# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Dieter Lentz' _publ_contact_author_email LENTZ@CHEMIE.FU-BERLIN.DE _publ_section_title ; Hydrometalation of Fluoroallenes ; loop_ _publ_author_name 'Dieter Lentz' 'Moritz F. Kuhnel' # Attachment '12 Cp2MoH2 x TFA .cif' data_mo3 _database_code_depnum_ccdc_archive 'CCDC 720718' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis(cyclopentadienyl)(1-difluoromethyl-2,2-difluorovinyl)hydridomolybdenum ; _chemical_name_common ;Bis(cyclopentadienyl)(1-difluoromethyl-2,2- difluorovinyl)hydridomolybdenum ; _chemical_melting_point 359 _chemical_formula_moiety 'C13 H12 F4 Mo' _chemical_formula_sum 'C13 H12 F4 Mo' _chemical_formula_weight 340.17 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mo Mo -1.6832 0.6857 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 13.1119(19) _cell_length_b 8.1128(16) _cell_length_c 23.437(4) _cell_angle_alpha 90.00 _cell_angle_beta 100.991(12) _cell_angle_gamma 90.00 _cell_volume 2447.4(7) _cell_formula_units_Z 8 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 982 _cell_measurement_theta_min 2.97 _cell_measurement_theta_max 26.35 _exptl_crystal_description prism _exptl_crystal_colour yellow _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.09 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.846 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1344 _exptl_absorpt_coefficient_mu 1.099 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details 'SADABS (Bruker-AXS)' _exptl_special_details ; 'Ratio of minimum to maximum apparent transmission: 0.905111' ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'SMART-CCD Bruker-AXS' _diffrn_measurement_method 'omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 10908 _diffrn_reflns_av_R_equivalents 0.0281 _diffrn_reflns_av_sigmaI/netI 0.0222 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -28 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_theta_min 1.77 _diffrn_reflns_theta_max 26.40 _reflns_number_total 2515 _reflns_number_gt 2194 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker-AXS)' _computing_cell_refinement 'SAINT (Bruker-AXS)' _computing_data_reduction 'SAINT (Bruker-AXS)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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. Voids of 31 cubic angstroem are found at 0 0 0 and symmetry related positions. However, the highest residual electron density is found at 0.7391 0.0299 0.5047. The voids are to small to accomodate any reasonable solvent molecules. ; _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^)+(0.0392P)^2^+33.6594P] 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 2515 _refine_ls_number_parameters 167 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0561 _refine_ls_R_factor_gt 0.0495 _refine_ls_wR_factor_ref 0.1196 _refine_ls_wR_factor_gt 0.1163 _refine_ls_goodness_of_fit_ref 1.181 _refine_ls_restrained_S_all 1.181 _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 Mo1 Mo 0.71696(3) 0.05187(5) 0.655749(19) 0.01822(15) Uani 1 1 d . . . C1R C 0.5334(4) 0.0516(8) 0.6329(3) 0.0334(13) Uani 1 1 d . . . H1R H 0.4925 -0.0114 0.6027 0.040 Uiso 1 1 calc R . . C2R C 0.5699(4) 0.2106(8) 0.6267(3) 0.0330(14) Uani 1 1 d . . . H2R H 0.5604 0.2733 0.5918 0.040 Uiso 1 1 calc R . . C3R C 0.6239(5) 0.2615(7) 0.6823(3) 0.0333(13) Uani 1 1 d . . . H3R H 0.6554 0.3661 0.6914 0.040 Uiso 1 1 calc R . . C4R C 0.6227(5) 0.1286(8) 0.7224(3) 0.0318(13) Uani 1 1 d . . . H4R H 0.6537 0.1278 0.7625 0.038 Uiso 1 1 calc R . . C5R C 0.5665(4) -0.0013(7) 0.6906(3) 0.0280(12) Uani 1 1 d . . . H5R H 0.5534 -0.1063 0.7057 0.034 Uiso 1 1 calc R . . C3 C 0.6807(5) -0.3138(9) 0.5956(3) 0.0448(17) Uani 1 1 d . . . H1 H 0.6621 -0.3743 0.5579 0.054 Uiso 1 1 calc R . . C2 C 0.6786(4) -0.1308(8) 0.5851(2) 0.0294(12) Uani 1 1 d . . . C1 C 0.6500(6) -0.0917(10) 0.5300(3) 0.0476(18) Uani 1 1 d . . . C6R C 0.8722(5) 0.0227(9) 0.6201(3) 0.0392(15) Uani 1 1 d . . . H6R H 0.8801 -0.0493 0.5893 0.047 Uiso 1 1 calc R . . C7R C 0.8383(5) 0.1874(9) 0.6139(3) 0.0412(17) Uani 1 1 d . . . H7R H 0.8188 0.2460 0.5784 0.049 Uiso 1 1 calc R . . C8R C 0.8387(5) 0.2492(8) 0.6702(3) 0.0375(15) Uani 1 1 d . . . H8R H 0.8200 0.3579 0.6793 0.045 Uiso 1 1 calc R . . C9R C 0.8718(4) 0.1213(8) 0.7114(3) 0.0340(14) Uani 1 1 d . . . H9R H 0.8787 0.1283 0.7524 0.041 Uiso 1 1 calc R . . C10R C 0.8922(4) -0.0175(8) 0.6792(3) 0.0318(13) Uani 1 1 d . . . H10R H 0.9158 -0.1216 0.6950 0.038 Uiso 1 1 calc R . . F1 F 0.6236(5) -0.1975(7) 0.48532(19) 0.0783(17) Uani 1 1 d . . . F2 F 0.6366(6) 0.0569(7) 0.50903(19) 0.088(2) Uani 1 1 d . . . F3 F 0.6166(5) -0.3594(6) 0.6321(2) 0.0744(15) Uani 1 1 d . . . F4 F 0.7756(4) -0.3653(6) 0.6255(2) 0.0676(14) Uani 1 1 d . . . H1M H 0.728(4) -0.127(6) 0.691(2) 0.009(12) 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 Mo1 0.0152(2) 0.0175(2) 0.0216(2) 0.00084(18) 0.00256(15) 0.00091(17) C1R 0.017(3) 0.045(4) 0.037(3) -0.006(3) 0.003(2) -0.002(3) C2R 0.024(3) 0.037(3) 0.037(3) 0.008(3) 0.003(2) 0.014(3) C3R 0.033(3) 0.022(3) 0.047(4) -0.002(3) 0.013(3) 0.008(2) C4R 0.029(3) 0.038(3) 0.028(3) -0.004(3) 0.006(2) 0.008(3) C5R 0.018(3) 0.031(3) 0.038(3) 0.001(3) 0.013(2) 0.001(2) C3 0.041(4) 0.040(4) 0.053(4) -0.018(3) 0.007(3) -0.004(3) C2 0.028(3) 0.032(3) 0.027(3) -0.005(2) 0.003(2) 0.004(2) C1 0.052(4) 0.050(4) 0.037(4) -0.014(3) -0.002(3) 0.011(3) C6R 0.020(3) 0.052(4) 0.049(4) 0.004(3) 0.017(3) 0.002(3) C7R 0.023(3) 0.053(4) 0.048(4) 0.023(3) 0.006(3) -0.002(3) C8R 0.027(3) 0.025(3) 0.060(4) 0.004(3) 0.005(3) -0.006(2) C9R 0.020(3) 0.039(3) 0.040(3) 0.000(3) -0.003(2) -0.007(2) C10R 0.014(2) 0.031(3) 0.050(4) 0.006(3) 0.006(2) 0.000(2) F1 0.101(4) 0.088(4) 0.037(2) -0.016(2) -0.007(3) 0.021(3) F2 0.168(6) 0.060(3) 0.030(2) 0.014(2) 0.002(3) 0.012(4) F3 0.101(4) 0.046(3) 0.078(3) 0.005(3) 0.021(3) -0.022(3) F4 0.091(4) 0.044(3) 0.063(3) 0.002(2) 0.002(3) 0.025(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 Mo1 C2 2.208(6) . ? Mo1 C8R 2.240(6) . ? Mo1 C3R 2.250(6) . ? Mo1 C4R 2.256(6) . ? Mo1 C9R 2.265(6) . ? Mo1 C7R 2.302(6) . ? Mo1 C2R 2.311(6) . ? Mo1 C5R 2.315(5) . ? Mo1 C10R 2.327(5) . ? Mo1 C6R 2.355(6) . ? Mo1 C1R 2.364(6) . ? C1R C2R 1.393(9) . ? C1R C5R 1.408(9) . ? C2R C3R 1.422(9) . ? C3R C4R 1.432(9) . ? C4R C5R 1.414(9) . ? C3 F3 1.361(9) . ? C3 F4 1.372(9) . ? C3 C2 1.504(9) . ? C2 C1 1.313(9) . ? C1 F2 1.301(9) . ? C1 F1 1.347(8) . ? C6R C10R 1.398(9) . ? C6R C7R 1.407(10) . ? C7R C8R 1.413(10) . ? C8R C9R 1.427(9) . ? C9R C10R 1.410(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 C2 Mo1 C8R 130.3(2) . . ? C2 Mo1 C3R 131.1(2) . . ? C8R Mo1 C3R 80.0(2) . . ? C2 Mo1 C4R 128.9(2) . . ? C8R Mo1 C4R 99.6(2) . . ? C3R Mo1 C4R 37.1(2) . . ? C2 Mo1 C9R 130.5(2) . . ? C8R Mo1 C9R 36.9(2) . . ? C3R Mo1 C9R 