data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Patrick Gamez' _publ_contact_author_email P.GAMEZ@CHEM.LEIDENUNIV.NL _publ_section_title ; Manganese(III)-mediated cyclodimerization of a hydrazinyl derivative generating an unprecedented 1,2,3,5,6-substituted verdazyl ring ; loop_ _publ_author_name 'Patrick Gamez' 'Jose Sanchez Costa' 'Ilpo Mutikainen' 'Sanjit Nayak' 'Roberta Pievo' 'Jan Reedijk' ; A.Robertazzi ; 'Olivier Roubeau' 'Jinkui Tang.' 'Simon J. Teat' # Attachment 'Compound_4.cif' data_cv2yel _database_code_depnum_ccdc_archive 'CCDC 711637' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C25 H22 N6 O3' _chemical_formula_sum 'C25 H22 N6 O3' _chemical_formula_weight 454.49 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/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 8.248(2) _cell_length_b 15.584(3) _cell_length_c 17.206(3) _cell_angle_alpha 90.00 _cell_angle_beta 95.15(3) _cell_angle_gamma 90.00 _cell_volume 2202.7(8) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 35597 _cell_measurement_theta_min 2.71 _cell_measurement_theta_max 27.50 _exptl_crystal_description block _exptl_crystal_colour yellow _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.30 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.370 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 952 _exptl_absorpt_coefficient_mu 0.094 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9724 _exptl_absorpt_correction_T_max 0.9724 _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type KappaCCD _diffrn_measurement_method \w-scan _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 35597 _diffrn_reflns_av_R_equivalents 0.0378 _diffrn_reflns_av_sigmaI/netI 0.0263 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 2.71 _diffrn_reflns_theta_max 27.55 _reflns_number_total 5039 _reflns_number_gt 3967 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 2002)' _computing_cell_refinement 'DirAx (Duisenberg 1992)' _computing_data_reduction 'COLLECT/EVAL (Nonius, 2002)' _computing_structure_solution 'SHELXS97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 1990)' _computing_publication_material 'SHELXTL (Sheldrick, 1990)' _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^)+(0.0417P)^2^+1.0490P] 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 0.0063(11) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 5039 _refine_ls_number_parameters 309 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0617 _refine_ls_R_factor_gt 0.0429 _refine_ls_wR_factor_ref 0.1031 _refine_ls_wR_factor_gt 0.0947 _refine_ls_goodness_of_fit_ref 1.044 _refine_ls_restrained_S_all 1.044 _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 0.64043(15) 0.38225(7) 0.32151(6) 0.0201(3) Uani 1 1 d . . . N2 N 0.57872(14) 0.34868(7) 0.25131(6) 0.0186(2) Uani 1 1 d . . . C3 C 0.63189(17) 0.37768(8) 0.18782(8) 0.0183(3) Uani 1 1 d . . . N4 N 0.73628(14) 0.44839(7) 