# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Heron, Bernard' _publ_contact_author_email b.m.heron@leeds.ac.uk _publ_section_title ; The Influence of a 1,1-Diarylvinyl Moiety on the Photochromism of Naphthopyrans ; loop_ _publ_author_name C.Gabbutt B.Heron C.Kilner S.Kolla # Attachment '- SK_3_31.CIF' data_sk_3_31 _database_code_depnum_ccdc_archive 'CCDC 777577' #TrackingRef '- SK_3_31.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; 1-(1,1-bis(4-dimethylaminophenyl)vinyl)-3-phenyl-1H-naphtho[2,1-b]pyran ; _chemical_name_common ;1-(1,1-bis(4-dimethylaminophenyl)vinyl)-3-phenyl-1H- naphtho(2,1-b)pyran ; _chemical_melting_point ? _chemical_formula_moiety 'C37 H34 N2 O' _chemical_formula_sum 'C37 H34 N2 O' _chemical_formula_weight 522.66 _chemical_absolute_configuration unk 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 0.0000 '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 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21' _symmetry_space_group_name_Hall 'P 2ac 2ab' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 10.9909(10) _cell_length_b 13.0053(11) _cell_length_c 20.0553(18) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2866.7(4) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 6269 _cell_measurement_theta_min 2.56 _cell_measurement_theta_max 25.14 _exptl_crystal_description fragment _exptl_crystal_colour colourless _exptl_crystal_size_max 0.19 _exptl_crystal_size_mid 0.11 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.211 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1112 _exptl_absorpt_coefficient_mu 0.072 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8278 _exptl_absorpt_correction_T_max 0.9964 _exptl_absorpt_process_details ; See Sheldrick, G. M. (2002). SADABS. Version 2.03. University of Gottingen, Germany. ; _exptl_special_details ; The crystal temperature was held constant using an Oxford Cryosystems Cryostream 600 system. ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source ; Bruker Nonius FR591 rotating anode generator ; _diffrn_radiation_monochromator ; graphite model mounted in "parallel" mode ; _diffrn_measurement_device_type ; Mach3 kappa-type 4-circle goniostat. ; _diffrn_radiation_detector 'ApexII camera' _diffrn_measurement_method 'rotation images' _diffrn_detector_area_resol_mean ; 120 microns ; _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 27053 _diffrn_reflns_av_R_equivalents 0.0786 _diffrn_reflns_av_sigmaI/netI 0.0588 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_theta_min 