# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'J. Derek Woollins' 'Petr Kilian' 'Alexandra M. Z. Slawin' _publ_contact_author_name 'Prof J Derek Woollins' _publ_contact_author_address ; Department of Chemistry University of St Andrews St Andrews Fife KY16 9ST UNITED KINGDOM ; _publ_contact_author_email JDW3@ST-AND.AC.UK _publ_requested_journal 'Chemical Communications' _publ_section_title ; New mode of sterically imposed phosphorus hypercoordination ; data_5 _database_code_CSD 203952 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C10 H6 Cl6 O P2' _chemical_formula_sum 'C10 H6 Cl6 O P2' _chemical_formula_weight 416.79 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' Cl Cl 0.1484 0.1585 '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)/c 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 6.9585(12) _cell_length_b 16.895(3) _cell_length_c 12.498(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.921(3) _cell_angle_gamma 90.00 _cell_volume 1469.1(4) _cell_formula_units_Z 4 _cell_measurement_temperature 125(2) _cell_measurement_reflns_used 96 _cell_measurement_theta_min 12 _cell_measurement_theta_max 168 _exptl_crystal_description prism _exptl_crystal_colour yellow _exptl_crystal_size_max .1 _exptl_crystal_size_mid .1 _exptl_crystal_size_min .05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.884 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 824 _exptl_absorpt_coefficient_mu 1.372 _exptl_absorpt_correction_type MULTISCAN _exptl_absorpt_correction_T_min 0.861225 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 125(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 0.9 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6089 _diffrn_reflns_av_R_equivalents 0.0283 _diffrn_reflns_av_sigmaI/netI 0.0278 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.03 _diffrn_reflns_theta_max 23.28 _reflns_number_total 2062 _reflns_number_gt 1753 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0339P)^2^+0.0000P] 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 SHELXL _refine_ls_extinction_coef 0.0009(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2062 _refine_ls_number_parameters 173 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0316 _refine_ls_R_factor_gt 0.0239 _refine_ls_wR_factor_ref 0.0549 _refine_ls_wR_factor_gt 0.0528 _refine_ls_goodness_of_fit_ref 0.971 _refine_ls_restrained_S_all 0.971 _refine_ls_shift/su_max 0.001 _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 Cl1 Cl 0.58584(9) 0.41344(4) 0.14696(5) 0.03005(19) Uani 1 1 d . . . Cl2 Cl 0.16879(10) 0.42148(4) 0.05941(5) 0.03234(19) Uani 1 1 d . . . P1 P 0.33620(9) 0.46519(4) 0.17383(5) 0.01832(17) Uani 1 1 d . . . O1 O 0.3710(2) 0.55277(10) 0.16370(12) 0.0208(4) Uani 1 1 d . . . C1 C 0.2563(3) 0.44082(14) 0.30169(19) 0.0173(5) Uani 1 1 d . . . C2 C 0.2257(3) 0.36238(14) 0.3247(2) 0.0196(6) Uani 1 1 d . . . H2A H 0.2249 0.3245 0.2684 0.023 