Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Robert H. Crabtree' 'Christopher Incarvito' 'Jose A. Mata' 'Eduardo Peris' _publ_contact_author_name 'Prof Robert H. Crabtree' _publ_contact_author_address ; Yale Chemistry Department 225 Prospect St PO Box 208107 New Haven CT 06520 UNITED STATES OF AMERICA ; _publ_contact_author_email ROBERT.CRABTREE@YALE.EDU _publ_requested_journal 'Chemical Communications' # 2. TITLE AND AUTHOR LIST _publ_section_title ; A methylene-bis-triazolium ligand promotes an unusual rearrangement of norbornadiene to nortricyclyl. ; _publ_section_abstract ; Reaction of [(nbd)RhCl]2 with a chelating bis-[1,2,4]-triazolium salt gives a nortricyclyl Rh complex. ; data_jm01 _database_code_CSD 197138 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C22 H34 I N6 O2 Rh' _chemical_formula_weight 644.36 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Rh Rh -1.1178 0.9187 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' I I -0.4742 1.8119 '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 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.5969(17) _cell_length_b 12.062(2) _cell_length_c 13.182(3) _cell_angle_alpha 84.79(3) _cell_angle_beta 80.10(3) _cell_angle_gamma 82.72(3) _cell_volume 1332.3(5) _cell_formula_units_Z 2 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description Plate _exptl_crystal_colour 'Pale yellow' _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.606 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 644 _exptl_absorpt_coefficient_mu 1.828 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.6101 _exptl_absorpt_correction_T_max 0.7711 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 296(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 'Nonius KappaCCD' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 9133 _diffrn_reflns_av_R_equivalents 0.0270 _diffrn_reflns_av_sigmaI/netI 0.0706 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.42 _diffrn_reflns_theta_max 27.48 _reflns_number_total 6017 _reflns_number_gt 3580 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect' _computing_cell_refinement Denzo _computing_data_reduction Denzo _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics XP _computing_publication_material XCIF _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^)+(0.0893P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6017 _refine_ls_number_parameters 290 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0911 _refine_ls_R_factor_gt 0.0408 _refine_ls_wR_factor_ref 0.1335 _refine_ls_wR_factor_gt 0.1054 _refine_ls_goodness_of_fit_ref 0.815 _refine_ls_restrained_S_all 0.815 _refine_ls_shift/su_max 0.011 _refine_ls_shift/su_mean 0.001 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 Rh1 Rh 0.15544(5) 0.27068(3) 0.25875(3) 0.05059(15) Uani 1 1 d . . . I1 I -0.14911(4) 0.40025(3) 0.29367(3) 0.06730(16) Uani 1 1 d . . . O1 O 0.0459(4) 0.1273(3) 