#------------------------------------------------------------------------------ #$Date: 2021-07-31 04:52:40 +0300 (Sat, 31 Jul 2021) $ #$Revision: 267842 $ #$URL: file:///home/coder/svn-repositories/cod/cif/1/56/42/1564278.cif $ #------------------------------------------------------------------------------ # # This file is available in the Crystallography Open Database (COD), # http://www.crystallography.net/ # # All data on this site have been placed in the public domain by the # contributors. # data_1564278 loop_ _publ_author_name 'Eagling, Louise' 'Leonard, Daniel J.' 'Schwarz, Maria' 'Urruzuno, I\~naki' 'Boden, Grace' 'Wailes, J. Steven' 'Ward, John W.' 'Clayden, Jonathan' _publ_section_title ; ‘Reverse biomimetic’ synthesis of l-arogenate and its stabilized analogues from l-tyrosine ; _journal_name_full 'Chemical Science' _journal_paper_doi 10.1039/D1SC03554A _journal_year 2021 _chemical_absolute_configuration unk _chemical_formula_moiety 'C16 H22 N2 O3' _chemical_formula_sum 'C16 H22 N2 O3' _chemical_formula_weight 290.35 _space_group_crystal_system monoclinic _space_group_IT_number 4 _space_group_name_Hall 'P 2yb' _space_group_name_H-M_alt 'P 1 21 1' _atom_sites_solution_hydrogens mixed _atom_sites_solution_primary iterative _audit_creation_date 2016-11-15 _audit_creation_method ; Olex2 1.2 (compiled 2016.11.07 svn.r3352 for OlexSys, GUI svn.r5261) ; _audit_update_record ; 2021-03-12 deposited with the CCDC. 2021-07-12 downloaded from the CCDC. ; _cell_angle_alpha 90 _cell_angle_beta 95.964(3) _cell_angle_gamma 90 _cell_formula_units_Z 2 _cell_length_a 5.7583(3) _cell_length_b 13.5711(6) _cell_length_c 9.6541(5) _cell_measurement_reflns_used 2145 _cell_measurement_temperature 100(2) _cell_measurement_theta_max 23.52 _cell_measurement_theta_min 2.60 _cell_volume 750.35(6) _computing_cell_refinement 'SAINT v8.37A (Bruker, 2015)' _computing_data_reduction 'SAINT v8.37A (Bruker, 2015)' _computing_molecular_graphics 'Olex2 (Dolomanov et al., 2009)' _computing_publication_material 'Olex2 (Dolomanov et al., 2009)' _computing_structure_refinement 'ShelXL (Sheldrick, 2015)' _computing_structure_solution ; Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008; Palatinus et al., 2012) ; _diffrn_ambient_temperature 100(2) _diffrn_detector 'Bruker area detector' _diffrn_detector_type 'CCD area detector' _diffrn_measured_fraction_theta_full 1.000 _diffrn_measured_fraction_theta_max 0.995 _diffrn_measurement_device 'Bruker Apex II kappa CCD area detector' _diffrn_measurement_device_type 'Bruker Apex II kappa CCD area detector' _diffrn_measurement_method '\f and \w scans' _diffrn_radiation_monochromator