# Supplementary Information (SI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2024

####################################################################### 
# 
# 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_FluTicot_300K
_database_code_depnum_ccdc_archive 'CCDC 2355167'
loop_
_audit_author_name
_audit_author_address
'Francielli Sousa Santana'
;Universidade Federal do Parana
Brazil
;
_audit_update_record             
;
2024-05-13 deposited with the CCDC.	2024-08-09 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_structural     '[TiC21H17]'
_chemical_formula_moiety         'C21 H17 Ti'
_chemical_formula_sum            'C21 H17 Ti'
_chemical_formula_weight         317.24

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'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_H-M_alt        'P n m a'
_space_group_name_Hall           '-P 2ac 2n'

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

_cell_length_a                   8.5539(5)
_cell_length_b                   15.9444(10)
_cell_length_c                   11.4097(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1556.13(16)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    9887
_cell_measurement_theta_min      2.55
_cell_measurement_theta_max      27.39
_exptl_crystal_description       parallelepiped
_exptl_crystal_colour            violet
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.354
_exptl_crystal_F_000             660
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.319
_exptl_crystal_size_mid          0.241
_exptl_crystal_size_min          0.104
_exptl_absorpt_coefficient_mu    0.543
_shelx_estimated_absorpt_T_min   0.846
_shelx_estimated_absorpt_T_max   0.946
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.7010
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   
;
SADABS-2012/1 - Bruker AXS area detector scaling and absorption correction 
;
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker D8 Venture/Photon 100 CMOS'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 10.4167
_diffrn_reflns_number            59572
_diffrn_reflns_av_unetI/netI     0.0151
_diffrn_reflns_av_R_equivalents  0.0510
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         2.976
_diffrn_reflns_theta_max         27.541
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             1856
_reflns_number_gt                1576
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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       'Bruker APEX3 (2015)'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT-2015 (Sheldrick, 2015a)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2015)'
_computing_molecular_graphics    'ORTEP (Johnson, 1976 and Farrugia, 2012)'
_computing_publication_material  
'SHELXL-97 (Sheldrick, 2008) and WINGX (Farrugia, 2012)'
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0412P)²+0.9777P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     'intrinsic phasing'
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         1856
_refine_ls_number_parameters     143
_refine_ls_number_restraints     9
_refine_ls_R_factor_all          0.0511
_refine_ls_R_factor_gt           0.0390
_refine_ls_wR_factor_ref         0.1008
_refine_ls_wR_factor_gt          0.0933
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_restrained_S_all      1.072
_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
Ti1 Ti 0.36599(5) 0.250000 0.47154(4) 0.03554(16) Uani 1 2 d S T P . .
C1 C 0.0954(3) 0.250000 0.5030(2) 0.0448(6) Uani 1 2 d S T P . .
C2 C 0.1535(2) 0.32197(13) 0.56238(17) 0.0414(4) Uani 1 1 d . . . . .
C3 C 0.1325(3) 0.40941(16) 0.5433(2) 0.0574(6) Uani 1 1 d D . . . .
C4 C 0.2068(3) 0.46474(16) 0.6147(3) 0.0696(7) Uani 1 1 d D . . . .
C5 C 0.3061(3) 0.43835(17) 0.7049(2) 0.0670(7) Uani 1 1 d . . . . .
C6 C 0.3325(3) 0.35575(16) 0.72488(19) 0.0522(5) Uani 1 1 d . . . . .
C7 C 0.2558(2) 0.29514(12) 0.65447(15) 0.0384(4) Uani 1 1 d . . . . .
C8 C 0.3607(5) 0.250000 0.2723(3) 0.117(3) Uani 1 2 d DS T P . .
C9 C 0.4010(5) 0.1704(3) 0.3081(4) 0.1166(19) Uani 1 1 d D . . . .
C10 C 0.4970(6) 0.1384(2) 0.3935(6) 0.1135(18) Uani 1 1 d D . . . .
C11 C 0.5904(5) 0.1719(3) 0.4778(4) 0.1081(17) Uani 1 1 d D . . . .
C12 C 0.6278(5) 0.250000 0.5118(4) 0.102(2) Uani 1 2 d DS T P . .
H1 H 0.026(4) 0.250000 0.444(3) 0.067(10) Uiso 1 2 d S . P . .
H3 H 0.069(3) 0.4259(16) 0.4842(18) 0.066(7) Uiso 1 1 d D . . . .
H4 H 0.195(4) 0.5202(12) 0.595(3) 0.087(9) Uiso 1 1 d D . . . .
H5 H 0.363(3) 0.4806(19) 0.745(3) 0.086(9) Uiso 1 1 d . . . . .
H6 H 0.403(3) 0.3375(16) 0.781(2) 0.063(7) Uiso 1 1 d . . . . .
H8 H 0.278(4) 0.250000 0.223(4) 0.120(18) Uiso 1 2 d DS . P . .
H9 H 0.331(4) 0.1359(16) 0.281(3) 0.139(15) Uiso 1 1 d D . . . .
H10 H 0.490(5) 0.0849(14) 0.412(4) 0.141(15) Uiso 1 1 d D . . . .
H11 H 0.620(5) 0.1352(17) 0.533(3) 0.146(17) Uiso 1 1 d D . . . .
H12 H 0.682(5) 0.250000 0.582(3) 0.117(17) Uiso 1 2 d DS . P . .