0.2297(2) 0.0584(8) Uani 1 1 d . . . O2 O 0.0785(4) 0.1539(3) 0.3860(2) 0.0663(10) Uani 1 1 d . . . N1 N 0.3199(5) 0.4711(3) 0.2720(3) 0.0634(12) Uani 1 1 d . . . N2 N 0.3520(6) 0.5460(4) 0.3368(4) 0.0791(14) Uani 1 1 d . . . N3 N 0.2258(6) 0.4080(4) 0.4202(3) 0.0704(13) Uani 1 1 d . . . N4 N 0.2846(5) 0.4435(3) 0.1037(3) 0.0579(10) Uani 1 1 d . . . N5 N 0.2844(6) 0.4928(4) 0.0041(4) 0.0719(13) Uani 1 1 d . . . N6 N 0.1359(5) 0.3532(3) 0.0396(3) 0.0580(11) Uani 1 1 d . . . C1 C 0.3864(7) 0.4845(5) 0.1644(4) 0.0710(15) Uani 1 1 d . . . H1A H 0.4915 0.4431 0.1522 0.085 Uiso 1 1 calc R . . H1B H 0.3964 0.5630 0.1445 0.085 Uiso 1 1 calc R . . C2 C 0.2418(6) 0.3866(4) 0.3197(4) 0.0575(13) Uani 1 1 d . . . C3 C 0.2932(9) 0.5045(5) 0.4254(5) 0.087(2) Uani 1 1 d . . . H3A H 0.2957 0.5360 0.4869 0.104 Uiso 1 1 calc R . . C4 C 0.1611(9) 0.3381(7) 0.5107(5) 0.092(2) Uani 1 1 d . . . H4A H 0.0701 0.3055 0.4966 0.111 Uiso 1 1 calc R . . H4B H 0.1264 0.3834 0.5693 0.111 Uiso 1 1 calc R . . C5 C 0.2916(17) 0.2444(10) 0.5355(8) 0.172(6) Uani 1 1 d . . . H5A H 0.2493 0.2012 0.5974 0.207 Uiso 1 1 calc R . . H5B H 0.3137 0.1947 0.4796 0.207 Uiso 1 1 calc R . . C6 C 0.4320(19) 0.2772(11) 0.5497(10) 0.203(6) Uani 1 1 d . . . H6A H 0.4105 0.3249 0.6071 0.244 Uiso 1 1 calc R . . H6B H 0.4728 0.3224 0.4886 0.244 Uiso 1 1 calc R . . C7 C 0.5632(18) 0.1827(11) 0.5712(12) 0.223(7) Uani 1 1 d . . . H7A H 0.6586 0.2146 0.5751 0.334 Uiso 1 1 calc R . . H7B H 0.5834 0.1329 0.5164 0.334 Uiso 1 1 calc R . . H7C H 0.5291 0.1418 0.6354 0.334 Uiso 1 1 calc R . . C8 C 0.1979(6) 0.3588(4) 0.1276(4) 0.0527(12) Uani 1 1 d . . . C9 C 0.1923(8) 0.4342(5) -0.0314(4) 0.0736(16) Uani 1 1 d . . . H9A H 0.1673 0.4459 -0.0978 0.088 Uiso 1 1 calc R . . C10 C 0.0239(8) 0.2777(5) 0.0228(4) 0.0754(16) Uani 1 1 d . . . H10A H -0.0078 0.2351 0.0875 0.090 Uiso 1 1 calc R . . H10B H -0.0704 0.3228 0.0048 0.090 Uiso 1 1 calc R . . C11 C 0.0797(11) 0.2007(9) -0.0548(8) 0.159(4) Uani 1 1 d . . . H11A H 0.1581 0.1449 -0.0293 0.191 Uiso 1 1 calc R . . H11B H 0.1339 0.2411 -0.1148 0.191 Uiso 1 1 calc R . . C12 C -0.0444(12) 0.1395(9) -0.0900(7) 0.136(4) Uani 1 1 d . . . H12A H 0.0074 0.0714 -0.1205 0.164 Uiso 1 1 calc R . . H12B H -0.1208 0.1184 -0.0304 0.164 Uiso 1 1 calc R . . C13 C -0.1276(18) 0.2080(10) -0.1646(11) 0.217(7) Uani 1 1 d . . . H13A H -0.2083 0.1682 -0.1819 0.326 Uiso 1 1 calc R . . H13B H -0.0536 0.2245 -0.2258 0.326 Uiso 1 1 calc R . . H13C H -0.1759 0.2767 -0.1356 0.326 Uiso 1 1 calc R . . C14 C 0.0260(7) 0.0986(5) 0.3251(4) 0.0653(14) Uani 1 1 d . . . C15 C -0.0609(10) -0.0003(6) 0.3660(5) 0.099(2) Uani 1 1 d . . . H15A H 0.0077 -0.0681 0.3514 0.149 Uiso 1 1 calc R . . H15B H -0.1531 0.0017 0.3335 0.149 Uiso 1 1 calc R . . H15C H -0.0932 0.0021 0.4392 0.149 Uiso 1 1 calc R . . C16 C 0.3713(7) 0.1691(5) 0.2374(4) 0.0664(14) Uani 1 1 d . . . H16A H 0.3704 0.1177 0.2994 0.080 Uiso 1 1 calc R . . C17 