graphite _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_reflns_av_R_equivalents 0.0447 _diffrn_reflns_av_unetI/netI 0.0519 _diffrn_reflns_Laue_measured_fraction_full 1.000 _diffrn_reflns_Laue_measured_fraction_max 0.995 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_number 10338 _diffrn_reflns_point_group_measured_fraction_full 0.968 _diffrn_reflns_point_group_measured_fraction_max 0.951 _diffrn_reflns_theta_full 26.000 _diffrn_reflns_theta_max 27.992 _diffrn_reflns_theta_min 2.121 _diffrn_source 'fine-focus sealed tube' _diffrn_standards_number 0 _exptl_absorpt_coefficient_mu 0.089 _exptl_absorpt_correction_T_max 0.7456 _exptl_absorpt_correction_T_min 0.6354 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0890 before and 0.0506 after correction. The Ratio of minimum to maximum transmission is 0.8522. The \l/2 correction factor is Not present. ; _exptl_crystal_colour colourless _exptl_crystal_colour_primary colourless _exptl_crystal_density_diffrn 1.285 _exptl_crystal_description plate _exptl_crystal_F_000 312 _exptl_crystal_size_max 0.534 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.136 _refine_diff_density_max 0.225 _refine_diff_density_min -0.210 _refine_diff_density_rms 0.042 _refine_ls_abs_structure_details ; Flack x determined using 1168 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61). ; _refine_ls_abs_structure_Flack -0.6(7) _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.025 _refine_ls_hydrogen_treatment mixed _refine_ls_matrix_type full _refine_ls_number_parameters 198 _refine_ls_number_reflns 3447 _refine_ls_number_restraints 1 _refine_ls_restrained_S_all 1.025 _refine_ls_R_factor_all 0.0519 _refine_ls_R_factor_gt 0.0411 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details 'w=1/[\s^2^(Fo^2^)+(0.0431P)^2^] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.0824 _refine_ls_wR_factor_ref 0.0867 _reflns_Friedel_coverage 0.835 _reflns_Friedel_fraction_full 0.933 _reflns_Friedel_fraction_max 0.903 _reflns_number_gt 2950 _reflns_number_total 3447 _reflns_threshold_expression 'I > 2\s(I)' _cod_data_source_file d1sc03554a2.cif _cod_data_source_block testm1 _cod_database_code 1564278 _shelxl_version_number 2013-4 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _olex2_refinement_description ; 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H) groups At 1.5 times of: All C(H,H,H) groups 2.a Ternary CH refined with riding coordinates: C2(H2), C3(H3A), C14(H14) 2.b Secondary CH2 refined with riding coordinates: C4(H4A,H4B) 2.c Aromatic/amide H refined with riding coordinates: C12(H12), C13(H13), C15(H15), C16(H16) 2.d Idealised