97.3(2) . . ? C4R Mo1 C9R 94.7(2) . . ? C2 Mo1 C7R 94.5(3) . . ? C8R Mo1 C7R 36.2(3) . . ? C3R Mo1 C7R 102.3(3) . . ? C4R Mo1 C7R 132.7(3) . . ? C9R Mo1 C7R 60.7(2) . . ? C2 Mo1 C2R 95.5(2) . . ? C8R Mo1 C2R 100.2(2) . . ? C3R Mo1 C2R 36.3(2) . . ? C4R Mo1 C2R 60.9(2) . . ? C9R Mo1 C2R 129.6(2) . . ? C7R Mo1 C2R 102.3(2) . . ? C2 Mo1 C5R 93.0(2) . . ? C8R Mo1 C5R 135.2(2) . . ? C3R Mo1 C5R 60.0(2) . . ? C4R Mo1 C5R 36.0(2) . . ? C9R Mo1 C5R 125.0(2) . . ? C7R Mo1 C5R 160.8(2) . . ? C2R Mo1 C5R 59.3(2) . . ? C2 Mo1 C10R 95.0(2) . . ? C8R Mo1 C10R 59.6(2) . . ? C3R Mo1 C10R 132.9(2) . . ? C4R Mo1 C10R 123.4(2) . . ? C9R Mo1 C10R 35.7(2) . . ? C7R Mo1 C10R 59.0(2) . . ? C2R Mo1 C10R 159.2(2) . . ? C5R Mo1 C10R 137.8(2) . . ? C2 Mo1 C6R 75.8(2) . . ? C8R Mo1 C6R 59.1(3) . . ? C3R Mo1 C6R 136.5(2) . . ? C4R Mo1 C6R 153.9(2) . . ? C9R Mo1 C6R 59.3(2) . . ? C7R Mo1 C6R 35.1(2) . . ? C2R Mo1 C6R 132.9(2) . . ? C5R Mo1 C6R 163.5(2) . . ? C10R Mo1 C6R 34.7(2) . . ? C2 Mo1 C1R 75.7(2) . . ? C8R Mo1 C1R 134.4(2) . . ? C3R Mo1 C1R 58.7(2) . . ? C4R Mo1 C1R 59.3(2) . . ? C9R Mo1 C1R 153.3(2) . . ? C7R Mo1 C1R 131.3(2) . . ? C2R Mo1 C1R 34.7(2) . . ? C5R Mo1 C1R 35.0(2) . . ? C10R Mo1 C1R 165.9(2) . . ? C6R Mo1 C1R 146.2(2) . . ? C2R C1R C5R 109.4(6) . . ? C2R C1R Mo1 70.6(3) . . ? C5R C1R Mo1 70.6(3) . . ? C1R C2R C3R 107.1(6) . . ? C1R C2R Mo1 74.8(3) . . ? C3R C2R Mo1 69.5(3) . . ? C2R C3R C4R 108.5(6) . . ? C2R C3R Mo1 74.2(3) . . ? C4R C3R Mo1 71.7(3) . . ? C5R C4R C3R 106.6(5) . . ? C5R C4R Mo1 74.3(3) . . ? C3R C4R Mo1 71.2(3) . . ? C1R C5R C4R 108.3(5) . . ? C1R C5R Mo1 74.4(3) . . ? C4R C5R Mo1 69.7(3) . . ? F3 C3 F4 101.8(6) . . ? F3 C3 C2 112.1(6) . . ? F4 C3 C2 111.8(6) . . ? C1 C2 C3 113.1(6) . . ? C1 C2 Mo1 123.8(5) . . ? C3 C2 Mo1 123.1(4) . . ? F2 C1 C2 126.0(6) . . ? F2 C1 F1 107.5(6) . . ? C2 C1 F1 126.4(7) . . ? C10R C6R C7R 108.7(6) . . ? C10R C6R Mo1 71.6(3) . . ? C7R C6R Mo1 70.4(3) . . ? C6R C7R C8R 107.2(6) . . ? C6R C7R Mo1 74.5(4) . . ? C8R C7R Mo1 69.5(3) . . ? C7R C8R C9R 108.7(6) . . ? C7R C8R Mo1 74.3(4) . . ? C9R C8R Mo1 72.5(3) . . ? C10R C9R C8R 106.5(6) . . ? C10R C9R Mo1 74.6(3) . . ? C8R C9R Mo1 70.6(3) . . ? C6R C10R C9R 109.0(6) . . ? C6R C10R Mo1 73.7(3) . . ? C9R C10R Mo1 69.7(3) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 26.40 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 1.608 _refine_diff_density_min -1.747 _refine_diff_density_rms 0.143 # Attachment '13 Cp2WHCl x TFA.cif' data_mo52 _database_code_depnum_ccdc_archive 'CCDC 720719' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis(cyclopentadienyl)(1-difluoromethyl-2,2-difluorovinyl)chlorotungsten ; _chemical_name_common ;Bis(cyclopentadienyl)(1-difluoromethyl-2,2- difluorovinyl)chlorotungsten ; _chemical_melting_point 448 _chemical_formula_moiety 'C13 H11 Cl F4 W' _chemical_formula_sum 'C13 H11 Cl F4 W' _chemical_formula_weight 462.52 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' W W -0.8490 6.8722 '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' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M Pnma loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z' 'x+1/2, -y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z' '-x-1/2, y-1/2, z-1/2' _cell_length_a 12.970(3) _cell_length_b 10.859(2) _cell_length_c 8.7092(18) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1226.7(4) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 982 _cell_measurement_theta_min 3.00 _cell_measurement_theta_max 30.51 _exptl_crystal_description prism _exptl_crystal_colour black _exptl_crystal_size_max 0.45 _exptl_crystal_size_mid 0.42 _exptl_crystal_size_min 0.35 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.504 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 864 _exptl_absorpt_coefficient_mu 9.665 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details 'SADABS (Bruker-AXS)' _exptl_special_details ; 'Ratio of minimum to maximum apparent transmission: 0.588058' ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'SMART-CCD Bruker-AXS' _diffrn_measurement_method 'omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 28238 _diffrn_reflns_av_R_equivalents 0.0365 _diffrn_reflns_av_sigmaI/netI 0.0137 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.82 _diffrn_reflns_theta_max 30.53 _reflns_number_total 1966 _reflns_number_gt 1900 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker-AXS)' _computing_cell_refinement 'SAINT (Bruker-AXS)' _computing_data_reduction 'SAINT (Bruker-AXS)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0171P)^2^+1.3597P] 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_extinction_coef ? _refine_ls_number_reflns 1966 _refine_ls_number_parameters 97 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0166 _refine_ls_R_factor_gt 0.0156 _refine_ls_wR_factor_ref 0.0417 _refine_ls_wR_factor_gt 0.0413 _refine_ls_goodness_of_fit_ref 1.287 _refine_ls_restrained_S_all 1.287 _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 W1 W 0.378700(8) 0.2500 0.178908(12) 0.01217(5) Uani 1 2 d S . . Cl1 Cl 0.55757(6) 0.2500 0.07832(10) 0.02768(18) Uani 1 2 d S . . C2R C 0.2651(2) 0.0964(3) 0.2194(4) 0.0313(5) Uani 1 1 d . . . H2R H 0.1947 0.1101 0.1944 0.038 Uiso 1 1 calc R . . C3R C 0.3417(3) 0.0426(2) 0.1233(3) 0.0325(6) Uani 1 1 d . . . H3R H 0.3306 0.0124 0.0223 0.039 Uiso 1 1 calc R . . C4R C 0.4349(2) 0.0414(2) 0.2012(3) 0.0316(6) Uani 1 1 d . . . H4R H 0.4979 0.0092 0.1623 0.038 Uiso 1 1 calc R . . C5R C 0.4216(2) 0.0956(3) 0.3475(3) 0.0296(5) Uani 1 1 d . . . H5R H 0.4735 0.1094 0.4225 0.036 Uiso 1 1 calc R . . C1R C 0.3149(2) 0.1255(3) 0.3601(3) 0.0288(5) Uani 1 1 d . . . H1R H 0.2824 0.1594 0.4482 0.035 Uiso 1 1 calc R . . C2 C 0.3297(3) 0.2500 -0.0661(4) 0.0222(6) Uani 1 2 d S . . C3 C 0.4027(3) 0.2500 -0.1980(4) 0.0269(7) Uani 1 2 d S . . H1 H 0.4752 0.2500 -0.1589 0.032 Uiso 1 2 calc SR . . C1 C 0.2324(3) 0.2500 -0.1101(5) 0.0373(10) Uani 1 2 d S . . F1 F 0.38770(17) 0.1495(2) -0.2926(2) 0.0481(5) Uani 1 1 d . . . F2 F 0.1970(2) 0.2500 -0.2537(3) 0.0492(7) Uani 1 2 d S . . F3 F 0.1502(2) 0.2500 -0.0179(4) 0.0698(12) Uani 1 2 d S . . 