# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2009 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Alan Brisdon' _publ_contact_author_email ALAN.BRISDON@MANCHESTER.AC.UK _publ_section_title ; A Generic Route to Fluoroalkyl-containing Phosphanes ; loop_ _publ_author_name 'Alan Brisdon' 'Christopher J Herbert' data_new _database_code_depnum_ccdc_archive 'CCDC 714473' _audit_creation_date 2007-08-06T16:40:30-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.3 _audit_conform_dict_location ftp://ftp.iucr.org/pub/cif_core.dic #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; diphenylperfluoroisopropylphosphine ; _chemical_formula_moiety 'C15 H10 F7 P1' _chemical_formula_sum 'C15 H10 F7 P' _chemical_formula_weight 354.12 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/c 1' _symmetry_space_group_name_Hall '-P 2ybc' _symmetry_Int_Tables_number 14 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 8.9091(2) _cell_length_b 26.2430(6) _cell_length_c 6.39280(10) _cell_angle_alpha 90 _cell_angle_beta 99.4060(10) _cell_angle_gamma 90 _cell_volume 1474.55(5) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 3321 _cell_measurement_theta_min 2 _cell_measurement_theta_max 25 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.15 _exptl_crystal_density_diffrn 1.595 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 712 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.257 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_absorpt_correction_T_min 0.905 _exptl_absorpt_correction_T_max 0.961 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_source 'Enraf Nonius FR590' _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_detector 'CCD plate' _diffrn_detector_area_resol_mean 9 _diffrn_orient_matrix_type 'by Nonius Collect from scalepack cell' _diffrn_orient_matrix_ub_11 0.502473E-1 _diffrn_orient_matrix_ub_12 -0.223714E-1 _diffrn_orient_matrix_ub_13 0.89505E-1 _diffrn_orient_matrix_ub_21 -0.166698E-1 _diffrn_orient_matrix_ub_22 0.289148E-1 _diffrn_orient_matrix_ub_23 0.701928E-1 _diffrn_orient_matrix_ub_31 -0.149459 _diffrn_orient_matrix_ub_32 -0.107462E-1 _diffrn_orient_matrix_ub_33 0.25366E-2 _diffrn_measurement_device '95mm CCD camera on \k-goniostat' _diffrn_measurement_device_type KappaCCD _diffrn_measurement_method 'CCD rotation images, thick slices' _diffrn_reflns_av_R_equivalents 0.047 _diffrn_reflns_av_unetI/netI 0.0289 _diffrn_reflns_number 2736 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -31 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 7 _diffrn_reflns_theta_min 3.1 _diffrn_reflns_theta_max 25.5 _diffrn_reflns_theta_full 25.5 _diffrn_measured_fraction_theta_full 0.997 _diffrn_measured_fraction_theta_max 0.997 _reflns_number_total 2736 _reflns_number_gt 1979 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Collect (Nonius BV, 1997-2000)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (Otwinowski & Minor 1997)' _computing_structure_solution 'SIR92 (Giacovazzo et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _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^)+(0.1369P)^2^+2.2413P] 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 