############################################################################ # # # # # ### # # ### ### # ### # # ### # # ### # ### # # # # # # # # # # # # # ## ## # ## # # # # # # # # # # ### # # ### ### # ### # # # ### # ## # ### ### # # # # # # # # # # # # # # # # # # ## # # # ### ### # # ### ### # # ### # # # # # # # # # # # # # # # # # ### ### ### # # # # # ## ## # # # # # # # # # # # # # # # ### # ### ### # ### # # # # # # # # # ## # # # # # # # # # # # ### # # # # # ### # # # # # ############################################################################ ############################################################################ # # # This Supplementary Material is written in the Crystallographic # # Information File (CIF) format. For further details see: S.R. Hall, # # F.H. Allen and I.D. Brown, Acta Cryst. (1991) A47, 655-685. # # # ############################################################################ data_5952 ############################################################################ # # _publ_requested_journal 'J.Am.Chem.Soc.' #_publ_requested_category ?FI ; full inorganic #_publ_requested_category ?FM ; full organometallic #_publ_requested_category ?FO ; full organic #?If CI, CM or CO remember to remove section "..._molecular_graphics" #_publ_requested_category ?CI ; electronic inorganic #_publ_requested_category ?CM ; electronic organometallic #_publ_requested_category ?CO ; electronic organic _publ_section_title ; Cycloisomerization Reactions Catalyzed by Low-Valent Iron Complexes: Preparative and Mechanistic Aspects Concerning the Alder-Ene, [5+2], [4+2], [2+2+2] Manifolds ; loop_ _publ_author_name _publ_author_address 'A. F\"urstner' ; Max-Planck-Institut f\"ur Kohlenforschung Kaiser-Wilhelm-Platz 1 D-45470 M\"ulheim an der Ruhr Germany ; 'K. Majima' ; Max-Planck-Institut f\"ur Kohlenforschung Kaiser-Wilhelm-Platz 1 D-45470 M\"ulheim an der Ruhr Germany ; 'R. Martin' ; Max-Planck-Institut f\"ur Kohlenforschung Kaiser-Wilhelm-Platz 1 D-45470 M\"ulheim an der Ruhr Germany ; 'H. Krause' ; Max-Planck-Institut f\"ur Kohlenforschung Kaiser-Wilhelm-Platz 1 D-45470 M\"ulheim an der Ruhr Germany ; 'E. Kattnig' ; Max-Planck-Institut f\"ur Kohlenforschung Kaiser-Wilhelm-Platz 1 D-45470 M\"ulheim an der Ruhr Germany ; 'R. Goddard' ; Max-Planck-Institut f\"ur Kohlenforschung Kaiser-Wilhelm-Platz 1 D-45470 M\"ulheim an der Ruhr Germany ; 'C.W. Lehmann' ; Max-Planck-Institut f\"ur Kohlenforschung Kaiser-Wilhelm-Platz 1 D-45470 M\"ulheim an der Ruhr Germany ; # # ############################################################################ _audit_creation_date 2007-09-05 _audit_block_code MJM-MC-193-01 _chemical_name_systematic ; tetramethyl-ethylenediamine-lithium-bis-ethylene-cyclopentadienyl-iron ; _chemical_melting_point ? _chemical_compound_source 'tetrahydrofuran' _chemical_formula_moiety 'C9 H13 Fe 1-, Li 1+, C6 H16 N2' _chemical_formula_sum 'C15 H29 Fe Li N2' _chemical_formula_weight 300.19 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' 'Fe' 'Fe' 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Li' 'Li' -0.0003 0.0001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-p 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.1030(2) _cell_length_b 9.4613(2) _cell_length_c 11.1671(2) _cell_angle_alpha 94.945(1) _cell_angle_beta 98.755(1) _cell_angle_gamma 107.135(1) _cell_volume 800.77(3) _cell_formula_units_Z 2 _cell_measurement_temperature 100 _cell_measurement_reflns_used 37181 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 40.25 _exptl_crystal_description prism _exptl_crystal_colour orange _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.11 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas none _exptl_crystal_density_diffrn 1.245 _exptl_crystal_density_method none _exptl_crystal_F_000 324 _exptl_absorpt_coefficient_mu 0.930 _exptl_absorpt_correction_type gaussian _exptl_absorpt_process_details 'XPREP, Siemens (1995)' _exptl_absorpt_correction_T_min 0.86537 _exptl_absorpt_correction_T_max 0.93035 _diffrn_ambient_temperature 100 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source '0.3 mm focus rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius KappaCCD' _diffrn_measurement_method 'CCD \w-scan' _diffrn_detector_area_resol_mean 18.18 _diffrn_standards_number 0 _diffrn_standards_decay_% 0.0 _diffrn_reflns_number 29174 _diffrn_reflns_av_R_equivalents 0.0407 _diffrn_reflns_av_sigmaI/netI 0.0317 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.92 _diffrn_reflns_theta_max 37.47 _reflns_number_total 8064 _reflns_number_gt 7358 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Collect software (Nonius, 1998)' _computing_cell_refinement 'Denzo / Scalepack (Otwinowski 1997)' _computing_data_reduction 'Denzo / Scalepack (Otwinowski 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'DIAMOND (Crystal Impact GbR, 2005)' _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. Highest peak 0.75 at 0.2493 0.5986 0.1678 [ 0.81 A from C10 ] Deepest hole -0.97 at 0.2207 0.1782 0.2240 [ 0.60 A from FE1 ] ; _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^)+(0.0422P)^2^+0.3209P] 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 8064 _refine_ls_number_parameters 172 