#------------------------------------------------------------------------------
#$Date: 2016-02-16 22:30:59 +0200 (Tue, 16 Feb 2016) $
#$Revision: 176467 $
#$URL: svn://www.crystallography.net/cod/cif/4/31/85/4318583.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_4318583
loop_
_publ_author_name
'A. Otero'
'J. Fernández-Baeza'
'A. Antiñolo'
'F. Carrillo-Hermosilla'
'J. Tejeda'
'A. Lara-Sánchez'
'L. Sánchez-Barba'
'M. Fernández-López'
'A. M. Rodríguez'
'I. López-Solera'
_publ_section_title
;
 Preparation of New Monoanionic "Scorpionate" Ligands: Synthesis and
 Structural Characterization of Titanium(IV) Complexes Bearing This Class
 of Ligand
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              5193
_journal_page_last               5202
_journal_paper_doi               10.1021/ic020319f
_journal_volume                  41
_journal_year                    2002
_chemical_formula_sum            'C36 H44 Cl14 N8 S6 Ti'
_chemical_formula_weight         1257.3
_chemical_name_systematic
;
 ?
;
_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_method           SHELXL-97
_cell_angle_alpha                90.000(0)
_cell_angle_beta                 91.670(3)
_cell_angle_gamma                90.000(0)
_cell_formula_units_Z            4
_cell_length_a                   22.380(4)
_cell_length_b                   13.837(9)
_cell_length_c                   18.574(4)
_cell_measurement_temperature    210(2)
_cell_volume                     5749(4)
_computing_cell_refinement       'Nonius (control program)'
_computing_data_collection       'Nonius (control program)'
_computing_data_reduction        'XCAD4 (Harms, Wocadlo, 1995)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      210(2)
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'four circle diffractometer Nonius-Mach3'
_diffrn_measurement_method       'ω/2θ 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  0.0879
_diffrn_reflns_av_sigmaI/netI    0.1818
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            5206
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_min         2.03
_diffrn_standards_interval_time  60
_diffrn_standards_number         2
_exptl_absorpt_coefficient_mu    1.049
_exptl_crystal_density_diffrn    1.448
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2544
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.704
_refine_diff_density_min         -0.419
_refine_diff_density_rms         0.086
_refine_ls_extinction_coef       0.0000(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   0.967
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         5037
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      0.990
_refine_ls_R_factor_all          0.2470
_refine_ls_R_factor_gt           0.0843
_refine_ls_shift/su_max          0.920
_refine_ls_shift/su_mean         0.013
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.1444P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2043
_refine_ls_wR_factor_ref         0.2794
_reflns_number_gt                2042
_reflns_number_total             5037
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic020319f_3.cif
_cod_data_source_block           7
_cod_original_cell_volume        5749(3)
_cod_original_formula_sum        'C36 H44 Cl14 N8 S6 Ti1'
_cod_database_code               4318583
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
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.0000 0.60414(14) -0.2500 0.0491(7) Uani 1 2 d S . .
Cl1 Cl -0.05086(11) 0.71982(15) -0.18577(14) 0.0646(8) Uani 1 1 d . . .
S1 S -0.04991(12) 0.57157(18) -0.36346(13) 0.0649(8) Uani 1 1 d . . .
S2 S -0.07536(15) 0.47771(19) -0.22945(14) 0.0776(10) Uani 1 1 d . . .
S3 S -0.27182(15) 0.5296(2) -0.35656(19) 0.0938(12) Uani 1 1 d . . .
N1 N -0.1530(3) 0.3368(5) -0.3243(4) 0.056(2) Uani 1 1 d . . .
N3 N -0.1321(3) 0.4235(5) -0.4350(4) 0.056(2) Uani 1 1 d . . .
N2 N -0.2132(4) 0.3425(6) -0.3120(5) 0.080(3) Uani 1 1 d . . .
N4 N -0.1817(4) 0.4673(6) -0.4648(5) 0.060(2) Uani 1 1 d . . .
C1 C -0.2283(5) 0.2610(7) -0.2798(7) 0.084(4) Uani 1 1 d . . .
C2 C -0.1797(5) 0.2015(7) -0.2728(6) 0.069(3) Uani 1 1 d . . .
H2 H -0.1784 0.1402 -0.2522 0.083 Uiso 1 1 calc . . .
C3 C -0.1333(4) 0.2513(6) -0.3025(5) 0.055(2) Uani 1 1 d . . .
C4 C -0.0687(5) 0.2227(9) -0.3072(6) 0.085(4) Uani 1 1 d . . .
H4A H -0.0473 0.2722 -0.3319 0.128 Uiso 1 1 calc . . .
H4B H -0.0659 0.1629 -0.3332 0.128 Uiso 1 1 calc . . .
H4C H -0.0517 0.2146 -0.2596 0.128 Uiso 1 1 calc . . .
C5 C -0.2926(7) 0.2436(12) -0.2597(13) 0.192(11) Uani 1 1 d . . .
