# Supplementary Material (ESI) for ChemComm # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 182/1626 data_global # 1. SUBMISSION DETAILS _publ_contact_author ; Prof. Dr. Konrad Seppelt Institut f\"ur Chemie / Anorganische und Analytische Chemie Freie Universit\"at Berlin Fabeckstr. 34-36 14195 Berlin Bundesrepublik Deutschland ; _publ_contact_author_phone '049 30 8384289' _publ_contact_author_fax '049 30 8382424' _publ_contact_author_email 'seppelt@chemie.fu-berlin.de' _publ_requested_journal ; Journal of the Chemical Society / Chemical communication, 2000 ; _publ_requested_coeditor_name ? _publ_contact_letter ; ? ; # 2. TITLE AND AUTHOR LIST loop_ _publ_section_title ; Pentamethylmolybdenum, preparation, epr spectrum, and crystal structure. ; loop_ _publ_author_name _public_author_address 'Prof. Dr. Konrad Seppelt' ; Institut f\"ur Chemie / Anorganische und Analytische Chemie Freie Universit\"at Berlin Fabeckstr. 34-36 14195 Berlin Bundesrepublik Deutschland ; 'Beatrice Roessler' ; Institut f\"ur Chemie / Anorganische und Analytische Chemie Freie Universit\"at Berlin Fabeckstr. 34-36 14195 Berlin Bundesrepublik Deutschland ; 'Sven Kleinhenz' ; Institut f\"ur Chemie / Anorganische und Analytische Chemie Freie Universit\"at Berlin Fabeckstr. 34-36 14195 Berlin Bundesrepublik Deutschland ; #========================================================================= # 4. TEXT _publ_section_abstract ; ; _publ_section_comment ; The structure is refined in I4 as twin (010,100,00-1), but can similarly refined as disordered in I4/mm. The choise of I4 was done because of the similarity to Ta(CH~3~)~5~ which is untwinned in I4. ; #======================================================================== data_mome5 _audit_creation_method SHELXL-97 _chemical_name_systematic ; Pentamethylmolybdenum(V) ; _chemical_name_common 'Pentamethylmolybdenum(V)' _chemical_melting_point ? _chemical_formula_moiety 'C~5~H~15~Mo' _chemical_formula_sum 'C5 H15 Mo' _chemical_formula_weight 171.11 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'Mo' 'Mo' -1.6832 0.6857 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' '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' _symmetry_cell_setting 'tetragonal' _symmetry_space_group_name_H-M 'I 4' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-y, x, z' 'y, -x, z' 'x+1/2, y+1/2, z+1/2' '-x+1/2, -y+1/2, z+1/2' '-y+1/2, x+1/2, z+1/2' 'y+1/2, -x+1/2, z+1/2' _cell_length_a 7.680(2) _cell_length_b 7.680(2) _cell_length_c 6.490(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 382.80(18) _cell_formula_units_Z 2 _cell_measurement_temperature '130' _cell_measurement_reflns_used 25 _cell_measurement_theta_min 20 _cell_measurement_theta_max 21 _exptl_crystal_description needles _exptl_crystal_colour turquoise _exptl_crystal_size_max 0.5 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.485 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 174 _exptl_absorpt_coefficient_mu 1.602 _exptl_absorpt_correction_type 'Psi-scan' _exptl_absorpt_correction_T_min 0.73 _exptl_absorpt_correction_T_max 0.91 _exptl_absorpt_process_details ? _exptl_special_details ; 7 reflections with chi >80^o^ were measured with psi in 10^o^ steps from 0^o^ to 360^o^, Io were corrected accordingly. ; _diffrn_ambient_temperature 130 _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Enraf-Nonius CAD4' _diffrn_measurement_method 'Omega-scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time '14400 sec' _diffrn_standards_decay_% 5 _diffrn_reflns_number 982 _diffrn_reflns_av_R_equivalents 0.0479 _diffrn_reflns_av_sigmaI/netI 0.0488 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -7 _diffrn_reflns_limit_l_max 7 _diffrn_reflns_theta_min 3.75 _diffrn_reflns_theta_max 24.84 _reflns_number_total 340 _reflns_number_gt 340 