0.18713(6) 0.0193(2) Uani 1 1 d . . . N5 N 0.73550(14) 0.50277(7) 0.25347(6) 0.0181(2) Uani 1 1 d . . . C6 C 0.75545(17) 0.45240(8) 0.32458(8) 0.0188(3) Uani 1 1 d . . . H6A H 0.7393 0.4898 0.3705 0.023 Uiso 1 1 calc R . . O7 O 0.91065(12) 0.41563(6) 0.33360(6) 0.0261(2) Uani 1 1 d . . . C8 C 1.0339(2) 0.47581(12) 0.35908(14) 0.0491(5) Uani 1 1 d . . . H8A H 1.1403 0.4473 0.3631 0.074 Uiso 1 1 calc R . . H8B H 1.0125 0.4985 0.4103 0.074 Uiso 1 1 calc R . . H8C H 1.0339 0.5230 0.3214 0.074 Uiso 1 1 calc R . . C11 C 0.55895(18) 0.36145(9) 0.38707(8) 0.0208(3) Uani 1 1 d . . . N12 N 0.61227(17) 0.40290(8) 0.45177(7) 0.0291(3) Uani 1 1 d . . . C13 C 0.5330(2) 0.38875(11) 0.51524(9) 0.0375(4) Uani 1 1 d . . . H13A H 0.5688 0.4186 0.5618 0.045 Uiso 1 1 calc R . . C14 C 0.4038(2) 0.33411(11) 0.51727(10) 0.0414(4) Uani 1 1 d . . . H14A H 0.3503 0.3269 0.5635 0.050 Uiso 1 1 calc R . . C15 C 0.3536(2) 0.28961(12) 0.44973(11) 0.0418(4) Uani 1 1 d . . . H15A H 0.2654 0.2503 0.4493 0.050 Uiso 1 1 calc R . . C16 C 0.4316(2) 0.30233(10) 0.38335(9) 0.0312(4) Uani 1 1 d . . . H16A H 0.3998 0.2719 0.3366 0.037 Uiso 1 1 calc R . . C21 C 0.88194(17) 0.44975(9) 0.14987(8) 0.0204(3) Uani 1 1 d . . . N22 N 0.95118(15) 0.52680(8) 0.14700(7) 0.0263(3) Uani 1 1 d . . . C23 C 1.0891(2) 0.53305(11) 0.11184(10) 0.0341(4) Uani 1 1 d . . . H23A H 1.1407 0.5875 0.1105 0.041 Uiso 1 1 calc R . . C24 C 1.1595(2) 0.46443(12) 0.07766(11) 0.0390(4) Uani 1 1 d . . . H24A H 1.2567 0.4714 0.0526 0.047 Uiso 1 1 calc R . . C25 C 1.0858(2) 0.38508(11) 0.08064(10) 0.0355(4) Uani 1 1 d . . . H25A H 1.1319 0.3366 0.0574 0.043 Uiso 1 1 calc R . . C26 C 0.94515(19) 0.37667(10) 0.11746(9) 0.0265(3) Uani 1 1 d . . . H26A H 0.8929 0.3226 0.1206 0.032 Uiso 1 1 calc R . . C31 C 0.56406(16) 0.34085(9) 0.11276(8) 0.0188(3) Uani 1 1 d . . . C32 C 0.50242(17) 0.25675(9) 0.10698(8) 0.0214(3) Uani 1 1 d . . . C33 C 0.43303(19) 0.22619(10) 0.03542(9) 0.0267(3) Uani 1 1 d . . . H33A H 0.3913 0.1694 0.0318 0.032 Uiso 1 1 calc R . . C34 C 0.42435(19) 0.27735(10) -0.03001(9) 0.0290(3) Uani 1 1 d . . . H34A H 0.3750 0.2561 -0.0782 0.035 Uiso 1 1 calc R . . C35 C 0.4875(2) 0.35976(10) -0.02577(8) 0.0286(3) Uani 1 1 d . . . H35A H 0.4832 0.3948 -0.0711 0.034 Uiso 1 1 calc R . . C36 C 0.55664(18) 0.39066(9) 0.04489(8) 0.0237(3) Uani 1 1 d . . . H36A H 0.6002 0.4471 0.0474 0.028 Uiso 1 1 calc R . . O37 O 0.50582(14) 0.20107(7) 0.16727(6) 0.0331(3) Uani 1 1 d . . . H37A H 0.5521 0.2242 0.2074 0.040 Uiso 1 1 calc R . . C41 C 0.60916(17) 0.56682(8) 0.24957(7) 0.0180(3) Uani 1 1 d . . . C42 C 0.65152(17) 0.64903(9) 0.22515(7) 0.0200(3) Uani 1 1 d . . . C43 C 0.54285(19) 0.71640(9) 0.23065(8) 0.0247(3) Uani 1 1 d . . . H43A H 0.5720 0.7726 0.2158 0.030 Uiso 1 1 calc R . . C44 C 0.39285(19) 0.70200(10) 0.25763(8) 0.0271(3) Uani 1 1 d . . . H44A H 0.3204 0.7487 0.2624 0.033 Uiso 1 1 calc R . . C45 C 0.34689(19) 0.62034(10) 0.27778(9) 