# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2011 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_cambridge 0177 #TrackingRef '15.cif' #============================================================================ # 1. SUBMISSION DETAILS _publ_contact_author ; Dr. J. F. Malone School of Chemistry and Chemical Engineering The Queen's University of Belfast Belfast UK BT9 5AG ; _publ_contact_author_phone '0044 2890 274421' _publ_contact_author_fax '0044 2890 974687' _publ_contact_author_email dr.boyd@qub.ac.uk _publ_requested_coeditor_name ? #============================================================================ # 2. TITLE AND AUTHOR LIST _publ_section_title ; Chemoenzymatic synthesis of a mixed phosphine-phosphine oxide catalyst and its application to the asymmetric allylation of aldehydes and hydrogenation of alkenes ; loop_ _publ_author_name _publ_author_address 'Boyd, Derek R.' ; School of Chemistry and Chemical Engineering The Queen's University of Belfast Belfast UK BT9 5AG ; 'Bell, Mark' ; School of Chemistry and Chemical Engineering The Queen's University of Belfast Belfast UK BT9 5AG ; 'Dunne, Katherine S.' ; Celtic Catalysts Ltd Nova Centre Belfield Innovation Park Dublin 4 Ireland ; 'Kelly, Brian' ; Celtic Catalysts Ltd Nova Centre Belfield Innovation Park Dublin 4 Ireland ; 'Stevenson, Paul J.' ; School of Chemistry and Chemical Engineering The Queen's University of Belfast Belfast UK BT9 5AG ; 'Malone, John F.' ; School of Chemistry and Chemical Engineering The Queen's University of Belfast Belfast UK BT9 5AG ; 'Allen, Christopher C.R.' ; School of Biological Sciences The Queen's University of Belfast Belfast UK BT9 5AG ; #============================================================================ data_15 _database_code_depnum_ccdc_archive 'CCDC 842558' #TrackingRef '15.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C30 H31 B O2 P2, C2 H6 O' _chemical_formula_sum 'C32 H37 B O3 P2' _chemical_formula_weight 542.37 _chemical_absolute_configuration ad 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' B B 0.0013 0.0007 '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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M P212121 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 9.310(4) _cell_length_b 12.038(3) _cell_length_c 27.103(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3037.6(16) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 100 _cell_measurement_theta_min 2.80 _cell_measurement_theta_max 12.46 _exptl_crystal_description prisms _exptl_crystal_colour colourless _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.186 