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0401 _refine_ls_R_factor_gt 0.0356 _refine_ls_wR_factor_ref 0.0927 _refine_ls_wR_factor_gt 0.0897 _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 C1 C 0.24550(13) 0.08296(11) 0.09937(8) 0.01706(15) Uani 1 1 d . . . H1A H 0.3549 0.0690 0.0844 0.020 Uiso 1 1 calc R . . H1B H 0.1415 0.0052 0.0552 0.020 Uiso 1 1 calc R . . C2 C 0.23771(15) 0.23299(12) 0.10837(9) 0.02052(17) Uani 1 1 d . . . H2A H 0.1290 0.2465 0.0694 0.025 Uiso 1 1 calc R . . H2B H 0.3423 0.3102 0.0987 0.025 Uiso 1 1 calc R . . C3 C -0.00482(13) 0.01458(12) 0.26109(10) 0.01976(16) Uani 1 1 d . . . H3A H -0.0565 -0.0501 0.1839 0.024 Uiso 1 1 calc R . . H3B H -0.0285 -0.0344 0.3323 0.024 Uiso 1 1 calc R . . C4 C -0.00936(14) 0.16529(12) 0.26578(10) 0.02144(17) Uani 1 1 d . . . H4A H -0.0362 0.2079 0.3398 0.026 Uiso 1 1 calc R . . H4B H -0.0642 0.1922 0.1915 0.026 Uiso 1 1 calc R . . C5 C 0.41514(14) 0.09306(12) 0.39037(9) 0.02041(17) Uani 1 1 d . . . H5 H 0.4255 -0.0077 0.3879 0.024 Uiso 1 1 calc R . . C6 C 0.50977(13) 0.21079(12) 0.33131(10) 0.02115(17) Uani 1 1 d . . . H6 H 0.5946 0.2040 0.2790 0.025 Uiso 1 1 calc R . . C7 C 0.46197(15) 0.34052(12) 0.36327(11) 0.02380(19) Uani 1 1 d . . . H7 H 0.5057 0.4374 0.3347 0.029 Uiso 1 1 calc R . . C8 C 0.33917(16) 0.30506(13) 0.44178(10) 0.0252(2) Uani 1 1 d . . . H8 H 0.2831 0.3730 0.4774 0.030 Uiso 1 1 calc R . . C9 C 0.31009(16) 0.15297(13) 0.45958(9) 0.02362(19) Uani 1 1 d . . . H9 H 0.2327 0.0989 0.5113 0.028 Uiso 1 1 calc R . . C10 C 0.33719(15) -0.35705(12) 0.21833(12) 0.02425(19) Uani 1 1 d . . . H10A H 0.4037 -0.3275 0.3012 0.029 Uiso 1 1 calc R . . H10B H 0.3813 -0.4291 0.1774 0.029 Uiso 1 1 calc R . . C11 C 0.14469(15) -0.42955(12) 0.22220(12) 0.0253(2) Uani 1 1 d . . . H11A H 0.0797 -0.4678 0.1396 0.030 Uiso 1 1 calc R . . H11B H 0.1328 -0.5131 0.2684 0.030 Uiso 1 1 calc R . . C12 C 0.55339(13) -0.14286(13) 0.17581(10) 0.02242(18) Uani 1 1 d . . . H12A H 0.5961 -0.1135 0.2621 0.034 Uiso 1 1 calc R . . H12B H 0.5725 -0.0556 0.1353 0.034 Uiso 1 1 calc R . . H12C H 0.6151 -0.2060 0.1445 0.034 Uiso 1 1 calc R . . C13 C 0.30230(15) -0.26866(14) 0.02096(10) 0.02500(19) Uani 1 1 d . . . H13A H 0.3211 -0.1808 -0.0188 0.037 Uiso 1 1 calc R . . H13B H 0.1792 -0.3237 0.0048 0.037 Uiso 1 1 calc R . . H13C H 0.3664 -0.3300 -0.0097 0.037 Uiso 1 1 calc R . . C14 C 0.12361(19) -0.29790(16) 0.41274(12) 0.0318(2) Uani 1 1 d . . . H14A H 0.2494 -0.2586 0.4339 0.048 Uiso 1 1 calc R . . H14B H 0.0842 -0.3912 0.4438 0.048 Uiso 1 1 calc R . . H14C H 0.0727 -0.2284 0.4479 0.048 Uiso 1 1 calc R . . C15 C -0.12328(16) -0.38184(14) 0.24819(13) 