Me refined as rotating group: C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C) ; _shelx_res_file ; TITL testm1 in P2(1) CELL 0.71073 5.7583 13.5711 9.6541 90 95.9635 90 ZERR 2 0.0003 0.0006 0.0005 0 0.0034 0 LATT -1 SYMM -X,0.5+Y,-Z SFAC C H N O UNIT 32 44 4 6 L.S. 4 0 0 PLAN 5 TEMP -173(2) fmap 2 53 MORE -1 BOND $H ACTA 52 CONF REM REM REM WGHT 0.043100 FVAR 0.45778 O1 4 1.040120 0.888630 0.248102 11.00000 0.02874 0.01420 = 0.02497 0.00114 0.00955 -0.00404 O2 4 0.434604 0.583801 0.308368 11.00000 0.01525 0.01820 = 0.01903 -0.00203 0.00178 -0.00358 O3 4 0.557361 0.345686 -0.124317 11.00000 0.02547 0.02180 = 0.02427 -0.00905 0.00582 -0.00686 N1 3 0.808191 0.830873 0.409110 11.00000 0.01820 0.01081 = 0.01568 0.00044 0.00290 0.00169 N2 3 0.778594 0.669744 0.349471 11.00000 0.01207 0.01261 = 0.01280 -0.00156 0.00238 -0.00111 C1 1 0.942861 0.820772 0.303949 11.00000 0.01567 0.01451 = 0.01498 -0.00099 0.00072 0.00082 C2 1 0.716491 0.737551 0.458256 11.00000 0.01355 0.01211 = 0.01393 -0.00156 0.00208 0.00036 AFIX 13 H2 2 0.542621 0.741901 0.454761 11.00000 -1.20000 AFIX 0 C3 1 0.955386 0.712732 0.268216 11.00000 0.01222 0.01218 = 0.01587 -0.00007 0.00420 -0.00030 AFIX 13 H3A 2 1.113791 0.685323 0.298389 11.00000 -1.20000 AFIX 0 C4 1 0.875165 0.684262 0.116552 11.00000 0.01858 0.01540 = 0.01351 -0.00093 0.00304 -0.00116 AFIX 23 H4A 2 1.010269 0.666373 0.066104 11.00000 -1.20000 H4B 2 0.789569 0.739251 0.066952 11.00000 -1.20000 AFIX 0 C5 1 0.712705 0.594388 0.128839 11.00000 0.01587 0.01307 = 0.01270 -0.00110 0.00031 0.00043 C6 1 0.618167 0.613931 0.270871 11.00000 0.01488 0.01065 = 0.01529 0.00038 -0.00057 0.00284 C7 1 0.734857 0.926864 0.454939 11.00000 0.04330 0.01262 = 0.02874 0.00105 0.01567 0.00651 AFIX 137 H7A 2 0.837890 0.947646 0.536922 11.00000 -1.50000 H7B 2 0.573905 0.922781 0.478947 11.00000 -1.50000 H7C 2 0.743300 0.974927 0.379868 11.00000 -1.50000 AFIX 0 C8 1 0.818311 0.705776 0.605866 11.00000 0.01289 0.01716 = 0.01291 0.00110 0.00076 -0.00163 C9 1 1.086215 0.705718 0.617772 11.00000 0.01625 0.02410 = 0.02040 0.00166 -0.00143 0.00106 AFIX 137 H9A 2 1.139584 0.660942 0.548002 11.00000 -1.50000 H9B 2 1.147710 0.683662 0.711095 11.00000 -1.50000 H9C 2 1.142392 0.772512 0.601821 11.00000 -1.50000 AFIX 0 C10 1 0.732805 0.775240 0.715107 11.00000 0.02033 0.02181 = 0.01479 -0.00227 0.00132 -0.00101 AFIX 137 H10A 2 0.804742 0.840200 0.707535 11.00000 -1.50000 H10B 2 0.776442 0.748365 0.808404 11.00000 -1.50000 H10C 2 0.562585 0.781550 0.699197 11.00000 -1.50000 AFIX 0 C11 1 0.728243 0.601920 0.631721 11.00000 0.02169 0.01926 = 0.01991 0.00300 0.00178 -0.00079 AFIX 137 H11A 2 