2.57 _diffrn_reflns_theta_max 27.94 _reflns_number_total 3842 _reflns_number_gt 2744 _reflns_threshold_expression >2sigma(I) _computing_data_collection ; APEX 2 software, Bruker Nonius 2004 ; _computing_cell_refinement ; APEX 2 software, Bruker Nonius 2004 ; _computing_data_reduction ; SAINT - Bruker Integration program embedded in APEX 2 software, Bruker Nonius 2004 ; _computing_structure_solution ; SHELXS-97 (Sheldrick, G. M. Acta Cryst. (2008). A64, 112) XSeed (L.J.Barbour, J.Supramol. Chem., 2003, 1, 189.) ; _computing_structure_refinement ; SHELXL-97 (Sheldrick, G. M. Acta Cryst. (2008). A64, 112) XSeed (L.J.Barbour, J.Supramol. Chem., 2003, 1, 189.) ; _computing_molecular_graphics 'ORTEP-III Version 1.08 (Farrugia, 2005)' _computing_publication_material ; enCIFer: A program for viewing, editing and visualising CIFs. F. H. Allen, O. Johnson, G. P. Shields, B. R. Smith, M. Towler, J. Applied Cryst., 37, 331-334, 2004 ; _refine_special_details ; The structure solved in the orthorhombic spacegroup P21 21 21. All hydrogen atoms could be located in the Fourier difference map but, in the final stages of the refinement, they were placed in calculated positions and refined using a riding model. C-H distances: CH3, 0.98\A; CH, 1.00\A; aromatic, 0.95\A. All Uiso(H) values were constrained to be 1.2 times (1.5 for methyl) Ueq of the parent atom. For hydrogen atoms bonded to carbon Uiso(H) values were constrained to be 1.2 times Ueq of the parent atom. In the absence of significant anomalous scattering effects, the absolute configuration could not be confirmed from the diffraction data and Friedel pairs were merged. An arbitrary choice of enantiomer has been made. C.Kilner 15 April 2008 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^)+(0.0601P)^2^+0.2454P] 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 3114 _refine_ls_number_parameters 365 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0669 _refine_ls_R_factor_gt 0.0431 _refine_ls_wR_factor_ref 0.1087 _refine_ls_wR_factor_gt 0.0957 _refine_ls_goodness_of_fit_ref 1.063 _refine_ls_restrained_S_all 1.063 _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 O4 O 0.83713(16) 0.84209(16) 0.12402(9) 0.0322(5) Uani 1 1 d . . . C31 C 0.7239(3) 0.7247(2) 0.05779(13) 0.0251(6) Uani 1 1 d . . . C1 C 0.6230(2) 0.9238(2) 0.19573(14) 0.0255(6) Uani 1 1 d . . . H1 H 0.5805 0.9003 0.2371 0.031 Uiso 1 1 calc R . . C13 C 0.7839(3) 1.0224(2) 0.26646(13) 0.0257(6) Uani 1 1 d . . . C2 C 0.6229(3) 0.8365(2) 0.14545(14) 