .
H11H H 0.0560 0.3731 0.3427 0.084 Uiso 1 1 calc R
C210 C 0.0747(2) -0.3389(3) 0.3115(2) 0.1006(15) Uani 1 1 d .
H21A H 0.0719 -0.4014 0.2876 0.151 Uiso 1 1 calc R
H21B H 0.0439 -0.3347 0.3287 0.151 Uiso 1 1 calc R
H21C H 0.1098 -0.3377 0.3464 0.151 Uiso 1 1 calc R
C211 C 0.05714(13) -0.1731(3) 0.11233(16) 0.0535(8) Uani 1 1 d .
C212 C 0.05680(16) -0.0836(3) 0.08029(19) 0.0738(11) Uani 1 1 d .
H21D H 0.0595 -0.0212 0.1016 0.089 Uiso 1 1 calc R
C213 C 0.05247(18) -0.0870(4) 0.0161(2) 0.0838(12) Uani 1 1 d .
H21E H 0.0511 -0.0257 -0.0061 0.101 Uiso 1 1 calc R
C214 C 0.05020(18) -0.1747(4) -0.0157(2) 0.0935(14) Uani 1 1 d .
H21F H 0.0482 -0.1748 -0.0590 0.112 Uiso 1 1 calc R
C215 C 0.05081(19) -0.2643(4) 0.0163(2) 0.0922(13) Uani 1 1 d .
H21G H 0.0490 -0.3262 -0.0053 0.111 Uiso 1 1 calc R
C216 C 0.05405(16) -0.2638(3) 0.08025(18) 0.0728(10) Uani 1 1 d .
H21H H 0.0541 -0.3253 0.1018 0.087 Uiso 1 1 calc R
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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
O3 Ti O4 100.74(11) .
O3 Ti O21 91.96(11) .
O4 Ti O21 98.02(10) .
O3 Ti O11 94.84(12) .
O4 Ti O11 93.55(9) .
O21 Ti O11 165.26(10) .
O3 Ti O22 168.59(11) .
O4 Ti O22 90.34(9) .
O21 Ti O22 83.74(9) .
O11 Ti O22 87.11(10) .
O3 Ti O12 89.53(13) .
O4 Ti O12 169.59(10) .
O21 Ti O12 83.21(9) .
O11 Ti O12 83.79(9) .
O22 Ti O12 79.49(10) .
C31 O3 Ti 157.6(6) .
Ti O4 Ti 160.95(17) 2
C11 O11 Ti 126.6(2) .
C14 O12 Ti 132.9(2) .
C21 O21 Ti 128.8(2) .
C24 O22 Ti 135.5(2) .
C11 N11 N12 110.6(3) .
C11 N11 C111 130.6(3) .
N12 N11 C111 118.8(3) .
C13 N12 N11 106.4(3) .
C21 N21 N22 110.8(3) .
C21 N21 C211 130.6(3) .
N22 N21 C211 118.5(3) .
C23 N22 N21 106.4(3) .
O11 C11 N11 122.4(3) .
O11 C11 C12 130.4(3) .
N11 C11 C12 107.1(3) .
C14 C12 C11 121.9(3) .
C14 C12 C13 133.9(4) .
C11 C12 C13 104.1(3) .
N12 C13 C12 111.7(4) .
N12 C13 C110 117.7(4) .
C12 C13 C110 130.6(4) .
O12 C14 C12 120.4(3) .
O12 C14 C15 114.7(4) .
C12 C14 C15 124.9(4) .
C16 C15 C14 119.2(4) .
C17 C16 C15 112.7(5) .
C17 C16 C18 111.5(7) .
C15 C16 C18 104.9(5) .
C17 C16 C19 112.7(6) .
C15 C16 C19 108.0(5) .
C18 C16 C19 106.6(5) .
O21 C21 N21 123.2(3) .
O21 C21 C22 130.0(3) .
N21 C21 C22 106.8(3) .
C24 C22 C21 121.9(3) .
C24 C22 C23 134.0(3) .
C21 C22 C23 104.1(3) .
N22 C23 C22 111.8(3) .
N22 C23 C210 117.9(3) .
C22 C23 C210 130.2(3) .
O22 C24 C22 119.3(3) .
O22 C24 C25 117.2(3) .
C22 C24 C25 123.4(3) .
C24 C25 C26 114.9(3) .
C28 C26 C27 108.6(4) .
C28 C26 C29 108.4(4) .
C27 C26 C29 110.7(4) .
C28 C26 C25 111.3(3) .
C27 C26 C25 111.3(3) .
C29 C26 C25 106.6(3) .
O3 C31 C32 137.5(11) .
C116 C111 C112 120.1(4) .
C116 C111 N11 121.7(3) .
C112 C111 N11 118.2(4) .
C113 C112 C111 120.1(5) .
C114 C113 C112 120.2(5) .
C113 C114 C115 120.6(5) .
C114 C115 C116 119.4(5) .
C111 C116 C115 119.6(4) .
C212 C211 C216 119.5(3) .
C212 C211 N21 121.9(3) .
C216 C211 N21 118.6(3) .
C211 C212 C213 118.8(4) .
C214 C213 C212 122.4(4) .
C213 C214 C215 118.8(4) .
C214 C215 C216 120.4(4) .
C211 C216 C215 120.0(4) .
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
Ti O3 1.746(3) .
Ti O4 1.7972(8) .
Ti O21 1.985(2) .
Ti O11 1.992(2) .
Ti O22 2.091(2) .
Ti O12 2.095(2) .
O3 C31 1.163(8) .
O4 Ti 1.7972(8) 2
O11 C11 1.280(4) .
O12 C14 1.282(4) .
O21 C21 1.277(3) .
O22 C24 1.267(4) .
N11 C11 1.359(4) .
N11 N12 1.404(4) .
N11 C111 1.418(5) .
N12 C13 1.305(5) .
N21 C21 1.365(4) .
N21 N22 1.401(4) .
N21 C211 1.409(4) .
N22 C23 1.301(4) .
C11 C12 1.417(5) .
C12 C14 1.382(5) .
C12 C13 1.436(5) .
C13 C110 1.499(5) .
C14 C15 1.518(5) .
C15 C16 1.506(7) .
C16 C17 1.470(8) .
C16 C18 1.518(8) .
C16 C19 1.527(7) .
C21 C22 1.417(4) .
C22 C24 1.410(4) .
C22 C23 1.442(4) .
C23 C210 1.494(5) .
C24 C25 1.489(5) .
C25 C26 1.545(5) .
C26 C28 1.515(6) .
C26 C27 1.523(6) .
C26 C29 1.528(5) .
C31 C32 1.300(9) .
C111 C116 1.359(5) .
C111 C112 1.386(5) .
C112 C113 1.373(7) .
C113 C114 1.346(7) .
C114 C115 1.383(6) .
C115 C116 1.395(5) .
C211 C212 1.375(5) .
C211 C216 1.380(5) .
C212 C213 1.384(5) .
C213 C214 1.345(6) .
C214 C215 1.374(6) .
C215 C216 1.385(5) .