0.557162 0.602482 0.623009 11.00000 -1.50000 H11B 2 0.787728 0.580406 0.725655 11.00000 -1.50000 H11C 2 0.782194 0.556405 0.563048 11.00000 -1.50000 AFIX 0 C12 1 0.847321 0.498257 0.141524 11.00000 0.01819 0.01750 = 0.01578 -0.00012 0.00001 0.00282 AFIX 43 H12 2 0.996633 0.497564 0.193632 11.00000 -1.20000 AFIX 0 C13 1 0.766130 0.415547 0.083356 11.00000 0.02248 0.01551 = 0.01792 0.00090 0.00152 0.00489 AFIX 43 H13 2 0.858792 0.357846 0.098172 11.00000 -1.20000 AFIX 0 C14 1 0.536833 0.406891 -0.004655 11.00000 0.02287 0.01930 = 0.01449 -0.00435 0.00380 -0.00537 AFIX 13 H14 2 0.425735 0.373453 0.053084 11.00000 -1.20000 AFIX 0 C15 1 0.436500 0.505999 -0.043939 11.00000 0.01681 0.02484 = 0.01210 -0.00164 0.00030 0.00094 AFIX 43 H15 2 0.310153 0.509212 -0.115369 11.00000 -1.20000 AFIX 0 C16 1 0.513741 0.589377 0.015143 11.00000 0.01681 0.01948 = 0.01401 0.00116 0.00058 0.00449 AFIX 43 H16 2 0.439696 0.649132 -0.015861 11.00000 -1.20000 AFIX 0 H3 2 0.682088 0.366938 -0.160567 11.00000 0.01974 HKLF 4 REM testm1 in P2(1) REM R1 = 0.0411 for 2950 Fo > 4sig(Fo) and 0.0519 for all 3447 data REM 198 parameters refined using 1 restraints END WGHT 0.0431 0.0000 REM Highest difference peak 0.225, deepest hole -0.210, 1-sigma level 0.042 Q1 1 0.9298 0.6982 0.1877 11.00000 0.05 0.23 Q2 1 0.7636 0.7238 0.5344 11.00000 0.05 0.20 Q3 1 0.7817 0.7398 0.6596 11.00000 0.05 0.18 Q4 1 0.6774 0.5868 0.2041 11.00000 0.05 0.18 Q5 1 0.6286 0.5950 0.0768 11.00000 0.05 0.17 ; _shelx_res_checksum 65407 _olex2_submission_special_instructions 'No special instructions were received' loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, y+1/2, -z' 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group O1 O 1.0401(3) 0.88863(12) 0.2481(2) 0.0222(4) Uani 1 1 d . . . . . O2 O 0.4346(3) 0.58380(13) 0.30837(17) 0.0175(4) Uani 1 1 d . . . . . O3 O 0.5574(3) 0.34569(14) -0.12432(19) 0.0236(4) Uani 1 1 d . . . . . N1 N 0.8082(3) 0.83087(15) 0.4091(2) 0.0148(4) Uani 1 1 d . . . . . N2 N 0.7786(3) 0.66974(15) 0.3495(2) 0.0124(4) Uani 1 1 d . . . . . C1 C 0.9429(4) 0.82077(18) 0.3039(2) 0.0151(5) Uani 1 1 d . . . . . C2 C 0.7165(4) 0.73755(17) 0.4583(2) 0.0132(5) Uani 1 1 d . . . . . H2 H 0.5426 0.7419 0.4548 0.016 Uiso 1 1 calc R . . . . C3 C 0.9554(4) 0.71273(17) 0.2682(2) 0.0132(5) Uani 1 1 d . . . . . H3A H 1.1138 0.6853 0.2984 0.016 Uiso 1 1 calc R . . . . C4 C 0.8752(4) 0.68426(17) 0.1166(3) 0.0157(5) Uani 1 1 d . . . . . H4A H 1.0103 0.6664 0.0661 0.019 Uiso 1 1 calc R . . . . H4B H 0.7896 0.7393 0.0670 0.019 Uiso 1 1 calc R . . . . C5 C 0.7127(4) 0.59439(19) 0.1288(2) 0.0140(5) Uani 1 1 d . . . . . C6 C 0.6182(4) 0.61393(16) 