0.0288(3) Uani 1 1 d . . . H45A H 0.2417 0.6105 0.2944 0.035 Uiso 1 1 calc R . . C46 C 0.45512(18) 0.55296(9) 0.27358(8) 0.0245(3) Uani 1 1 d . . . H46A H 0.4237 0.4967 0.2873 0.029 Uiso 1 1 calc R . . O47 O 0.79588(12) 0.66601(6) 0.19687(6) 0.0250(2) Uani 1 1 d . . . H47A H 0.8413 0.6197 0.1863 0.030 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 0.0257(6) 0.0184(6) 0.0162(5) -0.0003(4) 0.0023(5) -0.0046(5) N2 0.0227(6) 0.0160(5) 0.0171(5) -0.0010(4) 0.0011(4) -0.0007(5) C3 0.0195(7) 0.0148(6) 0.0206(7) -0.0005(5) 0.0023(5) 0.0018(5) N4 0.0245(6) 0.0160(5) 0.0180(5) -0.0037(4) 0.0061(5) -0.0022(5) N5 0.0238(6) 0.0145(5) 0.0163(5) -0.0019(4) 0.0036(4) -0.0001(5) C6 0.0224(7) 0.0154(6) 0.0186(6) 0.0001(5) 0.0022(5) -0.0010(5) O7 0.0220(5) 0.0197(5) 0.0359(6) 0.0013(4) -0.0020(4) 0.0003(4) C8 0.0282(9) 0.0342(10) 0.0814(15) 0.0037(10) -0.0135(9) -0.0074(8) C11 0.0252(7) 0.0171(6) 0.0204(7) 0.0041(5) 0.0044(5) 0.0037(6) N12 0.0419(8) 0.0264(7) 0.0193(6) 0.0014(5) 0.0047(5) -0.0013(6) C13 0.0605(12) 0.0317(9) 0.0217(8) 0.0016(6) 0.0112(7) 0.0040(8) C14 0.0588(12) 0.0350(9) 0.0345(9) 0.0092(7) 0.0265(8) 0.0054(9) C15 0.0413(10) 0.0404(10) 0.0462(10) 0.0076(8) 0.0180(8) -0.0086(8) C16 0.0322(9) 0.0323(8) 0.0297(8) 0.0020(6) 0.0068(7) -0.0064(7) C21 0.0212(7) 0.0230(7) 0.0173(6) 0.0007(5) 0.0032(5) 0.0000(6) N22 0.0265(7) 0.0250(6) 0.0285(7) -0.0014(5) 0.0086(5) -0.0042(5) C23 0.0284(9) 0.0361(9) 0.0391(9) 0.0020(7) 0.0110(7) -0.0084(7) C24 0.0251(9) 0.0503(11) 0.0442(10) 0.0031(8) 0.0170(7) 0.0019(8) C25 0.0319(9) 0.0388(9) 0.0373(9) -0.0011(7) 0.0120(7) 0.0110(7) C26 0.0280(8) 0.0245(7) 0.0277(8) -0.0004(6) 0.0058(6) 0.0037(6) C31 0.0189(7) 0.0185(7) 0.0193(6) -0.0022(5) 0.0027(5) 0.0019(5) C32 0.0203(7) 0.0220(7) 0.0217(7) 0.0000(5) 0.0011(5) -0.0001(6) C33 0.0264(8) 0.0251(7) 0.0284(8) -0.0064(6) 0.0005(6) -0.0043(6) C34 0.0308(8) 0.0347(8) 0.0206(7) -0.0067(6) -0.0018(6) 0.0020(7) C35 0.0363(9) 0.0301(8) 0.0192(7) 0.0011(6) 0.0014(6) 0.0041(7) C36 0.0295(8) 0.0200(7) 0.0220(7) -0.0007(5) 0.0040(6) 0.0021(6) O37 0.0473(7) 0.0247(6) 0.0255(6) 0.0032(4) -0.0063(5) -0.0156(5) C41 0.0235(7) 0.0160(6) 0.0144(6) -0.0022(5) 0.0007(5) 0.0008(5) C42 0.0255(7) 0.0204(7) 0.0135(6) -0.0014(5) -0.0017(5) -0.0032(6) C43 0.0347(8) 0.0162(7) 0.0222(7) -0.0006(5) -0.0022(6) 0.0001(6) C44 0.0312(8) 0.0247(7) 0.0247(7) -0.0025(6) -0.0022(6) 0.0075(6) C45 0.0241(8) 0.0307(8) 0.0322(8) -0.0011(6) 0.0057(6) 0.0030(6) C46 0.0268(8) 0.0208(7) 0.0264(7) 0.0015(6) 0.0053(6) -0.0019(6) O47 0.0293(6) 0.0169(5) 0.0294(5) 0.0001(4) 0.0058(4) -0.0040(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 N1 N2 1.3716(16) . ? N1 C11 1.4019(18) . ? N1 C6 1.4453(17) . ? N2 C3 1.2945(17) . ? C3 N4 1.3992(17) . ? C3 C31 1.4766(19) . ? N4 C21 1.4117(18) . ? N4 N5 1.4221(15) . ? N5 C41 1.4403(18) . ? N5 C6 1.4506(17) . ? C6 O7 1.3983(17) . ? C6 H6A 1.0000 . ? O7 C8 1.423(2) . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C11 N12 1.3274(19) . ? C11 C16 1.395(2) . ? N12 C13 1.341(2) . ? C13 C14 1.367(3) . ? C13 H13A 0.9500 . ? C14 C15 1.384(3) . ? C14 H14A 0.9500 . ? C15 C16 1.374(2) . ? C15 H15A 0.9500 . ? C16 H16A 0.9500 . ? C21 N22 1.3324(19) . ? C21 C26 1.390(2) . ? N22 C23 1.339(2) . ? C23 C24 1.374(2) . ? C23 H23A 0.9500 . ? C24 C25 1.381(3) . ? C24 H24A 0.9500 . ? C25 C26 1.377(2) . ? C25 H25A 0.9500 . ? C26 H26A 0.9500 . ? C31 C36 1.3990(19) . ? C31 C32 1.406(2) . ? C32 O37 1.3508(17) . ? C32 C33 1.394(2) . ? C33 C34 1.376(2) . ? C33 H33A 0.9500 . ? C34 C35 1.385(2) . ? C34 H34A 0.9500 . ? C35 C36 1.382(2) . ? C35 H35A 0.9500 . ? C36 H36A 0.9500 . ? O37 H37A 0.8400 . ? C41 C46 1.388(2) . ? C41 C42 1.4023(19) . ? C42 O47 1.3522(18) . ? C42 C43 1.389(2) . ? C43 C44 1.378(2) . ? C43 H43A 0.9500 . ? C44 C45 1.381(2) . ? C44 H44A 0.9500 . ? C45 C46 1.384(2) . ? C45 H45A 0.9500 . ? C46 H46A 0.9500 . ? O47 H47A 0.8400 . ? 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 N1 C11 116.98(11) . . ? N2 N1 C6 120.74(11) . . ? C11 N1 C6 120.39(11) . . ? C3 N2 N1 118.88(11) . . ? N2 C3 N4 122.50(12) . . ? N2 C3 C31 118.16(12) . . ? N4 C3 C31 118.93(12) . . ? C3 N4 C21 124.41(11) . . ? C3 N4 N5 114.54(10) . . ? C21 N4 N5 114.89(11) . . ? N4 N5 C41 115.53(11) . . ? N4 N5 C6 110.26(10) . . ? C41 N5 C6 116.18(11) . . ? O7 C6 N1 106.59(11) . . ? O7 C6 N5 110.41(11) . . ? N1 C6 N5 110.73(11) . . ? O7 C6 H6A 109.7 . . ? N1 C6 H6A 109.7 . . ? N5 C6 H6A 109.7 . . ? C6 O7 C8 112.70(12) . . ? O7 C8 H8A 109.5 . . ? O7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? O7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? N12 C11 C16 123.47(13) . . ? N12 C11 N1 114.56(13) . . ? C16 C11 N1 121.97(13) . . ? C11 N12 C13 117.00(14) . . ? N12 C13 C14 124.17(16) . . ? N12 C13 H13A 117.9 . . ? C14 C13 H13A 117.9 . . ? C13 C14 C15 117.77(15) . . ? C13 C14 H14A 121.1 . . ? C15 C14 H14A 121.1 . . ? C16 C15 C14 119.87(17) . . ? C16 C15 H15A 120.1 . . ? C14 C15 H15A 120.1 . . ? C15 C16 C11 117.64(16) . . ? C15 C16 H16A 121.2 . . ? C11 C16 H16A 121.2 . . ? N22 C21 C26 123.10(13) . . ? N22 C21 N4 114.54(12) . . ? C26 C21 N4 122.34(13) . . ? C21 N22 C23 117.82(13) . . ? N22 C23 C24 123.06(16) . . ? N22 C23 H23A 118.5 . . ? C24 C23 H23A 118.5 . . ? C23 C24 C25 118.47(15) . . ? C23 C24 H24A 120.8 . . ? C25 C24 H24A 120.8 . . ? C26 C25 C24 119.62(15) . . ? C26 C25 H25A 120.2 . . ? C24 C25 H25A 120.2 . . ? C25 C26 C21 117.93(15) . . ? C25 C26 H26A 121.0 . . ? C21 C26 H26A 121.0 . . ? C36 C31 C32 118.02(13) . . ? C36 C31 C3 119.95(12) . . ? C32 C31 C3 122.02(12) . . ? O37 C32 C33 115.93(13) . . ? O37 C32 C31 124.20(13) . . ? C33 C32 C31 119.87(13) . . ? C34 C33 C32 120.77(14) . . ? C34 C33 H33A 119.6 . . ? C32 C33 H33A 119.6 . . ? C33 C34 C35 120.16(14) . . ? C33 C34 H34A 119.9 . . ? C35 C34 H34A 119.9 . . ? C36 C35 C34 119.53(14) . . ? C36 C35 H35A 120.2 . . ? C34 