Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2004 data_global _journal_coden_Cambridge 222 loop_ _publ_author_name 'Dominic S. Wright' 'Felipe Garcia' 'Simon M. Humphrey' 'Richard A. Kowenicki' 'M. McPartlin' _publ_contact_author_name 'Dr Dominic S Wright' _publ_contact_author_address ; Department of Chemistry Cambridge University (U.K.) Lensfield Road Cambridge Cambridgeshire CB2 1EW UNITED KINGDOM ; _publ_contact_author_email DSW1000@CUS.CAM.AC.UK _publ_requested_journal 'Dalton Transactions' _publ_section_title ; Selective Formation of the [PhP(H)-PPh]- Anion in the Reaction of PhPHLi with MeAlCl2; Synthesis and Structure of the Unusual Tetramer [{PhP(H)-PPh}Li.thf]4 ; data_mw0343 _database_code_depnum_ccdc_archive 'CCDC 231520' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C64 H76 Li4 O4 P8' _chemical_formula_weight 1184.77 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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Li Li -0.0003 0.0001 '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' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M P-42(1)c 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' '-y, x, -z' 'y+1/2, x+1/2, z+1/2' 'y, -x, -z' '-y+1/2, -x+1/2, z+1/2' _cell_length_a 20.0636(6) _cell_length_b 20.0636(6) _cell_length_c 8.9176(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3589.76(17) _cell_formula_units_Z 2 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 6725 _cell_measurement_theta_min 1.02 _cell_measurement_theta_max 20.60 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.21 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.096 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1248 _exptl_absorpt_coefficient_mu 0.234 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.889 _exptl_absorpt_correction_T_max 0.960 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD' _diffrn_measurement_method 'Thin slice \w and \f scans' _diffrn_standards_number 0 _diffrn_reflns_number 7923 _diffrn_reflns_av_R_equivalents 0.0381 _diffrn_reflns_av_sigmaI/netI 0.0301 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_limit_l_max 8 _diffrn_reflns_theta_min 3.66 _diffrn_reflns_theta_max 20.59 _reflns_number_total 1801 _reflns_number_gt 1679 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Nonius B.V. 1998)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction ; HKL Denzo and Scalepack (Otwinowski & Minor 1997) ; _computing_structure_solution 'SIR-92 (Altomare et al. 