# Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2012 ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # ####################################################################### data_Compound_1_rg528bm _database_code_depnum_ccdc_archive 'CCDC 860498' #TrackingRef 'carbenes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H20 Mn2 N2 O10' _chemical_formula_weight 606.30 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' Mn Mn 0.3368 0.7283 '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 9.020(3) _cell_length_b 9.148(3) _cell_length_c 17.351(6) _cell_angle_alpha 105.056(6) _cell_angle_beta 90.211(6) _cell_angle_gamma 109.425(6) _cell_volume 1297.5(8) _cell_formula_units_Z 2 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 918 _cell_measurement_theta_min 2.854 _cell_measurement_theta_max 26.724 _exptl_crystal_description PRISM _exptl_crystal_colour YELLOW _exptl_crystal_size_max 0.43 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.552 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 616 _exptl_absorpt_coefficient_mu 1.032 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.764502 _exptl_absorpt_correction_T_max 1.000000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 12983 _diffrn_reflns_av_R_equivalents 0.0256 _diffrn_reflns_av_sigmaI/netI 0.0403 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 1.22 _diffrn_reflns_theta_max 28.28 _reflns_number_total 6312 _reflns_number_gt 4416 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0520P)^2^+0.0596P] 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 6312 _refine_ls_number_parameters 345 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0645 _refine_ls_R_factor_gt 0.0392 _refine_ls_wR_factor_ref 0.1035 _refine_ls_wR_factor_gt 0.0912 _refine_ls_goodness_of_fit_ref 1.005 _refine_ls_restrained_S_all 1.005 _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 0.83894(4) -0.15625(4) 0.811766(19) 0.03699(11) Uani 1 1 d . . . Mn2 Mn 0.72549(4) -0.00424(4) 0.69092(2) 0.03735(11) Uani 1 1 d . . . N1 N 1.0613(2) 0.0152(2) 0.83073(10) 0.0364(4) Uani 1 1 d . . . N2 N 0.9525(2) 0.1187(2) 0.67269(10) 0.0368(4) Uani 1 1 d . . . C1 C 0.6390(3) -0.2985(3) 0.79721(16) 0.0536(7) Uani 1 1 d . . . O1 O 0.5158(3) -0.3914(3) 0.79259(15) 0.0883(7) Uani 1 1 d . . . C2 C 0.9101(3) -0.3209(3) 0.80349(15) 0.0493(6) Uani 1 1 d . . . O2 O 0.9596(3) -0.4213(2) 0.80251(14) 0.0795(7) Uani 1 1 d . . . C3 C 0.8295(3) -0.1446(3) 0.91599(15) 0.0483(6) Uani 1 1 d . . . O3 O 0.8181(3) -0.1461(3) 0.98128(11) 0.0773(6) Uani 1 1 d . . . C4 C 0.5262(3) -0.1290(3) 0.69760(15) 0.0497(6) Uani 1 1 d . . . O4 O 0.3953(2) -0.2045(3) 0.69474(14) 0.0791(7) Uani 1 1 d . . . C5 C 0.6577(3) 0.1635(3) 0.70397(15) 0.0472(6) Uani 1 1 d . . . O5 O 0.6135(2) 0.2696(3) 0.71002(14) 0.0734(6) Uani 1 1 d . . . C6 C 0.6673(3) -0.0542(3) 0.58627(16) 0.0518(6) Uani 1 1 d . . . O6 O 0.6218(3) -0.0827(3) 0.52028(12) 0.0871(7) Uani 1 1 d . . . O7 O 0.78470(17) 0.04169(17) 0.81246(8) 0.0374(3) Uani 1 1 d . . . O8 O 0.82852(18) -0.16841(17) 0.69171(8) 0.0359(3) Uani 1 1 d . . . O9 O 0.7200(3) 0.3879(3) 0.92072(18) 0.1001(9) Uani 1 1 d . . . O10 O 0.9423(3) -0.4867(3) 0.59508(15) 0.0927(8) Uani 1 1 d . . . C11 C 1.2011(3) -0.0090(3) 0.82844(13) 0.0437(6) Uani 1 1 d . . . H11 H 1.2006 -0.1142 0.8180 0.052 Uiso 1 1 calc R . . C12 C 1.3431(3) 0.1136(3) 0.84069(15) 0.0520(6) Uani 1 1 d . . . H12 H 1.4369 0.0919 0.8390 0.062 Uiso 1 1 calc R . . C13 C 1.3458(3) 0.2696(3) 0.85561(17) 0.0581(7) Uani 1 1 d . . . H13 H 1.4412 0.3549 0.8636 0.070 Uiso 1 1 calc R . . C14 C 1.2055(3) 0.2974(3) 0.85848(15) 0.0516(6) Uani 1 1 d . . . H14 H 1.2046 0.4020 0.8683 0.062 Uiso 1 1 calc R . . C15 C 1.0644(3) 0.1678(3) 0.84651(13) 0.0387(5) Uani 1 1 d . . . C16 C 0.9059(3) 0.1881(3) 0.85264(14) 0.0415(5) Uani 1 1 d . . . H16 H 0.9046 0.2719 0.8273 0.050 Uiso 1 1 calc R . . C17 C 0.8823(3) 0.2431(3) 0.94191(15) 0.0570(7) Uani 1 1 d . . . H17A H 0.8675 0.1543 0.9652 0.068 Uiso 1 1 calc R . . H17B H 0.9770 0.3305 0.9695 0.068 Uiso 1 1 calc R . . C18 C 0.7426(3) 0.2991(4) 0.95497(18) 0.0645(8) Uani 1 1 d . . . C19 C 0.6382(5) 0.2449(6) 1.0160(3) 0.1232(17) Uani 1 1 d . . . H19A H 0.5623 0.2989 1.0241 0.185 Uiso 1 1 calc R . . H19B H 0.7009 0.2703 1.0656 0.185 Uiso 1 1 calc R . . H19C H 0.5840 0.1305 0.9974 0.185 Uiso 1 1 calc R . . C31 C 1.0137(3) 0.2750(3) 0.67407(14) 0.0452(6) Uani 1 1 d . . . H31 H 0.9489 0.3371 0.6844 0.054 Uiso 1 1 calc R . . C32 C 1.1670(3) 0.3469(3) 0.66098(16) 0.0513(6) Uani 1 1 d . . . H32 H 1.2057 0.4559 0.6633 0.062 Uiso 1 1 calc R . . C33 C 1.2624(3) 0.2557(3) 0.64433(15) 0.0522(6) Uani 1 1 d . . . H33 H 1.3673 0.3021 0.6356 0.063 Uiso 1 1 calc R . . C34 C 1.2012(3) 0.0944(3) 0.64077(15) 0.0473(6) Uani 1 1 d . . . H34 H 1.2641 0.0305 0.6291 0.057 Uiso 1 1 calc R . . C35 C 1.0459(3) 0.0285(3) 0.65471(12) 0.0362(5) Uani 1 1 d . . . C36 C 0.9674(3) -0.1464(3) 0.65219(12) 0.0364(5) Uani 1 1 d . . . H36 H 1.0406 -0.1783 0.6804 0.044 Uiso 1 1 calc R . . C37 C 0.9302(3) -0.2543(3) 0.56559(13) 0.0462(6) Uani 1 1 d . . . H37A H 0.8541 -0.2283 0.5370 0.055 Uiso 1 1 calc R . . H37B H 1.0257 -0.2358 0.5384 0.055 Uiso 1 1 calc R . . C38 C 0.8635(4) -0.4291(3) 0.56606(15) 0.0554(7) Uani 1 1 d . . . C39 C 0.7004(5) -0.5219(5) 0.5324(3) 0.1255(17) Uani 1 1 d . . . H39A H 0.6709 -0.6275 0.5403 0.188 Uiso 1 1 calc R . . H39B H 0.6911 -0.5312 0.4761 0.188 Uiso 1 1 calc R . . H39C H 0.6319 -0.4679 0.5587 0.188 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 0.0471(2) 0.03206(18) 0.03051(18) 0.01066(14) 0.00856(15) 0.01045(15) Mn2 0.0378(2) 0.0405(2) 0.03639(19) 0.01121(15) 0.00689(14) 0.01638(15) N1 0.0449(11) 0.0370(10) 0.0286(9) 0.0108(8) 0.0051(8) 0.0147(8) N2 0.0414(10) 0.0402(10) 0.0367(10) 0.0172(8) 0.0091(8) 0.0193(9) C1 0.0604(17) 0.0474(15) 0.0492(15) 0.0190(12) 0.0070(13) 0.0094(13) O1 0.0630(14) 0.0743(15) 0.1101(19) 0.0432(14) 0.0016(13) -0.0123(12) C2 0.0633(16) 0.0380(13) 0.0449(14) 0.0150(11) 0.0126(12) 0.0124(12) O2 0.1105(18) 0.0537(12) 0.0941(17) 0.0320(12) 0.0218(14) 0.0448(13) C3 0.0549(15) 0.0477(14) 0.0409(14) 0.0157(11) 0.0092(11) 0.0134(12) O3 0.0993(16) 0.0945(16) 0.0377(11) 0.0273(11) 0.0163(10) 0.0259(13) C4 0.0472(15) 0.0482(15) 0.0516(15) 0.0103(12) 0.0073(12) 0.0167(12) O4 0.0430(12) 0.0726(14) 0.1088(18) 0.0200(13) 0.0103(11) 0.0073(11) C5 0.0398(13) 0.0547(15) 0.0531(15) 0.0188(12) 0.0098(11) 0.0211(12) O5 0.0621(13) 0.0685(14) 0.1075(17) 0.0301(13) 0.0166(12) 0.0411(11) C6 0.0511(15) 0.0669(17) 0.0463(15) 0.0163(13) 0.0059(12) 0.0312(14) O6 0.0963(17) 0.136(2) 0.0443(12) 0.0205(13) 0.0001(11) 0.0638(16) O7 0.0422(9) 0.0338(8) 0.0342(8) 0.0067(6) 0.0078(7) 0.0127(7) O8 0.0453(9) 0.0353(8) 0.0292(7) 0.0090(6) 0.0079(6) 0.0166(7) O9 0.0822(17) 0.104(2) 0.140(2) 0.0441(19) 0.0341(16) 0.0579(16) O10 0.125(2) 0.0643(14) 0.1075(19) 0.0307(14) -0.0057(16) 0.0509(15) C11 0.0522(15) 0.0472(14) 0.0355(12) 0.0121(11) 0.0067(10) 0.0216(12) C12 0.0453(14) 0.0635(17) 0.0482(15) 0.0176(13) 0.0055(11) 0.0185(13) C13 0.0458(15) 0.0549(17) 0.0648(18) 0.0201(14) 0.0027(13) 0.0036(13) C14 0.0540(16) 0.0354(13) 0.0584(16) 0.0122(12) 0.0023(12) 0.0072(11) C15 0.0477(13) 0.0365(12) 0.0315(11) 0.0086(9) 0.0046(10) 0.0145(10) C16 0.0483(14) 0.0349(12) 0.0396(12) 0.0055(10) 0.0048(10) 0.0156(10) C17 0.0700(18) 0.0528(16) 0.0416(14) -0.0022(12) 0.0055(13) 0.0244(14) C18 0.0530(17) 0.0602(19) 0.0591(18) -0.0098(15) 0.0070(14) 0.0126(14) C19 0.084(3) 0.166(5) 0.104(3) 0.032(3) 0.042(2) 0.027(3) C31 0.0534(15) 0.0445(14) 0.0489(14) 0.0222(11) 0.0115(11) 0.0241(12) C32 0.0548(16) 0.0463(15) 0.0564(16) 0.0259(12) 0.0087(12) 0.0132(12) C33 0.0435(14) 0.0636(17) 0.0544(15) 0.0281(14) 0.0127(12) 0.0158(13) C34 0.0452(14) 0.0599(16) 0.0484(14) 0.0231(12) 0.0163(11) 0.0266(12) C35 0.0455(13) 0.0423(12) 0.0280(11) 0.0140(9) 0.0088(9) 0.0211(10) C36 0.0454(13) 0.0399(12) 0.0310(11) 0.0119(9) 0.0093(9) 0.0222(10) C37 0.0662(16) 0.0485(14) 0.0326(12) 0.0098(11) 0.0107(11) 0.0318(13) C38 0.079(2) 0.0514(16) 0.0388(14) 0.0074(12) 0.0095(13) 0.0309(15) C39 0.094(3) 0.105(3) 0.149(4) 0.055(3) -0.026(3) -0.017(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 Mn1 C3 1.788(2) . ? Mn1 C2 1.798(3) . ? Mn1 C1 1.810(3) . ? Mn1 O7 2.0238(16) . ? Mn1 N1 2.0559(19) . ? Mn1 O8 2.0573(16) . ? Mn1 Mn2 3.1342(8) . ? Mn2 C6 1.784(3) . ? Mn2 C5 1.796(3) . ? Mn2 C4 1.804(3) . ? Mn2 O8 2.0145(16) . ? Mn2 N2 2.0533(19) . ? Mn2 O7 2.0715(16) . ? N1 C15 1.341(3) . ? N1 C11 1.349(3) . ? N2 C31 1.344(3) . ? N2 C35 1.348(3) . ? C1 O1 1.140(3) . ? C2 O2 1.144(3) . ? C3 O3 1.141(3) . ? C4 O4 1.146(3) . ? C5 O5 1.148(3) . ? C6 O6 1.148(3) . ? O7 C16 1.418(3) . ? O8 C36 1.411(3) . ? O9 C18 1.190(4) . ? O10 C38 1.192(3) . ? C11 C12 1.365(3) . ? C12 C13 1.374(4) . ? C13 C14 1.369(4) . ? C14 C15 1.391(3) . ? C15 C16 1.502(3) . ? C16 C17 1.538(3) . ? C17 C18 1.508(4) . ? C18 C19 1.491(5) . ? C31 C32 1.368(3) . ? C32 C33 1.369(4) . ? C33 C34 1.377(3) . ? C34 C35 1.379(3) . ? C35 C36 1.508(3) . ? C36 C37 1.533(3) . ? C37 C38 1.512(4) . ? C38 C39 1.460(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 C3 Mn1 C2 87.03(11) . . ? C3 Mn1 C1 86.18(12) . . ? C2 Mn1 C1 88.88(12) . . ? C3 Mn1 O7 98.29(9) . . ? C2 Mn1 O7 171.90(9) . . ? C1 Mn1 O7 97.51(10) . . ? C3 Mn1 N1 93.03(9) . . ? C2 Mn1 N1 94.09(10) . . ? C1 Mn1 N1 176.88(11) . . ? O7 Mn1 N1 79.61(7) . . ? C3 Mn1 O8 174.53(9) . . ? C2 Mn1 O8 96.70(9) . . ? C1 Mn1 O8 89.88(9) . . ? O7 Mn1 O8 78.44(6) . . ? N1 Mn1 O8 90.70(6) . . ? C3 Mn1 Mn2 136.57(9) . . ? C2 Mn1 Mn2 135.57(8) . . ? C1 Mn1 Mn2 86.71(8) . . ? O7 Mn1 Mn2 40.63(4) . . ? N1 Mn1 Mn2 91.81(5) . . ? O8 Mn1 Mn2 39.17(4) . . ? C6 Mn2 C5 87.68(12) . . ? C6 Mn2 C4 85.63(12) . . ? C5 Mn2 C4 88.55(11) . . ? C6 Mn2 O8 100.37(9) . . ? C5 Mn2 O8 170.45(9) . . ? C4 Mn2 O8 97.13(10) . . ? C6 Mn2 N2 90.00(10) . . ? C5 Mn2 N2 95.55(9) . . ? C4 Mn2 N2 173.88(10) . . ? O8 Mn2 N2 79.43(7) . . ? C6 Mn2 O7 176.93(10) . . ? C5 Mn2 O7 93.89(9) . . ? C4 Mn2 O7 91.77(9) . . ? O8 Mn2 O7 78.32(6) . . ? N2 Mn2 O7 92.47(7) . . ? C6 Mn2 Mn1 138.55(9) . . ? C5 Mn2 Mn1 133.02(8) . . ? C4 Mn2 Mn1 87.73(9) . . ? O8 Mn2 Mn1 40.17(4) . . ? N2 Mn2 Mn1 92.75(5) . . ? O7 Mn2 Mn1 39.51(4) . . ? C15 N1 C11 117.6(2) . . ? C15 N1 Mn1 114.78(15) . . ? C11 N1 Mn1 127.58(16) . . ? C31 N2 C35 118.0(2) . . ? C31 N2 Mn2 127.00(16) . . ? C35 N2 Mn2 115.00(15) . . ? O1 C1 Mn1 175.1(2) . . ? O2 C2 Mn1 176.1(2) . . ? O3 C3 Mn1 176.1(2) . . ? O4 C4 Mn2 172.8(2) . . ? O5 C5 Mn2 178.1(2) . . ? O6 C6 Mn2 175.4(2) . . ? C16 O7 Mn1 113.13(13) . . ? C16 O7 Mn2 118.61(13) . . ? Mn1 O7 Mn2 99.86(6) . . ? C36 O8 Mn2 113.87(12) . . ? C36 O8 Mn1 119.74(13) . . ? Mn2 O8 Mn1 100.65(6) . . ? N1 C11 C12 123.1(2) . . ? C11 C12 C13 119.2(3) . . ? C14 C13 C12 118.9(2) . . ? C13 C14 C15 119.4(2) . . ? N1 C15 C14 121.8(2) . . ? N1 C15 C16 115.3(2) . . ? C14 C15 C16 122.9(2) . . ? O7 C16 C15 110.25(18) . . ? O7 C16 C17 111.4(2) . . ? C15 C16 C17 108.5(2) . . ? C18 C17 C16 112.7(2) . . ? O9 C18 C19 121.3(3) . . ? O9 C18 C17 121.7(3) . . ? C19 C18 C17 117.0(3) . . ? N2 C31 C32 122.9(2) . . ? C31 C32 C33 118.9(2) . . ? C32 C33 C34 119.1(2) . . ? C33 C34 C35 119.4(2) . . ? N2 C35 C34 121.6(2) . . ? N2 C35 C36 114.76(19) . . ? C34 C35 C36 123.7(2) . . ? O8 C36 C35 