0.2709(3) 0.0138(5) Uani 1 1 d . . . . . C7 C 0.7349(5) 0.9269(2) 0.4549(3) 0.0274(7) Uani 1 1 d . . . . . H7A H 0.8379 0.9476 0.5369 0.041 Uiso 1 1 calc GR . . . . H7B H 0.5739 0.9228 0.4789 0.041 Uiso 1 1 calc GR . . . . H7C H 0.7433 0.9749 0.3799 0.041 Uiso 1 1 calc GR . . . . C8 C 0.8183(4) 0.70578(18) 0.6059(2) 0.0144(5) Uani 1 1 d . . . . . C9 C 1.0862(4) 0.7057(2) 0.6178(3) 0.0205(6) Uani 1 1 d . . . . . H9A H 1.1396 0.6609 0.5480 0.031 Uiso 1 1 calc GR . . . . H9B H 1.1477 0.6837 0.7111 0.031 Uiso 1 1 calc GR . . . . H9C H 1.1424 0.7725 0.6018 0.031 Uiso 1 1 calc GR . . . . C10 C 0.7328(4) 0.77524(19) 0.7151(3) 0.0190(6) Uani 1 1 d . . . . . H10A H 0.8047 0.8402 0.7075 0.029 Uiso 1 1 calc GR . . . . H10B H 0.7764 0.7484 0.8084 0.029 Uiso 1 1 calc GR . . . . H10C H 0.5626 0.7816 0.6992 0.029 Uiso 1 1 calc GR . . . . C11 C 0.7282(5) 0.6019(2) 0.6317(3) 0.0203(6) Uani 1 1 d . . . . . H11A H 0.5572 0.6025 0.6230 0.030 Uiso 1 1 calc GR . . . . H11B H 0.7877 0.5804 0.7257 0.030 Uiso 1 1 calc GR . . . . H11C H 0.7822 0.5564 0.5630 0.030 Uiso 1 1 calc GR . . . . C12 C 0.8473(4) 0.49826(19) 0.1415(3) 0.0173(5) Uani 1 1 d . . . . . H12 H 0.9966 0.4976 0.1936 0.021 Uiso 1 1 calc R . . . . C13 C 0.7661(5) 0.41555(19) 0.0834(3) 0.0187(5) Uani 1 1 d . . . . . H13 H 0.8588 0.3578 0.0982 0.022 Uiso 1 1 calc R . . . . C14 C 0.5368(5) 0.40689(19) -0.0047(3) 0.0188(6) Uani 1 1 d . . . . . H14 H 0.4257 0.3735 0.0531 0.023 Uiso 1 1 calc R . . . . C15 C 0.4365(4) 0.50600(19) -0.0439(2) 0.0180(5) Uani 1 1 d . . . . . H15 H 0.3102 0.5092 -0.1154 0.022 Uiso 1 1 calc R . . . . C16 C 0.5137(4) 0.5894(2) 0.0151(2) 0.0168(5) Uani 1 1 d . . . . . H16 H 0.4397 0.6491 -0.0159 0.020 Uiso 1 1 calc R . . . . H3 H 0.682(5) 0.367(2) -0.161(3) 0.020(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 0.0287(11) 0.0142(9) 0.0250(10) 0.0011(7) 0.0096(8) -0.0040(8) O2 0.0152(9) 0.0182(9) 0.0190(9) -0.0020(8) 0.0018(7) -0.0036(8) O3 0.0255(11) 0.0218(11) 0.0243(10) -0.0091(8) 0.0058(8) -0.0069(8) N1 0.0182(11) 0.0108(10) 0.0157(10) 0.0004(8) 0.0029(8) 0.0017(9) N2 0.0121(10) 0.0126(10) 0.0128(10) -0.0016(8) 0.0024(8) -0.0011(8) C1 0.0157(12) 0.0145(12) 0.0150(11) -0.0010(10) 0.0007(9) 0.0008(10) C2 0.0135(11) 0.0121(12) 0.0139(12) -0.0016(9) 0.0021(9) 0.0004(9) C3 0.0122(11) 0.0122(12) 0.0159(12) -0.0001(9) 0.0042(9) -0.0003(9) C4 0.0186(13) 0.0154(14) 0.0135(12) -0.0009(9) 0.0030(10) -0.0012(10) C5 0.0159(11) 0.0131(12) 0.0127(11) -0.0011(10) 0.0003(9) 0.0004(10) C6 0.0149(12) 0.0106(12) 0.0153(12) 0.0004(9) -0.0006(9) 0.0028(9) C7 0.0433(18) 0.0126(13) 0.0287(16) 0.0010(11) 0.0157(13) 0.0065(12) C8 0.0129(11) 0.0172(12) 