constr _refine_ls_extinction_method none _refine_ls_number_reflns 2736 _refine_ls_number_parameters 208 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1047 _refine_ls_R_factor_gt 0.0796 _refine_ls_wR_factor_ref 0.2488 _refine_ls_wR_factor_gt 0.2181 _refine_ls_goodness_of_fit_ref 1.082 _refine_ls_restrained_S_all 1.082 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.916 _refine_diff_density_min -0.418 _refine_diff_density_rms 0.087 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.003 0.002 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.017 0.01 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.102 0.094 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 0.1257(5) 0.35549(17) 0.5908(7) 0.0456(10) Uani 1 1 d . . . C2 C -0.0076(5) 0.39008(18) 0.4954(8) 0.0540(11) Uani 1 1 d . . . C3 C 0.1262(5) 0.30682(19) 0.4589(8) 0.0540(11) Uani 1 1 d . . . C4 C 0.2897(5) 0.44611(17) 0.7649(7) 0.0495(10) Uani 1 1 d . . . C5 C 0.3440(5) 0.49088(19) 0.6864(9) 0.0618(13) Uani 1 1 d . . . H5 H 0.3821 0.4905 0.5593 0.074 Uiso 1 1 calc R . . C6 C 0.3409(6) 0.5363(2) 0.7999(12) 0.0780(18) Uani 1 1 d . . . H6 H 0.3798 0.566 0.7501 0.094 Uiso 1 1 calc R . . C7 C 0.2807(7) 0.5373(2) 0.9842(11) 0.0778(18) Uani 1 1 d . . . H7 H 0.2771 0.5678 1.0576 0.093 Uiso 1 1 calc R . . C8 C 0.2255(7) 0.4930(2) 1.0604(9) 0.0723(15) Uani 1 1 d . . . H8 H 0.1831 0.4936 1.1841 0.087 Uiso 1 1 calc R . . C9 C 0.2335(6) 0.4480(2) 0.9524(8) 0.0626(13) Uani 1 1 d . . . H9 H 0.2 0.4181 1.0078 0.075 Uiso 1 1 calc R . . C10 C 0.4465(5) 0.35042(17) 0.7883(7) 0.0467(10) Uani 1 1 d . . . C11 C 0.5864(5) 0.34249(17) 0.7232(8) 0.0519(11) Uani 1 1 d . . . H11 H 0.6019 0.3542 0.5912 0.062 Uiso 1 1 calc R . . C12 C 0.7019(5) 0.31747(18) 0.8525(9) 0.0586(12) Uani 1 1 d . . . H12 H 0.796 0.3134 0.8093 0.07 Uiso 1 1 calc R . . C13 C 0.6789(5) 0.29841(18) 1.0456(8) 0.0577(12) Uani 1 1 d . . . H13 H 0.7568 0.2812 1.1318 0.069 Uiso 1 1 calc R . . C14 C 0.5405(6) 0.3050(2) 1.1104(8) 0.0593(12) Uani 1 1 d . . . H14 H 0.5243 0.2912 1.2389 0.071 Uiso 1 1 calc R . . C15 C 0.4251(5) 0.3318(2) 0.9865(7) 0.0572(12) Uani 1 1 d . . . H15 H 0.3335 0.3374 1.0347 0.069 Uiso 1 1 calc R . . F1 F 0.0917(3) 0.33912(11) 0.7862(4) 0.0570(7) Uani 1 1 d . . . F2 F -0.1348(3) 0.36383(11) 0.4325(5) 0.0640(8) Uani 1 1 d . . . F3 F -0.0430(4) 0.42178(13) 0.6444(6) 0.0855(11) Uani 1 1 d . . . F4 F 0.0244(4) 0.41734(15) 0.3395(6) 0.0903(12) Uani 1 1 d . . . F5 F 0.0097(3) 0.27638(11) 0.4759(5) 0.0663(8) Uani 1 1 d . . . F6 F 0.2518(4) 0.28030(12) 0.5112(6) 0.0830(11) Uani 1 1 d . . . F7 F 0.1120(4) 0.31895(13) 0.2512(5) 0.0754(9) Uani 1 1 d . . . P1 P 0.31488(13) 0.38980(5) 0.60606(18) 0.0495(4) 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 C1 0.043(2) 0.052(2) 0.041(2) 0.0001(18) 0.0055(17) 0.0017(18) C2 0.043(2) 0.054(3) 0.064(3) 0.000(2) 0.005(2) -0.0006(19) C3 0.050(2) 0.059(3) 0.053(3) -0.001(2) 0.008(2) -0.003(2) C4 0.040(2) 0.053(2) 0.052(3) 0.006(2) -0.0046(18) -0.0041(18) C5 0.046(3) 0.060(3) 0.077(3) 0.017(3) 0.003(2) 0.000(2) C6 0.055(3) 0.049(3) 0.122(5) 0.024(3) -0.009(3) -0.003(2) C7 0.065(3) 0.055(3) 0.101(5) -0.015(3) -0.024(3) 0.002(3) C8 0.084(4) 