110.62(17) . . ? O8 C36 C37 110.39(19) . . ? C35 C36 C37 111.08(17) . . ? C38 C37 C36 109.30(19) . . ? O10 C38 C39 121.7(3) . . ? O10 C38 C37 120.1(3) . . ? C39 C38 C37 118.2(3) . . ? _diffrn_measured_fraction_theta_max 0.983 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.457 _refine_diff_density_min -0.330 _refine_diff_density_rms 0.057 data_Compound_3(ClO4)_rg518a _database_code_depnum_ccdc_archive 'CCDC 860499' #TrackingRef 'carbenes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H11 Cl Mn N O9' _chemical_formula_weight 403.61 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' 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' Cl Cl 0.1484 0.1585 '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 14.101(2) _cell_length_b 9.0131(15) _cell_length_c 13.155(2) _cell_angle_alpha 90.00 _cell_angle_beta 94.292(4) _cell_angle_gamma 90.00 _cell_volume 1667.3(5) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 814 _cell_measurement_theta_min 2.684 _cell_measurement_theta_max 22.729 _exptl_crystal_description PRISM _exptl_crystal_colour YELLOW _exptl_crystal_size_max 0.32 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.608 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 816 _exptl_absorpt_coefficient_mu 0.997 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.636362 _exptl_absorpt_correction_T_max 1.000000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 16251 _diffrn_reflns_av_R_equivalents 0.0738 _diffrn_reflns_av_sigmaI/netI 0.0835 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.45 _diffrn_reflns_theta_max 28.31 _reflns_number_total 4135 _reflns_number_gt 2024 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0621P)^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 4135 _refine_ls_number_parameters 222 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1316 _refine_ls_R_factor_gt 0.0511 _refine_ls_wR_factor_ref 0.1387 _refine_ls_wR_factor_gt 0.1064 _refine_ls_goodness_of_fit_ref 0.939 _refine_ls_restrained_S_all 0.939 _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 Mn1 Mn 0.35672(4) 0.20363(6) 0.19624(4) 0.0409(2) Uani 1 1 d . . . N1 N 0.2669(2) 0.1291(3) 0.0788(2) 0.0424(7) Uani 1 1 d . . . C1 C 0.4251(3) 0.2759(5) 0.3071(3) 0.0550(11) Uani 1 1 d . . . O1 O 0.4706(2) 0.3119(4) 0.3782(3) 0.0888(11) Uani 1 1 d . . . C2 C 0.4665(3) 0.1711(4) 0.1379(3) 0.0519(10) Uani 1 1 d . . . O2 O 0.5371(2) 0.1485(4) 0.1033(3) 0.0759(10) Uani 1 1 d . . . C3 C 0.3677(3) 0.0233(5) 0.2531(3) 0.0558(11) Uani 1 1 d . . . O3 O 0.3794(3) -0.0914(4) 0.2886(3) 0.0959(13) Uani 1 1 d . . . O4 O 0.22812(18) 0.2577(3) 0.24785(19) 0.0419(6) Uani 1 1 d . . . H4 H 0.206(3) 0.185(5) 0.285(3) 0.072(15) Uiso 1 1 d . . . O5 O 0.34247(19) 0.4105(3) 0.12963(19) 0.0500(7) Uani 1 1 d . . . C11 C 0.2861(3) 0.0305(4) 0.0064(3) 0.0513(10) Uani 1 1 d . . . H11 H 0.3476 -0.0069 0.0064 0.062 Uiso 1 1 calc R . . C12 C 0.2198(4) -0.0172(5) -0.0669(3) 0.0622(12) Uani 1 1 d . . . H12 H 0.2358 -0.0863 -0.1152 0.075 Uiso 1 1 calc R . . C13 C 0.1293(4) 0.0379(5) -0.0685(3) 0.0630(12) Uani 1 1 d . . . H13 H 0.0829 0.0072 -0.1180 0.076 Uiso 1 1 calc R . . C14 C 0.1080(3) 0.1409(5) 0.0054(3) 0.0574(11) Uani 1 1 d . . . H14 H 0.0472 0.1808 0.0054 0.069 Uiso 1 1 calc R . . C15 C 0.1779(3) 0.1828(4) 0.0782(3) 0.0406(9) Uani 1 1 d . . . C16 C 0.1614(3) 0.2893(4) 0.1628(3) 0.0450(9) Uani 1 1 d . . . H16 H 0.0967 0.2757 0.1837 0.054 Uiso 1 1 calc R . . C17 C 0.1744(3) 0.4508(4) 0.1322(3) 0.0489(10) Uani 1 1 d . . . H17A H 0.1336 0.4704 0.0710 0.059 Uiso 1 1 calc R . . H17B H 0.1533 0.5139 0.1858 0.059 Uiso 1 1 calc R . . C18 C 0.2733(3) 0.4928(4) 0.1130(3) 0.0511(10) Uani 1 1 d . . . C19 C 0.2881(4) 0.6461(5) 0.0734(4) 0.0750(14) Uani 1 1 d . . . H19A H 0.3547 0.6624 0.0674 0.113 Uiso 1 1 calc R . . H19B H 0.2648 0.7173 0.1197 0.113 Uiso 1 1 calc R . . H19C H 0.2543 0.6568 0.0077 0.113 Uiso 1 1 calc R . . Cl11 Cl 0.10917(8) -0.06872(14) 0.32249(9) 0.0674(4) Uani 1 1 d . . . O11 O 0.0702(3) -0.1445(5) 0.4021(3) 0.1292(17) Uani 1 1 d . . . O12 O 0.0398(3) 0.0021(6) 0.2621(4) 0.1356(18) Uani 1 1 d . . . O13 O 0.1760(2) 0.0381(4) 0.3661(2) 0.0774(10) Uani 1 1 d . . . O14 O 0.1583(4) -0.1681(7) 0.2654(5) 0.180(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 0.0354(3) 0.0417(3) 0.0459(3) -0.0007(3) 0.0062(2) 0.0023(3) N1 0.0471(19) 0.0374(17) 0.0439(18) 0.0002(14) 0.0117(15) -0.0018(15) C1 0.049(3) 0.059(3) 0.057(3) -0.002(2) 0.008(2) 0.006(2) O1 0.079(2) 0.117(3) 0.068(2) -0.025(2) -0.013(2) 0.000(2) C2 0.048(2) 0.051(3) 0.057(3) -0.011(2) 0.005(2) -0.007(2) O2 0.0489(19) 0.086(2) 0.096(2) -0.0261(19) 0.0271(18) -0.0036(17) C3 0.043(2) 0.062(3) 0.064(3) 0.009(2) 0.013(2) 0.010(2) O3 0.083(3) 0.072(3) 0.136(3) 0.049(2) 0.030(2) 0.027(2) O4 0.0408(15) 0.0453(16) 0.0404(15) 0.0028(12) 0.0076(12) 0.0030(12) O5 0.0523(17) 0.0415(16) 0.0565(17) 0.0010(13) 0.0066(14) -0.0040(13) C11 0.057(3) 0.043(2) 0.055(3) -0.001(2) 0.013(2) -0.003(2) C12 0.085(4) 0.052(3) 0.050(3) -0.008(2) 0.010(3) -0.014(3) C13 0.070(3) 0.066(3) 0.051(3) 0.004(2) -0.010(2) -0.026(3) C14 0.050(3) 0.060(3) 0.061(3) 0.007(2) -0.001(2) -0.008(2) C15 0.039(2) 0.039(2) 0.043(2) 0.0069(17) 0.0042(17) -0.0024(17) C16 0.036(2) 0.046(2) 0.053(2) 0.0063(19) 0.0058(18) 0.0038(18) C17 0.054(3) 0.041(2) 0.052(2) 0.0013(18) 0.004(2) 0.0122(19) C18 0.065(3) 0.040(2) 0.047(2) -0.0026(18) 0.000(2) -0.003(2) C19 0.093(4) 0.041(2) 0.089(4) 0.009(2) -0.006(3) -0.008(3) Cl11 0.0556(7) 0.0719(8) 0.0739(8) 0.0161(7) -0.0004(6) -0.0123(6) O11 0.101(3) 0.160(4) 0.123(3) 0.065(3) -0.012(3) -0.070(3) O12 0.106(3) 0.150(4) 0.142(4) 0.072(3) -0.051(3) -0.019(3) O13 0.076(2) 0.086(2) 0.070(2) 0.0164(18) 0.0027(18) -0.0309(19) O14 0.181(5) 0.161(5) 0.203(6) -0.097(4) 0.050(5) -0.009(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 Mn1 C3 1.791(5) . ? Mn1 C2 1.802(5) . ? Mn1 C1 1.808(5) . ? Mn1 N1 2.037(3) . ? Mn1 O4 2.042(3) . ? Mn1 O5 2.063(3) . ? N1 C15 1.345(5) . ? N1 C11 1.345(5) . ? C1 O1 1.142(5) . ? C2 O2 1.143(4) . ? C3 O3 1.141(5) . ? O4 C16 1.435(4) . ? O5 C18 1.233(5) . ? C11 C12 1.362(6) . ? C12 C13 1.367(7) . ? C13 C14 1.393(6) . ? C14 C15 1.375(5) . ? C15 C16 1.502(5) . ? C16 C17 1.525(5) . ? C17 C18 1.485(6) . ? C18 C19 1.496(6) . ? Cl11 O12 1.370(4) . ? Cl11 O14 1.388(5) . ? Cl11 O11 1.397(4) . ? Cl11 O13 1.437(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 C3 Mn1 C2 88.84(18) . . ? C3 Mn1 C1 88.0(2) . . ? C2 Mn1 C1 88.79(18) . . ? C3 Mn1 N1 92.67(17) . . ? C2 Mn1 N1 97.37(15) . . ? C1 Mn1 N1 173.81(15) . . ? C3 Mn1 O4 97.40(15) . . ? C2 Mn1 O4 173.01(16) . . ? C1 Mn1 O4 94.55(14) . . ? N1 Mn1 O4 79.26(11) . . ? C3 Mn1 O5 179.24(16) . . ? C2 Mn1 O5 91.48(15) . . ? C1 Mn1 O5 92.65(16) . . ? N1 Mn1 O5 86.60(11) . . ? O4 Mn1 O5 82.24(11) . . ? C15 N1 C11 118.1(3) . . ? C15 N1 Mn1 114.4(2) . . ? C11 N1 Mn1 127.5(3) . . ? O1 C1 Mn1 175.3(4) . . ? O2 C2 Mn1 178.1(4) . . ? O3 C3 Mn1 176.6(4) . . ? C16 O4 Mn1 109.6(2) . . ? C18 O5 Mn1 132.1(3) . . ? N1 C11 C12 123.1(4) . . ? C11 C12 C13 119.1(4) . . ? C12 C13 C14 118.8(4) . . ? C15 C14 C13 119.2(4) . . ? N1 C15 C14 121.7(4) . . ? N1 C15 C16 115.0(3) . . ? C14 C15 C16 123.3(4) . . ? O4 C16 C15 108.8(3) . . ? O4 C16 C17 108.1(3) . . ? C15 C16 C17 112.7(3) . . ? C18 C17 C16 115.0(3) . . ? O5 C18 C17 123.8(4) . . ? O5 C18 C19 119.2(4) . . ? C17 C18 C19 116.9(4) . . ? O12 Cl11 O14 110.5(4) . . ? O12 Cl11 O11 111.0(3) . . ? O14 Cl11 O11 109.3(4) . . ? O12 Cl11 O13 109.7(3) . . ? O14 Cl11 O13 108.0(3) . . ? O11 Cl11 O13 108.2(2) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 28.31 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.430 _refine_diff_density_min -0.285 _refine_diff_density_rms 0.073 data_Compound_3OTf_rg524cm _database_code_depnum_ccdc_archive 'CCDC 860500' #TrackingRef 'carbenes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C13 H11 F3 Mn N O8 S' _chemical_formula_weight 453.23 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 '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)/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 13.030(4) _cell_length_b 8.432(3) _cell_length_c 16.566(5) _cell_angle_alpha 90.00 _cell_angle_beta 105.772(6) _cell_angle_gamma 90.00 _cell_volume 1751.4(10) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 933 _cell_measurement_theta_min 2.320 _cell_measurement_theta_max 23.035 _exptl_crystal_description PLATE _exptl_crystal_colour YELLOW _exptl_crystal_size_max 0.43 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.719 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 912 _exptl_absorpt_coefficient_mu 0.946 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.799375 _exptl_absorpt_correction_T_max 1.000000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 11433 _diffrn_reflns_av_R_equivalents 0.0392 _diffrn_reflns_av_sigmaI/netI 0.0339 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.77 _diffrn_reflns_theta_max 23.32 _reflns_number_total 2542 _reflns_number_gt 1716 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0451P)^2^+0.3602P] 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 2542 _refine_ls_number_parameters 249 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0631 _refine_ls_R_factor_gt 0.0339 _refine_ls_wR_factor_ref 0.0915 _refine_ls_wR_factor_gt 0.0770 _refine_ls_goodness_of_fit_ref 0.997 _refine_ls_restrained_S_all 0.997 _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 Mn1 Mn 0.21157(4) 0.25491(7) -0.07175(3) 0.0519(2) Uani 1 1 d . . . N1 N 0.1533(2) 0.0412(3) -0.05025(16) 0.0504(7) Uani 1 1 d . . . C1 C 0.2686(3) 0.4506(6) -0.0795(2) 0.0620(11) Uani 1 1 d . . . O1 O 0.3004(2) 0.5724(4) -0.08846(17) 0.0841(9) Uani 1 1 d . . . C2 C 0.2399(3) 0.1972(6) -0.1675(2) 0.0735(12) Uani 1 1 d . . . O2 O 0.2555(3) 0.1607(5) -0.22886(19) 0.1179(14) Uani 1 1 d . . . C3 C 0.0856(3) 0.3290(5) -0.1321(2) 0.0604(10) Uani 1 1 d . . . O3 O 0.0070(2) 0.3818(4) -0.17002(17) 0.0849(9) Uani 1 1 d . . . H4 H 0.206(3) 0.371(5) 0.067(2) 0.073(14) Uiso 1 1 d . . . O4 O 0.18144(19) 0.2890(3) 0.04103(14) 0.0488(6) Uani 1 1 d . . . O5 O 0.35841(17) 0.1731(3) 0.00094(14) 0.0533(6) Uani 1 1 d . . . C11 C 0.1104(3) -0.0724(5) -0.1067(2) 0.0630(11) Uani 1 1 d . . . H11 H 0.1047 -0.0537 -0.1630 0.076 Uiso 1 1 calc R . . C12 C 0.0754(3) -0.2128(5) -0.0842(3) 0.0681(11) Uani 1 1 d . . . H12 H 0.0463 -0.2885 -0.1248 0.082 Uiso 1 1 calc R . . C13 C 0.0829(3) -0.2426(5) -0.0021(3) 0.0645(10) Uani 1 1 d . . . H13 H 0.0605 -0.3393 0.0141 0.077 Uiso 1 1 calc R . . C14 C 0.1243(3) -0.1271(4) 0.0566(2) 0.0581(10) Uani 1 1 d . . . H14 H 0.1296 -0.1445 0.1130 0.070 Uiso 1 1 calc R . . C15 C 0.1576(2) 0.0139(4) 0.0308(2) 0.0460(8) Uani 1 1 d . . . C16 C 0.2023(3) 0.1458(4) 0.09024(19) 0.0474(9) Uani 1 1 d . . . H16 H 0.1639 0.1503 0.1335 0.057 Uiso 1 1 calc R . . C17 C 0.3205(3) 0.1286(4) 0.1322(2) 0.0510(9) Uani 1 1 d . . . H17A H 0.3414 0.2101 0.1749 0.061 Uiso 1 1 calc R . . H17B H 0.3324 0.0267 0.1604 0.061 Uiso 1 1 calc R . . C18 C 0.3915(3) 0.1399(4) 0.0753(2) 0.0506(9) Uani 1 1 d . . . C19 C 0.5083(3) 0.1163(5) 0.1127(2) 0.0694(11) Uani 1 1 d . . . H19A H 0.5407 0.0842 0.0697 0.104 Uiso 1 1 calc R . . H19B H 0.5195 0.0356 0.1551 0.104 Uiso 1 1 calc R . . H19C H 0.5400 0.2138 0.1374 0.104 Uiso 1 1 calc R . . C51 C 0.4440(4) 0.6419(6) 0.1270(3) 0.0825(13) Uani 1 1 d . . . O51 O 0.2591(2) 0.5435(3) 0.12143(15) 0.0717(8) Uani 1 1 d . . . O52 O 0.4021(2) 0.4718(3) 0.24104(16) 0.0849(9) Uani 1 1 d . . . O53 O 0.3372(3) 0.7405(3) 0.22420(16) 0.0846(9) Uani 1 1 d . . . S51 S 0.35091(8) 0.59483(12) 0.18580(5) 0.0588(3) Uani 1 1 d . . . F51 F 0.4618(2) 0.5174(4) 0.08402(18) 0.1213(10) Uani 1 1 d . . . F52 F 0.4057(2) 0.7568(3) 0.07194(16) 0.1048(9) Uani 1 1 d . . . F53 F 0.5349(2) 0.6892(5) 0.1767(2) 0.1397(12) 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 0.0506(4) 0.0671(4) 0.0335(3) 0.0021(3) 0.0035(2) -0.0044(3) N1 0.0436(18) 0.062(2) 0.0399(16) -0.0040(15) 0.0022(13) -0.0005(14) C1 0.058(3) 0.082(3) 0.041(2) 0.010(2) 0.0044(18) -0.004(2) O1 0.093(2) 0.082(2) 0.0738(19) 0.0191(17) 0.0166(16) -0.0178(18) C2 0.063(3) 0.107(3) 0.045(2) -0.004(2) 0.005(2) -0.013(2) O2 0.109(3) 0.196(4) 0.0535(19) -0.036(2) 0.0300(19) -0.032(3) C3 0.060(3) 0.074(3) 0.042(2) 0.0019(19) 0.0042(19) -0.011(2) O3 0.067(2) 0.099(2) 0.0699(18) 0.0150(16) -0.0136(16) 0.0056(17) O4 0.0547(16) 0.0514(17) 0.0370(13) 0.0003(12) 0.0068(11) -0.0005(12) O5 0.0461(14) 0.0701(16) 0.0397(14) -0.0028(12) 0.0050(11) -0.0003(12) C11 0.056(2) 0.073(3) 0.051(2) -0.011(2) -0.0007(18) 0.002(2) C12 0.053(2) 0.062(3) 0.078(3) -0.017(2) -0.002(2) -0.003(2) C13 0.048(2) 0.056(2) 0.082(3) 0.003(2) 0.004(2) -0.0055(19) C14 0.044(2) 0.065(3) 0.062(2) 0.009(2) 0.0078(18) 0.0016(19) C15 0.0316(19) 0.056(2) 0.046(2) 0.0004(18) 0.0042(15) 0.0024(16) C16 0.048(2) 0.055(2) 0.0378(18) 0.0031(17) 0.0096(16) 0.0022(17) C17 0.056(2) 0.052(2) 0.0380(18) 0.0003(16) 0.0007(16) 0.0003(18) C18 0.050(2) 0.048(2) 0.048(2) -0.0046(17) 0.0024(18) -0.0029(17) C19 0.052(3) 0.084(3) 0.063(2) 0.002(2) 0.0003(19) 0.000(2) C51 0.078(3) 0.084(4) 0.083(3) -0.008(3) 0.017(3) -0.009(3) O51 0.0697(18) 0.0648(17) 0.0681(16) -0.0034(14) -0.0028(14) -0.0100(14) O52 0.103(2) 0.0699(18) 0.0633(17) 0.0189(15) -0.0092(15) -0.0095(16) O53 0.127(3) 0.0676(19) 0.0612(17) -0.0179(15) 0.0293(17) -0.0049(18) S51 0.0700(7) 0.0557(6) 0.0460(5) -0.0001(5) 0.0074(5) -0.0089(5) F51 0.119(2) 0.136(3) 0.122(2) -0.021(2) 0.0549(19) 0.024(2) F52 0.149(3) 0.094(2) 0.0797(17) 0.0156(15) 0.0452(17) -0.0232(18) F53 0.080(2) 0.206(3) 0.126(2) 0.000(2) 0.0177(18) -0.057(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 Mn1 C3 1.786(4) . ? Mn1 C2 1.790(4) . ? Mn1 C1 1.828(5) . ? Mn1 N1 2.025(3) . ? Mn1 O4 2.031(2) . ? Mn1 O5 2.082(2) . ? N1 C15 1.348(4) . ? N1 C11 1.348(4) . ? C1 O1 1.132(4) . ? C2 O2 1.133(4) . ? C3 O3 1.137(4) . ? O4 C16 1.441(4) . ? O5 C18 1.222(4) . ? C11 C12 1.357(5) . ? C12 C13 1.359(5) . ? C13 C14 1.378(5) . ? C14 C15 1.373(5) . ? C15 C16 1.495(5) . ? C16 C17 1.515(4) . ? C17 C18 1.493(5) . ? C18 C19 1.492(5) . ? C51 F53 1.308(5) . ? C51 F51 1.324(5) . ? C51 F52 1.331(5) . ? C51 S51 1.794(5) . ? O51 S51 1.436(2) . ? O52 S51 1.423(3) . ? O53 S51 1.417(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 C3 Mn1 C2 88.76(18) . . ? C3 Mn1 C1 88.52(17) . . ? C2 Mn1 C1 89.87(18) . . ? C3 Mn1 N1 94.49(15) . . ? C2 Mn1 N1 95.23(16) . . ? C1 Mn1 N1 174.12(13) . . ? C3 Mn1 O4 95.02(13) . . ? C2 Mn1 O4 172.29(16) . . ? C1 Mn1 O4 96.93(14) . . ? N1 Mn1 O4 77.80(11) . . ? C3 Mn1 O5 178.51(14) . . ? C2 Mn1 O5 92.52(15) . . ? C1 Mn1 O5 90.72(13) . . ? N1 Mn1 O5 86.15(10) . . ? O4 Mn1 O5 83.79(9) . . ? C15 N1 C11 117.8(3) . . ? C15 N1 Mn1 114.3(2) . . ? C11 N1 Mn1 127.9(2) . . ? O1 C1 Mn1 176.4(3) . . ? O2 C2 Mn1 178.5(4) . . ? O3 C3 Mn1 177.4(4) . . ? C16 O4 Mn1 110.4(2) . . ? C18 O5 Mn1 132.5(2) . . ? N1 C11 C12 122.4(4) . . ? C11 C12 C13 119.8(4) . . ? C12 C13 C14 118.9(4) . . ? C15 C14 C13 119.2(4) . . ? N1 C15 C14 121.8(3) . . ? N1 C15 C16 115.7(3) . . ? C14 C15 C16 122.6(3) . . ? O4 C16 C15 105.7(3) . . ? O4 C16 C17 110.6(3) . . ? C15 C16 C17 113.4(3) . . ? C18 C17 C16 115.5(3) . . ? O5 C18 C19 119.3(3) . . ? O5 C18 C17 122.8(3) . . ? C19 C18 C17 117.8(3) . . ? F53 C51 F51 108.6(4) . . ? F53 C51 F52 108.4(4) . . ? F51 C51 F52 107.3(4) . . ? F53 C51 S51 110.9(3) . . ? F51 C51 S51 111.1(3) . . ? F52 C51 S51 110.5(3) . . ? O53 S51 O52 115.93(17) . . ? O53 S51 O51 114.42(18) . . ? O52 S51 O51 114.08(16) . . ? O53 S51 C51 103.8(2) . . ? O52 S51 C51 104.0(2) . . ? O51 S51 C51 102.3(2) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 23.32 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.301 _refine_diff_density_min -0.169 _refine_diff_density_rms 0.048 data_Compound_5a_rg653xm _database_code_depnum_ccdc_archive 'CCDC 860501' #TrackingRef 'carbenes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H25 B Mn N O5' _chemical_formula_weight 401.14 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' B B 0.0013 0.0007 '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' 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 14.745(5) _cell_length_b 8.775(3) _cell_length_c 31.476(10) _cell_angle_alpha 90.00 _cell_angle_beta 99.237(9) _cell_angle_gamma 90.00 _cell_volume 4020(2) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 636 _cell_measurement_theta_min 2.41 _cell_measurement_theta_max 16.49 _exptl_crystal_description plate _exptl_crystal_colour yellow _exptl_crystal_size_max 0.31 _exptl_crystal_size_mid 0.19 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.326 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1680 _exptl_absorpt_coefficient_mu 0.683 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.682368 _exptl_absorpt_correction_T_max 1.000000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 16037 _diffrn_reflns_av_R_equivalents 0.0933 _diffrn_reflns_av_sigmaI/netI 0.0981 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -27 _diffrn_reflns_limit_l_max 33 _diffrn_reflns_theta_min 1.31 _diffrn_reflns_theta_max 22.03 _reflns_number_total 4935 _reflns_number_gt 2448 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.1388P)^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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4935 _refine_ls_number_parameters 477 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1783 _refine_ls_R_factor_gt 0.0916 _refine_ls_wR_factor_ref 0.2124 _refine_ls_wR_factor_gt 0.1842 _refine_ls_goodness_of_fit_ref 1.032 _refine_ls_restrained_S_all 1.032 _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 Mn1 Mn 0.25286(11) 0.84861(18) 0.13445(5) 0.0379(6) Uani 1 1 d . . . N1 N 0.3703(6) 0.7485(10) 0.1652(3) 0.041(2) Uani 1 1 d . . . B1 B 0.2371(11) 0.6031(15) 0.0665(4) 0.052(4) Uani 1 1 d . . . C1 C 0.1499(9) 0.9387(14) 0.1093(4) 0.049(3) Uani 1 1 d . . . O1 O 0.0871(6) 1.0049(11) 0.0940(3) 0.077(3) Uani 1 1 d . . . C2 C 0.2847(8) 1.0293(14) 0.1519(4) 0.045(3) Uani 1 1 d . . . O2 O 0.3035(8) 1.1559(10) 0.1615(4) 0.105(4) Uani 1 1 d . . . C3 C 0.2914(7) 0.8691(13) 0.0800(3) 0.043(3) Uani 1 1 d . . . O3 O 0.2795(5) 0.7522(9) 0.0536(2) 0.051(2) Uani 1 1 d . . . O4 O 0.2330(5) 0.6299(8) 0.1149(2) 0.044(2) Uani 1 1 d . . . O5 O 0.1918(5) 0.7686(9) 0.1872(2) 0.046(2) Uani 1 1 d . . . C11 C 0.4476(9) 0.8193(15) 0.1847(4) 0.061(4) Uani 1 1 d . . . H11 H 0.4538 0.9243 0.1823 0.073 Uiso 1 1 calc R . . C12 C 0.5177(10) 0.734(2) 0.2082(4) 0.085(5) Uani 1 1 d . . . H12 H 0.5714 0.7814 0.2211 0.103 Uiso 1 1 calc R . . C13 C 0.5082(13) 0.578(2) 0.2125(5) 0.096(6) Uani 1 1 d . . . H13 H 0.5545 0.5216 0.2288 0.115 Uiso 1 1 calc R . . C14 C 0.4310(11) 0.5104(15) 0.1928(4) 0.067(4) Uani 1 1 d . . . H14 H 0.4237 0.4055 0.1946 0.081 Uiso 1 1 calc R . . C15 C 0.3632(8) 0.5985(14) 0.1699(4) 0.049(3) Uani 1 1 d . . . C16 C 0.2745(9) 0.5245(13) 0.1480(4) 0.049(3) Uani 1 1 d . . . H16 H 0.2884 0.4280 0.1347 0.059 Uiso 1 1 calc R . . C17 C 0.2077(9) 0.4973(13) 0.1785(4) 0.061(4) Uani 1 1 d . . . H17A H 0.2376 0.4353 0.2022 0.073 Uiso 1 1 calc R . . H17B H 0.1563 0.4391 0.1636 0.073 Uiso 1 1 calc R . . C18 C 0.1707(8) 0.6384(16) 0.1968(4) 0.053(3) Uani 1 1 d . . . C19 C 0.1044(10) 0.6164(16) 0.2269(5) 0.086(5) Uani 1 1 d . . . H19A H 0.0506 0.5658 0.2122 0.128 Uiso 1 1 calc R . . H19B H 0.0875 0.7138 0.2371 0.128 Uiso 1 1 calc R . . H19C H 0.1321 0.5555 0.2508 0.128 Uiso 1 1 calc R . . C21 C 0.3051(10) 0.4680(14) 0.0580(4) 0.067(4) Uani 1 1 d . . . H21A H 0.3622 0.4782 0.0779 0.080 Uiso 1 1 calc R . . H21B H 0.2776 0.3712 0.0637 0.080 Uiso 1 1 calc R . . C22 C 0.3258(12) 0.4677(17) 0.0119(4) 0.094(5) Uani 1 1 d . . . H22A H 0.2692 0.4645 -0.0080 0.141 Uiso 1 1 calc R . . H22B H 0.3622 0.3798 0.0077 0.141 Uiso 1 1 calc R . . H22C H 0.3590 0.5584 0.0071 0.141 Uiso 1 1 calc R . . C23 C 0.1333(9) 0.5920(15) 0.0427(4) 0.068(4) Uani 1 1 d . . . H23A H 0.1046 0.6910 0.0442 0.082 Uiso 1 1 calc R . . H23B H 0.1337 0.5698 0.0125 0.082 Uiso 1 1 calc R . . C24 C 0.0748(11) 0.4751(19) 0.0601(5) 0.104(6) Uani 1 1 d . . . H24A H 0.1004 0.3756 0.0574 0.156 Uiso 1 1 calc R . . H24B H 0.0136 0.4788 0.0442 0.156 Uiso 1 1 calc R . . H24C H 0.0731 0.4961 0.0899 0.156 Uiso 1 1 calc R . . C31 C 0.3346(9) 1.0011(12) 0.0601(4) 0.054(3) Uani 1 1 d . . . H31A H 0.2915 1.0853 0.0583 0.064 Uiso 1 1 calc R . . H31B H 0.3883 1.0314 0.0803 0.064 Uiso 1 1 calc R . . C32 C 0.3633(9) 0.9871(13) 0.0179(4) 0.061(4) Uani 1 1 d . . . H32A H 0.3106 0.9667 -0.0035 0.092 Uiso 1 1 calc R . . H32B H 0.4065 0.9050 0.0185 0.092 Uiso 1 1 calc R . . H32C H 0.3916 1.0805 0.0110 0.092 Uiso 1 1 calc R . . Mn51 Mn 0.82340(11) -0.14605(18) 0.15290(5) 0.0405(6) Uani 1 1 d . . . N51 N 0.8615(6) -0.0924(11) 0.0947(3) 0.042(2) Uani 1 1 d . . . B51 B 0.6867(9) 0.1059(14) 0.1390(4) 0.043(4) Uani 1 1 d . . . C51 C 0.7846(8) -0.1944(13) 0.2014(4) 0.043(3) Uani 1 1 d . . . O51 O 0.7524(6) -0.2381(11) 0.2303(3) 0.072(3) Uani 1 1 d . . . C52 C 0.8508(9) -0.3312(14) 0.1501(5) 0.070(4) Uani 1 1 d . . . O52 O 0.8707(7) -0.4685(11) 0.1491(4) 0.104(4) Uani 1 1 d . . . C53 C 0.6981(7) -0.1653(14) 0.1264(3) 0.042(3) Uani 1 1 d . . . O53 O 0.6485(5) -0.0451(9) 0.1222(2) 0.051(2) Uani 1 1 d . . . O54 O 0.7973(5) 0.0847(7) 0.1507(2) 0.0370(19) Uani 1 1 d . . . O55 O 0.9558(5) -0.0687(9) 0.1808(2) 0.047(2) Uani 1 1 d . . . C61 C 0.8742(8) -0.1890(16) 0.0624(5) 0.065(4) Uani 1 1 d . . . H61 H 0.8719 -0.2937 0.0668 0.078 Uiso 1 1 calc R . . C62 C 0.8902(10) -0.135(2) 0.0237(5) 0.084(5) Uani 1 1 d . . . H62 H 0.8988 -0.2024 0.0019 0.100 Uiso 1 1 calc R . . C63 C 0.8935(9) 0.016(2) 0.0173(5) 0.075(5) Uani 1 1 d . . . H63 H 0.9038 0.0525 -0.0092 0.089 Uiso 1 1 calc R . . C64 C 0.8821(8) 0.1179(16) 0.0490(5) 0.061(4) Uani 1 1 d . . . H64 H 0.8852 0.2226 0.0449 0.074 Uiso 1 1 calc R . . C65 C 0.8653(7) 0.0544(13) 0.0886(3) 0.037(3) Uani 1 1 d . . . C66 C 0.8517(7) 0.1543(13) 0.1268(4) 0.049(3) Uani 1 1 d . . . H66 H 0.8230 0.2505 0.1160 0.059 Uiso 1 1 calc R . . C67 C 0.9431(8) 0.1888(13) 0.1551(4) 0.056(3) Uani 1 1 d . . . H67A H 0.9855 0.2266 0.1370 0.068 Uiso 1 1 calc R . . H67B H 0.9336 0.2699 0.1749 0.068 Uiso 1 1 calc R . . C68 C 0.9865(8) 0.0594(14) 0.1803(3) 0.044(3) Uani 1 1 d . . . C69 C 1.0802(8) 0.0917(15) 0.2073(4) 0.070(4) Uani 1 1 d . . . H69A H 1.1215 0.1288 0.1890 0.106 Uiso 1 1 calc R . . H69B H 1.1044 -0.0005 0.2212 0.106 Uiso 1 1 calc R . . H69C H 1.0736 0.1670 0.2287 0.106 Uiso 1 1 calc R . . C71 C 0.6570(8) 0.2326(13) 0.1014(4) 0.055(3) Uani 1 1 d . . . H71A H 0.6816 0.3311 0.1114 0.066 Uiso 