# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2005 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Prof M Bryce' _publ_contact_author_address ; Department of Chemistry University of Durham South Road DURHAM DH1 3LE ; _publ_contact_author_email M.R.BRYCE@DURHAM.AC.UK _publ_section_title ; A versatile synthesis of pyrazolo[3,4-c]isoquinoline derivatives by reaction of 4-aryl-5-aminopyrazoles with aryl/heteroaryl aldehydes: the effect of the heterocycle on the reaction pathways ; loop_ _publ_author_name 'M. Bryce' 'Andrei S. Batsanov' 'Natalya M. Bogdan' 'Sergei L. Bogza' 'Konstantin I. Kobrakov' ; S.B.Lyubchik ; 'Anna A. Malienko' 'Igor F. Perepichka' 'Sergei Yu. Sujkov' data_(10Dj) _database_code_depnum_ccdc_archive 'CCDC 232595' _audit_creation_method SHELXL-97 _chemical_name_systematic ; 1-Methyl-3-phenyl-5-(thienyl-2)-7,8-dimethoxypyrazolo[3,4]isoquinoline ; _chemical_name_common ;1-Methyl-3-phenyl-5-(thienyl-2)-7,8- dimethoxypyrazolo(3,4)isoquinoline ; _chemical_melting_point '209.5--210 \% C' _chemical_formula_moiety 'C23 H19 N3 O2 S' _chemical_formula_sum 'C23 H19 N3 O2 S' _chemical_formula_weight 401.47 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pca2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' 'x+1/2, -y, z' '-x+1/2, y, z+1/2' _cell_length_a 22.845(4) _cell_length_b 11.858(2) _cell_length_c 7.188(1) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1947.2(5) _cell_formula_units_Z 4 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used 686 _cell_measurement_theta_min 12 _cell_measurement_theta_max 25 _exptl_crystal_description prism _exptl_crystal_colour 'light brown' _exptl_crystal_size_max 0.33 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.361 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 840 _exptl_absorpt_coefficient_mu 0.190 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist -1.00 0.00 0.00 0.0400 1.00 0.00 0.00 0.0400 0.00 1.00 0.00 0.0750 0.00 -1.00 0.00 0.0750 1.00 0.00 1.00 0.1400 -1.00 0.00 -1.00 0.1400 _exptl_special_details ; The data collection nominally covered over a hemisphere of reciprocal space, by a combination of 4 sets of exposures; each set had a different \f and/or 2\q angles and each exposure (20 s) covered 0.3\% in \w. Crystal decay was monitored by repeating 50 initial frames at the end of data collection and comparing 156 duplicate reflections. Crystal to detector distance 4.53 cm. ; _diffrn_ambient_temperature 123(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 'SMART 1K CCD area detector' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 8 _diffrn_reflns_number 13783 _diffrn_reflns_av_R_equivalents 0.0480 _diffrn_reflns_av_sigmaI/netI 0.0501 _diffrn_reflns_limit_h_min -29 _diffrn_reflns_limit_h_max 29 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 1.93 _diffrn_reflns_theta_max 27.56 _reflns_number_total 4490 _reflns_number_gt 3735 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'SMART version 5.054 (Bruker, 1998)' _computing_cell_refinement 'SMART version 5.054 (Bruker, 1998)' _computing_data_reduction 'SAINT version 6.01 (Bruker, 1999)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL version 5.10 (Bruker, 1997)' _computing_publication_material 'SHELXTL version 5.10 (Bruker, 1997)' _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. ; _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^)+(0.0422P)^2^] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.02(7) _refine_ls_number_reflns 4490 _refine_ls_number_parameters 271 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0528 _refine_ls_R_factor_gt 0.0392 _refine_ls_wR_factor_ref 0.0847 _refine_ls_wR_factor_gt 0.0797 _refine_ls_goodness_of_fit_ref 1.015 _refine_ls_restrained_S_all 1.015 _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 S S 0.46793(2) 0.50811(4) 0.44862(9) 0.02268(12) Uani 1 1 d . . . O1 O 0.14273(6) 0.74403(11) 0.3812(2) 0.0229(3) Uani 1 1 d . . . O2 O 0.23732(5) 0.85657(10) 0.4524(2) 0.0227(3) Uani 1 1 d . . . N1 N 0.36562(7) 0.42059(13) 0.2429(2) 0.0186(4) Uani 1 1 d . . . N2 N 0.31067(7) 0.25164(13) 0.1756(3) 0.0200(4) Uani 1 1 d . . . N3 N 0.25285(8) 0.22000(13) 0.1601(2) 0.0203(4) Uani 1 1 d . . . C1 C 0.19373(9) 0.68581(17) 0.3586(3) 0.0189(4) Uani 1 1 d . . . C2 C 0.24553(9) 0.74783(15) 0.3959(3) 0.0182(4) Uani 1 1 d . . . C3 C 0.29884(9) 0.69741(17) 0.3733(3) 0.0188(4) Uani 1 1 d . . . H3 H 0.3333 0.7393 0.3984 0.023 Uiso 1 1 d R . . C4 C 0.30380(8) 0.58371(16) 0.3133(3) 0.0167(4) Uani 1 1 d . . . C5 C 0.25153(9) 0.52150(15) 0.2820(3) 0.0169(4) Uani 1 1 d . . . C6 C 0.19673(9) 0.57504(16) 0.3041(3) 0.0184(4) Uani 1 1 d . . . H6 