# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2012 data_added_by_encifer _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _data_manuscript_title ; 'Complexes with 2-Pyridylimidazo[1,5-a]pyridine Ligands by Spontaneous Dimerization of 2-Pyridine Carboxaldehyde within the Coordination Sphere of Manganese (II) in a One-pot Reaction.' ; _audit_creation_method SHELXL _pub_requested_journal 'Dalton Trans.' _publ_contact_author ; DANIEL MIGUEL IU CINQUIMA/Quimica Inorganica Facultad de Ciencias Universidad de Valladolid C/ Prado de la Magdalena s/n 47005 Valladolid SPAIN ; _publ_contact_author_phone +34-983-184096 _publ_contact_author_fax +34-983-423013 _publ_contact_author_email dmsj@qi.uva.es loop_ _publ_author_name _publ_author_address 'Celedonio M. Alvarez' ; IU CINQUIMA/Quimica Inorganica Facultad de Ciencias Universidad de Valladolid C/ Prado de la Magdalena s/n 47005 Valladolid SPAIN ; 'Lucia Alvarez' ; IU CINQUIMA/Quimica Inorganica Facultad de Ciencias Universidad de Valladolid C/ Prado de la Magdalena s/n 47005 Valladolid SPAIN ; 'Raul Garcia-Rodriguez' ; IU CINQUIMA/Quimica Inorganica Facultad de Ciencias Universidad de Valladolid C/ Prado de la Magdalena s/n 47005 Valladolid SPAIN ; 'Daniel Miguel' ; IU CINQUIMA/Quimica Inorganica Facultad de Ciencias Universidad de Valladolid C/ Prado de la Magdalena s/n 47005 Valladolid SPAIN ; _publ_contact_author_name 'DANIEL MIGUEL' #---------data section of block ----------------------- data_Compound_2a_lam19c _database_code_depnum_ccdc_archive 'CCDC 869438' #TrackingRef '- azaindolizine_ligands_REVISED.cif' _audit_creation_method SHELXL-97 _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_cell_refinement ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_data_reduction ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H29 Mn N3 O4 P2 S4' _chemical_formula_weight 620.58 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' 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 'P 1 21/n 1' 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 10.5548(4) _cell_length_b 17.5085(4) _cell_length_c 16.3988(4) _cell_angle_alpha 90.00 _cell_angle_beta 108.219(3) _cell_angle_gamma 90.00 _cell_volume 2878.56(15) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 5246 _cell_measurement_theta_min 2.0392 _cell_measurement_theta_max 29.4588 _exptl_crystal_description plate _exptl_crystal_colour yellow _exptl_crystal_size_max 0.3143 _exptl_crystal_size_mid 0.1678 _exptl_crystal_size_min 0.0673 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.432 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1284 _exptl_absorpt_coefficient_mu 0.890 _exptl_absorpt_correction_type analytical _exptl_absorpt_correction_T_min 0.711 _exptl_absorpt_correction_T_max 0.908 _exptl_absorpt_process_details ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) ; _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 'SuperNova, Dual, Cu at zero, Atlas' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 10.4757 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 14704 _diffrn_reflns_av_R_equivalents 0.0227 _diffrn_reflns_av_sigmaI/netI 0.0371 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.04 _diffrn_reflns_theta_max 29.52 _reflns_number_total 6697 _reflns_number_gt 4019 _reflns_threshold_expression >2sigma(I) _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0670P)^2^+2.9134P] 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 6697 _refine_ls_number_parameters 305 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1100 _refine_ls_R_factor_gt 0.0665 _refine_ls_wR_factor_ref 0.1849 _refine_ls_wR_factor_gt 0.1577 _refine_ls_goodness_of_fit_ref 1.036 _refine_ls_restrained_S_all 1.036 _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 0.56682(7) 0.77753(4) 0.91990(4) 0.0636(2) Uani 1 1 d . . . S1 S 0.75031(13) 0.77419(8) 0.84245(8) 0.0848(4) Uani 1 1 d . . . S2 S 0.45825(13) 0.68970(8) 0.78829(8) 0.0827(4) Uani 1 1 d . . . S3 S 0.67276(15) 0.67294(8) 1.03324(9) 0.0905(4) Uani 1 1 d . . . S4 S 0.38963(15) 0.76448(8) 0.99924(9) 0.0878(4) Uani 1 1 d . . . N1 N 0.4677(4) 0.8884(2) 0.8553(2) 0.0676(9) Uani 1 1 d . . . N2 N 0.6823(3) 0.87366(17) 0.99445(19) 0.0604(8) Uani 1 1 d . . . N3 N 0.7496(4) 0.99299(18) 0.9971(2) 0.0638(9) Uani 1 1 d . . . P1 P 0.62625(13) 0.70447(7) 0.76081(7) 0.0724(4) Uani 1 1 d . . . P2 P 0.51045(17) 0.68396(8) 1.06567(8) 0.0879(4) Uani 1 1 d . A . O34 O 0.5552(6) 0.6961(3) 1.1646(2) 0.148(2) Uani 1 1 d G . . C37A C 0.4783(5) 0.7252(6) 1.2154(4) 0.124(3) Uani 0.70 1 d PG A 1 H37A H 0.4309 0.6839 1.2326 0.149 Uiso 0.70 1 d PG A 1 H37B H 0.4134 0.7618 1.1824 0.149 Uiso 0.70 1 d PG A 1 C37B C 0.5507(12) 0.7711(3) 1.1992(4) 0.126(9) Uani 0.30 1 d PG A 2 H37C H 0.4651 0.7948 1.1711 0.151 Uiso 0.30 1 d PG A 2 H37D H 0.6201 0.8030 1.1899 0.151 Uiso 0.30 1 d PG A 2 C38 C 0.5712(7) 0.7632(4) 1.2933(3) 0.156(3) Uani 1 1 d G A . H38A H 0.6561 0.7378 1.3093 0.234 Uiso 1 1 d G A . H38B H 0.5344 0.7603 1.3398 0.234 Uiso 1 1 d G A . H38C H 0.5827 0.8158 1.2806 0.234 Uiso 1 1 d G A . C1 C 0.3500(5) 0.8928(3) 0.7925(3) 0.0795(13) Uani 1 1 d . . . H1 H 0.3112 0.8478 0.7660 0.095 Uiso 1 1 calc R . . C2 C 0.2848(6) 0.9601(3) 0.7660(3) 0.0910(15) Uani 1 1 d . . . H2 H 0.2042 0.9605 0.7216 0.109 Uiso 1 1 calc R . . C3 C 0.3389(5) 1.0274(3) 0.8053(3) 0.0884(16) Uani 1 1 d . . . H3 H 0.2940 1.0734 0.7890 0.106 Uiso 1 1 calc R . . C4 C 0.4604(5) 1.0257(3) 0.8689(3) 0.0728(12) Uani 1 1 d . . . H4 H 0.4999 1.0703 0.8959 0.087 Uiso 1 1 calc R . . C5 C 0.5231(4) 0.9539(2) 0.8917(2) 0.0590(10) Uani 1 1 d . . . C6 C 0.6492(4) 0.9425(2) 0.9591(2) 0.0554(9) Uani 1 1 d . . . C7 C 0.8015(4) 0.8788(2) 1.0560(2) 0.0648(11) Uani 1 1 d . . . H7 H 0.8447 0.8384 1.0903 0.078 Uiso 1 1 calc R . . C8 C 0.8502(4) 0.9518(2) 1.0612(3) 0.0664(11) Uani 1 1 d . . . C9 C 0.9642(5) 0.9901(3) 1.1094(3) 0.0894(15) Uani 1 1 d . . . H9 H 1.0289 0.9645 1.1526 0.107 Uiso 1 1 calc R . . C10 C 0.9810(6) 1.0642(3) 1.0937(4) 0.1029(18) Uani 1 1 d . . . H10 H 1.0574 1.0898 1.1260 0.123 Uiso 1 1 calc R . . C11 C 0.8837(6) 1.1030(3) 1.0286(5) 0.1040(19) Uani 1 1 d . . . H11 H 0.8974 1.1541 1.0182 0.125 Uiso 1 1 calc R . . C12 C 0.7721(6) 1.0687(3) 0.9811(4) 0.0878(15) Uani 1 1 d . . . H12 H 0.7098 1.0954 0.9376 0.105 Uiso 1 1 calc R . . O31 O 0.6936(4) 0.62635(18) 0.7509(2) 0.0959(11) Uani 1 1 d G . . C31 C 0.7473(7) 0.5781(3) 0.8239(2) 0.147(3) Uani 1 1 d G . . H31A H 0.6757 0.5557 0.8412 0.176 Uiso 1 1 d G . . H31B H 0.8035 0.6076 0.8716 0.176 Uiso 1 1 d G . . C32 C 0.8274(9) 0.5166(4) 0.7999(5) 0.195(4) Uani 1 1 d G . . H32A H 0.7699 0.4748 0.7741 0.292 Uiso 1 1 d G . . H32B H 0.8951 0.4990 0.8504 0.292 Uiso 1 1 d G . . H32C H 0.8685 0.5364 0.7597 0.292 Uiso 1 1 d G . . O32 O 0.6005(4) 0.72980(19) 0.66439(19) 0.0872(10) Uani 1 1 d . . . C33 C 0.5509(7) 0.8048(3) 0.6370(4) 0.114(2) Uani 1 1 d . . . H33A H 0.6135 0.8427 0.6697 0.137 Uiso 1 1 calc R . . H33B H 0.4666 0.8124 0.6479 0.137 Uiso 1 1 calc R . . C34 C 0.5322(7) 0.8152(4) 0.5464(4) 0.121(2) Uani 1 1 d . . . H34A H 0.6172 0.8140 0.5366 0.181 Uiso 1 1 calc R . . H34B H 0.4900 0.8635 0.5280 0.181 Uiso 1 1 calc R . . H34C H 0.4769 0.7749 0.5144 0.181 Uiso 1 1 calc R . . O33 O 0.4277(5) 0.6052(3) 1.0593(3) 0.1307(16) Uani 1 1 d G . . C35 C 0.3678(7) 0.5735(5) 0.9750(4) 0.186(4) Uani 1 1 d G A . H35A H 0.4257 0.5347 0.9638 0.224 Uiso 1 1 d G A . H35B H 0.3559 0.6133 0.9321 0.224 Uiso 1 1 d G A . C36 C 0.2372(7) 0.5395(5) 0.9695(5) 0.207(5) Uani 1 1 d G A . H36A H 0.2433 0.5141 1.0225 0.310 Uiso 1 1 d G A . H36B H 0.2123 0.5034 0.9232 0.310 Uiso 1 1 d G A . H36C H 0.1710 0.5791 0.9592 0.310 Uiso 1 1 d G A . 