# Supplementary Material (ESI) for Dalton Transactions
# This journal is (c) The Royal Society of Chemistry 2008

data_global
_journal_name_full               'Dalton Trans.'

_journal_coden_Cambridge         0222
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Aaron Odom'
_publ_contact_author_email       ODOM@CEM.MSU.EDU

_publ_section_title              
;
Effects of 5,5-Substitution on Dipyrrolylmethane
Ligand Isomerization
;
loop_
_publ_author_name
'Aaron Odom'
'Douglas L Swartz II'

# Attachment 'TiNMe2tmcpm_0ma.cif'

data_tinme2tmcpm_0ma
_database_code_depnum_ccdc_archive 'CCDC 686141'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C22 H36 N4 Ti'
_chemical_formula_sum            'C22 H36 N4 Ti'
_chemical_formula_weight         404.45

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

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'P 21/c'
_symmetry_int_tables_number      14

loop_
_symmetry_equiv_pos_as_xyz

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

_cell_length_a                   21.3114(2)
_cell_length_b                   8.58140(10)
_cell_length_c                   12.23980(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 98.1850(10)
_cell_angle_gamma                90.00
_cell_volume                     2215.63(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    9984
_cell_measurement_theta_min      2.56
_cell_measurement_theta_max      26.27

_exptl_crystal_description       plate
_exptl_crystal_colour            orange
_exptl_crystal_size_max          0.53
_exptl_crystal_size_mid          0.40
_exptl_crystal_size_min          0.24
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.212
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             872
_exptl_absorpt_coefficient_mu    0.400
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.8161
_exptl_absorpt_correction_T_max  0.9102
_exptl_absorpt_process_details   SADABS
_exptl_special_details           
;
Data was collected using a BRUKER CCD (charge coupled device) based
diffractometer equipped with an Oxford low-temperature apparatus operating at
173 K. A suitable crystal was chosen and mounted on a glass fiber or nylon loop
using Paratone oil for Mo radiation and Mineral oil for Copper radiation. Data
were measured using omega and phi scans of 0.5\% per frame
for 30 s. The total number of images were based on
results from the program COSMO where redundancy was expected to be 4 and
completeness to 100% out to 0.83\%A. Cell parameters were
retrieved using APEX II software and refined using SAINT on all observed
reflections.Data reduction was performed using the SAINT software which
corrects for Lp. Scaling and absorption corrections were applied using SADABS
multi-scan technique, supplied by George Sheldrick. The structures are solved
by the direct method using the SHELXS-97 program and refined by least squares
method on F2, SHELXL-97, incorporated in SHELXTL-PC V 6.14.

All H atoms were placed in calculated positions and refined using a riding
model.
C-H(aromatic) = 0.94 \%A and Uiso(H) = 1.2Ueq(C)
C-H (alaphatic) = 0.99 \%A and Uiso(H) = 1.2Ueq(C)
CH2 = 0.98 \%A and Uiso(H) = 1.2Ueq(C)
CH3 = 0.97\%A and Uiso(H) = 1.5Ueq(C)
N-H = 0.86 (0.92)\%A and Uiso(H) = 1.2 Ueq(N)
O-H(alcohol) = 0.85\%Aand Uiso(H) = 1.2Ueq(O)
O-H(acid) = 0.82\%A and Uiso(H) = 1.5Ueq(O)
;

_diffrn_ambient_temperature      173(2)
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       '\w,and/f 0.5 deg'
_diffrn_detector_area_resol_mean 836.6
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            35590
_diffrn_reflns_av_R_equivalents  0.0313
_diffrn_reflns_av_sigmaI/netI    0.0233
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         1.93
_diffrn_reflns_theta_max         26.27
_reflns_number_total             4471
_reflns_number_gt                3774
_reflns_threshold_expression     >2sigma(I)
_computing_data_collection       'COSMO (BRUKER, V1.56, 2007)'
_computing_cell_refinement       'APEX2 (BRUKER, V2.1-0, 2007)'
_computing_data_reduction        'SAINT (BRUKER, V7.34A, 2007)'
_computing_structure_solution    'BRUKER, SHELXS-90, V6.14)'
_computing_structure_refinement  'BRUKER, SHELXL-97, V6.14)'
_computing_molecular_graphics    'SHELXTL (BRUKER, 2000, V6.14)'
_computing_publication_material  'XCIF (Sheldrick and BRUKER, V6.14, 2001,)'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ 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 w=1/[\s^2^(Fo^2^)+(0.0553P)^2^+0.5262P] where P=(Fo^2^+2Fc^2^)/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_number_reflns         4471
_refine_ls_number_parameters     252
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0452
_refine_ls_R_factor_gt           0.0357
_refine_ls_wR_factor_ref         0.1010
_refine_ls_wR_factor_gt          0.0960
_refine_ls_goodness_of_fit_ref   1.110
_refine_ls_restrained_S_all      1.110
_refine_ls_shift/su_max          0.019
_refine_ls_shift/su_mean         0.001