H 0.1618 0.5342 0.2810 0.022 Uiso 1 1 d R . . C7 C 0.25833(8) 0.40574(15) 0.2332(3) 0.0179(4) Uani 1 1 d . . . C8 C 0.31509(9) 0.36426(15) 0.2199(3) 0.0182(4) Uani 1 1 d . . . C9 C 0.35970(8) 0.52892(16) 0.2895(3) 0.0172(4) Uani 1 1 d . . . C10 C 0.22142(9) 0.31156(16) 0.1943(3) 0.0188(4) Uani 1 1 d . . . C11 C 0.35567(9) 0.16955(16) 0.1525(3) 0.0204(4) Uani 1 1 d . . . C12 C 0.34694(9) 0.08292(16) 0.0257(3) 0.0254(5) Uani 1 1 d . . . H12 H 0.3126 0.0807 -0.0482 0.030 Uiso 1 1 d R . . C13 C 0.38941(10) -0.00057(18) 0.0087(3) 0.0318(6) Uani 1 1 d . . . H13 H 0.3837 -0.0607 -0.0763 0.038 Uiso 1 1 d R . . C14 C 0.43978(10) 0.00336(19) 0.1145(4) 0.0318(5) Uani 1 1 d . . . H14 H 0.4684 -0.0541 0.1031 0.038 Uiso 1 1 d R . . C15 C 0.44825(10) 0.09188(18) 0.2375(3) 0.0305(5) Uani 1 1 d . . . H15 H 0.4832 0.0955 0.3084 0.037 Uiso 1 1 d R . . C16 C 0.40631(9) 0.17499(17) 0.2579(3) 0.0259(5) Uani 1 1 d . . . H16 H 0.4121 0.2350 0.3431 0.031 Uiso 1 1 d R . . C17 C 0.15600(9) 0.30476(16) 0.1954(3) 0.0216(4) Uani 1 1 d . . . H171 H 0.14391(17) 0.2290(9) 0.1623(17) 0.027(3) Uiso 1 1 d R . . H172 H 0.1402(2) 0.3579(10) 0.1062(16) 0.027(3) Uiso 1 1 d R . . H173 H 0.14153(19) 0.3229(10) 0.3186(15) 0.027(3) Uiso 1 1 d R . . C18 C 0.08960(9) 0.68803(18) 0.3289(3) 0.0263(5) Uani 1 1 d . . . H181 H 0.0910(2) 0.6692(10) 0.1985(18) 0.031(4) Uiso 1 1 d R . . H182 H 0.0568(4) 0.7372(8) 0.3520(17) 0.031(4) Uiso 1 1 d R . . H183 H 0.0852(3) 0.6200(11) 0.4012(16) 0.031(4) Uiso 1 1 d R . . C19 C 0.28899(9) 0.92227(17) 0.4844(3) 0.0283(6) Uani 1 1 d . . . H191 H 0.3130(5) 0.8858(8) 0.581(2) 0.042(4) Uiso 1 1 d R . . H192 H 0.27779(17) 0.9985(11) 0.526(2) 0.042(4) Uiso 1 1 d R . . H193 H 0.3117(4) 0.9276(10) 0.3682(16) 0.042(4) Uiso 1 1 d R . . C20 C 0.41574(9) 0.58619(17) 0.3300(3) 0.0196(4) Uani 1 1 d . . . C21 C 0.43574(9) 0.69356(16) 0.2986(3) 0.0219(4) Uani 1 1 d . . . H21 H 0.4138 0.7495 0.2352 0.026 Uiso 1 1 d R . . C22 C 0.49275(9) 0.71233(18) 0.3711(3) 0.0246(5) Uani 1 1 d . . . H22 H 0.5131 0.7817 0.3601 0.030 Uiso 1 1 d R . . C23 C 0.51506(8) 0.61968(17) 0.4581(3) 0.0250(4) Uani 1 1 d . . . H23 H 0.5522 0.6175 0.5168 0.030 Uiso 1 1 d 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 S 0.0180(2) 0.0234(2) 0.0266(2) 0.0006(2) -0.0020(3) 0.0020(2) O1 0.0163(7) 0.0201(7) 0.0323(8) -0.0060(6) -0.0006(6) 0.0022(6) O2 0.0197(7) 0.0161(6) 0.0325(8) -0.0067(7) -0.0017(8) 0.0002(5) N1 0.0188(8) 0.0189(9) 0.0181(8) 0.0004(7) 0.0024(7) -0.0004(7) N2 0.0185(8) 0.0162(8) 0.0252(9) -0.0013(7) 0.0006(7) 0.0002(7) N3 0.0207(8) 0.0198(8) 0.0205(10) -0.0007(7) 0.0020(8) -0.0022(8) C1 0.0190(10) 0.0204(10) 0.0172(10) 0.0009(8) 0.0003(8) 0.0037(8) C2 0.0223(10) 0.0165(10) 0.0157(10) 0.0008(7) -0.0017(8) 0.0007(8) C3 0.0179(9) 0.0193(10) 0.0192(10) -0.0016(8) -0.0024(8) -0.0030(8) C4 0.0175(9) 0.0193(10) 0.0134(9) 0.0009(8) -0.0007(8) 0.0019(8) C5 0.0179(9) 0.0195(9) 0.0134(9) 0.0011(8) -0.0006(8) -0.0005(8) C6 0.0185(9) 0.0207(10) 0.0161(10) 0.0007(8) -0.0015(8) -0.0018(8) C7 0.0199(11) 0.0174(9) 0.0163(10) 0.0015(8) 0.0015(8) -0.0009(8) C8 0.0216(10) 0.0162(9) 0.0169(10) -0.0006(8) 0.0005(8) 0.0012(8) C9 0.0199(10) 0.0161(9) 0.0156(10) 0.0024(7) 0.0010(8) -0.0007(8) C10 0.0213(11) 0.0182(10) 0.0168(10) 0.0013(8) -0.0007(9) -0.0020(8) C11 0.0223(10) 0.0159(10) 0.0231(11) 0.0042(8) 0.0075(9) 0.0009(8) C12 0.0239(11) 0.0201(11) 0.0322(12) -0.0032(9) 0.0006(10) -0.0039(9) C13 0.0347(12) 0.0176(10) 0.0430(15) -0.0083(10) 0.0093(11) -0.0008(10) C14 0.0318(13) 0.0205(11) 0.0431(14) 0.0038(10) 0.0105(11) 0.0075(10) C15 0.0273(12) 0.0301(12) 0.0341(12) 0.0025(11) -0.0014(10) 0.0070(10) C16 0.0260(11) 0.0245(11) 0.0272(12) -0.0029(9) -0.0003(9) 0.0016(9) C17 0.0217(11) 0.0193(10) 0.0237(11) -0.0002(8) -0.0009(9) -0.0025(9) C18 0.0186(10) 0.0281(12) 0.0322(13) -0.0089(9) -0.0040(9) 0.0027(9) C19 0.0248(11) 0.0179(10) 0.0420(16) -0.0071(9) -0.0033(10) 0.0003(9) C20 0.0193(10) 0.0227(10) 0.0168(10) -0.0024(8) -0.0010(8) 0.0043(9) C21 0.0218(10) 0.0219(11) 0.0219(10) -0.0004(9) 0.0010(9) 0.0000(9) C22 0.0230(10) 0.0248(11) 0.0260(11) -0.0021(9) 0.0005(9) -0.0040(9) C23 0.0171(9) 0.0335(11) 0.0243(10) -0.0052(10) -0.0018(10) -0.0030(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 S C23 1.707(2) . ? S C20 1.734(2) . ? O1 C1 1.364(2) . ? O1 C18 1.434(2) . ? O2 C2 1.365(2) . ? O2 C19 1.433(2) . ? N1 C9 1.334(2) . ? N1 C8 1.344(2) . ? N2 C8 1.377(2) . ? N2 N3 1.378(2) . ? N2 C11 1.426(3) . ? N3 C10 1.325(2) . ? C1 C6 1.373(3) . ? C1 C2 1.419(3) . ? C2 C3 1.366(3) . ? C3 C4 1.420(3) . ? C4 C5 1.422(3) . ? C4 C9 1.443(3) . ? C5 C6 1.413(3) . ? C5 C7 1.425(3) . ? C7 C8 1.390(3) . ? C7 