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 0.0752(5) 0.0551(4) 0.0544(4) -0.0061(3) 0.0115(3) 0.0055(3) S1 0.0728(8) 0.1046(10) 0.0736(7) -0.0317(7) 0.0182(6) -0.0156(7) S2 0.0797(8) 0.0913(9) 0.0716(7) -0.0250(6) 0.0160(6) -0.0174(7) S3 0.0982(10) 0.0752(8) 0.0929(9) 0.0164(7) 0.0222(7) 0.0326(7) S4 0.0935(10) 0.0925(9) 0.0840(8) 0.0164(7) 0.0373(7) 0.0353(8) N1 0.071(2) 0.074(2) 0.0532(18) 0.0036(17) 0.0130(17) 0.0110(19) N2 0.075(2) 0.0468(17) 0.0499(17) -0.0015(14) 0.0058(15) 0.0117(16) N3 0.077(2) 0.0477(18) 0.069(2) -0.0021(16) 0.0256(18) 0.0142(17) P1 0.0789(8) 0.0753(8) 0.0577(6) -0.0174(6) 0.0136(5) -0.0014(6) P2 0.1189(12) 0.0777(8) 0.0683(8) 0.0141(6) 0.0308(7) 0.0257(8) O34 0.202(5) 0.162(4) 0.073(2) 0.024(3) 0.033(3) 0.069(4) C37A 0.105(7) 0.193(11) 0.090(6) 0.003(7) 0.053(6) 0.010(7) C37B 0.113(17) 0.107(16) 0.113(17) 0.029(13) -0.029(13) -0.046(13) C38 0.139(6) 0.231(10) 0.110(5) -0.036(6) 0.055(5) -0.022(6) C1 0.070(3) 0.098(4) 0.060(2) 0.004(2) 0.005(2) 0.002(3) C2 0.093(4) 0.094(4) 0.074(3) 0.013(3) 0.009(3) 0.012(3) C3 0.088(4) 0.099(4) 0.079(3) 0.035(3) 0.027(3) 0.043(3) C4 0.073(3) 0.076(3) 0.073(3) 0.015(2) 0.027(2) 0.016(2) C5 0.062(3) 0.063(2) 0.053(2) 0.0084(19) 0.0197(18) 0.017(2) C6 0.069(3) 0.0441(19) 0.051(2) -0.0038(16) 0.0155(18) 0.0105(18) C7 0.076(3) 0.051(2) 0.055(2) -0.0013(18) 0.003(2) 0.015(2) C8 0.071(3) 0.056(2) 0.066(2) -0.0087(19) 0.013(2) 0.011(2) C9 0.083(3) 0.073(3) 0.096(3) -0.015(3) 0.005(3) 0.008(3) C10 0.082(4) 0.075(3) 0.140(5) -0.022(3) 0.018(3) -0.003(3) C11 0.090(4) 0.058(3) 0.164(6) -0.003(3) 0.040(4) 0.003(3) C12 0.090(4) 0.052(3) 0.122(4) 0.003(3) 0.034(3) 0.013(3) O31 0.119(3) 0.085(2) 0.076(2) -0.0170(18) 0.018(2) 0.020(2) C31 0.220(9) 0.118(5) 0.084(4) 0.009(4) 0.020(5) 0.058(6) C32 0.264(11) 0.154(7) 0.163(8) 0.033(6) 0.063(8) 0.118(8) O32 0.112(3) 0.082(2) 0.0610(18) -0.0148(16) 0.0166(17) -0.0054(19) C33 0.158(6) 0.084(4) 0.088(4) -0.003(3) 0.020(4) -0.006(4) C34 0.130(5) 0.129(5) 0.097(4) 0.025(4) 0.026(4) -0.014(4) O33 0.182(5) 0.096(3) 0.133(4) 0.026(3) 0.076(3) 0.006(3) C35 0.244(12) 0.143(8) 0.201(10) -0.024(7) 0.112(9) -0.039(8) C36 0.230(11) 0.139(8) 0.312(14) -0.062(8) 0.172(11) -0.036(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 N2 2.209(3) . ? Mn1 N1 2.300(4) . ? Mn1 S3 2.5998(13) . ? Mn1 S4 2.6008(15) . ? Mn1 S2 2.6056(13) . ? Mn1 S1 2.6278(15) . ? S1 P1 1.9750(16) . ? S2 P1 1.9784(19) . ? S3 P2 1.956(2) . ? S4 P2 1.9828(18) . ? N1 C5 1.341(5) . ? N1 C1 1.345(5) . ? N2 C6 1.335(5) . ? N2 C7 1.347(5) . ? N3 C6 1.371(5) . ? N3 C12 1.386(6) . ? N3 C8 1.433(5) . ? P1 O31 1.573(3) . ? P1 O32 1.582(3) . ? P2 O34 1.556(4) . ? P2 O33 1.619(5) . ? O34 C37A 1.4270 . ? O34 C37B 1.4375 . ? C37A C38 1.5006 . ? C37B C38 1.4954 . ? C1 C2 1.365(7) . ? C2 C3 1.379(7) . ? C3 C4 1.377(6) . ? C4 C5 1.415(6) . ? C5 C6 1.454(5) . ? C7 C8 1.371(6) . ? C8 C9 1.388(6) . ? C9 C10 1.346(7) . ? C10 C11 1.404(8) . ? C11 C12 1.335(7) . ? O31 C31 1.4293 . ? C31 C32 1.4961 . ? O32 C33 1.434(7) . ? C33 C34 1.448(7) . ? O33 C35 1.4382 . ? C35 C36 1.4779 . ? 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 N2 Mn1 N1 72.83(12) . . ? N2 Mn1 S3 95.82(9) . . ? N1 Mn1 S3 162.86(9) . . ? N2 Mn1 S4 98.56(10) . . ? N1 Mn1 S4 90.56(10) . . ? S3 Mn1 S4 78.24(5) . . ? N2 Mn1 S2 158.68(10) . . ? N1 Mn1 S2 95.61(10) . . ? S3 Mn1 S2 98.97(5) . . ? S4 Mn1 S2 99.42(5) . . ? N2 Mn1 S1 85.52(10) . . ? N1 Mn1 S1 95.40(10) . . ? S3 Mn1 S1 96.47(5) . . ? S4 Mn1 S1 173.58(5) . . ? S2 Mn1 S1 77.66(4) . . ? P1 S1 Mn1 84.76(6) . . ? P1 S2 Mn1 85.30(5) . . ? P2 S3 Mn1 84.69(6) . . ? P2 S4 Mn1 84.13(6) . . ? C5 N1 C1 117.5(4) . . ? C5 N1 Mn1 116.5(3) . . ? C1 N1 Mn1 125.4(3) . . ? C6 N2 C7 108.7(3) . . ? C6 N2 Mn1 115.0(2) . . ? C7 N2 Mn1 133.7(3) . . ? C6 N3 C12 133.2(4) . . ? C6 N3 C8 107.4(3) . . ? C12 N3 C8 119.3(4) . . ? O31 P1 O32 94.71(18) . . ? O31 P1 S1 112.46(15) . . ? O32 P1 S1 111.99(15) . . ? O31 P1 S2 112.09(17) . . ? O32 P1 S2 112.25(16) . . ? S1 P1 S2 112.20(7) . . ? O34 P2 O33 99.6(3) . . ? O34 P2 S3 106.9(2) . . ? O33 P2 S3 113.52(19) . . ? O34 P2 S4 114.15(18) . . ? O33 P2 S4 109.2(2) . . ? S3 P2 S4 112.85(9) . . ? C37A O34 P2 127.9(4) . . ? C37B O34 P2 120.0(4) . . ? O34 C37A C38 108.4 . . ? O34 C37B C38 108.1 . . ? N1 C1 C2 123.1(5) . . ? C1 C2 C3 119.7(5) . . ? C4 C3 C2 119.1(5) . . ? C3 C4 C5 117.9(5) . . ? N1 C5 C4 122.7(4) . . ? N1 C5 C6 112.8(3) . . ? C4 C5 C6 124.4(4) . . ? N2 C6 N3 109.0(3) . . ? N2 C6 C5 120.5(4) . . ? N3 C6 C5 130.5(3) . . ? N2 C7 C8 110.7(3) . . ? C7 C8 C9 136.7(4) . . ? C7 C8 N3 104.2(4) . . ? C9 C8 N3 119.1(4) . . ? C10 C9 C8 119.9(5) . . ? C9 C10 C11 120.2(5) . . ? C12 C11 C10 121.9(5) . . ? C11 C12 N3 119.5(5) . . ? C31 O31 P1 120.1(3) . . ? O31 C31 C32 108.3 . . ? C33 O32 P1 120.1(3) . . ? O32 C33 C34 110.8(5) . . ? C35 O33 P2 117.2(4) . . ? O33 C35 C36 109.6 . . ? _diffrn_measured_fraction_theta_max 0.832 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.453 _refine_diff_density_min -0.436 _refine_diff_density_rms 0.059 #===END data_Compound_2b_mnqoxab _database_code_depnum_ccdc_archive 'CCDC 869439' #TrackingRef '- azaindolizine_ligands_REVISED.cif' _audit_creation_method SHELXL-97 _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) ; _computing_cell_refinement ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) ; _computing_data_reduction ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) ; _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C28 H33 Mn N3 O4 P2 S4' _chemical_formula_weight 720.69 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' 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 triclinic _symmetry_space_group_name_H-M 'P -1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.9962(4) _cell_length_b 10.7939(4) _cell_length_c 15.5695(8) _cell_angle_alpha 93.077(4) _cell_angle_beta 92.869(4) _cell_angle_gamma 94.410(3) _cell_volume 1670.04(13) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 6104 _cell_measurement_theta_min 2.0423 _cell_measurement_theta_max 29.4720 _exptl_crystal_description plate _exptl_crystal_colour orange-red _exptl_crystal_size_max 0.3987 _exptl_crystal_size_mid 0.3723 _exptl_crystal_size_min 0.1326 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.433 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 746 _exptl_absorpt_coefficient_mu 0.778 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.92412 _exptl_absorpt_correction_T_max 1.00000 loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist _exptl_oxdiff_crystal_face_indexfrac_h _exptl_oxdiff_crystal_face_indexfrac_k _exptl_oxdiff_crystal_face_indexfrac_l _exptl_oxdiff_crystal_face_x _exptl_oxdiff_crystal_face_y _exptl_oxdiff_crystal_face_z -12 -5 -5 0.1561 -12.0000 -5.0000 -5.0000 -0.4847 -0.8167 0.2580 -9 12 0 0.1742 -9.0000 12.0000 0.0000 0.0037 0.0048 0.9791 9 9 6 0.1477 9.0000 9.0000 6.0000 0.5306 0.8084 0.0688 11 -11 1 0.1813 11.0000 -11.0000 1.0000 0.0867 0.1366 -1.0137 0 -1 22 0.0427 -0.0000 -1.0000 22.0000 0.9689 -0.2593 -0.0411 -8 -11 -3 0.2101 -8.0000 -11.0000 -3.0000 -0.4056 -0.8663 -0.2096 0 0 -22 0.0768 0.0000 0.0000 -22.0000 -0.9815 0.2177 -0.0086 8 12 3 0.1513 8.0000 12.0000 3.0000 0.4183 0.9079 0.2594 11 9 3 0.1720 11.0000 9.0000 3.0000 0.4298 0.9478 -0.0172 _exptl_absorpt_process_details ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _diffrn_radiation_wavelength 0.7107 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'SuperNova (Mo) X-ray Source' _diffrn_radiation_monochromator mirror _diffrn_measurement_device_type 'SuperNova, Dual, Cu at zero, Atlas' _diffrn_detector_area_resol_mean 10.4757 _diffrn_reflns_number 14617 _diffrn_reflns_av_R_equivalents 0.0284 _diffrn_reflns_av_sigmaI/netI 0.0890 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.0423 _diffrn_reflns_theta_max 29.4720 _diffrn_orient_matrix_UB_11 0.0165053000 _diffrn_orient_matrix_UB_12 0.0126301000 _diffrn_orient_matrix_UB_13 0.0446097000 _diffrn_orient_matrix_UB_21 0.0548503000 _diffrn_orient_matrix_UB_22 0.0415166000 _diffrn_orient_matrix_UB_23 -0.0098711000 _diffrn_orient_matrix_UB_31 -0.0424134000 _diffrn_orient_matrix_UB_32 0.0497526000 _diffrn_orient_matrix_UB_33 0.0004157000 _diffrn_measurement_details ; #__ type_ start__ end____ width___ exp.time_ 1 omega 28.00 54.00 1.0000 13.0800 omega____ theta____ kappa____ phi______ frames - -11.8877 77.0000 60.0000 26 #__ type_ start__ end____ width___ exp.time_ 2 omega -19.00 91.00 1.0000 13.0800 omega____ theta____ kappa____ phi______ frames - 12.4346 77.0000 -30.0000 110 #__ type_ start__ end____ width___ exp.time_ 3 omega -2.00 82.00 1.0000 13.0800 omega____ theta____ kappa____ phi______ frames - 12.4346 77.0000 90.0000 84 #__ type_ start__ end____ width___ exp.time_ 4 omega -21.00 91.00 1.0000 13.0800 omega____ theta____ kappa____ phi______ frames - 12.4346 77.0000 -150.0000 112 ; _diffrn_measurement_method '\w scans' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _reflns_number_total 7756 _reflns_number_gt 5719 _reflns_threshold_expression >2sigma(I) _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0261P)^2^+10.8999P] 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 0.0026(6) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 7756 _refine_ls_number_parameters 386 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0939 _refine_ls_R_factor_gt 0.0704 _refine_ls_wR_factor_ref 0.1981 _refine_ls_wR_factor_gt 0.1866 _refine_ls_goodness_of_fit_ref 1.060 _refine_ls_restrained_S_all 1.060 _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 0.19467(9) 0.70963(8) 0.74195(5) 0.0385(2) Uani 1 1 d . . . S1 S 0.16659(18) 0.47735(15) 0.76778(12) 0.0549(4) Uani 1 1 d . . . S2 S 0.41997(18) 0.68176(16) 0.83082(12) 0.0566(5) Uani 1 1 d . . . S3 S 0.05405(19) 0.78911(15) 0.86657(11) 0.0552(5) Uani 1 1 d . . . S4 S 0.23121(18) 0.95681(15) 0.73558(12) 0.0555(5) Uani 1 1 d . . . N1 N 0.0305(4) 0.6816(4) 0.6227(3) 0.0359(10) Uani 1 1 d . . . N2 N 0.3014(5) 0.7097(4) 0.6195(3) 0.0387(10) Uani 1 1 d . . . N3 N 0.3051(5) 0.8084(4) 0.4987(3) 0.0373(10) Uani 1 1 d . . . P1 P 0.34206(17) 0.50953(15) 0.83477(10) 0.0450(4) Uani 1 1 d . . . P2 P 0.13103(17) 0.95628(15) 0.84164(11) 0.0446(4) Uani 1 1 d . A . C1 C -0.0975(5) 0.6255(5) 0.6218(4) 0.0390(12) Uani 1 1 d . . . C2 C -0.1723(6) 0.5934(5) 0.5435(4) 0.0427(13) Uani 1 1 d . . . C3 C -0.1151(6) 0.6245(6) 0.4670(4) 0.0490(15) Uani 1 1 d . . . H3 H -0.1637 0.6069 0.4147 0.059 Uiso 1 1 calc R . . C4 C 0.0119(6) 0.6807(6) 0.4687(4) 0.0471(14) Uani 1 1 d . . . H4 H 0.0515 0.7001 0.4178 0.057 Uiso 1 1 calc R . . C5 C 0.0822(6) 0.7087(5) 0.5487(3) 0.0368(12) Uani 1 1 d . . . C6 C 0.2264(5) 0.7503(5) 0.5559(4) 0.0364(12) Uani 1 1 d . . . C7 C 0.4324(6) 0.7367(5) 0.6024(4) 0.0408(13) Uani 1 1 d . . . H7 H 0.5063 0.7183 0.6366 0.049 Uiso 1 1 calc R . . C8 C 0.4379(5) 0.7952(5) 0.5268(4) 0.0399(12) Uani 1 1 d . . . C9 C 0.5442(6) 0.8368(6) 0.4738(4) 0.0490(15) Uani 1 1 d . . . H9 H 0.6326 0.8225 0.4889 0.059 Uiso 1 1 calc R . . C10 C 0.5156(7) 0.8960(6) 0.4030(4) 0.0555(17) Uani 1 1 d . . . H10 H 0.5832 0.9158 0.3660 0.067 Uiso 1 1 calc R . . C11 C 0.3819(7) 0.9295(6) 0.3833(4) 0.0488(15) Uani 1 1 d . . . C12 C 0.2757(6) 0.8913(5) 0.4337(4) 0.0406(13) Uani 1 1 d . . . C13 C -0.1516(6) 0.5937(6) 0.7000(4) 0.0501(15) Uani 1 1 d . . . H13 H -0.1040 0.6162 0.7520 0.060 Uiso 1 1 calc R . . C14 C -0.2768(7) 0.5285(7) 0.6986(5) 0.0595(18) Uani 1 1 d . . . H14 H -0.3123 0.5053 0.7499 0.071 Uiso 1 1 calc R . . C15 C -0.3498(7) 0.4974(7) 0.6210(5) 0.0621(19) Uani 1 1 d . . . H15 H -0.4340 0.4543 0.6214 0.075 Uiso 1 1 calc R . . C16 C -0.3013(6) 0.5283(6) 0.5456(5) 0.0517(16) Uani 1 1 d . . . H16 H -0.3522 0.5072 0.4946 0.062 Uiso 1 1 calc R . . C17 C 0.3554(8) 1.0137(7) 0.3186(4) 0.0617(19) Uani 1 1 d . . . H17 H 0.4223 1.0377 0.2822 0.074 Uiso 1 1 calc R . . C18 C 0.2323(10) 1.0595(7) 0.3096(5) 0.073(2) Uani 1 1 d . . . H18 H 0.2162 1.1149 0.2673 0.088 Uiso 1 1 calc R . . C19 C 0.1317(8) 1.0244(7) 0.3626(5) 0.0637(19) Uani 1 1 d . . . H19 H 0.0486 1.0570 0.3559 0.076 Uiso 1 1 calc R . . C20 C 0.1525(7) 0.9411(6) 0.4257(4) 0.0523(15) Uani 1 1 d . . . H20 H 0.0848 0.9190 0.4622 0.063 Uiso 1 1 calc R . . O31 O 0.4486(5) 0.4195(5) 0.8041(4) 0.0672(14) Uani 1 1 d . . . C31 C 0.4188(10) 0.2844(8) 0.8041(8) 0.098(3) Uani 1 1 d . . . H31A H 0.3383 0.2672 0.8351 0.118 Uiso 1 1 calc R . . H31B H 0.4005 0.2513 0.7452 0.118 