_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 C8 2.274(4) . ?
Ti1 C9 2.276(3) 7_565 ?
Ti1 C9 2.276(3) . ?
Ti1 C10 2.284(3) 7_565 ?
Ti1 C10 2.284(3) . ?
Ti1 C12 2.286(4) . ?
Ti1 C11 2.289(3) . ?
Ti1 C11 2.289(3) 7_565 ?
Ti1 C1 2.343(3) . ?
Ti1 C2 2.3865(18) 7_565 ?
Ti1 C2 2.3865(18) . ?
Ti1 C7 2.4005(17) 7_565 ?
C1 C2 1.422(3) 7_565 ?
C1 C2 1.422(3) . ?
C1 H1 0.90(4) . ?
C2 C3 1.422(3) . ?
C2 C7 1.433(3) . ?
C3 C4 1.359(4) . ?
C3 H3 0.905(16) . ?
C4 C5 1.399(4) . ?
C4 H4 0.917(17) . ?
C5 C6 1.356(4) . ?
C5 H5 0.95(3) . ?
C6 C7 1.417(3) . ?
C6 H6 0.93(3) . ?
C7 C7 1.440(4) 7_565 ?
C8 C9 1.378(7) 7_565 ?
C8 C9 1.378(7) . ?
C8 H8 0.90(2) . ?
C9 C10 1.373(7) . ?
C9 H9 0.873(19) . ?
C10 C11 1.360(7) . ?
C10 H10 0.881(19) . ?
C11 C12 1.343(7) . ?
C11 H11 0.898(19) . ?
C12 H12 0.92(2) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C8 Ti1 C9 35.24(18) . 7_565 ?
C8 Ti1 C9 35.24(18) . . ?
C9 Ti1 C9 67.8(3) 7_565 . ?
C8 Ti1 C10 67.67(18) . 7_565 ?
C9 Ti1 C10 35.04(19) 7_565 7_565 ?
C9 Ti1 C10 92.9(2) . 7_565 ?
C8 Ti1 C10 67.67(18) . . ?
C9 Ti1 C10 92.9(2) 7_565 . ?
C9 Ti1 C10 35.04(19) . . ?
C10 Ti1 C10 102.40(17) 7_565 . ?
C8 Ti1 C12 102.74(16) . . ?
C9 Ti1 C12 92.05(15) 7_565 . ?
C9 Ti1 C12 92.05(15) . . ?
C10 Ti1 C12 66.28(18) 7_565 . ?
C10 Ti1 C12 66.28(18) . . ?
C8 Ti1 C11 92.74(15) . . ?
C9 Ti1 C11 102.63(11) 7_565 . ?
C9 Ti1 C11 67.1(2) . . ?
C10 Ti1 C11 91.4(2) 7_565 . ?
C10 Ti1 C11 34.59(19) . . ?
C12 Ti1 C11 34.15(17) . . ?
C8 Ti1 C11 92.74(15) . 7_565 ?
C9 Ti1 C11 67.1(2) 7_565 7_565 ?
C9 Ti1 C11 102.63(11) . 7_565 ?
C10 Ti1 C11 34.59(19) 7_565 7_565 ?
C10 Ti1 C11 91.4(2) . 7_565 ?
C12 Ti1 C11 34.15(17) . 7_565 ?
C11 Ti1 C11 65.9(3) . 7_565 ?
C8 Ti1 C1 97.68(14) . . ?
C9 Ti1 C1 104.82(12) 7_565 . ?
C9 Ti1 C1 104.82(12) . . ?
C10 Ti1 C1 122.99(14) 7_565 . ?
C10 Ti1 C1 122.99(14) . . ?
C12 Ti1 C1 159.58(13) . . ?
C11 Ti1 C1 145.46(13) . . ?
C11 Ti1 C1 145.46(13) 7_565 . ?
C8 Ti1 C2 114.78(11) . 7_565 ?
C9 Ti1 C2 136.42(14) 7_565 7_565 ?
C9 Ti1 C2 100.84(11) . 7_565 ?
C10 Ti1 C2 156.59(12) 7_565 7_565 ?
C10 Ti1 C2 99.69(10) . 7_565 ?
C12 Ti1 C2 131.21(9) . 7_565 ?
C11 Ti1 C2 111.31(12) . 7_565 ?
C11 Ti1 C2 152.46(12) 7_565 7_565 ?
C1 Ti1 C2 34.99(6) . 7_565 ?
