Supplementary Material (Not for Publication)

Supplementary Material (not for publication)

CCDC deposited CIF entries for compounds (1) - (3)

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Compound (1): MORPHOABA: gs15gs27 Reference: Smith, G.: J. Chem. Cryst., 2016. CCDC xxxxxx ------data_(1)

_audit_creation_method SHELXL-97 _chemical_name_systematic ; tetrahydro-2H-1,4-oxazin-4-ium 2-aminobenzoate ; _chemical_name_common 'morpholinium anthranilate' _chemical_melting_point ? _chemical_formula_moiety 'C7 H6 N O2, C4 H10 N O' _chemical_formula_sum 'C11 H16 N2 O3' _chemical_formula_weight 224.26 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 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y+1/2, z+1/2'

_cell_length_a 11.0696(9) _cell_length_b 7.8775(6) _cell_length_c 13.0180(11) _cell_angle_alpha 90.00 _cell_angle_beta 95.804(8) _cell_angle_gamma 90.00 _cell_volume 1129.36(16) _cell_formula_units_Z 4 _cell_measurement_temperature 200(1) _cell_measurement_reflns_used 1115 _cell_measurement_theta_min 3.47 _cell_measurement_theta_max 28.33

_exptl_crystal_description 'plate' _exptl_crystal_colour 'colourless' _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.319 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 480 _exptl_absorpt_coefficient_mu 0.097 _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min 0.941 _exptl_absorpt_correction_T_max 0.980 _exptl_absorpt_process_details 'CrysAlis PRO (Agilent, 2014)'

_exptl_special_details ; ? ; _diffrn_ambient_temperature 200(1) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Enhance (Mo) X-ray source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Oxford Diffraction Gemini-S CCD-detector diffractometer' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 16.077 _diffrn_standards_number 0 _diffrn_standards_interval_count . _diffrn_standards_interval_time . _diffrn_standards_decay_% ? _diffrn_reflns_number 4383 _diffrn_reflns_av_R_equivalents 0.0303 _diffrn_reflns_av_sigmaI/netI 0.0445 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 3.18 _diffrn_reflns_theta_max 26.00 _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.999

_reflns_number_total 2218 _reflns_number_gt 1661 _reflns_threshold_expression 'I>2\s(I)'

_computing_data_collection 'CrysAlis PRO (Agilent, 2014)' _computing_cell_refinement 'CrysAlis PRO' _computing_data_reduction 'CrysAlis PRO' _computing_structure_solution 'SIR92 (Altomare et al., 2003)' _computing_structure_refinement 'SHELXL97 (Sheldrick, 1997) within WinGX (Farrugia, 2012)' _computing_molecular_graphics 'PLATON (Spek, 2009)' _computing_publication_material 'PLATON'

_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^)+(0.0464P)^2^+0.0632P] 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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2218 _refine_ls_number_parameters 157 _refine_ls_number_restraints 4 _refine_ls_R_factor_all 0.0715 _refine_ls_R_factor_gt 0.0472 _refine_ls_wR_factor_ref 0.1079 _refine_ls_wR_factor_gt 0.0974 _refine_ls_goodness_of_fit_ref 1.059 _refine_ls_restrained_S_all 1.059 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 0.167 _refine_diff_density_min -0.184 _refine_diff_density_rms 0.038 loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group