C 0.4134(8) 0.0946(5) 0.1449(6) 0.090(2) Uani 1 1 d . . . H17A H 0.3312 0.0506 0.1325 0.108 Uiso 1 1 calc R . . C18 C 0.4820(9) 0.1719(7) 0.0559(6) 0.102(2) Uani 1 1 d . . . H18A H 0.5380 0.1310 -0.0020 0.122 Uiso 1 1 calc R . . H18B H 0.4012 0.2276 0.0330 0.122 Uiso 1 1 calc R . . C19 C 0.5688(9) 0.0298(6) 0.1681(7) 0.105(2) Uani 1 1 d . . . H19A H 0.5531 -0.0195 0.2304 0.126 Uiso 1 1 calc R . . H19B H 0.6233 -0.0128 0.1108 0.126 Uiso 1 1 calc R . . C20 C 0.5268(7) 0.2183(5) 0.2223(5) 0.0741(16) Uani 1 1 d . . . H20A H 0.5465 0.2736 0.2673 0.089 Uiso 1 1 calc R . . C21 C 0.5926(8) 0.2226(6) 0.1094(5) 0.0842(18) Uani 1 1 d . . . H21A H 0.6580 0.2805 0.0755 0.101 Uiso 1 1 calc R . . C22 C 0.6544(8) 0.1276(6) 0.1820(6) 0.095(2) Uani 1 1 d . . . H22A H 0.7623 0.1191 0.1987 0.113 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 Rh1 0.0610(3) 0.0559(2) 0.0372(2) -0.00361(17) -0.00067(17) -0.02550(19) I1 0.0686(3) 0.0824(3) 0.0495(2) -0.01390(18) 0.00482(17) -0.0163(2) O1 0.073(2) 0.066(2) 0.043(2) 0.0002(16) -0.0130(16) -0.0324(17) O2 0.090(3) 0.076(2) 0.0425(18) 0.0061(17) -0.0166(18) -0.046(2) N1 0.081(3) 0.058(2) 0.052(3) -0.011(2) 0.008(2) -0.033(2) N2 0.091(4) 0.074(3) 0.078(3) -0.027(3) 0.005(3) -0.044(3) N3 0.082(3) 0.088(3) 0.047(2) -0.018(2) 0.006(2) -0.048(3) N4 0.069(3) 0.060(2) 0.042(2) -0.0007(19) 0.0080(19) -0.020(2) N5 0.086(3) 0.065(3) 0.056(3) 0.005(2) 0.010(2) -0.012(3) N6 0.068(3) 0.063(3) 0.041(2) -0.002(2) -0.001(2) -0.010(2) C1 0.079(4) 0.066(3) 0.066(4) -0.004(3) 0.014(3) -0.033(3) C2 0.060(3) 0.066(3) 0.047(3) -0.009(2) 0.005(2) -0.027(3) C3 0.114(5) 0.095(4) 0.060(4) -0.029(3) 0.007(4) -0.056(4) C4 0.114(5) 0.127(6) 0.049(3) -0.009(4) 0.000(3) -0.079(5) C5 0.259(14) 0.185(10) 0.111(7) 0.070(7) -0.075(8) -0.167(11) C6 0.282(17) 0.179(11) 0.194(13) 0.068(9) -0.148(13) -0.107(12) C7 0.257(17) 0.168(11) 0.277(19) 0.059(12) -0.134(15) -0.081(11) C8 0.058(3) 0.051(3) 0.045(3) -0.006(2) 0.006(2) -0.011(2) C9 0.084(4) 0.078(4) 0.050(3) 0.009(3) 0.006(3) -0.010(3) C10 0.098(5) 0.086(4) 0.047(3) -0.004(3) -0.017(3) -0.025(3) C11 0.130(7) 0.207(10) 0.156(9) -0.113(8) 0.009(6) -0.048(7) C12 0.136(8) 0.172(9) 0.113(7) -0.067(7) -0.003(6) -0.046(7) C13 0.256(16) 0.186(12) 0.197(14) -0.032(10) -0.073(12) 0.087(12) C14 0.077(4) 0.071(3) 0.054(3) 0.004(3) -0.012(3) -0.037(3) C15 0.148(6) 0.093(5) 0.073(4) 0.014(4) -0.027(4) -0.077(5) C16 0.071(4) 0.071(4) 0.059(3) 0.004(3) -0.011(3) -0.018(3) C17 0.079(4) 0.077(4) 0.121(6) -0.037(4) -0.008(4) -0.019(3) C18 0.075(4) 0.146(7) 0.086(5) -0.039(5) -0.004(4) -0.004(4) C19 0.087(5) 0.084(5) 0.140(7) -0.013(5) -0.015(5) 0.003(4) C20 0.068(4) 0.081(4) 0.080(4) -0.015(3) -0.018(3) -0.020(3) C21 0.079(4) 0.092(4) 0.080(4) -0.009(4) -0.004(3) -0.012(4) C22 0.068(4) 0.106(5) 0.113(6) -0.010(5) -0.026(4) -0.008(4) _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 Rh1 C8 1.949(5) . ? Rh1 C2 1.955(5) . ? Rh1 C16 