0.0299(2) Uani 1 1 d . . . H15A H -0.1600 -0.3978 0.1609 0.045 Uiso 1 1 calc R . . H15B H -0.1736 -0.3121 0.2837 0.045 Uiso 1 1 calc R . . H15C H -0.1621 -0.4749 0.2796 0.045 Uiso 1 1 calc R . . Fe1 Fe 0.239704(16) 0.160260(14) 0.273377(11) 0.01335(4) Uani 1 1 d . . . Li1 Li 0.1958(3) -0.1130(2) 0.21919(18) 0.0191(3) Uani 1 1 d . . . N1 N 0.36391(11) -0.22500(10) 0.15367(8) 0.01790(14) Uani 1 1 d . . . N2 N 0.06935(12) -0.32166(10) 0.27931(9) 0.02052(15) 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 0.0204(4) 0.0173(4) 0.0143(3) 0.0024(3) 0.0023(3) 0.0075(3) C2 0.0285(5) 0.0187(4) 0.0171(4) 0.0053(3) 0.0042(3) 0.0108(3) C3 0.0162(4) 0.0199(4) 0.0222(4) 0.0029(3) 0.0034(3) 0.0043(3) C4 0.0194(4) 0.0237(4) 0.0229(4) 0.0024(3) 0.0031(3) 0.0100(3) C5 0.0235(4) 0.0181(4) 0.0173(4) 0.0019(3) -0.0046(3) 0.0075(3) C6 0.0161(4) 0.0221(4) 0.0218(4) 0.0014(3) -0.0027(3) 0.0043(3) C7 0.0228(4) 0.0158(4) 0.0261(5) 0.0003(3) -0.0056(4) 0.0017(3) C8 0.0287(5) 0.0231(5) 0.0199(4) -0.0071(3) -0.0042(4) 0.0095(4) C9 0.0280(5) 0.0264(5) 0.0130(4) 0.0009(3) -0.0007(3) 0.0061(4) C10 0.0237(4) 0.0188(4) 0.0323(5) 0.0069(4) 0.0031(4) 0.0099(3) C11 0.0246(4) 0.0145(4) 0.0347(5) 0.0037(4) 0.0039(4) 0.0038(3) C12 0.0171(4) 0.0253(5) 0.0246(4) 0.0021(4) 0.0019(3) 0.0076(3) C13 0.0239(4) 0.0265(5) 0.0222(4) -0.0029(4) -0.0015(3) 0.0088(4) C14 0.0377(6) 0.0306(6) 0.0230(5) 0.0103(4) 0.0036(4) 0.0038(5) C15 0.0210(4) 0.0240(5) 0.0403(6) 0.0047(5) 0.0044(4) 0.0007(4) Fe1 0.01444(6) 0.01265(6) 0.01203(6) 0.00107(4) -0.00012(4) 0.00432(4) Li1 0.0203(8) 0.0170(8) 0.0198(8) 0.0028(6) 0.0035(6) 0.0058(6) N1 0.0176(3) 0.0165(3) 0.0200(3) 0.0033(3) 0.0021(3) 0.0065(3) N2 0.0195(3) 0.0173(3) 0.0239(4) 0.0057(3) 0.0041(3) 0.0037(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 C1 C2 1.4349(14) . y C1 Fe1 2.0288(9) . y C1 Li1 2.354(2) . y C2 Fe1 2.0212(10) . y C3 C4 1.4339(15) . y C3 Fe1 2.0297(10) . y C3 Li1 2.368(2) . y C4 Fe1 2.0217(10) . y C5 C6 1.4285(15) . y C5 C9 1.4326(16) . y C5 Fe1 2.0597(10) . y C5 Li1 2.626(2) . y C6 C7 1.4250(16) . y C6 Fe1 2.0821(10) . y C7 C8 1.4110(18) . y C7 Fe1 2.1224(10) . y C8 C9 1.4245(17) . y C8 Fe1 2.1229(10) . y C9 Fe1 2.0834(10) . y C10 N1 1.4740(14) . y C10 C11 1.5168(16) . y C11 N2 1.4815(15) . y C12 N1 1.4733(14) . y C13 N1 1.4710(14) . y C14 N2 1.4659(16) . y C15 N2 1.4691(15) . y Fe1 Li1 2.5097(19) . y Li1 N1 2.129(2) . y Li1 N2 2.155(2) . y 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 C1 Fe1 68.97(5) . . y C2 C1 Li1 136.90(8) . . y Fe1 C1 Li1 69.42(5) . . y C1 C2 Fe1 69.53(5) . . y C4 C3 Fe1 68.97(6) . . y C4 C3 Li1 136.27(9) . . y Fe1 C3 Li1 69.10(6) . . y