C8 Ti1 C2 114.78(11) . . ?
C9 Ti1 C2 100.84(11) 7_565 . ?
C9 Ti1 C2 136.42(14) . . ?
C10 Ti1 C2 99.69(10) 7_565 . ?
C10 Ti1 C2 156.59(12) . . ?
C12 Ti1 C2 131.21(9) . . ?
C11 Ti1 C2 152.46(12) . . ?
C11 Ti1 C2 111.31(12) 7_565 . ?
C1 Ti1 C2 34.99(6) . . ?
C2 Ti1 C2 57.48(10) 7_565 . ?
C8 Ti1 C7 149.49(11) . 7_565 ?
C9 Ti1 C7 158.67(11) 7_565 7_565 ?
C9 Ti1 C7 126.65(14) . 7_565 ?
C10 Ti1 C7 139.92(16) 7_565 7_565 ?
C10 Ti1 C7 107.32(13) . 7_565 ?
C12 Ti1 C7 102.10(11) . 7_565 ?
C11 Ti1 C7 97.98(9) . 7_565 ?
C11 Ti1 C7 117.71(13) 7_565 7_565 ?
C1 Ti1 C7 58.59(8) . 7_565 ?
C2 Ti1 C7 34.84(6) 7_565 7_565 ?
C2 Ti1 C7 57.83(6) . 7_565 ?
C2 C1 C2 107.6(2) 7_565 . ?
C2 C1 Ti1 74.20(13) 7_565 . ?
C2 C1 Ti1 74.20(13) . . ?
C2 C1 H1 126.0(2) 7_565 . ?
C2 C1 H1 126.0(2) . . ?
Ti1 C1 H1 123(2) . . ?
C1 C2 C3 132.4(2) . . ?
C1 C2 C7 108.78(18) . . ?
C3 C2 C7 118.81(19) . . ?
C1 C2 Ti1 70.81(13) . . ?
C3 C2 Ti1 120.05(14) . . ?
C7 C2 Ti1 73.11(10) . . ?
C4 C3 C2 119.0(2) . . ?
C4 C3 H3 122.7(17) . . ?
C2 C3 H3 118.3(17) . . ?
C3 C4 C5 122.0(2) . . ?
C3 C4 H4 116(2) . . ?
C5 C4 H4 122(2) . . ?
C6 C5 C4 121.2(2) . . ?
C6 C5 H5 121.5(18) . . ?
C4 C5 H5 117.0(18) . . ?
C5 C6 C7 119.3(2) . . ?
C5 C6 H6 122.0(16) . . ?
C7 C6 H6 118.6(16) . . ?
C6 C7 C2 119.6(2) . . ?
C6 C7 C7 132.99(13) . 7_565 ?
C2 C7 C7 107.36(11) . 7_565 ?
C6 C7 Ti1 121.05(13) . . ?
C2 C7 Ti1 72.05(10) . . ?
C7 C7 Ti1 72.55(5) 7_565 . ?
C9 C8 C9 134.3(5) 7_565 . ?
C9 C8 Ti1 72.5(2) 7_565 . ?
C9 C8 Ti1 72.5(2) . . ?
C9 C8 H8 112.4(4) 7_565 . ?
C9 C8 H8 112.4(4) . . ?
Ti1 C8 H8 130(3) . . ?
C10 C9 C8 134.6(4) . . ?
C10 C9 Ti1 72.78(19) . . ?
C8 C9 Ti1 72.3(2) . . ?
C10 C9 H9 116(2) . . ?
C8 C9 H9 108(2) . . ?
Ti1 C9 H9 124(3) . . ?
C11 C10 C9 135.0(4) . . ?
C11 C10 Ti1 72.9(2) . . ?
C9 C10 Ti1 72.18(19) . . ?
C11 C10 H10 104(3) . . ?
C9 C10 H10 120(3) . . ?
Ti1 C10 H10 129(3) . . ?
C12 C11 C10 135.1(4) . . ?
C12 C11 Ti1 72.8(2) . . ?
C10 C11 Ti1 72.5(2) . . ?
C12 C11 H11 109(2) . . ?
C10 C11 H11 114(2) . . ?
Ti1 C11 H11 128(3) . . ?
C11 C12 C11 136.0(5) 7_565 . ?
C11 C12 Ti1 73.1(2) 7_565 . ?
C11 C12 Ti1 73.1(2) . . ?
C11 C12 H12 111.7(3) 7_565 . ?
C11 C12 H12 111.7(3) . . ?
Ti1 C12 H12 132(3) . . ?