0.0266(6) Uani 1 1 d . . . H2 H 0.5478 0.8026 0.1375 0.032 Uiso 1 1 calc R . . N57 N 0.1710(2) 0.82241(19) 0.38343(12) 0.0334(6) Uani 1 1 d . . . C52 C 0.3428(3) 1.0363(2) 0.30145(13) 0.0274(6) Uani 1 1 d . . . H52 H 0.3674 1.1045 0.3117 0.033 Uiso 1 1 calc R . . C3 C 0.7206(2) 0.8035(2) 0.11134(13) 0.0256(6) Uani 1 1 d . . . C61 C 0.3952(2) 1.1518(2) 0.15994(13) 0.0253(6) Uani 1 1 d . . . C56 C 0.3287(2) 0.8955(2) 0.22478(13) 0.0252(6) Uani 1 1 d . . . H56 H 0.3451 0.8661 0.1824 0.030 Uiso 1 1 calc R . . C14 C 0.7558(2) 0.9516(2) 0.21327(13) 0.0246(6) Uani 1 1 d . . . C6 C 0.9759(2) 0.9326(2) 0.19239(14) 0.0306(7) Uani 1 1 d . . . H6 H 1.0394 0.9008 0.1678 0.037 Uiso 1 1 calc R . . C64 C 0.2951(3) 1.3307(2) 0.09458(14) 0.0306(7) Uani 1 1 d . . . C36 C 0.8363(3) 0.6937(2) 0.02905(14) 0.0296(7) Uani 1 1 d . . . H36 H 0.9101 0.7235 0.0444 0.036 Uiso 1 1 calc R . . C65 C 0.2203(3) 1.2559(2) 0.12459(15) 0.0320(7) Uani 1 1 d . . . H65 H 0.1345 1.2646 0.1232 0.038 Uiso 1 1 calc R . . C33 C 0.6208(3) 0.6042(2) -0.01717(14) 0.0329(7) Uani 1 1 d . . . H33 H 0.5475 0.5740 -0.0329 0.040 Uiso 1 1 calc R . . C12 C 0.6919(3) 1.0708(2) 0.30623(14) 0.0293(7) Uani 1 1 d . . . H12 H 0.6089 1.0539 0.2988 0.035 Uiso 1 1 calc R . . C32 C 0.6165(3) 0.6777(2) 0.03325(14) 0.0287(7) Uani 1 1 d . . . H32 H 0.5401 0.6968 0.0516 0.034 Uiso 1 1 calc R . . C66 C 0.2683(3) 1.1701(2) 0.15613(14) 0.0295(7) Uani 1 1 d . . . H66 H 0.2142 1.1220 0.1759 0.035 Uiso 1 1 calc R . . C11 C 0.7212(3) 1.1412(2) 0.35495(14) 0.0329(7) Uani 1 1 d . . . H11 H 0.6583 1.1723 0.3804 0.040 Uiso 1 1 calc R . . C5 C 0.8511(2) 0.9098(2) 0.17736(13) 0.0270(6) Uani 1 1 d . . . N67 N 0.2472(3) 1.4141(2) 0.05939(13) 0.0402(7) Uani 1 1 d . . . C55 C 0.2635(3) 0.8377(2) 0.27153(14) 0.0273(6) Uani 1 1 d . . . H55 H 0.2359 0.7706 0.2603 0.033 Uiso 1 1 calc R . . C53 C 0.2796(3) 0.9791(2) 0.34960(14) 0.0284(7) Uani 1 1 d . . . H53 H 0.2642 1.0083 0.3922 0.034 Uiso 1 1 calc R . . C41 C 0.4450(2) 1.0540(2) 0.18760(13) 0.0247(6) Uani 1 1 d . . . C10 C 0.8444(3) 1.1677(3) 0.36763(15) 0.0377(8) Uani 1 1 d . . . H10 H 0.8638 1.2169 0.4009 0.045 Uiso 1 1 calc R . . C59 C 0.1305(3) 0.7179(3) 0.36583(18) 0.0418(8) Uani 1 1 d . . . H59A H 0.0847 0.7201 0.3239 0.063 Uiso 1 1 calc R . . H59B H 0.0783 0.6909 0.4014 0.063 Uiso 1 1 calc R . . H59C H 0.2016 0.6731 0.3605 0.063 Uiso 1 1 calc R . . C9 C 0.9356(3) 1.1214(2) 0.33123(15) 0.0364(8) Uani 1 1 d . . . H9 H 1.0180 1.1385 0.3402 0.044 Uiso 1 1 calc R . . C54 C 0.2385(2) 0.8786(2) 0.33546(13) 