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1152 _exptl_absorpt_coefficient_mu 0.173 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 P4 diffractometer' _diffrn_measurement_method 'omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 6142 _diffrn_reflns_av_R_equivalents 0.0606 _diffrn_reflns_av_sigmaI/netI 0.1040 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 1 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 1 _diffrn_reflns_limit_l_min -38 _diffrn_reflns_limit_l_max 1 _diffrn_reflns_theta_min 2.26 _diffrn_reflns_theta_max 30.00 _reflns_number_total 5876 _reflns_number_gt 2773 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker XSCANS' _computing_cell_refinement 'Bruker XSCANS' _computing_data_reduction 'Bruker XSCANS' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.1174P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.1(2) _refine_ls_number_reflns 5876 _refine_ls_number_parameters 349 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.1624 _refine_ls_R_factor_gt 0.0699 _refine_ls_wR_factor_ref 0.2326 _refine_ls_wR_factor_gt 0.1765 _refine_ls_goodness_of_fit_ref 0.976 _refine_ls_restrained_S_all 0.976 _refine_ls_shift/su_max 0.004 _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 C1 C 0.3173(6) 0.6350(5) 0.0296(2) 0.0505(14) Uani 1 1 d . . . H1 H 0.3380 0.6805 0.0005 0.061 Uiso 1 1 calc R . . O1 O 0.4471(5) 0.5810(4) 0.04172(19) 0.0752(14) Uani 1 1 d . . . H1A H 0.4331 0.5375 0.0645 0.113 Uiso 1 1 calc R . . C2 C 0.2732(6) 0.7154(5) 0.06980(19) 0.0474(14) Uani 1 1 d . . . H2 H 0.3454 0.7590 0.0835 0.057 Uiso 1 1 calc R . . C3 C 0.1410(6) 0.7297(4) 0.08742(19) 0.0411(12) Uani 1 1 d . . . C4 C 0.0147(6) 0.6603(4) 0.06734(17) 0.0405(11) Uani 1 1 d . . . H4 H -0.0697 0.7087 0.0649 0.049 Uiso 1 1 calc R . . C5 C 0.0524(6) 0.6185(5) 0.01499(19) 0.0483(14) Uani 1 1 d . . . H5A H -0.0226 0.5689 0.0035 0.058 Uiso 1 1 calc R . . H5B H 0.0570 0.6812 -0.0074 0.058 Uiso 1 1 calc R . . C6 C 0.1973(6) 0.5569(5) 0.0147(2) 0.0523(14) Uani 1 1 d . . . H6A H 0.1935 0.4947 0.0374 0.063 Uiso 1 1 calc R . . H6B H 0.2160 0.5280 -0.0181 0.063 Uiso 1 1 calc R . . P3 P 0.10372(17) 0.84317(12) 0.13041(5) 0.0462(4) Uani 1 1 d . . . B3 B -0.0642(9) 0.9258(6) 0.1120(3) 0.072(2) Uani 1 1 d . . . H3A H -0.1481 0.8808 0.1171 0.108 Uiso 1 1 calc R . . H3B H -0.0579 0.9462 0.0779 0.108 Uiso 1 1 calc R . . H3C H -0.0707 0.9916 0.1319 0.108 Uiso 1 1 calc R . . C7 C 0.1026(7) 0.7845(5) 0.1923(2) 0.0492(13) Uani 1 1 d . . . C8 C 0.1952(8) 0.6997(6) 0.2056(2) 0.0635(18) Uani 1 1 d . . . H8 H 0.2555 0.6679 0.1822 0.076 Uiso 1 1 calc R . . C9 C 0.1979(10) 0.6616(7) 