# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2011 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Rourke, J.' _publ_contact_author_email j.rourke@warwick.ac.uk _publ_section_title ; Platinum(IV) centres with agostic interactions from either sp2 or sp3 C-H bonds ; loop_ _publ_author_name S.Crosby R.Deeth G.Clarkson J.Rourke # Attachment '- sc14.cif' data_sc14 _database_code_depnum_ccdc_archive 'CCDC 790276' #TrackingRef '- sc14.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C15 H15 Cl3 F N Pt' _chemical_formula_weight 529.72 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' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 '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' Pt Pt -1.7033 8.3905 '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 13.0861(2) _cell_length_b 8.07835(10) _cell_length_c 15.9059(3) _cell_angle_alpha 90.00 _cell_angle_beta 111.7518(19) _cell_angle_gamma 90.00 _cell_volume 1561.75(4) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 11638 _cell_measurement_theta_min 3.02 _cell_measurement_theta_max 30.75 _exptl_crystal_description plate _exptl_crystal_colour colourless _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.01 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.253 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1000 _exptl_absorpt_coefficient_mu 9.499 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.42 _exptl_absorpt_correction_T_max 1.00 _exptl_absorpt_process_details 'ABSPACK(CrysAlis, Oxford Diffraction)' _exptl_special_details ; The temperature of the crystal was controlled using the Oxford Cryosystem Cryostream Cobra. The data collection nominally covered over a hemisphere of Reciprocal space, by a combination of four sets of exposures with different \f angles for the crystal; each 10 s exposure covered 0.3\% in \w. The crystal-to-detector distance was 5.5 cm. Crystal decay was found to be negligible by by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. Hydrogen atoms were added at calculated positions and refined using a riding model except the CHs on C16 which were located in a difference map. Their position was allowed to refined freely. Anisotropic displacement parameters were used for all non-H atoms; H-atoms were given isotropic displacement parameter equal to 1.2 (or 1.5 for methyl H-atoms) times the equivalent isotropic displacement parameter of the atom to which they are attached. ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Oxford Diffraction Gemini R' _diffrn_measurement_method '\f & \w scans' _diffrn_detector_area_resol_mean 10.2833 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% nil _diffrn_reflns_number 18193 _diffrn_reflns_av_R_equivalents 0.0402 _diffrn_reflns_av_sigmaI/netI 0.0351 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 3.03 _diffrn_reflns_theta_max 30.82 _reflns_number_total 4551 _reflns_number_gt 3917 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrysAlis CCD, Oxford Diffraction Ltd' _computing_cell_refinement 'CrysAlis RED, Oxford Diffraction Ltd' _computing_data_reduction 'CrysAlis RED, Oxford Diffraction Ltd' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 1997)' _computing_publication_material 'SHELXTL (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^)+(0.0207P)^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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4551 _refine_ls_number_parameters 201 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0270 _refine_ls_R_factor_gt 