C10 1.427(3) . ? C9 C20 1.478(3) . ? C10 C17 1.497(3) . ? C11 C16 1.385(3) . ? C11 C12 1.388(3) . ? C12 C13 1.392(3) . ? C13 C14 1.380(3) . ? C14 C15 1.386(3) . ? C15 C16 1.382(3) . ? C20 C21 1.371(3) . ? C21 C22 1.420(3) . ? C22 C23 1.363(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 C23 S C20 92.27(10) . . ? C1 O1 C18 117.24(15) . . ? C2 O2 C19 116.63(15) . . ? C9 N1 C8 114.98(17) . . ? C8 N2 N3 110.68(16) . . ? C8 N2 C11 129.53(17) . . ? N3 N2 C11 119.75(16) . . ? C10 N3 N2 106.35(15) . . ? O1 C1 C6 124.12(18) . . ? O1 C1 C2 115.33(17) . . ? C6 C1 C2 120.56(18) . . ? O2 C2 C3 124.84(18) . . ? O2 C2 C1 115.54(17) . . ? C3 C2 C1 119.62(17) . . ? C2 C3 C4 121.51(18) . . ? C3 C4 C5 118.28(17) . . ? C3 C4 C9 122.29(17) . . ? C5 C4 C9 119.40(17) . . ? C6 C5 C4 119.56(17) . . ? C6 C5 C7 123.85(18) . . ? C4 C5 C7 116.57(17) . . ? C1 C6 C5 120.42(18) . . ? C8 C7 C5 117.35(17) . . ? C8 C7 C10 105.11(16) . . ? C5 C7 C10 137.53(19) . . ? N1 C8 N2 125.01(18) . . ? N1 C8 C7 128.08(17) . . ? N2 C8 C7 106.91(17) . . ? N1 C9 C4 123.58(18) . . ? N1 C9 C20 113.82(17) . . ? C4 C9 C20 122.42(17) . . ? N3 C10 C7 110.95(17) . . ? N3 C10 C17 119.87(17) . . ? C7 C10 C17 129.13(18) . . ? C16 C11 C12 120.94(19) . . ? C16 C11 N2 120.48(19) . . ? C12 C11 N2 118.56(19) . . ? C11 C12 C13 118.9(2) . . ? C14 C13 C12 120.6(2) . . ? C13 C14 C15 119.6(2) . . ? C16 C15 C14 120.7(2) . . ? C15 C16 C11 119.2(2) . . ? C21 C20 C9 133.05(18) . . ? C21 C20 S 110.33(15) . . ? C9 C20 S 116.57(14) . . ? C20 C21 C22 113.00(19) . . ? C23 C22 C21 112.64(19) . . ? C22 C23 S 111.74(16) . . ? 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 C18 O1 C1 C2 174.48(17) . . . . ? O1 C1 C2 O2 1.1(2) . . . . ? C1 C2 O2 C19 -177.80(18) . . . . ? N1 C9 C20 S -38.4(2) . . . . ? N3 N2 C11 C12 34.3(3) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 27.56 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.207 _refine_diff_density_min -0.278 _refine_diff_density_rms 0.046 #===========================================END data_(11D) _database_code_depnum_ccdc_archive 'CCDC 232596' _audit_creation_method SHELXL-97 _chemical_name_systematic ; 1-methyl-3-phenyl-7,8-dimethoxypyrazolo[3,4-c]isoquinoline, acetonitile solvate ; _chemical_name_common ;1-methyl-3-phenyl-7,8-dimethoxypyrazolo(3,4-c)isoquinoline, acetonitile solvate ; _chemical_melting_point '166--166.5 \% C' _chemical_formula_moiety 'C19 H17 N3 O2,C2 H3 N' _chemical_formula_sum 'C21 H20 N4 O2' _chemical_formula_weight 360.41 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 Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.086(1) _cell_length_b 10.791(3) _cell_length_c 12.850(2) _cell_angle_alpha 104.16(2) _cell_angle_beta 105.87(2) _cell_angle_gamma 95.86(1) _cell_volume 901.2(3) _cell_formula_units_Z 2 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 917 _cell_measurement_theta_min 12.0 _cell_measurement_theta_max 26.0 _exptl_crystal_description trapetzoid _exptl_crystal_colour colourless _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.328 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 380 _exptl_absorpt_coefficient_mu 0.088 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.9490 _exptl_absorpt_correction_T_max 0.9895 _exptl_absorpt_process_details 'XPREP (SHELXTL), R(int)=0.039 before correction' loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist 0.00 -1.00 1.00 0.0700 0.00 1.00 -1.00 0.0700 0.00 0.00 1.00 0.0600 0.00 0.00 -1.00 0.0600 -1.00 0.00 1.00 0.2800 1.00 0.00 1.00 0.2800 _exptl_special_details ; The data collection nominally covered full sphere of reciprocal space, by a combination of 5 sets of \w scans; each set at different \f and/or 2\q angles and each scan (10 sec exposure) covering 0.3\% in \w. Crystal to detector distance 4.4 cm. Crystal decay was monitored by repeating 50 initial frames at the end of data collection and comparing 64 duplicate reflections. ; _diffrn_ambient_temperature 120(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 'SMART 1K CCD area detector' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 8 _diffrn_reflns_number 10258 _diffrn_reflns_av_R_equivalents 0.0326 _diffrn_reflns_av_sigmaI/netI 0.0385 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.72 _diffrn_reflns_theta_max 27.54 _reflns_number_total 4128 _reflns_number_gt 2988 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'SMART version 5.049 (Bruker, 1997)' _computing_cell_refinement 'SMART version 5.049 (Bruker, 1997)' _computing_data_reduction 'SAINT version 5.00 (Bruker, 1998)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL version 5.10 (Bruker, 1997)' _computing_publication_material 