Uiso 1 1 calc R . . C3 C 0.1957(3) 0.33758(15) 0.4296(2) 0.0213(6) Uani 1 1 d . . . H3A H 0.1675 0.2838 0.4449 0.026 Uiso 1 1 calc R . . C4 C 0.2079(3) 0.39244(14) 0.5100(2) 0.0195(6) Uani 1 1 d . . . H4A H 0.1930 0.3754 0.5818 0.023 Uiso 1 1 calc R . . C5 C 0.2419(3) 0.47352(14) 0.48996(18) 0.0162(5) Uani 1 1 d . . . C6 C 0.2611(3) 0.52757(15) 0.57651(19) 0.0193(6) Uani 1 1 d . . . H6A H 0.2479 0.5092 0.6479 0.023 Uiso 1 1 calc R . . C7 C 0.2982(3) 0.60519(14) 0.5580(2) 0.0187(6) Uani 1 1 d . . . H7A H 0.3203 0.6402 0.6165 0.022 Uiso 1 1 calc R . . C8 C 0.3040(3) 0.63387(15) 0.45285(19) 0.0187(6) Uani 1 1 d . . . H8A H 0.3276 0.6886 0.4417 0.022 Uiso 1 1 calc R . . C9 C 0.2767(3) 0.58531(14) 0.36482(18) 0.0153(5) Uani 1 1 d . . . C10 C 0.2579(3) 0.50176(14) 0.38239(18) 0.0145(5) Uani 1 1 d . . . P9 P 0.24846(8) 0.63519(4) 0.23074(5) 0.01590(17) Uani 1 1 d . . . Cl3 Cl 0.52396(8) 0.68992(4) 0.24345(5) 0.02573(18) Uani 1 1 d . . . Cl4 Cl 0.21716(9) 0.68199(4) 0.07133(5) 0.02434(17) Uani 1 1 d . . . Cl5 Cl -0.02650(8) 0.57641(4) 0.20477(5) 0.02034(16) Uani 1 1 d . . . Cl6 Cl 0.10405(9) 0.73733(4) 0.29071(5) 0.02348(17) 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 Cl1 0.0306(4) 0.0323(4) 0.0275(4) -0.0031(3) 0.0069(3) 0.0130(3) Cl2 0.0432(4) 0.0304(4) 0.0230(4) -0.0069(3) -0.0130(3) 0.0019(3) P1 0.0211(4) 0.0178(4) 0.0161(4) -0.0018(3) -0.0012(3) 0.0025(3) O1 0.0224(9) 0.0221(10) 0.0180(9) 0.0003(7) 0.0028(7) 0.0041(7) C1 0.0142(12) 0.0191(14) 0.0184(13) -0.0002(10) -0.0032(10) -0.0006(10) C2 0.0151(12) 0.0194(14) 0.0241(14) -0.0026(11) -0.0043(10) 0.0008(11) C3 0.0175(12) 0.0155(14) 0.0307(15) 0.0053(11) -0.0031(11) -0.0032(11) C4 0.0116(12) 0.0236(15) 0.0233(14) 0.0077(11) -0.0002(11) 0.0009(10) C5 0.0088(12) 0.0224(14) 0.0175(13) 0.0020(11) -0.0010(10) 0.0005(10) C6 0.0134(12) 0.0294(17) 0.0152(13) 0.0016(11) 0.0005(10) 0.0017(11) C7 0.0162(12) 0.0209(15) 0.0190(14) -0.0043(10) -0.0021(10) 0.0028(11) C8 0.0135(12) 0.0200(14) 0.0225(14) -0.0009(11) -0.0012(10) 0.0010(11) C9 0.0107(11) 0.0167(13) 0.0184(13) 0.0000(10) 0.0019(10) 0.0017(10) C10 0.0070(11) 0.0164(14) 0.0202(14) 0.0013(10) 0.0003(10) 0.0016(10) P9 0.0169(3) 0.0144(4) 0.0165(3) 0.0010(3) 0.0013(3) 0.0016(3) Cl3 0.0209(3) 0.0249(4) 0.0315(4) 0.0031(3) 0.0027(3) -0.0063(3) Cl4 0.0322(4) 0.0225(4) 0.0184(3) 0.0064(3) 0.0032(3) 0.0025(3) Cl5 0.0167(3) 0.0254(4) 0.0189(3) 0.0027(2) -0.0019(2) -0.0003(3) Cl6 0.0283(3) 0.0188(4) 0.0234(4) -0.0001(3) -0.0005(3) 0.0086(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 Cl1 P1 1.9783(9) . ? Cl2 P1 1.9733(9) . ? P1 O1 1.5049(18) . ? P1 C1 1.750(2) . ? O1 P9 1.8415(17) . ? C1 C2 1.373(3) . ? C1 C10 1.441(3) . ? C2 C3 1.395(3) . ? C3 C4 1.369(3) . ? C4 C5 1.413(3) . ? C5 C6 1.420(3) . ? C5 C10 1.433(3) . ? C6 C7 1.357(3) . ? C7 C8 1.402(3) . ? C8 C9 1.383(3) . ? C9 C10 1.435(3) . ? C9 P9 1.883(2) . ? P9 Cl3 2.1320(9) . ? P9 Cl6 2.1385(9) . ? P9 Cl4 2.1513(9) . ? P9 Cl5 2.1754(9) . ? 