# Supplementary Material (ESI) for ChemComm # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 182/1755 data_global #============================================================================== # 1. SUBMISSION DETAILS #============================================================================== _publ_contact_author ; Regitz, Manfred Universit\"at Kaiserslautern Fachbereich Chemie Erwin-Schr\"odinger-Strasse 67663 Kaiserslautern ; _publ_contact_author_phone '++49 (0)631 205-2431' _publ_contact_author_fax '++49 (0)631 205-3921' _publ_requested_journal ' J. Chem. Soc. Chem. Comm.' #============================================================================== # 2. TITLE AND AUTHOR LIST #============================================================================== _publ_section_title ; 'Unusual addition reactions of lithium alkoxides to 2,4,6-tri-tert-butyl- 1,3,5-triphosphabenzene' ; # The loop structure below should contain the name and adresses of all authors, # in the required order of publication. loop_ _publ_author_name _publ_author_address 'M. Krein' ; Universit\"at Kaiserslautern Fachbereich Chemie Erwin-Schr\"odinger-Strasse 67663 Kaiserslautern ; 'U. Bergstr\"a\&ser' ; Universit\"at Kaiserslautern Fachbereich Chemie Erwin-Schr\"odinger-Strasse 67663 Kaiserslautern ; 'C. Peters' ; Universit\"at Kaiserslautern Fachbereich Chemie Erwin-Schr\"odinger-Strasse 67663 Kaiserslautern ; 'S. G. Ruf' ; Universit\"at Kaiserslautern Fachbereich Chemie Erwin-Schr\"odinger-Strasse 67663 Kaiserslautern ; 'Manfred Regitz' ; Universit\"at Kaiserslautern Fachbereich Chemie Erwin-Schr\"odinger-Strasse 67663 Kaiserslautern ; #============================================================================== # 3. CRYSTAL DATA OF STRUCTURE 4a #============================================================================== data_krein _audit_creation_method SHELXL _chemical_name_systematic ; '2,4,6-tri-tert-butyl-1,3,5-methoxy-1,3,5-triphosphacyclohexane' ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C18 H39 O3 P3' _chemical_formula_weight 396.40 _chemical_melting_point 51 _chemical_compound_source ? 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' '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 monoclinic _symmetry_space_group_name_H-M P2(1)/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 9.384(2) _cell_length_b 24.807(5) _cell_length_c 10.901(2) _cell_angle_alpha 90.00 _cell_angle_beta 111.90(3) _cell_angle_gamma 90.00 _cell_volume 2354.8(8) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ; 5000 quasi-centered reflections selected from the whole data were selected with the program SELECT 2.87 (Fa. STOE, 1998) ; _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.80 _exptl_crystal_size_mid 0.50 _exptl_crystal_size_min 0.30 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.118 _exptl_crystal_density_method ? _exptl_crystal_F_000 864 _exptl_absorpt_coefficient_mu 0.265 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _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 'STOE-IPDS-diffractometer' _diffrn_measurement_method ; 167 exposures were taken in the 0-200 phi range with a crystal to detector distance of 80 mm and an exposure time of 3.00 minutes. Dynamic profiles (17-21 pixels) were used for integration. ; _diffrn_standards_number ; At least 50 reflections with a I/s(I) > 6 taken from each frame were used to calculate the decay. ; _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 15039 _diffrn_reflns_av_R_equivalents 0.0579 _diffrn_reflns_av_sigmaI/netI 0.0373 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.59 _diffrn_reflns_theta_max 24.12 _reflns_number_total 3641 _reflns_number_observed 2731 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'STOE-EXPOSE 2.87 (STOE-1998)' _computing_cell_refinement 'STOE-CELL 2.87 (STOE-1998)' _computing_data_reduction 'STOE-INTEGRATE 2.87 (STOE-1998)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'SHELXTL-PLUS Siemens Ver. 5.03' _computing_publication_material 'SHELXTL-PLUS Siemens Ver. 5.03' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 6 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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. All H atoms belonging to aromatic C atoms were refined riding on their C atom with U~iso~ set to 1.2 the U~eq~ of the corresponding C atom. H atoms at methyl or methylen groups were refined riding on the corresponding C atom with U~iso~ set to 1.5 U~eq~ of the corresponding C atom. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.0580P)^2^+0.0804P] 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 ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3635 _refine_ls_number_parameters 241 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0618 _refine_ls_R_factor_obs 0.0478 _refine_ls_wR_factor_all 0.1315 _refine_ls_wR_factor_obs 0.1223 _refine_ls_goodness_of_fit_all 1.279 _refine_ls_goodness_of_fit_obs 1.437 _refine_ls_restrained_S_all 1.325 _refine_ls_restrained_S_obs 1.437 _refine_ls_shift/esd_max 0.208 _refine_ls_shift/esd_mean 0.005 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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group P1 P 0.64959(7) 0.08514(3) 0.89092(7) 0.0610(2) Uani 1 d . . P3 P 0.53934(8) 0.16563(3) 1.04318(7) 0.0655(2) Uani 1 d . . P5 P 0.30199(8) 0.14177(3) 0.76992(8) 0.0699(2) Uani 1 d . . O1 O 0.6411(2) 0.01827(7) 0.8887(2) 0.0860(6) Uani 1 d . . O3 O 0.5858(2) 0.19363(7) 0.9255(2) 0.0733(5) Uani 1 d . . O5 O 0.1680(2) 0.09488(10) 0.7416(2) 0.1009(8) Uani 1 d . . C2 C 0.6195(3) 0.09773(11) 1.0461(3) 0.0590(6) Uani 1 d . . H2 H 0.5554(31) 0.0748(12) 1.0503(29) 0.073(8) Uiso 1 d . . C4 C 0.3380(3) 0.15117(12) 0.9459(3) 0.0664(7) Uani 1 d . . H4 H 0.3249(25) 0.1199(11) 0.9782(24) 0.055(7) Uiso 1 d . . C6 C 0.4566(3) 0.09661(11) 0.7584(3) 0.0590(6) Uani 1 d . . H6 H 0.4213(28) 0.0655(12) 0.7549(26) 0.065(8) Uiso 1 d . . C11 C 0.7616(5) -0.0119(2) 0.8702(5) 0.136(2) Uani 1 d . . H11A H 0.7185(7) -0.0358(11) 0.7963(24) 0.204 Uiso 1 calc R . H11B H 0.8151(29) -0.0325(12) 0.9484(15) 0.204 Uiso 1 calc R . H11C H 0.8320(25) 0.0124(2) 0.8537(39) 0.204 Uiso 1 calc R . C31 C 0.6724(5) 