# Electronic Supplementary Material (ESI) for Photochemical & Photobiological Sciences.
# This journal is © The Royal Society of Chemistry and Owner Societies 2017

####################################################################### 
# 
# 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_m_TS
_database_code_depnum_ccdc_archive 'CCDC 1562512'
_audit_update_record             
;
2017-07-17 deposited with the CCDC.
2017-09-06 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C44 H38 Si'
_chemical_formula_weight         594.83

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'
Si Si 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P2/c

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

_cell_length_a                   8.6135(7)
_cell_length_b                   10.2226(8)
_cell_length_c                   19.2641(15)
_cell_angle_alpha                90.00
_cell_angle_beta                 93.739(2)
_cell_angle_gamma                90.00
_cell_volume                     1692.6(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    233(2)
_cell_measurement_reflns_used    2093
_cell_measurement_theta_min      2.256
_cell_measurement_theta_max      23.578

_exptl_crystal_description       block
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.07
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.167
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             632
_exptl_absorpt_coefficient_mu    0.099
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9837
_exptl_absorpt_correction_T_max  0.9934
_exptl_absorpt_process_details   'SADABS (Sheldrick, 1996)'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      233(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  'Bruker SMART 1000 CCD diffractometer'
_diffrn_measurement_method       ω-scans
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            17009
_diffrn_reflns_av_R_equivalents  0.0636
_diffrn_reflns_av_sigmaI/netI    0.0818
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         1.99
_diffrn_reflns_theta_max         28.30
_reflns_number_total             4210
_reflns_number_gt                2062
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (Bruker, 1999)'
_computing_cell_refinement       'SMART (Bruker, 1999)'
_computing_data_reduction        'SAINT-Plus (Bruker, 1999)'
_computing_structure_solution    'SHELXL-2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/5 (Sheldrick, 2014)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'SHELXL-2014/5 (Sheldrick, 2014)'