0.2546(3) 0.082(2) Uani 1 1 d . . . H9 H 0.2598 0.6044 0.2635 0.098 Uiso 1 1 calc R . . C10 C 0.1109(11) 0.7079(7) 0.2889(3) 0.089(3) Uani 1 1 d . . . H10 H 0.1135 0.6826 0.3213 0.107 Uiso 1 1 calc R . . C11 C 0.0176(11) 0.7933(7) 0.2758(3) 0.093(3) Uani 1 1 d . . . H11 H -0.0408 0.8254 0.2997 0.112 Uiso 1 1 calc R . . C12 C 0.0108(8) 0.8313(6) 0.2272(2) 0.0674(18) Uani 1 1 d . . . H12 H -0.0538 0.8867 0.2182 0.081 Uiso 1 1 calc R . . C13 C 0.2653(7) 0.9301(5) 0.1283(2) 0.0530(15) Uani 1 1 d . . . C14 C 0.3753(7) 0.9216(6) 0.1619(3) 0.071(2) Uani 1 1 d . . . H14 H 0.3670 0.8723 0.1882 0.085 Uiso 1 1 calc R . . C15 C 0.4965(10) 0.9847(7) 0.1572(3) 0.095(3) Uani 1 1 d . . . H15 H 0.5704 0.9772 0.1801 0.114 Uiso 1 1 calc R . . C16 C 0.5101(10) 1.0586(7) 0.1194(4) 0.092(3) Uani 1 1 d . . . H16 H 0.5929 1.1012 0.1163 0.110 Uiso 1 1 calc R . . C17 C 0.4019(12) 1.0693(7) 0.0863(4) 0.100(3) Uani 1 1 d . . . H17 H 0.4101 1.1202 0.0606 0.120 Uiso 1 1 calc R . . C18 C 0.2793(9) 1.0049(6) 0.0904(3) 0.076(2) Uani 1 1 d . . . H18 H 0.2060 1.0124 0.0673 0.091 Uiso 1 1 calc R . . P4 P -0.02889(16) 0.54446(12) 0.10968(6) 0.0445(4) Uani 1 1 d . . . O4 O 0.0982(4) 0.4955(3) 0.13487(14) 0.0567(11) Uani 1 1 d . . . C19 C -0.1228(7) 0.4378(4) 0.0747(2) 0.0493(14) Uani 1 1 d . . . C20 C -0.2492(7) 0.4549(5) 0.0490(2) 0.0571(15) Uani 1 1 d . . . H20 H -0.2858 0.5266 0.0465 0.068 Uiso 1 1 calc R . . C21 C -0.3213(8) 0.3698(6) 0.0274(3) 0.073(2) Uani 1 1 d . . . H21 H -0.4070 0.3839 0.0110 0.088 Uiso 1 1 calc R . . C22 C -0.2689(10) 0.2624(6) 0.0295(3) 0.074(2) Uani 1 1 d . . . H22 H -0.3186 0.2042 0.0148 0.089 Uiso 1 1 calc R . . C23 C -0.1426(10) 0.2437(6) 0.0538(3) 0.076(2) Uani 1 1 d . . . H23 H -0.1059 0.1720 0.0553 0.091 Uiso 1 1 calc R . . C24 C -0.0681(8) 0.3302(5) 0.0762(2) 0.0610(17) Uani 1 1 d . . . H24 H 0.0183 0.3161 0.0922 0.073 Uiso 1 1 calc R . . C25 C -0.1601(6) 0.5953(5) 0.1531(2) 0.0512(14) Uani 1 1 d . . . C26 C -0.2813(7) 0.6549(6) 0.1391(3) 0.0713(19) Uani 1 1 d . . . H26 H -0.2933 0.6758 0.1063 0.086 Uiso 1 1 calc R . . C27 C -0.3852(10) 0.6833(8) 0.1740(4) 0.105(3) Uani 1 1 d . . . H27 H -0.4691 0.7193 0.1645 0.126 Uiso 1 1 calc R . . C28 C -0.3607(12) 0.6567(10) 0.2237(4) 0.113(4) Uani 1 1 d . . . H28 H -0.4272 0.6781 0.2475 0.136 Uiso 1 1 calc R . . C29 C -0.2426(11) 0.6009(8) 0.2372(3) 0.097(3) Uani 1 1 d . . . H29 H -0.2293 0.5832 0.2703 0.116 Uiso 1 1 calc R . . C30 C -0.1384(9) 0.5684(6) 0.2027(2) 0.071(2) Uani 1 1 d . . . H30 H -0.0568 0.5298 0.2126 0.085 Uiso 1 1 calc R . . C31 C 0.5639(15) 0.3667(12) 0.1736(7) 0.232(8) Uani 1 1 d D . . H31A H 0.6279 0.3914 0.1481 0.348 Uiso 