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 0.339513(12) 0.69190(3) 1.01734(2) 0.02116(11) Uani 1 1 d . . .
N1 N 0.27132(7) 0.5383(2) 1.09871(12) 0.0356(4) Uani 1 1 d . . .
N4 N 0.35583(7) 0.89432(17) 0.96627(12) 0.0308(3) Uani 1 1 d . . .
N3 N 0.41979(6) 0.62585(17) 1.09038(11) 0.0261(3) Uani 1 1 d . . .
N2 N 0.32788(6) 0.55008(16) 0.88396(10) 0.0234(3) Uani 1 1 d . . .
C42 C 0.41408(10) 0.9096(3) 0.91796(19) 0.0554(6) Uani 1 1 d . . .
H42A H 0.4406 0.9912 0.9569 0.083 Uiso 1 1 calc R . .
H42B H 0.4038 0.9375 0.8398 0.083 Uiso 1 1 calc R . .
H42C H 0.4371 0.8104 0.9246 0.083 Uiso 1 1 calc R . .
C41 C 0.32031(13) 1.0401(2) 0.9533(2) 0.0544(6) Uani 1 1 d . . .
H41A H 0.3473 1.1257 0.9854 0.082 Uiso 1 1 calc R . .
H41B H 0.2829 1.0322 0.9912 0.082 Uiso 1 1 calc R . .
H41C H 0.3069 1.0604 0.8747 0.082 Uiso 1 1 calc R . .
C5B C 0.10540(10) 0.1516(3) 0.9797(2) 0.0527(6) Uani 1 1 d . . .
H5BA H 0.1359 0.0964 1.0337 0.079 Uiso 1 1 calc R . .
H5BB H 0.1050 0.1044 0.9067 0.079 Uiso 1 1 calc R . .
H5BC H 0.0630 0.1440 1.0015 0.079 Uiso 1 1 calc R . .
C3B C 0.05165(9) 0.5976(3) 0.73581(16) 0.0459(5) Uani 1 1 d . . .
H3BA H 0.0073 0.5958 0.7484 0.069 Uiso 1 1 calc R . .
H3BB H 0.0583 0.5176 0.6814 0.069 Uiso 1 1 calc R . .
H3BC H 0.0618 0.7003 0.7080 0.069 Uiso 1 1 calc R . .
C5A C 0.12325(9) 0.3938(3) 1.09098(15) 0.0418(5) Uani 1 1 d . . .
H5AA H 0.1494 0.3301 1.1463 0.063 Uiso 1 1 calc R . .
H5AB H 0.0795 0.3956 1.1071 0.063 Uiso 1 1 calc R . .
H5AC H 0.1400 0.5003 1.0930 0.063 Uiso 1 1 calc R . .
C13 C 0.26021(9) 0.7988(2) 1.11373(16) 0.0392(5) Uani 1 1 d . . .
H13A H 0.2602 0.9057 1.1462 0.047 Uiso 1 1 calc R . .
C3A C 0.08213(9) 0.6953(2) 0.92420(17) 0.0386(5) Uani 1 1 d . . .
H3AA H 0.0375 0.6922 0.9356 0.058 Uiso 1 1 calc R . .
H3AB H 0.0914 0.7962 0.8926 0.058 Uiso 1 1 calc R . .
H3AC H 0.1093 0.6811 0.9951 0.058 Uiso 1 1 calc R . .
C32 C 0.43234(9) 0.4609(2) 1.10667(16) 0.0378(4) Uani 1 1 d . . .
H32A H 0.4703 0.4326 1.0743 0.057 Uiso 1 1 calc R . .
H32B H 0.3960 0.4009 1.0709 0.057 Uiso 1 1 calc R . .
H32C H 0.4392 0.4377 1.1859 0.057 Uiso 1 1 calc R . .
C14 C 0.28467(9) 0.6657(3) 1.16738(15) 0.0375(5) Uani 1 1 d . . .
H14A H 0.3046 0.6607 1.2463 0.045 Uiso 1 1 calc R . .
C31 C 0.47101(8) 0.7207(2) 1.14595(15) 0.0350(4) Uani 1 1 d . . .
H31A H 0.5097 0.7010 1.1135 0.052 Uiso 1 1 calc R . .
H31B H 0.4783 0.6941 1.2246 0.052 Uiso 1 1 calc R . .
H31C H 0.4596 0.8311 1.1373 0.052 Uiso 1 1 calc R . .
C4 C 0.07778(8) 0.4032(2) 0.88485(15) 0.0322(4) Uani 1 1 d . . .
H4A H 0.0716 0.3330 0.8201 0.039 Uiso 1 1 calc R . .
H4B H 0.0364 0.4119 0.9123 0.039 Uiso 1 1 calc R . .
C5 C 0.12457(8) 0.3237(2) 0.97544(15) 0.0320(4) Uani 1 1 d . . .
C23 C 0.34967(8) 0.3853(2) 0.75154(14) 0.0309(4) Uani 1 1 d . . .
H23A H 0.3714 0.3324 0.7000 0.037 Uiso 1 1 calc R . .