_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 w=1/[σ²(Fo²)+(0.0598P)²+1.4434P] where P=(Fo²+2Fc²)/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_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         4210
_refine_ls_number_parameters     207
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1499
_refine_ls_R_factor_gt           0.0595
_refine_ls_wR_factor_ref         0.1981
_refine_ls_wR_factor_gt          0.1397
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_restrained_S_all      1.038
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Si Si 0.5000 0.75114(12) 0.2500 0.0407(3) Uani 1 2 d S . .
C1 C 0.3914(3) 0.8786(3) 0.19616(14) 0.0421(7) Uani 1 1 d . . .
C2 C 0.4396(3) 0.9982(3) 0.21999(14) 0.0409(7) Uani 1 1 d . . .
C3 C 0.2645(3) 0.8551(3) 0.14195(15) 0.0436(7) Uani 1 1 d . . .
C4 C 0.2825(4) 0.7601(4) 0.09128(15) 0.0541(8) Uani 1 1 d . . .
H4 H 0.3739 0.7097 0.0922 0.065 Uiso 1 1 calc R . .
C5 C 0.1657(4) 0.7401(4) 0.03946(17) 0.0679(11) Uani 1 1 d . . .
H5 H 0.1796 0.6774 0.0047 0.081 Uiso 1 1 calc R . .
C6 C 0.0300(4) 0.8104(4) 0.03816(18) 0.0702(11) Uani 1 1 d . . .
H6 H -0.0470 0.7964 0.0021 0.084 Uiso 1 1 calc R . .
C7 C 0.0049(4) 0.9021(4) 0.08936(18) 0.0582(9) Uani 1 1 d . . .
C8 C 0.1241(4) 0.9230(3) 0.14051(17) 0.0499(8) Uani 1 1 d . . .
H8 H 0.1093 0.9852 0.1754 0.060 Uiso 1 1 calc R . .
C9 C -0.1464(4) 0.9758(4) 0.0911(2) 0.0815(13) Uani 1 1 d . . .
H9A H -0.1974 0.9786 0.0447 0.122 Uiso 1 1 calc R . .
H9B H -0.1258 1.0643 0.1074 0.122 Uiso 1 1 calc R . .
H9C H -0.2135 0.9321 0.1223 0.122 Uiso 1 1 calc R . .
C10 C 0.3787(3) 1.1244(3) 0.18911(15) 0.0442(7) Uani 1 1 d . . .
C11 C 0.2895(4) 1.2093(3) 0.22624(18) 0.0533(8) Uani 1 1 d . . .
H11 H 0.2736 1.1920 0.2732 0.064 Uiso 1 1 calc R . .
C12 C 0.2235(4) 1.3202(3) 0.1942(2) 0.0604(9) Uani 1 1 d . . .
H12 H 0.1609 1.3767 0.2188 0.073 Uiso 1 1 calc R . .
C13 C 0.2512(4) 1.3453(4) 0.1267(2) 0.0609(9) Uani 1 1 d . . .
H13 H 0.2056 1.4201 0.1056 0.073 Uiso 1 1 calc R . .
C14 C 0.3417(4) 1.2675(3) 0.08792(17) 0.0519(8) Uani 1 1 d . . .
C15 C 0.4049(3) 1.1534(3) 0.12072(16) 0.0500(8) Uani 1 1 d . . .
H15 H 0.4658 1.0964 0.0955 0.060 Uiso 1 1 calc R . .
C16 C 0.3801(5) 1.2996(5) 0.0156(2) 0.0823(13) Uani 1 1 d . . .
H16A H 0.2871 1.3297 -0.0107 0.123 Uiso 1 1 calc R . .
H16B H 0.4198 1.2221 -0.0063 0.123 Uiso 1 1 calc R . .
H16C H 0.4585 1.3679 0.0168 0.123 Uiso 1 1 calc R . .
C17 C 0.3617(3) 0.6466(3) 0.29597(14) 0.0404(7) Uani 1 1 d . . .
C18 C 0.4092(3) 0.5290(3) 0.32786(16) 0.0479(8) Uani 1 1 d . . .
H18 H 0.5126 0.5012 0.3251 0.057 Uiso 1 1 calc R . .
C19 C 0.3084(4) 0.4528(3) 0.36318(16) 0.0519(8) Uani 1 1 d . . .
H19 H 0.3437 0.3747 0.3846 0.062 Uiso 1 1 calc R . .
C20 C 0.1560(4) 0.4912(3) 0.36697(16) 0.0522(8) Uani 1 1 d . . .
H20 H 0.0872 0.4394 0.3911 0.063 Uiso 1 1 calc R . .
C21 C 0.1046(3) 0.6050(3) 0.33566(16) 0.0514(8) Uani 1 1 d . . .
H21 H 0.0003 0.6308 0.3380 0.062 Uiso 1 1 calc R . .
C22 C 0.2064(3) 0.6823(3) 0.30044(15) 0.0447(7) Uani 1 1 d . . .
H22 H 0.1698 0.7602 0.2792 0.054 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
Si C17 1.866(3) 2_655 ?
Si C17 1.866(3) . ?
Si C1 1.877(3) 2_655 ?
Si C1 1.877(3) . ?
C1 C2 1.361(4) . ?
C1 C3 1.482(4) . ?
C2 C10 1.500(4) . ?
C2 C2 1.504(5) 2_655 ?
C3 C4 1.393(4) . ?
C3 C8 1.393(4) . ?
C4 C5 1.386(4) . ?
C5 C6 1.370(5) . ?
C6 C7 1.388(5) . ?
C7 C8 1.393(4) . ?