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
C2 C1 C2 C3 -179.14(15) 7_565 . . . ?
Ti1 C1 C2 C3 113.6(2) . . . . ?
C2 C1 C2 C7 3.6(3) 7_565 . . . ?
Ti1 C1 C2 C7 -63.69(13) . . . . ?
C2 C1 C2 Ti1 67.26(18) 7_565 . . . ?
C1 C2 C3 C4 -178.7(2) . . . . ?
C7 C2 C3 C4 -1.7(3) . . . . ?
Ti1 C2 C3 C4 -88.0(2) . . . . ?
C2 C3 C4 C5 1.4(4) . . . . ?
C3 C4 C5 C6 0.0(4) . . . . ?
C4 C5 C6 C7 -1.2(4) . . . . ?
C5 C6 C7 C2 0.8(3) . . . . ?
C5 C6 C7 C7 -178.52(15) . . . 7_565 ?
C5 C6 C7 Ti1 86.7(2) . . . . ?
C1 C2 C7 C6 178.30(19) . . . . ?
C3 C2 C7 C6 0.6(3) . . . . ?
Ti1 C2 C7 C6 116.07(16) . . . . ?
C1 C2 C7 C7 -2.21(18) . . . 7_565 ?
C3 C2 C7 C7 -179.92(15) . . . 7_565 ?
Ti1 C2 C7 C7 -64.43(5) . . . 7_565 ?
C1 C2 C7 Ti1 62.23(16) . . . . ?
C3 C2 C7 Ti1 -115.49(18) . . . . ?
C9 C8 C9 C10 0.1(10) 7_565 . . . ?
Ti1 C8 C9 C10 -41.2(4) . . . . ?
C9 C8 C9 Ti1 41.3(6) 7_565 . . . ?
C8 C9 C10 C11 0.4(7) . . . . ?
Ti1 C9 C10 C11 -40.7(4) . . . . ?
C8 C9 C10 Ti1 41.1(4) . . . . ?
C9 C10 C11 C12 -0.3(7) . . . . ?
Ti1 C10 C11 C12 -40.8(4) . . . . ?
C9 C10 C11 Ti1 40.5(4) . . . . ?
C10 C11 C12 C11 -0.3(9) . . . 7_565 ?
Ti1 C11 C12 C11 -41.1(6) . . . 7_565 ?
C10 C11 C12 Ti1 40.7(4) . . . . ?