2.081(6) . ? Rh1 O2 2.159(3) . ? Rh1 O1 2.164(3) . ? Rh1 C14 2.496(5) . ? Rh1 I1 2.8615(11) . ? O1 C14 1.262(6) . ? O2 C14 1.262(6) . ? N1 C2 1.340(6) . ? N1 N2 1.381(6) . ? N1 C1 1.438(7) . ? N2 C3 1.276(8) . ? N3 C2 1.354(6) . ? N3 C3 1.377(7) . ? N3 C4 1.466(7) . ? N4 C8 1.324(6) . ? N4 N5 1.391(6) . ? N4 C1 1.440(7) . ? N5 C9 1.294(7) . ? N6 C9 1.366(7) . ? N6 C8 1.368(6) . ? N6 C10 1.462(7) . ? C4 C5 1.543(14) . ? C5 C6 1.364(13) . ? C6 C7 1.541(16) . ? C10 C11 1.424(9) . ? C11 C12 1.526(11) . ? C12 C13 1.452(13) . ? C14 C15 1.498(7) . ? C16 C20 1.505(8) . ? C16 C17 1.546(8) . ? C17 C18 1.515(10) . ? C17 C19 1.523(9) . ? C18 C21 1.493(10) . ? C19 C22 1.508(10) . ? C20 C21 1.497(9) . ? C20 C22 1.511(9) . ? C21 C22 1.527(10) . ? 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 C8 Rh1 C2 86.7(2) . . ? C8 Rh1 C16 94.9(2) . . ? C2 Rh1 C16 93.5(2) . . ? C8 Rh1 O2 167.47(16) . . ? C2 Rh1 O2 105.52(17) . . ? C16 Rh1 O2 87.26(19) . . ? C8 Rh1 O1 107.02(17) . . ? C2 Rh1 O1 166.19(17) . . ? C16 Rh1 O1 87.11(18) . . ? O2 Rh1 O1 60.71(12) . . ? C8 Rh1 C14 137.25(19) . . ? C2 Rh1 C14 135.82(19) . . ? C16 Rh1 C14 87.7(2) . . ? O2 Rh1 C14 30.36(14) . . ? O1 Rh1 C14 30.38(14) . . ? C8 Rh1 I1 87.58(14) . . ? C2 Rh1 I1 88.33(16) . . ? C16 Rh1 I1 176.94(16) . . ? O2 Rh1 I1 89.90(11) . . ? O1 Rh1 I1 90.50(10) . . ? C14 Rh1 I1 89.23(14) . . ? C14 O1 Rh1 89.5(3) . . ? C14 O2 Rh1 89.8(3) . . ? C2 N1 N2 114.9(4) . . ? C2 N1 C1 127.1(4) . . ? N2 N1 C1 117.7(4) . . ? C3 N2 N1 102.1(4) . . ? C2 N3 C3 108.2(5) . . ? C2 N3 C4 127.5(4) . . ? C3 N3 C4 124.1(5) . . ? C8 N4 N5 114.6(4) . . ? C8 N4 C1 128.3(4) . . ? N5 N4 C1 116.9(4) . . ? C9 N5 N4 102.0(4) . . ? C9 N6 C8 108.2(5) . . ? C9 N6 C10 124.5(5) . . ? C8 N6 C10 127.3(4) . . ? N1 C1 N4 109.4(4) . . ? N1 C2 N3 102.2(4) . . ? N1 C2 Rh1 128.8(4) . . ? N3 C2 Rh1 128.8(4) . . ? N2 C3 N3 112.7(5) . . ? N3 C4 C5 108.8(6) . . ? C6 C5 C4 116.8(9) . . ? C5 C6 C7 116.3(11) . . ? N4 C8 N6 102.8(4) . . ? N4 C8 Rh1 128.8(4) . . ? N6 C8 Rh1 128.2(4) . . ? N5 C9 N6 112.3(5) . . ? C11 C10 N6 116.3(6) . . ? C10 C11 C12 116.9(8) . . ? C13 C12 C11 112.1(11) . . ? O2 C14 O1 119.9(5) . . ? O2 C14 C15 120.1(5) . . ? O1 C14 C15 120.1(5) . . ? O2 C14 Rh1 59.9(3) . . ? O1 C14 Rh1 60.1(2) . . ? C15 C14 Rh1 176.6(5) . . ? C20 C16 C17 96.7(5) . . ? C20 C16 Rh1 121.2(4) . . ? C17 C16 Rh1 119.8(4) . . ? C18 C17 C19 98.2(6) . . ? C18 C17 C16 104.2(5) . . ? C19 C17 C16 100.4(6) . . ? C21 C18 C17 98.5(6) . . ? C22 C19 C17 98.6(5) . . ? C21 C20 C16 107.9(5) . . ? C21 C20 C22 61.0(4) . . ? C16 C20 C22 106.7(5) . . ? C18 C21 C20 107.8(6) . . ? C18 C21 C22 104.9(6) . . ? C20 C21 C22 59.9(4) . . ? C19 C22 C20 105.9(5) . . ? C19 C22 C21 104.8(6) . . ? C20 C22 C21 59.0(4) . . ? _diffrn_measured_fraction_theta_max 0.986 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.986 _refine_diff_density_max 0.678 _refine_diff_density_min -0.554 _refine_diff_density_rms 0.082