'SHELXTL version 5.10 (Bruker, 1997)' _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. ; _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^)+(0.0523P)^2^+0.1401P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4128 _refine_ls_number_parameters 324 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0653 _refine_ls_R_factor_gt 0.0404 _refine_ls_wR_factor_ref 0.1050 _refine_ls_wR_factor_gt 0.0951 _refine_ls_goodness_of_fit_ref 1.024 _refine_ls_restrained_S_all 1.024 _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 O1 O 0.26383(15) 0.80985(9) 0.41678(8) 0.0246(2) Uani 1 1 d . . . O2 O 0.25986(15) 0.62183(9) 0.25037(8) 0.0251(2) Uani 1 1 d . . . N1 N 0.24487(17) 0.28036(11) 0.56571(10) 0.0202(3) Uani 1 1 d . . . N2 N 0.23851(17) 0.37579(10) 0.75689(9) 0.0193(3) Uani 1 1 d . . . N3 N 0.23686(17) 0.49667(10) 0.82351(10) 0.0204(3) Uani 1 1 d . . . N4 N 0.3137(2) 1.12121(14) 0.22088(13) 0.0411(4) Uani 1 1 d . . . C1 C 0.2588(2) 0.69227(13) 0.43823(12) 0.0200(3) Uani 1 1 d . . . C2 C 0.25868(19) 0.58726(13) 0.34553(11) 0.0202(3) Uani 1 1 d . . . C3 C 0.25811(19) 0.46446(13) 0.35749(12) 0.0195(3) Uani 1 1 d . . . H3 H 0.265(2) 0.3938(15) 0.2973(13) 0.022(4) Uiso 1 1 d . . . C4 C 0.25252(19) 0.44106(13) 0.46066(11) 0.0184(3) Uani 1 1 d . . . C5 C 0.24965(18) 0.54479(12) 0.55177(11) 0.0182(3) Uani 1 1 d . . . C6 C 0.25491(19) 0.67144(13) 0.53888(12) 0.0192(3) Uani 1 1 d . . . H6 H 0.261(2) 0.7444(14) 0.6013(13) 0.020(4) Uiso 1 1 d . . . C7 C 0.24434(19) 0.51134(12) 0.65145(11) 0.0177(3) Uani 1 1 d . . . C8 C 0.24208(19) 0.38179(13) 0.65144(11) 0.0185(3) Uani 1 1 d . . . C9 C 0.25027(19) 0.31329(13) 0.47384(12) 0.0199(3) Uani 1 1 d . . . H9 H 0.253(2) 0.2440(13) 0.4089(12) 0.014(3) Uiso 1 1 d . . . C10 C 0.23892(19) 0.57750(13) 0.76064(11) 0.0191(3) Uani 1 1 d . . . C11 C 0.2412(2) 0.26979(13) 0.80391(12) 0.0197(3) Uani 1 1 d . . . C12 C 0.3011(2) 0.29575(14) 0.92108(12) 0.0242(3) Uani 1 1 d . . . H12 H 0.348(2) 0.3868(16) 0.9691(14) 0.031(4) Uiso 1 1 d . . . C13 C 0.2971(2) 0.19338(14) 0.96854(13) 0.0277(3) Uani 1 1 d . . . H13 H 0.338(2) 0.2134(16) 1.0490(15) 0.035(5) Uiso 1 1 d . . . C14 C 0.2382(2) 0.06618(15) 0.90100(14) 0.0283(3) Uani 1 1 d . . . H14 H 0.239(2) -0.0046(16) 0.9350(14) 0.033(4) Uiso 1 1 d . . . C15 C 0.1823(2) 0.04155(14) 0.78454(13) 0.0274(3) Uani 1 1 d . . . H15 H 0.142(2) -0.0478(16) 0.7338(14) 0.035(4) Uiso 1 1 d . . . C16 C 0.1820(2) 0.14217(13) 0.73534(13) 0.0234(3) Uani 1 1 d . . . H16 H 0.140(2) 0.1247(14) 0.6541(14) 0.027(4) Uiso 1 1 d . . . C17 C 0.2282(2) 0.71667(13) 0.80839(13) 0.0230(3) Uani 1 1 d . . . H171 H 0.344(2) 0.7779(15) 0.8058(13) 0.031(4) Uiso 1 1 d . . . H172 H 0.234(2) 0.7359(15) 0.8905(15) 0.032(4) Uiso 1 1 d . . . H173 H 0.104(3) 0.7377(15) 0.7662(14) 0.036(5) Uiso 1 1 d . . . C18 C 0.2627(3) 0.91857(15) 0.50626(14) 0.0275(3) Uani 1 1 d . . . H181 H 0.384(2) 0.9360(15) 0.5744(14) 0.029(4) Uiso 1 1 d . . . H182 H 0.137(2) 0.9046(15) 0.5276(14) 0.028(4) Uiso 1 1 d . . . H183 H 0.269(2) 0.9938(15) 0.4765(13) 0.027(4) Uiso 1 1 d . . . C19 C 0.2463(2) 0.51938(16) 0.15274(13) 0.0262(3) Uani 1 1 d . . . H191 H 0.370(2) 0.4750(15) 0.1663(13) 0.032(4) Uiso 1 1 d . . . H192 H 0.123(3) 0.4571(16) 0.1282(14) 0.033(4) Uiso 1 1 d . . . H193 H 0.249(2) 0.5605(15) 0.0943(14) 0.031(4) Uiso 1 1 d . . . C20 C 0.2950(2) 1.01055(16) 0.19631(13) 0.0286(3) Uani 1 1 d . . . C21 C 0.2716(3) 0.86967(17) 0.16571(18) 0.0373(4) Uani 1 1 d . . . H211 H 0.372(3) 0.843(2) 0.1306(18) 0.065(6) Uiso 1 1 d . . . H212 H 0.141(3) 0.832(2) 0.1105(18) 0.064(6) Uiso 1 1 d . . . H213 H 0.292(4) 0.839(2) 0.231(2) 0.090(8) Uiso 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 O1 0.0349(6) 0.0205(5) 0.0229(5) 0.0091(4) 0.0122(4) 0.0085(4) O2 0.0349(6) 0.0259(5) 0.0191(5) 0.0091(4) 0.0121(4) 0.0085(4) N1 0.0211(6) 0.0198(6) 0.0205(6) 0.0053(5) 0.0077(5) 0.0053(4) N2 0.0240(6) 0.0161(6) 0.0180(6) 0.0035(5) 0.0078(5) 0.0043(4) N3 0.0234(6) 0.0174(6) 0.0210(6) 0.0046(5) 0.0080(5) 0.0052(4) N4 0.0521(10) 0.0349(8) 0.0370(8) 0.0085(6) 0.0192(7) 0.0001(7) C1 0.0180(7) 0.0215(7) 0.0227(7) 0.0095(6) 0.0064(5) 0.0052(5) C2 0.0183(7) 0.0268(7) 0.0181(7) 0.0092(6) 0.0071(5) 0.0051(5) C3 0.0176(7) 0.0232(7) 0.0180(7) 0.0046(6) 0.0066(5) 0.0053(5) C4 0.0144(6) 0.0219(7) 0.0193(7) 0.0057(6) 0.0058(5) 0.0036(5) C5 0.0143(6) 0.0207(7) 0.0193(7) 0.0055(6) 0.0049(5) 0.0033(5) C6 0.0182(7) 0.0196(7) 0.0194(7) 0.0044(6) 0.0061(5) 0.0041(5) C7 0.0153(6) 0.0176(6) 0.0204(7) 0.0056(5) 0.0056(5) 0.0036(5) C8 0.0163(7) 0.0207(7) 0.0192(7) 0.0061(5) 0.0059(5) 0.0040(5) C9 0.0181(7) 0.0216(7) 0.0194(7) 0.0036(6) 0.0068(5) 