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 W1 0.01243(7) 0.01565(7) 0.00843(6) 0.000 0.00013(3) 0.000 Cl1 0.0153(3) 0.0466(5) 0.0212(4) 0.000 0.0022(3) 0.000 C2R 0.0246(11) 0.0284(12) 0.0407(14) -0.0009(12) 0.0039(11) -0.0124(10) C3R 0.0482(16) 0.0195(11) 0.0298(13) -0.0065(10) 0.0005(12) -0.0065(11) C4R 0.0404(15) 0.0185(11) 0.0360(14) 0.0031(10) 0.0065(12) 0.0073(10) C5R 0.0393(15) 0.0245(12) 0.0251(11) 0.0097(10) -0.0048(11) 0.0054(11) C1R 0.0383(14) 0.0261(12) 0.0220(11) 0.0061(10) 0.0127(10) -0.0050(10) C2 0.0243(15) 0.0313(16) 0.0110(13) 0.000 -0.0045(11) 0.000 C3 0.0341(18) 0.036(2) 0.0104(13) 0.000 -0.0032(13) 0.000 C1 0.0272(18) 0.065(3) 0.0196(17) 0.000 -0.0097(15) 0.000 F1 0.0639(14) 0.0469(13) 0.0334(9) -0.0180(9) -0.0004(8) 0.0103(9) F2 0.0405(15) 0.080(2) 0.0274(13) 0.000 -0.0217(11) 0.000 F3 0.0187(12) 0.149(4) 0.0412(16) 0.000 -0.0071(12) 0.000 _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 W1 C2 2.226(3) . ? W1 C1R 2.236(2) 7_565 ? W1 C1R 2.236(2) . ? W1 C2R 2.253(3) 7_565 ? W1 C2R 2.253(3) . ? W1 C5R 2.297(2) 7_565 ? W1 C5R 2.297(2) . ? W1 C3R 2.354(3) . ? W1 C3R 2.354(3) 7_565 ? W1 C4R 2.388(3) 7_565 ? W1 C4R 2.388(3) . ? W1 Cl1 2.4798(9) . ? C2R C1R 1.421(4) . ? C2R C3R 1.424(4) . ? C3R C4R 1.387(5) . ? C4R C5R 1.415(4) . ? C5R C1R 1.426(4) . ? C2 C1 1.319(5) . ? C2 C3 1.489(5) . ? C3 F1 1.381(3) . ? C3 F1 1.381(3) 7_565 ? C1 F2 1.333(5) . ? C1 F3 1.334(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 C2 W1 C1R 124.79(10) . 7_565 ? C2 W1 C1R 124.79(10) . . ? C1R W1 C1R 74.36(15) 7_565 . ? C2 W1 C2R 87.89(10) . 7_565 ? C1R W1 C2R 36.89(11) 7_565 7_565 ? C1R W1 C2R 95.44(11) . 7_565 ? C2 W1 C2R 87.89(10) . . ? C1R W1 C2R 95.44(11) 7_565 . ? C1R W1 C2R 36.89(11) . . ? C2R W1 C2R 95.49(15) 7_565 . ? C2 W1 C5R 132.99(7) . 7_565 ? C1R W1 C5R 36.65(11) 7_565 7_565 ? C1R W1 C5R 94.58(11) . 7_565 ? C2R W1 C5R 61.21(11) 7_565 7_565 ? C2R W1 C5R 126.78(11) . 7_565 ? C2 W1 C5R 132.99(7) . . ? C1R W1 C5R 94.58(11) 7_565 . ? C1R W1 C5R 36.65(11) . . ? C2R W1 C5R 126.78(11) 7_565 . ? C2R W1 C5R 61.21(11) . . ? C5R W1 C5R 93.74(15) 7_565 . ? C2 W1 C3R 75.20(8) . . ? C1R W1 C3R 130.39(11) 7_565 . ? C1R W1 C3R 59.42(10) . . ? C2R W1 C3R 127.38(11) 7_565 . ? C2R W1 C3R 35.93(10) . . ? C5R W1 C3R 151.58(10) 7_565 . ? C5R W1 C3R 58.84(11) . . ? C2 W1 C3R 75.20(8) . 7_565 ? C1R W1 C3R 59.42(10) 7_565 7_565 ? C1R W1 C3R 130.39(11) . 7_565 ? C2R W1 C3R 35.93(10) 7_565 7_565 ? C2R W1 C3R 127.38(11) . 7_565 ? C5R W1 C3R 58.84(11) 7_565 7_565 ? C5R W1 C3R 151.58(10) . 7_565 ? C3R W1 C3R 146.30(16) . 7_565 ? C2 W1 C4R 99.50(8) . 7_565 ? C1R W1 C4R 58.83(10) 7_565 7_565 ? C1R W1 C4R 128.99(10) . 7_565 ? C2R W1 C4R 58.99(11) 7_565 7_565 ? C2R W1 C4R 152.78(11) . 7_565 ? C5R W1 C4R 35.08(10) 7_565 7_565 ? C5R W1 C4R 124.50(11) . 7_565 ? C3R W1 C4R 170.78(10) . 7_565 ? C3R W1 C4R 34.01(11) 7_565 7_565 ? C2 W1 C4R 99.50(8) . . ? C1R W1 C4R 128.99(10) 7_565 . ? C1R W1 C4R 58.83(10) . . ? C2R W1 C4R 152.78(11) 7_565 . ? C2R W1 C4R 58.99(11) . . ? C5R W1 C4R 124.50(11) 7_565 . ? C5R W1 C4R 35.08(10) . . ? C3R W1 C4R 34.01(11) . . ? C3R W1 C4R 170.78(10) 7_565 . ? C4R W1 C4R 143.15(16) 7_565 . ? C2 W1 Cl1 85.90(10) . . ? C1R W1 Cl1 126.55(8) 7_565 . ? C1R W1 Cl1 126.55(8) . . ? C2R W1 Cl1 131.84(8) 7_565 . ? C2R W1 Cl1 131.84(8) . . ? C5R W1 Cl1 89.94(8) 7_565 . ? C5R W1 Cl1 89.94(8) . . ? C3R W1 Cl1 96.79(8) . . ? C3R W1 Cl1 96.79(8) 7_565 . ? C4R W1 Cl1 75.10(8) 7_565 . ? C4R W1 Cl1 75.10(8) . . ? C1R C2R C3R 106.3(3) . . ? C1R C2R W1 70.91(14) . . ? C3R C2R W1 75.88(15) . . ? C4R C3R C2R 109.0(3) . . ? C4R C3R W1 74.35(15) . . ? C2R C3R W1 68.19(14) . . ? C3R C4R C5R 109.3(3) . . ? C3R C4R W1 71.64(15) . . ? C5R C4R W1 68.95(15) . . ? C4R C5R C1R 106.4(3) . . ? C4R C5R W1 75.97(15) . . ? C1R C5R W1 69.36(14) . . ? C2R C1R C5R 108.9(2) . . ? C2R C1R W1 72.19(15) . . ? C5R C1R W1 73.99(14) . . ? C1 C2 C3 112.6(3) . . ? C1 C2 W1 123.5(3) . . ? C3 C2 W1 123.9(3) . . ? F1 C3 F1 104.4(3) . 7_565 ? F1 C3 C2 111.8(2) . . ? F1 C3 C2 111.8(2) 7_565 . ? C2 C1 F2 127.0(4) . . ? C2 C1 F3 126.1(4) . . ? F2 C1 F3 106.8(3) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 30.53 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.480 _refine_diff_density_min -1.913 _refine_diff_density_rms 0.194 # Attachment '14 Cp2MoHCl x TFA.cif' data_shelxl _database_code_depnum_ccdc_archive 'CCDC 720720' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis(cyclopentadienyl)(1-difluoromethyl-2,2-difluorovinyl)chloromolybdenum ; _chemical_name_common ;Bis(cyclopentadienyl)(1-difluoromethyl-2,2- difluorovinyl)chloromolybdenum ; _chemical_melting_point 457 _chemical_formula_moiety 'C13 H11 Cl F4 Mo' _chemical_formula_sum 'C13 H11 Cl F4 Mo' _chemical_formula_weight 374.61 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' 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' Mo Mo -1.6832 0.6857 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 13.625(3) _cell_length_b 7.2802(14) _cell_length_c 25.146(5) _cell_angle_alpha 90.00 _cell_angle_beta 94.399(4) _cell_angle_gamma 90.00 _cell_volume 2487.0(8) _cell_formula_units_Z 8 _cell_measurement_temperature 133(2) _cell_measurement_reflns_used 999 _cell_measurement_theta_min 3.25 _cell_measurement_theta_max 30.51 _exptl_crystal_description needle _exptl_crystal_colour black _exptl_crystal_size_max 0.85 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.001 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1472 _exptl_absorpt_coefficient_mu 1.300 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.6067 _exptl_absorpt_correction_T_max 0.7461 _exptl_absorpt_process_details 'SADABS (Bruker-AXS)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 133(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'SMART-CCD Bruker-AXS' _diffrn_measurement_method 'omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 19599 _diffrn_reflns_av_R_equivalents 0.0172 _diffrn_reflns_av_sigmaI/netI 0.0124 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -35 _diffrn_reflns_limit_l_max 35 _diffrn_reflns_theta_min 3.00 _diffrn_reflns_theta_max 30.51 _reflns_number_total 3792 _reflns_number_gt 3641 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker-AXS)' _computing_cell_refinement 'SAINT (Bruker-AXS)' _computing_data_reduction 'SAINT (Bruker-AXS)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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. Due to the disorder problem of the CF2H group, this hydrogen atom could not be located in the difference fourier map. Thus the atom list has one H atom less than the molecular formula requires. ; _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^)+(0.0139P)^2^+9.8900P] 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_extinction_coef ? _refine_ls_number_reflns 3792 _refine_ls_number_parameters 182 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0294 _refine_ls_R_factor_gt 0.0281 _refine_ls_wR_factor_ref 0.0628 _refine_ls_wR_factor_gt 0.0621 _refine_ls_goodness_of_fit_ref 1.153 _refine_ls_restrained_S_all 1.153 _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 Mo1 Mo 0.308852(12) 0.52079(2) 0.357026(6) 0.01619(5) Uani 1 1 d . . . C1 C 0.37106(19) 0.5504(5) 0.47915(10) 0.0367(6) Uani 1 1 d . . . C2 C 0.35679(16) 0.6491(3) 0.43538(9) 0.0241(4) Uani 1 1 d . . . C3 C 0.3835(2) 0.8459(4) 0.44312(14) 0.0462(7) Uani 1 1 d . . . C1R C 0.48276(15) 0.5127(3) 0.36551(9) 0.0259(4) Uani 1 1 d . . . H1R H 0.5221 0.5778 0.3920 0.031 Uiso 