1 1 calc R . . H31B H 0.5889 0.2924 0.1832 0.348 Uiso 1 1 calc R . . H31C H 0.5717 0.4152 0.2016 0.348 Uiso 1 1 calc R . . C32 C 0.4085(13) 0.3684(11) 0.1542(7) 0.259(12) Uani 1 1 d D . . H32A H 0.3935 0.3052 0.1326 0.310 Uiso 1 1 calc R . . H32B H 0.3426 0.3617 0.1817 0.310 Uiso 1 1 calc R . . O32 O 0.3784(7) 0.4685(8) 0.1278(4) 0.162(4) Uani 1 1 d D . . H32 H 0.2912 0.4757 0.1247 0.242 Uiso 1 1 calc R . . 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 C1 0.050(3) 0.048(3) 0.054(3) -0.003(3) 0.006(3) 0.001(3) O1 0.057(3) 0.079(3) 0.090(4) -0.011(3) 0.008(3) 0.019(3) C2 0.047(3) 0.046(3) 0.050(3) -0.002(3) 0.002(3) -0.007(3) C3 0.046(3) 0.036(3) 0.042(3) 0.001(2) -0.002(3) 0.003(3) C4 0.039(3) 0.040(2) 0.042(3) 0.006(2) 0.000(2) -0.004(3) C5 0.053(3) 0.049(3) 0.043(3) -0.001(3) -0.004(3) -0.008(3) C6 0.063(4) 0.044(3) 0.050(3) -0.006(3) 0.010(3) 0.003(3) P3 0.0519(8) 0.0392(7) 0.0476(7) -0.0014(7) 0.0017(7) 0.0016(8) B3 0.083(6) 0.053(4) 0.079(5) -0.013(4) -0.011(5) 0.019(4) C7 0.055(3) 0.044(3) 0.049(3) -0.003(3) 0.002(3) -0.012(3) C8 0.071(4) 0.062(4) 0.057(4) 0.003(3) -0.004(3) 0.000(4) C9 0.112(6) 0.075(5) 0.059(4) 0.011(4) -0.018(4) -0.002(6) C10 0.140(8) 0.078(5) 0.051(4) 0.007(4) -0.004(5) -0.010(6) C11 0.137(8) 0.083(5) 0.060(4) -0.013(4) 0.039(5) -0.021(7) C12 0.085(5) 0.060(4) 0.058(4) -0.009(3) 0.021(4) 0.003(4) C13 0.064(4) 0.044(3) 0.051(3) -0.003(3) 0.003(3) -0.001(3) C14 0.064(4) 0.069(4) 0.081(5) -0.006(4) -0.003(4) -0.020(4) C15 0.095(6) 0.100(6) 0.090(6) -0.020(5) 0.003(5) -0.036(6) C16 0.086(6) 0.073(5) 0.116(7) -0.014(5) 0.013(6) -0.032(5) C17 0.118(7) 0.084(6) 0.099(6) 0.013(5) 0.026(6) -0.029(6) C18 0.088(5) 0.069(4) 0.071(4) 0.009(4) 0.004(4) -0.023(5) P4 0.0421(7) 0.0417(7) 0.0498(7) 0.0039(7) 0.0031(7) 0.0027(7) O4 0.052(2) 0.059(2) 0.059(2) 0.012(2) -0.002(2) 0.003(2) C19 0.056(3) 0.039(3) 0.053(3) 0.001(3) 0.006(3) -0.004(3) C20 0.053(3) 0.045(3) 0.073(4) -0.004(3) -0.003(3) -0.002(3) C21 0.062(4) 0.078(5) 0.080(5) -0.015(4) 0.006(4) -0.018(4) C22 0.090(6) 0.050(4) 0.082(5) -0.016(4) 0.013(5) -0.013(4) C23 0.107(7) 0.042(3) 0.079(5) -0.004(3) 0.023(5) 0.008(4) C24 0.077(5) 0.043(3) 0.063(4) 0.002(3) 0.003(3) 0.006(4) C25 0.047(3) 0.052(3) 0.055(3) -0.002(3) 0.011(3) -0.007(3) C26 0.063(4) 0.062(4) 0.089(5) -0.009(4) 0.015(4) 0.008(4) C27 0.074(5) 0.099(7) 0.141(9) -0.014(6) 0.036(6) 0.011(6) C28 0.101(7) 0.116(8) 0.122(8) -0.040(7) 0.069(7) -0.030(7) C29 0.108(7) 0.103(7) 0.079(5) -0.017(5) 0.042(6) -0.034(6) C30 0.086(5) 0.065(4) 0.062(4) 0.003(3) 0.014(4) -0.015(4) C31 0.25(2) 0.129(11) 0.31(2) 0.053(14) -0.037(19) 0.027(15) C32 0.106(9) 0.185(16) 