_refine_diff_density_max         0.271
_refine_diff_density_min         -0.427
_refine_diff_density_rms         0.070



_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_FluTicot_100K
_database_code_depnum_ccdc_archive 'CCDC 2355169'
loop_
_audit_author_name
_audit_author_address
'Francielli Sousa Santana'
;Universidade Federal do Parana
Brazil
;
_audit_update_record             
;
2024-05-13 deposited with the CCDC.	2024-08-09 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_structural     '[TiC21H17]'
_chemical_formula_moiety         'C21 H17 Ti'
_chemical_formula_sum            'C21 H17 Ti'
_chemical_formula_weight         317.24

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'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_H-M_alt        'P n m a'
_space_group_name_Hall           '-P 2ac 2n'

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

_cell_length_a                   8.3693(5)
_cell_length_b                   15.9237(8)
_cell_length_c                   11.3545(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1513.22(14)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9975
_cell_measurement_theta_min      2.20
_cell_measurement_theta_max      27.51
_exptl_crystal_description       rhomb
_exptl_crystal_colour            violet
_exptl_crystal_size_min          0.160
_exptl_crystal_size_mid          0.274
_exptl_crystal_size_max          0.465
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.393
_exptl_crystal_F_000             660
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_absorpt_coefficient_mu    0.558
_shelx_estimated_absorpt_T_min   0.880
_shelx_estimated_absorpt_T_max   0.928
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.7069
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   
;
SADABS-2012/1 - Bruker AXS area detector scaling and absorption correction 
;
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker D8 Venture/Photon 100 CMOS'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 10.4167
_diffrn_reflns_number            33264
_diffrn_reflns_av_unetI/netI     0.0109
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         2.203
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             1805
_reflns_number_gt                1679
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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       'Bruker APEX3 (2015)'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT-2015 (Sheldrick, 2015a)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    
'Diamond (H. Putz & K. Brandenburg, 2006, v. 4.6.4)'
_computing_publication_material  
'SHELXL-2014/7 (Sheldrick, 2015) and WINGX (Farrugia, 2012)'

_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0276P)²+1.3633P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     'intrinsic phasing'
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_coef       0.0096(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         1805
_refine_ls_number_parameters     144
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0320
_refine_ls_R_factor_gt           0.0294
_refine_ls_wR_factor_ref         0.0713
_refine_ls_wR_factor_gt          0.0701
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_restrained_S_all      1.048
_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
Ti Ti 0.37113(4) 0.250000 0.47248(3) 0.01223(12) Uani 1 2 d S T P . .
C1 C 0.0941(2) 0.250000 0.50105(16) 0.0154(4) Uani 1 2 d S T P . .
C2 C 0.15281(14) 0.32204(8) 0.56174(11) 0.0146(3) Uani 1 1 d . . . . .
C3 C 0.13157(16) 0.40990(9) 0.54163(12) 0.0187(3) Uani 1 1 d . . . . .
C4 C 0.20639(17) 0.46598(9) 0.61430(13) 0.0218(3) Uani 1 1 d . . . . .
C5 C 0.30738(17) 0.43915(9) 0.70753(12) 0.0217(3) Uani 1 1 d . . . . .
C6 C 0.33435(16) 0.35556(9) 0.72778(11) 0.0177(3) Uani 1 1 d . . . . .
C7 C 0.25694(14) 0.29555(8) 0.65563(10) 0.0139(3) Uani 1 1 d . . . . .
C8 C 0.3607(3) 0.250000 0.26994(18) 0.0350(6) Uani 1 2 d S T P . .
C9 C 0.4029(2) 0.16882(12) 0.30553(14) 0.0346(4) Uani 1 1 d . . . . .
C10 C 0.5028(2) 0.13555(10) 0.39276(16) 0.0334(4) Uani 1 1 d . . . . .
C11 C 0.60105(19) 0.16895(11) 0.48025(14) 0.0308(4) Uani 1 1 d . . . . .
C12 C 0.6422(2) 0.250000 0.51636(18) 0.0294(5) Uani 1 2 d S T P . .
H11 H 0.636(3) 0.1287(14) 0.5343(19) 0.045(6) Uiso 1 1 d . . . . .
H10 H 0.486(3) 0.0804(15) 0.4040(19) 0.048(6) Uiso 1 1 d . . . . .
H12 H 0.699(4) 0.250000 0.590(3) 0.045(8) Uiso 1 2 d S . P . .
H9 H 0.338(3) 0.1289(14) 0.275(2) 0.052(6) Uiso 1 1 d . . . . .
H8 H 0.270(4) 0.250000 0.218(3) 0.045(8) Uiso 1 2 d S . P . .
H3 H 0.065(2) 0.4280(11) 0.4813(15) 0.020(4) Uiso 1 1 d . . . . .
H5 H 0.362(2) 0.4824(12) 0.7556(17) 0.030(5) Uiso 1 1 d . . . . .
H4 H 0.193(2) 0.5251(12) 0.6001(16) 0.031(5) Uiso 1 1 d . . . . .
H6 H 0.408(2) 0.3377(11) 0.7904(15) 0.021(4) Uiso 1 1 d . . . . .
H1 H 0.019(3) 0.250000 0.434(2) 0.027(6) Uiso 1 2 d S . P . .