1 1 calc R . . C2R C 0.45530(17) 0.5760(4) 0.31402(10) 0.0313(5) Uani 1 1 d . . . H2R H 0.4729 0.6914 0.2999 0.038 Uiso 1 1 calc R . . C3R C 0.39712(19) 0.4406(5) 0.28635(10) 0.0389(6) Uani 1 1 d . . . H3R H 0.3676 0.4489 0.2510 0.047 Uiso 1 1 calc R . . C4R C 0.39157(18) 0.2896(4) 0.32188(12) 0.0369(6) Uani 1 1 d . . . H4R H 0.3593 0.1763 0.3137 0.044 Uiso 1 1 calc R . . C5R C 0.44212(16) 0.3355(3) 0.37157(11) 0.0306(5) Uani 1 1 d . . . H5R H 0.4476 0.2617 0.4028 0.037 Uiso 1 1 calc R . . C6R C 0.1500(2) 0.5702(4) 0.3756(2) 0.0670(13) Uani 1 1 d . . . H6R H 0.1319 0.6901 0.3861 0.080 Uiso 1 1 calc R . . C7R C 0.1493(2) 0.5033(7) 0.32256(17) 0.0752(16) Uani 1 1 d . . . H7R H 0.1291 0.5673 0.2907 0.090 Uiso 1 1 calc R . . C8R C 0.1840(3) 0.3263(6) 0.32712(17) 0.0672(14) Uani 1 1 d . . . H8R H 0.1926 0.2450 0.2983 0.081 Uiso 1 1 calc R . . C9R C 0.2041(2) 0.2863(5) 0.37989(19) 0.0574(10) Uani 1 1 d . . . H9R H 0.2300 0.1734 0.3937 0.069 Uiso 1 1 calc R . . C10R C 0.1816(2) 0.4310(6) 0.40880(12) 0.0575(11) Uani 1 1 d . . . H10R H 0.1867 0.4364 0.4467 0.069 Uiso 1 1 calc R . . Cl1 Cl 0.28690(5) 0.83852(9) 0.32111(3) 0.04113(16) Uani 1 1 d . . . F1 F 0.35809(14) 0.3708(3) 0.48387(7) 0.0507(5) Uani 1 1 d . . . F2 F 0.40276(14) 0.6119(4) 0.52784(6) 0.0647(7) Uani 1 1 d . . . F3 F 0.30736(18) 0.9524(3) 0.45121(12) 0.0755(8) Uani 1 1 d . . . F4A F 0.4437(2) 0.9073(4) 0.41308(13) 0.0418(10) Uani 0.563(5) 1 d P . . F4B F 0.4696(4) 0.8866(8) 0.4683(3) 0.081(2) Uani 0.437(5) 1 d P . . 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 Mo1 0.01529(8) 0.01546(8) 0.01787(8) 0.00067(6) 0.00151(5) -0.00096(6) C1 0.0278(11) 0.0610(18) 0.0209(10) -0.0023(11) -0.0010(8) -0.0012(12) C2 0.0192(9) 0.0302(11) 0.0231(9) -0.0060(8) 0.0027(7) -0.0004(8) C3 0.0371(14) 0.0370(15) 0.064(2) -0.0262(14) 0.0038(13) -0.0072(12) C1R 0.0140(8) 0.0334(11) 0.0308(10) -0.0054(9) 0.0050(7) -0.0019(8) C2R 0.0226(10) 0.0409(13) 0.0315(11) 0.0015(10) 0.0099(9) -0.0099(9) C3R 0.0283(12) 0.0634(18) 0.0261(11) -0.0145(12) 0.0101(9) -0.0135(12) C4R 0.0255(11) 0.0301(12) 0.0573(16) -0.0213(12) 0.0172(11) -0.0052(9) C5R 0.0189(10) 0.0269(11) 0.0468(14) 0.0034(10) 0.0081(9) 0.0064(8) C6R 0.0226(13) 0.0309(14) 0.152(4) -0.021(2) 0.0361(19) -0.0018(11) C7R 0.0307(15) 0.117(4) 0.072(2) 0.062(3) -0.0321(16) -0.037(2) C8R 0.0445(18) 0.085(3) 0.077(2) -0.053(2) 0.0338(17) -0.0464(19) C9R 0.0205(12) 0.0373(16) 0.115(3) 0.0258(19) 0.0079(15) -0.0056(11) C10R 0.0378(15) 0.101(3) 0.0348(14) -0.0016(17) 0.0076(12) -0.0421(19) Cl1 0.0475(4) 0.0244(3) 0.0492(4) 0.0164(3) -0.0115(3) -0.0029(2) F1 0.0572(11) 0.0593(12) 0.0351(9) 0.0246(8) 0.0001(8) 0.0048(9) F2 0.0480(10) 0.124(2) 0.0207(7) -0.0098(10) -0.0057(7) -0.0099(12) F3 0.0747(15) 0.0339(10) 0.124(2) -0.0081(12) 0.0488(15) 0.0100(10) F4A 0.0407(17) 0.0280(14) 0.058(2) -0.0035(13) 0.0109(14) -0.0137(12) F4B 0.061(3) 0.076(4) 0.101(5) -0.030(3) -0.026(3) -0.028(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 Mo1 C2 2.232(2) . ? Mo1 C4R 2.244(2) . ? Mo1 C5R 2.269(2) . ? Mo1 C6R 2.277(3) . ? Mo1 C7R 2.281(3) . ? Mo1 C8R 2.295(3) . ? Mo1 C3R 2.297(2) . ? Mo1 C9R 2.325(3) . ? Mo1 C10R 2.340(3) . ? Mo1 C1R 2.364(2) . ? Mo1 C2R 2.376(2) . ? Mo1 Cl1 2.4929(7) . ? C1 C2 1.316(4) . ? C1 F1 1.326(4) . ? C1 F2 1.343(3) . ? C2 C3 1.488(4) . ? C3 F4A 1.240(4) . ? C3 F3 1.323(4) . ? C3 F4B 1.324(5) . ? C1R C2R 1.398(3) . ? C1R C5R 1.417(3) . ? C2R C3R 1.414(4) . ? C3R C4R 1.422(4) . ? C4R C5R 1.420(4) . ? C6R C10R 1.361(6) . ? C6R C7R 1.420(6) . ? C7R C8R 1.374(6) . ? C8R C9R 1.366(6) . ? C9R C10R 1.329(6) . ? F4A F4B 1.415(7) . ? 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 C2 Mo1 C4R 122.65(10) . . ? C2 Mo1 C5R 85.99(9) . . ? C4R Mo1 C5R 36.66(10) . . ? C2 Mo1 C6R 88.34(14) . . ? C4R Mo1 C6R 135.48(11) . . ? C5R Mo1 C6R 145.28(13) . . ? C2 Mo1 C7R 124.37(16) . . ? C4R Mo1 C7R 107.52(17) . . ? C5R Mo1 C7R 139.06(16) . . ? C6R Mo1 C7R 36.30(17) . . ? C2 Mo1 C8R 134.96(11) . . ? C4R Mo1 C8R 77.88(12) . . ? C5R Mo1 C8R 104.46(14) . . ? C6R Mo1 C8R 58.18(13) . . ? C7R Mo1 C8R 34.95(16) . . ? C2 Mo1 C3R 130.86(9) . . ? C4R Mo1 C3R 36.49(11) . . ? C5R Mo1 C3R 60.89(11) . . ? C6R Mo1 C3R 139.59(15) . . ? C7R Mo1 C3R 103.42(15) . . ? C8R Mo1 C3R 90.49(10) . . ? C2 Mo1 C9R 103.44(13) . . ? C4R Mo1 C9R 83.28(12) . . ? C5R Mo1 C9R 91.28(10) . . ? C6R Mo1 C9R 56.93(12) . . ? C7R Mo1 C9R 57.85(12) . . ? C8R Mo1 C9R 34.37(15) . . ? C3R Mo1 C9R 111.87(14) . . ? C2 Mo1 C10R 78.75(10) . . ? C4R Mo1 C10R 115.19(14) . . ? C5R Mo1 C10R 111.24(13) . . ? C6R Mo1 C10R 34.25(15) . . ? C7R Mo1 C10R 58.03(13) . . ? C8R Mo1 C10R 56.48(12) . . ? C3R Mo1 C10R 144.49(13) . . ? C9R Mo1 C10R 33.11(14) . . ? C2 Mo1 C1R 72.98(8) . . ? C4R Mo1 C1R 59.11(9) . . ? C5R Mo1 C1R 35.55(8) . . ? C6R Mo1 C1R 161.31(14) . . ? C7R Mo1 C1R 162.26(15) . . ? C8R Mo1 C1R 136.62(12) . . ? C3R Mo1 C1R 58.84(9) . . ? C9R Mo1 C1R 126.11(10) . . ? C10R Mo1 C1R 136.34(11) . . ? C2 Mo1 C2R 97.57(8) . . ? C4R Mo1 C2R 58.87(10) . . ? C5R Mo1 C2R 58.96(9) . . ? C6R Mo1 C2R 155.69(14) . . ? C7R Mo1 C2R 130.22(12) . . ? C8R Mo1 C2R 125.63(10) . . ? C3R Mo1 C2R 35.19(9) . . ? C9R Mo1 C2R 142.15(12) . . ? C10R Mo1 C2R 169.97(13) . . ? C1R Mo1 C2R 34.31(8) . . ? C2 Mo1 Cl1 87.16(7) . . ? C4R Mo1 Cl1 127.09(8) . . ? C5R Mo1 Cl1 133.03(7) . . ? C6R Mo1 Cl1 80.70(10) . . ? C7R Mo1 Cl1 80.21(11) . . ? C8R Mo1 Cl1 112.87(14) . . ? C3R Mo1 Cl1 90.62(9) . . ? C9R Mo1 Cl1 135.40(8) . . ? C10R Mo1 Cl1 112.79(12) . . ? C1R Mo1 Cl1 98.47(6) . . ? C2R Mo1 Cl1 76.09(7) . . ? C2 C1 F1 126.9(2) . . ? C2 C1 F2 126.7(3) . . ? F1 C1 F2 106.4(2) . . ? C1 C2 C3 113.4(2) . . ? C1 C2 Mo1 121.62(19) . . ? C3 C2 Mo1 124.8(2) . . ? F4A C3 F3 116.5(3) . . ? F4A C3 F4B 66.9(4) . . ? F3 C3 F4B 118.2(4) . . ? F4A C3 C2 115.7(3) . . ? F3 C3 C2 113.4(2) . . ? F4B C3 C2 118.5(4) . . ? C2R C1R C5R 108.7(2) . . ? C2R C1R Mo1 73.32(13) . . ? C5R C1R Mo1 68.59(12) . . ? C1R C2R C3R 109.0(2) . . ? C1R C2R Mo1 72.37(12) . . ? C3R C2R Mo1 69.35(13) . . ? C2R C3R C4R 106.5(2) . . ? C2R C3R Mo1 75.47(14) . . ? C4R C3R Mo1 69.76(13) . . ? C5R C4R C3R 109.0(2) . . ? C5R C4R Mo1 72.62(13) . . ? C3R C4R Mo1 73.75(15) . . ? C1R C5R C4R 106.7(2) . . ? C1R C5R Mo1 75.86(13) . . ? C4R C5R Mo1 70.72(14) . . ? C10R C6R C7R 107.5(3) . . ? C10R C6R Mo1 75.41(18) . . ? C7R C6R Mo1 72.01(18) . . ? C8R C7R C6R 105.4(3) . . ? C8R C7R Mo1 73.08(18) . . ? C6R C7R Mo1 71.70(16) . . ? C9R C8R C7R 108.8(3) . . ? C9R C8R Mo1 74.02(18) . . ? C7R C8R Mo1 71.96(17) . . ? C10R C9R C8R 109.0(3) . . ? C10R C9R Mo1 74.05(18) . . ? C8R C9R Mo1 71.61(17) . . ? C9R C10R C6R 109.3(3) . . ? C9R C10R Mo1 72.84(18) . . ? C6R C10R Mo1 70.34(17) . . ? C3 F4A F4B 59.4(3) . . ? C3 F4B F4A 53.7(3) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 30.51 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.769 _refine_diff_density_min -0.593 _refine_diff_density_rms 0.083 # Attachment '15a Cp(CO)3MoH x DFA.cif' data_mo13m _database_code_depnum_ccdc_archive 'CCDC 720721' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Cyclopentadienyl(2,2-difluoro-1-methylvinyl)tricarbonylmolybdenum ; _chemical_name_common ;Cyclopentadienyl(2,2-difluoro-1- methylvinyl)tricarbonylmolybdenum ; _chemical_melting_point ? _chemical_formula_moiety 'C11 H8 F2 Mo O3' _chemical_formula_sum 'C11 H8 F2 Mo O3' _chemical_formula_weight 322.11 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mo Mo -1.6832 0.6857 '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 11.084(2) _cell_length_b 8.951(2) _cell_length_c 11.548(2) _cell_angle_alpha 90.00 _cell_angle_beta 95.309(4) _cell_angle_gamma 90.00 _cell_volume 1140.8(4) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 806 _cell_measurement_theta_min 2.67 _cell_measurement_theta_max 30.12 _exptl_crystal_description prism _exptl_crystal_colour yellow _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.875 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 632 _exptl_absorpt_coefficient_mu 1.168 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details 'SADABS (Bruker-AXS)' _exptl_special_details ; 'Ratio of minimum to maximum apparent transmission: 0.874809' ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'SMART-CCD Bruker-AXS' _diffrn_measurement_method 'omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 7686 _diffrn_reflns_av_R_equivalents 0.0226 _diffrn_reflns_av_sigmaI/netI 0.0339 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.44 _diffrn_reflns_theta_max 30.49 _reflns_number_total 3439 _reflns_number_gt 2625 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker-AXS)' _computing_cell_refinement 'SAINT (Bruker-AXS)' _computing_data_reduction 'SAINT (Bruker-AXS)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0264P)^2^+0.5270P] 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_extinction_coef ? _refine_ls_number_reflns 3439 _refine_ls_number_parameters 155 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0465 _refine_ls_R_factor_gt 0.0272 _refine_ls_wR_factor_ref 0.0636 _refine_ls_wR_factor_gt 0.0568 _refine_ls_goodness_of_fit_ref 1.037 _refine_ls_restrained_S_all 1.037 _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 Mo1 Mo 0.723381(17) 0.29097(2) 0.467649(16) 0.02143(6) Uani 1 1 d . . . F1 F 0.93239(17) 0.4182(2) 0.80177(15) 0.0584(5) Uani 1 1 d . . . F2 F 0.96707(16) 0.4472(3) 0.62339(17) 0.0635(6) Uani 1 1 d . . . O3 O 0.78387(19) 0.6341(2) 0.47324(17) 0.0439(5) Uani 1 1 d . . . C3O C 0.7598(2) 0.5100(3) 0.4741(2) 0.0303(5) Uani 1 1 d . . . O1 O 0.47528(19) 0.2272(3) 0.5680(2) 0.0601(6) Uani 1 1 d . . . C2 C 0.7796(3) 0.3357(3) 0.6576(2) 0.0337(6) Uani 1 1 d . . . O2 O 0.5236(2) 0.4207(3) 0.2844(2) 0.0576(6) Uani 1 1 d . . . C1R C 0.7665(3) 0.0342(3) 0.4521(3) 0.0415(7) Uani 1 1 d . . . H1R H 0.7217 -0.0385 0.4865 0.050 Uiso 1 1 calc R . . C5R C 0.8720(3) 0.1021(3) 0.5023(3) 0.0444(7) Uani 1 1 d . . . H5R H 0.9093 0.0828 0.5763 0.053 Uiso 1 1 calc R . . C2R C 0.7400(3) 0.0948(3) 0.3404(2) 0.0414(7) Uani 1 1 d . . . H2R H 0.6740 0.0701 0.2883 0.050 Uiso 1 1 calc R . . C4R C 0.9125(2) 0.2048(4) 0.4219(3) 0.0465(8) Uani 1 1 d . . . H4R H 0.9808 0.2651 0.4335 0.056 Uiso 1 1 calc R . . C1 C 0.8844(3) 0.3959(3) 0.6898(2) 0.0412(7) Uani 1 1 d . . . C3R C 0.8314(3) 0.2001(4) 0.3212(3) 0.0455(7) Uani 1 1 d . . . H3R H 0.8367 0.2560 0.2540 0.055 Uiso 1 1 calc R . . C1O C 0.5672(3) 0.2551(3) 0.5357(2) 0.0387(6) Uani 1 1 d . . . C2O C 0.5974(3) 0.3748(3) 0.3509(2) 0.0380(6) Uani 1 1 d . . . C3 C 0.7069(3) 0.2853(4) 0.7549(2) 0.0598(10) Uani 1 1 d . . . H3 H 0.7535 0.3004 0.8282 0.090 Uiso 1 1 calc R . . H2 H 0.6877 0.1812 0.7454 0.090 Uiso 1 1 calc R . . H1 H 0.6334 0.3422 0.7528 0.090 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 Mo1 0.02046(9) 0.02384(10) 0.01994(9) -0.00014(9) 0.00163(6) 0.00121(9) F1 0.0648(12) 0.0613(12) 0.0441(10) -0.0086(9) -0.0221(9) 0.0067(10) F2 0.0394(10) 0.0907(16) 0.0588(12) -0.0037(11) -0.0030(9) -0.0169(10) O3 0.0510(12) 0.0322(11) 0.0472(11) -0.0015(9) -0.0023(9) -0.0019(10) C3O 0.0299(12) 0.0336(14) 0.0266(12) -0.0011(10) -0.0014(10) 0.0013(11) O1 0.0333(11) 0.0847(18) 0.0646(15) 0.0016(13) 0.0169(10) -0.0046(12) C2 0.0427(15) 0.0310(13) 0.0263(11) 0.0006(10) -0.0023(10) 0.0058(11) O2 0.0545(14) 0.0539(14) 0.0586(14) 0.0150(12) -0.0259(11) -0.0041(12) C1R 0.0478(16) 0.0276(14) 0.0510(17) -0.0021(12) 0.0140(13) 0.0018(12) C5R 0.0432(16) 0.0446(17) 0.0437(15) -0.0096(13) -0.0050(13) 0.0223(14) C2R 0.0425(15) 0.0404(16) 0.0405(15) -0.0180(12) -0.0008(12) 0.0040(13) C4R 0.0269(13) 0.0423(16) 0.073(2) -0.0217(16) 0.0163(13) -0.0023(13) C1 0.0423(16) 0.0450(17) 0.0342(13) -0.0035(12) -0.0083(12) 0.0060(13) C3R 0.0579(18) 0.0449(17) 0.0376(14) -0.0019(13) 0.0254(13) 0.0086(16) C1O 0.0322(13) 0.0463(16) 0.0377(14) 0.0008(12) 0.0045(11) 0.0009(12) C2O 0.0396(15) 0.0329(14) 0.0404(14) 0.0013(12) -0.0027(12) -0.0049(12) C3 0.079(2) 0.074(2) 0.0266(13) 0.0031(15) 0.0045(14) -0.023(2) _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 Mo1 C1O 1.993(3) . ? Mo1 C2O 1.996(3) . ? Mo1 C3O 2.002(3) . ? Mo1 C2 2.260(3) . ? Mo1 C2R 2.308(3) . ? Mo1 C3R 2.308(3) . ? Mo1 C4R 2.339(3) . ? Mo1 C1R 2.358(3) . ? Mo1 C5R 2.369(3) . ? F1 C1 1.367(3) . ? F2 C1 1.330(3) . ? O3 C3O 1.142(3) . ? O1 C1O 1.144(3) . ? C2 C1 1.302(4) . ? C2 C3 1.510(4) . ? O2 C2O 1.146(3) . ? C1R C5R 1.395(4) . ? C1R C2R 1.405(4) . ? C5R C4R 1.410(4) . ? C2R C3R 1.416(4) . ? C4R C3R 1.402(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 C1O Mo1 C2O 75.40(12) . . ? C1O Mo1 C3O 108.83(11) . . ? C2O Mo1 C3O 77.48(11) . . ? C1O Mo1 C2 79.48(11) . . ? C2O Mo1 C2 134.60(11) . . ? C3O Mo1 C2 75.74(10) . . ? C1O Mo1 C2R 104.59(11) . . ? C2O Mo1 C2R 87.02(11) . . ? C3O Mo1 C2R 137.84(10) . . ? C2 Mo1 C2R 136.19(10) . . ? C1O Mo1 C3R 139.51(12) . . ? C2O Mo1 C3R 90.89(12) . . ? C3O Mo1 C3R 104.84(11) . . ? C2 Mo1 C3R 131.16(11) . . ? C2R Mo1 C3R 35.72(11) . . ? C1O Mo1 C4R 149.93(12) . . ? C2O Mo1 C4R 123.84(12) . . ? C3O Mo1 C4R 98.59(11) . . ? C2 Mo1 C4R 96.04(11) . . ? C2R Mo1 C4R 58.63(11) . . ? C3R Mo1 C4R 35.12(11) . . ? C1O Mo1 C1R 93.60(11) . . ? C2O Mo1 C1R 116.69(11) . . ? C3O Mo1 C1R 156.34(10) . . ? C2 Mo1 C1R 101.94(10) . . ? C2R Mo1 C1R 35.03(10) . . ? C3R Mo1 C1R 58.53(10) . . ? C4R Mo1 C1R 57.94(11) . . ? C1O Mo1 C5R 115.74(12) . . ? C2O Mo1 C5R 144.57(11) . . ? C3O Mo1 C5R 123.93(11) . . ? C2 Mo1 C5R 80.63(10) . . ? C2R Mo1 C5R 57.95(10) . . ? C3R Mo1 C5R 58.17(11) . . ? C4R Mo1 C5R 34.85(11) . . ? C1R Mo1 C5R 34.33(10) . . ? O3 C3O Mo1 176.6(2) . . ? C1 C2 C3 115.7(3) . . ? C1 C2 Mo1 120.6(2) . . ? C3 C2 Mo1 123.4(2) . . ? C5R C1R C2R 108.0(3) . . ? C5R C1R Mo1 