O11A O Uani 0.37446(12) 0.06851(15) 0.06179(9) 1.000 0.0377(4) d . . . O12A O Uani 0.47144(12) 0.26790(16) 0.15705(10) 1.000 0.0409(5) d . . . N2A N Uani 0.39038(16) 0.3505(2) 0.33745(13) 1.000 0.0432(6) d D . . C1A C Uani 0.28185(15) 0.17370(19) 0.20519(12) 1.000 0.0244(5) d . . . C2A C Uani 0.29125(16) 0.2587(2) 0.30149(12) 1.000 0.0263(5) d . . . C3A C Uani 0.19273(18) 0.2477(2) 0.36125(14) 1.000 0.0345(6) d . . . C4A C Uani 0.08895(17) 0.1622(2) 0.32700(15) 1.000 0.0407(7) d . . . C5A C Uani 0.07780(17) 0.0837(2) 0.23210(16) 1.000 0.0405(7) d . . . C6A C Uani 0.17399(16) 0.0902(2) 0.17319(14) 1.000 0.0317(6) d . . . C11A C Uani 0.38258(16) 0.1690(2) 0.13702(12) 1.000 0.0277(5) d . . . O4B O Uani 0.85088(12) 0.41948(15) -0.03448(10) 1.000 0.0382(4) d . . . N1B N Uani 0.64780(14) 0.24756(19) 0.03303(12) 1.000 0.0323(5) d D . . C2B C Uani 0.63417(16) 0.3877(2) -0.04351(14) 1.000 0.0352(6) d . . . C3B C Uani 0.74396(17) 0.3930(2) -0.10230(14) 1.000 0.0364(6) d . . . C5B C Uani 0.86875(17) 0.2875(2) 0.03868(14) 1.000 0.0362(6) d . . . C6B C Uani 0.76258(17) 0.2673(2) 0.10149(14) 1.000 0.0360(6) d . . . H3A H Uiso 0.19840 0.30100 0.42700 1.000 0.0410 c R . . H4A H Uiso 0.02380 0.15690 0.36920 1.000 0.0490 c R . . H5A H Uiso 0.00510 0.02620 0.20780 1.000 0.0490 c R . . H6A H Uiso 0.16640 0.03530 0.10790 1.000 0.0380 c R . . H21A H Uiso 0.4496(15) 0.358(2) 0.2954(13) 1.000 0.0390 d D . . H22A H Uiso 0.3991(17) 0.385(2) 0.4009(12) 1.000 0.0390 d D . . H11B H Uiso 0.6483(16) 0.1453(19) -0.0041(13) 1.000 0.0390 d D . . H12B H Uiso 0.5809(14) 0.250(2) 0.0740(13) 1.000 0.0390 d D . . H21B H Uiso 0.62540 0.49720 -0.00760 1.000 0.0420 c R . . H22B H Uiso 0.56040 0.36930 -0.09180 1.000 0.0420 c R . . H31B H Uiso 0.75080 0.28470 -0.13990 1.000 0.0440 c R . . H32B H Uiso 0.73490 0.48590 -0.15370 1.000 0.0440 c R . . H51B H Uiso 0.94280 0.31130 0.08560 1.000 0.0430 c R . . H52B H Uiso 0.88170 0.17960 0.00240 1.000 0.0430 c R . . H61B H Uiso 0.77540 0.16640 0.14660 1.000 0.0430 c R . . H62B H Uiso 0.75680 0.36820 0.14610 1.000 0.0430 c 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 O11A 0.0506(9) 0.0371(7) 0.0269(7) -0.0053(6) 0.0120(6) 0.0047(6) O12A 0.0373(8) 0.0431(8) 0.0462(8) -0.0070(6) 0.0227(6) -0.0089(6) N2A 0.0410(10) 0.0586(11) 0.0309(9) -0.0152(8) 0.0086(8) -0.0122(8) C1A 0.0280(9) 0.0227(9) 0.0231(9) 0.0034(7) 0.0050(7) 0.0021(7) C2A 0.0284(10) 0.0276(9) 0.0238(9) 0.0027(7) 0.0064(7) 0.0039(7) C3A 0.0413(12) 0.0355(10) 0.0288(10) 0.0026(8) 0.0136(8) 0.0094(9) C4A 0.0330(11) 0.0413(11) 0.0512(13) 0.0131(10) 0.0216(9) 0.0073(9) C5A 0.0280(10) 0.0394(11) 0.0541(13) 0.0085(9) 0.0037(9) -0.0043(8) C6A 0.0331(10) 0.0290(9) 0.0328(10) 0.0002(8) 0.0022(8) 0.0001(8) C11A 0.0338(10) 0.0261(9) 0.0241(9) 0.0025(8) 0.0076(7) 0.0053(8) O4B 0.0316(7) 0.0403(8) 0.0451(8) 0.0013(6) 0.0151(6) -0.0041(6) N1B 0.0308(9) 0.0323(9) 0.0361(9) -0.0044(7) 0.0146(7) -0.0051(7) C2B 0.0295(10) 0.0340(10) 0.0427(11) 0.0004(8) 0.0063(8) 0.0025(8) C3B 0.0405(12) 0.0358(10) 0.0345(10) 0.0055(8) 0.0110(9) 0.0028(9) C5B 0.0304(10) 0.0391(10) 0.0392(11) -0.0031(8) 0.0038(8) 0.0037(8) C6B 0.0413(12) 0.0377(10) 0.0298(10) -0.0013(8) 0.0075(8) -0.0032(8)