0.0043(5) C10 0.0165(7) 0.0205(7) 0.0201(7) 0.0066(6) 0.0046(5) 0.0029(5) C11 0.0192(7) 0.0199(7) 0.0238(7) 0.0102(6) 0.0083(6) 0.0063(5) C12 0.0296(8) 0.0221(7) 0.0219(7) 0.0069(6) 0.0086(6) 0.0053(6) C13 0.0335(9) 0.0303(8) 0.0226(8) 0.0118(7) 0.0092(7) 0.0083(6) C14 0.0348(9) 0.0259(8) 0.0317(9) 0.0160(7) 0.0132(7) 0.0109(6) C15 0.0357(9) 0.0188(7) 0.0295(8) 0.0074(6) 0.0120(7) 0.0065(6) C16 0.0280(8) 0.0221(7) 0.0206(7) 0.0060(6) 0.0080(6) 0.0056(6) C17 0.0284(8) 0.0182(7) 0.0224(8) 0.0046(6) 0.0087(6) 0.0046(6) C18 0.0374(9) 0.0197(7) 0.0261(8) 0.0067(6) 0.0107(7) 0.0056(6) C19 0.0313(9) 0.0301(8) 0.0184(7) 0.0061(6) 0.0102(6) 0.0067(7) C20 0.0301(8) 0.0354(9) 0.0232(8) 0.0113(7) 0.0112(6) 0.0036(6) C21 0.0390(10) 0.0319(9) 0.0478(11) 0.0162(8) 0.0190(9) 0.0095(7) _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 O1 C1 1.3618(16) . ? O1 C18 1.4302(18) . ? O2 C2 1.3647(16) . ? O2 C19 1.4280(18) . ? N1 C9 1.3223(18) . ? N1 C8 1.3559(18) . ? N2 N3 1.3772(16) . ? N2 C8 1.3793(17) . ? N2 C11 1.4178(17) . ? N3 C10 1.3275(18) . ? N4 C20 1.142(2) . ? C1 C6 1.373(2) . ? C1 C2 1.429(2) . ? C2 C3 1.3706(19) . ? C3 C4 1.4189(19) . ? C3 H3 0.961(16) . ? C4 C5 1.4144(19) . ? C4 C9 1.4287(19) . ? C5 C6 1.4144(19) . ? C5 C7 1.4221(19) . ? C6 H6 0.965(15) . ? C7 C8 1.3964(19) . ? C7 C10 1.4229(19) . ? C9 H9 0.981(14) . ? C10 C17 1.495(2) . ? C11 C16 1.391(2) . ? C11 C12 1.395(2) . ? C12 C13 1.388(2) . ? C12 H12 0.991(17) . ? C13 C14 1.383(2) . ? C13 H13 0.956(18) . ? C14 C15 1.388(2) . ? C14 H14 0.968(17) . ? C15 C16 1.384(2) . ? C15 H15 0.985(17) . ? C16 H16 0.968(16) . ? C17 H171 1.011(17) . ? C17 H172 1.013(17) . ? C17 H173 0.981(17) . ? C18 H181 1.009(17) . ? C18 H182 1.011(17) . ? C18 H183 0.980(16) . ? C19 H191 1.034(16) . ? C19 H192 0.971(17) . ? C19 H193 0.965(17) . ? C20 C21 1.454(2) . ? C21 H211 0.98(2) . ? C21 H212 0.98(2) . ? C21 H213 0.95(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 C1 O1 C18 116.81(11) . . ? C2 O2 C19 116.84(11) . . ? C9 N1 C8 113.45(12) . . ? N3 N2 C8 110.67(11) . . ? N3 N2 C11 118.61(11) . . ? C8 N2 C11 130.70(12) . . ? C10 N3 N2 106.34(11) . . ? O1 C1 C6 124.90(13) . . ? O1 C1 C2 114.28(12) . . ? C6 C1 C2 120.82(13) . . ? O2 C2 C3 125.76(12) . . ? O2 C2 C1 114.45(12) . . ? C3 C2 C1 119.78(13) . . ? C2 C3 C4 120.11(13) . . ? C2 C3 H3 120.7(9) . . ? C4 C3 H3 119.2(9) . . ? C5 C4 C3 120.01(12) . . ? C5 C4 C9 119.37(12) . . ? C3 C4 C9 120.62(12) . . ? C4 C5 C6 119.16(13) . . ? C4 C5 C7 115.68(12) . . ? C6 C5 C7 125.15(12) . . ? C1 C6 C5 120.10(13) . . ? C1 C6 H6 119.4(9) . . ? C5 C6 H6 120.5(9) . . ? C8 C7 C5 118.34(12) . . ? C8 C7 C10 105.06(12) . . ? C5 C7 C10 136.60(12) . . ? N1 C8 N2 125.83(12) . . ? N1 C8 C7 127.38(13) . . ? N2 C8 C7 106.78(12) . . ? N1 C9 C4 125.78(13) . . ? N1 C9 H9 117.2(8) . . ? C4 C9 H9 117.0(8) . . ? N3 C10 C7 111.14(12) . . ? N3 C10 C17 119.06(13) . . ? C7 C10 C17 129.76(12) . . ? C16 C11 C12 120.21(13) . . ? C16 C11 N2 121.13(13) . . ? C12 C11 N2 118.65(12) . . ? C13 C12 C11 119.44(14) . . ? C13 C12 H12 121.0(9) . . ? C11 C12 H12 119.5(10) . . ? C14 C13 C12 120.73(15) . . ? C14 C13 H13 121.2(10) . . ? C12 C13 H13 118.0(10) . . ? C13 C14 C15 119.26(14) . . ? C13 C14 H14 120.1(10) . . ? C15 C14 H14 120.7(10) . . ? C16 C15 C14 121.00(14) . . ? C16 C15 H15 117.5(10) . . ? C14 C15 H15 121.5(10) . . ? C15 C16 C11 119.35(14) . . ? C15 C16 H16 120.8(9) . . ? C11 C16 H16 119.9(9) . . ? C10 C17 H171 111.9(9) . . ? C10 C17 H172 111.2(9) . . ? H171 C17 H172 106.5(13) . . ? C10 C17 H173 110.5(10) . . ? H171 C17 H173 108.2(13) . . ? H172 C17 H173 108.3(13) . . ? O1 C18 H181 112.2(9) . . ? O1 C18 H182 110.2(9) . . ? H181 C18 H182 110.5(13) . . ? O1 C18 H183 105.5(9) . . ? H181 C18 H183 107.2(13) . . ? H182 C18 H183 111.2(12) . . ? O2 C19 H191 110.9(9) . . ? O2 C19 H192 111.9(10) . . ? H191 C19 H192 111.8(13) . . ? O2 C19 H193 105.9(10) . . ? H191 C19 H193 107.0(13) . . ? H192 C19 H193 109.1(13) . . ? N4 C20 C21 179.67(18) . . ? C20 C21 H211 109.3(12) . . ? C20 C21 H212 109.4(12) . . ? H211 C21 H212 107.8(18) . . ? C20 C21 H213 111.1(15) . . ? H211 C21 H213 106.8(19) . . ? H212 C21 H213 112(2) . . ? 