0.24183(13) 0.9501(5) 0.1116(13) Uani 1 d . . H31A H 0.6204(18) 0.2680(4) 0.8835(17) 0.167 Uiso 1 calc R . H31B H 0.7720(13) 0.2346(3) 0.9481(31) 0.167 Uiso 1 calc R . H31C H 0.6836(30) 0.2557(7) 1.0355(13) 0.167 Uiso 1 calc R . C51 C 0.0269(4) 0.0992(2) 0.6284(5) 0.168(2) Uani 1 d . . H51A H -0.0583(5) 0.0992(20) 0.6569(6) 0.252 Uiso 1 calc R . H51B H 0.0180(27) 0.0692(10) 0.5704(23) 0.252 Uiso 1 calc R . H51C H 0.0270(24) 0.1322(10) 0.5823(28) 0.252 Uiso 1 calc R . C21 C 0.7630(3) 0.08952(14) 1.1753(3) 0.0854(9) Uani 1 d . . C22 C 0.7070(5) 0.0893(2) 1.2908(4) 0.1223(15) Uani 1 d . . H22A H 0.6370(31) 0.0599(8) 1.2803(18) 0.184 Uiso 1 calc R . H22B H 0.6556(34) 0.1227(6) 1.2918(20) 0.184 Uiso 1 calc R . H22C H 0.7932(6) 0.0852(14) 1.3725(5) 0.184 Uiso 1 calc R . C23 C 0.8426(5) 0.0356(2) 1.1743(5) 0.136(2) Uani 1 d . . H23A H 0.7685(9) 0.0070(3) 1.1538(36) 0.204 Uiso 1 calc R . H23B H 0.9210(29) 0.0294(7) 1.2598(11) 0.204 Uiso 1 calc R . H23C H 0.8882(36) 0.0367(6) 1.1088(25) 0.204 Uiso 1 calc R . C24 C 0.8796(4) 0.1344(2) 1.1931(4) 0.1216(15) Uani 1 d . . H24A H 0.9081(29) 0.1357(9) 1.1172(15) 0.182 Uiso 1 calc R . H24B H 0.9691(16) 0.1275(7) 1.2708(19) 0.182 Uiso 1 calc R . H24C H 0.8351(14) 0.1683(3) 1.2024(34) 0.182 Uiso 1 calc R . C41 C 0.2302(4) 0.19493(15) 0.9708(4) 0.1020(12) Uani 1 d . . C42 C 0.2454(5) 0.1904(2) 1.1150(5) 0.134(2) Uani 1 d . . H42A H 0.2212(41) 0.1543(4) 1.1323(11) 0.201 Uiso 1 calc R . H42B H 0.1758(32) 0.2151(11) 1.1312(11) 0.201 Uiso 1 calc R . H42C H 0.3488(13) 0.1989(15) 1.1720(5) 0.201 Uiso 1 calc R . C43 C 0.2747(6) 0.2512(2) 0.9418(6) 0.142(2) Uani 1 d . . H43A H 0.2684(45) 0.2529(5) 0.8519(12) 0.213 Uiso 1 calc R . H43B H 0.3778(19) 0.2591(7) 1.0004(26) 0.213 Uiso 1 calc R . H43C H 0.2058(31) 0.2772(2) 0.9547(41) 0.213 Uiso 1 calc R . C44 C 0.0616(4) 0.1840(2) 0.8850(5) 0.152(2) Uani 1 d . . H44A H 0.0355(15) 0.1478(6) 0.8999(33) 0.228 Uiso 1 calc R . H44B H 0.0465(12) 0.1883(18) 0.7934(6) 0.228 Uiso 1 calc R . H44C H -0.0027(6) 0.2089(12) 0.9077(31) 0.228 Uiso 1 calc R . C61 C 0.4740(4) 0.10675(13) 0.6230(3) 0.0856(9) Uani 1 d . . C62 C 0.5421(5) 0.1628(2) 0.6214(4) 0.1133(13) Uani 1 d . . H62A H 0.6471(12) 0.1635(4) 0.6821(23) 0.170 Uiso 1 calc R . H62B H 0.4842(22) 0.1893(2) 0.6474(30) 0.170 Uiso 1 calc R . H62C H 0.5377(33) 0.1707(5) 0.5339(8) 0.170 Uiso 1 calc R . C63 C 0.3179(5) 0.1024(2) 0.5084(4) 0.1290(15) Uani 1 d . . H63A H 0.2805(20) 0.0661(4) 0.5026(23) 0.193 Uiso 1 calc R . H63B H 0.3293(10) 0.1119(14) 0.4271(6) 0.193 Uiso 1 calc R . H63C H 0.2462(13) 0.1265(11) 0.5236(18) 0.193 Uiso 1 calc R . C64 C 0.5814(5) 0.0635(2) 0.6004(4) 0.1208(14) Uani 1 d . . H64A H 0.5465(24) 0.0283(2) 0.6123(34) 0.181 Uiso 1 calc R . H64B H 0.6842(9) 0.0689(9) 0.6628(22) 0.181 Uiso 1 calc R . H64C H 0.5799(31) 0.0668(9) 0.5122(12) 0.181 Uiso 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 P1 0.0581(4) 0.0606(4) 0.0706(5) -0.0063(3) 0.0314(3) -0.0006(3) P3 0.0781(4) 0.0624(4) 0.0620(5) -0.0118(3) 0.0332(4) -0.0039(3) P5 0.0628(4) 0.0713(5) 0.0695(5) 0.0125(4) 0.0174(3) 0.0063(3) O1 0.0894(13) 