Uiso 1 1 calc R . . C32 C 0.5208(12) 0.2244(10) 0.8408(10) 0.147(6) Uani 1 1 d . . . H32A H 0.5188 0.2336 0.9024 0.221 Uiso 1 1 calc R . . H32B H 0.6054 0.2599 0.8231 0.221 Uiso 1 1 calc R . . H32C H 0.5099 0.1377 0.8227 0.221 Uiso 1 1 calc R . . O32 O 0.3281(6) 0.4671(5) 0.9292(3) 0.0707(15) Uani 1 1 d . . . C33 C 0.2404(13) 0.5245(9) 0.9878(6) 0.104(4) Uani 1 1 d . . . H33A H 0.2844 0.6027 1.0120 0.125 Uiso 1 1 calc R . . H33B H 0.1588 0.5426 0.9561 0.125 Uiso 1 1 calc R . . C34 C 0.2068(14) 0.4487(11) 1.0544(7) 0.137(5) Uani 1 1 d . . . H34A H 0.2848 0.4096 1.0744 0.205 Uiso 1 1 calc R . . H34B H 0.1377 0.3859 1.0338 0.205 Uiso 1 1 calc R . . H34C H 0.1749 0.4982 1.1010 0.205 Uiso 1 1 calc R . . O33 O 0.0095(5) 1.0424(4) 0.8384(3) 0.0583(12) Uani 1 1 d . . . C35 C 0.0309(8) 1.1723(6) 0.8218(6) 0.074(2) Uani 1 1 d . . . H35A H 0.0661 1.1811 0.7654 0.088 Uiso 1 1 calc R . . H35B H 0.0956 1.2139 0.8645 0.088 Uiso 1 1 calc R . . C36 C -0.0973(10) 1.2284(8) 0.8258(9) 0.116(4) Uani 1 1 d . . . H36A H -0.1282 1.2247 0.8830 0.174 Uiso 1 1 calc R . . H36B H -0.1622 1.1836 0.7858 0.174 Uiso 1 1 calc R . . H36C H -0.0855 1.3136 0.8111 0.174 Uiso 1 1 calc R . . O34 O 0.2312(6) 1.0212(5) 0.9151(3) 0.0772(16) Uani 1 1 d G . . C37A C 0.2007(8) 1.0267(16) 1.0043(4) 0.087(5) Uani 0.60 1 d PG A 1 H37A H 0.1696 0.9447 1.0212 0.104 Uiso 0.60 1 d PG A 1 H37B H 0.1304 1.0823 1.0137 0.104 Uiso 0.60 1 d PG A 1 C37B C 0.2946(18) 0.9697(8) 0.9888(6) 0.121(11) Uani 0.40 1 d PG A 2 H37C H 0.3765 0.9337 0.9730 0.146 Uiso 0.40 1 d PG A 2 H37D H 0.2348 0.9050 1.0105 0.146 Uiso 0.40 1 d PG A 2 C38 C 0.3260(11) 1.0735(11) 1.0563(4) 0.126(4) Uani 1 1 d G A . H38A H 0.3668 1.1412 1.0313 0.188 Uiso 1 1 d G A . H38B H 0.3924 1.0129 1.0693 0.188 Uiso 1 1 d G A . H38C H 0.2831 1.0936 1.1072 0.188 Uiso 1 1 d G A . 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 0.0439(5) 0.0367(5) 0.0349(5) 0.0027(3) 0.0052(4) -0.0002(4) S1 0.0568(10) 0.0399(8) 0.0658(11) 0.0102(7) -0.0072(8) -0.0081(7) S2 0.0556(10) 0.0487(9) 0.0622(11) 0.0043(8) -0.0114(8) -0.0088(7) S3 0.0689(11) 0.0411(8) 0.0564(10) 0.0020(7) 0.0273(8) -0.0049(7) S4 0.0625(10) 0.0407(8) 0.0643(11) 0.0033(7) 0.0280(9) -0.0043(7) N1 0.038(2) 0.037(2) 0.032(2) -0.0009(18) 0.0040(19) -0.0001(19) N2 0.039(2) 0.042(3) 0.036(2) 0.004(2) 0.004(2) 0.002(2) N3 0.041(2) 0.037(2) 0.035(2) 0.0012(19) 0.007(2) 0.0034(19) P1 0.0500(9) 0.0443(9) 0.0416(8) 0.0081(7) 0.0050(7) 0.0045(7) P2 0.0497(9) 0.0377(8) 0.0454(9) -0.0037(6) 0.0093(7) -0.0021(7) C1 0.034(3) 0.035(3) 0.048(3) 0.000(2) 0.006(2) 0.002(2) C2 0.034(3) 0.040(3) 0.052(3) -0.009(3) -0.002(3) 0.003(2) C3 0.050(4) 0.054(4) 0.040(3) -0.009(3) -0.006(3) 0.002(3) C4 0.052(4) 0.054(4) 0.035(3) -0.002(3) 0.003(3) 0.005(3) C5 0.040(3) 0.036(3) 0.034(3) -0.001(2) 0.003(2) 0.003(2) C6 0.036(3) 0.037(3) 0.037(3) 0.001(2) 0.007(2) 0.002(2) C7 0.037(3) 0.041(3) 0.044(3) 0.002(2) 0.006(2) 0.004(2) C8 0.034(3) 0.041(3) 0.044(3) 0.000(2) 0.008(2) 0.003(2) C9 0.043(3) 0.050(4) 0.054(4) 0.001(3) 0.015(3) 0.000(3) C10 0.058(4) 0.057(4) 0.052(4) -0.001(3) 0.027(3) -0.011(3) C11 0.061(4) 0.046(3) 0.038(3) 0.003(3) 0.008(3) -0.011(3) C12 0.050(3) 0.038(3) 0.033(3) 0.000(2) 0.004(2) 0.000(2) C13 0.041(3) 0.059(4) 0.048(4) 0.001(3) 0.005(3) -0.006(3) C14 0.045(4) 0.064(4) 0.070(5) 0.012(4) 0.014(3) -0.006(3) C15 0.039(3) 0.053(4) 0.092(6) -0.005(4) 0.003(4) -0.009(3) C16 0.039(3) 0.047(4) 0.067(4) -0.012(3) -0.007(3) -0.001(3) C17 0.085(5) 0.061(4) 0.036(3) 0.013(3) 0.004(3) -0.018(4) C18 0.106(7) 0.063(5) 0.049(4) 0.024(4) -0.016(4) -0.008(5) C19 0.074(5) 0.060(4) 0.057(4) 0.011(3) -0.010(4) 0.007(4) C20 0.057(4) 0.051(4) 0.050(4) 0.009(3) 0.001(3) 0.008(3) O31 0.059(3) 0.053(3) 0.092(4) 0.001(3) 0.016(3) 0.009(2) C31 0.093(7) 0.050(5) 0.152(10) -0.011(5) 0.018(7) 0.013(5) C32 0.105(9) 0.075(7) 0.260(18) 0.032(9) -0.046(10) 0.024(6) O32 0.094(4) 0.071(3) 0.050(3) 0.019(2) 0.010(3) 0.017(3) C33 0.171(11) 0.084(7) 0.064(6) 0.010(5) 0.046(6) 0.019(7) C34 0.193(14) 0.123(10) 0.107(9) 0.036(7) 0.082(9) 0.027(9) O33 0.055(3) 0.044(2) 0.077(3) -0.001(2) 0.018(2) 0.004(2) C35 0.073(5) 0.040(4) 0.110(7) 0.011(4) 0.018(5) 0.003(3) C36 0.090(7) 0.042(5) 0.223(14) 0.011(6) 0.052(8) 0.016(4) O34 0.099(4) 0.067(3) 0.058(3) -0.008(3) -0.012(3) -0.022(3) C37A 0.089(11) 0.113(13) 0.055(8) -0.013(8) 0.023(8) -0.018(9) C37B 0.12(3) 0.078(18) 0.16(3) -0.022(18) -0.03(2) -0.002(16) C38 0.137(10) 0.162(12) 0.068(6) -0.017(7) -0.029(7) -0.007(9) _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 N2 2.231(5) . ? Mn1 N1 2.406(5) . ? Mn1 S1 2.5569(18) . ? Mn1 S3 2.5992(18) . ? Mn1 S2 2.629(2) . ? Mn1 S4 2.6728(18) . ? S1 P1 1.992(2) . ? S2 P1 1.965(2) . ? S3 P2 1.972(2) . ? S4 P2 1.974(2) . ? N1 C5 1.324(7) . ? N1 C1 1.371(7) . ? N2 C6 1.326(7) . ? N2 C7 1.363(7) . ? N3 C6 1.364(7) . ? N3 C8 1.397(7) . ? N3 C12 1.420(7) . ? P1 O31 1.571(5) . ? P1 O32 1.573(5) . ? P2 O34 1.579(5) . ? P2 O33 1.585(5) . ? C1 C13 1.405(8) . ? C1 C2 1.411(8) . ? C2 C3 1.391(9) . ? C2 C16 1.424(8) . ? C3 C4 1.363(9) . ? C4 C5 1.406(8) . ? C5 C6 1.474(8) . ? C7 C8 1.366(8) . ? C8 C9 1.437(8) . ? C9 C10 1.333(9) . ? C10 C11 1.434(10) . ? C11 C12 1.402(8) . ? C11 C17 1.421(9) . ? C12 C20 1.383(9) . ? C13 C14 1.387(9) . ? C14 C15 1.391(10) . ? C15 C16 1.340(10) . ? C17 C18 1.364(11) . ? C18 C19 1.376(11) . ? C19 C20 1.387(9) . ? O31 C31 1.466(9) . ? C31 C32 1.367(13) . ? O32 C33 1.445(10) . ? C33 C34 1.394(12) . ? O33 C35 1.441(8) . ? C35 C36 1.461(11) . ? O34 C37A 1.4355 . ? O34 C37B 1.4416 . ? C37A C38 1.4960 . ? C37B C38 1.4983 . ? 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 N2 Mn1 N1 71.26(16) . . ? N2 Mn1 S1 101.80(13) . . ? N1 Mn1 S1 90.81(12) . . ? N2 Mn1 S3 159.14(13) . . ? N1 Mn1 S3 102.30(12) . . ? S1 Mn1 S3 98.05(6) . . ? N2 Mn1 S2 90.98(13) . . ? N1 Mn1 S2 157.47(12) . . ? S1 Mn1 S2 79.09(6) . . ? S3 Mn1 S2 99.04(7) . . ? N2 Mn1 S4 83.50(13) . . ? N1 Mn1 S4 95.24(12) . . ? S1 Mn1 S4 173.01(7) . . ? S3 Mn1 S4 77.27(5) . . ? S2 Mn1 S4 96.41(6) . . ? P1 S1 Mn1 84.53(7) . . ? P1 S2 Mn1 83.11(8) . . ? P2 S3 Mn1 85.36(7) . . ? P2 S4 Mn1 83.35(7) . . ? C5 N1 C1 118.9(5) . . ? C5 N1 Mn1 112.4(4) . . ? C1 N1 Mn1 127.8(4) . . ? C6 N2 C7 107.4(5) . . ? C6 N2 Mn1 111.4(4) . . ? C7 N2 Mn1 132.4(4) . . ? C6 N3 C8 106.1(5) . . ? C6 N3 C12 131.9(5) . . ? C8 N3 C12 120.6(5) . . ? O31 P1 O32 99.2(3) . . ? O31 P1 S2 108.4(2) . . ? O32 P1 S2 113.0(2) . . ? O31 P1 S1 112.2(2) . . ? O32 P1 S1 110.0(2) . . ? S2 P1 S1 113.14(10) . . ? O34 P2 O33 104.2(3) . . ? O34 P2 S3 114.5(2) . . ? O33 P2 S3 106.30(19) . . ? O34 P2 S4 105.8(2) . . ? O33 P2 S4 112.8(2) . . ? S3 P2 S4 113.07(10) . . ? N1 C1 C13 119.2(5) . . ? N1 C1 C2 121.0(5) . . ? C13 