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 C18 O1 C1 C2 179.55(12) . . . . ? O1 C1 C2 O2 -1.17(17) . . . . ? C1 C2 O2 C19 -175.93(12) . . . . ? N3 N2 C11 C12 -18.87(18) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A C21 H213 O1 0.95(3) 2.54(3) 3.455(2) 160(2) . C21 H213 O2 0.95(3) 2.41(3) 3.126(2) 131(2) . _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 27.54 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.231 _refine_diff_density_min -0.247 _refine_diff_density_rms 0.044 #=============================================END data_(10Cd) _database_code_depnum_ccdc_archive 'CCDC 232597' _audit_creation_method SHELXL-97 _chemical_name_systematic ; 5-{4-(dimethylamino)phenyl}- 7,8-dimethoxypyrazolo[3,4-c]isoquinoline ; _chemical_name_common ;5-(4-(dimethylamino)phenyl)-7,8-dimethoxypyrazolo(3,4- c)isoquinoline ; _chemical_melting_point '200--200.5 \% C' _chemical_formula_moiety 'C35 H34 N4 O2' _chemical_formula_sum 'C35 H34 N4 O2' _chemical_formula_weight 542.66 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 Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.944(4) _cell_length_b 12.945(5) _cell_length_c 13.918(7) _cell_angle_alpha 64.13(2) _cell_angle_beta 73.04(2) _cell_angle_gamma 81.00(2) _cell_volume 1386.1(12) _cell_formula_units_Z 2 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 421 _cell_measurement_theta_min 10.13 _cell_measurement_theta_max 20.79 _exptl_crystal_description plate _exptl_crystal_colour 'pale yellow' _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.300 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 576 _exptl_absorpt_coefficient_mu 0.082 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ;The data collection nominally covered full sphere of reciprocal space, by a combination of 4 sets of \w scans; each set at different \f and/or 2\q angles and each scan (40 sec exposure) covering 0.3\% in \w. Crystal to detector distance 4.95 cm. The absense of crystal decay was monitored by repeating 57 initial frames at the end of data collection and comparing duplicate reflections. ; _diffrn_ambient_temperature 120(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source '60W microfocus Bede Microsource with glass polycapillary optics' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'APEX CCD area detector' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 8 _diffrn_reflns_number 10374 _diffrn_reflns_av_R_equivalents 0.0923 _diffrn_reflns_av_sigmaI/netI 0.1520 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.38 _diffrn_reflns_theta_max 25.35 _reflns_number_total 5074 _reflns_number_gt 2568 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'SMART version 5.625 (Bruker, 2001)' _computing_cell_refinement 'SMART version 5.625 (Bruker, 2001)' _computing_data_reduction 'SAINT version 6.28A (Bruker, 2002)' _computing_structure_solution 'SHELXTL version 6.12 (Bruker, 2001)' _computing_structure_refinement 'SHELXTL version 6.12 (Bruker, 2001)' _computing_molecular_graphics 'SHELXTL version 5.10 (Bruker, 1997)' _computing_publication_material 'SHELXTL version 5.10 (Bruker, 1997)' _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. Methyl groups were refined as rigid (rotating) bodies with a common refined U(H) for each group. Other H atoms - riding. ; _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^)+(0.0099P)^2^P] 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 5074 _refine_ls_number_parameters 378 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1166 _refine_ls_R_factor_gt 0.0505 _refine_ls_wR_factor_ref 0.0932 _refine_ls_wR_factor_gt 0.0787 _refine_ls_goodness_of_fit_ref 0.835 _refine_ls_restrained_S_all 0.835 _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 O1 O 0.8299(2) 0.44709(15) 0.56955(13) 0.0237(5) Uani 1 1 d . . . O2 O 0.7850(2) 0.42841(15) 0.40565(13) 0.0238(5) Uani 1 1 d . . . N1 N 0.1638(3) 0.22023(18) 0.71685(16) 0.0198(5) Uani 1 1 d . . . N2 N 0.0853(3) 0.21062(18) 0.90192(16) 0.0198(5) Uani 1 1 d . . . N3 N 0.1495(3) 0.23273(18) 0.96949(16) 0.0210(5) Uani 1 1 d . . . N4 N 0.1847(3) 0.13706(18) 0.29479(16) 0.0208(5) Uani 1 1 d . . . C1 C 0.6929(3) 0.4000(2) 0.5907(2) 0.0186(6) Uani 1 1 d . . . C2 C 0.6680(3) 0.3879(2) 0.4999(2) 0.0186(6) Uani 1 1 d . . . C3 C 0.5350(3) 0.3403(2) 0.5115(2) 0.0181(6) Uani 1 1 d . . . H3 H 0.5193 0.3331 0.4501 0.022 Uiso 1 1 d R . . C4 C 0.4191(3) 0.3004(2) 0.6135(2) 0.0174(6) Uani 1 1 d . . . C5 C 0.4438(3) 0.3161(2) 0.70259(19) 0.0180(6) Uani 1 1 d . . . C6 C 0.5817(3) 0.3652(2) 0.6891(2) 0.0181(6) Uani 1 1 d . . . H6 H 0.5981 0.3748 0.7492 0.022 Uiso 1 1 d R . . C7 C 0.3197(3) 0.2810(2) 0.80076(19) 0.0179(6) Uani 1 1 d . . . C8 C 0.1889(3) 0.2392(2) 0.7992(2) 0.0180(6) Uani 1 1 d . . . C9 C 0.2815(3) 0.2473(2) 0.6267(2) 0.0186(6) Uani 1 1 d . . . C10 C 0.2876(3) 0.2754(2) 0.9100(2) 0.0189(6) Uani 1 1 d . . . C11 C -0.0586(3) 0.1548(2) 0.9464(2) 0.0189(6) Uani 1 1 d . . . C12 C -0.1114(3) 0.0969(2) 1.0602(2) 0.0215(7) Uani 1 1 d . . . H12 H -0.0506 0.0938 1.1071 0.026 Uiso 1 1 d R . . C13 C -0.2523(3) 0.0437(2) 1.1043(2) 0.0257(7) Uani 1 1 d . . . H13 H -0.2885 0.0043 1.1820 0.031 