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 C1 111.24(10) . . ? O1 P1 Cl2 113.63(7) . . ? C1 P1 Cl2 112.41(8) . . ? O1 P1 Cl1 106.10(7) . . ? C1 P1 Cl1 110.12(8) . . ? Cl2 P1 Cl1 102.79(4) . . ? P1 O1 P9 128.97(10) . . ? C2 C1 C10 122.9(2) . . ? C2 C1 P1 118.08(18) . . ? C10 C1 P1 118.17(18) . . ? C1 C2 C3 120.8(2) . . ? C4 C3 C2 118.6(2) . . ? C3 C4 C5 122.3(2) . . ? C4 C5 C6 120.1(2) . . ? C4 C5 C10 120.3(2) . . ? C6 C5 C10 119.5(2) . . ? C7 C6 C5 120.5(2) . . ? C6 C7 C8 120.1(2) . . ? C9 C8 C7 122.3(2) . . ? C8 C9 C10 118.3(2) . . ? C8 C9 P9 116.96(18) . . ? C10 C9 P9 124.60(17) . . ? C5 C10 C9 118.7(2) . . ? C5 C10 C1 114.8(2) . . ? C9 C10 C1 126.5(2) . . ? O1 P9 C9 91.37(9) . . ? O1 P9 Cl3 86.53(6) . . ? C9 P9 Cl3 92.69(7) . . ? O1 P9 Cl6 173.33(6) . . ? C9 P9 Cl6 95.29(8) . . ? Cl3 P9 Cl6 92.92(4) . . ? O1 P9 Cl4 84.10(6) . . ? C9 P9 Cl4 174.96(8) . . ? Cl3 P9 Cl4 89.26(3) . . ? Cl6 P9 Cl4 89.25(3) . . ? O1 P9 Cl5 89.96(6) . . ? C9 P9 Cl5 90.43(7) . . ? Cl3 P9 Cl5 175.36(4) . . ? Cl6 P9 Cl5 90.20(3) . . ? Cl4 P9 Cl5 87.35(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 C1 P1 O1 P9 -30.92(16) . . . . ? Cl2 P1 O1 P9 97.14(12) . . . . ? Cl1 P1 O1 P9 -150.67(10) . . . . ? O1 P1 C1 C2 -177.41(17) . . . . ? Cl2 P1 C1 C2 53.9(2) . . . . ? Cl1 P1 C1 C2 -60.07(19) . . . . ? O1 P1 C1 C10 -7.9(2) . . . . ? Cl2 P1 C1 C10 -136.62(15) . . . . ? Cl1 P1 C1 C10 109.43(17) . . . . ? C10 C1 C2 C3 -0.6(3) . . . . ? P1 C1 C2 C3 168.41(18) . . . . ? C1 C2 C3 C4 -3.5(3) . . . . ? C2 C3 C4 C5 2.6(3) . . . . ? C3 C4 C5 C6 -177.4(2) . . . . ? C3 C4 C5 C10 2.4(3) . . . . ? C4 C5 C6 C7 178.4(2) . . . . ? C10 C5 C6 C7 -1.4(3) . . . . ? C5 C6 C7 C8 4.7(3) . . . . ? C6 C7 C8 C9 -1.3(3) . . . . ? C7 C8 C9 C10 -5.3(3) . . . . ? C7 C8 C9 P9 170.24(17) . . . . ? C4 C5 C10 C9 175.0(2) . . . . ? C6 C5 C10 C9 -5.2(3) . . . . ? C4 C5 C10 C1 -6.0(3) . . . . ? C6 C5 C10 C1 173.8(2) . . . . ? C8 C9 C10 C5 8.4(3) . . . . ? P9 C9 C10 C5 -166.80(16) . . . . ? C8 C9 C10 C1 -170.5(2) . . . . ? P9 C9 C10 C1 14.4(3) . . . . ? C2 C1 C10 C5 5.3(3) . . . . ? P1 C1 C10 C5 -163.71(16) . . . . ? C2 C1 C10 C9 -175.9(2) . . . . ? P1 C1 C10 C9 15.2(3) . . . . ? P1 O1 P9 C9 48.47(14) . . . . ? P1 O1 P9 Cl3 141.08(12) . . . . ? P1 O1 P9 Cl6 -133.4(5) . . . . ? P1 O1 P9 Cl4 -129.30(13) . . . . ? P1 O1 P9 Cl5 -41.96(13) . . . . ? C8 C9 P9 O1 146.26(17) . . . . ? C10 C9 P9 O1 -38.53(19) . . . . ? C8 C9 P9 Cl3 59.67(17) . . . . ? C10 C9 P9 Cl3 -125.12(18) . . . . ? C8 C9 P9 Cl6 -33.52(18) . . . . ? C10 C9 P9 Cl6 141.69(18) . . . . ? C8 C9 P9 Cl4 172.3(7) . . . . ? C10 C9 P9 Cl4 -12.4(10) . . . . ? C8 C9 P9 Cl5 -123.76(17) . . . . ? C10 C9 P9 Cl5 51.45(18) . . . . ? _diffrn_measured_fraction_theta_max 0.974 _diffrn_reflns_theta_full 23.28 _diffrn_measured_fraction_theta_full 0.974 _refine_diff_density_max 0.304 _refine_diff_density_min -0.303 _refine_diff_density_rms 0.059