0.0260(6) Uani 1 1 d . . . C7 C 1.0026(3) 1.0002(2) 0.24208(14) 0.0304(7) Uani 1 1 d . . . H7 H 1.0854 1.0156 0.2515 0.037 Uiso 1 1 calc R . . C51 C 0.3706(2) 0.9952(2) 0.23826(13) 0.0240(6) Uani 1 1 d . . . C34 C 0.7327(3) 0.5743(2) -0.04497(14) 0.0345(7) Uani 1 1 d . . . H34 H 0.7357 0.5239 -0.0792 0.041 Uiso 1 1 calc R . . C35 C 0.8394(3) 0.6199(2) -0.02144(15) 0.0346(7) Uani 1 1 d . . . H35 H 0.9154 0.6004 -0.0401 0.041 Uiso 1 1 calc R . . C8 C 0.9089(3) 1.0486(2) 0.28052(14) 0.0282(7) Uani 1 1 d . . . C69 C 0.1163(3) 1.4167(3) 0.04437(18) 0.0465(9) Uani 1 1 d . . . H69A H 0.0950 1.3577 0.0163 0.070 Uiso 1 1 calc R . . H69B H 0.0967 1.4805 0.0208 0.070 Uiso 1 1 calc R . . H69C H 0.0699 1.4135 0.0861 0.070 Uiso 1 1 calc R . . C62 C 0.4695(3) 1.2309(2) 0.13422(14) 0.0305(7) Uani 1 1 d . . . H62 H 0.5552 1.2246 0.1387 0.037 Uiso 1 1 calc R . . C63 C 0.4232(3) 1.3175(2) 0.10270(15) 0.0318(7) Uani 1 1 d . . . H63 H 0.4774 1.3685 0.0863 0.038 Uiso 1 1 calc R . . C68 C 0.3272(3) 1.4786(3) 0.01885(17) 0.0457(9) Uani 1 1 d . . . H68A H 0.3917 1.5073 0.0470 0.069 Uiso 1 1 calc R . . H68B H 0.2799 1.5347 -0.0010 0.069 Uiso 1 1 calc R . . H68C H 0.3637 1.4370 -0.0167 0.069 Uiso 1 1 calc R . . C40 C 0.5555(2) 1.0164(2) 0.16754(13) 0.0261(6) Uani 1 1 d . . . H40 H 0.5944 1.0521 0.1321 0.031 Uiso 1 1 calc R . . C58 C 0.1985(3) 0.8380(3) 0.45386(15) 0.0495(10) Uani 1 1 d . . . H58A H 0.2827 0.8174 0.4627 0.074 Uiso 1 1 calc R . . H58B H 0.1432 0.7963 0.4810 0.074 Uiso 1 1 calc R . . H58C H 0.1880 0.9108 0.4651 0.074 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 O4 0.0194(10) 0.0465(13) 0.0308(11) -0.0107(10) 0.0008(9) -0.0024(10) C31 0.0259(15) 0.0289(15) 0.0205(13) 0.0044(12) -0.0012(12) 0.0005(13) C1 0.0196(14) 0.0319(16) 0.0249(14) -0.0007(14) 0.0017(11) -0.0032(12) C13 0.0284(15) 0.0283(15) 0.0205(13) 0.0040(13) 0.0001(12) 0.0013(13) C2 0.0222(14) 0.0300(16) 0.0275(14) 0.0011(14) 0.0010(12) -0.0045(13) N57 0.0395(14) 0.0326(14) 0.0282(13) 0.0015(11) 0.0072(12) -0.0019(12) C52 0.0268(15) 0.0275(15) 0.0280(14) -0.0048(13) -0.0021(12) -0.0006(13) C3 0.0198(14) 0.0311(16) 0.0259(14) 0.0045(13) 0.0003(12) -0.0032(12) C61 0.0232(14) 0.0277(15) 0.0252(14) -0.0019(13) -0.0018(12) -0.0009(12) C56 0.0243(14) 0.0309(16) 0.0204(13) -0.0037(12) -0.0008(11) 0.0035(13) C14 0.0200(14) 0.0296(15) 0.0241(14) 0.0049(12) 0.0004(11) 0.0000(12) C6 0.0210(15) 0.0407(19) 0.0300(15) -0.0017(15) 0.0006(12) 0.0037(13) C64 0.0339(17) 0.0290(16) 0.0290(15) -0.0028(14) -0.0011(13) 0.0013(14) C36 