_geom_special_details ; Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag O11A C11A 1.255(2) . . no O12A C11A 1.261(2) . . no O4B C5B 1.410(2) . . no O4B C3B 1.419(2) . . no N2A C2A 1.357(2) . . no N2A H22A 0.866(16) . . no N2A H21A 0.898(17) . . no N1B C6B 1.485(2) . . no N1B C2B 1.485(2) . . no N1B H11B 0.940(15) . . no N1B H12B 0.956(16) . . no C1A C6A 1.390(2) . . no C1A C2A 1.416(2) . . no C1A C11A 1.494(2) . . no C2A C3A 1.405(3) . . no C3A C4A 1.367(3) . . no C4A C5A 1.376(3) . . no C5A C6A 1.375(3) . . no C3A H3A 0.9500 . . no C4A H4A 0.9500 . . no C5A H5A 0.9500 . . no C6A H6A 0.9500 . . no C2B C3B 1.501(3) . . no C5B C6B 1.507(3) . . no C2B H21B 0.9900 . . no C2B H22B 0.9900 . . no C3B H31B 0.9900 . . no C3B H32B 0.9900 . . no C5B H51B 0.9900 . . no C5B H52B 0.9900 . . no C6B H61B 0.9900 . . no C6B H62B 0.9900 . . no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C3B O4B C5B 111.29(13) . . . no H21A N2A H22A 122.9(16) . . . no C2A N2A H22A 120.3(12) . . . no C2A N2A H21A 116.1(11) . . . no C2B N1B C6B 110.35(13) . . . no C6B N1B H11B 110.5(11) . . . no C2B N1B H12B 109.1(10) . . . no H11B N1B H12B 110.5(14) . . . no C6B N1B H12B 109.1(10) . . . no C2B N1B H11B 107.3(10) . . . no C2A C1A C11A 123.04(15) . . . no C2A C1A C6A 118.25(15) . . . no C6A C1A C11A 118.71(14) . . . no N2A C2A C1A 122.81(16) . . . no C1A C2A C3A 118.00(15) . . . no N2A C2A C3A 119.19(15) . . . no C2A C3A C4A 121.58(16) . . . no C3A C4A C5A 120.69(18) . . . no C4A C5A C6A 118.68(17) . . . no C1A C6A C5A 122.75(16) . . . no O12A C11A C1A 118.37(14) . . . no O11A C11A C1A 118.69(15) . . . no O11A C11A O12A 122.93(16) . . . no C4A C3A H3A 119.00 . . . no C2A C3A H3A 119.00 . . . no C5A C4A H4A 120.00 . . . no C3A C4A H4A 120.00 . . . no C6A C5A H5A 121.00 . . . no C4A C5A H5A 121.00 . . . no C1A C6A H6A 119.00 . . . no C5A C6A H6A 119.00 . . . no N1B C2B C3B 109.29(14) . . . no O4B C3B C2B 110.76(15) . . . no O4B C5B C6B 112.37(14) . . . no N1B C6B C5B 110.64(15) . . . no N1B C2B H21B 110.00 . . . no N1B C2B H22B 110.00 . . . no C3B C2B H21B 110.00 . . . no C3B C2B H22B 110.00 . . . no H21B C2B H22B 108.00 . . . no O4B C3B H31B 109.00 . . . no O4B C3B H32B 109.00 . . . no C2B C3B H31B 110.00 . . . no C2B C3B H32B 109.00 . . . no H31B C3B H32B 108.00 . . . no O4B C5B H51B 109.00 . . . no O4B C5B H52B 109.00 . . . no C6B C5B H51B 109.00 . . . no C6B C5B H52B 109.00 . . . no H51B C5B H52B 108.00 . . . no N1B C6B H61B 110.00 . . . no N1B C6B H62B 110.00 . . . no C5B C6B H61B 110.00 . . . no C5B C6B H62B 109.00 . . . no H61B C6B H62B 108.00 . . . no 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 C5B O4B C3B C2B 60.58(17) . . . . no C3B O4B C5B C6B -57.46(18) . . . . no C6B N1B C2B C3B 55.62(18) . . . . no C2B N1B C6B C5B -52.55(17) . . . . no C11A C1A C2A C3A -177.00(15) . . . . no C2A C1A C6A C5A -1.5(2) . . . . no C2A C1A C11A O11A 168.38(15) . . . . no C2A C1A C11A O12A -12.5(2) . . . . no C6A C1A C11A O11A -11.3(2) . . . . no C6A C1A C11A O12A 167.91(15) . . . . no C11A C1A C2A N2A 3.5(2) . . . . no C6A C1A C2A N2A -176.83(16) . . . . no C11A C1A C6A C5A 178.12(15) . . . . no C6A C1A C2A C3A 2.6(2) . . . . no C1A C2A C3A C4A -1.9(2) . . . . no N2A C2A C3A C4A 177.55(16) . . . . no C2A C3A C4A C5A 0.0(3) . . . . no C3A C4A C5A C6A 1.2(3) . . . . no C4A C5A C6A C1A -0.4(3) . . . . no N1B C2B C3B O4B -59.56(17) . . . . no O4B C5B C6B N1B 53.44(18) . . . . no 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 _geom_hbond_publ_flag # #D H A D - H H...A D...A D - H...A symm(A) # N1B H11B O11A 0.940(15) 1.851(15) 2.7789(19) 168.8(16) 3_655 yes N1B H12B O12A 0.956(16) 1.709(16) 2.661(2) 173.5(14) . yes N2A H21A O12A 0.898(17) 1.973(17) 2.678(2) 134.2(14) . yes N2A H22A O11A 0.866(16) 2.170(16) 3.012(2) 164.0(17) 4_555 yes C4A H4A O4B 0.95 2.47 3.402(2) 168 4_455 yes C6A H6A O11A 0.95 2.45 2.776(2) 100 . no