1 1 calc R . . H71B H 0.6840 0.2053 0.0762 0.066 Uiso 1 1 calc R . . C72 C 0.5547(9) 0.2457(17) 0.0886(5) 0.095(5) Uani 1 1 d . . . H72A H 0.5290 0.1464 0.0819 0.142 Uiso 1 1 calc R . . H72B H 0.5410 0.3104 0.0638 0.142 Uiso 1 1 calc R . . H72C H 0.5286 0.2886 0.1120 0.142 Uiso 1 1 calc R . . C73 C 0.6528(9) 0.1391(14) 0.1835(4) 0.066(4) Uani 1 1 d . . . H73A H 0.5862 0.1363 0.1788 0.079 Uiso 1 1 calc R . . H73B H 0.6745 0.0575 0.2034 0.079 Uiso 1 1 calc R . . C74 C 0.6843(11) 0.2916(17) 0.2049(5) 0.099(6) Uani 1 1 d . . . H74A H 0.7502 0.2959 0.2099 0.149 Uiso 1 1 calc R . . H74B H 0.6619 0.3003 0.2318 0.149 Uiso 1 1 calc R . . H74C H 0.6604 0.3739 0.1863 0.149 Uiso 1 1 calc R . . C81 C 0.6494(8) -0.3059(13) 0.1080(4) 0.057(3) Uani 1 1 d . . . H81A H 0.6867 -0.3528 0.0888 0.069 Uiso 1 1 calc R . . H81B H 0.6471 -0.3767 0.1315 0.069 Uiso 1 1 calc R . . C82 C 0.5558(10) -0.2890(16) 0.0843(5) 0.085(5) Uani 1 1 d . . . H82A H 0.5558 -0.2157 0.0616 0.127 Uiso 1 1 calc R . . H82B H 0.5158 -0.2548 0.1036 0.127 Uiso 1 1 calc R . . H82C H 0.5345 -0.3854 0.0721 0.127 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 0.0400(11) 0.0315(10) 0.0431(12) 0.0040(8) 0.0091(8) 0.0010(8) N1 0.048(6) 0.036(6) 0.036(6) 0.003(4) 0.001(5) -0.009(5) B1 0.075(11) 0.041(9) 0.040(10) 0.003(6) 0.010(8) -0.016(8) C1 0.047(8) 0.072(9) 0.031(8) 0.019(6) 0.015(6) 0.012(7) O1 0.061(7) 0.113(9) 0.054(6) 0.010(5) 0.003(5) 0.042(6) C2 0.047(8) 0.038(8) 0.053(8) -0.009(6) 0.017(6) -0.006(6) O2 0.147(10) 0.026(6) 0.164(11) -0.004(6) 0.093(8) 0.007(6) C3 0.045(7) 0.043(8) 0.039(8) 0.012(6) -0.002(6) 0.012(6) O3 0.059(5) 0.050(5) 0.045(5) -0.010(4) 0.014(4) -0.007(4) O4 0.060(5) 0.037(5) 0.036(5) 0.018(4) 0.008(4) -0.005(4) O5 0.045(5) 0.053(5) 0.042(5) 0.011(4) 0.013(4) 0.002(4) C11 0.044(8) 0.068(10) 0.070(10) -0.014(8) 0.007(7) -0.009(8) C12 0.042(9) 0.152(18) 0.058(11) -0.028(11) -0.005(8) 0.015(11) C13 0.097(15) 0.103(15) 0.079(13) -0.012(11) -0.012(10) 0.059(13) C14 0.082(12) 0.050(9) 0.067(10) 0.009(7) 0.006(9) 0.038(8) C15 0.055(9) 0.057(9) 0.033(8) -0.002(6) 0.004(6) 0.012(7) C16 0.072(9) 0.039(7) 0.035(8) 0.002(6) 0.005(7) 0.002(6) C17 0.078(10) 0.042(8) 0.063(10) -0.003(6) 0.015(8) -0.005(7) C18 0.048(8) 0.075(10) 0.039(8) 0.022(7) 0.015(6) -0.017(7) C19 0.083(11) 0.091(12) 0.093(12) 0.036(9) 0.044(9) 0.015(9) C21 0.094(11) 0.052(9) 0.059(10) 0.003(7) 0.026(8) 0.000(8) C22 0.131(15) 0.099(13) 0.055(11) -0.006(8) 0.025(9) 0.028(11) C23 0.073(10) 0.060(9) 0.067(10) 0.000(7) -0.002(8) -0.010(8) C24 0.087(13) 0.136(16) 0.085(13) 0.011(11) 0.002(10) -0.034(11) C31 0.070(9) 0.045(8) 0.047(9) 0.003(6) 0.015(7) -0.016(6) C32 0.068(10) 0.061(9) 0.061(10) 0.020(7) 0.027(7) -0.002(7) Mn51 0.0431(11) 0.0291(10) 0.0476(12) -0.0028(8) 0.0019(8) 0.0017(8) N51 0.035(6) 0.051(7) 0.041(6) -0.010(5) 0.003(4) 0.001(5) B51 0.042(8) 0.031(8) 0.059(10) 0.001(6) 0.011(7) 0.007(6) C51 0.041(7) 0.046(8) 0.037(8) 0.011(6) -0.008(6) -0.002(6) O51 0.069(7) 0.088(7) 0.055(7) 0.024(5) -0.005(5) 0.001(5) C52 0.070(9) 0.021(8) 0.112(12) -0.002(7) -0.004(8) 0.002(7) O52 0.094(8) 0.040(6) 0.170(11) -0.005(6) -0.003(7) 0.021(6) C53 0.031(7) 0.058(8) 0.040(8) -0.006(6) 0.011(5) -0.014(7) O53 0.033(5) 0.043(5) 0.074(6) 0.010(4) 0.002(4) 0.002(4) O54 0.044(5) 0.027(4) 0.041(5) 0.005(3) 0.008(4) 0.024(4) O55 0.049(5) 0.038(5) 0.054(5) -0.009(4) 0.002(4) 0.007(4) C61 0.056(9) 0.077(10) 0.056(10) -0.022(8) -0.010(7) 0.006(7) C62 0.067(10) 0.131(16) 0.052(12) -0.024(11) 0.007(8) 0.014(11) C63 0.045(9) 0.136(16) 0.042(10) 0.003(11) 0.005(7) 0.005(10) C64 0.041(8) 0.072(10) 0.071(11) 0.021(9) 0.009(7) 0.002(7) C65 0.026(6) 0.040(8) 0.043(8) 0.009(6) 0.002(5) -0.001(5) C66 0.030(7) 0.028(7) 0.082(10) -0.011(7) -0.013(6) 0.004(6) C67 0.041(8) 0.048(8) 0.079(10) 0.006(7) 0.006(7) -0.010(6) C68 0.036(7) 0.049(8) 0.048(8) -0.001(6) 0.013(6) 0.002(7) C69 0.053(9) 0.068(10) 0.084(11) -0.016(8) -0.006(7) -0.005(7) C71 0.044(8) 0.041(7) 0.080(10) 0.012(6) 0.007(7) -0.007(6) C72 0.050(10) 0.090(12) 0.132(14) 0.016(10) -0.020(9) 0.017(8) C73 0.060(9) 0.051(9) 0.090(11) 0.014(8) 0.025(8) 0.013(7) C74 0.122(14) 0.107(14) 0.072(11) -0.027(9) 0.025(10) 0.042(11) C81 0.043(8) 0.044(8) 0.082(10) -0.006(7) 0.000(7) -0.006(6) C82 0.073(11) 0.081(11) 0.095(12) -0.034(9) -0.003(9) -0.024(8) _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 C2 1.718(12) . ? Mn1 C1 1.781(13) . ? Mn1 C3 1.900(11) . ? Mn1 O4 2.022(7) . ? Mn1 N1 2.041(9) . ? Mn1 O5 2.130(7) . ? N1 C15 1.331(13) . ? N1 C11 1.356(14) . ? B1 O3 1.532(15) . ? B1 O4 1.554(15) . ? B1 C23 1.596(19) . ? B1 C21 1.602(19) . ? C1 O1 1.132(13) . ? C2 O2 1.173(12) . ? C3 O3 1.313(12) . ? C3 C31 1.505(15) . ? O4 C16 1.452(12) . ? O5 C18 1.234(13) . ? C11 C12 1.391(18) . ? C12 C13 1.38(2) . ? C13 C14 1.35(2) . ? C14 C15 1.373(16) . ? C15 C16 1.523(16) . ? C16 C17 1.501(16) . ? C17 C18 1.504(16) . ? C18 C19 1.479(15) . ? C21 C22 1.529(16) . ? C23 C24 1.499(17) . ? C31 C32 1.463(15) . ? Mn51 C52 1.680(12) . ? Mn51 C51 1.767(13) . ? Mn51 C53 1.909(11) . ? Mn51 N51 2.054(9) . ? Mn51 O54 2.060(7) . ? Mn51 O55 2.119(8) . ? N51 C65 1.305(13) . ? N51 C61 1.360(14) . ? B51 O53 1.503(15) . ? B51 C73 1.587(17) . ? B51 O54 1.623(15) . ? B51 C71 1.633(17) . ? C51 O51 1.157(12) . ? C52 O52 1.241(13) . ? C53 O53 1.278(12) . ? C53 C81 1.496(15) . ? O54 C66 1.333(13) . ? O55 C68 1.213(13) . ? C61 C62 1.361(18) . ? C62 C63 1.344(19) . ? C63 C64 1.368(18) . ? C64 C65 1.423(15) . ? C65 C66 1.527(15) . ? C66 C67 1.523(15) . ? C67 C68 1.471(15) . ? C68 C69 1.528(16) . ? C71 C72 1.503(16) . ? C73 C74 1.536(18) . ? C81 C82 1.468(17) . ? 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 Mn1 C1 84.3(6) . . ? C2 Mn1 C3 95.5(5) . . ? C1 Mn1 C3 85.1(5) . . ? C2 Mn1 O4 172.6(4) . . ? C1 Mn1 O4 102.4(5) . . ? C3 Mn1 O4 82.2(4) . . ? C2 Mn1 N1 94.5(5) . . ? C1 Mn1 N1 178.1(4) . . ? C3 Mn1 N1 96.6(4) . . ? O4 Mn1 N1 78.8(3) . . ? C2 Mn1 O5 100.5(4) . . ? C1 Mn1 O5 93.2(4) . . ? C3 Mn1 O5 163.7(4) . . ? O4 Mn1 O5 82.3(3) . . ? N1 Mn1 O5 85.5(3) . . ? C15 N1 C11 118.5(10) . . ? C15 N1 Mn1 113.8(8) . . ? C11 N1 Mn1 127.2(8) . . ? O3 B1 O4 102.2(9) . . ? O3 B1 C23 109.3(10) . . ? O4 B1 C23 106.5(10) . . ? O3 B1 C21 107.2(10) . . ? O4 B1 C21 113.5(10) . . ? C23 B1 C21 117.1(11) . . ? O1 C1 Mn1 175.5(13) . . ? O2 C2 Mn1 176.0(12) . . ? O3 C3 C31 111.2(9) . . ? O3 C3 Mn1 117.9(8) . . ? C31 C3 Mn1 131.0(9) . . ? C3 O3 B1 121.3(9) . . ? C16 O4 B1 121.9(9) . . ? C16 O4 Mn1 111.3(6) . . ? B1 O4 Mn1 114.6(6) . . ? C18 O5 Mn1 130.5(7) . . ? N1 C11 C12 119.4(13) . . ? C13 C12 C11 120.6(15) . . ? C14 C13 C12 118.9(15) . . ? C13 C14 C15 118.9(14) . . ? N1 C15 C14 123.5(12) . . ? N1 C15 C16 116.6(10) . . ? C14 C15 C16 119.9(12) . . ? O4 C16 C17 108.4(10) . . ? O4 C16 C15 106.6(9) . . ? C17 C16 C15 112.4(10) . . ? C16 C17 C18 115.4(10) . . ? O5 C18 C19 119.7(12) . . ? O5 C18 C17 123.2(10) . . ? C19 C18 C17 117.1(11) . . ? C22 C21 B1 112.6(10) . . ? C24 C23 B1 115.8(11) . . ? C32 C31 C3 121.1(10) . . ? C52 Mn51 C51 85.9(6) . . ? C52 Mn51 C53 96.6(6) . . ? C51 Mn51 C53 86.1(5) . . ? C52 Mn51 N51 94.1(6) . . ? C51 Mn51 N51 176.9(4) . . ? C53 Mn51 N51 90.8(4) . . ? C52 Mn51 O54 173.7(5) . . ? C51 Mn51 O54 100.4(4) . . ? C53 Mn51 O54 84.8(4) . . ? N51 Mn51 O54 79.7(3) . . ? C52 Mn51 O55 96.8(5) . . ? C51 Mn51 O55 97.1(4) . . ? C53 Mn51 O55 166.4(4) . . ? N51 Mn51 O55 86.0(3) . . ? O54 Mn51 O55 81.6(3) . . ? C65 N51 C61 119.3(11) . . ? C65 N51 Mn51 112.5(7) . . ? C61 N51 Mn51 127.9(9) . . ? O53 B51 C73 108.6(9) . . ? O53 B51 O54 106.5(8) . . ? C73 B51 O54 105.6(10) . . ? O53 B51 C71 107.6(10) . . ? C73 B51 C71 115.5(10) . . ? O54 B51 C71 112.6(9) . . ? O51 C51 Mn51 171.9(11) . . ? O52 C52 Mn51 178.4(13) . . ? O53 C53 C81 114.2(10) . . ? O53 C53 Mn51 118.0(8) . . ? C81 C53 Mn51 127.8(9) . . ? C53 O53 B51 121.0(9) . . ? C66 O54 B51 119.6(8) . . ? C66 O54 Mn51 110.1(6) . . ? B51 O54 Mn51 107.2(6) . . ? C68 O55 Mn51 127.8(7) . . ? N51 C61 C62 121.1(14) . . ? C63 C62 C61 119.5(15) . . ? C62 C63 C64 121.6(15) . . ? C63 C64 C65 116.2(13) . . ? N51 C65 C64 122.3(11) . . ? N51 C65 C66 115.9(10) . . ? C64 C65 C66 121.9(11) . . ? O54 C66 C67 108.5(10) . . ? O54 C66 C65 110.4(9) . . ? C67 C66 C65 111.1(9) . . ? C68 C67 C66 115.4(10) . . ? O55 C68 C67 126.2(11) . . ? O55 C68 C69 118.1(11) . . ? C67 C68 C69 115.6(11) . . ? C72 C71 B51 112.7(10) . . ? C74 C73 B51 115.5(11) . . ? C82 C81 C53 117.8(11) . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 22.03 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 1.789 _refine_diff_density_min -0.512 _refine_diff_density_rms 0.132 data_Compound_6_rg453am _database_code_depnum_ccdc_archive 'CCDC 860502' #TrackingRef 'carbenes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H10 B F3 Mn N O5' _chemical_formula_weight 370.96 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' B B 0.0013 0.0007 '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' 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 Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.089(7) _cell_length_b 7.997(8) _cell_length_c 13.897(10) _cell_angle_alpha 97.627(16) _cell_angle_beta 96.696(15) _cell_angle_gamma 105.950(15) _cell_volume 741.1(12) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 829 _cell_measurement_theta_min 2.843 _cell_measurement_theta_max 27.790 _exptl_crystal_description BLOCK _exptl_crystal_colour YELLOW _exptl_crystal_size_max 0.44 _exptl_crystal_size_mid 0.26 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.662 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 372 _exptl_absorpt_coefficient_mu 0.947 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.764568 _exptl_absorpt_correction_T_max 1.000000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 7344 _diffrn_reflns_av_R_equivalents 0.0181 _diffrn_reflns_av_sigmaI/netI 0.0231 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.69 _diffrn_reflns_theta_max 28.37 _reflns_number_total 3630 _reflns_number_gt 3084 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0572P)^2^+0.0819P] 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 3630 _refine_ls_number_parameters 209 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0412 _refine_ls_R_factor_gt 0.0334 _refine_ls_wR_factor_ref 0.0953 _refine_ls_wR_factor_gt 0.0900 _refine_ls_goodness_of_fit_ref 1.037 _refine_ls_restrained_S_all 1.037 _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 Mn1 Mn 0.48657(4) 0.77010(3) 0.697153(17) 0.03514(10) Uani 1 1 d . . . N1 N 0.3666(2) 0.8259(2) 0.81851(10) 0.0384(3) Uani 1 1 d . . . B1 B 0.7087(3) 0.5459(3) 0.81527(18) 0.0477(5) Uani 1 1 d . . . F1 F 0.75885(19) 0.6308(2) 0.91226(10) 0.0759(4) Uani 1 1 d . . . F2 F 0.85182(17) 0.61170(18) 0.76087(10) 0.0641(3) Uani 1 1 d . . . F3 F 0.6799(2) 0.36859(18) 0.81332(11) 0.0743(4) Uani 1 1 d . . . C1 C 0.5980(3) 0.7027(3) 0.59303(15) 0.0520(5) Uani 1 1 d . . . O1 O 0.6781(3) 0.6710(3) 0.53016(14) 0.0853(6) Uani 1 1 d . . . C2 C 0.4206(3) 0.9335(3) 0.63519(16) 0.0542(5) Uani 1 1 d . . . O2 O 0.3775(4) 1.0377(3) 0.59661(16) 0.0956(7) Uani 1 1 d . . . C3 C 0.7236(3) 0.9242(2) 0.74545(14) 0.0444(4) Uani 1 1 d . . . O3 O 0.8755(2) 1.0239(2) 0.77331(13) 0.0685(4) Uani 1 1 d . . . O4 O 0.52228(17) 0.57502(16) 0.77139(9) 0.0406(3) Uani 