0.0264(16) 0.0346(17) 0.0278(15) 0.0024(13) 0.0016(13) 0.0005(14) C65 0.0253(15) 0.0337(17) 0.0369(17) 0.0020(14) -0.0004(14) 0.0014(13) C33 0.0351(17) 0.0372(18) 0.0265(15) 0.0016(15) -0.0009(13) -0.0064(15) C12 0.0312(16) 0.0310(17) 0.0255(14) 0.0047(13) 0.0024(12) 0.0020(13) C32 0.0249(15) 0.0365(17) 0.0248(14) 0.0018(14) 0.0004(12) -0.0008(14) C66 0.0235(15) 0.0347(16) 0.0302(15) 0.0017(14) 0.0041(13) -0.0018(13) C11 0.0409(18) 0.0316(17) 0.0263(15) 0.0033(14) 0.0027(14) 0.0034(14) C5 0.0240(15) 0.0364(16) 0.0207(14) -0.0009(13) -0.0006(12) -0.0005(13) N67 0.0409(16) 0.0331(15) 0.0465(15) 0.0104(13) -0.0059(13) -0.0002(13) C55 0.0251(14) 0.0274(15) 0.0293(15) -0.0012(13) -0.0004(12) 0.0006(13) C53 0.0292(16) 0.0338(16) 0.0221(14) -0.0031(13) 0.0024(12) 0.0016(13) C41 0.0239(14) 0.0275(16) 0.0226(14) -0.0028(12) 0.0013(11) -0.0034(12) C10 0.048(2) 0.0357(18) 0.0293(16) -0.0049(14) -0.0081(15) -0.0005(16) C59 0.0404(19) 0.0395(19) 0.045(2) 0.0031(16) 0.0103(16) -0.0039(16) C9 0.0355(17) 0.0400(19) 0.0338(17) -0.0034(15) -0.0077(14) -0.0019(15) C54 0.0201(14) 0.0329(16) 0.0251(14) 0.0042(13) -0.0008(11) 0.0039(12) C7 0.0245(14) 0.0377(19) 0.0292(15) -0.0007(15) -0.0036(12) -0.0017(13) C51 0.0188(13) 0.0294(16) 0.0237(14) 0.0020(13) -0.0003(11) 0.0026(12) C34 0.0477(19) 0.0317(17) 0.0240(15) -0.0027(13) 0.0007(14) -0.0009(15) C35 0.0354(18) 0.0375(18) 0.0307(16) 0.0010(15) 0.0067(14) 0.0051(15) C8 0.0285(15) 0.0305(17) 0.0256(15) 0.0031(13) -0.0033(12) -0.0009(13) C69 0.041(2) 0.047(2) 0.051(2) 0.0090(18) -0.0094(16) 0.0105(17) C62 0.0222(15) 0.0348(17) 0.0345(17) -0.0028(14) -0.0004(13) -0.0036(13) C63 0.0289(16) 0.0293(17) 0.0373(17) 0.0019(14) 0.0001(13) -0.0061(14) C68 0.062(2) 0.0369(19) 0.0386(18) 0.0059(16) 0.0078(17) 0.0009(18) C40 0.0254(15) 0.0310(16) 0.0217(14) 0.0005(13) 0.0020(11) -0.0018(12) C58 0.055(2) 0.066(2) 0.0282(17) 0.0068(17) 0.0031(15) -0.013(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag O4 C5 1.394(3) . ? O4 C3 1.399(3) . ? C31 C32 1.417(4) . ? C31 C36 1.422(4) . ? C31 C3 1.485(4) . ? C1 C2 1.519(4) . ? C1 C40 1.523(4) . ? C1 C14 1.544(4) . ? C1 H1 1.0000 . ? C13 C12 1.433(4) . ? C13 C14 1.443(4) . ? C13 C8 1.443(4) . ? C2 C3 1.344(4) . ? C2 H2 0.9500 . ? N57 C54 1.418(4) . ? N57 C58 1.459(4) . ? N57 C59 1.473(4) . ? C52 C53 1.403(4) . ? C52 C51 1.409(4) . ? C52 H52 0.9500 . ? C61 C62 1.411(4) . ? C61 C66 1.417(4) . ? C61 C41 1.492(4) . ? C56 C55 1.399(4) . ? C56 C51 1.402(4) . ? C56 H56 0.9500 . ? C14 C5 1.383(4) . ? C6 C7 1.361(4) . ? C6 