H5A H -0.3160 0.3002 -0.2705 0.288 Uiso 1 1 calc . . .
H5B H -0.2941 0.2297 -0.2091 0.288 Uiso 1 1 calc . . .
H5C H -0.3085 0.1897 -0.2867 0.288 Uiso 1 1 calc . . .
C6 C -0.1761(4) 0.4715(7) -0.5353(6) 0.059(3) Uani 1 1 d . . .
C7 C -0.1217(4) 0.4315(7) -0.5525(5) 0.059(3) Uani 1 1 d . . .
H7 H -0.1064 0.4252 -0.5984 0.071 Uiso 1 1 calc . . .
C8 C -0.0949(4) 0.4031(6) -0.4893(5) 0.053(2) Uani 1 1 d . . .
C9 C -0.0350(5) 0.3548(9) -0.4742(6) 0.083(3) Uani 1 1 d . . .
H9A H -0.0299 0.3435 -0.4234 0.124 Uiso 1 1 calc . . .
H9B H -0.0035 0.3960 -0.4902 0.124 Uiso 1 1 calc . . .
H9C H -0.0337 0.2943 -0.4994 0.124 Uiso 1 1 calc . . .
C10 C -0.2233(5) 0.5123(10) -0.5855(7) 0.093(4) Uani 1 1 d . . .
H10A H -0.2567 0.5333 -0.5583 0.140 Uiso 1 1 calc . . .
H10B H -0.2362 0.4634 -0.6192 0.140 Uiso 1 1 calc . . .
H10C H -0.2072 0.5662 -0.6111 0.140 Uiso 1 1 calc . . .
C11 C -0.1235(4) 0.4158(6) -0.3584(5) 0.051(2) Uani 1 1 d . . .
C12 C -0.0884(5) 0.4785(7) -0.3219(5) 0.064(3) Uani 1 1 d . . .
C13 C -0.4447(7) 0.4060(16) -0.1675(14) 0.225(10) Uiso 1 1 d D . .
H13A H -0.4803 0.4162 -0.1975 0.270 Uiso 1 1 calc . A 1
H13B H -0.4343 0.3386 -0.1747 0.270 Uiso 1 1 calc . B 1
Cl2 Cl -0.3885(8) 0.4676(11) -0.2174(12) 0.254(13) Uani 0.50 1 d PD C 1
Cl3 Cl -0.4711(8) 0.4046(13) -0.0878(8) 0.269(9) Uani 0.50 1 d P C 1
Cl2A Cl -0.3710(6) 0.4431(13) -0.1701(9) 0.156(6) Uani 0.50 1 d PD C 2
Cl3A Cl -0.5110(4) 0.4905(6) -0.1770(5) 0.135(3) Uani 0.50 1 d PD C 2
C14 C 0.1422(13) 0.1978(17) -0.4578(12) 0.266(13) Uiso 1 1 d D . .
H14A H 0.1833 0.1843 -0.4428 0.319 Uiso 1 1 calc . D 1
H14B H 0.1199 0.1377 -0.4579 0.319 Uiso 1 1 calc . E 1
Cl4 Cl 0.1094(4) 0.2840(5) -0.3982(5) 0.114(3) Uani 0.50 1 d PD F 1
Cl5 Cl 0.1395(13) 0.249(2) -0.5417(14) 0.391(19) Uani 0.50 1 d PD F 1
Cl4A Cl 0.0823(8) 0.182(3) -0.4001(12) 0.58(3) Uani 0.50 1 d PD F 2
Cl5A Cl 0.1848(7) 0.2607(9) -0.5261(6) 0.179(6) Uani 0.50 1 d PD F 2
C15 C -0.1259(6) 0.1387(12) -0.5564(8) 0.147(6) Uiso 1 1 d D . .
H15A H -0.1435 0.1007 -0.5955 0.176 Uiso 1 1 calc . G 1
H15B H -0.0953 0.1827 -0.5724 0.176 Uiso 1 1 calc . H 1
Cl6 Cl -0.1765(7) 0.1870(12) -0.4956(8) 0.174(6) Uani 0.50 1 d PDU I 1
Cl7 Cl -0.1104(7) 0.0817(10) -0.4854(7) 0.189(5) Uani 0.50 1 d PDU I 1
Cl6A Cl -0.1978(7) 0.2029(11) -0.5480(10) 0.222(9) Uani 0.50 1 d PD I 2
Cl7A Cl -0.0605(6) 0.0911(7) -0.4953(7) 0.154(4) Uani 0.50 1 d PD I 2
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'
S S 0.1246 0.1234 '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'
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
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
Cl1 Ti1 Cl1 92.52(13) 2_554 . ?
Cl1 Ti1 S1 111.05(10) 2_554 2_554 ?
Cl1 Ti1 S1 84.29(9) . 2_554 ?
Cl1 Ti1 S1 84.29(9) 2_554 . ?
Cl1 Ti1 S1 111.05(10) . . ?
S1 Ti1 S1 158.34(15) 2_554 . ?