0.0129(11) 0.0011(10) 0.0008(9) -0.0016(10) C9 0.0162(12) 0.0241(14) 0.0204(13) 0.0017(11) -0.0014(10) 0.0011(11) C10 0.0203(14) 0.0218(14) 0.0148(12) -0.0023(10) 0.0013(10) -0.0010(10) C11 0.0217(13) 0.0193(14) 0.0199(13) 0.0030(11) 0.0018(10) -0.0008(11) C12 0.0182(13) 0.0175(13) 0.0158(12) -0.0001(10) 0.0000(10) 0.0028(10) C13 0.0225(14) 0.0155(13) 0.0179(13) 0.0009(10) 0.0015(10) 0.0049(10) C14 0.0229(14) 0.0193(14) 0.0145(12) -0.0043(10) 0.0038(10) -0.0054(10) C15 0.0168(13) 0.0248(14) 0.0121(12) -0.0016(10) 0.0003(10) 0.0009(11) C16 0.0168(12) 0.0195(13) 0.0140(12) 0.0012(11) 0.0006(9) 0.0045(11) 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' 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 C14 O3 H3 105.6(19) . . ? C1 N1 C2 114.20(19) . . ? C1 N1 C7 122.0(2) . . ? C7 N1 C2 123.3(2) . . ? C2 N2 C3 111.52(19) . . ? C6 N2 C2 123.0(2) . . ? C6 N2 C3 113.00(19) . . ? O1 C1 N1 125.3(2) . . ? O1 C1 C3 126.3(2) . . ? N1 C1 C3 108.4(2) . . ? N1 C2 H2 109.3 . . ? N1 C2 C8 115.07(19) . . ? N2 C2 N1 100.77(18) . . ? N2 C2 H2 109.3 . . ? N2 C2 C8 112.80(19) . . ? C8 C2 H2 109.3 . . ? N2 C3 C1 102.21(19) . . ? N2 C3 H3A 111.0 . . ? N2 C3 C4 104.61(18) . . ? C1 C3 H3A 111.0 . . ? C1 C3 C4 116.4(2) . . ? C4 C3 H3A 111.0 . . ? C3 C4 H4A 110.9 . . ? C3 C4 H4B 110.9 . . ? C3 C4 C5 104.41(19) . . ? H4A C4 H4B 108.9 . . ? C5 C4 H4A 110.9 . . ? C5 C4 H4B 110.9 . . ? C4 C5 C6 101.74(19) . . ? C12 C5 C4 112.08(19) . . ? C12 C5 C6 107.42(19) . . ? C16 C5 C4 113.6(2) . . ? C16 C5 C6 110.0(2) . . ? C16 C5 C12 111.4(2) . . ? O2 C6 N2 125.3(2) . . ? O2 C6 C5 126.8(2) . . ? N2 C6 C5 107.9(2) . . ? N1 C7 H7A 109.5 . . ? N1 C7 H7B 109.5 . . ? N1 C7 H7C 109.5 . . ? H7A C7 H7B 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C9 C8 C2 110.57(19) . . ? C10 C8 C2 110.2(2) . . ? C10 C8 C9 109.9(2) . . ? C11 C8 C2 107.74(19) . . ? C11 C8 C9 110.0(2) . . ? C11 C8 C10 108.4(2) . . ? C8 C9 H9A 109.5 . . ? C8 C9 H9B 109.5 . . ? C8 C9 H9C 109.5 . . ? H9A C9 H9B 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C8 C10 H10A 109.5 . . ? C8 C10 H10B 109.5 . . ? C8 C10 H10C 109.5 . . ? H10A C10 H10B 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? C8 C11 H11A 109.5 . . ? C8 C11 H11B 109.5 . . ? C8 C11 H11C 109.5 . . ? H11A C11 H11B 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C5 C12 H12 118.6 . . ? C13 C12 C5 122.8(2) . . ? C13 C12 H12 118.6 . . ? C12 C13 H13 118.0 . . ? C12 C13 C14 124.1(2) . . ? C14 C13 H13 118.0 . . ? O3 C14 C13 111.1(2) . . ? O3 C14 H14 107.2 . . ? O3 C14 C15 112.2(2) . . ? C13 C14 H14 107.2 . . ? C15 C14 C13 111.5(2) . . ? C15 C14 H14 107.2 . . ? C14 C15 H15 118.1 . . ? C16 C15 C14 123.7(2) . . ? C16 C15 H15 118.1 . . ? C5 C16 H16 118.3 . . ? C15 C16 C5 123.4(2) . . ? C15 C16 H16 118.3 . . ? 