C5 1.435(4) . ? C6 H6 0.9500 . ? C64 N67 1.397(4) . ? C64 C65 1.409(4) . ? C64 C63 1.427(4) . ? C36 C35 1.395(4) . ? C36 H36 0.9500 . ? C65 C66 1.387(4) . ? C65 H65 0.9500 . ? C33 C32 1.392(4) . ? C33 C34 1.405(4) . ? C33 H33 0.9500 . ? C12 C11 1.377(4) . ? C12 H12 0.9500 . ? C32 H32 0.9500 . ? C66 H66 0.9500 . ? C11 C10 1.420(4) . ? C11 H11 0.9500 . ? N67 C68 1.462(4) . ? N67 C69 1.470(4) . ? C55 C54 1.415(4) . ? C55 H55 0.9500 . ? C53 C54 1.412(4) . ? C53 H53 0.9500 . ? C41 C40 1.369(4) . ? C41 C51 1.512(4) . ? C10 C9 1.378(4) . ? C10 H10 0.9500 . ? C59 H59A 0.9800 . ? C59 H59B 0.9800 . ? C59 H59C 0.9800 . ? C9 C8 1.420(4) . ? C9 H9 0.9500 . ? C7 C8 1.433(4) . ? C7 H7 0.9500 . ? C34 C35 1.396(4) . ? C34 H34 0.9500 . ? C35 H35 0.9500 . ? C69 H69A 0.9800 . ? C69 H69B 0.9800 . ? C69 H69C 0.9800 . ? C62 C63 1.388(4) . ? C62 H62 0.9500 . ? C63 H63 0.9500 . ? C68 H68A 0.9800 . ? C68 H68B 0.9800 . ? C68 H68C 0.9800 . ? C40 H40 0.9500 . ? C58 H58A 0.9800 . ? C58 H58B 0.9800 . ? C58 H58C 0.9800 . ? 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 O4 C3 117.9(2) . . ? C32 C31 C36 117.4(2) . . ? C32 C31 C3 121.9(3) . . ? C36 C31 C3 120.7(2) . . ? C2 C1 C40 110.2(2) . . ? C2 C1 C14 109.0(2) . . ? C40 C1 C14 111.1(2) . . ? C2 C1 H1 108.8 . . ? C40 C1 H1 108.8 . . ? C14 C1 H1 108.8 . . ? C12 C13 C14 122.7(3) . . ? C12 C13 C8 117.3(2) . . ? C14 C13 C8 119.9(2) . . ? C3 C2 C1 125.2(2) . . ? C3 C2 H2 117.4 . . ? C1 C2 H2 117.4 . . ? C54 N57 C58 118.5(3) . . ? C54 N57 C59 118.1(2) . . ? C58 N57 C59 115.0(3) . . ? C53 C52 C51 121.6(3) . . ? C53 C52 H52 119.2 . . ? C51 C52 H52 119.2 . . ? C2 C3 O4 121.6(2) . . ? C2 C3 C31 127.4(3) . . ? O4 C3 C31 110.9(2) . . ? C62 C61 C66 115.3(3) . . ? C62 C61 C41 123.1(2) . . ? C66 C61 C41 121.6(2) . . ? C55 C56 C51 122.4(3) . . ? C55 C56 H56 118.8 . . ? C51 C56 H56 118.8 . . ? C5 C14 C13 118.3(2) . . ? C5 C14 C1 120.4(2) . . ? C13 C14 C1 121.3(2) . . ? C7 C6 C5 119.6(3) . . ? C7 C6 H6 120.2 . . ? C5 C6 H6 120.2 . . ? N67 C64 C65 122.1(3) . . ? N67 C64 C63 121.5(3) . . ? C65 C64 C63 116.4(3) . . ? C35 C36 C31 120.7(3) . . ? C35 C36 H36 119.7 . . ? C31 C36 H36 119.7 . . ? C66 C65 C64 121.9(3) . . ? C66 C65 H65 119.1 . . ? C64 C65 H65 119.1 . . ? C32 C33 C34 120.5(3) . . ? C32 C33 H33 119.7 . . ? C34 C33 H33 119.7 . . ? C11 C12 C13 121.4(3) . . ? C11 C12 H12 119.3 . . ? C13 C12 H12 119.3 . . ? C33 C32 C31 121.3(3) . . ? C33 C32 H32 119.3 . . ? C31 C32 H32 119.3 . . ? C65 C66 C61 122.3(3) . . ? C65 C66 H66 118.9 . . ? C61 C66 H66 118.9 . . ? C12 