C3 C 0.09492(7) 0.5645(2) 0.84491(14) 0.0285(4) Uani 1 1 d . . .
C24 C 0.37303(8) 0.5019(2) 0.82077(13) 0.0289(4) Uani 1 1 d . . .
H24A H 0.4145 0.5443 0.8251 0.035 Uiso 1 1 calc R . .
C12 C 0.22960(7) 0.7532(2) 1.00922(14) 0.0275(4) Uani 1 1 d . . .
H12A H 0.2040 0.8215 0.9536 0.033 Uiso 1 1 calc R . .
C22 C 0.28647(8) 0.3577(2) 0.77109(13) 0.0275(4) Uani 1 1 d . . .
H22A H 0.2579 0.2828 0.7350 0.033 Uiso 1 1 calc R . .
C6 C 0.19122(8) 0.32825(19) 0.94152(14) 0.0265(4) Uani 1 1 d . . .
H6A H 0.1921 0.2540 0.8799 0.032 Uiso 1 1 calc R . .
H6B H 0.2216 0.2897 1.0045 0.032 Uiso 1 1 calc R . .
C2 C 0.16371(7) 0.5620(2) 0.81926(13) 0.0246(4) Uani 1 1 d . . .
H2A H 0.1765 0.6709 0.8074 0.030 Uiso 1 1 calc R . .
H2B H 0.1638 0.5060 0.7485 0.030 Uiso 1 1 calc R . .
C11 C 0.23587(7) 0.5932(2) 1.00348(12) 0.0235(3) Uani 1 1 d . . .
C21 C 0.27458(7) 0.45942(18) 0.85188(12) 0.0210(3) Uani 1 1 d . . .
C1 C 0.21551(7) 0.48742(19) 0.90559(12) 0.0206(3) Uani 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Ti1 0.01685(16) 0.02194(18) 0.02422(16) -0.00021(12) 0.00131(11) -0.00017(11)
N1 0.0274(7) 0.0477(10) 0.0317(8) 0.0005(7) 0.0038(6) -0.0087(7)
N4 0.0343(8) 0.0248(8) 0.0322(7) 0.0023(6) 0.0012(6) -0.0016(6)
N3 0.0217(7) 0.0263(8) 0.0295(7) 0.0019(6) 0.0010(5) -0.0003(6)
N2 0.0184(6) 0.0266(8) 0.0255(6) 0.0001(6) 0.0042(5) 0.0010(5)
C42 0.0443(12) 0.0652(16) 0.0580(13) 0.0281(12) 0.0120(10) -0.0077(11)
C41 0.0799(17) 0.0264(11) 0.0568(13) 0.0074(10) 0.0085(12) 0.0107(10)
C5B 0.0402(11) 0.0409(12) 0.0770(15) 0.0180(12) 0.0087(11) -0.0111(9)
C3B 0.0281(9) 0.0658(15) 0.0417(10) 0.0093(10) -0.0025(8) 0.0121(10)
C5A 0.0278(9) 0.0637(14) 0.0351(9) 0.0124(10) 0.0080(8) 0.0006(9)
C13 0.0268(9) 0.0487(13) 0.0445(10) -0.0243(10) 0.0130(8) -0.0075(8)
C3A 0.0257(9) 0.0381(11) 0.0540(12) -0.0039(9) 0.0129(8) 0.0036(8)
C32 0.0362(10) 0.0335(11) 0.0412(10) 0.0036(9) -0.0034(8) 0.0074(8)
C14 0.0311(9) 0.0559(13) 0.0265(8) -0.0094(9) 0.0070(7) -0.0134(9)
C31 0.0248(9) 0.0401(11) 0.0376(9) -0.0010(9) -0.0038(7) -0.0041(8)
C4 0.0200(8) 0.0374(11) 0.0382(9) -0.0021(8) 0.0002(7) -0.0049(7)
C5 0.0252(9) 0.0307(10) 0.0401(9) 0.0072(8) 0.0047(7) -0.0042(7)
C23 0.0323(9) 0.0339(10) 0.0279(8) 0.0002(8) 0.0088(7) 0.0134(8)
C3 0.0201(8) 0.0325(10) 0.0319(8) 0.0027(8) 0.0006(7) 0.0037(7)
C24 0.0214(8) 0.0363(10) 0.0306(8) 0.0021(8) 0.0087(7) 0.0053(7)
C12 0.0172(7) 0.0300(9) 0.0354(9) -0.0079(8) 0.0039(7) -0.0015(7)
C22 0.0322(9) 0.0242(9) 0.0253(8) -0.0028(7) 0.0014(7) 0.0049(7)
C6 0.0257(8) 0.0232(9) 0.0300(8) 0.0026(7) 0.0021(7) -0.0004(7)
C2 0.0227(8) 0.0265(9) 0.0242(8) 0.0026(7) 0.0017(6) 0.0041(7)
C11 0.0158(7) 0.0307(9) 0.0251(8) -0.0038(7) 0.0069(6) -0.0034(6)
C21 0.0219(7) 0.0203(8) 0.0202(7) 0.0033(6) 0.0008(6) 0.0033(6)
C1 0.0193(7) 0.0209(8) 0.0215(7) 0.0007(6) 0.0022(6) 0.0004(6)