C35 H35A 120.2 . . ? C35 C36 C31 121.63(14) . . ? C35 C36 H36A 119.2 . . ? C31 C36 H36A 119.2 . . ? C32 O37 H37A 109.5 . . ? C46 C41 C42 119.40(13) . . ? C46 C41 N5 123.79(12) . . ? C42 C41 N5 116.65(12) . . ? O47 C42 C43 118.10(12) . . ? O47 C42 C41 122.53(13) . . ? C43 C42 C41 119.37(13) . . ? C44 C43 C42 120.27(14) . . ? C44 C43 H43A 119.9 . . ? C42 C43 H43A 119.9 . . ? C43 C44 C45 120.63(14) . . ? C43 C44 H44A 119.7 . . ? C45 C44 H44A 119.7 . . ? C44 C45 C46 119.54(14) . . ? C44 C45 H45A 120.2 . . ? C46 C45 H45A 120.2 . . ? C45 C46 C41 120.62(14) . . ? C45 C46 H46A 119.7 . . ? C41 C46 H46A 119.7 . . ? C42 O47 H47A 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C11 N1 N2 C3 168.18(12) . . . . ? C6 N1 N2 C3 3.76(18) . . . . ? N1 N2 C3 N4 -7.32(19) . . . . ? N1 N2 C3 C31 -179.97(11) . . . . ? N2 C3 N4 C21 130.44(14) . . . . ? C31 C3 N4 C21 -56.96(18) . . . . ? N2 C3 N4 N5 -20.44(18) . . . . ? C31 C3 N4 N5 152.16(12) . . . . ? C3 N4 N5 C41 -84.69(14) . . . . ? C21 N4 N5 C41 121.58(13) . . . . ? C3 N4 N5 C6 49.53(15) . . . . ? C21 N4 N5 C6 -104.20(13) . . . . ? N2 N1 C6 O7 -94.12(14) . . . . ? C11 N1 C6 O7 101.99(14) . . . . ? N2 N1 C6 N5 26.00(16) . . . . ? C11 N1 C6 N5 -137.89(12) . . . . ? N4 N5 C6 O7 66.84(14) . . . . ? C41 N5 C6 O7 -159.27(11) . . . . ? N4 N5 C6 N1 -50.98(14) . . . . ? C41 N5 C6 N1 82.92(14) . . . . ? N1 C6 O7 C8 -163.55(13) . . . . ? N5 C6 O7 C8 76.11(16) . . . . ? N2 N1 C11 N12 -172.92(12) . . . . ? C6 N1 C11 N12 -8.44(18) . . . . ? N2 N1 C11 C16 6.6(2) . . . . ? C6 N1 C11 C16 171.06(13) . . . . ? C16 C11 N12 C13 -2.9(2) . . . . ? N1 C11 N12 C13 176.61(13) . . . . ? C11 N12 C13 C14 0.9(3) . . . . ? N12 C13 C14 C15 1.1(3) . . . . ? C13 C14 C15 C16 -1.1(3) . . . . ? C14 C15 C16 C11 -0.7(3) . . . . ? N12 C11 C16 C15 2.9(2) . . . . ? N1 C11 C16 C15 -176.61(15) . . . . ? C3 N4 C21 N22 171.10(13) . . . . ? N5 N4 C21 N22 -38.11(17) . . . . ? C3 N4 C21 C26 -7.6(2) . . . . ? N5 N4 C21 C26 143.23(13) . . . . ? C26 C21 N22 C23 -0.8(2) . . . . ? N4 C21 N22 C23 -179.43(13) . . . . ? C21 N22 C23 C24 1.3(2) . . . . ? N22 C23 C24 C25 -0.9(3) . . . . ? C23 C24 C25 C26 -0.1(3) . . . . ? C24 C25 C26 C21 0.6(2) . . . . ? N22 C21 C26 C25 -0.1(2) . . . . ? N4 C21 C26 C25 178.40(14) . . . . ? N2 C3 C31 C36 151.24(13) . . . . ? N4 C3 C31 C36 -21.68(19) . . . . ? N2 C3 C31 C32 -27.4(2) . . . . ? N4 C3 C31 C32 159.69(13) . . . . ? C36 C31 C32 O37 178.17(13) . . . . ? C3 C31 C32 O37 -3.2(2) . . . . ? C36 C31 C32 C33 -1.5(2) . . . . ? C3 C31 C32 C33 177.15(13) . . . . ? O37 C32 C33 C34 -179.53(14) . . . . ? C31 C32 C33 C34 0.2(2) . . . . ? C32 C33 C34 C35 1.2(2) . . . . ? C33 C34 C35 C36 -1.1(2) . . . . ? C34 C35 C36 C31 -0.3(2) . . . . ? C32 C31 C36 C35 1.6(2) . . . . ? C3 C31 C36 C35 -177.09(13) . . . . ? N4 N5 C41 C46 88.22(16) . . . . ? C6 N5 C41 C46 -43.26(18) . . . . ? N4 N5 C41 C42 -96.50(14) . . . . ? C6 N5 C41 C42 132.01(12) . . . . ? C46 C41 C42 O47 -176.15(12) . . . . ? N5 C41 C42 O47 8.35(19) . . . . ? C46 C41 C42 C43 4.54(19) . . . . ? N5 C41 C42 C43 -170.96(12) . . . . ? O47 C42 C43 C44 178.69(12) . . . . ? C41 C42 C43 C44 -2.0(2) . . . . ? C42 C43 C44 C45 -1.5(2) . . . . ? C43 C44 C45 C46 2.4(2) . . . . ? C44 C45 C46 C41 0.2(2) . . . . ? C42 C41 C46 C45 -3.7(2) . . . . ? N5 C41 C46 C45 171.48(13) . . . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 27.55 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 0.239 _refine_diff_density_min -0.230 _refine_diff_density_rms 0.045 # Attachment 'Revised_Compound_5.CIF' data_jk233 _database_code_depnum_ccdc_archive 'CCDC 713054' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H20 Mn N6 O2' _chemical_formula_weight 479.40 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C -0.0020 0.0020 '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 -0.0031 0.0040 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O -0.0041 0.0074 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.2237 0.8587 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M Pbcn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z+1/2' '-x, y, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z-1/2' 'x, -y, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 20.661(2) _cell_length_b 8.9103(10) _cell_length_c 11.1550(12) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2053.6(4) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 4155 _cell_measurement_theta_min 3.36 _cell_measurement_theta_max 33.26 _exptl_crystal_description needle _exptl_crystal_colour yellow _exptl_crystal_size_max 0.22 _exptl_crystal_size_mid 0.02 _exptl_crystal_size_min 0.01 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.551 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 988 _exptl_absorpt_coefficient_mu 0.949 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.83 _exptl_absorpt_correction_T_max 0.99 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.77490 _diffrn_radiation_type synchrotron _diffrn_radiation_source 'ALS beamline 11.3.1' _diffrn_radiation_monochromator 'silicon 111' _diffrn_measurement_device_type 'Bruker APEX II CCD diffractometer' _diffrn_measurement_method '\w rotation with narrow frames' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time . _diffrn_standards_decay_% . _diffrn_reflns_number 14462 _diffrn_reflns_av_R_equivalents 0.0530 _diffrn_reflns_av_sigmaI/netI 0.0416 _diffrn_reflns_limit_h_min -29 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 3.37 _diffrn_reflns_theta_max 33.56 _reflns_number_total 3113 _reflns_number_gt 2596 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SIR97 (Altomare, 1999)' _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. All non-hydrogens were refined anisotropically. All hydrogens were found in difference Fourier maps and placed geometricalli on their riding