# END

_iucr_refine_instructions_details ; TITL gs15gs27 MORPHANTH CELL 0.71073 11.0696 7.8775 13.0180 90.000 95.804 90.000 ZERR 4.00 0.0009 0.0006 0.0011 0.000 0.008 0.000 LATT 1 SYMM - X, 1/2 + Y, 1/2 - Z SFAC C H N O UNIT 44 64 8 12 MERG 2 OMIT -4.00 52.00 DFIX 0.92 0.02 N1B H11B N1B H12B DFIX 0.90 0.02 N2A H21A N2A H22A FMAP 2 PLAN 10 ACTA BOND $H L.S. 10 TEMP -73.00 WGHT 0.046400 0.063200 FVAR 6.36698 O12A 4 0.471445 0.267904 0.157054 11.00000 0.03727 0.04310 = 0.04622 -0.00703 0.02270 -0.00894 O11A 4 0.374460 0.068512 0.061788 11.00000 0.05062 0.03714 = 0.02689 -0.00533 0.01202 0.00469 C1A 1 0.281847 0.173701 0.205193 11.00000 0.02803 0.02274 = 0.02307 0.00340 0.00504 0.00213 N2A 3 0.390383 0.350542 0.337453 11.00000 0.04098 0.05864 = 0.03090 -0.01516 0.00860 -0.01217 C11A 1 0.382582 0.168993 0.137018 11.00000 0.03378 0.02608 = 0.02408 0.00253 0.00756 0.00528 C4A 1 0.088947 0.162186 0.326995 11.00000 0.03297 0.04129 = 0.05116 0.01313 0.02159 0.00725 AFIX 43 H4A 2 0.023845 0.156875 0.369167 11.00000 -1.20000 AFIX 0 C2A 1 0.291246 0.258661 0.301485 11.00000 0.02836 0.02755 = 0.02377 0.00265 0.00636 0.00386 C5A 1 0.077801 0.083734 0.232099 11.00000 0.02805 0.03939 = 0.05414 0.00851 0.00369 -0.00434 AFIX 43 H5A 2 0.005054 0.026229 0.207756 11.00000 -1.20000 AFIX 0 C6A 1 0.173987 0.090177 0.173188 11.00000 0.03307 0.02901 = 0.03279 0.00021 0.00223 0.00013 AFIX 43 H6A 2 0.166418 0.035255 0.107884 11.00000 -1.20000 AFIX 0 C3A 1 0.192733 0.247717 0.361250 11.00000 0.04132 0.03548 = 0.02878 0.00258 0.01361 0.00942 AFIX 43 H3A 2 0.198366 0.301010 0.427024 11.00000 -1.20000 AFIX 0 O4B 4 0.850881 0.419484 -0.034482 11.00000 0.03160 0.04026 = 0.04513 0.00127 0.01515 -0.00412 C2B 1 0.634169 0.387710 -0.043510 11.00000 0.02950 0.03395 = 0.04268 0.00042 0.00628 0.00248 AFIX 23 H21B 2 0.625437 0.497158 -0.007622 11.00000 -1.20000 H22B 2 0.560356 0.369349 -0.091818 11.00000 -1.20000 AFIX 0 C5B 1 0.868753 0.287456 0.038677 11.00000 0.03037 0.03909 = 0.03917 -0.00308 0.00384 0.00366 AFIX 23 H51B 2 0.942830 0.311324 0.085639 11.00000 -1.20000 H52B 2 0.881738 0.179574 0.002364 11.00000 -1.20000 AFIX 0 C3B 1 0.743958 0.393032 -0.102296 11.00000 0.04050 0.03577 = 0.03449 0.00547 0.01096 0.00277 AFIX 23 H31B 2 0.750753 0.284727 -0.139858 11.00000 -1.20000 H32B 2 0.734887 0.485883 -0.153748 11.00000 -1.20000 AFIX 0 C6B 1 0.762583 0.267332 0.101486 11.00000 0.04133 0.03766 = 0.02976 -0.00132 0.00746 -0.00318 AFIX 23 H61B 2 0.775352 0.166419 0.146604 11.00000 -1.20000 H62B 2 0.756803 0.368203 0.146086 11.00000 -1.20000 AFIX 0 N1B 3 0.647801 0.247564 0.033031 11.00000 0.03077 0.03233 = 0.03606 -0.00436 0.01464 -0.00510 H21A 2 0.449586 0.357563 0.295433 11.00000 -1.20000 H22A 2 0.399068 0.385290 0.400920 11.00000 -1.20000 H11B 2 0.648260 0.145299 -0.004059 11.00000 -1.20000 H12B 2 0.580937 0.250148 0.074000 11.00000 -1.20000 HKLF 4