0.063(3) 0.065(3) -0.009(3) -0.002(3) 0.002(3) C9 0.070(3) 0.054(3) 0.060(3) 0.000(2) 0.002(2) -0.012(2) C10 0.039(2) 0.050(2) 0.050(2) -0.0027(19) 0.0021(17) -0.0027(17) C11 0.048(2) 0.053(2) 0.056(3) -0.004(2) 0.013(2) -0.0079(19) C12 0.040(2) 0.056(3) 0.080(3) -0.008(2) 0.011(2) -0.003(2) C13 0.049(3) 0.051(3) 0.067(3) -0.005(2) -0.007(2) 0.001(2) C14 0.056(3) 0.073(3) 0.047(3) 0.003(2) 0.000(2) 0.000(2) C15 0.045(2) 0.075(3) 0.052(3) -0.001(2) 0.011(2) 0.001(2) F1 0.0504(14) 0.0808(18) 0.0409(13) 0.0050(12) 0.0103(11) -0.0151(13) F2 0.0404(14) 0.0767(19) 0.0714(18) -0.0009(14) -0.0014(12) -0.0044(12) F3 0.0609(19) 0.090(2) 0.101(2) -0.033(2) -0.0017(17) 0.0185(16) F4 0.0583(18) 0.108(3) 0.103(3) 0.056(2) 0.0078(17) 0.0113(17) F5 0.0618(17) 0.0609(17) 0.0726(19) -0.0012(14) 0.0006(14) -0.0127(13) F6 0.0590(18) 0.0650(19) 0.117(3) -0.0235(18) -0.0098(17) 0.0141(14) F7 0.083(2) 0.091(2) 0.0535(17) -0.0166(15) 0.0150(15) -0.0078(17) P1 0.0418(6) 0.0599(8) 0.0471(7) 0.0049(5) 0.0084(5) -0.0041(5) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 F1 1.400(5) . ? C1 C3 1.531(7) . ? C1 C2 1.539(6) . ? C1 P1 1.900(4) . ? C2 F4 1.296(6) . ? C2 F2 1.331(5) . ? C2 F3 1.341(6) . ? C3 F6 1.314(6) . ? C3 F5 1.328(5) . ? C3 F7 1.351(6) . ? C4 C9 1.374(7) . ? C4 C5 1.395(6) . ? C4 P1 1.827(5) . ? C5 C6 1.398(8) . ? C5 H5 0.93 . ? C6 C7 1.372(9) . ? C6 H6 0.93 . ? C7 C8 1.383(8) . ? C7 H7 0.93 . ? C8 C9 1.376(7) . ? C8 H8 0.93 . ? C9 H9 0.93 . ? C10 C11 1.392(6) . ? C10 C15 1.400(6) . ? C10 P1 1.831(4) . ? C11 C12 1.377(7) . ? C11 H11 0.93 . ? C12 C13 1.378(7) . ? C12 H12 0.93 . ? C13 C14 1.374(7) . ? C13 H13 0.93 . ? C14 C15 1.383(7) . ? C14 H14 0.93 . ? C15 H15 0.93 . ? 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 F1 C1 C3 104.8(4) . . ? F1 C1 C2 105.6(3) . . ? C3 C1 C2 110.2(4) . . ? F1 C1 P1 114.8(3) . . ? C3 C1 P1 109.9(3) . . ? C2 C1 P1 111.2(3) . . ? F4 C2 F2 109.7(4) . . ? F4 C2 F3 108.1(4) . . ? F2 C2 F3 104.4(4) . . ? F4 C2 C1 112.2(4) . . ? F2 C2 C1 112.2(4) . . ? F3 C2 C1 109.9(4) . . ? F6 C3 F5 107.8(4) . . ? F6 C3 F7 108.3(4) . . ? F5 C3 F7 105.9(4) . . ? F6 C3 C1 112.4(4) . . ? F5 C3 C1 112.6(4) . . ? F7 C3 C1 109.7(4) . . ? C9 C4 C5 118.8(5) . . ? C9 C4 P1 127.6(4) . . ? C5 C4 P1 113.6(4) . . ? C4 C5 C6 119.6(5) . . ? C4 C5 H5 120.2 . . ? C6 C5 H5 120.2 . . ? C7 C6 C5 120.4(5) . . ? C7 C6 H6 119.8 . . ? C5 C6 H6 119.8 . . ? C6 C7 C8 119.8(5) . . ? C6 C7 H7 120.1 . . ? C8 C7 H7 120.1 . . ? C9 C8 C7 119.6(6) . . ? C9 C8 H8 120.2 . . ? C7 C8 H8 120.2 . . ? C4 C9 C8 121.7(5) . . ? C4 C9 H9 119.1 . . ? C8 C9 H9 119.1 . . ? C11 C10 C15 118.6(4) . . ? C11 C10 P1 113.9(3) . . ? C15 C10 P1 127.2(3) . . ? C12 C11 C10 120.6(5) . . ? C12 C11 H11 119.7 . . ? C10 C11 H11 119.7 . . ? C11 C12 C13 120.3(4) . . ? C11 C12 H12 119.8 . . ? C13 C12 H12 119.8 . . ? C14 C13 C12 119.8(5) . . ? C14 C13 H13 120.1 . . ? C12 C13 H13 120.1 . . ? C13 C14 C15 120.7(5) . . ? C13 C14 H14 119.6 . . ? C15 C14 H14 119.6 . . ? C14 C15 C10 119.8(4) . . ? C14 C15 H15 120.1 . . ? C10 C15 H15 120.1 . . ? C4 P1 C10 103.11(19) . . ? C4 P1 C1 102.90(19) . . ? C10 P1 C1 103.64(19) . . ? _chemical_name_common diphenylperfluoroisopropylphosphine