C3 C4 Fe1 69.57(6) . . y C6 C5 C9 106.97(9) . . y C6 C5 Fe1 70.67(6) . . y C9 C5 Fe1 70.66(6) . . y C6 C5 Li1 107.57(8) . . y C9 C5 Li1 106.64(8) . . y Fe1 C5 Li1 63.43(5) . . y C7 C6 C5 108.32(10) . . y C7 C6 Fe1 71.72(6) . . y C5 C6 Fe1 68.98(6) . . y C8 C7 C6 108.30(10) . . y C8 C7 Fe1 70.61(6) . . y C6 C7 Fe1 68.67(6) . . y C7 C8 C9 108.04(10) . . y C7 C8 Fe1 70.57(6) . . y C9 C8 Fe1 68.72(6) . . y C8 C9 C5 108.37(10) . . y C8 C9 Fe1 71.71(6) . . y C5 C9 Fe1 68.88(6) . . y N1 C10 C11 111.74(9) . . y N2 C11 C10 111.26(9) . . y C2 Fe1 C4 88.92(4) . . y C2 Fe1 C1 41.50(4) . . y C4 Fe1 C1 104.02(4) . . y C2 Fe1 C3 104.62(4) . . y C4 Fe1 C3 41.45(4) . . y C1 Fe1 C3 90.71(4) . . y C2 Fe1 C5 134.84(4) . . y C4 Fe1 C5 136.06(5) . . y C1 Fe1 C5 108.19(4) . . y C3 Fe1 C5 108.72(4) . . y C2 Fe1 C6 99.40(4) . . y C4 Fe1 C6 160.46(5) . . y C1 Fe1 C6 93.74(4) . . y C3 Fe1 C6 148.22(4) . . y C5 Fe1 C6 40.35(4) . . y C2 Fe1 C9 160.66(5) . . y C4 Fe1 C9 100.16(5) . . y C1 Fe1 C9 147.53(4) . . y C3 Fe1 C9 93.30(4) . . y C5 Fe1 C9 40.45(5) . . y C6 Fe1 C9 67.01(5) . . y C2 Fe1 C7 94.59(5) . . y C4 Fe1 C7 122.57(5) . . y C1 Fe1 C7 115.80(5) . . y C3 Fe1 C7 153.35(5) . . y C5 Fe1 C7 67.14(4) . . y C6 Fe1 C7 39.61(4) . . y C9 Fe1 C7 66.12(5) . . y C2 Fe1 C8 123.30(5) . . y C4 Fe1 C8 94.37(5) . . y C1 Fe1 C8 154.60(5) . . y C3 Fe1 C8 114.58(5) . . y C5 Fe1 C8 67.26(4) . . y C6 Fe1 C8 66.27(5) . . y C9 Fe1 C8 39.58(5) . . y C7 Fe1 C8 38.83(5) . . y C2 Fe1 Li1 102.23(5) . . y C4 Fe1 Li1 102.44(5) . . y C1 Fe1 Li1 61.41(5) . . y C3 Fe1 Li1 61.83(5) . . y C5 Fe1 Li1 69.35(5) . . y C6 Fe1 Li1 93.11(5) . . y C9 Fe1 Li1 92.53(6) . . y C7 Fe1 Li1 132.14(5) . . y C8 Fe1 Li1 131.67(6) . . y N1 Li1 N2 85.48(8) . . y N1 Li1 C1 98.48(8) . . y N2 Li1 C1 159.83(10) . . y N1 Li1 C3 171.46(10) . . y N2 Li1 C3 98.28(8) . . y C1 Li1 C3 75.39(7) . . y N1 Li1 Fe1 130.80(9) . . y N2 Li1 Fe1 138.70(9) . . y C1 Li1 Fe1 49.18(4) . . y C3 Li1 Fe1 49.07(4) . . y N1 Li1 C5 102.10(8) . . y N2 Li1 C5 115.49(9) . . y C1 Li1 C5 83.18(7) . . y C3 Li1 C5 83.27(7) . . y Fe1 Li1 C5 47.22(4) . . y C13 N1 C12 108.27(8) . . y C13 N1 C10 111.19(9) . . y C12 N1 C10 108.59(8) . . y C13 N1 Li1 107.51(8) . . y C12 N1 Li1 117.44(8) . . y C10 N1 Li1 103.79(8) . . y C14 N2 C15 108.91(10) . . y C14 N2 C11 110.82(10) . . y C15 N2 C11 108.71(9) . . y C14 N2 Li1 105.75(9) . . y C15 N2 Li1 118.06(9) . . y C11 N2 Li1 104.46(8) . . y _diffrn_measured_fraction_theta_max 0.960 _diffrn_reflns_theta_full 37.47 _diffrn_measured_fraction_theta_full 0.960 _refine_diff_density_max 0.747 _refine_diff_density_min -0.973 _refine_diff_density_rms 0.074