REM gs15gs27 MORPHANTH REM R1 = 0.0472 for 1661 Fo > 4sig(Fo) and 0.0715 for all 2218 data REM 157 parameters refined using 4 restraints

END

WGHT 0.0464 0.0619 REM Highest difference peak 0.167, deepest hole -0.184, 1-sigma level 0.038 Q1 1 0.2530 0.0882 0.2048 11.00000 0.05 0.17 Q2 1 0.8126 0.2709 0.0631 11.00000 0.05 0.16 Q3 1 0.2792 0.2670 0.2338 11.00000 0.05 0.15 Q4 1 0.0748 0.1782 0.2595 11.00000 0.05 0.15 Q5 1 0.3177 0.2017 0.1631 11.00000 0.05 0.14 Q6 1 0.2193 0.2963 0.3038 11.00000 0.05 0.14 Q7 1 0.2937 0.0443 0.0518 11.00000 0.05 0.14 Q8 1 0.4050 0.0992 -0.0089 11.00000 0.05 0.13 Q9 1 0.3604 0.2433 0.3445 11.00000 0.05 0.13 Q10 1 0.3413 0.1415 0.2012 11.00000 0.05 0.13

; ------Compound (2): MORPHMABA: gs15gs28 Reference: Smith, G.: J. Chem. Cryst., 2016. CCDC xxxxxx ------data_MORPHMABA

_audit_creation_method SHELXL-97 _chemical_name_systematic ; tetrahydro-2H-1,4-oxazin-4-ium 3-aminobenzoate ; _chemical_name_common 'morpholinium 3-aminobenzoate' _chemical_melting_point ? _chemical_formula_moiety 'C7 H6 N O2, C4 H10 N O' _chemical_formula_sum 'C11 H16 N2 O3' _chemical_formula_weight 224.26 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 'orthorhombic' _symmetry_space_group_name_H-M 'P n a 21' _symmetry_space_group_name_Hall 'P 2c -2n' loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 -x,-y,1/2+z 3 1/2-x,1/2+y,1/2+z 4 1/2+x,1/2-y,z

_cell_length_a 9.3899(4) _cell_length_b 16.6789(7) _cell_length_c 7.4463(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1166.19(8) _cell_formula_units_Z 4 _cell_measurement_temperature 200(1) _cell_measurement_reflns_used 1961 _cell_measurement_theta_min 3.70 _cell_measurement_theta_max 28.41

_exptl_crystal_description block _exptl_crystal_colour 'colourless' _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.22 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.277 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 480 _exptl_absorpt_coefficient_mu 0.094 _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min 0.965 _exptl_absorpt_correction_T_max 0.990 _exptl_absorpt_process_details 'CrysAlis PRO (Agilent, 2014)'

