# Electronic Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2011 data_paper _journal_name_full 'New J.Chem.' _journal_coden_cambridge 0440 #TrackingRef 'web_deposit_cif_file_0_lise-mariechamoreau_ #1309969192.jdo-tetrah-publi.cif' _publ_contact_author ; Eric Rose ; _publ_contact_author_phone '00 33 1 44 27 62 35' _publ_contact_author_fax '00 33 1 44 27 xx xx' _publ_contact_author_email eric.rose@upmc.fr _publ_section_title # Title of paper ; Lithiation / electrophilic quench sequence of benzilic position of \h^5^-tetramethylcyclohexadienyl)tricarbonyl manganese complex ; loop_ _publ_author_name _publ_author_address 'J. Dubarle-Offner' ; Institut Parisien de Chimie Mol\'eculaire UPMC - Paris 06 CNRS UMR 7201 Case 181 - 4 place Jussieu 75252 Paris cedex 5 France ; 'E. Rose' ; Institut Parisien de Chimie Mol\'eculaire UPMC - Paris 06 CNRS UMR 7201 Case 181 - 4 place Jussieu 75252 Paris cedex 5 France ; H.Gerard ; Laboratoire de chimie Th\'eorique UPMC - Paris 06 CNRS UMR 7616 4 place Jussieu 75252 Paris cedex 5 France ; _publ_contact_author_name 'Eric Rose' #################### Material relevant to compound 1 #################### data_jdo-tetrah _database_code_depnum_ccdc_archive 'CCDC 812616' #TrackingRef 'web_deposit_cif_file_0_lise-mariechamoreau_ #1309969192.jdo-tetrah-publi.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C13 H15 Mn1 O3' _chemical_formula_sum 'C13 H15 Mn O3' _chemical_formula_weight 274.19 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' O O 0.0106 0.0060 '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 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' _symmetry_Int_Tables_number 14 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 11.8868(10) _cell_length_b 9.2279(9) _cell_length_c 12.5852(7) _cell_angle_alpha 90.00 _cell_angle_beta 108.932(7) _cell_angle_gamma 90.00 _cell_volume 1305.80(18) _cell_formula_units_Z 4 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used 157 _cell_measurement_theta_min 4 _cell_measurement_theta_max 24 _exptl_crystal_description plate _exptl_crystal_colour yellow _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.395 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 568 _exptl_absorpt_coefficient_mu 1.004 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.529 _exptl_absorpt_correction_T_max 0.904 _exptl_absorpt_process_details ; R.H. Blessing, Acta Cryst. (1995), A51, 33-38 ; _diffrn_ambient_temperature 200(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type KappaCCD _diffrn_measurement_method 'CCD rotation images, thick slices' _diffrn_detector_area_resol_mean 9 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 10505 _diffrn_reflns_av_R_equivalents 0.0303 _diffrn_reflns_av_sigmaI/netI 0.0438 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 3.62 _diffrn_reflns_theta_max 30.00 _reflns_number_total 3772 _reflns_number_gt 2731 _reflns_threshold_expression >2\s(I) _computing_data_collection 'Collect (Nonius BV, 1997-2000)' _computing_cell_refinement 'Dirax/lsq (Duisenberg & Schreurs, 1989-2000)' _computing_data_reduction 'EvalCCD (Duisenberg & Schreurs 1990-2000)' _computing_structure_solution 'SIR-92 (Giacovazzo, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'DIAMOND (Brandenburg, 1999)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' _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^ > 2\s(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^)+(0.0356P)^2^+0.1675P] 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 3772 _refine_ls_number_parameters 158 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0593 _refine_ls_R_factor_gt 0.0333 _refine_ls_wR_factor_ref 0.0801 _refine_ls_wR_factor_gt 0.0727 _refine_ls_goodness_of_fit_ref 1.045 _refine_ls_restrained_S_all 1.045 _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 0.22784(2) 0.23715(2) 0.878368(18) 0.02329(8) Uani 1 1 d . . . O1 O 0.40031(13) 0.39712(18) 1.06008(11) 0.0609(4) Uani 1 1 d . . . O2 O 0.01115(13) 0.32987(19) 0.92338(12) 0.0604(4) Uani 1 1 d . . . O3 O 0.22740(11) -0.02792(14) 1.00792(10) 0.0414(3) Uani 1 1 d . . . C1 C 0.25028(15) 0.41277(17) 0.76616(13) 0.0290(4) Uani 1 1 d . . . C2 C 0.15394(14) 0.32390(18) 0.71123(13) 0.0277(3) Uani 1 1 d . . . C3 C 0.17353(14) 0.17305(18) 0.70789(12) 0.0258(3) Uani 1 1 d . . . H3 H 0.1095 0.1111 0.6693 0.031 Uiso 1 1 calc R . . C4 C 0.28787(14) 0.11327(17) 0.76163(13) 0.0253(3) Uani 1 1 d . . . C5 C 0.38057(14) 0.20731(18) 0.81383(13) 0.0261(3) Uani 1 1 d . . . C6 C 0.37211(14) 0.36114(17) 0.77199(13) 0.0282(3) Uani 1 1 d . . . H6A H 0.4343 0.4221 0.8243 0.034 Uiso 1 1 calc R . . H6B H 0.3819 0.3649 0.6969 0.034 Uiso 1 1 calc R . . C7 C 0.23568(19) 0.57165(19) 0.78219(17) 0.0452(5) Uani 1 1 d . . . H7A H 0.2336 0.6238 0.7138 0.068 Uiso 1 1 calc R . . H7B H 0.3027 0.6067 0.8454 0.068 Uiso 1 1 calc R . . H7C H 0.1612 0.5884 0.7979 0.068 Uiso 1 1 calc R . . C8 C 0.50277(15) 0.1549(2) 0.87847(16) 0.0401(4) Uani 1 1 d . . . H8A H 0.4973 0.0609 0.9127 0.060 Uiso 1 1 calc R . . H8B H 0.5415 0.2250 0.9375 0.060 Uiso 1 1 calc R . . H8C H 0.5496 0.1445 0.8276 0.060 Uiso 1 1 calc R . . C9 C 0.02941(16) 0.3810(2) 0.65943(15) 0.0423(5) Uani 1 1 d . . . H9A H 0.0133 0.4542 0.7090 0.063 Uiso 1 1 calc R . . H9B H -0.0275 0.3011 0.6491 0.063 Uiso 1 1 calc R . . H9C H 0.0214 0.4249 0.5864 0.063 Uiso 1 1 calc R . . C10 C 0.30124(17) -0.04869(18) 0.76334(16) 0.0386(4) Uani 1 1 d . . . H10A H 0.3350 -0.0783 0.7052 0.058 Uiso 1 1 calc R . . H10B H 0.2232 -0.0941 0.7488 0.058 Uiso 1 1 calc R . . H10C H 0.3543 -0.0793 0.8371 0.058 Uiso 1 1 calc R . . C11 C 0.33040(16) 0.3345(2) 0.99112(14) 0.0366(4) Uani 1 1 d . . . C12 C 0.09521(16) 0.2933(2) 0.90595(15) 0.0367(4) Uani 1 1 d . . . C13 C 0.22791(13) 0.07465(19) 0.95691(13) 0.0282(3) 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 Mn1 0.02372(12) 0.02442(14) 0.02167(12) -0.00053(10) 0.00727(9) -0.00108(10) O1 0.0680(10) 0.0767(11) 0.0376(7) -0.0235(7) 0.0164(7) -0.0379(9) O2 0.0478(9) 0.0884(12) 0.0536(9) 0.0106(9) 0.0282(7) 0.0262(8) O3 0.0398(7) 0.0408(8) 0.0391(7) 0.0153(6) 0.0066(6) -0.0041(6) C1 0.0382(9) 0.0210(8) 0.0301(8) 0.0030(7) 0.0143(7) 0.0029(7) C2 0.0289(8) 0.0307(9) 0.0235(7) 0.0059(7) 0.0086(6) 0.0050(7) C3 0.0256(8) 0.0276(8) 0.0230(7) -0.0016(7) 0.0063(6) -0.0039(7) C4 0.0318(8) 0.0208(8) 0.0253(7) -0.0012(6) 0.0122(7) 0.0003(6) C5 0.0246(8) 0.0266(8) 0.0276(7) 0.0007(6) 0.0091(6) 0.0012(6) C6 0.0299(8) 0.0235(8) 0.0313(8) -0.0013(7) 0.0102(7) -0.0054(7) C7 0.0626(13) 0.0235(9) 0.0539(12) -0.0009(9) 0.0250(10) 0.0033(9) C8 0.0267(9) 0.0457(12) 0.0453(10) 0.0057(9) 0.0081(8) 0.0050(8) C9 0.0343(9) 0.0518(12) 0.0391(9) 0.0126(9) 0.0095(8) 0.0139(9) C10 