C11 C10 120.8(3) . . ? C12 C11 H11 119.6 . . ? C10 C11 H11 119.6 . . ? C14 C5 O4 124.3(2) . . ? C14 C5 C6 122.2(3) . . ? O4 C5 C6 113.4(2) . . ? C64 N67 C68 120.0(3) . . ? C64 N67 C69 119.4(3) . . ? C68 N67 C69 117.5(3) . . ? C56 C55 C54 120.3(3) . . ? C56 C55 H55 119.8 . . ? C54 C55 H55 119.8 . . ? C52 C53 C54 120.7(3) . . ? C52 C53 H53 119.6 . . ? C54 C53 H53 119.6 . . ? C40 C41 C61 121.3(2) . . ? C40 C41 C51 119.7(3) . . ? C61 C41 C51 118.9(2) . . ? C9 C10 C11 119.5(3) . . ? C9 C10 H10 120.2 . . ? C11 C10 H10 120.2 . . ? N57 C59 H59A 109.5 . . ? N57 C59 H59B 109.5 . . ? H59A C59 H59B 109.5 . . ? N57 C59 H59C 109.5 . . ? H59A C59 H59C 109.5 . . ? H59B C59 H59C 109.5 . . ? C10 C9 C8 121.3(3) . . ? C10 C9 H9 119.3 . . ? C8 C9 H9 119.3 . . ? C53 C54 C55 117.9(3) . . ? C53 C54 N57 120.5(2) . . ? C55 C54 N57 121.5(3) . . ? C6 C7 C8 121.5(3) . . ? C6 C7 H7 119.3 . . ? C8 C7 H7 119.3 . . ? C56 C51 C52 117.0(3) . . ? C56 C51 C41 121.1(2) . . ? C52 C51 C41 122.0(3) . . ? C35 C34 C33 118.9(3) . . ? C35 C34 H34 120.6 . . ? C33 C34 H34 120.6 . . ? C36 C35 C34 121.2(3) . . ? C36 C35 H35 119.4 . . ? C34 C35 H35 119.4 . . ? C9 C8 C7 122.0(3) . . ? C9 C8 C13 119.6(3) . . ? C7 C8 C13 118.4(3) . . ? N67 C69 H69A 109.5 . . ? N67 C69 H69B 109.5 . . ? H69A C69 H69B 109.5 . . ? N67 C69 H69C 109.5 . . ? H69A C69 H69C 109.5 . . ? H69B C69 H69C 109.5 . . ? C63 C62 C61 123.1(3) . . ? C63 C62 H62 118.4 . . ? C61 C62 H62 118.4 . . ? C62 C63 C64 120.7(3) . . ? C62 C63 H63 119.6 . . ? C64 C63 H63 119.6 . . ? N67 C68 H68A 109.5 . . ? N67 C68 H68B 109.5 . . ? H68A C68 H68B 109.5 . . ? N67 C68 H68C 109.5 . . ? H68A C68 H68C 109.5 . . ? H68B C68 H68C 109.5 . . ? C41 C40 C1 127.2(2) . . ? C41 C40 H40 116.4 . . ? C1 C40 H40 116.4 . . ? N57 C58 H58A 109.5 . . ? N57 C58 H58B 109.5 . . ? H58A C58 H58B 109.5 . . ? N57 C58 H58C 109.5 . . ? H58A C58 H58C 109.5 . . ? H58B C58 H58C 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 C40 C1 C2 C3 109.4(3) . . . . ? C14 C1 C2 C3 -12.8(4) . . . . ? C1 C2 C3 O4 5.9(4) . . . . ? C1 C2 C3 C31 -174.5(3) . . . . ? C5 O4 C3 C2 5.5(4) . . . . ? C5 O4 C3 C31 -174.1(2) . . . . ? C32 C31 C3 C2 3.8(4) . . . . ? C36 C31 C3 C2 -176.3(3) . . . . ? C32 C31 C3 O4 -176.6(3) . . . . ? C36 C31 C3 O4 3.3(4) . . . . ? C12 C13 C14 C5 179.4(3) . . . . ? C8 C13 C14 C5 0.6(4) . . . . ? C12 C13 C14 C1 0.3(4) . . . . ? C8 C13 C14 C1 -178.5(3) . . . . ? C2 C1 C14 C5 9.4(4) . . . . ? C40 C1 C14 C5 -112.2(3) . . . . ? C2 C1 C14 C13 -171.6(2) . . . . ? C40 C1 C14 C13 66.8(3) . . . . ? C32 C31 C36 