Uiso 1 1 d R . . C14 C -0.3420(3) 0.0468(2) 1.0376(2) 0.0254(7) Uani 1 1 d . . . H14 H -0.4395 0.0103 1.0690 0.030 Uiso 1 1 d R . . C15 C -0.2880(3) 0.1032(2) 0.9244(2) 0.0245(7) Uani 1 1 d . . . H15 H -0.3487 0.1051 0.8779 0.029 Uiso 1 1 d R . . C16 C -0.1474(3) 0.1569(2) 0.8787(2) 0.0225(7) Uani 1 1 d . . . H16 H -0.1110 0.1951 0.8008 0.027 Uiso 1 1 d R . . C17 C 0.3838(3) 0.3113(2) 0.96244(19) 0.0204(7) Uani 1 1 d . . . H171 H 0.4940 0.2860 0.9414 0.027 Uiso 1 1 d R . . H172 H 0.3464 0.2716 1.0436 0.027 Uiso 1 1 d R . . C18 C 0.8598(3) 0.4678(2) 0.6552(2) 0.0262(7) Uani 1 1 d . . . H181 H 0.7853 0.5267 0.6694 0.035(5) Uiso 1 1 d R . . H182 H 0.9664 0.4944 0.6320 0.035(5) Uiso 1 1 d R . . H183 H 0.8484 0.3965 0.7227 0.035(5) Uiso 1 1 d R . . C19 C 0.7650(3) 0.4192(2) 0.3117(2) 0.0258(7) Uani 1 1 d . . . H191 H 0.7562 0.3382 0.3288 0.024(4) Uiso 1 1 d R . . H192 H 0.8554 0.4507 0.2492 0.024(4) Uiso 1 1 d R . . H193 H 0.6698 0.4623 0.2925 0.024(4) Uiso 1 1 d R . . C20 C 0.2588(3) 0.2189(2) 0.53944(19) 0.0181(6) Uani 1 1 d . . . C21 C 0.3720(3) 0.1574(2) 0.4900(2) 0.0210(6) Uani 1 1 d . . . H21 H 0.4686 0.1356 0.5102 0.025 Uiso 1 1 d R . . C22 C 0.3460(3) 0.1274(2) 0.41262(19) 0.0210(7) Uani 1 1 d . . . H22 H 0.4245 0.0842 0.3817 0.025 Uiso 1 1 d R . . C23 C 0.2077(3) 0.1594(2) 0.37818(19) 0.0204(7) Uani 1 1 d . . . C24 C 0.0933(3) 0.2183(2) 0.4305(2) 0.0206(6) Uani 1 1 d . . . H24 H -0.0042 0.2394 0.4115 0.025 Uiso 1 1 d R . . C25 C 0.1196(3) 0.2462(2) 0.50937(19) 0.0196(6) Uani 1 1 d . . . H25 H 0.0391 0.2855 0.5437 0.024 Uiso 1 1 d R . . C26 C 0.3767(3) 0.4397(2) 0.93011(19) 0.0191(6) Uani 1 1 d . . . C27 C 0.5098(3) 0.5038(2) 0.87536(19) 0.0227(7) Uani 1 1 d . . . H27 H 0.6077 0.4667 0.8581 0.027 Uiso 1 1 d R . . C28 C 0.5029(4) 0.6218(2) 0.8452(2) 0.0280(7) Uani 1 1 d . . . H28 H 0.5951 0.6647 0.8070 0.034 Uiso 1 1 d R . . C29 C 0.3611(4) 0.6764(2) 0.8709(2) 0.0315(8) Uani 1 1 d . . . H29 H 0.3556 0.7570 0.8498 0.038 Uiso 1 1 d R . . C30 C 0.2283(4) 0.6134(2) 0.9275(2) 0.0319(8) Uani 1 1 d . . . H30 H 0.1314 0.6505 0.9470 0.038 Uiso 1 1 d R . . C31 C 0.2353(3) 0.4954(2) 0.9561(2) 0.0250(7) Uani 1 1 d . . . H31 H 0.1428 0.4528 0.9937 0.030 Uiso 1 1 d R . . C32 C 0.2908(3) 0.0591(2) 0.2547(2) 0.0256(7) Uani 1 1 d . . . H321 H 0.3995 0.0806 0.2391 0.033 Uiso 1 1 d R . . H322 H 0.2726 0.0690 0.1843 0.033 Uiso 1 1 d R . . C33 C 0.2741(4) -0.0672(2) 0.3345(2) 0.0331(8) Uani 1 1 d . . . H331 H 0.2861 -0.0775 0.4059 0.041(5) Uiso 1 1 d R . . H332 H 0.3549 -0.1135 0.3046 0.041(5) Uiso 1 1 d R . . H333 H 0.1706 -0.0919 0.3442 0.041(5) Uiso 1 1 d R . . C34 C 0.0408(3) 0.1729(2) 0.2592(2) 0.0242(7) Uani 1 1 d . . . H341 H 0.0617 0.1791 0.1831 0.032 Uiso 1 1 d R . . H342 H 0.0090 0.2506 0.2570 0.032 Uiso 1 1 d R . . C35 C -0.0951(4) 0.0940(2) 0.3311(2) 0.0335(8) Uani 1 1 d . . . H351 H -0.0712 0.0198 0.3259 0.040(5) Uiso 1 1 d R . . H352 H -0.1897 0.1292 0.3058 0.040(5) Uiso 1 1 d R . . H353 H -0.1122 0.0822 0.4080 0.040(5) Uiso 1 1 d 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 O1 0.0197(12) 0.0348(12) 0.0247(10) -0.0181(9) -0.0055(9) -0.0054(10) O2 0.0228(12) 0.0322(12) 0.0186(10) -0.0135(9) -0.0021(9) -0.0041(9) N1 0.0193(14) 0.0247(14) 0.0188(12) -0.0110(11) -0.0067(11) -0.0002(11) N2 0.0219(14) 0.0248(14) 0.0177(12) -0.0113(10) -0.0054(11) -0.0059(11) N3 0.0212(14) 0.0245(14) 0.0210(12) -0.0118(11) -0.0053(11) -0.0041(11) N4 0.0242(14) 0.0246(14) 0.0195(12) -0.0136(10) -0.0089(11) 0.0035(11) C1 0.0156(16) 0.0197(16) 0.0245(15) -0.0116(13) -0.0073(13) 0.0002(13) C2 0.0190(17) 0.0183(16) 0.0169(14) -0.0076(12) -0.0019(13) -0.0002(13) C3 0.0187(16) 0.0196(16) 0.0196(14) -0.0110(12) -0.0068(13) 0.0020(13) C4 0.0202(16) 0.0148(16) 0.0191(14) -0.0078(12) -0.0078(13) 0.0023(13) C5 0.0215(17) 0.0141(16) 0.0215(14) -0.0084(12) -0.0111(13) 0.0048(13) C6 0.0187(16) 0.0220(16) 0.0172(14) -0.0109(12) -0.0058(12) 0.0004(13) C7 0.0226(17) 0.0136(16) 0.0186(14) -0.0066(12) -0.0076(13) 0.0006(13) C8 0.0198(17) 0.0136(16) 0.0167(14) -0.0044(12) -0.0022(13) -0.0005(13) C9 0.0230(17) 0.0146(16) 0.0203(14) -0.0065(12) -0.0112(13) 0.0029(13) C10 0.0209(17) 0.0185(16) 0.0189(14) -0.0084(12) -0.0064(13) -0.0002(13) C11 0.0146(16) 0.0183(16) 0.0248(15) -0.0118(13) -0.0014(13) -0.0013(13) C12 0.0235(17) 0.0229(17) 0.0216(15) -0.0125(13) -0.0053(13) -0.0011(14) C13 0.0295(19) 0.0240(17) 0.0200(14) -0.0086(13) -0.0001(14) -0.0047(15) C14 0.0192(17) 0.0258(18) 0.0315(16) -0.0134(14) -0.0009(14) -0.0070(14) C15 0.0236(18) 0.0255(18) 0.0267(15) -0.0120(14) -0.0073(14) -0.0016(14) C16 0.0211(17) 0.0253(17) 0.0200(14) -0.0088(13) -0.0046(13) -0.0010(14) C17 0.0244(17) 