_exptl_special_details ; ? ;

_diffrn_ambient_temperature 200(1) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Enhance (Mo) X-ray source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Oxford Diffraction Gemini-S CCD-detector diffractometer' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 16.077 _diffrn_standards_number 0 _diffrn_standards_interval_count . _diffrn_standards_interval_time . _diffrn_standards_decay_% ? _diffrn_reflns_number 5365 _diffrn_reflns_av_R_equivalents 0.0289 _diffrn_reflns_av_sigmaI/netI 0.0332 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 5 _diffrn_reflns_theta_min 3.27 _diffrn_reflns_theta_max 29.13 _diffrn_measured_fraction_theta_max 0.890 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.998

_reflns_number_total 2005 _reflns_number_gt 1764 _reflns_threshold_expression 'I>2\s(I)'

_computing_data_collection 'CrysAlis PRO (Agilent, 2014)' _computing_cell_refinement 'CrysAlis PRO' _computing_data_reduction 'CrysAlis PRO' _computing_structure_solution 'SIR92 (Altomare et al., 1993)' _computing_structure_refinement 'SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012)' _computing_molecular_graphics 'PLATON (Spek, 2009)' _computing_publication_material 'PLATON'

_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^)+(0.0310P)^2^+0.1746P] 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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details '(Flack, 1983)' _refine_ls_abs_structure_Flack 0.4(13) _refine_ls_number_reflns 2005 _refine_ls_number_parameters 157 _refine_ls_number_restraints 5 _refine_ls_R_factor_all 0.0459 _refine_ls_R_factor_gt 0.0379 _refine_ls_wR_factor_ref 0.0802 _refine_ls_wR_factor_gt 0.0761 _refine_ls_goodness_of_fit_ref 1.057 _refine_ls_restrained_S_all 1.057 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 0.159 _refine_diff_density_min -0.196 _refine_diff_density_rms 0.037 loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group