_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 N4 1.8950(15) . ?
Ti1 N3 1.9006(13) . ?
Ti1 N2 2.0230(13) . ?
Ti1 N1 2.2922(16) . ?
Ti1 C14 2.3239(18) . ?
Ti1 C11 2.3492(15) . ?
Ti1 C13 2.3785(19) . ?
Ti1 C12 2.3891(16) . ?
N1 C11 1.379(2) . ?
N1 C14 1.384(3) . ?
N4 C42 1.455(3) . ?
N4 C41 1.459(2) . ?
N3 C31 1.451(2) . ?
N3 C32 1.449(2) . ?
N2 C24 1.381(2) . ?
N2 C21 1.387(2) . ?
C42 H42A 0.9800 . ?
C42 H42B 0.9800 . ?
C42 H42C 0.9800 . ?
C41 H41A 0.9800 . ?
C41 H41B 0.9800 . ?
C41 H41C 0.9800 . ?
C5B C5 1.536(3) . ?
C5B H5BA 0.9800 . ?
C5B H5BB 0.9800 . ?
C5B H5BC 0.9800 . ?
C3B C3 1.537(2) . ?
C3B H3BA 0.9800 . ?
C3B H3BB 0.9800 . ?
C3B H3BC 0.9800 . ?
C5A C5 1.541(3) . ?
C5A H5AA 0.9800 . ?
C5A H5AB 0.9800 . ?
C5A H5AC 0.9800 . ?
C13 C14 1.382(3) . ?
C13 C12 1.406(2) . ?
C13 H13A 1.0000 . ?
C3A C3 1.534(3) . ?
C3A H3AA 0.9800 . ?
C3A H3AB 0.9800 . ?
C3A H3AC 0.9800 . ?
C32 H32A 0.9800 . ?
C32 H32B 0.9800 . ?
C32 H32C 0.9800 . ?
C14 H14A 1.0000 . ?
C31 H31A 0.9800 . ?
C31 H31B 0.9800 . ?
C31 H31C 0.9800 . ?
C4 C3 1.529(3) . ?
C4 C5 1.541(2) . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C5 C6 1.536(2) . ?
C23 C24 1.359(3) . ?
C23 C22 1.421(2) . ?
C23 H23A 0.9500 . ?
C3 C2 1.542(2) . ?
C24 H24A 0.9500 . ?
C12 C11 1.383(3) . ?
C12 H12A 1.0000 . ?
C22 C21 1.370(2) . ?
C22 H22A 0.9500 . ?
C6 C1 1.547(2) . ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
C2 C1 1.553(2) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C11 C1 1.516(2) . ?
C21 C1 1.520(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
N4 Ti1 N3 103.49(6) . . ?
N4 Ti1 N2 107.01(6) . . ?
N3 Ti1 N2 101.47(6) . . ?
N4 Ti1 N1 145.90(6) . . ?
N3 Ti1 N1 102.01(6) . . ?
N2 Ti1 N1 89.55(5) . . ?
N4 Ti1 C14 119.07(7) . . ?
N3 Ti1 C14 96.88(6) . . ?
N2 Ti1 C14 124.19(6) . . ?
N1 Ti1 C14 34.89(6) . . ?
N4 Ti1 C11 121.44(6) . . ?
N3 Ti1 C11 134.47(6) . . ?
N2 Ti1 C11 73.67(5) . . ?
N1 Ti1 C11 34.53(5) . . ?
C14 Ti1 C11 56.54(6) . . ?
N4 Ti1 C13 89.25(7) . . ?
N3 Ti1 C13 122.50(7) . . ?
N2 Ti1 C13 128.18(6) . . ?
N1 Ti1 C13 57.79(7) . . ?
C14 Ti1 C13 34.15(7) . . ?
C11 Ti1 C13 56.47(6) . . ?
N4 Ti1 C12 90.53(6) . . ?
N3 Ti1 C12 153.75(6) . . ?
N2 Ti1 C12 95.29(5) . . ?
N1 Ti1 C12 57.74(6) . . ?
C14 Ti1 C12 56.88(6) . . ?
C11 Ti1 C12 33.92(6) . . ?
C13 Ti1 C12 34.31(6) . . ?
C11 N1 C14 106.49(16) . . ?
C11 N1 Ti1 75.00(9) . . ?
C14 N1 Ti1 73.81(10) . . ?
C42 N4 C41 109.76(17) . . ?
C42 N4 Ti1 115.08(13) . . ?
C41 N4 Ti1 134.83(14) . . ?
C31 N3 C32 111.82(14) . . ?
C31 N3 Ti1 128.31(12) . . ?
C32 N3 Ti1 119.49(11) . . ?
C24 N2 C21 106.35(13) . . ?
C24 N2 Ti1 128.09(11) . . ?
C21 N2 Ti1 124.57(10) . . ?
N4 C42 H42A 109.5 . . ?
N4 C42 H42B 109.5 . . ?
H42A C42 H42B 109.5 . . ?
N4 C42 H42C 109.5 . . ?
H42A C42 H42C 109.5 . . ?
H42B C42 H42C 109.5 . . ?
N4 C41 H41A 109.5 . . ?
N4 C41 H41B 109.5 . . ?
H41A C41 H41B 109.5 . . ?