0.0221(17) 0.0183(14) -0.0098(12) -0.0077(13) -0.0018(13) C18 0.0248(18) 0.0334(19) 0.0250(15) -0.0130(14) -0.0090(14) -0.0058(15) C19 0.0243(18) 0.0357(19) 0.0207(14) -0.0140(14) -0.0081(13) 0.0021(15) C20 0.0212(17) 0.0180(16) 0.0144(13) -0.0049(12) -0.0050(13) -0.0028(13) C21 0.0181(16) 0.0230(17) 0.0230(14) -0.0091(13) -0.0085(13) 0.0014(13) C22 0.0206(17) 0.0219(17) 0.0226(14) -0.0123(13) -0.0053(13) 0.0023(13) C23 0.0237(17) 0.0179(17) 0.0188(14) -0.0056(12) -0.0058(13) -0.0037(13) C24 0.0194(17) 0.0223(16) 0.0216(14) -0.0090(13) -0.0088(13) 0.0021(13) C25 0.0209(17) 0.0196(16) 0.0187(14) -0.0097(12) -0.0035(13) 0.0007(13) C26 0.0263(18) 0.0224(17) 0.0149(13) -0.0100(12) -0.0105(13) -0.0008(14) C27 0.0261(18) 0.0296(19) 0.0166(14) -0.0127(13) -0.0051(13) -0.0030(14) C28 0.040(2) 0.0254(19) 0.0217(15) -0.0073(14) -0.0125(15) -0.0078(16) C29 0.048(2) 0.0198(18) 0.0345(17) -0.0110(14) -0.0223(17) 0.0004(16) C30 0.031(2) 0.034(2) 0.0400(18) -0.0232(16) -0.0150(16) 0.0084(16) C31 0.0260(18) 0.0272(18) 0.0288(16) -0.0152(14) -0.0090(14) -0.0045(14) C32 0.0284(18) 0.0293(19) 0.0230(14) -0.0154(14) -0.0080(13) 0.0052(14) C33 0.040(2) 0.0301(19) 0.0348(17) -0.0191(15) -0.0113(15) 0.0045(16) C34 0.0277(18) 0.0267(18) 0.0223(14) -0.0124(13) -0.0095(13) 0.0010(14) C35 0.0314(19) 0.040(2) 0.0298(16) -0.0138(15) -0.0086(15) -0.0031(16) _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 O1 C1 1.351(3) . ? O1 C18 1.432(3) . ? O2 C2 1.364(3) . ? O2 C19 1.427(3) . ? N1 C9 1.329(3) . ? N1 C8 1.356(3) . ? N2 N3 1.377(3) . ? N2 C8 1.383(3) . ? N2 C11 1.413(3) . ? N3 C10 1.317(3) . ? N4 C23 1.387(3) . ? N4 C34 1.449(3) . ? N4 C32 1.454(3) . ? C1 C6 1.369(3) . ? C1 C2 1.422(3) . ? C2 C3 1.360(3) . ? C3 C4 1.423(3) . ? C4 C5 1.421(3) . ? C4 C9 1.429(4) . ? C5 C6 1.403(4) . ? C5 C7 1.427(3) . ? C7 C8 1.372(4) . ? C7 C10 1.434(3) . ? C9 C20 1.487(3) . ? C10 C17 1.508(3) . ? C11 C16 1.388(4) . ? C11 C12 1.390(3) . ? C12 C13 1.375(4) . ? C13 C14 1.378(4) . ? C14 C15 1.382(3) . ? C15 C16 1.375(4) . ? C17 C26 1.516(3) . ? C20 C25 1.374(4) . ? C20 C21 1.397(3) . ? C21 C22 1.380(3) . ? C22 C23 1.394(4) . ? C23 C24 1.402(3) . ? C24 C25 1.383(3) . ? C26 C27 1.383(4) . ? C26 C31 1.387(4) . ? C27 C28 1.393(3) . ? C28 C29 1.382(4) . ? C29 C30 1.376(4) . ? C30 C31 1.396(4) . ? C32 C33 1.524(4) . ? C34 C35 1.520(4) . ? 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 O1 C18 117.8(2) . . ? C2 O2 C19 116.5(2) . . ? C9 N1 C8 114.6(2) . . ? N3 N2 C8 109.8(2) . . ? N3 N2 C11 119.4(2) . . ? C8 N2 C11 130.5(2) . . ? C10 N3 N2 106.6(2) . . ? C23 N4 C34 121.2(2) . . ? C23 N4 C32 120.6(2) . . ? C34 N4 C32 117.2(2) . . ? O1 C1 C6 125.7(2) . . ? O1 C1 C2 114.5(2) . . ? C6 C1 C2 119.8(3) . . ? C3 C2 O2 125.8(2) . . ? C3 C2 C1 119.9(2) . . ? O2 C2 C1 114.3(2) . . ? C2 C3 C4 121.7(2) . . ? C5 C4 C3 117.7(2) . . ? C5 C4 C9 120.6(2) . . ? C3 C4 C9 121.7(2) . . ? C6 C5 C4 119.8(2) . . ? C6 C5 C7 124.8(2) . . ? C4 C5 C7 115.3(2) . . ? C1 C6 C5 121.1(2) . . ? C8 C7 C5 117.8(2) . . ? C8 C7 C10 104.6(2) . . ? C5 C7 C10 137.6(2) . . ? N1 C8 C7 128.1(2) . . ? N1 C8 N2 123.8(2) . . ? C7 C8 N2 107.9(2) . . ? N1 C9 C4 123.1(2) . . ? N1 C9 C20 114.7(2) . . ? C4 C9 C20 122.2(2) . . ? N3 C10 C7 111.2(2) . . ? N3 C10 C17 118.3(2) . . ? C7 C10 C17 130.5(2) . . ? C16 C11 C12 119.7(3) . . ? C16 C11 N2 121.3(2) . . ? C12 C11 N2 119.0(2) . . ? C13 C12 C11 119.5(3) . . ? C12 C13 C14 121.1(3) . . ? C13 C14 C15 119.2(3) . . ? C16 C15 C14 120.6(3) . . ? C15 C16 C11 119.9(2) . . ? C10 C17 C26 113.7(2) . . ? C25 C20 C21 117.2(2) . . ? C25 C20 C9 120.5(2) . . ? C21 C20 C9 122.1(3) . . ? C22 C21 C20 121.3(3) . . ? C21 C22 C23 121.7(2) . . ? N4 C23 C22 122.3(2) . . ? N4 C23 C24 121.3(3) . . ? C22 C23 C24 116.4(2) . . ? C25 C24 C23 121.3(3) . . ? C20 C25 C24 122.0(2) . . ? C27 C26 C31 118.5(3) . . ? C27 C26 C17 121.3(2) . . ? C31 C26 C17 120.2(2) . . ? C26 C27 C28 121.2(3) . . ? C29 C28 C27 119.7(3) . . ? C30 C29 C28 119.7(3) . . ? C29 C30 C31 120.3(3) . . ? C26 C31 C30 120.5(3) . . ? N4 C32 C33 114.2(2) . . ? N4 C34 C35 115.1(2) . . ? 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 C18 O1 C1 C2 176.7(2) . . . . ? O1 C1 C2 C19 -2.0(5) . . . . ? N3 C10 C17 C26 -100.4(3) . . . . ? C10 C17 C26 C31 61.8(3) . . . . ? N1 C9 C20 C25 46.1(3) . . . . ? C28 C29 N4 C32 12.5(4) . . . . ? C23 N4 C32 C33 72.6(3) . . . . ? C33 C32 N4 C34 -96.4(3) . . . . ? C32 N4 C34 C35 87.7(3) . . . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 25.35 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.221 _refine_diff_density_min -0.268 _refine_diff_density_rms 0.055 #==========================================END