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick 1997)' _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^)+(0.1387P)^2^+3.8370P] 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 mixed _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 0.0(3) _refine_ls_number_reflns 1801 _refine_ls_number_parameters 182 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0626 _refine_ls_R_factor_gt 0.0570 _refine_ls_wR_factor_ref 0.1885 _refine_ls_wR_factor_gt 0.1800 _refine_ls_goodness_of_fit_ref 1.071 _refine_ls_restrained_S_all 1.071 _refine_ls_shift/su_max 0.002 _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 P1 P 0.93828(8) 0.89611(8) 0.8790(2) 0.0426(6) Uani 1 1 d . . . P2 P 0.90215(9) 0.97599(8) 0.7420(2) 0.0437(6) Uani 1 1 d . . . H2P H 0.9127 0.9550 0.6053 0.07(2) Uiso 1 1 d . . . Li1 Li 0.9079(5) 0.9360(5) 1.1430(13) 0.047(3) Uani 1 1 d . . . O1T O 0.8298(2) 0.8932(2) 1.2293(6) 0.0515(13) Uani 1 1 d . . . C2T C 0.7836(5) 0.9278(4) 1.3156(11) 0.082(3) Uani 1 1 d . . . H2T1 H 0.7668 0.9665 1.2583 0.098 Uiso 1 1 calc R . . H2T2 H 0.8055 0.9447 1.4075 0.098 Uiso 1 1 calc R . . C3T C 0.7291(5) 0.8857(5) 1.3562(16) 0.102(4) Uani 1 1 d . . . H3T1 H 0.6861 0.9086 1.3378 0.122 Uiso 1 1 calc R . . H3T2 H 0.7317 0.8734 1.4635 0.122 Uiso 1 1 calc R . . C4T C 0.7351(4) 0.8253(4) 1.2597(13) 0.079(3) Uani 1 1 d . . . H4T1 H 0.7247 0.7844 1.3174 0.095 Uiso 1 1 calc R . . H4T2 H 0.7046 0.8281 1.1726 0.095 Uiso 1 1 calc R . . C5T C 0.8069(4) 0.8251(3) 1.2092(9) 0.056(2) Uani 1 1 d . . . H5T1 H 0.8336 0.7940 1.2708 0.067 Uiso 1 1 calc R . . H5T2 H 0.8103 0.8117 1.1027 0.067 Uiso 1 1 calc R . . C11 C 0.9024(3) 0.8180(3) 0.8091(8) 0.0375(16) Uani 1 1 d . . . C12 C 0.8672(3) 0.8100(3) 0.6788(8) 0.0420(18) Uani 1 1 d . . . H12 H 0.8587 0.8477 0.6172 0.050 Uiso 1 1 calc R . . C13 C 0.8432(4) 0.7470(3) 0.6342(8) 0.0498(19) Uani 1 1 d . . . H13 H 0.8190 0.7428 0.5431 0.060 Uiso 1 1 calc R . . C14 C 0.8545(4) 0.6918(3) 0.7209(8) 0.0522(19) Uani 1 1 d . . . H14 H 0.8383 0.6494 0.6909 0.063 Uiso 1 1 calc R . . C15 C 0.8896(4) 0.6991(3) 0.8524(8) 0.0491(18) Uani 1 1 d . . . H15 H 0.8983 0.6612 0.9132 0.059 Uiso 1 1 calc R . . C16 C 0.9123(3) 0.7610(3) 0.8968(8) 0.0428(17) Uani 1 1 d . . . H16 H 0.9353 0.7650 0.9895 0.051 Uiso 1 1 calc R . . C21 C 0.8109(3) 0.9752(3) 0.7422(7) 0.0417(17) Uani 1 1 d . . . C22 C 0.7773(4) 1.0208(3) 0.6455(8) 0.0517(18) Uani 1 1 d . . . H22 H 0.8027 1.0476 0.5788 0.062 Uiso 1 1 calc R . . C23 C 0.7108(4) 1.0267(4) 0.6464(10) 0.066(2) Uani 1 1 d . . . H23 H 0.6895 1.0578 0.5817 0.080 Uiso 1 1 calc R . . C24 C 0.6721(4) 0.9866(4) 0.7442(12) 0.075(3) Uani 1 1 d . . . H24 H 0.6248 0.9889 0.7428 0.090 Uiso 1 1 calc R . . C25 C 0.7045(4) 0.9441(4) 0.8413(10) 0.063(2) Uani 1 1 d . . . H25 H 0.6794 0.9180 0.9099 0.076 Uiso 1 1 calc R . . C26 C 0.7721(3) 0.9391(3) 0.8399(8) 0.0458(18) Uani 1 1 d . . . H26 H 0.7932 0.9097 0.9085 0.055 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 P1 0.0337(10) 0.0364(11) 0.0577(12) -0.0029(9) -0.0038(8) -0.0017(7) P2 0.0420(11) 0.0362(10) 0.0529(10) -0.0006(9) 0.0017(9) -0.0064(8) Li1 0.052(7) 0.026(5) 0.062(7) 0.000(5) 0.006(6) -0.002(5) O1T 0.042(3) 0.038(3) 0.074(3) -0.006(3) 0.010(3) -0.008(2) C2T 0.100(7) 0.054(5) 