1 1 d . . . O5 O 0.21328(18) 0.59035(16) 0.63971(9) 0.0407(3) Uani 1 1 d . . . C11 C 0.3367(3) 0.9794(3) 0.85458(16) 0.0558(5) Uani 1 1 d . . . H11 H 0.3725 1.0742 0.8215 0.067 Uiso 1 1 calc R . . C12 C 0.2559(3) 1.0011(4) 0.9381(2) 0.0754(8) Uani 1 1 d . . . H12 H 0.2363 1.1088 0.9611 0.090 Uiso 1 1 calc R . . C13 C 0.2043(3) 0.8642(5) 0.98730(18) 0.0813(10) Uani 1 1 d . . . H13 H 0.1477 0.8767 1.0439 0.098 Uiso 1 1 calc R . . C14 C 0.2364(3) 0.7066(4) 0.95283(15) 0.0652(7) Uani 1 1 d . . . H14 H 0.2037 0.6118 0.9862 0.078 Uiso 1 1 calc R . . C15 C 0.3177(2) 0.6919(3) 0.86798(13) 0.0416(4) Uani 1 1 d . . . C16 C 0.3600(3) 0.5266(2) 0.82454(14) 0.0435(4) Uani 1 1 d . . . H16 H 0.3999 0.4693 0.8783 0.052 Uiso 1 1 calc R . . C17 C 0.1837(3) 0.3966(2) 0.75679(15) 0.0470(4) Uani 1 1 d . . . H17A H 0.2155 0.2870 0.7399 0.056 Uiso 1 1 calc R . . H17B H 0.0722 0.3719 0.7925 0.056 Uiso 1 1 calc R . . C18 C 0.1202(3) 0.4542(2) 0.66419(13) 0.0406(4) Uani 1 1 d . . . C19 C -0.0620(3) 0.3348(3) 0.59919(17) 0.0599(6) Uani 1 1 d . . . H19A H -0.0859 0.3834 0.5410 0.090 Uiso 1 1 calc R . . H19B H -0.1736 0.3233 0.6335 0.090 Uiso 1 1 calc R . . H19C H -0.0440 0.2207 0.5812 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 Mn1 0.03602(15) 0.03324(15) 0.03573(15) 0.00951(10) 0.00772(10) 0.00703(10) N1 0.0323(7) 0.0444(8) 0.0369(7) 0.0030(6) 0.0018(6) 0.0122(6) B1 0.0378(10) 0.0507(12) 0.0571(13) 0.0075(10) 0.0027(9) 0.0202(9) F1 0.0460(7) 0.1063(11) 0.0621(8) -0.0113(7) -0.0083(6) 0.0195(7) F2 0.0386(6) 0.0775(9) 0.0838(9) 0.0181(7) 0.0181(6) 0.0242(6) F3 0.0823(10) 0.0574(8) 0.1000(11) 0.0266(7) 0.0165(8) 0.0412(7) C1 0.0528(11) 0.0490(11) 0.0501(11) 0.0069(8) 0.0155(9) 0.0060(9) O1 0.0972(14) 0.0914(13) 0.0711(11) 0.0062(10) 0.0488(11) 0.0231(11) C2 0.0625(13) 0.0479(11) 0.0489(11) 0.0155(9) 0.0036(9) 0.0100(9) O2 0.1292(18) 0.0763(12) 0.0931(14) 0.0490(11) 0.0015(13) 0.0403(12) C3 0.0475(10) 0.0393(9) 0.0443(10) 0.0115(7) 0.0104(8) 0.0060(8) O3 0.0525(9) 0.0560(9) 0.0799(11) 0.0129(8) 0.0022(8) -0.0092(7) O4 0.0288(6) 0.0422(7) 0.0542(7) 0.0191(5) 0.0070(5) 0.0109(5) O5 0.0389(6) 0.0412(6) 0.0392(6) 0.0076(5) 0.0040(5) 0.0081(5) C11 0.0453(11) 0.0587(12) 0.0594(12) -0.0084(10) -0.0030(9) 0.0220(9) C12 0.0440(12) 0.097(2) 0.0713(16) -0.0367(15) -0.0033(11) 0.0271(13) C13 0.0401(11) 0.142(3) 0.0449(12) -0.0213(15) 0.0061(10) 0.0169(15) C14 0.0364(10) 0.113(2) 0.0372(10) 0.0152(11) 0.0047(8) 0.0060(11) C15 0.0257(7) 0.0610(11) 0.0346(8) 0.0116(7) 0.0004(6) 0.0072(7) C16 0.0313(8) 0.0505(10) 0.0510(10) 0.0269(8) 0.0052(7) 0.0080(7) C17 0.0366(9) 0.0399(9) 0.0636(12) 0.0202(8) 0.0063(8) 0.0053(7) C18 0.0340(8) 0.0398(9) 0.0461(9) 0.0029(7) 0.0079(7) 0.0093(7) C19 0.0496(12) 0.0573(13) 0.0562(12) 0.0001(10) -0.0009(10) -0.0031(10) _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 C3 1.781(2) . ? Mn1 C2 1.791(2) . ? Mn1 C1 1.817(2) . ? Mn1 N1 2.0275(18) . ? Mn1 O4 2.0362(19) . ? Mn1 O5 2.064(2) . ? N1 C15 1.337(3) . ? N1 C11 1.344(3) . ? B1 F2 1.367(3) . ? B1 F3 1.372(3) . ? B1 F1 1.384(3) . ? B1 O4 1.480(3) . ? C1 O1 1.134(3) . ? C2 O2 1.139(3) . ? C3 O3 1.137(3) . ? O4 C16 1.431(2) . ? O5 C18 1.222(2) . ? C11 C12 1.365(4) . ? C12 C13 1.355(5) . ? C13 C14 1.375(4) . ? C14 C15 1.377(3) . ? C15 C16 1.500(3) . ? C16 C17 1.510(3) . ? C17 C18 1.485(3) . ? C18 C19 1.489(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 C3 Mn1 C2 89.44(11) . . ? C3 Mn1 C1 86.81(11) . . ? C2 Mn1 C1 89.83(11) . . ? C3 Mn1 N1 93.89(9) . . ? C2 Mn1 N1 95.42(10) . . ? C1 Mn1 N1 174.71(8) . . ? C3 Mn1 O4 96.68(9) . . ? C2 Mn1 O4 172.09(8) . . ? C1 Mn1 O4 95.49(9) . . ? N1 Mn1 O4 79.21(7) . . ? C3 Mn1 O5 179.29(7) . . ? C2 Mn1 O5 90.59(10) . . ? C1 Mn1 O5 92.48(9) . . ? N1 Mn1 O5 86.82(8) . . ? O4 Mn1 O5 83.35(7) . . ? C15 N1 C11 118.10(19) . . ? C15 N1 Mn1 114.00(13) . . ? C11 N1 Mn1 127.88(15) . . ? F2 B1 F3 110.68(18) . . ? F2 B1 F1 111.56(19) . . ? F3 B1 F1 108.6(2) . . ? F2 B1 O4 107.54(18) . . ? F3 B1 O4 109.52(17) . . ? F1 B1 O4 108.92(17) . . ? O1 C1 Mn1 175.3(2) . . ? O2 C2 Mn1 179.2(2) . . ? O3 C3 Mn1 177.77(17) . . ? C16 O4 B1 114.86(15) . . ? C16 O4 Mn1 108.63(11) . . ? B1 O4 Mn1 128.86(12) . . ? C18 O5 Mn1 132.28(13) . . ? N1 C11 C12 122.3(2) . . ? C13 C12 C11 119.3(3) . . ? C12 C13 C14 119.5(2) . . ? C13 C14 C15 118.7(3) . . ? N1 C15 C14 122.0(2) . . ? N1 C15 C16 114.98(16) . . ? C14 C15 C16 123.0(2) . . ? O4 C16 C15 108.25(15) . . ? O4 C16 C17 109.41(17) . . ? C15 C16 C17 113.31(16) . . ? C18 C17 C16 115.57(15) . . ? O5 C18 C17 122.74(17) . . ? O5 C18 C19 120.35(18) . . ? C17 C18 C19 116.89(17) . . ? _diffrn_measured_fraction_theta_max 0.978 _diffrn_reflns_theta_full 28.37 _diffrn_measured_fraction_theta_full 0.978 _refine_diff_density_max 0.377 _refine_diff_density_min -0.268 _refine_diff_density_rms 0.052 data_compound_7(re)_rg659am _database_code_depnum_ccdc_archive 'CCDC 860503' #TrackingRef 'carbenes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C14 H13 F3 N O8 Re S' _chemical_formula_weight 598.51 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' 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' Re Re -1.0185 7.2310 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 '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 8.830(2) _cell_length_b 9.860(2) _cell_length_c 11.793(3) _cell_angle_alpha 109.086(4) _cell_angle_beta 104.152(4) _cell_angle_gamma 91.234(4) _cell_volume 935.0(4) _cell_formula_units_Z 2 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 903 _cell_measurement_theta_min 2.88 _cell_measurement_theta_max 28.31 _exptl_crystal_description BLOCK _exptl_crystal_colour COLORLESS _exptl_crystal_size_max 0.29 _exptl_crystal_size_mid 0.17 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.126 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 572 _exptl_absorpt_coefficient_mu 6.681 _exptl_absorpt_correction_type MULTI-SCAN _exptl_absorpt_correction_T_min 0.365 _exptl_absorpt_correction_T_max 0.626 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8209 _diffrn_reflns_av_R_equivalents 0.0266 _diffrn_reflns_av_sigmaI/netI 0.0335 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.90 _diffrn_reflns_theta_max 26.40 _reflns_number_total 3803 _reflns_number_gt 3491 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0295P)^2^+0.3712P] 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 3803 _refine_ls_number_parameters 255 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0271 _refine_ls_R_factor_gt 0.0229 _refine_ls_wR_factor_ref 0.0593 _refine_ls_wR_factor_gt 0.0567 _refine_ls_goodness_of_fit_ref 1.057 _refine_ls_restrained_S_all 1.057 _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 Re1 Re 0.249164(16) 0.766362(16) 0.859426(14) 0.03735(7) Uani 1 1 d . . . N1 N 0.4654(4) 0.7284(3) 0.9727(3) 0.0363(7) Uani 1 1 d . . . C1 C 0.0607(5) 0.7740(6) 0.7402(5) 0.0580(12) Uani 1 1 d . . . O1 O -0.0538(4) 0.7710(5) 0.6679(4) 0.0896(13) Uani 1 1 d . . . C2 C 0.2240(5) 0.9524(5) 0.9617(4) 0.0491(10) Uani 1 1 d . . . O2 O 0.2102(5) 1.0640(4) 1.0284(4) 0.0716(10) Uani 1 1 d . . . C3 C 0.1206(5) 0.6941(5) 0.9394(4) 0.0459(10) Uani 1 1 d . . . O3 O 0.0460(4) 0.6530(4) 0.9901(3) 0.0683(9) Uani 1 1 d . . . O4 O 0.3113(3) 0.5606(3) 0.7508(3) 0.0418(6) Uani 1 1 d . . . O5 O 0.4086(3) 0.8450(3) 0.7732(3) 0.0425(6) Uani 1 1 d . . . C11 C 0.5232(5) 0.7921(5) 1.0970(4) 0.0464(10) Uani 1 1 d . . . H11 H 0.4667 0.8587 1.1407 0.056 Uiso 1 1 calc R . . C12 C 0.6618(5) 0.7620(5) 1.1606(4) 0.0532(11) Uani 1 1 d . . . H12 H 0.6988 0.8082 1.2462 0.064 Uiso 1 1 calc R . . C13 C 0.7467(5) 0.6628(5) 1.0977(4) 0.0504(10) Uani 1 1 d . . . H13 H 0.8420 0.6423 1.1399 0.061 Uiso 1 1 calc R . . C14 C 0.6883(5) 0.5948(4) 0.9717(4) 0.0442(9) Uani 1 1 d . . . H14 H 0.7425 0.5260 0.9276 0.053 Uiso 1 1 calc R . . C15 C 0.5499(4) 0.6293(4) 0.9119(4) 0.0371(8) Uani 1 1 d . . . C16 C 0.4814(4) 0.5616(4) 0.7728(3) 0.0395(8) Uani 1 1 d . . . H16 H 0.5063 0.4616 0.7464 0.047 Uiso 1 1 calc R . . C17 C 0.5445(5) 0.6398(4) 0.7000(4) 0.0430(9) Uani 1 1 d . . . H17A H 0.6581 0.6419 0.7218 0.052 Uiso 1 1 calc R . . H17B H 0.5058 0.5832 0.6122 0.052 Uiso 1 1 calc R . . C18 C 0.5057(4) 0.7906(5) 0.7174(4) 0.0420(9) Uani 1 1 d . . . C19 C 0.5889(6) 0.8768(5) 0.6643(4) 0.0557(11) Uani 1 1 d . . . H19A H 0.5376 0.9617 0.6645 0.084 Uiso 1 1 calc R . . H19B H 0.5869 0.8199 0.5804 0.084 Uiso 1 1 calc R . . H19C H 0.6959 0.9045 0.7136 0.084 Uiso 1 1 calc R . . C40 C 0.2201(6) 0.4631(5) 0.6288(4) 0.0610(12) Uani 1 1 d . . . H40A H 0.2304 0.5018 0.5658 0.091 Uiso 1 1 calc R . . H40B H 0.1114 0.4533 0.6281 0.091 Uiso 1 1 calc R . . H40C H 0.2585 0.3701 0.6122 0.091 Uiso 1 1 calc R . . S1 S 0.76313(15) 0.30349(13) 0.64141(11) 0.0559(3) Uani 1 1 d . . . O11 O 0.8827(5) 0.4100(4) 0.7307(4) 0.0845(12) Uani 1 1 d . . . O12 O 0.6423(7) 0.2580(5) 0.6862(6) 0.125(2) Uani 1 1 d . . . O13 O 0.7081(8) 0.3291(5) 0.5293(5) 0.133(2) Uani 1 1 d . . . C51 C 0.8585(7) 0.1430(6) 0.5977(6) 0.0728(15) Uani 1 1 d . . . F1 F 0.7650(5) 0.0324(4) 0.5168(4) 0.1029(12) Uani 1 1 d . . . F2 F 0.9799(6) 0.1659(5) 0.5614(7) 0.174(3) Uani 1 1 d . . . F3 F 0.9157(6) 0.1016(5) 0.6940(6) 0.148(2) 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 Re1 0.03105(9) 0.03861(10) 0.04622(10) 0.01577(7) 0.01502(7) 0.00897(6) N1 0.0343(16) 0.0333(16) 0.0420(17) 0.0115(13) 0.0128(13) 0.0071(13) C1 0.041(2) 0.071(3) 0.071(3) 0.034(3) 0.017(2) 0.018(2) O1 0.054(2) 0.124(4) 0.091(3) 0.046(3) 0.005(2) 0.030(2) C2 0.043(2) 0.048(3) 0.067(3) 0.027(2) 0.023(2) 0.0151(19) O2 0.082(3) 0.047(2) 0.089(3) 0.0137(18) 0.040(2) 0.0209(18) C3 0.039(2) 0.045(2) 0.057(2) 0.017(2) 0.0204(19) 0.0081(18) O3 0.059(2) 0.077(2) 0.086(2) 0.036(2) 0.0379(19) 0.0068(18) O4 0.0344(14) 0.0385(15) 0.0468(15) 0.0100(12) 0.0072(11) 0.0023(11) O5 0.0432(15) 0.0406(15) 0.0489(15) 0.0168(12) 0.0193(12) 0.0074(12) C11 0.049(2) 0.045(2) 0.043(2) 0.0103(18) 0.0157(18) 0.0070(19) C12 0.052(3) 0.062(3) 0.041(2) 0.016(2) 0.0047(19) 0.004(2) C13 0.039(2) 0.059(3) 0.057(2) 0.027(2) 0.0082(19) 0.0088(19) C14 0.039(2) 0.048(2) 0.054(2) 0.0228(19) 0.0184(18) 0.0140(18) C15 0.0366(19) 0.036(2) 0.045(2) 0.0167(16) 0.0185(16) 0.0053(15) C16 0.0350(19) 0.039(2) 0.044(2) 0.0110(17) 0.0130(16) 0.0094(16) C17 0.041(2) 0.047(2) 0.043(2) 0.0135(18) 0.0178(17) 0.0124(17) C18 0.036(2) 0.049(2) 0.040(2) 0.0125(17) 0.0118(16) 0.0057(17) C19 0.056(3) 0.059(3) 0.062(3) 0.022(2) 0.030(2) 0.005(2) C40 0.056(3) 0.057(3) 0.054(3) 0.006(2) 0.003(2) -0.004(2) S1 0.0594(7) 0.0450(6) 0.0589(7) 0.0119(5) 0.0152(5) 0.0167(5) O11 0.088(3) 0.064(2) 0.073(2) -0.0007(19) 0.003(2) 0.001(2) O12 0.121(4) 0.084(3) 0.199(6) 0.030(4) 0.120(4) 0.024(3) O13 0.184(6) 0.085(3) 0.094(3) 0.044(3) -0.042(4) 0.000(3) C51 0.069(4) 0.051(3) 0.105(5) 0.022(3) 0.040(3) 0.012(3) F1 0.112(3) 0.0509(19) 0.124(3) -0.0065(19) 0.043(2) 0.0017(19) F2 0.153(5) 0.084(3) 0.306(8) 0.015(4) 0.171(5) 0.013(3) F3 0.131(4) 0.089(3) 0.210(6) 0.075(4) -0.013(4) 0.030(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 Re1 C2 1.890(5) . ? Re1 C3 1.900(4) . ? Re1 C1 1.919(5) . ? Re1 N1 2.164(3) . ? Re1 O4 2.180(3) . ? Re1 O5 2.187(3) . ? N1 C11 1.350(5) . ? N1 C15 1.364(5) . ? C1 O1 1.145(6) . ? C2 O2 1.153(5) . ? C3 O3 1.138(5) . ? O4 C16 1.459(5) . ? O4 C40 1.462(5) . ? O5 C18 1.234(5) . ? C11 C12 1.364(6) . ? C12 C13 1.378(7) . ? C13 C14 1.371(6) . ? C14 C15 1.364(5) . ? C15 C16 1.512(5) . ? C16 C17 1.513(5) . ? C17 C18 1.493(6) . ? C18 C19 1.483(6) . ? S1 O13 1.399(5) . ? S1 O11 1.418(4) . ? S1 O12 1.424(5) . ? S1 C51 1.793(6) . ? C51 F2 1.289(7) . ? C51 F1 1.295(7) . ? C51 F3 1.320(8) . ? 