N4 C41 H41C 109.5 . . ?
H41A C41 H41C 109.5 . . ?
H41B C41 H41C 109.5 . . ?
C5 C5B H5BA 109.5 . . ?
C5 C5B H5BB 109.5 . . ?
H5BA C5B H5BB 109.5 . . ?
C5 C5B H5BC 109.5 . . ?
H5BA C5B H5BC 109.5 . . ?
H5BB C5B H5BC 109.5 . . ?
C3 C3B H3BA 109.5 . . ?
C3 C3B H3BB 109.5 . . ?
H3BA C3B H3BB 109.5 . . ?
C3 C3B H3BC 109.5 . . ?
H3BA C3B H3BC 109.5 . . ?
H3BB C3B H3BC 109.5 . . ?
C5 C5A H5AA 109.5 . . ?
C5 C5A H5AB 109.5 . . ?
H5AA C5A H5AB 109.5 . . ?
C5 C5A H5AC 109.5 . . ?
H5AA C5A H5AC 109.5 . . ?
H5AB C5A H5AC 109.5 . . ?
C14 C13 C12 107.30(17) . . ?
C14 C13 Ti1 70.76(11) . . ?
C12 C13 Ti1 73.26(10) . . ?
C14 C13 H13A 126.2 . . ?
C12 C13 H13A 126.2 . . ?
Ti1 C13 H13A 126.2 . . ?
C3 C3A H3AA 109.5 . . ?
C3 C3A H3AB 109.5 . . ?
H3AA C3A H3AB 109.5 . . ?
C3 C3A H3AC 109.5 . . ?
H3AA C3A H3AC 109.5 . . ?
H3AB C3A H3AC 109.5 . . ?
N3 C32 H32A 109.5 . . ?
N3 C32 H32B 109.5 . . ?
H32A C32 H32B 109.5 . . ?
N3 C32 H32C 109.5 . . ?
H32A C32 H32C 109.5 . . ?
H32B C32 H32C 109.5 . . ?
N1 C14 C13 109.48(16) . . ?
N1 C14 Ti1 71.31(10) . . ?
C13 C14 Ti1 75.09(11) . . ?
N1 C14 H14A 125.1 . . ?
C13 C14 H14A 125.1 . . ?
Ti1 C14 H14A 125.1 . . ?
N3 C31 H31A 109.5 . . ?
N3 C31 H31B 109.5 . . ?
H31A C31 H31B 109.5 . . ?
N3 C31 H31C 109.5 . . ?
H31A C31 H31C 109.5 . . ?
H31B C31 H31C 109.5 . . ?
C3 C4 C5 118.11(13) . . ?
C3 C4 H4A 107.8 . . ?
C5 C4 H4A 107.8 . . ?
C3 C4 H4B 107.8 . . ?
C5 C4 H4B 107.8 . . ?
H4A C4 H4B 107.1 . . ?
C6 C5 C5B 107.13(16) . . ?
C6 C5 C5A 112.12(14) . . ?
C5B C5 C5A 107.73(17) . . ?
C6 C5 C4 108.84(15) . . ?
C5B C5 C4 107.60(15) . . ?
C5A C5 C4 113.15(16) . . ?
C24 C23 C22 106.85(15) . . ?
C24 C23 H23A 126.6 . . ?
C22 C23 H23A 126.6 . . ?
C4 C3 C3A 112.83(15) . . ?
C4 C3 C3B 107.68(15) . . ?
C3A C3 C3B 106.01(15) . . ?
C4 C3 C2 109.24(14) . . ?
C3A C3 C2 113.51(14) . . ?
C3B C3 C2 107.21(14) . . ?
C23 C24 N2 110.30(15) . . ?
C23 C24 H24A 124.8 . . ?
N2 C24 H24A 124.8 . . ?
C11 C12 C13 106.66(16) . . ?
C11 C12 Ti1 71.46(9) . . ?
C13 C12 Ti1 72.43(10) . . ?
C11 C12 H12A 126.5 . . ?
C13 C12 H12A 126.5 . . ?
Ti1 C12 H12A 126.5 . . ?
C21 C22 C23 107.00(15) . . ?
C21 C22 H22A 126.5 . . ?
C23 C22 H22A 126.5 . . ?
C5 C6 C1 117.33(14) . . ?
C5 C6 H6A 108.0 . . ?
C1 C6 H6A 108.0 . . ?
C5 C6 H6B 108.0 . . ?
C1 C6 H6B 108.0 . . ?
H6A C6 H6B 107.2 . . ?
C3 C2 C1 118.14(13) . . ?
C3 C2 H2A 107.8 . . ?
C1 C2 H2A 107.8 . . ?
C3 C2 H2B 107.8 . . ?
C1 C2 H2B 107.8 . . ?
H2A C2 H2B 107.1 . . ?
N1 C11 C12 109.99(14) . . ?
N1 C11 C1 121.61(15) . . ?
C12 C11 C1 128.01(14) . . ?
N1 C11 Ti1 70.47(9) . . ?
C12 C11 Ti1 74.62(9) . . ?
C1 C11 Ti1 115.66(10) . . ?
C22 C21 N2 109.50(14) . . ?
C22 C21 C1 131.52(15) . . ?
N2 C21 C1 118.97(13) . . ?
C11 C1 C21 105.96(12) . . ?
C11 C1 C6 111.93(13) . . ?
C21 C1 C6 108.35(13) . . ?
C11 C1 C2 112.75(13) . . ?
C21 C1 C2 108.86(12) . . ?
C6 C1 C2 108.83(12) . . ?