_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
Ti C8 2.301(2) . ?
Ti C9 2.3098(15) . ?
Ti C9 2.3098(15) 7_565 ?
Ti C10 2.3140(15) 7_565 ?
Ti C10 2.3141(15) . ?
Ti C11 2.3187(15) 7_565 ?
Ti C11 2.3187(15) . ?
Ti C12 2.323(2) . ?
Ti C1 2.3413(18) . ?
Ti C2 2.3836(12) . ?
Ti C2 2.3836(12) 7_565 ?
Ti C7 2.4008(12) . ?
C1 C2 1.4256(16) . ?
C1 C2 1.4256(16) 7_565 ?
C1 H1 0.98(3) . ?
C2 C3 1.4287(19) . ?
C2 C7 1.4401(17) . ?
C3 C4 1.368(2) . ?
C3 H3 0.930(18) . ?
C4 C5 1.420(2) . ?
C4 H4 0.961(19) . ?
C5 C6 1.370(2) . ?
C5 H5 0.991(19) . ?
C6 C7 1.4157(18) . ?
C6 H6 0.982(17) . ?
C7 C7 1.451(3) 7_565 ?
C8 C9 1.400(2) . ?
C8 C9 1.400(2) 7_565 ?
C8 H8 0.96(3) . ?
C9 C10 1.400(3) . ?
C9 H9 0.91(2) . ?
C10 C11 1.395(3) . ?
C10 H10 0.90(2) . ?
C11 C12 1.397(2) . ?
C11 H11 0.94(2) . ?
C12 H12 0.96(3) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C8 Ti C9 35.35(5) . . ?
C8 Ti C9 35.35(5) . 7_565 ?
C9 Ti C9 68.07(10) . 7_565 ?
C8 Ti C10 68.11(6) . 7_565 ?
C9 Ti C10 93.72(7) . 7_565 ?
C9 Ti C10 35.25(7) 7_565 7_565 ?
C8 Ti C10 68.11(6) . . ?
C9 Ti C10 35.25(7) . . ?
C9 Ti C10 93.72(6) 7_565 . ?
C10 Ti C10 103.92(8) 7_565 . ?
C8 Ti C11 93.99(6) . 7_565 ?
C9 Ti C11 104.31(6) . 7_565 ?
C9 Ti C11 67.92(7) 7_565 7_565 ?
C10 Ti C11 35.05(7) 7_565 7_565 ?
C10 Ti C11 93.33(6) . 7_565 ?
C8 Ti C11 93.99(6) . . ?
C9 Ti C11 67.92(7) . . ?
C9 Ti C11 104.30(6) 7_565 . ?
C10 Ti C11 93.33(6) 7_565 . ?
C10 Ti C11 35.05(7) . . ?
C11 Ti C11 67.64(10) 7_565 . ?
C8 Ti C12 104.57(8) . . ?
C9 Ti C12 93.64(6) . . ?
C9 Ti C12 93.64(6) 7_565 . ?
C10 Ti C12 67.59(6) 7_565 . ?
C10 Ti C12 67.60(6) . . ?
C11 Ti C12 35.04(5) 7_565 . ?
C11 Ti C12 35.04(5) . . ?
C8 Ti C1 95.79(7) . . ?
C9 Ti C1 103.17(6) . . ?
C9 Ti C1 103.17(6) 7_565 . ?
C10 Ti C1 121.72(5) 7_565 . ?
C10 Ti C1 121.72(5) . . ?
C11 Ti C1 144.75(5) 7_565 . ?
C11 Ti C1 144.75(5) . . ?
C12 Ti C1 159.65(7) . . ?
C8 Ti C2 113.32(6) . . ?
C9 Ti C2 134.97(6) . . ?
C9 Ti C2 99.67(5) 7_565 . ?
C10 Ti C2 98.76(5) 7_565 . ?
C10 Ti C2 155.55(5) . . ?
C11 Ti C2 110.62(5) 7_565 . ?
C11 Ti C2 152.60(5) . . ?
C12 Ti C2 131.11(5) . . ?
C1 Ti C2 35.11(4) . . ?
C8 Ti C2 113.32(6) . 7_565 ?