C1 C2 119.7(5) . . ? C3 C2 C1 118.3(5) . . ? C3 C2 C16 122.8(6) . . ? C1 C2 C16 118.9(6) . . ? C4 C3 C2 120.2(6) . . ? C3 C4 C5 118.8(6) . . ? N1 C5 C4 122.7(5) . . ? N1 C5 C6 114.3(5) . . ? C4 C5 C6 122.2(5) . . ? N2 C6 N3 110.6(5) . . ? N2 C6 C5 118.1(5) . . ? N3 C6 C5 130.2(5) . . ? N2 C7 C8 109.1(5) . . ? C7 C8 N3 106.5(5) . . ? C7 C8 C9 134.7(6) . . ? N3 C8 C9 118.7(5) . . ? C10 C9 C8 119.8(6) . . ? C9 C10 C11 120.8(6) . . ? C12 C11 C17 117.5(7) . . ? C12 C11 C10 120.8(6) . . ? C17 C11 C10 121.3(6) . . ? C20 C12 C11 121.4(6) . . ? C20 C12 N3 121.8(5) . . ? C11 C12 N3 116.5(5) . . ? C14 C13 C1 119.2(6) . . ? C13 C14 C15 120.6(7) . . ? C16 C15 C14 121.4(6) . . ? C15 C16 C2 120.3(6) . . ? C18 C17 C11 120.5(7) . . ? C17 C18 C19 120.6(7) . . ? C18 C19 C20 120.9(7) . . ? C12 C20 C19 119.0(7) . . ? C31 O31 P1 120.0(5) . . ? C32 C31 O31 113.3(9) . . ? C33 O32 P1 121.9(5) . . ? C34 C33 O32 112.2(9) . . ? C35 O33 P2 120.9(4) . . ? O33 C35 C36 108.7(6) . . ? C37A O34 P2 122.8(5) . . ? C37B O34 P2 130.1(6) . . ? O34 C37A C38 108.0 . . ? O34 C37B C38 107.6 . . ? _diffrn_measured_fraction_theta_max 0.833 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.819 _refine_diff_density_min -0.419 _refine_diff_density_rms 0.100 #===END data_Compound_2c_mnoxabre _database_code_depnum_ccdc_archive 'CCDC 869440' #TrackingRef '- azaindolizine_ligands.cif' _audit_creation_method SHELXL-97 _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_cell_refinement ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_data_reduction ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H27 Br2 Mn N3 O4 P2 S4' _chemical_formula_weight 778.39 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' 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' 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 11.4966(15) _cell_length_b 12.8094(16) _cell_length_c 13.1346(17) _cell_angle_alpha 98.074(11) _cell_angle_beta 110.662(13) _cell_angle_gamma 115.699(12) _cell_volume 1528.8(3) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 4480 _cell_measurement_theta_min 2.0231 _cell_measurement_theta_max 29.3712 _exptl_crystal_description chunk _exptl_crystal_colour pale-yellow _exptl_crystal_size_max 0.3885 _exptl_crystal_size_mid 0.2838 _exptl_crystal_size_min 0.1131 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.691 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 778 _exptl_absorpt_coefficient_mu 3.454 _exptl_absorpt_correction_type analytical _exptl_absorpt_correction_T_min 0.431 _exptl_absorpt_correction_T_max 0.674 _exptl_absorpt_process_details ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) ; _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 'SuperNova, Dual, Cu at zero, Atlas' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 10.4757 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 12602 _diffrn_reflns_av_R_equivalents 0.0339 _diffrn_reflns_av_sigmaI/netI 0.0595 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.03 _diffrn_reflns_theta_max 29.44 _reflns_number_total 7069 _reflns_number_gt 4764 _reflns_threshold_expression >2sigma(I) _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0392P)^2^+0.0377P] 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 7069 _refine_ls_number_parameters 329 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0756 _refine_ls_R_factor_gt 0.0453 _refine_ls_wR_factor_ref 0.1163 _refine_ls_wR_factor_gt 0.0978 _refine_ls_goodness_of_fit_ref 1.112 _refine_ls_restrained_S_all 1.112 _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 0.07416(6) 0.33265(5) 0.74625(5) 0.04022(16) Uani 1 1 d . . . S1 S 0.09560(13) 0.13900(9) 0.74502(10) 0.0542(3) Uani 1 1 d . . . S2 S 0.34146(12) 0.41473(10) 0.78033(11) 0.0587(3) Uani 1 1 d . . . S3 S -0.05246(12) 0.30159(10) 0.52578(8) 0.0501(3) Uani 1 1 d . . . S4 S -0.20582(12) 0.20821(10) 0.69045(9) 0.0521(3) Uani 1 1 d . . . P1 P 0.29201(13) 0.24217(10) 0.75952(9) 0.0512(3) Uani 1 1 d . . . P2 P -0.22903(12) 0.25162(10) 0.54888(9) 0.0463(3) Uani 1 1 d . . . O1 O 0.4127(4) 0.2334(3) 0.8581(3) 0.0711(9) Uani 1 1 d . . . O2 O 0.3108(4) 0.1851(3) 0.6554(3) 0.0696(9) Uani 1 1 d . . . O3 O -0.2662(3) 0.3571(3) 0.5587(2) 0.0549(7) Uani 1 1 d . . . O4 O -0.3718(3) 0.1483(3) 0.4363(2) 0.0641(8) Uani 1 1 d . . . Br1 Br 0.29567(6) 0.31512(4) 1.22874(4) 0.06374(16) Uani 1 1 d . . . Br2 Br 0.15862(6) 0.97831(4) 1.10373(4) 0.06921(17) Uani 1 1 d . . . N1 N 0.1447(3) 0.4056(3) 0.9444(2) 0.0364(7) Uani 1 1 d . . . N2 N 0.1036(3) 0.5206(3) 0.7930(3) 0.0412(7) Uani 1 1 d . . . N3 N 0.1316(3) 0.6810(3) 0.9103(2) 0.0356(7) Uani 1 1 d . . . C1 C 0.1806(4) 0.3490(3) 1.0162(3) 0.0393(8) Uani 1 1 d . . . H1 H 0.1636 0.2709 0.9851 0.047 Uiso 1 1 calc R . . C2 C 0.2421(4) 0.4017(3) 1.1351(3) 0.0399(8) Uani 1 1 d . . . C3 C 0.2659(5) 0.5155(4) 1.1815(3) 0.0540(11) Uani 1 1 d . . . H3 H 0.3064 0.5524 1.2614 0.065 Uiso 1 1 calc R . . C4 C 0.2282(5) 0.5744(4) 1.1073(3) 0.0526(11) Uani 1 1 d . . . H4 H 0.2432 0.6519 1.1372 0.063 Uiso 1 1 calc R . . C5 C 0.1690(4) 0.5196(3) 0.9899(3) 0.0351(8) Uani 1 1 d . . . C6 C 0.1346(4) 0.5736(3) 0.9018(3) 0.0365(8) Uani 1 1 d . . . C7 C 0.0837(4) 0.5931(4) 0.7312(3) 0.0485(10) Uani 1 1 d . . . H7 H 0.0618 0.5769 0.6534 0.058 Uiso 1 1 calc R . . C8 C 0.1009(4) 0.6947(3) 0.8018(3) 0.0423(9) Uani 1 1 d . . . C9 C 0.0949(4) 0.8006(4) 0.7864(4) 0.0476(10) Uani 1 1 d . . . H9 H 0.0772 0.8118 0.7153 0.057 Uiso 1 1 calc R . . C10 C 0.1149(5) 0.8837(4) 0.8749(4) 0.0544(11) Uani 1 1 d . . . H10 H 0.1121 0.9534 0.8658 0.065 Uiso 1 1 calc R . . C11 C 0.1406(4) 0.8646(3) 0.9830(4) 0.0459(9) Uani 1 1 d . . . C12 C 0.1498(4) 0.7670(3) 1.0009(3) 0.0405(8) Uani 1 1 d . . . H12 H 0.1681 0.7572 1.0727 0.049 Uiso 1 1 calc R . . C31 C 0.4493(7) 0.2802(6) 0.9767(4) 0.104(2) Uani 1 1 d . . . H31A H 0.3645 0.2731 0.9823 0.125 Uiso 1 1 calc R . . H31B H 0.5250 0.3670 1.0098 0.125 Uiso 1 1 calc R . . C32 C 0.5001(6) 0.2128(6) 1.0421(5) 0.0992(19) Uani 1 1 d . . . H32A H 0.4266 0.1264 1.0076 0.149 Uiso 1 1 calc R . . H32B H 0.5194 0.2432 1.1208 0.149 Uiso 1 1 calc R . . H32C H 0.5878 0.2244 1.0408 0.149 Uiso 1 1 calc R . . C33 C 0.2137(7) 0.1581(5) 0.5365(4) 0.0843(16) Uani 1 1 d . . . H33A H 0.1784 0.2146 0.5333 0.101 Uiso 1 1 calc R . . H33B H 0.1304 0.0746 0.5052 0.101 Uiso 1 1 calc R . . C34 C 0.2928(8) 0.1712(6) 0.4670(6) 0.111(2) Uani 1 1 d . . . H34A H 0.3822 0.2500 0.5045 0.166 Uiso 1 1 calc R . . H34B H 0.2336 0.1656 0.3911 0.166 Uiso 1 1 calc R . . H34C H 0.3139 0.1066 0.4604 0.166 Uiso 1 1 calc R . . C35 C -0.2966(6) 0.4040(5) 0.4647(4) 0.0724(14) Uani 1 1 d . . . H35A H -0.3849 0.3390 0.3966 0.087 Uiso 1 1 calc R . . H35B H -0.2170 0.4316 0.4450 0.087 Uiso 