0.092(6) -0.017(5) 0.046(5) -0.009(5) C3T 0.070(6) 0.076(6) 0.160(10) -0.039(7) 0.052(7) -0.018(5) C4T 0.059(5) 0.048(5) 0.130(8) -0.021(6) 0.023(6) -0.014(4) C5T 0.049(5) 0.040(4) 0.078(5) 0.000(4) 0.010(4) -0.005(4) C11 0.027(4) 0.031(4) 0.054(4) -0.006(3) 0.002(3) 0.004(3) C12 0.043(4) 0.033(4) 0.049(4) 0.002(3) 0.002(4) -0.001(3) C13 0.060(5) 0.038(4) 0.051(4) -0.006(4) -0.002(4) -0.008(3) C14 0.067(5) 0.033(4) 0.056(5) -0.012(4) 0.013(4) -0.010(3) C15 0.059(5) 0.037(4) 0.051(5) 0.007(3) 0.011(4) 0.004(3) C16 0.048(4) 0.038(4) 0.043(4) -0.001(4) 0.004(3) 0.002(3) C21 0.050(4) 0.029(3) 0.047(4) -0.012(4) -0.005(4) 0.000(3) C22 0.051(5) 0.044(4) 0.060(4) -0.001(4) -0.010(4) 0.007(4) C23 0.073(7) 0.039(4) 0.088(6) -0.003(4) -0.019(5) 0.010(4) C24 0.031(4) 0.066(6) 0.127(8) -0.026(6) -0.025(5) 0.015(4) C25 0.056(6) 0.036(4) 0.098(6) -0.008(4) 0.001(5) -0.002(4) C26 0.039(5) 0.028(4) 0.070(5) -0.001(4) -0.005(4) 0.000(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 C11 1.833(6) . ? P1 P2 2.142(2) . ? P1 Li1 2.542(10) 5_757 ? P1 Li1 2.560(11) . ? P2 C21 1.832(7) . ? P2 Li1 2.634(11) 7_577 ? Li1 O1T 1.945(11) . ? Li1 P1 2.542(10) 7_577 ? Li1 P2 2.634(11) 5_757 ? O1T C2T 1.390(9) . ? O1T C5T 1.453(8) . ? C2T C3T 1.428(12) . ? C3T C4T 1.492(13) . ? C4T C5T 1.509(11) . ? C11 C12 1.370(10) . ? C11 C16 1.400(9) . ? C12 C13 1.410(10) . ? C13 C14 1.370(10) . ? C14 C15 1.376(10) . ? C15 C16 1.381(10) . ? C21 C26 1.374(10) . ? C21 C22 1.426(9) . ? C22 C23 1.341(11) . ? C23 C24 1.418(11) . ? C24 C25 1.379(12) . ? C25 C26 1.360(10) . ? 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 C11 P1 P2 108.2(2) . . ? C11 P1 Li1 116.3(3) . 5_757 ? P2 P1 Li1 102.8(3) . 5_757 ? C11 P1 Li1 119.1(3) . . ? P2 P1 Li1 102.1(2) . . ? Li1 P1 Li1 106.2(4) 5_757 . ? C21 P2 P1 109.4(2) . . ? C21 P2 Li1 105.3(3) . 7_577 ? P1 P2 Li1 110.6(3) . 7_577 ? O1T Li1 P1 113.2(5) . 7_577 ? O1T Li1 P1 114.7(5) . . ? P1 Li1 P1 105.1(4) 7_577 . ? O1T Li1 P2 116.4(5) . 5_757 ? P1 Li1 P2 111.6(4) 7_577 5_757 ? P1 Li1 P2 93.8(3) . 5_757 ? C2T O1T C5T 109.0(6) . . ? C2T O1T Li1 122.5(6) . . ? C5T O1T Li1 128.4(5) . . ? O1T C2T C3T 110.9(7) . . ? C2T C3T C4T 105.8(8) . . ? C5T C4T C3T 104.5(7) . . ? O1T C5T C4T 105.3(6) . . ? C12 C11 C16 116.8(6) . . ? C12 C11 P1 126.2(5) . . ? C16 C11 P1 116.9(5) . . ? C11 C12 C13 121.4(6) . . ? C14 C13 C12 120.6(7) . . ? C15 C14 C13 118.7(6) . . ? C14 C15 C16 120.6(7) . . ? C11 C16 C15 121.9(6) . . ? C26 C21 C22 117.1(6) . . ? C26 C21 P2 124.8(5) . . ? C22 C21 P2 117.8(5) . . ? C23 C22 C21 121.6(8) . . ? C22 C23 C24 119.9(7) . . ? C25 C24 C23 118.6(7) . . ? C24 C25 C26 120.7(8) . . ? C21 C26 C25 122.1(7) . . ? _diffrn_measured_fraction_theta_max 0.976 _diffrn_reflns_theta_full 20.59 _diffrn_measured_fraction_theta_full 0.976 _refine_diff_density_max 0.794 _refine_diff_density_min -0.468 _refine_diff_density_rms 0.079