atom. ; _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^)+(0.0814P)^2^+0.4477P] 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 3113 _refine_ls_number_parameters 150 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0541 _refine_ls_R_factor_gt 0.0445 _refine_ls_wR_factor_ref 0.1274 _refine_ls_wR_factor_gt 0.1194 _refine_ls_goodness_of_fit_ref 1.043 _refine_ls_restrained_S_all 1.043 _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 0.5000 -0.05508(4) 0.2500 0.01939(12) Uani 1 2 d S . . N1 N 0.45011(6) -0.22856(16) 0.36386(12) 0.0228(3) Uani 1 1 d . . . C2 C 0.39301(8) -0.2931(2) 0.33714(16) 0.0294(3) Uani 1 1 d . . . H2A H 0.3734 -0.2693 0.2625 0.035 Uiso 1 1 calc R . . C3 C 0.36178(8) -0.3909(2) 0.41134(18) 0.0320(4) Uani 1 1 d . . . H3A H 0.3214 -0.4338 0.3891 0.038 Uiso 1 1 calc R . . C4 C 0.39061(9) -0.42606(19) 0.52039(17) 0.0298(4) Uani 1 1 d . . . H4A H 0.3700 -0.4939 0.5739 0.036 Uiso 1 1 calc R . . C5 C 0.44872(8) -0.36278(19) 0.55046(15) 0.0262(3) Uani 1 1 d . . . H5A H 0.4692 -0.3862 0.6243 0.031 Uiso 1 1 calc R . . C6 C 0.47719(7) -0.26231(17) 0.46904(14) 0.0212(3) Uani 1 1 d . . . N7 N 0.53516(6) -0.19730(15) 0.49615(12) 0.0224(3) Uani 1 1 d . . . H7A H 0.5559 -0.2197 0.5627 0.027 Uiso 1 1 calc R . . N8 N 0.55996(6) -0.09553(15) 0.41586(11) 0.0196(2) Uani 1 1 d . . . C9 C 0.61450(7) -0.03603(17) 0.44609(14) 0.0209(3) Uani 1 1 d . . . H9A H 0.6324 -0.0654 0.5209 0.025 Uiso 1 1 calc R . . C10 C 0.65040(7) 0.07074(17) 0.37645(14) 0.0202(3) Uani 1 1 d . . . C11 C 0.71115(7) 0.11208(19) 0.42241(15) 0.0250(3) Uani 1 1 d . . . H11A H 0.7259 0.0662 0.4942 0.030 Uiso 1 1 calc R . . C12 C 0.74975(8) 0.2161(2) 0.36742(16) 0.0293(3) Uani 1 1 d . . . H12A H 0.7907 0.2419 0.4003 0.035 Uiso 1 1 calc R . . C13 C 0.72794(9) 0.2832(2) 0.26274(16) 0.0297(4) Uani 1 1 d . . . H13A H 0.7541 0.3561 0.2237 0.036 Uiso 1 1 calc R . . C14 C 0.66871(8) 0.24509(19) 0.21496(15) 0.0258(3) Uani 1 1 d . . . H14A H 0.6550 0.2923 0.1430 0.031 Uiso 1 1 calc R . . C15 C 0.62781(8) 0.13845(18) 0.26928(14) 0.0209(3) Uani 1 1 d . . . O16 O 0.57104(6) 0.10930(14) 0.22294(10) 0.0239(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 Mn1 0.01425(17) 0.0269(2) 0.01706(19) 0.000 -0.00322(10) 0.000 N1 0.0175(6) 0.0297(7) 0.0211(6) -0.0005(5) -0.0023(4) -0.0021(5) C2 0.0215(7) 0.0375(9) 0.0293(8) -0.0010(7) -0.0046(6) -0.0044(6) C3 0.0216(7) 0.0344(9) 0.0401(10) -0.0039(7) 0.0014(7) -0.0069(6) C4 0.0260(8) 0.0283(8) 0.0352(9) 0.0007(7) 0.0075(7) -0.0032(6) C5 0.0266(7) 0.0284(7) 0.0238(7) 0.0025(6) 0.0024(6) 0.0003(6) C6 0.0182(6) 0.0252(7) 0.0202(7) -0.0025(5) 0.0005(5) 0.0010(5) N7 0.0195(6) 0.0305(7) 0.0170(6) 0.0039(5) -0.0026(4) -0.0026(5) N8 0.0155(5) 0.0257(6) 0.0176(6) 0.0009(5) -0.0011(4) -0.0005(5) C9 0.0162(6) 0.0277(7) 0.0186(6) -0.0001(5) -0.0029(5) 0.0022(5) C10 0.0147(6) 0.0256(7) 0.0202(7) -0.0023(5) -0.0016(5) 0.0009(5) C11 0.0176(6) 0.0323(8) 0.0250(7) -0.0018(6) -0.0043(5) 0.0003(6) C12 