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
N4 Ti1 N1 C11 59.66(15) . . . . ?
N3 Ti1 N1 C11 -162.64(10) . . . . ?
N2 Ti1 N1 C11 -61.01(10) . . . . ?
C14 Ti1 N1 C11 112.57(15) . . . . ?
C13 Ti1 N1 C11 76.34(11) . . . . ?
C12 Ti1 N1 C11 35.53(9) . . . . ?
N4 Ti1 N1 C14 -52.90(15) . . . . ?
N3 Ti1 N1 C14 84.79(12) . . . . ?
N2 Ti1 N1 C14 -173.58(11) . . . . ?
C11 Ti1 N1 C14 -112.57(15) . . . . ?
C13 Ti1 N1 C14 -36.23(11) . . . . ?
C12 Ti1 N1 C14 -77.03(12) . . . . ?
N3 Ti1 N4 C42 43.02(15) . . . . ?
N2 Ti1 N4 C42 -63.67(14) . . . . ?
N1 Ti1 N4 C42 -179.59(12) . . . . ?
C14 Ti1 N4 C42 148.94(13) . . . . ?
C11 Ti1 N4 C42 -144.60(13) . . . . ?
C13 Ti1 N4 C42 166.35(14) . . . . ?
C12 Ti1 N4 C42 -159.37(14) . . . . ?
N3 Ti1 N4 C41 -144.37(18) . . . . ?
N2 Ti1 N4 C41 108.93(18) . . . . ?
N1 Ti1 N4 C41 -7.0(2) . . . . ?
C14 Ti1 N4 C41 -38.5(2) . . . . ?
C11 Ti1 N4 C41 28.0(2) . . . . ?
C13 Ti1 N4 C41 -21.05(19) . . . . ?
C12 Ti1 N4 C41 13.24(19) . . . . ?
N4 Ti1 N3 C31 29.30(16) . . . . ?
N2 Ti1 N3 C31 140.13(14) . . . . ?
N1 Ti1 N3 C31 -127.87(15) . . . . ?
C14 Ti1 N3 C31 -92.86(15) . . . . ?
C11 Ti1 N3 C31 -141.58(14) . . . . ?
C13 Ti1 N3 C31 -68.57(17) . . . . ?
C12 Ti1 N3 C31 -91.2(2) . . . . ?
N4 Ti1 N3 C32 -158.41(13) . . . . ?
N2 Ti1 N3 C32 -47.58(14) . . . . ?
N1 Ti1 N3 C32 44.42(14) . . . . ?
C14 Ti1 N3 C32 79.43(14) . . . . ?
C11 Ti1 N3 C32 30.72(17) . . . . ?
C13 Ti1 N3 C32 103.72(14) . . . . ?
C12 Ti1 N3 C32 81.05(19) . . . . ?
N4 Ti1 N2 C24 69.29(15) . . . . ?
N3 Ti1 N2 C24 -38.83(15) . . . . ?
N1 Ti1 N2 C24 -140.99(14) . . . . ?
C14 Ti1 N2 C24 -145.43(14) . . . . ?
C11 Ti1 N2 C24 -172.10(15) . . . . ?
C13 Ti1 N2 C24 172.18(13) . . . . ?
C12 Ti1 N2 C24 161.47(14) . . . . ?
N4 Ti1 N2 C21 -123.65(12) . . . . ?
N3 Ti1 N2 C21 128.23(12) . . . . ?
N1 Ti1 N2 C21 26.06(13) . . . . ?
C14 Ti1 N2 C21 21.63(15) . . . . ?
C11 Ti1 N2 C21 -5.05(12) . . . . ?
C13 Ti1 N2 C21 -20.76(16) . . . . ?
C12 Ti1 N2 C21 -31.47(13) . . . . ?
N4 Ti1 C13 C14 -152.24(11) . . . . ?
N3 Ti1 C13 C14 -46.68(13) . . . . ?
N2 Ti1 C13 C14 96.55(12) . . . . ?