0.0204 _refine_ls_wR_factor_ref 0.0428 _refine_ls_wR_factor_gt 0.0420 _refine_ls_goodness_of_fit_ref 0.972 _refine_ls_restrained_S_all 0.972 _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 Pt1 Pt 0.229160(8) 0.563377(12) 0.415608(6) 0.01009(4) Uani 1 1 d . . . N1 N 0.21776(18) 0.7518(3) 0.32817(14) 0.0099(4) Uani 1 1 d . . . Cl1 Cl 0.24001(6) 0.34887(8) 0.51348(4) 0.01704(14) Uani 1 1 d . . . Cl2 Cl 0.07393(5) 0.66141(8) 0.43649(4) 0.01446(13) Uani 1 1 d . . . C2 C 0.1641(2) 0.7436(3) 0.23670(17) 0.0116(5) Uani 1 1 d . . . Cl3 Cl 0.38087(6) 0.46633(8) 0.39059(5) 0.01678(14) Uani 1 1 d . . . C3 C 0.1653(2) 0.8813(3) 0.18565(18) 0.0151(6) Uani 1 1 d . . . H3A H 0.1302 0.8769 0.1216 0.018 Uiso 1 1 calc R . . C4 C 0.2172(2) 1.0263(3) 0.22676(19) 0.0157(6) Uani 1 1 d . . . H4A H 0.2169 1.1207 0.1911 0.019 Uiso 1 1 calc R . . C5 C 0.2691(2) 1.0325(3) 0.31962(19) 0.0149(6) Uani 1 1 d . . . H5A H 0.3037 1.1314 0.3486 0.018 Uiso 1 1 calc R . . C6 C 0.2699(2) 0.8927(3) 0.36981(18) 0.0128(5) Uani 1 1 d . . . C7 C 0.3275(2) 0.8766(3) 0.46789(18) 0.0126(5) Uani 1 1 d . . . C8 C 0.3894(2) 1.0035(4) 0.52401(19) 0.0151(6) Uani 1 1 d . . . H8A H 0.3932 1.1090 0.4989 0.018 Uiso 1 1 calc R . . C9 C 0.4450(2) 0.9764(4) 0.61559(19) 0.0172(6) Uani 1 1 d . . . H9A H 0.4856 1.0625 0.6542 0.021 Uiso 1 1 calc R . . F10 F 0.49603(14) 0.7931(2) 0.73880(10) 0.0262(4) Uani 1 1 d . . . C10 C 0.4398(2) 0.8207(4) 0.64904(18) 0.0177(6) Uani 1 1 d . . . C11 C 0.3797(2) 0.6911(4) 0.59802(18) 0.0153(6) Uani 1 1 d . . . H11A H 0.3770 0.5859 0.6238 0.018 Uiso 1 1 calc R . . C12 C 0.3237(2) 0.7234(3) 0.50704(18) 0.0125(5) Uani 1 1 d . . . C13 C 0.1080(2) 0.5831(3) 0.18995(17) 0.0117(5) Uani 1 1 d . . . C14 C -0.0062(2) 0.6261(4) 0.11820(19) 0.0168(6) Uani 1 1 d . . . H14A H 0.0028 0.7020 0.0734 0.025 Uiso 1 1 calc R . . H14B H -0.0514 0.6789 0.1478 0.025 Uiso 1 1 calc R . . H14C H -0.0424 0.5245 0.0879 0.025 Uiso 1 1 calc R . . C15 C 0.1804(2) 0.5044(4) 0.14307(19) 0.0152(6) Uani 1 1 d . . . H15A H 0.1926 0.5848 0.1016 0.023 Uiso 1 1 calc R . . H15B H 0.1433 0.4065 0.1089 0.023 Uiso 1 1 calc R . . H15C H 0.2513 0.4718 0.1889 0.023 Uiso 1 1 calc R . . C16 C 0.0864(3) 0.4547(4) 0.25242(19) 0.0159(6) Uani 1 1 d . . . H16A H 0.159(3) 0.406(4) 0.299(2) 0.024 Uiso 1 1 d . . . H16B H 0.049(3) 0.358(4) 0.209(2) 0.024 Uiso 1 1 d . . . H16C H 0.037(3) 0.501(4) 0.275(2) 0.024 Uiso 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 Pt1 0.01123(5) 0.01042(5) 0.00885(5) 0.00020(4) 0.00399(4) 0.00071(4) N1 0.0103(11) 0.0099(10) 0.0111(10) 0.0008(9) 0.0056(9) 0.0013(9) Cl1 0.0217(4) 0.0141(3) 0.0149(3) 0.0040(3) 0.0062(3) 0.0008(3) Cl2 0.0140(3) 0.0195(3) 0.0112(3) 0.0006(3) 0.0063(3) 0.0028(3) C2 0.0094(13) 0.0146(13) 0.0117(12) -0.0015(10) 0.0050(10) 0.0007(10) Cl3 0.0137(3) 0.0186(3) 0.0190(3) -0.0028(3) 0.0072(3) 0.0025(3) C3 0.0165(14) 0.0201(13) 0.0085(12) 0.0009(11) 0.0043(11) 0.0018(12) C4 0.0200(15) 0.0134(13) 0.0158(13) 0.0034(11) 0.0089(12) 0.0017(11) C5 0.0171(14) 0.0133(13) 0.0157(13) 0.0008(11) 0.0076(11) 0.0006(11) C6 0.0131(13) 0.0117(12) 0.0163(13) -0.0012(11) 0.0085(11) 0.0007(11) C7 0.0107(13) 0.0146(12) 0.0127(13) -0.0017(11) 0.0045(11) 0.0010(11) C8 0.0151(14) 0.0148(13) 0.0182(14) -0.0031(12) 0.0096(12) -0.0018(12) C9 0.0146(14) 0.0204(14) 0.0142(13) -0.0079(11) 0.0025(11) -0.0016(12) F10 0.0301(10) 0.0295(10) 0.0113(8) -0.0013(7) -0.0013(7) -0.0013(9) C10 0.0158(14) 0.0247(15) 0.0110(13) -0.0020(12) 0.0031(11) 0.0046(13) C11 0.0160(14) 0.0175(13) 0.0137(13) 0.0013(11) 