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Enraf-Nonius CAD4' _computing_cell_refinement 'Enraf-Nonius CAD4' _computing_data_reduction 'Molen Delft Instruments' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XPMA, ZORTEP' _computing_publication_material 'SHELXL-97' _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^)+(0.0148P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.3(6) _refine_ls_number_reflns 340 _refine_ls_number_parameters 25 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0253 _refine_ls_R_factor_gt 0.0253 _refine_ls_wR_factor_ref 0.0446 _refine_ls_wR_factor_gt 0.0446 _refine_ls_goodness_of_fit_ref 1.111 _refine_ls_restrained_S_all 1.111 _refine_ls_shift/su_max 1.293 _refine_ls_shift/su_mean 0.053 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 0.0000 1.0000 1.0000 0.0202(2) Uani 1 4 d S . . C1 C -0.027(3) 0.7487(8) 1.1280(10) 0.050(5) Uani 1 1 d G . . H1A H 0.0842 0.6909 1.1268 0.061(13) Uiso 1 1 calc R . . H1B H -0.1086 0.6827 1.0481 0.061(13) Uiso 1 1 calc R . . H1C H -0.0676 0.7581 1.2673 0.061(13) Uiso 1 1 calc R . . C2 C 0.0000 1.0000 0.6820(14) 0.034(2) Uani 1 4 d SG . . H2A H -0.0444 0.8908 0.6327 0.061(13) Uiso 0.25 1 calc PR . . H2B H 0.1167 1.0161 0.6327 0.061(13) Uiso 0.25 1 calc PR . . H2C H -0.0723 1.0930 0.6327 0.061(13) Uiso 0.25 1 calc PR . . 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 0.0202(2) 0.0202(2) 0.0202(3) 0.000 0.000 0.000 C1 0.078(15) 0.028(3) 0.045(3) 0.007(3) 0.009(7) -0.006(6) C2 0.041(3) 0.041(3) 0.021(5) 0.000 0.000 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 Mo1 C2 2.064(9) . ? Mo1 C1 2.111(7) . ? Mo1 C1 2.111(7) 3_665 ? Mo1 C1 2.111(7) 4_465 ? Mo1 C1 2.111(7) 2_575 ? C1 H1A 0.9600 . ? C1 H1B 0.9600 . ? C1 H1C 0.9600 . ? C2 H2A 0.9665 . ? C2 H2B 0.9665 . ? C2 H2C 0.9665 . ? 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 C1 113.17(18) . . ? C2 Mo1 C1 113.17(18) . 3_665 ? C1 Mo1 C1 81.09(14) . 3_665 ? C2 Mo1 C1 113.17(18) . 4_465 ? C1 Mo1 C1 81.09(14) . 4_465 ? C1 Mo1 C1 133.7(4) 3_665 4_465 ? C2 Mo1 C1 113.17(18) . 2_575 ? C1 Mo1 C1 133.7(4) . 2_575 ? C1 Mo1 C1 81.09(13) 3_665 2_575 ? C1 Mo1 C1 81.09(13) 4_465 2_575 ? Mo1 C1 H1A 109.5 . . ? Mo1 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? Mo1 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? Mo1 C2 H2A 109.9 . . ? Mo1 C2 H2B 109.9 . . ? H2A C2 H2B 109.0 . . ? Mo1 C2 H2C 109.9 . . ? H2A C2 H2C 109.0 . . ? H2B C2 H2C 109.0 . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 24.84 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.300 _refine_diff_density_min -0.294 _refine_diff_density_rms 0.072 #=================================================================== #===END # 4. TEXT _publ_section_abstract ; ; _publ_section_comment ; If refined as a twin (010,100,00-1), the Flack parameter is 0.06. Since there is hardly any influence on the structural parameters, this 6% twinning was neglected. ; #==================================================================== data_tame5 _audit_creation_method SHELXL-97 _chemical_name_systematic ; Pentamethyltantal ; _chemical_name_common 'Pentamethyltantal' _chemical_melting_point ? _chemical_formula_moiety 'C~5~H~15~Ta' _chemical_formula_sum 'C5 H15 Ta' _chemical_formula_weight 256.12 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'Ta' 'Ta' -0.7052 6.5227 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' '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' _symmetry_cell_setting 'tetragonal' _symmetry_space_group_name_H-M 'I 4' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-y, x, z' 'y, -x, z' 'x+1/2, y+1/2, z+1/2' '-x+1/2, -y+1/2, z+1/2' '-y+1/2, x+1/2, z+1/2' 'y+1/2, -x+1/2, z+1/2' _cell_length_a 7.8500(10) _cell_length_b 7.8500(10) _cell_length_c 6.4200(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 395.62(9) _cell_formula_units_Z 2 _cell_measurement_temperature '120' _cell_measurement_reflns_used 25 _cell_measurement_theta_min 13 _cell_measurement_theta_max 26 _exptl_crystal_description needles _exptl_crystal_colour 'pale yellow' _exptl_crystal_size_max 0.4 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.150 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 236 _exptl_absorpt_coefficient_mu 13.784 _exptl_absorpt_correction_type 'Psi-scan' _exptl_absorpt_correction_T_min 0.73 _exptl_absorpt_correction_T_max 0.93 _exptl_absorpt_process_details ? _exptl_special_details ; 7 reflections with chi >80^o^ were measured with psi in 10^o^ steps from 0^o^ to 360^o^, Io were corrected accordingly. ; _diffrn_ambient_temperature 120 _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Enraf-Nonius CAD4' _diffrn_measurement_method 'Omega-scan' _diffrn_detector_area_resol_mean 0.62 _diffrn_standards_number 3 _diffrn_standards_interval_count 400 _diffrn_standards_interval_time '14400 sec' _diffrn_standards_decay_% 2.49 _diffrn_reflns_number 874 _diffrn_reflns_av_R_equivalents 0.0320 _diffrn_reflns_av_sigmaI/netI 0.0264 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 3.67 _diffrn_reflns_theta_max 44.79 _reflns_number_total 802 _reflns_number_gt 802 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Enraf-Nonius CAD4' _computing_cell_refinement 'Enraf-Nonius CAD4' _computing_data_reduction 'NRCVAX package' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XPMA, ZORTEP' _computing_publication_material 'SHELXL' _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^)+(0.0357P)^2^+0.9251P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.01(7) _refine_ls_number_reflns 802 _refine_ls_number_parameters 18 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0229 _refine_ls_R_factor_gt 0.0229 _refine_ls_wR_factor_ref 0.0564 _refine_ls_wR_factor_gt 0.0564 _refine_ls_goodness_of_fit_ref 1.058 _refine_ls_restrained_S_all 1.057 _refine_ls_shift/su_max 0.258 _refine_ls_shift/su_mean 0.015 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 Ta Ta 0.0000 0.0000 0.0010(3) 0.01762(7) Uani 1 4 d S . . C1 C 0.0000 0.0000 0.324(2) 0.035(2) Uani 1 4 d S . . H1A H 0.0600 0.1013 0.3748 0.053 Uiso 0.25 1 calc PR . . H1B H 0.0577 -0.1026 0.3748 0.053 Uiso 0.25 1 calc PR . . H1C H -0.1177 0.0013 0.3748 0.053 Uiso 0.25 1 calc PR . . C2 C -0.2518(9) 0.0449(11) -0.1197(11) 0.0403(14) Uani 1 1 d . . . H2A H -0.2475 0.0494 -0.2722 0.061 Uiso 1 1 calc R . . H2B H -0.2950 0.1535 -0.0659 0.061 Uiso 1 1 calc R . . H2C H -0.3276 -0.0476 -0.0760 0.061 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 Ta 0.01777(8) 0.01777(8) 0.01732(11) 0.000 0.000 0.000 C1 0.039(4) 0.039(4) 0.027(5) 0.000 0.000 0.000 C2 0.024(2) 0.057(4) 0.040(3) 0.006(3) -0.005(2) 0.009(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 Ta C1 2.073(13) . ? Ta C2 2.152(6) 2 ? Ta C2 2.152(6) 4 ? Ta C2 2.152(6) 3 ? Ta C2 2.152(6) . ? C1 H1A 0.9931 . ? C1 H1B 0.9931 . ? C1 H1C 0.9931 . ? C2 H2A 0.9800 . ? C2 H2B 0.9800 . ? C2 H2C 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 C1 Ta C2 111.1(2) . 2 ? C1 Ta C2 111.1(2) . 4 ? C2 Ta C2 82.55(14) 2 4 ? C1 Ta C2 111.1(2) . 3 ? C2 Ta C2 82.55(14) 2 3 ? C2 Ta C2 137.8(4) 4 3 ? C1 Ta C2 111.1(2) . . ? C2 Ta C2 137.8(4) 2 . ? C2 Ta C2 82.55(14) 4 . ? C2 Ta C2 82.55(14) 3 . ? Ta C1 H1A 110.3 . . ? Ta C1 H1B 110.3 . . ? H1A C1 H1B 108.6 . . ? Ta C1 H1C 110.3 . . ? H1A C1 H1C 108.6 . . ? H1B C1 H1C 108.6 . . ? Ta C2 H2A 109.5 . . ? Ta C2 H2B 109.5 . . ? H2A C2 H2B 109.5 . . ? Ta C2 H2C 109.5 . . ? H2A C2 H2C 109.5 . . ? H2B C2 H2C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.642 _diffrn_reflns_theta_full 44.79 _diffrn_measured_fraction_theta_full 0.642 _refine_diff_density_max 1.870 _refine_diff_density_min -1.855 _refine_diff_density_rms 0.209 #===================================================================