N1 Ti1 C13 C14 37.02(10) . . . . ?
C11 Ti1 C13 C14 78.38(12) . . . . ?
C12 Ti1 C13 C14 115.71(16) . . . . ?
N4 Ti1 C13 C12 92.04(12) . . . . ?
N3 Ti1 C13 C12 -162.39(11) . . . . ?
N2 Ti1 C13 C12 -19.17(15) . . . . ?
N1 Ti1 C13 C12 -78.69(12) . . . . ?
C14 Ti1 C13 C12 -115.71(16) . . . . ?
C11 Ti1 C13 C12 -37.34(11) . . . . ?
C11 N1 C14 C13 -2.5(2) . . . . ?
Ti1 N1 C14 C13 65.93(14) . . . . ?
C11 N1 C14 Ti1 -68.46(11) . . . . ?
C12 C13 C14 N1 1.1(2) . . . . ?
Ti1 C13 C14 N1 -63.51(13) . . . . ?
C12 C13 C14 Ti1 64.65(12) . . . . ?
N4 Ti1 C14 N1 149.23(10) . . . . ?
N3 Ti1 C14 N1 -101.14(11) . . . . ?
N2 Ti1 C14 N1 7.77(13) . . . . ?
C11 Ti1 C14 N1 38.86(9) . . . . ?
C13 Ti1 C14 N1 117.03(15) . . . . ?
C12 Ti1 C14 N1 79.71(11) . . . . ?
N4 Ti1 C14 C13 32.20(13) . . . . ?
N3 Ti1 C14 C13 141.83(11) . . . . ?
N2 Ti1 C14 C13 -109.26(11) . . . . ?
N1 Ti1 C14 C13 -117.03(15) . . . . ?
C11 Ti1 C14 C13 -78.17(11) . . . . ?
C12 Ti1 C14 C13 -37.32(10) . . . . ?
C3 C4 C5 C6 -50.3(2) . . . . ?
C3 C4 C5 C5B -166.03(17) . . . . ?
C3 C4 C5 C5A 75.1(2) . . . . ?
C5 C4 C3 C3A -78.7(2) . . . . ?
C5 C4 C3 C3B 164.64(16) . . . . ?
C5 C4 C3 C2 48.5(2) . . . . ?
C22 C23 C24 N2 0.15(19) . . . . ?
C21 N2 C24 C23 -0.16(18) . . . . ?
Ti1 N2 C24 C23 168.76(11) . . . . ?
C14 C13 C12 C11 0.7(2) . . . . ?
Ti1 C13 C12 C11 63.71(11) . . . . ?
C14 C13 C12 Ti1 -63.00(13) . . . . ?
N4 Ti1 C12 C11 157.07(10) . . . . ?
N3 Ti1 C12 C11 -79.81(16) . . . . ?
N2 Ti1 C12 C11 49.93(10) . . . . ?
N1 Ti1 C12 C11 -36.18(9) . . . . ?
C14 Ti1 C12 C11 -77.90(11) . . . . ?
C13 Ti1 C12 C11 -115.04(16) . . . . ?
N4 Ti1 C12 C13 -87.89(12) . . . . ?
N3 Ti1 C12 C13 35.2(2) . . . . ?
N2 Ti1 C12 C13 164.98(12) . . . . ?
N1 Ti1 C12 C13 78.86(12) . . . . ?
C14 Ti1 C12 C13 37.15(12) . . . . ?
C11 Ti1 C12 C13 115.04(16) . . . . ?
C24 C23 C22 C21 -0.08(19) . . . . ?
C5B C5 C6 C1 166.52(16) . . . . ?
C5A C5 C6 C1 -75.50(19) . . . . ?
C4 C5 C6 C1 50.4(2) . . . . ?
C4 C3 C2 C1 -47.12(19) . . . . ?
C3A C3 C2 C1 79.74(19) . . . . ?
C3B C3 C2 C1 -163.53(16) . . . . ?
C14 N1 C11 C12 3.01(18) . . . . ?
Ti1 N1 C11 C12 -64.63(12) . . . . ?