73.25(16) . . ? C2R C1R Mo1 70.53(16) . . ? C1R C5R C4R 108.4(3) . . ? C1R C5R Mo1 72.42(16) . . ? C4R C5R Mo1 71.42(16) . . ? C1R C2R C3R 108.0(3) . . ? C1R C2R Mo1 74.45(16) . . ? C3R C2R Mo1 72.16(15) . . ? C3R C4R C5R 107.9(3) . . ? C3R C4R Mo1 71.25(15) . . ? C5R C4R Mo1 73.73(15) . . ? C2 C1 F2 128.5(3) . . ? C2 C1 F1 126.1(3) . . ? F2 C1 F1 105.4(2) . . ? C4R C3R C2R 107.7(3) . . ? C4R C3R Mo1 73.63(15) . . ? C2R C3R Mo1 72.12(15) . . ? O1 C1O Mo1 174.8(3) . . ? O2 C2O Mo1 178.7(3) . . ? _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 30.49 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 0.889 _refine_diff_density_min -0.450 _refine_diff_density_rms 0.091 # Attachment '16b (CO)5MnH x DFA.cif' data_mo14m _database_code_depnum_ccdc_archive 'CCDC 720722' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Pentacarbonyl(1,1-difluoromethylvinyl)manganese ; _chemical_name_common Pentacarbonyl(1,1-difluoromethylvinyl)manganese _chemical_melting_point ? _chemical_formula_moiety 'C8 H3 F2 Mn O5' _chemical_formula_sum 'C8 H3 F2 Mn O5' _chemical_formula_weight 272.04 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.3368 0.7283 '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 9.847(4) _cell_length_b 7.692(3) _cell_length_c 13.472(5) _cell_angle_alpha 90.00 _cell_angle_beta 91.411(8) _cell_angle_gamma 90.00 _cell_volume 1020.1(7) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 895 _cell_measurement_theta_min 3.03 _cell_measurement_theta_max 27.11 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.42 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.771 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 536 _exptl_absorpt_coefficient_mu 1.325 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details 'SADABS (Bruker-AXS)' _exptl_special_details ; 'Ratio of minimum to maximum apparent transmission: 0.675784' ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'SMART-CCD Bruker-AXS' _diffrn_measurement_method 'omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 9805 _diffrn_reflns_av_R_equivalents 0.0358 _diffrn_reflns_av_sigmaI/netI 0.0307 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.07 _diffrn_reflns_theta_max 27.52 _reflns_number_total 2331 _reflns_number_gt 1845 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker-AXS)' _computing_cell_refinement 'SAINT (Bruker-AXS)' _computing_data_reduction 'SAINT (Bruker-AXS)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0489P)^2^+0.4903P] 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_extinction_coef ? _refine_ls_number_reflns 2331 _refine_ls_number_parameters 145 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0531 _refine_ls_R_factor_gt 0.0361 _refine_ls_wR_factor_ref 0.0969 _refine_ls_wR_factor_gt 0.0850 _refine_ls_goodness_of_fit_ref 1.092 _refine_ls_restrained_S_all 1.092 _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 Mn1 Mn 0.72044(3) 0.19947(4) 0.12309(2) 0.02749(13) Uani 1 1 d . . . C2O C 0.8944(3) 0.1930(3) 0.07111(18) 0.0325(5) Uani 1 1 d . . . O2 O 1.0010(2) 0.1953(3) 0.04250(15) 0.0465(5) Uani 1 1 d . . . F2 F 0.6904(3) 0.4188(3) 0.33686(13) 0.0743(6) Uani 1 1 d . . . O1 O 0.6126(2) 0.4031(3) -0.05156(14) 0.0479(5) Uani 1 1 d . . . F1 F 0.9068(3) 0.3731(3) 0.32741(17) 0.0865(8) Uani 1 1 d . . . O3 O 0.8234(2) -0.0044(3) 0.29960(14) 0.0465(5) Uani 1 1 d . . . C4O C 0.5557(3) 0.2429(4) 0.18486(19) 0.0381(6) Uani 1 1 d . . . O5 O 0.6287(2) -0.1313(3) 0.02782(16) 0.0515(5) Uani 1 1 d . . . O4 O 0.4555(2) 0.2721(3) 0.22079(17) 0.0598(6) Uani 1 1 d . . . C1O C 0.6543(3) 0.3258(3) 0.01356(18) 0.0344(5) Uani 1 1 d . . . C5O C 0.6630(3) -0.0058(3) 0.06502(18) 0.0358(5) Uani 1 1 d . . . C3O C 0.7854(2) 0.0775(3) 0.23458(18) 0.0331(5) Uani 1 1 d . . . C2 C 0.7889(2) 0.4407(3) 0.17905(19) 0.0337(5) Uani 1 1 d . . . C1 C 0.8295(3) 0.5755(4) 0.1244(2) 0.0495(7) Uani 1 1 d . . . H1A H 0.8620 0.6758 0.1554 0.059 Uiso 1 1 calc R . . H1B H 0.8251 0.5690 0.0555 0.059 Uiso 1 1 calc R . . C3 C 0.8020(3) 0.4708(4) 0.2871(2) 0.0487(7) Uani 1 1 d . . . H3 H 0.8191 0.5944 0.2999 0.058 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 Mn1 0.0293(2) 0.02624(19) 0.0270(2) 0.00108(14) 0.00137(13) -0.00052(14) C2O 0.0369(13) 0.0301(11) 0.0305(11) 0.0013(10) 0.0010(10) 0.0015(10) O2 0.0386(10) 0.0524(12) 0.0488(11) 0.0061(9) 0.0109(9) 0.0028(9) F2 0.1212(18) 0.0636(12) 0.0390(9) -0.0108(9) 0.0236(10) -0.0190(12) O1 0.0528(12) 0.0515(11) 0.0393(10) 0.0123(9) 0.0011(9) 0.0130(9) F1 0.1222(19) 0.0556(11) 0.0785(14) -0.0081(11) -0.0618(14) 0.0185(12) O3 0.0514(11) 0.0478(11) 0.0404(10) 0.0124(9) -0.0009(9) 0.0040(9) C4O 0.0369(14) 0.0428(13) 0.0345(13) 0.0054(11) 0.0002(11) -0.0012(11) O5 0.0630(13) 0.0344(10) 0.0562(12) -0.0046(9) -0.0155(10) -0.0042(9) O4 0.0400(12) 0.0789(16) 0.0612(14) 0.0068(12) 0.0149(10) 0.0077(11) C1O 0.0368(13) 0.0328(12) 0.0337(12) -0.0005(10) 0.0036(10) 0.0032(10) C5O 0.0396(13) 0.0342(13) 0.0332(12) 0.0030(10) -0.0049(10) 0.0011(10) C3O 0.0307(12) 0.0331(12) 0.0357(13) -0.0003(10) 0.0033(10) -0.0013(10) C2 0.0321(12) 0.0305(12) 0.0384(13) -0.0030(10) -0.0012(10) 0.0009(9) C1 0.0581(18) 0.0346(13) 0.0560(17) 0.0007(12) 0.0023(14) -0.0103(12) C3 0.0688(19) 0.0333(13) 0.0433(15) -0.0021(12) -0.0122(14) -0.0004(13) _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 Mn1 C5O 1.844(3) . ? Mn1 C2O 1.868(3) . ? Mn1 C1O 1.870(3) . ? Mn1 C3O 1.870(3) . ? Mn1 C4O 1.871(3) . ? Mn1 C2 2.107(2) . ? C2O O2 1.127(3) . ? F2 C3 1.361(4) . ? O1 C1O 1.129(3) . ? F1 C3 1.377(3) . ? O3 C3O 1.135(3) . ? C4O O4 1.132(3) . ? O5 C5O 1.135(3) . ? C2 C1 1.339(4) . ? C2 C3 1.476(4) . ? 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 C5O Mn1 C2O 95.31(11) . . ? C5O Mn1 C1O 90.74(11) . . ? C2O Mn1 C1O 91.31(11) . . ? C5O Mn1 C3O 90.38(11) . . ? C2O Mn1 C3O 89.36(10) . . ? C1O Mn1 C3O 178.64(10) . . ? C5O Mn1 C4O 94.68(12) . . ? C2O Mn1 C4O 170.01(11) . . ? C1O Mn1 C4O 88.24(11) . . ? C3O Mn1 C4O 90.89(11) . . ? C5O Mn1 C2 175.85(10) . . ? C2O Mn1 C2 82.48(10) . . ? C1O Mn1 C2 85.82(10) . . ? C3O Mn1 C2 93.10(10) . . ? C4O Mn1 C2 87.53(11) . . ? O2 C2O Mn1 176.8(2) . . ? O4 C4O Mn1 178.5(3) . . ? O1 C1O Mn1 178.8(2) . . ? O5 C5O Mn1 178.8(2) . . ? O3 C3O Mn1 176.4(2) . . ? C1 C2 C3 113.6(2) . . ? C1 C2 Mn1 125.6(2) . . ? C3 C2 Mn1 120.68(18) . . ? F2 C3 F1 104.6(2) . . ? F2 C3 C2 112.8(2) . . ? F1 C3 C2 110.4(2) . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 27.52 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.710 _refine_diff_density_min -0.472 _refine_diff_density_rms 0.087 # Attachment '6a Cp(CO)3MoH x TFA.cif' data_mor12m _database_code_depnum_ccdc_archive 'CCDC 720723' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point 336 _chemical_formula_moiety 'C11 H6 F4 Mo O3' _chemical_formula_sum 'C11 H6 F4 Mo O3' _chemical_formula_weight 358.10 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mo Mo -1.6832 0.6857 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/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 8.0792(11) _cell_length_b 12.7380(18) _cell_length_c 11.6673(18) _cell_angle_alpha 90.00 _cell_angle_beta 93.838(13) _cell_angle_gamma 90.00 _cell_volume 1198.0(3) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 983 _cell_measurement_theta_min 2.97 _cell_measurement_theta_max 30.46 _exptl_crystal_description plate _exptl_crystal_colour yellow _exptl_crystal_size_max 0.46 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.985 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 696 _exptl_absorpt_coefficient_mu 1.146 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details 'SADABS (Bruker-AXS)' _exptl_special_details ; 'Ratio of minimum to maximum apparent transmission: 0.805289' ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'SMART-CCD Bruker-AXS' _diffrn_measurement_method 'omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 14540 _diffrn_reflns_av_R_equivalents 0.0220 _diffrn_reflns_av_sigmaI/netI 0.0196 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.37 _diffrn_reflns_theta_max 30.52 _reflns_number_total 3634 _reflns_number_gt 3122 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker-AXS)' _computing_cell_refinement 'SAINT (Bruker-AXS)' _computing_data_reduction 'SAINT (Bruker-AXS)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0376P)^2^+0.8010P] 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_extinction_coef ? _refine_ls_number_reflns 3634 _refine_ls_number_parameters 172 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0315 _refine_ls_R_factor_gt 0.0242 _refine_ls_wR_factor_ref 0.0701 _refine_ls_wR_factor_gt 0.0653 _refine_ls_goodness_of_fit_ref 1.055 _refine_ls_restrained_S_all 1.055 _refine_ls_shift/su_max 0.000 _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 Mo1 Mo 0.172436(17) 0.221070(12) 0.303300(13) 0.02135(6) Uani 1 1 d . . . C1 C -0.0775(3) 0.3751(2) 0.4136(2) 0.0445(6) Uani 1 1 d . . . C2 C -0.0278(3) 0.34271(17) 0.3154(2) 0.0309(4) Uani 1 1 d . . . C3 C -0.1334(3) 0.3824(2) 0.2145(2) 0.0392(5) Uani 1 1 d . . . H1 H -0.2384 0.4129 0.2409 0.047 Uiso 1 1 calc R . . C1O C 0.1758(3) 0.27691(19) 0.1429(2) 0.0356(5) Uani 1 1 d . . . C2O C 0.4131(3) 0.2169(2) 0.2740(2) 0.0437(6) Uani 1 1 d . . . C3O C 0.2824(3) 0.32671(18) 0.41027(19) 0.0343(4) Uani 1 1 d . . . C1R C 0.0629(3) 0.11035(17) 0.4387(2) 0.0342(4) Uani 1 1 d . . . H1R H 0.0474 0.1343 0.5144 0.041 Uiso 1 1 calc R . . C2R C 0.2087(3) 0.06491(18) 0.4002(2) 0.0355(5) Uani 1 1 d . . . H2R H 0.3087 0.0523 0.4457 0.043 Uiso 1 1 calc R . . C3R C 0.1796(3) 0.04150(19) 0.2816(2) 0.0405(5) Uani 1 1 d . . . H3R H 0.2569 0.0108 0.2337 0.049 Uiso 1 1 calc R . . C4R C 0.0151(3) 0.07196(19) 0.2475(2) 0.0407(5) Uani 1 1 d . . . H4R H -0.0377 0.0653 0.1726 0.049 Uiso 1 1 calc R . . C5R C -0.0560(3) 0.11374(18) 0.3440(2) 0.0383(5) Uani 1 1 d . . . H5R H -0.1659 0.1400 0.3455 0.046 Uiso 1 1 calc R . . F2 F -0.0102(2) 0.35052(15) 0.51701(14) 0.0584(4) Uani 1 1 d . . . F1 F -0.2088(3) 0.43597(18) 0.4312(2) 0.0824(7) Uani 1 1 d . . . F3 F -0.0495(2) 0.45728(14) 0.15591(16) 0.0595(5) Uani 1 1 d . . . F4 F -0.16943(18) 0.30495(13) 0.13656(14) 0.0453(3) Uani 1 1 d . . . O1 O 0.1818(3) 0.30066(19) 0.04916(16) 0.0541(5) Uani 1 1 d . . . O2 O 0.5512(2) 0.2167(2) 0.2596(2) 0.0711(8) Uani 1 1 d . . . O3 O 0.3516(3) 0.38461(16) 0.47034(17) 0.0531(5) 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 Mo1 0.02025(8) 0.02252(9) 0.02105(9) 0.00035(6) -0.00022(5) -0.00005(5) C1 0.0484(13) 0.0404(13) 0.0453(14) -0.0049(11) 0.0090(11) 0.0112(11) C2 0.0311(9) 0.0251(9) 0.0365(11) 0.0008(8) 0.0023(8) 0.0029(8) C3 0.0348(10) 0.0340(12) 0.0482(14) 0.0075(10) -0.0014(9) 0.0025(9) C1O 0.0337(10) 0.0409(13) 0.0325(11) 0.0008(9) 0.0054(8) -0.0023(9) C2O 0.0297(10) 0.0640(18) 0.0372(13) -0.0018(12) 0.0013(9) -0.0015(10) C3O 0.0399(11) 0.0312(11) 0.0309(11) 0.0027(9) -0.0037(8) -0.0030(9) C1R 0.0402(11) 0.0289(10) 0.0339(11) 0.0056(9) 0.0048(9) -0.0027(8) C2R 0.0395(11) 0.0271(10) 0.0388(12) 0.0031(9) -0.0058(9) 0.0051(8) C3R 0.0505(13) 0.0274(11) 0.0426(13) -0.0077(9) -0.0034(10) 0.0059(9) C4R 0.0479(13) 0.0303(11) 0.0416(13) 0.0006(9) -0.0136(10) -0.0087(9) C5R 0.0299(9) 0.0302(11) 0.0543(15) 0.0082(10) -0.0006(9) -0.0061(8) F2 0.0751(11) 0.0673(11) 0.0337(8) -0.0079(8) 0.0114(7) 0.0130(9) F1 0.0839(14) 0.0756(14) 0.0903(15) -0.0142(12) 0.0251(12) 0.0351(12) F3 0.0634(10) 0.0472(9) 0.0653(11) 0.0282(8) -0.0156(8) -0.0123(8) F4 0.0383(7) 0.0502(8) 0.0454(9) 0.0011(7) -0.0122(6) -0.0037(6) O1 0.0601(12) 0.0723(14) 0.0308(9) 0.0096(9) 0.0099(8) -0.0033(10) O2 0.0277(9) 0.122(2) 0.0637(15) -0.0009(14) 0.0066(9) -0.0030(11) O3 0.0673(12) 0.0453(11) 0.0441(11) -0.0037(9) -0.0154(9) -0.0140(9) _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 Mo1 C2O 1.997(2) . ? Mo1 C3O 2.002(2) . ? Mo1 C1O 2.004(2) . ? Mo1 C2 2.252(2) . ? Mo1 C2R 2.297(2) . ? Mo1 C3R 2.302(2) . ? Mo1 C1R 2.336(2) . ? Mo1 C4R 2.353(2) . ? Mo1 C5R 2.370(2) . ? C1 C2 1.305(3) . ? C1 F2 1.327(3) . ? C1 F1 1.341(3) . ? C2 C3 1.495(3) . ? C3 F4 1.360(3) . ? C3 F3 1.378(3) . ? C1O O1 1.139(3) . ? C2O O2 1.140(3) . ? C3O O3 1.138(3) . ? C1R C5R 1.415(3) . ? C1R C2R 1.413(3) . ? C2R C3R 1.419(3) . ? C3R C4R 1.416(3) . ? C4R C5R 1.402(4) . ? 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 C2O Mo1 C3O 74.22(10) . . ? C2O Mo1 C1O 77.03(11) . . ? C3O Mo1 C1O 108.09(10) . . ? C2O Mo1 C2 137.81(10) . . ? C3O Mo1 C2 77.82(9) . . ? C1O Mo1 C2 82.47(9) . . ? C2O Mo1 C2R 88.14(10) . . ? C3O Mo1 C2R 103.80(9) . . ? C1O Mo1 C2R 139.26(9) . . ? C2 Mo1 C2R 129.32(8) . . ? C2O Mo1 C3R 85.58(11) . . ? C3O Mo1 C3R 136.28(9) . . ? C1O Mo1 C3R 104.37(10) . . ? C2 Mo1 C3R 135.57(8) . . ? C2R Mo1 C3R 35.94(8) . . ? C2O Mo1 C1R 121.14(10) . . ? C3O Mo1 C1R 99.01(9) . . ? C1O Mo1 C1R 151.09(9) . . ? C2 Mo1 C1R 93.82(8) . . ? C2R Mo1 C1R 35.51(8) . . ? C3R Mo1 C1R 59.19(9) . . ? C2O Mo1 C4R 116.45(11) . . ? C3O Mo1 C4R 157.50(9) . . ? C1O Mo1 C4R 93.95(9) . . ? C2 Mo1 C4R 101.28(9) . . ? C2R Mo1 C4R 59.07(8) . . ? C3R Mo1 C4R 35.40(9) . . ? C1R Mo1 C4R 58.50(9) . . ? C2O Mo1 C5R 143.03(10) . . ? C3O Mo1 C5R 125.57(9) . . ? C1O Mo1 C5R 116.82(9) . . ? C2 Mo1 C5R 79.16(8) . . ? C2R Mo1 C5R 58.49(8) . . ? C3R Mo1 C5R 58.31(9) . . ? C1R Mo1 C5R 34.99(8) . . ? C4R Mo1 C5R 34.54(9) . . ? C2 C1 F2 126.3(2) . . ? C2 C1 F1 127.5(3) . . ? F2 C1 F1 106.1(2) . . ? C1 C2 C3 113.1(2) . . ? C1 C2 Mo1 122.45(18) . . ? C3 C2 Mo1 123.90(16) . . ? F4 C3 F3 105.1(2) . . ? F4 C3 C2 111.52(19) . . ? F3 C3 C2 110.5(2) . . ? O1 C1O Mo1 174.4(2) . . ? O2 C2O Mo1 178.1(3) . . ? O3 C3O Mo1 176.9(2) . . ? C5R C1R C2R 107.5(2) . . ? C5R C1R Mo1 73.83(13) . . ? C2R