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 1.231(3) . ? O2 C6 1.223(3) . ? O3 C14 1.438(3) . ? O3 H3 0.88(3) . ? N1 C1 1.347(3) . ? N1 C2 1.470(3) . ? N1 C7 1.453(3) . ? N2 C2 1.468(3) . ? N2 C3 1.469(3) . ? N2 C6 1.363(3) . ? C1 C3 1.510(3) . ? C2 H2 1.0000 . ? C2 C8 1.545(3) . ? C3 H3A 1.0000 . ? C3 C4 1.538(3) . ? C4 H4A 0.9900 . ? C4 H4B 0.9900 . ? C4 C5 1.549(3) . ? C5 C6 1.550(3) . ? C5 C12 1.516(3) . ? C5 C16 1.504(3) . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 C9 1.535(3) . ? C8 C10 1.533(3) . ? C8 C11 1.531(4) . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? C12 H12 0.9500 . ? C12 C13 1.319(4) . ? C13 H13 0.9500 . ? C13 C14 1.499(4) . ? C14 H14 1.0000 . ? C14 C15 1.497(4) . ? C15 H15 0.9500 . ? C15 C16 1.323(4) . ? C16 H16 0.9500 . ? 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 O1 C1 C3 N2 -170.9(2) . . . . ? O1 C1 C3 C4 -57.6(3) . . . . ? O3 C14 C15 C16 -138.7(3) . . . . ? N1 C1 C3 N2 9.7(2) . . . . ? N1 C1 C3 C4 123.0(2) . . . . ? N1 C2 C8 C9 -52.5(3) . . . . ? N1 C2 C8 C10 69.2(2) . . . . ? N1 C2 C8 C11 -172.8(2) . . . . ? N2 C2 C8 C9 62.4(3) . . . . ? N2 C2 C8 C10 -175.9(2) . . . . ? N2 C2 C8 C11 -57.9(2) . . . . ? N2 C3 C4 C5 -21.2(2) . . . . ? C1 N1 C2 N2 -10.3(2) . . . . ? C1 N1 C2 C8 111.3(2) . . . . ? C1 C3 C4 C5 -133.1(2) . . . . ? C2 N1 C1 O1 -179.0(2) . . . . ? C2 N1 C1 C3 0.4(3) . . . . ? C2 N2 C3 C1 -16.7(2) . . . . ? C2 N2 C3 C4 -138.52(19) . . . . ? C2 N2 C6 O2 -28.8(4) . . . . ? C2 N2 C6 C5 152.3(2) . . . . ? C3 N2 C2 N1 16.7(2) . . . . ? C3 N2 C2 C8 -106.5(2) . . . . ? C3 N2 C6 O2 -167.5(2) . . . . ? C3 N2 C6 C5 13.6(3) . . . . ? C3 C4 C5 C6 28.0(2) . . . . ? C3 C4 C5 C12 -86.5(2) . . . . ? C3 C4 C5 C16 146.2(2) . . . . ? C4 C5 C6 O2 155.2(2) . . . . ? C4 C5 C6 N2 -26.0(2) . . . . ? C4 C5 C12 C13 -143.2(2) . . . . ? C4 C5 C16 C15 141.5(3) . . . . ? C5 C12 C13 C14 1.8(4) . . . . ? C6 N2 C2 N1 -122.5(2) . . . . ? C6 N2 C2 C8 114.3(2) . . . . ? C6 N2 C3 C1 126.8(2) . . . . ? C6 N2 C3 C4 5.0(3) . . . . ? C6 C5 C12 C13 105.8(3) . . . . ? C6 C5 C16 C15 -105.2(3) . . . . ? C7 N1 C1 O1 9.3(4) . . . . ? C7 N1 C1 C3 -171.3(2) . . . . ? C7 N1 C2 N2 161.2(2) . . . . ? C7 N1 C2 C8 -77.1(3) . . . . ? C12 C5 C6 O2 -87.0(3) . . . . ? C12 C5 C6 N2 91.9(2) . . . . ? C12 C5 C16 C15 13.8(4) . . . . ? C12 C13 C14 O3 138.3(3) . . . . ? C12 C13 C14 C15 12.4(4) . . . . ? C13 C14 C15 C16 -13.4(4) . . . . ? C14 C15 C16 C5 0.2(4) . . . . ? C16 C5 C6 O2 34.4(3) . . . . ? C16 C5 C6 N2 -146.7(2) . . . . ? C16 C5 C12 C13 -14.7(3) . . . . ?