C35 0.2(4) . . . . ? C3 C31 C36 C35 -179.8(3) . . . . ? N67 C64 C65 C66 176.2(3) . . . . ? C63 C64 C65 C66 -4.6(4) . . . . ? C14 C13 C12 C11 -177.4(3) . . . . ? C8 C13 C12 C11 1.4(4) . . . . ? C34 C33 C32 C31 0.3(4) . . . . ? C36 C31 C32 C33 -0.2(4) . . . . ? C3 C31 C32 C33 179.8(3) . . . . ? C64 C65 C66 C61 -0.3(5) . . . . ? C62 C61 C66 C65 4.9(4) . . . . ? C41 C61 C66 C65 -173.4(3) . . . . ? C13 C12 C11 C10 -0.4(4) . . . . ? C13 C14 C5 O4 -178.7(2) . . . . ? C1 C14 C5 O4 0.4(4) . . . . ? C13 C14 C5 C6 1.6(4) . . . . ? C1 C14 C5 C6 -179.3(3) . . . . ? C3 O4 C5 C14 -8.6(4) . . . . ? C3 O4 C5 C6 171.1(3) . . . . ? C7 C6 C5 C14 -2.2(5) . . . . ? C7 C6 C5 O4 178.0(3) . . . . ? C65 C64 N67 C68 -168.6(3) . . . . ? C63 C64 N67 C68 12.2(4) . . . . ? C65 C64 N67 C69 -9.3(4) . . . . ? C63 C64 N67 C69 171.5(3) . . . . ? C51 C56 C55 C54 -0.7(4) . . . . ? C51 C52 C53 C54 -1.8(4) . . . . ? C62 C61 C41 C40 -25.8(4) . . . . ? C66 C61 C41 C40 152.4(3) . . . . ? C62 C61 C41 C51 154.8(3) . . . . ? C66 C61 C41 C51 -27.0(4) . . . . ? C12 C11 C10 C9 -0.8(5) . . . . ? C11 C10 C9 C8 0.9(5) . . . . ? C52 C53 C54 C55 0.2(4) . . . . ? C52 C53 C54 N57 -177.8(3) . . . . ? C56 C55 C54 C53 1.0(4) . . . . ? C56 C55 C54 N57 178.9(3) . . . . ? C58 N57 C54 C53 -33.4(4) . . . . ? C59 N57 C54 C53 179.9(3) . . . . ? C58 N57 C54 C55 148.7(3) . . . . ? C59 N57 C54 C55 2.1(4) . . . . ? C5 C6 C7 C8 0.7(4) . . . . ? C55 C56 C51 C52 -0.9(4) . . . . ? C55 C56 C51 C41 177.6(3) . . . . ? C53 C52 C51 C56 2.1(4) . . . . ? C53 C52 C51 C41 -176.4(3) . . . . ? C40 C41 C51 C56 -61.8(4) . . . . ? C61 C41 C51 C56 117.5(3) . . . . ? C40 C41 C51 C52 116.6(3) . . . . ? C61 C41 C51 C52 -64.0(3) . . . . ? C32 C33 C34 C35 -0.3(4) . . . . ? C31 C36 C35 C34 -0.3(4) . . . . ? C33 C34 C35 C36 0.3(4) . . . . ? C10 C9 C8 C7 179.7(3) . . . . ? C10 C9 C8 C13 0.1(4) . . . . ? C6 C7 C8 C9 -178.2(3) . . . . ? C6 C7 C8 C13 1.4(4) . . . . ? C12 C13 C8 C9 -1.3(4) . . . . ? C14 C13 C8 C9 177.6(3) . . . . ? C12 C13 C8 C7 179.1(3) . . . . ? C14 C13 C8 C7 -2.0(4) . . . . ? C66 C61 C62 C63 -4.7(4) . . . . ? C41 C61 C62 C63 173.6(3) . . . . ? C61 C62 C63 C64 -0.1(5) . . . . ? N67 C64 C63 C62 -176.0(3) . . . . ? C65 C64 C63 C62 4.8(4) . . . . ? C61 C41 C40 C1 173.9(2) . . . . ? C51 C41 C40 C1 -6.8(4) . . . . ? C2 C1 C40 C41 109.8(3) . . . . ? C14 C1 C40 C41 -129.3(3) . . . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 25.83 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.190 _refine_diff_density_min -0.182 _refine_diff_density_rms 0.044