0.0577(11) 0.121(2) -0.0051(10) 0.0512(13) 0.0137(9) O3 0.0957(13) 0.0550(10) 0.0796(14) -0.0102(9) 0.0447(11) -0.0189(9) O5 0.0553(11) 0.111(2) 0.113(2) 0.0118(13) 0.0051(11) -0.0117(10) C2 0.0549(13) 0.063(2) 0.059(2) 0.0035(12) 0.0214(12) -0.0020(12) C4 0.0668(15) 0.062(2) 0.081(2) 0.0133(14) 0.0397(14) 0.0107(13) C6 0.0694(15) 0.0512(14) 0.059(2) -0.0059(11) 0.0268(13) -0.0116(12) C11 0.141(3) 0.102(3) 0.186(5) -0.010(3) 0.085(3) 0.051(3) C31 0.136(3) 0.072(2) 0.142(4) -0.018(2) 0.070(3) -0.041(2) C51 0.073(2) 0.198(6) 0.170(5) 0.019(4) -0.027(3) -0.021(3) C21 0.071(2) 0.108(2) 0.066(2) 0.014(2) 0.0127(15) 0.005(2) C22 0.115(3) 0.180(4) 0.059(2) 0.021(2) 0.017(2) 0.003(3) C23 0.118(3) 0.146(4) 0.118(4) 0.047(3) 0.014(3) 0.054(3) C24 0.076(2) 0.170(4) 0.091(3) -0.003(3) -0.001(2) -0.030(2) C41 0.109(3) 0.103(3) 0.124(3) 0.021(2) 0.079(2) 0.037(2) C42 0.163(4) 0.145(4) 0.142(4) 0.008(3) 0.113(4) 0.039(3) C43 0.195(5) 0.078(2) 0.206(5) 0.027(3) 0.136(4) 0.059(3) C44 0.089(3) 0.205(5) 0.182(5) 0.043(4) 0.075(3) 0.066(3) C61 0.119(2) 0.086(2) 0.059(2) -0.0120(15) 0.042(2) -0.020(2) C62 0.172(4) 0.102(3) 0.088(3) 0.011(2) 0.075(3) -0.033(2) C63 0.165(4) 0.150(4) 0.052(2) -0.008(2) 0.017(2) -0.022(3) C64 0.170(4) 0.126(3) 0.100(3) -0.036(2) 0.089(3) -0.015(3) _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 P1 O1 1.660(2) . ? P1 C2 1.843(3) . ? P1 C6 1.870(3) . ? P3 O3 1.653(2) . ? P3 C4 1.824(3) . ? P3 C2 1.840(3) . ? P5 O5 1.656(2) . ? P5 C4 1.834(3) . ? P5 C6 1.874(3) . ? O1 C11 1.431(4) . ? O3 C31 1.414(3) . ? O5 C51 1.438(4) . ? C2 C21 1.557(4) . ? C4 C41 1.575(4) . ? C6 C61 1.564(4) . ? C21 C24 1.522(5) . ? C21 C23 1.534(5) . ? C21 C22 1.535(5) . ? C41 C43 1.524(5) . ? C41 C44 1.533(6) . ? C41 C42 1.529(5) . ? C61 C63 1.534(5) . ? C61 C62 1.533(4) . ? C61 C64 1.553(5) . ? 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 P1 C2 99.19(12) . . ? O1 P1 C6 96.51(12) . . ? C2 P1 C6 104.34(11) . . ? O3 P3 C4 98.45(12) . . ? O3 P3 C2 100.00(11) . . ? C4 P3 C2 99.10(12) . . ? O5 P5 C4 96.61(14) . . ? O5 P5 C6 96.94(13) . . ? C4 P5 C6 107.51(12) . . ? C11 O1 P1 119.2(2) . . ? C31 O3 P3 120.5(2) . . ? C51 O5 P5 119.9(3) . . ? C21 C2 P3 110.2(2) . . ? C21 C2 P1 115.5(2) . . ? P3 C2 P1 109.93(14) . . ? C41 C4 P3 110.9(2) . . ? C41 C4 P5 112.8(2) . . ? P3 C4 P5 112.33(14) . . ? C61 C6 P1 110.0(2) . . ? C61 C6 P5 108.8(2) . . ? P1 C6 P5 126.15(14) . . ? C24 C21 C23 108.0(3) . . ? C24 C21 C22 110.4(3) . . ? C23 C21 C22 108.6(3) . . ? C24 C21 C2 111.0(3) . . ? C23 C21 C2 111.6(3) . . ? C22 C21 C2 107.3(3) . . ? C43 C41 C44 109.6(4) . . ? C43 C41 C42 110.7(4) . . ? C44 C41 C42 107.1(3) . . ? C43 C41 C4 110.6(2) . . ? C44 C41 C4 110.8(3) . . ? C42 C41 C4 107.9(3) . . ? C63 C61 C62 109.3(3) . . ? C63 C61 C64 107.6(3) . . ? C62 C61 C64 109.0(3) . . ? C63 C61 C6 110.7(3) . . ? C62 C61 C6 110.3(2) . . ? C64 C61 C6 109.9(3) . . ? _refine_diff_density_max 0.543 _refine_diff_density_min -0.223 _refine_diff_density_rms 0.043 #========================================================================== _eof # END OF CRYSTALLOGRAPHIC INFORMATION FILE