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 Re1 C3 86.41(19) . . ? C2 Re1 C1 88.3(2) . . ? C3 Re1 C1 88.0(2) . . ? C2 Re1 N1 100.15(16) . . ? C3 Re1 N1 93.66(16) . . ? C1 Re1 N1 171.44(17) . . ? C2 Re1 O4 172.46(14) . . ? C3 Re1 O4 98.07(15) . . ? C1 Re1 O4 97.85(17) . . ? N1 Re1 O4 73.61(11) . . ? C2 Re1 O5 94.63(15) . . ? C3 Re1 O5 176.72(14) . . ? C1 Re1 O5 95.16(17) . . ? N1 Re1 O5 83.09(11) . . ? O4 Re1 O5 80.57(11) . . ? C11 N1 C15 117.3(3) . . ? C11 N1 Re1 126.3(3) . . ? C15 N1 Re1 116.3(2) . . ? O1 C1 Re1 176.4(5) . . ? O2 C2 Re1 177.1(4) . . ? O3 C3 Re1 178.3(4) . . ? C16 O4 C40 114.8(3) . . ? C16 O4 Re1 111.2(2) . . ? C40 O4 Re1 126.8(3) . . ? C18 O5 Re1 134.5(3) . . ? N1 C11 C12 122.2(4) . . ? C11 C12 C13 119.8(4) . . ? C14 C13 C12 118.9(4) . . ? C15 C14 C13 119.2(4) . . ? C14 C15 N1 122.6(4) . . ? C14 C15 C16 121.9(3) . . ? N1 C15 C16 115.5(3) . . ? O4 C16 C15 106.2(3) . . ? O4 C16 C17 111.7(3) . . ? C15 C16 C17 113.1(3) . . ? C18 C17 C16 117.2(3) . . ? O5 C18 C19 119.5(4) . . ? O5 C18 C17 122.9(4) . . ? C19 C18 C17 117.6(4) . . ? O13 S1 O11 113.8(3) . . ? O13 S1 O12 114.1(4) . . ? O11 S1 O12 116.3(3) . . ? O13 S1 C51 103.3(4) . . ? O11 S1 C51 105.0(3) . . ? O12 S1 C51 102.1(3) . . ? F2 C51 F1 111.5(6) . . ? F2 C51 F3 104.1(6) . . ? F1 C51 F3 104.4(5) . . ? F2 C51 S1 111.3(4) . . ? F1 C51 S1 113.6(4) . . ? F3 C51 S1 111.3(5) . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 26.40 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.679 _refine_diff_density_min -0.756 _refine_diff_density_rms 0.097 data_C_8_rg740cm _database_code_depnum_ccdc_archive 'CCDC 860504' #TrackingRef 'carbenes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C9 H7 Br Mn N O4' _chemical_formula_weight 328.01 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' Br Br -0.2901 2.4595 '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 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 16.534(6) _cell_length_b 11.294(4) _cell_length_c 13.542(5) _cell_angle_alpha 90.00 _cell_angle_beta 114.688(5) _cell_angle_gamma 90.00 _cell_volume 2297.7(13) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 736 _cell_measurement_theta_min 2.440 _cell_measurement_theta_max 18.205 _exptl_crystal_description BLOCK _exptl_crystal_colour ORANGE _exptl_crystal_size_max 0.09 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.896 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1280 _exptl_absorpt_coefficient_mu 4.623 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.585207 _exptl_absorpt_correction_T_max 1.000000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8735 _diffrn_reflns_av_R_equivalents 0.0872 _diffrn_reflns_av_sigmaI/netI 0.0931 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.26 _diffrn_reflns_theta_max 25.41 _reflns_number_total 2117 _reflns_number_gt 948 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0342P)^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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2117 _refine_ls_number_parameters 142 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1443 _refine_ls_R_factor_gt 0.0481 _refine_ls_wR_factor_ref 0.1019 _refine_ls_wR_factor_gt 0.0799 _refine_ls_goodness_of_fit_ref 0.841 _refine_ls_restrained_S_all 0.841 _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 Mn1 Mn 0.70486(8) 0.45927(10) 0.09018(10) 0.0398(4) Uani 1 1 d . . . Br1 Br 0.79036(6) 0.42767(7) -0.02718(7) 0.0461(3) Uani 1 1 d . . . N1 N 0.8226(4) 0.5215(5) 0.2070(5) 0.0342(16) Uani 1 1 d . . . C1 C 0.6087(6) 0.3838(7) -0.0094(8) 0.053(3) Uani 1 1 d . . . O1 O 0.5452(4) 0.3384(6) -0.0728(6) 0.084(2) Uani 1 1 d . . . C2 C 0.6628(6) 0.5973(8) 0.0188(7) 0.055(3) Uani 1 1 d . . . O2 O 0.6334(5) 0.6827(6) -0.0243(6) 0.091(3) Uani 1 1 d . . . C3 C 0.6464(5) 0.4816(7) 0.1729(7) 0.044(2) Uani 1 1 d . . . O3 O 0.6039(2) 0.4946(3) 0.2219(3) 0.073(2) Uani 1 1 d . . . O4 O 0.7627(2) 0.3061(3) 0.1725(3) 0.0396(14) Uani 1 1 d R . . H4 H 0.7475 0.2344 0.1561 0.048 Uiso 1 1 d R . . C11 C 0.8473(5) 0.6365(6) 0.2285(7) 0.042(2) Uani 1 1 d . . . H11 H 0.8084 0.6946 0.1862 0.051 Uiso 1 1 calc R . . C12 C 0.9275(5) 0.6721(7) 0.3102(7) 0.046(2) Uani 1 1 d . . . H12 H 0.9412 0.7522 0.3223 0.056 Uiso 1 1 calc R . . C13 C 0.9877(5) 0.5867(8) 0.3740(7) 0.047(2) Uani 1 1 d . . . H13 H 1.0419 0.6083 0.4296 0.056 Uiso 1 1 calc R . . C14 C 0.9640(5) 0.4689(8) 0.3520(6) 0.046(2) Uani 1 1 d . . . H14 H 1.0030 0.4098 0.3923 0.055 Uiso 1 1 calc R . . C15 C 0.8815(5) 0.4386(7) 0.2692(6) 0.0356(19) Uani 1 1 d . . . C16 C 0.8553(5) 0.3121(7) 0.2405(7) 0.047(2) Uani 1 1 d . . . H16A H 0.8888 0.2788 0.2031 0.057 Uiso 1 1 calc R . . H16B H 0.8686 0.2665 0.3062 0.057 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 0.0359(8) 0.0321(7) 0.0443(9) 0.0010(6) 0.0099(7) 0.0025(6) Br1 0.0474(6) 0.0438(5) 0.0455(6) -0.0068(5) 0.0177(5) -0.0070(5) N1 0.034(4) 0.032(4) 0.035(4) -0.002(3) 0.013(4) 0.004(3) C1 0.057(7) 0.040(5) 0.056(7) 0.003(5) 0.018(6) 0.015(5) O1 0.053(5) 0.073(5) 0.091(6) -0.017(4) -0.006(4) -0.017(4) C2 0.055(6) 0.060(7) 0.046(6) -0.006(5) 0.017(5) -0.002(5) O2 0.091(6) 0.061(4) 0.100(7) 0.038(4) 0.020(5) 0.035(4) C3 0.038(6) 0.032(5) 0.049(6) -0.004(4) 0.006(5) 0.006(4) O3 0.062(5) 0.077(5) 0.090(6) -0.008(4) 0.042(5) 0.007(4) O4 0.039(3) 0.022(3) 0.048(4) 0.008(3) 0.008(3) -0.004(3) C11 0.046(6) 0.027(5) 0.054(6) -0.001(4) 0.021(5) 0.006(4) C12 0.046(6) 0.041(5) 0.054(7) -0.022(5) 0.023(5) -0.020(5) C13 0.043(6) 0.060(6) 0.032(5) -0.010(5) 0.010(4) -0.005(5) C14 0.039(5) 0.056(6) 0.037(6) 0.003(5) 0.010(5) -0.001(5) C15 0.025(5) 0.031(5) 0.048(6) 0.001(4) 0.012(4) 0.002(4) C16 0.044(6) 0.035(5) 0.055(7) -0.007(4) 0.011(5) -0.002(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 Mn1 C3 1.777(9) . ? Mn1 C1 1.812(10) . ? Mn1 C2 1.813(10) . ? Mn1 N1 2.053(6) . ? Mn1 O4 2.064(4) . ? Mn1 Br1 2.5550(16) . ? N1 C11 1.356(9) . ? N1 C15 1.360(8) . ? C1 O1 1.161(9) . ? C2 O2 1.127(9) . ? C3 O3 1.161(9) . ? O4 C16 1.421(8) . ? C11 C12 1.384(10) . ? C12 C13 1.397(10) . ? C13 C14 1.384(10) . ? C14 C15 1.399(9) . ? C15 C16 1.497(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 C3 Mn1 C1 89.8(4) . . ? C3 Mn1 C2 91.5(4) . . ? C1 Mn1 C2 89.2(4) . . ? C3 Mn1 N1 93.2(3) . . ? C1 Mn1 N1 171.8(3) . . ? C2 Mn1 N1 98.4(3) . . ? C3 Mn1 O4 91.7(3) . . ? C1 Mn1 O4 94.1(3) . . ? C2 Mn1 O4 175.4(3) . . ? N1 Mn1 O4 78.1(2) . . ? C3 Mn1 Br1 179.4(3) . . ? C1 Mn1 Br1 90.7(3) . . ? C2 Mn1 Br1 88.7(3) . . ? N1 Mn1 Br1 86.25(18) . . ? O4 Mn1 Br1 88.12(12) . . ? C11 N1 C15 116.9(7) . . ? C11 N1 Mn1 126.7(5) . . ? C15 N1 Mn1 116.4(5) . . ? O1 C1 Mn1 177.6(8) . . ? O2 C2 Mn1 176.8(9) . . ? O3 C3 Mn1 176.2(7) . . ? C16 O4 Mn1 116.2(4) . . ? N1 C11 C12 123.5(8) . . ? C11 C12 C13 119.4(8) . . ? C14 C13 C12 117.8(8) . . ? C13 C14 C15 120.1(8) . . ? N1 C15 C14 122.3(7) . . ? N1 C15 C16 116.2(6) . . ? C14 C15 C16 121.4(7) . . ? O4 C16 C15 109.3(6) . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 25.41 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.762 _refine_diff_density_min -0.469 _refine_diff_density_rms 0.111 data_Compound_((Re)_rg741cm _database_code_depnum_ccdc_archive 'CCDC 860505' #TrackingRef 'carbenes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C13 H15 Br N O5 Re' _chemical_formula_weight 531.37 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' Re Re -1.0185 7.2310 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 '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 9.083(3) _cell_length_b 9.093(3) _cell_length_c 11.271(4) _cell_angle_alpha 75.642(5) _cell_angle_beta 66.993(5) _cell_angle_gamma 74.222(5) _cell_volume 813.9(4) _cell_formula_units_Z 2 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 886 _cell_measurement_theta_min 2.858 _cell_measurement_theta_max 25.350 _exptl_crystal_description BLOCK _exptl_crystal_colour COLORLESS _exptl_crystal_size_max 0.33 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.168 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 500 _exptl_absorpt_coefficient_mu 9.938 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.441382 _exptl_absorpt_correction_T_max 1.000000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6731 _diffrn_reflns_av_R_equivalents 0.0384 _diffrn_reflns_av_sigmaI/netI 0.0431 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 1.99 _diffrn_reflns_theta_max 25.73 _reflns_number_total 3080 _reflns_number_gt 2640 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0419P)^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 constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0037(5) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3080 _refine_ls_number_parameters 189 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0356 _refine_ls_R_factor_gt 0.0289 _refine_ls_wR_factor_ref 0.0717 _refine_ls_wR_factor_gt 0.0693 _refine_ls_goodness_of_fit_ref 0.987 _refine_ls_restrained_S_all 0.987 _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 Re1 Re 0.55306(2) 0.79500(3) 0.76609(2) 0.04097(12) Uani 1 1 d . . . Br1 Br 0.73875(8) 0.70044(8) 0.54406(6) 0.05597(18) Uani 1 1 d . . . N1 N 0.6520(5) 1.0056(5) 0.6783(4) 0.0417(11) Uani 1 1 d . . . C1 C 0.4962(8) 0.5946(9) 0.8370(6) 0.0589(16) Uani 1 1 d . . . O1 O 0.4612(7) 0.4753(6) 0.8769(6) 0.0858(16) Uani 1 1 d . . . C2 C 0.3604(7) 0.8572(7) 0.7250(6) 0.0525(15) Uani 1 1 d . . . O2 O 0.2411(5) 0.8942(7) 0.7042(5) 0.0799(15) Uani 1 1 d . . . C3 C 0.4308(8) 0.8648(8) 0.9294(7) 0.0609(17) Uani 1 1 d . . . O3 O 0.3502(4) 0.9056(4) 1.0267(3) 0.0902(18) Uani 1 1 d . . . O4 O 0.7801(4) 0.7498(4) 0.8038(3) 0.0575(11) Uani 1 1 d R . . H4 H 0.8366 0.6523 0.8141 0.10(3) Uiso 1 1 d R . . C11 C 0.5766(8) 1.1360(7) 0.6211(6) 0.0573(16) Uani 1 1 d . . . H11 H 0.4754 1.1383 0.6175 0.069 Uiso 1 1 calc R . . C12 C 0.6440(10) 1.2651(8) 0.5683(7) 0.073(2) Uani 1 1 d . . . H12 H 0.5880 1.3543 0.5311 0.087 Uiso 1 1 calc R . . C13 C 0.7939(9) 1.2625(8) 0.5704(6) 0.0628(18) Uani 1 1 d . . . H13 H 0.8413 1.3496 0.5350 0.075 Uiso 1 1 calc R . . C14 C 0.8727(8) 1.1304(8) 0.6251(6) 0.0564(16) Uani 1 1 d . . . H14 H 0.9757 1.1256 0.6263 0.068 Uiso 1 1 calc R . . C15 C 0.8000(7) 1.0043(7) 0.6786(5) 0.0425(13) Uani 1 1 d . . . C16 C 0.8817(7) 0.8595(8) 0.7423(6) 0.0563(16) Uani 1 1 d . . . H16A H 0.9801 0.8148 0.6772 0.068 Uiso 1 1 calc R . . H16B H 0.9133 0.8845 0.8067 0.068 Uiso 1 1 calc R . . C51 C 1.1309(10) 0.4569(11) 0.8067(10) 0.095(3) Uani 1 1 d . . . H51A H 1.1540 0.5265 0.8470 0.114 Uiso 1 1 calc R . . H51B H 1.1940 0.4706 0.7141 0.114 Uiso 1 1 calc R . . O51 O 0.9647(7) 0.4857(6) 0.8270(8) 0.107(2) Uani 1 1 d . . . C52 C 1.1701(12) 0.2963(12) 0.8673(10) 0.103(3) Uani 1 1 d . . . H52A H 1.2698 0.2419 0.8099 0.123 Uiso 1 1 calc R . . H52B H 1.1841 0.2921 0.9492 0.123 Uiso 1 1 calc R . . C53 C 1.0336(16) 0.2282(12) 0.8893(14) 0.140(5) Uani 1 1 d . . . H53A H 0.9864 0.1879 0.9813 0.168 Uiso 1 1 calc R . . H53B H 1.0687 