Cl1 Ti1 S2 156.70(9) 2_554 . ?
Cl1 Ti1 S2 93.55(9) . . ?
S1 Ti1 S2 91.93(11) 2_554 . ?
S1 Ti1 S2 72.53(9) . . ?
Cl1 Ti1 S2 93.55(9) 2_554 2_554 ?
Cl1 Ti1 S2 156.70(9) . 2_554 ?
S1 Ti1 S2 72.53(9) 2_554 2_554 ?
S1 Ti1 S2 91.93(11) . 2_554 ?
S2 Ti1 S2 89.69(17) . 2_554 ?
C12 S1 Ti1 88.4(4) . . ?
C12 S2 Ti1 86.5(3) . . ?
C3 N1 N2 108.7(7) . . ?
C3 N1 C11 131.6(7) . . ?
N2 N1 C11 119.7(7) . . ?
C8 N3 N4 107.5(8) . . ?
C8 N3 C11 130.9(8) . . ?
N4 N3 C11 121.2(7) . . ?
C1 N2 N1 106.9(8) . . ?
C6 N4 N3 108.7(8) . . ?
N2 C1 C2 110.0(8) . . ?
N2 C1 C5 120.2(11) . . ?
C2 C1 C5 129.7(10) . . ?
C1 C2 C3 105.6(8) . . ?
N1 C3 C2 108.8(8) . . ?
N1 C3 C4 122.0(8) . . ?
C2 C3 C4 129.1(9) . . ?
N4 C6 C7 108.8(9) . . ?
N4 C6 C10 123.2(9) . . ?
C7 C6 C10 128.0(10) . . ?
C8 C7 C6 106.5(8) . . ?
C7 C8 N3 108.4(8) . . ?
C7 C8 C9 130.7(8) . . ?
N3 C8 C9 120.8(9) . . ?
C12 C11 N1 122.6(8) . . ?
C12 C11 N3 120.9(7) . . ?
N1 C11 N3 116.4(8) . . ?
C11 C12 S2 125.2(7) . . ?
C11 C12 S1 122.9(7) . . ?
S2 C12 S1 111.9(6) . . ?
Cl3 C13 Cl2A 114.0(19) . . ?
Cl3 C13 Cl2 140(2) . . ?
Cl2A C13 Cl2 33.2(10) . . ?
Cl3 C13 Cl3A 77.6(11) . . ?
Cl2A C13 Cl3A 124.0(14) . . ?
Cl2 C13 Cl3A 102.5(13) . . ?
Cl5 C14 Cl4A 127(3) . . ?
Cl5 C14 Cl4 106(2) . . ?
Cl4A C14 Cl4 51.4(14) . . ?
Cl5 C14 Cl5A 34.6(9) . . ?
Cl4A C14 Cl5A 155(2) . . ?
Cl4 C14 Cl5A 110.0(13) . . ?
Cl7 C15 Cl6 77.4(11) . . ?
Cl7 C15 Cl6A 110.1(13) . . ?
Cl6 C15 Cl6A 35.2(7) . . ?
Cl7 C15 Cl7A 36.2(6) . . ?
Cl6 C15 Cl7A 104.1(11) . . ?
Cl6A C15 Cl7A 139.3(12) . . ?
C15 Cl6 Cl7 47.3(7) . . ?
C15 Cl7 Cl6 55.4(8) . . ?
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 Cl1 2.315(2) 2_554 ?
Ti1 Cl1 2.315(2) . ?
Ti1 S1 2.399(3) 2_554 ?
Ti1 S1 2.399(3) . ?
Ti1 S2 2.468(3) . ?
Ti1 S2 2.468(3) 2_554 ?
S1 C12 1.742(9) . ?
S2 C12 1.733(10) . ?
N1 C3 1.322(11) . ?
N1 N2 1.376(10) . ?
N1 C11 1.434(10) . ?
N3 C8 1.356(10) . ?
N3 N4 1.369(10) . ?
N3 C11 1.434(11) . ?
N2 C1 1.326(12) . ?
N4 C6 1.320(12) . ?
C1 C2 1.368(14) . ?
C1 C5 1.516(15) . ?
C2 C3 1.376(12) . ?
C3 C4 1.504(13) . ?
C6 C7 1.384(13) . ?
C6 C10 1.498(15) . ?
C7 C8 1.361(13) . ?
C8 C9 1.516(14) . ?
C11 C12 1.342(12) . ?
C13 Cl3 1.61(2) . ?
C13 Cl2A 1.730(18) . ?
C13 Cl2 1.799(16) . ?
C13 Cl3A 1.895(17) . ?
C14 Cl5 1.71(2) . ?
C14 Cl4A 1.754(19) . ?
C14 Cl4 1.799(19) . ?
C14 Cl5A 1.829(18) . ?
C15 Cl7 1.566(16) . ?
C15 Cl6 1.754(17) . ?
C15 Cl6A 1.849(17) . ?
C15 Cl7A 1.940(15) . ?
Cl6 Cl7 2.08(2) . ?