0.48(3) 0.12(2) 0.030(15) 0.067(11) O32 0.081(4) 0.205(8) 0.199(8) 0.101(7) 0.015(5) 0.041(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 C1 O1 1.410(7) . ? C1 C2 1.513(8) . ? C1 C6 1.516(8) . ? C1 H1 0.9800 . ? O1 H1A 0.8200 . ? C2 C3 1.331(7) . ? C2 H2 0.9300 . ? C3 C4 1.542(7) . ? C3 P3 1.829(5) . ? C4 C5 1.546(7) . ? C4 P4 1.851(5) . ? C4 H4 0.9800 . ? C5 C6 1.540(8) . ? C5 H5A 0.9700 . ? C5 H5B 0.9700 . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? P3 C7 1.820(6) . ? P3 C13 1.834(6) . ? P3 B3 1.919(8) . ? B3 H3A 0.9600 . ? B3 H3B 0.9600 . ? B3 H3C 0.9600 . ? C7 C8 1.384(9) . ? C7 C12 1.394(8) . ? C8 C9 1.404(9) . ? C8 H8 0.9300 . ? C9 C10 1.353(11) . ? C9 H9 0.9300 . ? C10 C11 1.391(12) . ? C10 H10 0.9300 . ? C11 C12 1.397(9) . ? C11 H11 0.9300 . ? C12 H12 0.9300 . ? C13 C18 1.372(9) . ? C13 C14 1.375(9) . ? C14 C15 1.367(10) . ? C14 H14 0.9300 . ? C15 C16 1.363(12) . ? C15 H15 0.9300 . ? C16 C17 1.356(12) . ? C16 H16 0.9300 . ? C17 C18 1.384(11) . ? C17 H17 0.9300 . ? C18 H18 0.9300 . ? P4 O4 1.488(4) . ? P4 C25 1.803(6) . ? P4 C19 1.820(6) . ? C19 C20 1.382(9) . ? C19 C24 1.393(8) . ? C20 C21 1.358(9) . ? C20 H20 0.9300 . ? C21 C22 1.383(10) . ? C21 H21 0.9300 . ? C22 C23 1.366(11) . ? C22 H22 0.9300 . ? C23 C24 1.391(10) . ? C23 H23 0.9300 . ? C24 H24 0.9300 . ? C25 C26 1.390(9) . ? C25 C30 1.399(9) . ? C26 C27 1.397(10) . ? C26 H26 0.9300 . ? C27 C28 1.401(15) . ? C27 H27 0.9300 . ? C28 C29 1.341(14) . ? C28 H28 0.9300 . ? C29 C30 1.403(11) . ? C29 H29 0.9300 . ? C30 H30 0.9300 . ? C31 C32 1.5390(12) . ? C31 H31A 0.9600 . ? C31 H31B 0.9600 . ? C31 H31C 0.9600 . ? C32 O32 1.4295(11) . ? C32 H32A 0.9700 . ? C32 H32B 0.9700 . ? O32 H32 0.8200 . ? 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 O1 C1 C2 111.1(5) . . ? O1 C1 C6 114.1(5) . . ? C2 C1 C6 112.9(5) . . ? O1 C1 H1 106.0 . . ? C2 C1 H1 106.0 . . ? C6 C1 H1 106.0 . . ? C1 O1 H1A 109.5 . . ? C3 C2 C1 126.3(5) . . ? C3 C2 H2 116.9 . . ? C1 C2 H2 116.9 . . ? C2 C3 C4 120.6(5) . . ? C2 C3 P3 120.0(4) . . ? C4 C3 P3 119.0(4) . . ? C3 C4 C5 109.1(4) . . ? C3 C4 P4 110.9(3) . . ? C5 C4 P4 111.9(4) . . ? C3 C4 H4 108.3 . . ? C5 C4 H4 108.3 . . ? P4 C4 H4 108.3 . . ? C6 C5 C4 111.2(4) . . ? C6 C5 H5A 109.4 . . ? C4 C5 H5A 109.4 . . ? C6 C5 H5B 109.4 . . ? C4 C5 H5B 109.4 . . ? H5A C5 H5B 108.0 . . ? C1 C6 C5 110.2(4) . . ? C1 C6 H6A 109.6 . . ? C5 C6 H6A 109.6 . . ? C1 C6 H6B 109.6 . . ? C5 C6 H6B 109.6 . . ? H6A C6 H6B 108.1 . . ? C7 P3 C3 107.4(3) . . ? C7 P3 C13 104.8(3) . . ? C3 P3 C13 104.5(3) . . ? C7 P3 B3 115.8(4) . . ? C3 P3 B3 112.1(3) . . ? C13 P3 B3 111.4(3) . . ? P3 B3 H3A 109.5 . . ? P3 B3 