C14 N1 C11 C1 176.39(14) . . . . ?
Ti1 N1 C11 C1 108.74(14) . . . . ?
C14 N1 C11 Ti1 67.64(11) . . . . ?
C13 C12 C11 N1 -2.33(18) . . . . ?
Ti1 C12 C11 N1 62.03(11) . . . . ?
C13 C12 C11 C1 -175.17(15) . . . . ?
Ti1 C12 C11 C1 -110.80(15) . . . . ?
C13 C12 C11 Ti1 -64.36(12) . . . . ?
N4 Ti1 C11 N1 -145.45(10) . . . . ?
N3 Ti1 C11 N1 24.14(13) . . . . ?
N2 Ti1 C11 N1 114.29(11) . . . . ?
C14 Ti1 C11 N1 -39.28(11) . . . . ?
C13 Ti1 C11 N1 -80.50(11) . . . . ?
C12 Ti1 C11 N1 -118.28(14) . . . . ?
N4 Ti1 C11 C12 -27.17(12) . . . . ?
N3 Ti1 C11 C12 142.41(10) . . . . ?
N2 Ti1 C11 C12 -127.43(10) . . . . ?
N1 Ti1 C11 C12 118.28(14) . . . . ?
C14 Ti1 C11 C12 79.00(12) . . . . ?
C13 Ti1 C11 C12 37.77(10) . . . . ?
N4 Ti1 C11 C1 98.03(12) . . . . ?
N3 Ti1 C11 C1 -92.39(13) . . . . ?
N2 Ti1 C11 C1 -2.23(11) . . . . ?
N1 Ti1 C11 C1 -116.53(16) . . . . ?
C14 Ti1 C11 C1 -155.80(15) . . . . ?
C13 Ti1 C11 C1 162.97(15) . . . . ?
C12 Ti1 C11 C1 125.20(16) . . . . ?
C23 C22 C21 N2 -0.01(18) . . . . ?
C23 C22 C21 C1 178.63(15) . . . . ?
C24 N2 C21 C22 0.10(17) . . . . ?
Ti1 N2 C21 C22 -169.31(11) . . . . ?
C24 N2 C21 C1 -178.74(13) . . . . ?
Ti1 N2 C21 C1 11.85(19) . . . . ?
N1 C11 C1 C21 -74.38(18) . . . . ?
C12 C11 C1 C21 97.71(18) . . . . ?
Ti1 C11 C1 C21 7.59(15) . . . . ?
N1 C11 C1 C6 43.53(19) . . . . ?
C12 C11 C1 C6 -144.38(16) . . . . ?
Ti1 C11 C1 C6 125.50(12) . . . . ?
N1 C11 C1 C2 166.64(14) . . . . ?
C12 C11 C1 C2 -21.3(2) . . . . ?
Ti1 C11 C1 C2 -111.39(12) . . . . ?
C22 C21 C1 C11 169.67(16) . . . . ?
N2 C21 C1 C11 -11.79(18) . . . . ?
C22 C21 C1 C6 49.4(2) . . . . ?
N2 C21 C1 C6 -132.07(14) . . . . ?
C22 C21 C1 C2 -68.8(2) . . . . ?
N2 C21 C1 C2 109.73(15) . . . . ?
C5 C6 C1 C11 76.07(17) . . . . ?
C5 C6 C1 C21 -167.45(13) . . . . ?
C5 C6 C1 C2 -49.23(19) . . . . ?
C3 C2 C1 C11 -77.33(18) . . . . ?
C3 C2 C1 C21 165.39(14) . . . . ?
C3 C2 C1 C6 47.49(19) . . . . ?

_diffrn_measured_fraction_theta_max 0.995
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         0.330
_refine_diff_density_min         -0.292
_refine_diff_density_rms         0.049