0.1438 0.8399 0.168 Uiso 1 1 calc R . . C54 C 0.9147(13) 0.3496(11) 0.8468(13) 0.121(4) Uani 1 1 d . . . H54A H 0.9108 0.3324 0.7666 0.146 Uiso 1 1 calc R . . H54B H 0.8069 0.3520 0.9131 0.146 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 Re1 0.03443(15) 0.03878(17) 0.04965(16) -0.00141(10) -0.01545(10) -0.01095(10) Br1 0.0522(3) 0.0470(4) 0.0623(4) -0.0148(3) -0.0116(3) -0.0068(3) N1 0.035(2) 0.036(3) 0.049(3) -0.005(2) -0.011(2) -0.005(2) C1 0.052(4) 0.064(5) 0.062(4) -0.002(3) -0.022(3) -0.018(3) O1 0.107(4) 0.054(3) 0.105(4) 0.017(3) -0.044(3) -0.046(3) C2 0.042(3) 0.051(4) 0.065(4) -0.007(3) -0.021(3) -0.009(3) O2 0.041(3) 0.093(4) 0.113(4) -0.020(3) -0.037(3) -0.006(3) C3 0.056(4) 0.067(5) 0.067(4) -0.008(3) -0.016(3) -0.034(3) O3 0.096(4) 0.099(5) 0.066(3) -0.029(3) 0.003(3) -0.036(3) O4 0.048(2) 0.048(3) 0.085(3) 0.007(2) -0.042(2) -0.010(2) C11 0.049(3) 0.039(4) 0.073(4) -0.001(3) -0.021(3) 0.002(3) C12 0.091(6) 0.037(4) 0.079(5) 0.004(3) -0.032(4) -0.003(4) C13 0.072(5) 0.043(4) 0.068(4) 0.003(3) -0.017(4) -0.025(4) C14 0.055(4) 0.052(4) 0.063(4) -0.006(3) -0.012(3) -0.027(3) C15 0.044(3) 0.039(3) 0.047(3) -0.013(2) -0.016(2) -0.006(3) C16 0.046(3) 0.056(4) 0.071(4) 0.005(3) -0.026(3) -0.022(3) C51 0.073(5) 0.091(7) 0.125(8) -0.008(6) -0.049(5) -0.010(5) O51 0.077(4) 0.050(4) 0.211(7) -0.007(4) -0.085(4) -0.001(3) C52 0.087(6) 0.087(7) 0.124(8) -0.009(6) -0.048(6) 0.009(6) C53 0.152(11) 0.056(7) 0.227(15) 0.006(7) -0.108(11) -0.007(7) C54 0.107(8) 0.061(6) 0.218(13) -0.027(7) -0.077(8) -0.016(6) _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 Re1 C2 1.888(6) . ? Re1 C3 1.903(7) . ? Re1 C1 1.921(8) . ? Re1 O4 2.177(3) . ? Re1 N1 2.181(5) . ? Re1 Br1 2.6124(9) . ? N1 C15 1.342(7) . ? N1 C11 1.347(8) . ? C1 O1 1.147(8) . ? C2 O2 1.141(7) . ? C3 O3 1.142(7) . ? O4 C16 1.410(7) . ? C11 C12 1.366(10) . ? C12 C13 1.365(10) . ? C13 C14 1.359(9) . ? C14 C15 1.368(8) . ? C15 C16 1.489(8) . ? C51 O51 1.394(9) . ? C51 C52 1.462(12) . ? O51 C54 1.370(10) . ? C52 C53 1.443(13) . ? C53 C54 1.452(13) . ? 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 Re1 C3 88.3(3) . . ? C2 Re1 C1 87.5(3) . . ? C3 Re1 C1 91.2(3) . . ? C2 Re1 O4 173.5(2) . . ? C3 Re1 O4 91.5(2) . . ? C1 Re1 O4 99.0(2) . . ? C2 Re1 N1 99.1(2) . . ? C3 Re1 N1 93.2(2) . . ? C1 Re1 N1 172.2(2) . . ? O4 Re1 N1 74.44(15) . . ? C2 Re1 Br1 95.31(19) . . ? C3 Re1 Br1 176.10(19) . . ? C1 Re1 Br1 90.3(2) . . ? O4 Re1 Br1 84.70(9) . . ? N1 Re1 Br1 84.91(11) . . ? C15 N1 C11 117.6(5) . . ? C15 N1 Re1 117.8(4) . . ? C11 N1 Re1 124.6(4) . . ? O1 C1 Re1 178.5(6) . . ? O2 C2 Re1 177.9(6) . . ? O3 C3 Re1 176.3(5) . . ? C16 O4 Re1 117.7(3) . . ? N1 C11 C12 122.1(7) . . ? C13 C12 C11 119.6(7) . . ? C14 C13 C12 118.7(6) . . ? C13 C14 C15 119.8(6) . . ? N1 C15 C14 122.1(6) . . ? N1 C15 C16 117.0(5) . . ? C14 C15 C16 120.9(6) . . ? O4 C16 C15 112.2(5) . . ? O51 C51 C52 105.6(8) . . ? C54 O51 C51 110.2(7) . . ? C53 C52 C51 105.8(8) . . ? C52 C53 C54 107.1(9) . . ? O51 C54 C53 106.2(8) . . ? _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 25.73 _diffrn_measured_fraction_theta_full 0.990 _refine_diff_density_max 1.032 _refine_diff_density_min -1.266 _refine_diff_density_rms 0.126 data_C_9_Cis_rgbutmbm _database_code_depnum_ccdc_archive 'CCDC 860506' #TrackingRef 'carbenes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H12 Mn2 N2 O8' _chemical_formula_weight 494.18 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' 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 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 10.874(2) _cell_length_b 10.940(2) _cell_length_c 15.741(4) _cell_angle_alpha 90.00 _cell_angle_beta 91.706(4) _cell_angle_gamma 90.00 _cell_volume 1871.8(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 777 _cell_measurement_theta_min 2.589 _cell_measurement_theta_max 25.122 _exptl_crystal_description PLATE _exptl_crystal_colour YELLOW _exptl_crystal_size_max 0.17 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.754 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 992 _exptl_absorpt_coefficient_mu 1.401 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.482768 _exptl_absorpt_correction_T_max 1.000000 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 7187 _diffrn_reflns_av_R_equivalents 0.0387 _diffrn_reflns_av_sigmaI/netI 0.0319 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.59 _diffrn_reflns_theta_max 25.36 _reflns_number_total 1723 _reflns_number_gt 1327 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0483P)^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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1723 _refine_ls_number_parameters 136 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0474 _refine_ls_R_factor_gt 0.0304 _refine_ls_wR_factor_ref 0.0814 _refine_ls_wR_factor_gt 0.0736 _refine_ls_goodness_of_fit_ref 0.981 _refine_ls_restrained_S_all 0.981 _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 Mn1 Mn 0.50429(3) 0.16173(3) 0.34987(2) 0.03170(16) Uani 1 1 d . . . N1 N 0.52823(18) 0.34793(18) 0.35357(13) 0.0313(5) Uani 1 1 d . . . O4 O 0.61759(14) 0.18220(14) 0.25226(11) 0.0304(4) Uani 1 1 d . . . C1 C 0.4923(2) -0.0031(3) 0.34453(18) 0.0404(7) Uani 1 1 d . . . O1 O 0.4843(2) -0.10734(18) 0.34727(14) 0.0634(7) Uani 1 1 d . . . C2 C 0.3952(3) 0.1555(2) 0.43310(19) 0.0389(6) Uani 1 1 d . . . O2 O 0.3310(2) 0.14806(19) 0.48940(15) 0.0628(6) Uani 1 1 d . . . C3 C 0.6246(3) 0.1408(2) 0.42963(19) 0.0426(7) Uani 1 1 d . . . O3 O 0.6994(2) 0.1251(2) 0.48144(16) 0.0694(7) Uani 1 1 d . . . C11 C 0.4629(2) 0.4318(2) 0.39528(17) 0.0387(7) Uani 1 1 d . . . H11 H 0.3968 0.4057 0.4268 0.046 Uiso 1 1 calc R . . C12 C 0.4895(3) 0.5544(2) 0.39343(18) 0.0436(7) Uani 1 1 d . . . H12 H 0.4413 0.6102 0.4221 0.052 Uiso 1 1 calc R . . C13 C 0.5886(3) 0.5931(2) 0.34858(19) 0.0461(7) Uani 1 1 d . . . H13 H 0.6088 0.6757 0.3469 0.055 Uiso 1 1 calc R . . C14 C 0.6577(2) 0.5086(2) 0.30595(18) 0.0389(6) Uani 1 1 d . . . H14 H 0.7256 0.5333 0.2757 0.047 Uiso 1 1 calc R . . C15 C 0.6246(2) 0.3863(2) 0.30886(16) 0.0313(6) Uani 1 1 d . . . C16 C 0.6923(2) 0.2864(2) 0.26406(18) 0.0347(6) Uani 1 1 d . . . H16A H 0.7179 0.3159 0.2092 0.042 Uiso 1 1 calc R . . H16B H 0.7655 0.2644 0.2973 0.042 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 0.0319(2) 0.0203(2) 0.0430(3) 0.00368(17) 0.00318(17) -0.00150(16) N1 0.0339(12) 0.0242(11) 0.0360(12) -0.0014(9) 0.0044(10) -0.0011(9) O4 0.0264(9) 0.0207(8) 0.0441(10) -0.0031(8) 0.0020(8) -0.0016(7) C1 0.0410(16) 0.0311(15) 0.0489(18) 0.0059(13) -0.0006(13) -0.0019(12) O1 0.0889(17) 0.0231(11) 0.0779(17) 0.0076(10) -0.0046(14) -0.0038(11) C2 0.0409(15) 0.0251(14) 0.0508(17) 0.0061(13) 0.0013(14) -0.0007(12) O2 0.0665(15) 0.0559(14) 0.0676(16) 0.0112(12) 0.0275(13) 0.0029(11) C3 0.0477(17) 0.0269(14) 0.0532(18) 0.0072(13) 0.0021(15) -0.0040(12) O3 0.0681(15) 0.0578(15) 0.0804(17) 0.0196(13) -0.0286(14) -0.0094(12) C11 0.0416(16) 0.0347(15) 0.0401(16) -0.0033(12) 0.0067(13) -0.0003(12) C12 0.0546(18) 0.0289(14) 0.0472(18) -0.0111(13) 0.0007(14) 0.0042(13) C13 0.0569(18) 0.0228(14) 0.0587(19) -0.0038(13) -0.0009(15) -0.0062(13) C14 0.0366(14) 0.0300(14) 0.0501(17) 0.0019(13) 0.0026(13) -0.0107(12) C15 0.0279(13) 0.0248(13) 0.0411(15) -0.0019(11) -0.0007(11) -0.0022(11) C16 0.0249(13) 0.0278(13) 0.0517(17) -0.0021(12) 0.0050(12) -0.0012(11) _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 C2 1.795(3) . ? Mn1 C3 1.800(3) . ? Mn1 C1 1.809(3) . ? Mn1 O4 2.0104(17) . ? Mn1 N1 2.054(2) . ? Mn1 O4 2.0650(17) 2_655 ? Mn1 Mn1 3.1428(11) 2_655 ? N1 C11 1.344(3) . ? N1 C15 1.347(3) . ? O4 C16 1.409(3) . ? O4 Mn1 2.0651(17) 2_655 ? C1 O1 1.145(3) . ? C2 O2 1.148(3) . ? C3 O3 1.147(3) . ? C11 C12 1.373(4) . ? C12 C13 1.372(4) . ? C13 C14 1.379(4) . ? C14 C15 1.387(3) . ? C15 C16 1.506(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 C2 Mn1 C3 88.18(13) . . ? C2 Mn1 C1 87.03(12) . . ? C3 Mn1 C1 87.43(12) . . ? C2 Mn1 O4 174.62(9) . . ? C3 Mn1 O4 95.64(10) . . ? C1 Mn1 O4 96.91(10) . . ? C2 Mn1 N1 95.90(10) . . ? C3 Mn1 N1 91.01(10) . . ? C1 Mn1 N1 176.65(10) . . ? O4 Mn1 N1 80.28(7) . . ? C2 Mn1 O4 98.60(10) . 2_655 ? C3 Mn1 O4 173.10(10) . 2_655 ? C1 Mn1 O4 91.63(9) . 2_655 ? O4 Mn1 O4 77.68(7) . 2_655 ? N1 Mn1 O4 89.56(7) . 2_655 ? C2 Mn1 Mn1 136.87(9) . 2_655 ? C3 Mn1 Mn1 134.19(9) . 2_655 ? C1 Mn1 Mn1 87.34(9) . 2_655 ? O4 Mn1 Mn1 40.18(5) . 2_655 ? N1 Mn1 Mn1 91.62(6) . 2_655 ? O4 Mn1 Mn1 38.91(5) 2_655 2_655 ? C11 N1 C15 118.2(2) . . ? C11 N1 Mn1 128.52(18) . . ? C15 N1 Mn1 113.24(16) . . ? C16 O4 Mn1 110.70(14) . . ? C16 O4 Mn1 123.00(15) . 2_655 ? Mn1 O4 Mn1 100.91(7) . 2_655 ? O1 C1 Mn1 175.2(3) . . ? O2 C2 Mn1 175.8(2) . . ? O3 C3 Mn1 178.2(3) . . ? N1 C11 C12 122.8(3) . . ? C13 C12 C11 118.8(3) . . ? C12 C13 C14 119.4(3) . . ? C13 C14 C15 119.0(3) . . ? N1 C15 C14 121.7(2) . . ? N1 C15 C16 114.6(2) . . ? C14 C15 C16 123.7(2) . . ? O4 C16 C15 111.18(19) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.36 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.351 _refine_diff_density_min -0.399 _refine_diff_density_rms 0.064 data_Compound_10a_rg749cm _database_code_depnum_ccdc_archive 'CCDC 860507' #TrackingRef 'carbenes.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C37 H44 B Mn N O5 P' _chemical_formula_weight 679.45 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' P P 0.1023 0.0942 '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' B B 0.0013 0.0007 '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 12.581(6) _cell_length_b 17.889(9) _cell_length_c 16.664(9) _cell_angle_alpha 90.00 _cell_angle_beta 106.245(11) _cell_angle_gamma 90.00 _cell_volume 3601(3) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 986 _cell_measurement_theta_min 2.54 _cell_measurement_theta_max 20.44 _exptl_crystal_description BLOCK _exptl_crystal_colour YELLOW _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.21 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.253 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1432 _exptl_absorpt_coefficient_mu 0.452 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.780007 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 28738 _diffrn_reflns_av_R_equivalents 0.0593 _diffrn_reflns_av_sigmaI/netI 0.0601 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 1.71 _diffrn_reflns_theta_max 25.39 _reflns_number_total 6614 _reflns_number_gt 3784 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.1027P)^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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6614 _refine_ls_number_parameters 409 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1057 _refine_ls_R_factor_gt 0.0527 _refine_ls_wR_factor_ref 0.1781 _refine_ls_wR_factor_gt 0.1450 _refine_ls_goodness_of_fit_ref 0.979 _refine_ls_restrained_S_all 0.979 _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 0.31732(5) 0.59278(3) 0.23297(3) 0.0453(2) Uani 1 1 d . . . C1 C 0.2864(3) 0.5117(2) 0.1693(2) 0.0530(10) Uani 1 1 d . . . O1 O 0.2671(3) 0.46136(17) 0.12297(19) 0.0765(9) Uani 1 1 d . . . C2 C 0.2336(3) 0.6430(2) 0.1483(2) 0.0552(10) Uani 1 1 d . . . O2 O 0.1785(3) 0.67663(18) 0.09175(19) 0.0857(10) Uani 1 1 d . . . N1 N 0.3696(3) 0.68440(16) 0.30775(19) 