0.0069(11) 0.0047(12) C12 0.0104(13) 0.0134(13) 0.0141(13) -0.0032(10) 0.0049(11) 0.0016(11) C13 0.0120(13) 0.0139(13) 0.0107(12) -0.0034(10) 0.0058(10) -0.0032(11) C14 0.0136(14) 0.0197(14) 0.0156(14) -0.0033(12) 0.0037(11) -0.0014(12) C15 0.0184(15) 0.0137(12) 0.0170(14) -0.0013(12) 0.0106(12) 0.0003(12) C16 0.0204(15) 0.0161(14) 0.0123(13) -0.0009(11) 0.0074(12) -0.0044(12) _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 Pt1 C12 1.996(3) . ? Pt1 N1 2.029(2) . ? Pt1 Cl1 2.2984(6) . ? Pt1 Cl3 2.3021(7) . ? Pt1 Cl2 2.3161(6) . ? Pt1 H16A 2.16(3) . ? N1 C2 1.363(3) . ? N1 C6 1.366(3) . ? C2 C3 1.381(4) . ? C2 C13 1.539(4) . ? C3 C4 1.389(4) . ? C3 H3A 0.9500 . ? C4 C5 1.379(4) . ? C4 H4A 0.9500 . ? C5 C6 1.380(4) . ? C5 H5A 0.9500 . ? C6 C7 1.465(4) . ? C7 C12 1.394(4) . ? C7 C8 1.403(4) . ? C8 C9 1.383(4) . ? C8 H8A 0.9500 . ? C9 C10 1.377(4) . ? C9 H9A 0.9500 . ? F10 C10 1.361(3) . ? C10 C11 1.379(4) . ? C11 C12 1.383(4) . ? C11 H11A 0.9500 . ? C13 C16 1.533(4) . ? C13 C15 1.544(4) . ? C13 C14 1.546(4) . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C14 H14C 0.9800 . ? C15 H15A 0.9800 . ? C15 H15B 0.9800 . ? C15 H15C 0.9800 . ? C16 H16A 1.04(3) . ? C16 H16B 1.03(3) . ? C16 H16C 0.93(3) . ? 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 C12 Pt1 N1 83.21(10) . . ? C12 Pt1 Cl1 97.41(8) . . ? N1 Pt1 Cl1 179.30(7) . . ? C12 Pt1 Cl3 90.30(8) . . ? N1 Pt1 Cl3 89.20(6) . . ? Cl1 Pt1 Cl3 91.12(2) . . ? C12 Pt1 Cl2 90.78(8) . . ? N1 Pt1 Cl2 89.79(6) . . ? Cl1 Pt1 Cl2 89.88(2) . . ? Cl3 Pt1 Cl2 178.42(2) . . ? C12 Pt1 H16A 164.0(9) . . ? N1 Pt1 H16A 87.3(8) . . ? Cl1 Pt1 H16A 92.2(8) . . ? Cl3 Pt1 H16A 76.7(9) . . ? Cl2 Pt1 H16A 102.1(9) . . ? C2 N1 C6 121.7(2) . . ? C2 N1 Pt1 124.98(17) . . ? C6 N1 Pt1 113.34(17) . . ? N1 C2 C3 118.4(2) . . ? N1 C2 C13 121.4(2) . . ? C3 C2 C13 120.1(2) . . ? C2 C3 C4 120.8(2) . . ? C2 C3 H3A 119.6 . . ? C4 C3 H3A 119.6 . . ? C5 C4 C3 119.7(3) . . ? C5 C4 H4A 120.2 . . ? C3 C4 H4A 120.2 . . ? C4 C5 C6 119.0(3) . . ? C4 C5 H5A 120.5 . . ? C6 C5 H5A 120.5 . . ? N1 C6 C5 120.4(2) . . ? N1 C6 C7 114.2(2) . . ? C5 C6 C7 125.4(3) . . ? C12 C7 C8 118.2(2) . . ? C12 C7 C6 117.7(2) . . ? C8 C7 C6 124.1(3) . . ? C9 C8 C7 120.6(3) . . ? C9 C8 H8A 119.7 . . ? C7 C8 H8A 119.7 . . ? C10 C9 C8 118.0(3) . . ? C10 C9 H9A 121.0 . . ? C8 C9 H9A 121.0 . . ? F10 C10 C9 118.1(2) . . ? F10 C10 C11 117.5(3) . . ? C9 C10 C11 124.4(3) . . ? C10 C11 C12 115.9(3) . . ? C10 C11 H11A 122.0 . . ? C12 C11 H11A 122.0 . . ? C11 C12 C7 122.8(3) . . ? C11 C12 Pt1 125.8(2) . . ? C7 C12 Pt1 111.38(19) . . ? C16 C13 C2 115.2(2) . . ? C16 C13 C15 109.1(2) . . ? C2 C13 C15 108.1(2) . . ? C16 C13 C14 105.7(2) . . ? C2 C13 C14 109.0(2) . . ? C15 C13 C14 109.5(2) . . ? C13 C14 H14A 109.5 . . ? C13 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C13 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C13 C15 H15A 109.5 . . ? C13 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? C13 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? C13 C16 H16A 112.2(18) . . ? C13 C16 H16B 103.6(17) . . ? H16A C16 H16B 105(2) . . ? C13 C16 H16C 107(2) . . ? H16A C16 H16C 118(3) . . ? H16B C16 H16C 110(3) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A C3 H3A Cl2 0.95 2.78 3.707(3) 167.0 4_575 C9 H9A F10 0.95 2.47 3.344(3) 152.3 2_656 _diffrn_measured_fraction_theta_max 0.927 _diffrn_reflns_theta_full 29.50 _diffrn_measured_fraction_theta_full 0.990 _refine_diff_density_max 1.400 _refine_diff_density_min -1.780 _refine_diff_density_rms 0.146