0.0172(6) 0.0383(9) 0.0323(8) -0.0021(7) -0.0037(6) -0.0042(6) C13 0.0232(8) 0.0349(9) 0.0309(8) 0.0007(7) 0.0026(6) -0.0077(7) C14 0.0237(7) 0.0320(8) 0.0216(7) 0.0015(6) -0.0014(6) -0.0044(6) C15 0.0168(6) 0.0264(7) 0.0194(6) -0.0028(5) -0.0021(5) 0.0000(5) O16 0.0190(5) 0.0317(6) 0.0210(5) 0.0031(4) -0.0061(4) -0.0045(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 O16 2.0954(12) . ? Mn1 O16 2.0954(12) 3_655 ? Mn1 N1 2.2505(14) 3_655 ? Mn1 N1 2.2505(14) . ? Mn1 N8 2.2556(13) . ? Mn1 N8 2.2556(13) 3_655 ? N1 C6 1.334(2) . ? N1 C2 1.346(2) . ? C2 C3 1.364(3) . ? C2 H2A 0.9500 . ? C3 C4 1.390(3) . ? C3 H3A 0.9500 . ? C4 C5 1.368(2) . ? C4 H4A 0.9500 . ? C5 C6 1.404(2) . ? C5 H5A 0.9500 . ? C6 N7 1.364(2) . ? N7 N8 1.3737(18) . ? N7 H7A 0.8800 . ? N8 C9 1.2902(18) . ? C9 C10 1.435(2) . ? C9 H9A 0.9500 . ? C10 C11 1.405(2) . ? C10 C15 1.418(2) . ? C11 C12 1.368(2) . ? C11 H11A 0.9500 . ? C12 C13 1.387(3) . ? C12 H12A 0.9500 . ? C13 C14 1.378(2) . ? C13 H13A 0.9500 . ? C14 C15 1.409(2) . ? C14 H14A 0.9500 . ? C15 O16 1.3079(18) . ? 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 O16 Mn1 O16 91.30(7) . 3_655 ? O16 Mn1 N1 94.47(5) . 3_655 ? O16 Mn1 N1 151.91(5) 3_655 3_655 ? O16 Mn1 N1 151.91(5) . . ? O16 Mn1 N1 94.47(5) 3_655 . ? N1 Mn1 N1 93.24(7) 3_655 . ? O16 Mn1 N8 81.09(4) . . ? O16 Mn1 N8 112.22(5) 3_655 . ? N1 Mn1 N8 95.83(5) 3_655 . ? N1 Mn1 N8 71.27(5) . . ? O16 Mn1 N8 112.22(5) . 3_655 ? O16 Mn1 N8 81.09(4) 3_655 3_655 ? N1 Mn1 N8 71.27(5) 3_655 3_655 ? N1 Mn1 N8 95.83(5) . 3_655 ? N8 Mn1 N8 161.61(7) . 3_655 ? C6 N1 C2 117.78(14) . . ? C6 N1 Mn1 117.32(10) . . ? C2 N1 Mn1 124.75(11) . . ? N1 C2 C3 123.60(17) . . ? N1 C2 H2A 118.2 . . ? C3 C2 H2A 118.2 . . ? C2 C3 C4 118.17(16) . . ? C2 C3 H3A 120.9 . . ? C4 C3 H3A 120.9 . . ? C5 C4 C3 119.85(16) . . ? C5 C4 H4A 120.1 . . ? C3 C4 H4A 120.1 . . ? C4 C5 C6 118.15(16) . . ? C4 C5 H5A 120.9 . . ? C6 C5 H5A 120.9 . . ? N1 C6 N7 117.87(14) . . ? N1 C6 C5 122.45(14) . . ? N7 C6 C5 119.67(14) . . ? C6 N7 N8 117.59(12) . . ? C6 N7 H7A 121.2 . . ? N8 N7 H7A 121.2 . . ? C9 N8 N7 115.25(13) . . ? C9 N8 Mn1 128.93(11) . . ? N7 N8 Mn1 115.81(9) . . ? N8 C9 C10 125.63(14) . . ? N8 C9 H9A 117.2 . . ? C10 C9 H9A 117.2 . . ? C11 C10 C15 119.35(14) . . ? C11 C10 C9 115.98(14) . . ? C15 C10 C9 124.63(13) . . ? C12 C11 C10 122.33(15) . . ? C12 C11 H11A 118.8 . . ? C10 C11 H11A 118.8 . . ? C11 C12 C13 118.70(15) . . ? C11 C12 H12A 120.6 . . ? C13 C12 H12A 120.6 . . ? C14 C13 C12 120.52(16) . . ? C14 C13 H13A 119.7 . . ? C12 C13 H13A 119.7 . . ? C13 C14 C15 122.20(16) . . ? C13 C14 H14A 118.9 . . ? C15 C14 H14A 118.9 . . ? O16 C15 C14 120.12(14) . . ? O16 C15 C10 122.95(14) . . ? C14 C15 C10 116.89(14) . . ? C15 O16 Mn1 135.24(10) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 33.56 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.922 _refine_diff_density_min -0.512 _refine_diff_density_rms 0.086