C7 C9 1.508(5) . ?
C10 C15 1.383(4) . ?
C10 C11 1.388(4) . ?
C11 C12 1.394(4) . ?
C12 C13 1.361(5) . ?
C13 C14 1.369(5) . ?
C14 C15 1.419(4) . ?
C14 C16 1.489(5) . ?
C17 C22 1.395(4) . ?
C17 C18 1.399(4) . ?
C18 C19 1.378(4) . ?
C19 C20 1.377(4) . ?
C20 C21 1.371(4) . ?
C21 C22 1.389(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
C17 Si C17 110.14(18) 2_655 . ?
C17 Si C1 110.46(13) 2_655 2_655 ?
C17 Si C1 116.47(12) . 2_655 ?
C17 Si C1 116.47(12) 2_655 . ?
C17 Si C1 110.45(13) . . ?
C1 Si C1 92.04(18) 2_655 . ?
C2 C1 C3 125.3(3) . . ?
C2 C1 Si 107.9(2) . . ?
C3 C1 Si 126.5(2) . . ?
C1 C2 C10 123.2(2) . . ?
C1 C2 C2 116.07(16) . 2_655 ?
C10 C2 C2 120.75(15) . 2_655 ?
C4 C3 C8 118.0(3) . . ?
C4 C3 C1 119.8(3) . . ?
C8 C3 C1 122.2(3) . . ?
C5 C4 C3 119.9(3) . . ?
C6 C5 C4 120.9(4) . . ?
C5 C6 C7 120.9(3) . . ?
C6 C7 C8 117.7(3) . . ?
C6 C7 C9 121.9(3) . . ?
C8 C7 C9 120.4(4) . . ?
C7 C8 C3 122.5(3) . . ?
C15 C10 C11 119.1(3) . . ?
C15 C10 C2 119.2(3) . . ?
C11 C10 C2 121.6(3) . . ?
C10 C11 C12 120.3(3) . . ?
C13 C12 C11 119.0(4) . . ?
C12 C13 C14 123.6(3) . . ?
C13 C14 C15 116.7(3) . . ?
C13 C14 C16 123.5(3) . . ?
C15 C14 C16 119.7(4) . . ?
C10 C15 C14 121.2(3) . . ?
C22 C17 C18 116.8(3) . . ?
C22 C17 Si 121.6(2) . . ?
C18 C17 Si 121.6(2) . . ?
C19 C18 C17 121.8(3) . . ?
C20 C19 C18 119.9(3) . . ?
C21 C20 C19 120.1(3) . . ?
C20 C21 C22 120.1(3) . . ?
C21 C22 C17 121.3(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
C17 Si C1 C2 -114.1(2) 2_655 . . . ?
C17 Si C1 C2 119.3(2) . . . . ?
C1 Si C1 C2 0.03(15) 2_655 . . . ?
C17 Si C1 C3 71.5(3) 2_655 . . . ?
C17 Si C1 C3 -55.1(3) . . . . ?
C1 Si C1 C3 -174.4(3) 2_655 . . . ?
C3 C1 C2 C10 -5.9(5) . . . . ?
Si C1 C2 C10 179.6(2) . . . . ?
C3 C1 C2 C2 174.4(3) . . . 2_655 ?
Si C1 C2 C2 -0.1(4) . . . 2_655 ?
C2 C1 C3 C4 138.5(3) . . . . ?
Si C1 C3 C4 -48.0(4) . . . . ?
C2 C1 C3 C8 -43.1(4) . . . . ?
Si C1 C3 C8 130.4(3) . . . . ?
C8 C3 C4 C5 3.1(5) . . . . ?
C1 C3 C4 C5 -178.4(3) . . . . ?
C3 C4 C5 C6 -1.6(5) . . . . ?
C4 C5 C6 C7 -1.1(6) . . . . ?
C5 C6 C7 C8 2.1(5) . . . . ?
C5 C6 C7 C9 -176.9(3) . . . . ?
C6 C7 C8 C3 -0.5(5) . . . . ?
C9 C7 C8 C3 178.5(3) . . . . ?
C4 C3 C8 C7 -2.1(5) . . . . ?
C1 C3 C8 C7 179.5(3) . . . . ?
C1 C2 C10 C15 -63.2(4) . . . . ?
C2 C2 C10 C15 116.5(4) 2_655 . . . ?
C1 C2 C10 C11 113.3(4) . . . . ?
C2 C2 C10 C11 -67.0(5) 2_655 . . . ?
C15 C10 C11 C12 1.9(5) . . . . ?
C2 C10 C11 C12 -174.5(3) . . . . ?
C10 C11 C12 C13 -1.6(5) . . . . ?
C11 C12 C13 C14 -0.3(5) . . . . ?
C12 C13 C14 C15 1.8(5) . . . . ?
C12 C13 C14 C16 -175.9(3) . . . . ?
C11 C10 C15 C14 -0.4(4) . . . . ?
C2 C10 C15 C14 176.1(3) . . . . ?
C13 C14 C15 C10 -1.4(4) . . . . ?
C16 C14 C15 C10 176.4(3) . . . . ?
C17 Si C17 C22 -143.5(3) 2_655 . . . ?
C1 Si C17 C22 89.7(3) 2_655 . . . ?
C1 Si C17 C22 -13.5(3) . . . . ?
C17 Si C17 C18 36.7(2) 2_655 . . . ?
C1 Si C17 C18 -90.0(3) 2_655 . . . ?
C1 Si C17 C18 166.8(2) . . . . ?
C22 C17 C18 C19 -1.1(4) . . . . ?
Si C17 C18 C19 178.6(2) . . . . ?
C17 C18 C19 C20 0.8(5) . . . . ?
C18 C19 C20 C21 0.0(5) . . . . ?
C19 C20 C21 C22 -0.4(5) . . . . ?
C20 C21 C22 C17 0.1(5) . . . . ?
C18 C17 C22 C21 0.7(4) . . . . ?
Si C17 C22 C21 -179.0(2) . . . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        28.30
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.424
_refine_diff_density_min         -0.251
_refine_diff_density_rms         0.052