0.0501(11) 0.0217(9) 0.0475(10) -0.0016(8) 0.0205(9) 0.0029(8) C11 0.0436(10) 0.0404(11) 0.0294(8) -0.0050(8) 0.0167(8) -0.0113(9) C12 0.0381(10) 0.0440(11) 0.0300(8) 0.0039(8) 0.0140(8) 0.0064(8) C13 0.0213(8) 0.0354(10) 0.0250(7) -0.0006(7) 0.0036(6) -0.0034(7) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 C11 1.7844(18) . ? Mn1 C13 1.7958(17) . ? Mn1 C12 1.7970(19) . ? Mn1 C3 2.1145(15) . ? Mn1 C2 2.1536(15) . ? Mn1 C4 2.1575(15) . ? Mn1 C1 2.2218(16) . ? Mn1 C5 2.2335(16) . ? O1 C11 1.145(2) . ? O2 C12 1.142(2) . ? O3 C13 1.1448(19) . ? C1 C2 1.396(2) . ? C1 C7 1.498(2) . ? C1 C6 1.504(2) . ? C2 C3 1.414(2) . ? C2 C9 1.506(2) . ? C3 C4 1.419(2) . ? C3 H3 0.9500 . ? C4 C5 1.389(2) . ? C4 C10 1.502(2) . ? C5 C8 1.496(2) . ? C5 C6 1.506(2) . ? C6 H6A 0.9900 . ? C6 H6B 0.9900 . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? 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 C11 Mn1 C13 95.99(8) . . ? C11 Mn1 C12 96.73(9) . . ? C13 Mn1 C12 88.74(8) . . ? C11 Mn1 C3 148.50(7) . . ? C13 Mn1 C3 105.69(7) . . ? C12 Mn1 C3 106.17(7) . . ? C11 Mn1 C2 123.14(8) . . ? C13 Mn1 C2 140.82(7) . . ? C12 Mn1 C2 88.64(7) . . ? C3 Mn1 C2 38.69(6) . . ? C11 Mn1 C4 121.10(7) . . ? C13 Mn1 C4 89.50(7) . . ? C12 Mn1 C4 142.09(8) . . ? C3 Mn1 C4 38.77(6) . . ? C2 Mn1 C4 69.64(6) . . ? C11 Mn1 C1 86.93(7) . . ? C13 Mn1 C1 168.58(7) . . ? C12 Mn1 C1 101.91(7) . . ? C3 Mn1 C1 67.62(6) . . ? C2 Mn1 C1 37.16(6) . . ? C4 Mn1 C1 79.58(6) . . ? C11 Mn1 C5 85.70(7) . . ? C13 Mn1 C5 104.00(7) . . ? C12 Mn1 C5 166.75(7) . . ? C3 Mn1 C5 67.24(6) . . ? C2 Mn1 C5 79.20(6) . . ? C4 Mn1 C5 36.83(6) . . ? C1 Mn1 C5 65.13(6) . . ? C2 C1 C7 121.98(16) . . ? C2 C1 C6 117.42(14) . . ? C7 C1 C6 117.09(15) . . ? C2 C1 Mn1 68.76(9) . . ? C7 C1 Mn1 125.83(12) . . ? C6 C1 Mn1 92.88(10) . . ? C1 C2 C3 118.46(14) . . ? C1 C2 C9 122.82(16) . . ? C3 C2 C9 118.67(15) . . ? C1 C2 Mn1 74.07(9) . . ? C3 C2 Mn1 69.16(9) . . ? C9 C2 Mn1 125.81(11) . . ? C2 C3 C4 120.67(14) . . ? C2 C3 Mn1 72.15(9) . . ? C4 C3 Mn1 72.25(9) . . ? C2 C3 H3 119.7 . . ? C4 C3 H3 119.7 . . ? Mn1 C3 H3 128.1 . . ? C5 C4 C3 118.22(14) . . ? C5 C4 C10 123.42(15) . . ? C3 C4 C10 118.31(15) . . ? C5 C4 Mn1 74.56(9) . . ? C3 C4 Mn1 68.98(9) . . ? C10 C4 Mn1 125.04(11) . . ? C4 C5 C8 122.45(15) . . ? C4 C5 C6 118.09(14) . . ? C8 C5 C6 115.95(14) . . ? C4 C5 Mn1 68.61(9) . . ? C8 C5 Mn1 127.04(12) . . ? C6 C5 Mn1 92.35(9) . . ? C1 C6 C5 105.65(13) . . ? C1 C6 H6A 110.6 . . ? C5 C6 H6A 110.6 . . ? C1 C6 H6B 110.6 . . ? C5 C6 H6B 110.6 . . ? H6A C6 H6B 108.7 . . ? C1 C7 H7A 109.5 . . ? C1 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C1 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C5 C8 H8A 109.5 . . ? C5 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C5 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C2 C9 H9A 109.5 . . ? C2 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C2 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C4 C10 H10A 109.5 . . ? C4 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C4 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? O1 C11 Mn1 176.27(15) . . ? O2 C12 Mn1 179.54(19) . . ? O3 C13 Mn1 179.11(15) . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 30.00 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.297 _refine_diff_density_min -0.234 _refine_diff_density_rms 0.056