C9 Ti C2 99.67(5) . 7_565 ?
C9 Ti C2 134.97(6) 7_565 7_565 ?
C10 Ti C2 155.55(5) 7_565 7_565 ?
C10 Ti C2 98.76(5) . 7_565 ?
C11 Ti C2 152.60(5) 7_565 7_565 ?
C11 Ti C2 110.62(5) . 7_565 ?
C12 Ti C2 131.11(5) . 7_565 ?
C1 Ti C2 35.11(4) . 7_565 ?
C2 Ti C2 57.53(6) . 7_565 ?
C8 Ti C7 148.26(6) . . ?
C9 Ti C7 157.79(5) . . ?
C9 Ti C7 125.99(6) 7_565 . ?
C10 Ti C7 106.89(5) 7_565 . ?
C10 Ti C7 140.02(5) . . ?
C11 Ti C7 97.42(5) 7_565 . ?
C11 Ti C7 117.74(5) . . ?
C12 Ti C7 101.71(6) . . ?
C1 Ti C7 59.05(5) . . ?
C2 Ti C7 35.03(4) . . ?
C2 Ti C7 58.12(4) 7_565 . ?
C2 C1 C2 107.15(16) . 7_565 ?
C2 C1 Ti 74.07(9) . . ?
C2 C1 Ti 74.07(9) 7_565 . ?
C2 C1 H1 126.32(11) . . ?
C2 C1 H1 126.32(12) 7_565 . ?
Ti C1 H1 121.5(15) . . ?
C1 C2 C3 131.89(12) . . ?
C1 C2 C7 109.32(12) . . ?
C3 C2 C7 118.72(12) . . ?
C1 C2 Ti 70.83(9) . . ?
C3 C2 Ti 119.91(9) . . ?
C7 C2 Ti 73.14(7) . . ?
C4 C3 C2 119.07(13) . . ?
C4 C3 H3 121.1(11) . . ?
C2 C3 H3 119.8(11) . . ?
C3 C4 C5 121.72(13) . . ?
C3 C4 H4 119.0(12) . . ?
C5 C4 H4 119.2(12) . . ?
C6 C5 C4 121.03(13) . . ?
C6 C5 H5 120.5(11) . . ?
C4 C5 H5 118.4(11) . . ?
C5 C6 C7 118.92(12) . . ?
C5 C6 H6 120.4(10) . . ?
C7 C6 H6 120.7(10) . . ?
C6 C7 C2 120.50(12) . . ?
C6 C7 C7 132.46(8) . 7_565 ?
C2 C7 C7 107.03(7) . 7_565 ?
C6 C7 Ti 121.53(9) . . ?
C2 C7 Ti 71.83(7) . . ?
C7 C7 Ti 72.42(3) 7_565 . ?
C9 C8 C9 134.9(2) . 7_565 ?
C9 C8 Ti 72.66(10) . . ?
C9 C8 Ti 72.66(10) 7_565 . ?
C9 C8 H8 112.11(19) . . ?
C9 C8 H8 112.11(18) 7_565 . ?
Ti C8 H8 129.8(18) . . ?
C8 C9 C10 134.79(16) . . ?
C8 C9 Ti 72.00(10) . . ?
C10 C9 Ti 72.54(9) . . ?
C8 C9 H9 112.7(15) . . ?
C10 C9 H9 111.3(15) . . ?
Ti C9 H9 129.3(15) . . ?
C11 C10 C9 135.35(15) . . ?
C11 C10 Ti 72.66(9) . . ?
C9 C10 Ti 72.21(9) . . ?
C11 C10 H10 111.4(15) . . ?
C9 C10 H10 112.1(15) . . ?
Ti C10 H10 129.7(14) . . ?
C10 C11 C12 134.94(16) . . ?
C10 C11 Ti 72.29(9) . . ?
C12 C11 Ti 72.63(10) . . ?
C10 C11 H11 113.0(14) . . ?
C12 C11 H11 111.3(14) . . ?
Ti C11 H11 131.9(13) . . ?
C11 C12 C11 134.9(2) 7_565 . ?
C11 C12 Ti 72.33(10) 7_565 . ?
C11 C12 Ti 72.33(10) . . ?
C11 C12 H12 112.14(18) 7_565 . ?
C11 C12 H12 112.14(18) . . ?
Ti C12 H12 132.1(19) . . ?