1 1 calc R . . C36 C -0.3145(6) 0.5068(5) 0.5003(5) 0.0819(16) Uani 1 1 d . . . H36A H -0.3937 0.4789 0.5193 0.123 Uiso 1 1 calc R . . H36B H -0.3351 0.5379 0.4380 0.123 Uiso 1 1 calc R . . H36C H -0.2264 0.5714 0.5671 0.123 Uiso 1 1 calc R . . C37 C -0.3868(5) 0.0354(4) 0.3788(4) 0.0733(14) Uani 1 1 d . . . H37A H -0.4467 -0.0319 0.3975 0.088 Uiso 1 1 calc R . . H37B H -0.2918 0.0443 0.4051 0.088 Uiso 1 1 calc R . . C38 C -0.4549(7) 0.0081(6) 0.2529(5) 0.112(2) Uani 1 1 d . . . H38A H -0.5444 0.0075 0.2286 0.167 Uiso 1 1 calc R . . H38B H -0.4748 -0.0714 0.2137 0.167 Uiso 1 1 calc R . . H38C H -0.3900 0.0702 0.2340 0.167 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 0.0512(4) 0.0376(3) 0.0319(3) 0.0086(3) 0.0152(3) 0.0274(3) S1 0.0681(7) 0.0381(6) 0.0564(7) 0.0152(5) 0.0256(6) 0.0306(5) S2 0.0555(7) 0.0460(6) 0.0682(8) 0.0131(6) 0.0278(6) 0.0243(5) S3 0.0585(6) 0.0620(7) 0.0362(5) 0.0176(5) 0.0215(5) 0.0367(6) S4 0.0569(6) 0.0555(7) 0.0486(6) 0.0213(5) 0.0268(5) 0.0304(6) P1 0.0610(7) 0.0547(7) 0.0427(6) 0.0101(5) 0.0191(5) 0.0399(6) P2 0.0502(6) 0.0472(6) 0.0376(6) 0.0089(5) 0.0138(5) 0.0292(5) O1 0.082(2) 0.094(2) 0.0509(19) 0.0170(18) 0.0207(17) 0.067(2) O2 0.089(2) 0.086(2) 0.055(2) 0.0152(18) 0.0333(18) 0.064(2) O3 0.0714(19) 0.0601(18) 0.0471(17) 0.0189(15) 0.0254(15) 0.0468(17) O4 0.0545(18) 0.0607(19) 0.0521(18) -0.0022(15) 0.0046(15) 0.0327(16) Br1 0.0900(4) 0.0584(3) 0.0480(3) 0.0256(2) 0.0230(3) 0.0476(3) Br2 0.0955(4) 0.0537(3) 0.0712(3) 0.0135(2) 0.0380(3) 0.0518(3) N1 0.0459(18) 0.0342(16) 0.0303(16) 0.0112(14) 0.0163(14) 0.0229(15) N2 0.0536(19) 0.0366(17) 0.0334(17) 0.0104(14) 0.0173(15) 0.0264(16) N3 0.0384(16) 0.0321(16) 0.0353(17) 0.0103(14) 0.0150(14) 0.0197(14) C1 0.047(2) 0.033(2) 0.040(2) 0.0121(17) 0.0193(18) 0.0231(18) C2 0.047(2) 0.039(2) 0.033(2) 0.0139(17) 0.0150(18) 0.0250(18) C3 0.080(3) 0.051(3) 0.029(2) 0.0095(19) 0.016(2) 0.041(2) C4 0.078(3) 0.044(2) 0.040(2) 0.0104(19) 0.020(2) 0.042(2) C5 0.040(2) 0.0336(19) 0.0297(18) 0.0073(16) 0.0156(16) 0.0189(16) C6 0.043(2) 0.0303(19) 0.034(2) 0.0079(16) 0.0156(17) 0.0205(17) C7 0.063(3) 0.049(2) 0.038(2) 0.021(2) 0.022(2) 0.032(2) C8 0.050(2) 0.042(2) 0.038(2) 0.0164(19) 0.0186(19) 0.0269(19) C9 0.057(3) 0.046(2) 0.052(2) 0.027(2) 0.026(2) 0.032(2) C10 0.064(3) 0.044(2) 0.063(3) 0.023(2) 0.025(2) 0.036(2) C11 0.048(2) 0.036(2) 0.055(3) 0.0105(19) 0.021(2) 0.0264(19) C12 0.047(2) 0.039(2) 0.040(2) 0.0114(18) 0.0208(18) 0.0254(18) C31 0.111(5) 0.151(6) 0.045(3) 0.001(3) 0.005(3) 0.099(5) C32 0.075(4) 0.127(5) 0.069(4) 0.041(4) 0.021(3) 0.039(4) C33 0.113(5) 0.096(4) 0.050(3) 0.018(3) 0.034(3) 0.064(4) C34 0.168(6) 0.134(6) 0.095(5) 0.070(4) 0.092(5) 0.095(5) C35 0.101(4) 0.091(4) 0.056(3) 0.034(3) 0.037(3) 0.071(3) C36 0.114(5) 0.092(4) 0.074(4) 0.041(3) 0.045(3) 0.075(4) C37 0.069(3) 0.047(3) 0.069(3) 0.003(2) 0.005(3) 0.029(3) C38 0.126(5) 0.124(5) 0.068(4) -0.006(4) 0.019(4) 0.085(5) _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 N2 2.240(3) . ? Mn1 N1 2.339(3) . ? Mn1 S1 2.5953(11) . ? Mn1 S2 2.6161(13) . ? Mn1 S3 2.6196(12) . ? Mn1 S4 2.6450(14) . ? S1 P1 1.9798(17) . ? S2 P1 1.9785(15) . ? S3 P2 1.9962(15) . ? S4 P2 1.9765(15) . ? P1 O2 1.586(3) . ? P1 O1 1.589(3) . ? P2 O4 1.576(3) . ? P2 O3 1.586(3) . ? O1 C31 1.420(5) . ? O2 C33 1.445(5) . ? O3 C35 1.447(5) . ? O4 C37 1.441(5) . ? Br1 C2 1.887(3) . ? Br2 C11 1.880(4) . ? N1 C1 1.327(4) . ? N1 C5 1.360(4) . ? N2 C6 1.338(4) . ? N2 C7 1.357(4) . ? N3 C6 1.381(4) . ? N3 C12 1.389(4) . ? N3 C8 1.398(4) . ? C1 C2 1.380(5) . ? C2 C3 1.364(5) . ? C3 C4 1.378(5) . ? C4 C5 1.369(5) . ? C5 C6 1.454(5) . ? C7 C8 1.379(5) . ? C8 C9 1.426(5) . ? C9 C10 1.336(6) . ? C10 C11 1.424(5) . ? C11 C12 1.346(5) . ? C31 C32 1.454(7) . ? C33 C34 1.478(7) . ? C35 C36 1.458(6) . ? C37 C38 1.469(7) . ? 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 N2 Mn1 N1 71.17(10) . . ? N2 Mn1 S1 165.28(9) . . ? N1 Mn1 S1 96.63(7) . . ? N2 Mn1 S2 94.67(9) . . ? N1 Mn1 S2 93.44(8) . . ? S1 Mn1 S2 77.48(4) . . ? N2 Mn1 S3 89.76(8) . . ? N1 Mn1 S3 157.63(7) . . ? S1 Mn1 S3 103.74(4) . . ? S2 Mn1 S3 99.84(4) . . ? N2 Mn1 S4 95.94(8) . . ? N1 Mn1 S4 92.77(8) . . ? S1 Mn1 S4 92.78(4) . . ? S2 Mn1 S4 168.99(4) . . ? S3 Mn1 S4 77.28(4) . . ? P1 S1 Mn1 85.85(5) . . ? P1 S2 Mn1 85.31(5) . . ? P2 S3 Mn1 83.58(5) . . ? P2 S4 Mn1 83.27(5) . . ? O2 P1 O1 95.83(16) . . ? O2 P1 S2 112.23(13) . . ? O1 P1 S2 112.43(14) . . ? O2 P1 S1 112.52(14) . . ? O1 P1 S1 112.12(14) . . ? S2 P1 S1 110.96(7) . . ? O4 P2 O3 99.31(16) . . ? O4 P2 S4 113.61(13) . . ? O3 P2 S4 107.81(11) . . ? O4 P2 S3 111.44(13) . . ? O3 P2 S3 112.37(13) . . ? S4 P2 S3 111.67(6) . . ? C31 O1 P1 120.8(3) . . ? C33 O2 P1 120.9(3) . . ? C35 O3 P2 120.7(2) . . ? C37 O4 P2 122.4(3) . . ? C1 N1 C5 118.6(3) . . ? C1 N1 Mn1 123.0(2) . . ? C5 N1 Mn1 117.7(2) . . ? C6 N2 C7 108.6(3) . . ? C6 N2 Mn1 117.3(2) . . ? C7 N2 Mn1 133.8(3) . . ? C6 N3 C12 132.3(3) . . ? C6 N3 C8 107.4(3) . . ? C12 N3 C8 120.3(3) . . ? N1 C1 C2 122.5(3) . . ? C3 C2 C1 119.3(3) . . ? C3 C2 Br1 122.0(3) . . ? C1 C2 Br1 118.7(3) . . ? C2 C3 C4 118.4(4) . . ? C5 C4 C3 120.5(3) . . ? N1 C5 C4 120.6(3) . . ? N1 C5 C6 112.3(3) . . ? C4 C5 C6 126.9(3) . . ? N2 C6 N3 108.9(3) . . ? N2 C6 C5 120.9(3) . . ? N3 C6 C5 130.2(3) . . ? N2 C7 C8 109.3(3) . . ? C7 C8 N3 105.8(3) . . ? C7 C8 C9 134.7(4) . . ? N3 C8 C9 119.4(3) . . ? C10 C9 C8 119.7(4) . . ? C9 C10 C11 119.5(3) . . ? C12 C11 C10 122.2(4) . . ? C12 C11 Br2 119.0(3) . . ? C10 C11 Br2 118.8(3) . . ? C11 C12 N3 118.9(3) . . ? O1 C31 C32 111.0(5) . . ? O2 C33 C34 109.2(5) . . ? O3 C35 C36 109.3(4) . . ? O4 C37 C38 109.1(4) . . ? _diffrn_measured_fraction_theta_max 0.836 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.442 _refine_diff_density_min -0.783 _refine_diff_density_rms 0.096 #===END data_Compound_3b_qindze _database_code_depnum_ccdc_archive 'CCDC 869441' #TrackingRef '- azaindolizine_ligands.cif' _audit_creation_method SHELXL-97 _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) ; _computing_cell_refinement ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) ; _computing_data_reduction ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) ; _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H13 N3' _chemical_formula_weight 295.33 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/c 1' 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 5.9555(7) _cell_length_b 14.379(2) _cell_length_c 17.069(2) _cell_angle_alpha 90.00 _cell_angle_beta 96.393(10) _cell_angle_gamma 90.00 _cell_volume 1452.6(3) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 1525 _cell_measurement_theta_min 2.3966 _cell_measurement_theta_max 29.2800 _exptl_crystal_description needle _exptl_crystal_colour white _exptl_crystal_size_max 0.2836 _exptl_crystal_size_mid 0.1067 _exptl_crystal_size_min 0.0472 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.350 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 616 _exptl_absorpt_coefficient_mu 0.082 _exptl_absorpt_correction_type analytical _exptl_absorpt_correction_T_min 0.985 _exptl_absorpt_correction_T_max 0.997 _exptl_absorpt_process_details ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) ; _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 'SuperNova, Dual, Cu at zero, Atlas' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 10.4757 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 7479 _diffrn_reflns_av_R_equivalents 0.0659 _diffrn_reflns_av_sigmaI/netI 0.1308 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 2.40 _diffrn_reflns_theta_max 29.34 _reflns_number_total 3432 _reflns_number_gt 1407 _reflns_threshold_expression >2sigma(I) _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0218P)^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 0.0062(8) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3432 _refine_ls_number_parameters 209 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1997 _refine_ls_R_factor_gt 0.0820 _refine_ls_wR_factor_ref 0.1220 _refine_ls_wR_factor_gt 0.0913 _refine_ls_goodness_of_fit_ref 0.966 _refine_ls_restrained_S_all 0.966 _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 N1 N 0.3101(3) 0.50095(17) 0.18906(11) 0.0416(6) Uani 1 1 d . . . N2 N 0.4041(4) 0.48274(19) 0.39524(13) 0.0623(8) Uani 1 1 d . . . N3 N 0.1638(3) 0.39015(17) 0.32190(11) 0.0441(6) Uani 1 1 d . . . C1 C 0.3935(4) 0.54856(19) 0.12928(14) 0.0406(7) Uani 1 1 d . . . C2 C 0.6105(4) 0.5873(2) 0.13617(15) 0.0457(8) Uani 1 1 d . . . C3 C 0.7484(4) 0.5728(2) 0.20755(17) 0.0559(9) Uani 1 1 d . . . H3 H 0.8955 0.5955 0.2140 0.067 Uiso 1 1 calc R . . C4 C 0.6668(4) 0.5259(2) 0.26656(16) 0.0541(8) Uani 1 1 d . . . H4 H 0.7567 0.5164 0.3140 0.065 Uiso 1 1 calc R . . C5 C 0.4432(4) 0.4912(2) 0.25575(14) 0.0418(7) Uani 1 1 d . . . C6 C 0.3450(4) 0.4505(2) 0.32288(15) 0.0470(8) Uani 1 1 d . . . C7 C 0.2555(5) 0.4455(2) 0.44133(16) 0.0642(10) Uani 1 1 d . . . H7 H 0.2582 0.4565 0.4951 0.077 Uiso 1 1 calc R . . C8 C 0.1025(5) 0.3903(2) 0.39883(15) 0.0549(9) Uani 1 1 d . . . C9 C -0.0941(5) 0.3421(3) 0.41473(18) 0.0656(10) Uani 1 1 d . . . H9 H -0.1381 0.3429 0.4653 0.079 Uiso 1 1 calc R . . C10 C -0.2168(5) 0.2955(2) 0.35753(18) 0.0636(10) Uani 1 1 d . . . H10 H -0.3546 0.2698 0.3670 0.076 Uiso 1 1 calc R . . C11 C -0.1385(4) 0.2845(2) 0.28162(16) 0.0507(8) Uani 1 1 d . . . C12 C 0.0597(4) 0.3290(2) 0.26469(14) 0.0414(7) Uani 1 1 d . . . C13 C 0.2519(4) 0.5594(2) 0.05874(14) 0.0479(8) Uani 1 1 d . . . H13 H 0.1089 0.5326 0.0535 0.057 Uiso 1 1 calc R . . C14 C 0.3207(5) 0.6085(2) -0.00186(15) 0.0610(9) Uani 1 1 d . . . H14 H 0.2256 0.6145 -0.0486 0.073 Uiso 1 1 calc R . . C15 C 0.5343(5) 0.6501(2) 0.00555(17) 0.0687(10) Uani 1 1 d . . . H15 H 0.5793 0.6850 -0.0358 0.082 Uiso 1 1 calc R . . C16 C 0.6761(4) 0.6396(2) 0.07286(18) 0.0612(9) Uani 1 1 d . . . H16 H 0.8182 0.6673 0.0772 0.073 Uiso 1 1 calc R . . C17 C -0.2474(4) 0.2258(2) 0.22504(19) 0.0635(9) Uani 1 1 d . . . H17 H -0.3840 0.1989 0.2343 0.076 Uiso 1 1 calc R . . C18 C -0.1606(5) 0.2064(2) 0.15641(17) 0.0675(10) Uani 1 1 d . . . H18 H -0.2370 0.1671 0.1192 0.081 Uiso 1 1 calc R . . C19 C 0.0437(5) 0.2462(2) 0.14282(15) 0.0621(9) Uani 1 1 d . . . H19 H 0.1076 0.2315 0.0971 0.075 Uiso 1 1 calc R . . C20 C 0.1526(4) 0.3072(2) 0.19618(14) 0.0483(8) Uani 1 1 d . . . H20 H 0.2890 0.3338 0.1863 0.058 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 N1 0.0383(12) 0.0372(18) 0.0481(13) -0.0017(11) -0.0003(9) -0.0033(11) N2 0.0773(16) 0.053(2) 0.0534(15) -0.0072(14) -0.0074(12) 0.0049(15) N3 0.0491(13) 0.0408(19) 0.0424(13) 0.0056(11) 0.0051(10) 0.0044(12) C1 0.0403(14) 0.031(2) 0.0507(16) -0.0031(13) 0.0075(11) -0.0015(14) C2 0.0379(14) 0.035(2) 0.0654(19) -0.0053(15) 0.0128(13) -0.0022(14) C3 0.0344(15) 0.045(3) 0.089(2) -0.0081(18) 0.0056(14) -0.0050(15) C4 0.0398(15) 0.044(3) 0.075(2) -0.0056(17) -0.0100(13) 0.0010(15) C5 0.0418(15) 0.031(2) 0.0513(16) -0.0041(14) 0.0000(12) 0.0029(13) C6 0.0486(16) 0.042(2) 0.0487(17) 0.0014(15) -0.0032(12) 0.0039(15) C7 0.093(2) 0.055(3) 0.0435(17) 0.0043(17) 0.0057(17) 0.012(2) C8 0.071(2) 0.047(3) 0.0479(17) 0.0087(16) 0.0092(15) 0.0110(18) C9 0.082(2) 0.052(3) 0.068(2) 0.0270(19) 0.0311(17) 0.018(2) C10 0.0579(18) 0.047(3) 0.089(2) 0.0264(19) 0.0252(17) 0.0102(17) C11 0.0460(16) 0.042(2) 0.0644(19) 0.0173(16) 0.0080(14) 0.0044(15) C12 0.0441(15) 0.033(2) 0.0464(16) 0.0071(14) 0.0009(12) 0.0016(14) C13 0.0501(15) 0.041(2) 0.0525(17) -0.0030(15) 0.0057(13) -0.0018(15) C14 0.073(2) 0.056(3) 0.0548(18) 0.0026(17) 0.0105(14) 0.0056(18) C15 0.086(2) 0.057(3) 0.070(2) 0.0055(18) 0.0368(18) 0.003(2) C16 0.0542(17) 0.047(3) 0.087(2) -0.0061(18) 0.0307(16) -0.0052(17) C17 0.0484(17) 0.055(3) 0.085(2) 0.0260(19) -0.0030(15) -0.0091(17) C18 0.074(2) 0.054(3) 0.069(2) 0.0092(17) -0.0153(16) -0.0211(19) C19 0.082(2) 0.051(3) 0.0529(18) -0.0052(16) 0.0058(14) -0.0156(19) C20 0.0536(16) 0.038(2) 0.0531(17) 0.0011(15) 0.0046(13) -0.0077(15) _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 N1 C5 1.320(3) . ? N1 C1 1.367(3) . ? N2 C6 1.330(3) . ? N2 C7 1.358(3) . ? N3 C6 1.383(3) . ? N3 C8 1.402(3) . ? N3 C12 1.405(3) . ? C1 C13 1.399(3) . ? C1 C2 1.400(3) . ? C2 C16 1.407(4) . ? C2 C3 1.407(3) . ? C3 C4 1.347(3) . ? C4 C5 1.415(3) . ? C5 C6 1.466(3) . ? C7 C8 1.357(4) . ? C8 C9 1.412(4) . ? C9 C10 1.333(4) . ? C10 C11 1.434(3) . ? C11 C17 1.388(4) . ? C11 C12 1.401(3) . ? C12 C20 1.384(3) . ? C13 C14 1.352(3) . ? C14 C15 1.399(4) . ? C15 C16 1.357(3) . ? C17 C18 1.361(4) . ? C18 C19 1.388(4) . ? C19 C20 1.374(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 C5 N1 C1 117.6(2) . . ? C6 N2 C7 106.2(3) . . ? C6 N3 C8 105.8(2) . . ? C6 N3 C12 133.1(2) . . ? C8 N3 C12 120.7(2) . . ? N1 C1 C13 117.6(2) . . ? N1 C1 C2 123.0(2) . . ? C13 C1 C2 119.3(2) . . ? C1 C2 C16 118.8(3) . . ? C1 C2 C3 117.2(2) . . ? C16 C2 C3 124.0(3) . . ? C4 C3 C2 119.8(2) . . ? C3 C4 C5 119.4(2) . . ? N1 C5 C4 122.8(2) . . ? N1 C5 C6 117.6(2) . . ? C4 C5 C6 119.4(2) . . ? N2 C6 N3 110.8(2) . . ? N2 C6 C5 119.9(3) . . ? N3 C6 C5 128.3(2) . . ? N2 C7 C8 111.3(3) . . ? C7 C8 N3 105.8(2) . . ? C7 C8 C9 134.9(3) . . ? N3 C8 C9 119.2(3) . . ? C10 C9 C8 120.3(3) . . ? C9 C10 C11 120.7(3) . . ? C17 C11 C12 118.3(2) . . ? C17 C11 C10 121.5(3) . . ? C12 C11 C10 120.1(3) . . ? C20 C12 C11 119.7(3) . . ? C20 C12 N3 122.8(2) . . ? C11 C12 N3 117.3(2) . . ? C14 