C1R Mo1 70.75(13) . . ? C1R C2R C3R 108.0(2) . . ? C1R C2R Mo1 73.74(12) . . ? C3R C2R Mo1 72.24(13) . . ? C4R C3R C2R 107.9(2) . . ? C4R C3R Mo1 74.25(14) . . ? C2R C3R Mo1 71.82(13) . . ? C5R C4R C3R 107.8(2) . . ? C5R C4R Mo1 73.39(13) . . ? C3R C4R Mo1 70.35(13) . . ? C4R C5R C1R 108.8(2) . . ? C4R C5R Mo1 72.06(13) . . ? C1R C5R Mo1 71.18(12) . . ? _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 30.52 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 1.358 _refine_diff_density_min -0.627 _refine_diff_density_rms 0.083 # Attachment '7a (CO)5MnH x TFA.cif' data_mo112m _database_code_depnum_ccdc_archive 'CCDC 720724' _audit_creation_method SHELXL-97 _chemical_name_systematic ; (Pentacarbonyl)(1-difluoromethyl-2,2-difluorovinyl)manganese ; _chemical_name_common (Pentacarbonyl)(1-difluoromethyl-2,2-difluorovinyl)manganese _chemical_melting_point 288 _chemical_formula_moiety 'C8 H F4 Mn O5' _chemical_formula_sum 'C8 H F4 Mn O5' _chemical_formula_weight 308.03 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/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 11.495(4) _cell_length_b 7.687(4) _cell_length_c 13.148(4) _cell_angle_alpha 90.00 _cell_angle_beta 115.410(5) _cell_angle_gamma 90.00 _cell_volume 1049.4(7) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 880 _cell_measurement_theta_min 3.12 _cell_measurement_theta_max 30.31 _exptl_crystal_description plate _exptl_crystal_colour colourless _exptl_crystal_size_max 0.48 _exptl_crystal_size_mid 0.11 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.950 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 600 _exptl_absorpt_coefficient_mu 1.327 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details 'SADABS (Bruker-AXS)' _exptl_special_details ; 'Ratio of minimum to maximum apparent transmission: 0.820669' ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'SMART-CCD Bruker-AXS' _diffrn_measurement_method 'omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 12396 _diffrn_reflns_av_R_equivalents 0.0303 _diffrn_reflns_av_sigmaI/netI 0.0295 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.98 _diffrn_reflns_theta_max 30.50 _reflns_number_total 3179 _reflns_number_gt 2443 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker-AXS)' _computing_cell_refinement 'SAINT (Bruker-AXS)' _computing_data_reduction 'SAINT (Bruker-AXS)' _computing_structure_solution 'SIR97 (Altomare et al, 1999)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0538P)^2^+0.3731P] 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_extinction_coef ? _refine_ls_number_reflns 3179 _refine_ls_number_parameters 167 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0572 _refine_ls_R_factor_gt 0.0373 _refine_ls_wR_factor_ref 0.1009 _refine_ls_wR_factor_gt 0.0885 _refine_ls_goodness_of_fit_ref 1.057 _refine_ls_restrained_S_all 1.057 _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 Mn1 Mn 0.75374(3) 0.23296(4) 0.46291(2) 0.02271(10) Uani 1 1 d . . . F3 F 0.43885(13) 0.4275(2) 0.32523(15) 0.0570(5) Uani 1 1 d . . . F1 F 0.63213(14) 0.75614(16) 0.49799(13) 0.0400(3) Uani 1 1 d . . . F2 F 0.78746(14) 0.59835(18) 0.61238(11) 0.0410(3) Uani 1 1 d . . . F4 F 0.55851(15) 0.4569(2) 0.23567(11) 0.0503(4) Uani 1 1 d . . . C3O C 0.91174(19) 0.3396(3) 0.54974(17) 0.0266(4) Uani 1 1 d . . . O1 O 0.50311(16) 0.0487(2) 0.32896(16) 0.0465(4) Uani 1 1 d . . . O5 O 0.88530(15) -0.1114(2) 0.50478(15) 0.0397(4) Uani 1 1 d . . . C4O C 0.71667(18) 0.2215(3) 0.58925(19) 0.0283(4) Uani 1 1 d . . . O4 O 0.69107(17) 0.2185(2) 0.66259(16) 0.0442(4) Uani 1 1 d . . . C1O C 0.5958(2) 0.1227(3) 0.37760(18) 0.0307(4) Uani 1 1 d . . . C2O C 0.7818(2) 0.2739(3) 0.33462(19) 0.0301(4) Uani 1 1 d . . . O3 O 1.00950(14) 0.3987(2) 0.60212(14) 0.0374(4) Uani 1 1 d . . . O2 O 0.80192(17) 0.2990(3) 0.25906(15) 0.0452(4) Uani 1 1 d . . . C5O C 0.83479(18) 0.0203(3) 0.48920(18) 0.0286(4) Uani 1 1 d . . . C3 C 0.5444(2) 0.5166(3) 0.32835(19) 0.0331(5) Uani 1 1 d . . . C2 C 0.65994(18) 0.4757(3) 0.43449(17) 0.0256(4) Uani 1 1 d . . . C1 C 0.6912(2) 0.6012(3) 0.50915(18) 0.0295(4) Uani 1 1 d . . . H1 H 0.521(2) 0.638(3) 0.315(2) 0.033(6) 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 Mn1 0.01837(14) 0.02603(16) 0.01989(16) 0.00055(11) 0.00456(11) -0.00232(10) F3 0.0224(6) 0.0601(10) 0.0701(11) 0.0094(8) 0.0024(6) -0.0063(6) F1 0.0443(8) 0.0291(6) 0.0442(8) -0.0006(5) 0.0167(6) 0.0065(5) F2 0.0435(7) 0.0420(7) 0.0254(7) -0.0066(5) 0.0032(6) 0.0032(6) F4 0.0545(9) 0.0577(9) 0.0228(7) 0.0008(6) 0.0014(6) 0.0153(7) C3O 0.0269(9) 0.0293(9) 0.0223(10) 0.0012(7) 0.0094(7) -0.0016(7) O1 0.0319(8) 0.0489(10) 0.0421(10) 0.0016(8) 0.0000(7) -0.0155(7) O5 0.0303(8) 0.0330(8) 0.0497(11) -0.0010(7) 0.0114(7) 0.0025(6) C4O 0.0205(8) 0.0326(10) 0.0289(11) 0.0083(8) 0.0079(8) 0.0024(7) O4 0.0415(9) 0.0610(11) 0.0352(10) 0.0144(8) 0.0215(8) 0.0079(8) C1O 0.0286(9) 0.0310(10) 0.0259(10) 0.0035(8) 0.0056(8) -0.0029(8) C2O 0.0272(9) 0.0340(10) 0.0260(11) -0.0040(8) 0.0085(8) -0.0047(8) O3 0.0262(7) 0.0459(9) 0.0339(9) -0.0052(7) 0.0069(6) -0.0099(6) O2 0.0456(10) 0.0615(11) 0.0314(9) -0.0028(8) 0.0193(8) -0.0054(8) C5O 0.0227(9) 0.0303(10) 0.0288(10) -0.0033(8) 0.0072(7) -0.0054(7) C3 0.0259(9) 0.0355(11) 0.0302(11) 0.0022(9) 0.0048(8) 0.0006(8) C2 0.0230(8) 0.0279(9) 0.0240(10) 0.0033(7) 0.0081(7) -0.0013(7) C1 0.0296(9) 0.0291(10) 0.0264(10) 0.0023(8) 0.0089(8) 0.0012(7) _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 Mn1 C5O 1.840(2) . ? Mn1 C3O 1.869(2) . ? Mn1 C2O 1.875(2) . ? Mn1 C1O 1.878(2) . ? Mn1 C4O 1.886(2) . ? Mn1 C2 2.106(2) . ? F3 C3 1.379(3) . ? F1 C1 1.347(2) . ? F2 C1 1.334(2) . ? F4 C3 1.375(3) . ? C3O O3 1.131(2) . ? O1 C1O 1.132(2) . ? O5 C5O 1.141(3) . ? C4O O4 1.123(3) . ? C2O O2 1.130(3) . ? C3 C2 1.490(3) . ? C2 C1 1.312(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 C5O Mn1 C3O 89.65(9) . . ? C5O Mn1 C2O 92.84(10) . . ? C3O Mn1 C2O 88.79(9) . . ? C5O Mn1 C1O 89.60(9) . . ? C3O Mn1 C1O 178.98(9) . . ? C2O Mn1 C1O 91.93(9) . . ? C5O Mn1 C4O 94.63(9) . . ? C3O Mn1 C4O 90.58(9) . . ? C2O Mn1 C4O 172.50(9) . . ? C1O Mn1 C4O 88.80(10) . . ? C5O Mn1 C2 179.19(9) . . ? C3O Mn1 C2 90.53(9) . . ? C2O Mn1 C2 87.95(9) . . ? C1O Mn1 C2 90.21(9) . . ? C4O Mn1 C2 84.58(8) . . ? O3 C3O Mn1 177.52(19) . . ? O4 C4O Mn1 177.59(18) . . ? O1 C1O Mn1 176.57(19) . . ? O2 C2O Mn1 178.23(19) . . ? O5 C5O Mn1 179.4(2) . . ? F4 C3 F3 104.18(18) . . ? F4 C3 C2 111.31(18) . . ? F3 C3 C2 110.03(18) . . ? C1 C2 C3 113.16(18) . . ? C1 C2 Mn1 124.33(15) . . ? C3 C2 Mn1 122.39(15) . . ? C2 C1 F2 126.18(18) . . ? C2 C1 F1 127.26(19) . . ? F2 C1 F1 106.55(17) . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 30.50 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.863 _refine_diff_density_min -0.366 _refine_diff_density_rms 0.102