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
C2 C1 C2 C3 -179.35(9) 7_565 . . . ?
Ti C1 C2 C3 113.41(15) . . . . ?
C2 C1 C2 C7 3.81(19) 7_565 . . . ?
Ti C1 C2 C7 -63.43(9) . . . . ?
C2 C1 C2 Ti 67.24(12) 7_565 . . . ?
C1 C2 C3 C4 -178.70(15) . . . . ?
C7 C2 C3 C4 -2.10(19) . . . . ?
Ti C2 C3 C4 -88.30(14) . . . . ?
C2 C3 C4 C5 1.4(2) . . . . ?
C3 C4 C5 C6 0.4(2) . . . . ?
C4 C5 C6 C7 -1.4(2) . . . . ?
C5 C6 C7 C2 0.62(19) . . . . ?
C5 C6 C7 C7 -178.35(8) . . . 7_565 ?
C5 C6 C7 Ti 87.00(14) . . . . ?
C1 C2 C7 C6 178.43(13) . . . . ?
C3 C2 C7 C6 1.11(18) . . . . ?
Ti C2 C7 C6 116.46(11) . . . . ?
C1 C2 C7 C7 -2.37(12) . . . 7_565 ?
C3 C2 C7 C7 -179.68(9) . . . 7_565 ?
Ti C2 C7 C7 -64.34(3) . . . 7_565 ?
C1 C2 C7 Ti 61.97(10) . . . . ?
C3 C2 C7 Ti -115.35(11) . . . . ?
C9 C8 C9 C10 1.4(4) 7_565 . . . ?
Ti C8 C9 C10 -39.9(2) . . . . ?
C9 C8 C9 Ti 41.3(2) 7_565 . . . ?
C8 C9 C10 C11 0.1(3) . . . . ?
Ti C9 C10 C11 -39.62(18) . . . . ?
C8 C9 C10 Ti 39.8(2) . . . . ?
C9 C10 C11 C12 -0.9(3) . . . . ?
Ti C10 C11 C12 -40.42(19) . . . . ?
C9 C10 C11 Ti 39.51(18) . . . . ?
C10 C11 C12 C11 0.5(4) . . . 7_565 ?
Ti C11 C12 C11 -39.8(2) . . . 7_565 ?
C10 C11 C12 Ti 40.33(19) . . . . ?

_refine_diff_density_max         0.854
_refine_diff_density_min         -0.477
_refine_diff_density_rms         0.050



_chemical_properties_physical    Air-sensitive,Moisture-sensitive