C13 C1 120.8(3) . . ? C13 C14 C15 120.2(3) . . ? C16 C15 C14 120.2(3) . . ? C15 C16 C2 120.6(3) . . ? C18 C17 C11 122.0(3) . . ? C17 C18 C19 118.9(3) . . ? C20 C19 C18 120.7(3) . . ? C19 C20 C12 120.1(2) . . ? _diffrn_measured_fraction_theta_max 0.860 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.133 _refine_diff_density_min -0.152 _refine_diff_density_rms 0.037 #===END data_Compound_3c_br2indzl _database_code_depnum_ccdc_archive 'CCDC 869442' #TrackingRef '- azaindolizine_ligands.cif' _audit_creation_method SHELXL-97 _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_cell_refinement ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_data_reduction ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H7 Br2 N3' _chemical_formula_weight 353.03 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' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/n 1' 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 12.464(5) _cell_length_b 3.9278(15) _cell_length_c 23.727(6) _cell_angle_alpha 90.00 _cell_angle_beta 100.62(3) _cell_angle_gamma 90.00 _cell_volume 1141.7(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 1593 _cell_measurement_theta_min 2.0112 _cell_measurement_theta_max 29.4349 _exptl_crystal_description needle _exptl_crystal_colour white _exptl_crystal_size_max 0.3195 _exptl_crystal_size_mid 0.1683 _exptl_crystal_size_min 0.0408 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.054 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 680 _exptl_absorpt_coefficient_mu 7.078 _exptl_absorpt_correction_type analytical _exptl_absorpt_correction_T_min 0.384 _exptl_absorpt_correction_T_max 0.746 _exptl_absorpt_process_details ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) ; _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 'SuperNova, Dual, Cu at zero, Atlas' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 10.4757 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4866 _diffrn_reflns_av_R_equivalents 0.0341 _diffrn_reflns_av_sigmaI/netI 0.0588 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -3 _diffrn_reflns_limit_k_max 5 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_theta_min 2.02 _diffrn_reflns_theta_max 29.50 _reflns_number_total 2608 _reflns_number_gt 1777 _reflns_threshold_expression >2sigma(I) _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0244P)^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 2608 _refine_ls_number_parameters 154 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0715 _refine_ls_R_factor_gt 0.0376 _refine_ls_wR_factor_ref 0.0751 _refine_ls_wR_factor_gt 0.0631 _refine_ls_goodness_of_fit_ref 0.986 _refine_ls_restrained_S_all 0.986 _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 Br1 Br 0.64096(3) -0.08708(11) 0.182972(16) 0.04037(14) Uani 1 1 d . . . Br2 Br 0.91740(4) -0.23952(11) 0.556892(18) 0.04788(16) Uani 1 1 d . . . N1 N 0.7103(3) -0.0029(8) 0.40590(13) 0.0383(8) Uani 1 1 d . . . N2 N 0.4439(3) 0.4001(9) 0.39602(14) 0.0421(8) Uani 1 1 d . . . N3 N 0.5180(2) 0.2203(7) 0.32296(12) 0.0286(7) Uani 1 1 d . . . C1 C 0.7947(3) -0.1080(10) 0.44560(15) 0.0376(10) Uani 1 1 d . . . H1 H 0.8548 -0.2038 0.4335 0.045 Uiso 1 1 calc R . . C2 C 0.7959(3) -0.0797(10) 0.50344(16) 0.0339(9) Uani 1 1 d . . . C3 C 0.7078(3) 0.0600(10) 0.52218(16) 0.0405(10) Uani 1 1 d . . . H3 H 0.7070 0.0792 0.5612 0.049 Uiso 1 1 calc R . . C4 C 0.6209(3) 0.1709(10) 0.48210(16) 0.0393(10) Uani 1 1 d . . . H4 H 0.5605 0.2690 0.4936 0.047 Uiso 1 1 calc R . . C5 C 0.6242(3) 0.1348(10) 0.42435(15) 0.0312(9) Uani 1 1 d . . . C6 C 0.5311(3) 0.2485(10) 0.38191(16) 0.0326(9) Uani 1 1 d . . . C7 C 0.3746(3) 0.4691(10) 0.34686(18) 0.0420(11) Uani 1 1 d . . . H7 H 0.3071 0.5740 0.3448 0.050 Uiso 1 1 calc R . . C8 C 0.4165(3) 0.3639(9) 0.29994(16) 0.0320(9) Uani 1 1 d . . . C9 C 0.3834(3) 0.3742(10) 0.23968(17) 0.0368(10) Uani 1 1 d . . . H9 H 0.3168 0.4718 0.2235 0.044 Uiso 1 1 calc R . . C10 C 0.4487(3) 0.2420(10) 0.20554(16) 0.0380(10) Uani 1 1 d . . . H10 H 0.4275 0.2489 0.1659 0.046 Uiso 1 1 calc R . . C11 C 0.5495(3) 0.0928(10) 0.23088(15) 0.0303(8) Uani 1 1 d . . . C12 C 0.5846(3) 0.0802(9) 0.28810(15) 0.0291(8) Uani 1 1 d . . . H12 H 0.6511 -0.0191 0.3037 0.035 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 Br1 0.0432(3) 0.0490(3) 0.0297(2) -0.00121(19) 0.00862(17) 0.0026(2) Br2 0.0521(3) 0.0492(3) 0.0360(3) 0.0025(2) -0.00869(19) 0.0067(2) N1 0.030(2) 0.054(2) 0.0293(18) -0.0042(15) 0.0009(14) 0.0069(16) N2 0.038(2) 0.053(2) 0.036(2) -0.0030(17) 0.0084(16) 0.0083(18) N3 0.0264(17) 0.0327(19) 0.0256(17) 0.0002(14) 0.0017(13) -0.0017(14) C1 0.033(2) 0.050(3) 0.029(2) -0.0036(19) 0.0033(17) 0.010(2) C2 0.039(2) 0.032(2) 0.029(2) 0.0011(18) 0.0001(17) 0.001(2) C3 0.052(3) 0.045(3) 0.024(2) -0.0010(18) 0.0080(19) -0.002(2) C4 0.041(3) 0.048(3) 0.031(2) -0.0047(18) 0.0115(18) 0.006(2) C5 0.029(2) 0.035(2) 0.029(2) -0.0004(17) 0.0051(16) 0.0006(18) C6 0.031(2) 0.037(2) 0.029(2) -0.0031(17) 0.0053(16) 0.0021(19) C7 0.030(2) 0.052(3) 0.042(3) -0.003(2) 0.0016(19) 0.013(2) C8 0.026(2) 0.030(2) 0.037(2) 0.0016(17) -0.0018(17) 0.0019(18) C9 0.032(2) 0.032(2) 0.042(3) 0.0038(19) -0.0046(18) 0.0006(19) C10 0.042(3) 0.040(3) 0.027(2) 0.0022(18) -0.0063(18) -0.005(2) C11 0.030(2) 0.032(2) 0.029(2) -0.0028(17) 0.0060(16) -0.0028(18) C12 0.026(2) 0.030(2) 0.029(2) -0.0006(17) 0.0009(16) -0.0021(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 Br1 C11 1.889(4) . ? Br2 C2 1.894(4) . ? N1 C1 1.341(4) . ? N1 C5 1.344(5) . ? N2 C6 1.335(5) . ? N2 C7 1.345(5) . ? N3 C6 1.383(4) . ? N3 C12 1.389(4) . ? N3 C8 1.401(4) . ? C1 C2 1.374(5) . ? C2 C3 1.372(5) . ? C3 C4 1.375(5) . ? C4 C5 1.386(5) . ? C5 C6 1.459(5) . ? C7 C8 1.377(5) . ? C8 C9 1.414(5) . ? C9 C10 1.353(5) . ? C10 C11 1.416(5) . ? C11 C12 1.348(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 C1 N1 C5 117.7(3) . . ? C6 N2 C7 107.2(3) . . ? C6 N3 C12 131.5(3) . . ? C6 N3 C8 107.0(3) . . ? C12 N3 C8 121.5(3) . . ? N1 C1 C2 122.6(4) . . ? C3 C2 C1 119.6(3) . . ? C3 C2 Br2 120.3(3) . . ? C1 C2 Br2 120.1(3) . . ? C2 C3 C4 118.6(4) . . ? C3 C4 C5 119.2(4) . . ? N1 C5 C4 122.3(3) . . ? N1 C5 C6 118.6(3) . . ? C4 C5 C6 119.1(3) . . ? N2 C6 N3 109.8(3) . . ? N2 C6 C5 123.0(3) . . ? N3 C6 C5 127.2(3) . . ? N2 C7 C8 111.2(4) . . ? C7 C8 N3 104.8(3) . . ? C7 C8 C9 136.5(4) . . ? N3 C8 C9 118.7(3) . . ? C10 C9 C8 119.9(4) . . ? C9 C10 C11 119.3(4) . . ? C12 C11 C10 122.7(3) . . ? C12 C11 Br1 118.2(3) . . ? C10 C11 Br1 119.1(3) . . ? C11 C12 N3 117.8(3) . . ? _diffrn_measured_fraction_theta_max 0.817 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.486 _refine_diff_density_min -0.503 _refine_diff_density_rms 0.100 #===END