H3B 109.5 . . ? H3A B3 H3B 109.5 . . ? P3 B3 H3C 109.5 . . ? H3A B3 H3C 109.5 . . ? H3B B3 H3C 109.5 . . ? C8 C7 C12 120.2(6) . . ? C8 C7 P3 121.6(5) . . ? C12 C7 P3 118.2(5) . . ? C7 C8 C9 119.9(7) . . ? C7 C8 H8 120.1 . . ? C9 C8 H8 120.1 . . ? C10 C9 C8 120.3(8) . . ? C10 C9 H9 119.9 . . ? C8 C9 H9 119.9 . . ? C9 C10 C11 120.2(7) . . ? C9 C10 H10 119.9 . . ? C11 C10 H10 119.9 . . ? C10 C11 C12 120.7(7) . . ? C10 C11 H11 119.7 . . ? C12 C11 H11 119.7 . . ? C7 C12 C11 118.7(7) . . ? C7 C12 H12 120.7 . . ? C11 C12 H12 120.7 . . ? C18 C13 C14 118.3(6) . . ? C18 C13 P3 118.4(5) . . ? C14 C13 P3 123.2(5) . . ? C15 C14 C13 120.8(7) . . ? C15 C14 H14 119.6 . . ? C13 C14 H14 119.6 . . ? C16 C15 C14 120.6(9) . . ? C16 C15 H15 119.7 . . ? C14 C15 H15 119.7 . . ? C17 C16 C15 119.4(8) . . ? C17 C16 H16 120.3 . . ? C15 C16 H16 120.3 . . ? C16 C17 C18 120.4(8) . . ? C16 C17 H17 119.8 . . ? C18 C17 H17 119.8 . . ? C13 C18 C17 120.4(8) . . ? C13 C18 H18 119.8 . . ? C17 C18 H18 119.8 . . ? O4 P4 C25 112.0(3) . . ? O4 P4 C19 110.0(3) . . ? C25 P4 C19 104.7(3) . . ? O4 P4 C4 114.1(2) . . ? C25 P4 C4 107.3(3) . . ? C19 P4 C4 108.3(2) . . ? C20 C19 C24 117.7(6) . . ? C20 C19 P4 124.4(5) . . ? C24 C19 P4 117.7(5) . . ? C21 C20 C19 121.6(6) . . ? C21 C20 H20 119.2 . . ? C19 C20 H20 119.2 . . ? C20 C21 C22 120.9(7) . . ? C20 C21 H21 119.5 . . ? C22 C21 H21 119.5 . . ? C23 C22 C21 118.5(7) . . ? C23 C22 H22 120.8 . . ? C21 C22 H22 120.8 . . ? C22 C23 C24 121.1(7) . . ? C22 C23 H23 119.4 . . ? C24 C23 H23 119.4 . . ? C23 C24 C19 120.0(7) . . ? C23 C24 H24 120.0 . . ? C19 C24 H24 120.0 . . ? C26 C25 C30 120.0(6) . . ? C26 C25 P4 123.2(5) . . ? C30 C25 P4 116.8(5) . . ? C25 C26 C27 120.2(8) . . ? C25 C26 H26 119.9 . . ? C27 C26 H26 119.9 . . ? C26 C27 C28 118.9(9) . . ? C26 C27 H27 120.6 . . ? C28 C27 H27 120.6 . . ? C29 C28 C27 120.7(9) . . ? C29 C28 H28 119.6 . . ? C27 C28 H28 119.6 . . ? C28 C29 C30 121.6(9) . . ? C28 C29 H29 119.2 . . ? C30 C29 H29 119.2 . . ? C25 C30 C29 118.5(8) . . ? C25 C30 H30 120.8 . . ? C29 C30 H30 120.8 . . ? C32 C31 H31A 109.5 . . ? C32 C31 H31B 109.5 . . ? H31A C31 H31B 109.5 . . ? C32 C31 H31C 109.5 . . ? H31A C31 H31C 109.5 . . ? H31B C31 H31C 109.5 . . ? O32 C32 C31 111.5(10) . . ? O32 C32 H32A 109.3 . . ? C31 C32 H32A 109.3 . . ? O32 C32 H32B 109.3 . . ? C31 C32 H32B 109.3 . . ? H32A C32 H32B 108.0 . . ? C32 O32 H32 109.5 . . ? 