0.0483(8) Uani 1 1 d . . . O4 O 0.43092(19) 0.54514(13) 0.33634(14) 0.0448(6) Uani 1 1 d . . . P1 P 0.16169(8) 0.57480(6) 0.28589(6) 0.0477(3) Uani 1 1 d . . . C3 C 0.4507(4) 0.6010(2) 0.1972(2) 0.0545(10) Uani 1 1 d . . . O3 O 0.5397(2) 0.57119(16) 0.24058(16) 0.0604(7) Uani 1 1 d . . . C11 C 0.3574(4) 0.7569(2) 0.2846(3) 0.0627(11) Uani 1 1 d . . . H11 H 0.3223 0.7680 0.2289 0.075 Uiso 1 1 calc R . . C12 C 0.3936(4) 0.8142(2) 0.3383(3) 0.0796(14) Uani 1 1 d . . . H12 H 0.3840 0.8633 0.3193 0.096 Uiso 1 1 calc R . . C13 C 0.4452(4) 0.7994(2) 0.4222(3) 0.0791(14) Uani 1 1 d . . . H13 H 0.4687 0.8378 0.4607 0.095 Uiso 1 1 calc R . . C14 C 0.4600(4) 0.7262(2) 0.4455(3) 0.0664(12) Uani 1 1 d . . . H14 H 0.4956 0.7144 0.5009 0.080 Uiso 1 1 calc R . . C15 C 0.4229(3) 0.6696(2) 0.3885(2) 0.0489(9) Uani 1 1 d . . . C16 C 0.4326(3) 0.5878(2) 0.4089(2) 0.0471(9) Uani 1 1 d . . . H16A H 0.5011 0.5784 0.4520 0.057 Uiso 1 1 calc R . . H16B H 0.3716 0.5725 0.4302 0.057 Uiso 1 1 calc R . . B1 B 0.5402(4) 0.5233(3) 0.3180(3) 0.0532(11) Uani 1 1 d . . . C21 C 0.4657(4) 0.6376(3) 0.1188(3) 0.0796(14) Uani 1 1 d . . . H21A H 0.4038 0.6708 0.0953 0.096 Uiso 1 1 calc R . . H21B H 0.5328 0.6675 0.1333 0.096 Uiso 1 1 calc R . . C22 C 0.4729(8) 0.5823(4) 0.0564(4) 0.156(3) Uani 1 1 d . . . H22A H 0.5391 0.5533 0.0770 0.234 Uiso 1 1 calc R . . H22B H 0.4745 0.6072 0.0058 0.234 Uiso 1 1 calc R . . H22C H 0.4096 0.5499 0.0454 0.234 Uiso 1 1 calc R . . C31 C 0.5295(4) 0.4379(2) 0.2875(3) 0.0650(12) Uani 1 1 d . . . H31A H 0.4594 0.4317 0.2451 0.078 Uiso 1 1 calc R . . H31B H 0.5880 0.4274 0.2616 0.078 Uiso 1 1 calc R . . C32 C 0.5361(4) 0.3809(3) 0.3566(3) 0.0847(15) Uani 1 1 d . . . H32A H 0.6044 0.3873 0.3997 0.127 Uiso 1 1 calc R . . H32B H 0.5329 0.3314 0.3340 0.127 Uiso 1 1 calc R . . H32C H 0.4750 0.3882 0.3798 0.127 Uiso 1 1 calc R . . C41 C 0.6486(3) 0.5435(3) 0.3897(3) 0.0633(11) Uani 1 1 d . . . H41A H 0.6478 0.5966 0.4015 0.076 Uiso 1 1 calc R . . H41B H 0.6473 0.5168 0.4401 0.076 Uiso 1 1 calc R . . C42 C 0.7563(4) 0.5248(3) 0.3686(3) 0.0918(16) Uani 1 1 d . . . H42A H 0.7621 0.4716 0.3634 0.138 Uiso 1 1 calc R . . H42B H 0.8181 0.5427 0.4124 0.138 Uiso 1 1 calc R . . H42C H 0.7563 0.5483 0.3168 0.138 Uiso 1 1 calc R . . C51 C 0.1501(3) 0.4873(2) 0.3405(2) 0.0532(10) Uani 1 1 d . . . C52 C 0.0575(4) 0.4707(3) 0.3654(3) 0.0804(14) Uani 1 1 d . . . H52 H -0.0019 0.5038 0.3532 0.097 Uiso 1 1 calc R . . C53 C 0.0516(5) 0.4067(3) 0.4075(4) 0.1000(18) Uani 1 1 d . . . H53 H -0.0116 0.3964 0.4240 0.120 Uiso 1 1 calc R . . C54 C 0.1383(6) 0.3567(3) 0.4261(3) 0.0907(18) Uani 1 1 d . . . H54 H 0.1338 0.3130 0.4552 0.109 Uiso 1 1 calc R . . C55 C 0.2306(5) 0.3718(2) 0.4016(3) 0.0764(14) Uani 1 1 d . . . H55 H 0.2894 0.3382 0.4139 0.092 Uiso 1 1 calc R . . C56 C 0.2372(4) 0.4372(2) 0.3585(2) 0.0580(11) Uani 1 1 d . . . H56 H 0.3002 0.4472 0.3416 0.070 Uiso 1 1 calc R . . C61 C 0.1472(3) 0.6464(2) 0.3603(2) 0.0509(9) Uani 1 1 d . . . C62 C 0.1285(4) 0.7195(3) 0.3324(3) 0.0766(14) Uani 1 1 d . . . H62 H 0.1176 0.7303 0.2761 0.092 Uiso 1 1 calc R . . C63 C 0.1257(5) 0.7773(3) 0.3886(4) 0.0940(17) Uani 1 1 d . . . H63 H 0.1111 0.8260 0.3691 0.113 Uiso 1 1 calc R . . C64 C 0.1440(5) 0.7628(3) 0.4704(4) 0.0932(17) Uani 1 1 d . . . H64 H 0.1432 0.8015 0.5074 0.112 Uiso 1 1 calc R . . C65 C 0.1638(4) 0.6908(3) 0.4996(3) 0.0802(14) Uani 1 1 d . . . H65 H 0.1763 0.6808 0.5562 0.096 Uiso 1 1 calc R . . C66 C 0.1651(3) 0.6330(2) 0.4441(3) 0.0585(10) Uani 1 1 d . . . H66 H 0.1784 0.5844 0.4641 0.070 Uiso 1 1 calc R . . C71 C 0.0259(3) 0.5749(2) 0.2066(2) 0.0582(11) Uani 1 1 d . . . C72 C 0.0116(4) 0.5308(2) 0.1365(3) 0.0673(12) Uani 1 1 d . . . H72 H 0.0712 0.5036 0.1293 0.081 Uiso 1 1 calc R . . C73 C -0.0887(4) 0.5263(3) 0.0773(3) 0.0784(14) Uani 1 1 d . . . H73 H -0.0962 0.4961 0.0306 0.094 Uiso 1 1 calc R . . C74 C -0.1762(5) 0.5650(4) 0.0859(3) 0.105(2) Uani 1 1 d . . . H74 H -0.2432 0.5633 0.0443 0.127 Uiso 1 1 calc R . . C75 C -0.1663(5) 0.6061(5) 0.1550(4) 0.151(3) Uani 1 1 d . . . H75 H -0.2280 0.6305 0.1627 0.181 Uiso 1 1 calc R . . C76 C -0.0640(4) 0.6127(4) 0.2158(4) 0.116(2) Uani 1 1 d . . . H76 H -0.0575 0.6429 0.2624 0.140 Uiso 1 1 calc R . . C91 C 0.1830(10) 0.6384(5) 0.8016(12) 0.254(7) Uani 1 1 d G . . H91A H 0.1068 0.6359 0.8036 0.304 Uiso 1 1 calc R . . H91B H 0.2042 0.5895 0.7862 0.304 Uiso 1 1 calc R . . O91 O 0.1935(10) 0.6944(10) 0.7390(5) 0.318(6) Uani 1 1 d G . . C92 C 0.2533(13) 0.6594(10) 0.8816(8) 0.331(10) Uani 1 1 d G . . H92A H 0.3159 0.6256 0.8986 0.397 Uiso 1 1 calc R . . H92B H 0.2129 0.6581 0.9233 0.397 Uiso 1 1 calc R . . C93 C 0.2906(11) 0.7350(10) 0.8720(9) 0.311(10) Uani 1 1 d G . . H93A H 0.3707 0.7369 0.8854 0.373 Uiso 1 1 calc R . . H93B H 0.2662 0.7694 0.9083 0.373 Uiso 1 1 calc R . . C94 C 0.2390(13) 0.7543(6) 0.7820(11) 0.362(13) Uani 1 1 d G . . H94A H 0.1828 0.7923 0.7780 0.435 Uiso 1 1 calc R . . H94B H 0.2951 0.7744 0.7583 0.435 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 0.0504(4) 0.0487(4) 0.0321(3) 0.0020(2) 0.0041(2) 0.0013(3) C1 0.054(2) 0.060(3) 0.041(2) 0.008(2) 0.0077(19) 0.0026(19) O1 0.088(2) 0.074(2) 0.0595(19) -0.0240(17) 0.0064(17) -0.0033(17) C2 0.060(3) 0.057(2) 0.043(2) 0.0033(19) 0.006(2) -0.006(2) O2 0.088(2) 0.091(2) 0.060(2) 0.0304(17) -0.0091(18) 0.0058(18) N1 0.0505(19) 0.0489(19) 0.0423(18) 0.0026(14) 0.0078(15) -0.0006(14) O4 0.0495(15) 0.0490(15) 0.0329(13) -0.0003(11) 0.0070(11) 0.0045(11) P1 0.0462(6) 0.0541(6) 0.0385(5) 0.0023(4) 0.0047(4) 0.0027(4) C3 0.065(3) 0.057(2) 0.039(2) 0.0023(18) 0.010(2) -0.001(2) O3 0.0574(17) 0.080(2) 0.0455(16) 0.0077(14) 0.0180(14) 0.0088(14) C11 0.074(3) 0.050(3) 0.056(3) 0.009(2) 0.006(2) -0.004(2) C12 0.093(4) 0.046(3) 0.094(4) -0.004(3) 0.017(3) -0.006(2) C13 0.097(4) 0.052(3) 0.078(3) -0.020(2) 0.009(3) -0.005(2) C14 0.072(3) 0.069(3) 0.050(3) -0.012(2) 0.004(2) -0.008(2) C15 0.049(2) 0.052(2) 0.043(2) -0.0058(18) 0.0097(18) 0.0011(17) C16 0.050(2) 0.057(2) 0.0325(19) -0.0035(17) 0.0080(17) 0.0037(17) B1 0.055(3) 0.062(3) 0.042(2) 0.003(2) 0.012(2) 0.009(2) C21 0.087(4) 0.097(4) 0.063(3) 0.022(3) 0.036(3) 0.007(3) C22 0.246(10) 0.175(7) 0.070(4) -0.013(4) 0.079(5) -0.044(6) C31 0.070(3) 0.069(3) 0.050(2) -0.007(2) 0.007(2) 0.018(2) C32 0.097(4) 0.069(3) 0.080(3) 0.005(3) 0.012(3) 0.018(3) C41 0.055(3) 0.079(3) 0.053(3) -0.002(2) 0.010(2) 0.010(2) C42 0.058(3) 0.131(5) 0.083(4) -0.008(3) 0.014(3) 0.008(3) C51 0.060(3) 0.053(2) 0.043(2) -0.0015(18) 0.0071(19) -0.008(2) C52 0.077(3) 0.070(3) 0.101(4) 0.009(3) 0.036(3) -0.011(3) C53 0.108(5) 0.089(4) 0.110(5) 0.013(4) 0.043(4) -0.030(4) C54 0.136(5) 0.063(3) 0.067(3) 0.007(3) 0.018(4) -0.039(4) C55 0.098(4) 0.052(3) 0.061(3) 0.001(2) -0.007(3) -0.007(3) C56 0.071(3) 0.050(2) 0.047(2) -0.0013(19) 0.005(2) -0.004(2) C61 0.047(2) 0.051(2) 0.054(2) 0.0041(19) 0.0121(19) 0.0028(17) C62 0.086(3) 0.071(3) 0.077(3) 0.010(3) 0.031(3) 0.014(3) C63 0.112(5) 0.056(3) 0.123(5) -0.007(3) 0.047(4) 0.014(3) C64 0.103(4) 0.083(4) 0.102(5) -0.035(3) 0.041(4) 0.000(3) C65 0.076(3) 0.101(4) 0.067(3) -0.026(3) 0.026(3) -0.009(3) C66 0.056(3) 0.063(3) 0.056(3) -0.005(2) 0.015(2) -0.002(2) C71 0.050(2) 0.075(3) 0.045(2) 0.005(2) 0.0053(19) 0.004(2) C72 0.058(3) 0.071(3) 0.061(3) -0.006(2) -0.002(2) 0.005(2) C73 0.065(3) 0.104(4) 0.055(3) -0.010(3) -0.002(2) -0.005(3) C74 0.067(4) 0.161(6) 0.067(4) -0.025(4) -0.016(3) 0.016(4) C75 0.070(4) 0.242(9) 0.110(5) -0.067(6) -0.024(4) 0.070(5) C76 0.068(4) 0.182(6) 0.080(4) -0.051(4) -0.010(3) 0.042(4) C91 0.308(19) 0.251(15) 0.229(15) 0.008(15) 0.119(16) -0.059(13) O91 0.384(15) 0.376(17) 0.167(8) -0.001(11) 0.034(8) -0.100(12) C92 0.37(2) 0.37(3) 0.192(16) 0.001(16) -0.016(15) -0.05(2) C93 0.39(2) 0.238(17) 0.27(2) -0.121(15) 0.034(19) -0.076(17) C94 0.49(3) 0.235(17) 0.29(2) 0.019(16) 0.00(2) -0.195(18) _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 C2 1.754(4) . ? Mn1 C1 1.774(4) . ? Mn1 C3 1.938(4) . ? Mn1 N1 2.053(3) . ? Mn1 O4 2.088(2) . ? Mn1 P1 2.3834(15) . ? C1 O1 1.168(4) . ? C2 O2 1.168(4) . ? N1 C11 1.349(5) . ? N1 C15 1.351(4) . ? O4 C16 1.425(4) . ? O4 B1 1.540(5) . ? P1 C61 1.827(4) . ? P1 C51 1.836(4) . ? P1 C71 1.844(4) . ? C3 O3 1.268(5) . ? C3 C21 1.519(6) . ? O3 B1 1.547(5) . ? C11 C12 1.355(6) . ? C12 C13 1.392(7) . ? C13 C14 1.363(6) . ? C14 C15 1.378(5) . ? C15 C16 1.500(5) . ? B1 C41 1.584(6) . ? B1 C31 1.603(6) . ? C21 C22 1.456(7) . ? C31 C32 1.524(6) . ? C41 C42 1.529(6) . ? C51 C52 1.374(6) . ? C51 C56 1.382(6) . ? C52 C53 1.357(7) . ? C53 C54 1.377(8) . ? C54 C55 1.362(7) . ? C55 C56 1.387(6) . ? C61 C66 1.372(5) . ? C61 C62 1.385(6) . ? C62 C63 1.401(7) . ? C63 C64 1.343(8) . ? C64 C65 1.374(7) . ? C65 C66 1.391(6) . ? C71 C76 1.363(6) . ? C71 C72 1.379(6) . ? C72 C73 1.369(6) . ? C73 C74 1.342(7) . ? C74 C75 1.344(8) . ? C75 C76 1.402(7) . ? C91 C92 1.4279 . ? C91 O91 1.4781 . ? O91 C94 1.3263 . ? C92 C93 1.4549 . ? C93 C94 1.4981 . ? 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 Mn1 C1 87.47(18) . . ? C2 Mn1 C3 95.15(18) . . ? C1 Mn1 C3 86.70(17) . . ? C2 Mn1 N1 95.60(16) . . ? C1 Mn1 N1 174.24(16) . . ? C3 Mn1 N1 88.16(15) . . ? C2 Mn1 O4 172.43(15) . . ? C1 Mn1 O4 98.32(14) . . ? C3 Mn1 O4 80.40(14) . . ? N1 Mn1 O4 78.22(11) . . ? C2 Mn1 P1 89.81(14) . . ? C1 Mn1 P1 92.59(13) . . ? C3 Mn1 P1 174.96(12) . . ? N1 Mn1 P1 92.30(9) . . ? O4 Mn1 P1 94.77(8) . . ? O1 C1 Mn1 175.3(3) . . ? O2 C2 Mn1 179.6(4) . . ? C11 N1 C15 117.3(3) . . ? C11 N1 Mn1 127.0(3) . . ? C15 N1 Mn1 115.7(2) . . ? C16 O4 B1 120.2(3) . . ? C16 O4 Mn1 109.02(19) . . ? B1 O4 Mn1 112.5(2) . . ? C61 P1 C51 102.99(18) . . ? C61 P1 C71 103.72(19) . . ? C51 P1 C71 99.81(19) . . ? C61 P1 Mn1 113.85(13) . . ? C51 P1 Mn1 119.05(14) . . ? C71 P1 Mn1 115.26(14) . . ? O3 C3 C21 111.7(4) . . ? O3 C3 Mn1 119.6(3) . . ? C21 C3 Mn1 128.6(3) . . ? C3 O3 B1 120.4(3) . . ? N1 C11 C12 123.2(4) . . ? C11 C12 C13 119.7(4) . . ? C14 C13 C12 117.3(4) . . ? C13 C14 C15 121.1(4) . . ? N1 C15 C14 121.4(4) . . ? N1 C15 C16 113.8(3) . . ? C14 C15 C16 124.8(4) . . ? O4 C16 C15 110.4(3) . . ? O4 B1 O3 103.3(3) . . ? O4 B1 C41 114.8(3) . . ? O3 B1 C41 107.7(4) . . ? O4 B1 C31 107.8(3) . . ? O3 B1 C31 106.4(3) . . ? C41 B1 C31 115.8(3) . . ? C22 C21 C3 111.6(5) . . ? C32 C31 B1 114.5(4) . . ? C42 C41 B1 114.0(4) . . ? C52 C51 C56 118.8(4) . . ? C52 C51 P1 121.7(3) . . ? C56 C51 P1 119.5(3) . . ? C53 C52 C51 120.8(5) . . ? C52 C53 C54 120.7(6) . . ? C55 C54 C53 119.5(5) . . ? C54 C55 C56 120.1(5) . . ? C51 C56 C55 120.1(4) . . ? C66 C61 C62 118.0(4) . . ? C66 C61 P1 123.3(3) . . ? C62 C61 P1 118.4(3) . . ? C61 C62 C63 120.4(5) . . ? C64 C63 C62 120.4(5) . . ? C63 C64 C65 120.3(5) . . ? C64 C65 C66 119.7(5) . . ? C61 C66 C65 121.2(4) . . ? C76 C71 C72 117.6(4) . . ? C76 C71 P1 123.5(3) . . ? C72 C71 P1 118.8(3) . . ? C73 C72 C71 121.4(4) . . ? C74 C73 C72 120.7(5) . . ? C73 C74 C75 119.5(5) . . ? C74 C75 C76 120.8(5) . . ? C71 C76 C75 120.0(5) . . ? C92 C91 O91 109.1 . . ? C94 O91 C91 106.0 . . ? C91 C92 C93 106.1 . . ? C92 C93 C94 105.1 . . ? O91 C94 C93 110.8 . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 25.39 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.607 _refine_diff_density_min -0.248 _refine_diff_density_rms 0.061 #===END