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 O1 C1 C2 C3 -137.6(6) . . . . ? C6 C1 C2 C3 -8.0(8) . . . . ? C1 C2 C3 C4 0.6(9) . . . . ? C1 C2 C3 P3 -172.1(4) . . . . ? C2 C3 C4 C5 -23.2(7) . . . . ? P3 C3 C4 C5 149.5(4) . . . . ? C2 C3 C4 P4 100.5(5) . . . . ? P3 C3 C4 P4 -86.7(4) . . . . ? C3 C4 C5 C6 53.5(6) . . . . ? P4 C4 C5 C6 -69.5(5) . . . . ? O1 C1 C6 C5 165.7(5) . . . . ? C2 C1 C6 C5 37.6(6) . . . . ? C4 C5 C6 C1 -62.4(6) . . . . ? C2 C3 P3 C7 -99.5(5) . . . . ? C4 C3 P3 C7 87.7(4) . . . . ? C2 C3 P3 C13 11.4(5) . . . . ? C4 C3 P3 C13 -161.4(4) . . . . ? C2 C3 P3 B3 132.2(5) . . . . ? C4 C3 P3 B3 -40.6(5) . . . . ? C3 P3 C7 C8 35.8(6) . . . . ? C13 P3 C7 C8 -74.9(5) . . . . ? B3 P3 C7 C8 162.0(5) . . . . ? C3 P3 C7 C12 -147.5(5) . . . . ? C13 P3 C7 C12 101.8(5) . . . . ? B3 P3 C7 C12 -21.4(6) . . . . ? C12 C7 C8 C9 -0.9(10) . . . . ? P3 C7 C8 C9 175.7(6) . . . . ? C7 C8 C9 C10 -0.3(12) . . . . ? C8 C9 C10 C11 0.3(13) . . . . ? C9 C10 C11 C12 1.0(13) . . . . ? C8 C7 C12 C11 2.0(10) . . . . ? P3 C7 C12 C11 -174.7(6) . . . . ? C10 C11 C12 C7 -2.1(12) . . . . ? C7 P3 C13 C18 -165.6(5) . . . . ? C3 P3 C13 C18 81.6(6) . . . . ? B3 P3 C13 C18 -39.6(6) . . . . ? C7 P3 C13 C14 16.5(6) . . . . ? C3 P3 C13 C14 -96.3(6) . . . . ? B3 P3 C13 C14 142.5(6) . . . . ? C18 C13 C14 C15 -1.1(10) . . . . ? P3 C13 C14 C15 176.8(5) . . . . ? C13 C14 C15 C16 0.8(12) . . . . ? C14 C15 C16 C17 0.1(13) . . . . ? C15 C16 C17 C18 -0.8(14) . . . . ? C14 C13 C18 C17 0.4(11) . . . . ? P3 C13 C18 C17 -177.6(6) . . . . ? C16 C17 C18 C13 0.5(13) . . . . ? C3 C4 P4 O4 -34.9(4) . . . . ? C5 C4 P4 O4 87.2(4) . . . . ? C3 C4 P4 C25 89.8(4) . . . . ? C5 C4 P4 C25 -148.1(4) . . . . ? C3 C4 P4 C19 -157.7(4) . . . . ? C5 C4 P4 C19 -35.6(5) . . . . ? O4 P4 C19 C20 176.7(5) . . . . ? C25 P4 C19 C20 56.2(6) . . . . ? C4 P4 C19 C20 -58.0(6) . . . . ? O4 P4 C19 C24 0.6(6) . . . . ? C25 P4 C19 C24 -119.8(5) . . . . ? C4 P4 C19 C24 125.9(5) . . . . ? C24 C19 C20 C21 2.3(9) . . . . ? P4 C19 C20 C21 -173.8(5) . . . . ? C19 C20 C21 C22 -1.2(11) . . . . ? C20 C21 C22 C23 -0.2(11) . . . . ? C21 C22 C23 C24 0.4(11) . . . . ? C22 C23 C24 C19 0.8(10) . . . . ? C20 C19 C24 C23 -2.1(9) . . . . ? P4 C19 C24 C23 174.3(5) . . . . ? O4 P4 C25 C26 173.2(5) . . . . ? C19 P4 C25 C26 -67.7(6) . . . . ? C4 P4 C25 C26 47.3(6) . . . . ? O4 P4 C25 C30 -9.3(6) . . . . ? C19 P4 C25 C30 109.8(5) . . . . ? C4 P4 C25 C30 -135.3(5) . . . . ? C30 C25 C26 C27 -3.1(10) . . . . ? P4 C25 C26 C27 174.3(6) . . . . ? C25 C26 C27 C28 3.8(13) . . . . ? C26 C27 C28 C29 -2.8(15) . . . . ? C27 C28 C29 C30 0.9(15) . . . . ? C26 C25 C30 C29 1.3(10) . . . . ? P4 C25 C30 C29 -176.3(6) . . . . ? C28 C29 C30 C25 -0.2(13) . . . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 30.00 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.365 _refine_diff_density_min -0.380 _refine_diff_density_rms 0.093