O11A O Uani 0.82527(14) 0.11895(8) 0.4386(2) 1.000 0.0407(5) d . . . O12A O Uani 0.69148(12) 0.22047(8) 0.5232(2) 1.000 0.0342(4) d . . . N3A N Uani 0.2139(2) 0.15910(13) 0.2163(4) 1.000 0.0594(9) d D . . C1A C Uani 0.59493(18) 0.12652(10) 0.3126(3) 1.000 0.0240(5) d . . . C2A C Uani 0.45849(18) 0.15847(11) 0.3181(3) 1.000 0.0282(5) d . . . C3A C Uani 0.34952(19) 0.12628(11) 0.2133(3) 1.000 0.0321(6) d . . . C4A C Uani 0.3809(2) 0.06229(12) 0.1003(3) 1.000 0.0360(7) d . . . C5A C Uani 0.5176(2) 0.03237(12) 0.0906(3) 1.000 0.0373(6) d . . . C6A C Uani 0.62455(19) 0.06350(11) 0.1964(3) 1.000 0.0291(6) d . . . C11A C Uani 0.71078(17) 0.15743(10) 0.4331(3) 1.000 0.0243(5) d . . . O4B O Uani 0.46177(14) 0.41197(9) 0.9906(2) 1.000 0.0366(4) d . . . N1B N Uani 0.50835(17) 0.31965(10) 0.6776(2) 1.000 0.0294(5) d D . . C2B C Uani 0.4576(2) 0.28217(12) 0.8466(3) 1.000 0.0365(6) d . . . C3B C Uani 0.3771(2) 0.34286(13) 0.9557(3) 1.000 0.0397(7) d . . . C5B C Uani 0.5014(2) 0.44963(12) 0.8262(3) 1.000 0.0348(6) d . . . C6B C Uani 0.5902(2) 0.39396(11) 0.7134(3) 1.000 0.0322(6) d . . . H2A H Uiso 0.43910 0.20290 0.39420 1.000 0.0340 c R . . H4A H Uiso 0.30770 0.03900 0.02930 1.000 0.0430 c R . . H5A H Uiso 0.53830 -0.01020 0.01010 1.000 0.0450 c R . . H6A H Uiso 0.71810 0.04200 0.18990 1.000 0.0350 c R . . H31A H Uiso 0.143(2) 0.1321(14) 0.169(4) 1.000 0.0710 d D . . H32A H Uiso 0.192(3) 0.1938(15) 0.303(3) 1.000 0.0710 d D . . H11B H Uiso 0.4317(18) 0.3337(12) 0.607(3) 1.000 0.0350 d D . . H12B H Uiso 0.5658(19) 0.2825(11) 0.616(3) 1.000 0.0350 d D . . H21B H Uiso 0.53980 0.26200 0.91640 1.000 0.0440 c R . . H22B H Uiso 0.39480 0.23620 0.81840 1.000 0.0440 c R . . H31B H Uiso 0.29000 0.35900 0.89010 1.000 0.0480 c R . . H32B H Uiso 0.34760 0.31840 1.07100 1.000 0.0480 c R . . H51B H Uiso 0.55620 0.49900 0.85210 1.000 0.0420 c R . . H52B H Uiso 0.41460 0.46500 0.75890 1.000 0.0420 c R . . H61B H Uiso 0.61530 0.42030 0.59860 1.000 0.0390 c R . . H62B H Uiso 0.67960 0.38070 0.77740 1.000 0.0390 c 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 O11A 0.0313(7) 0.0410(8) 0.0499(10) -0.0160(8) -0.0139(7) 0.0115(6) O12A 0.0295(6) 0.0315(7) 0.0415(8) -0.0129(7) -0.0044(7) 0.0017(5) N3A 0.0326(10) 0.0607(14) 0.0850(19) -0.0399(14) -0.0240(12) 0.0128(9) C1A 0.0259(9) 0.0216(8) 0.0244(9) 0.0037(8) -0.0002(8) -0.0016(7) C2A 0.0297(9) 0.0237(9) 0.0311(10) -0.0057(9) -0.0055(9) 0.0007(7) C3A 0.0316(10) 0.0296(10) 0.0350(11) -0.0032(9) -0.0083(10) 0.0007(7) C4A 0.0356(11) 0.0366(12) 0.0359(11) -0.0068(10) -0.0126(10) -0.0026(8) C5A 0.0424(11) 0.0333(11) 0.0362(11) -0.0136(10) -0.0019(11) 0.0021(9) C6A 0.0281(9) 0.0293(10) 0.0298(10) -0.0039(9) 0.0012(9) 0.0007(7) C11A 0.0252(9) 0.0228(9) 0.0249(10) 0.0008(8) 0.0018(8) -0.0011(7) O4B 0.0386(7) 0.0392(8) 0.0321(8) -0.0084(7) 0.0003(7) 0.0000(6) N1B 0.0264(8) 0.0319(8) 0.0299(9) -0.0075(8) -0.0057(8) 0.0058(7) C2B 0.0394(11) 0.0319(10) 0.0383(12) -0.0012(10) 0.0005(11) -0.0020(8) C3B 0.0366(10) 0.0429(12) 0.0396(13) -0.0044(11) 0.0081(10) -0.0052(9) C5B 0.0380(11) 0.0300(10) 0.0363(11) -0.0045(10) -0.0004(10) 0.0014(8) C6B 0.0307(10) 0.0338(10) 0.0320(11) -0.0016(10) -0.0001(9) -0.0035(7)

_geom_special_details ; Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag O11A C11A 1.253(2) . . no O12A C11A 1.260(2) . . no O4B C5B 1.425(3) . . no O4B C3B 1.424(3) . . no N3A C3A 1.386(3) . . no N3A H32A 0.89(2) . . no N3A H31A 0.88(2) . . no N1B C6B 1.483(2) . . no N1B C2B 1.484(3) . . no N1B H11B 0.922(19) . . no N1B H12B 0.941(19) . . no C1A C6A 1.390(3) . . no C1A C2A 1.388(2) . . no C1A C11A 1.501(3) . . no C2A C3A 1.394(3) . . no C3A C4A 1.391(3) . . no C4A C5A 1.379(3) . . no C5A C6A 1.378(3) . . no C2A H2A 0.9500 . . no C4A H4A 0.9500 . . no C5A H5A 0.9500 . . no C6A H6A 0.9500 . . no C2B C3B 1.502(3) . . no C5B C6B 1.504(3) . . no C2B H21B 0.9900 . . no C2B H22B 0.9900 . . no C3B H31B 0.9900 . . no C3B H32B 0.9900 . . no C5B H51B 0.9900 . . no C5B H52B 0.9900 . . no C6B H61B 0.9900 . . no C6B H62B 0.9900 . . no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C3B O4B C5B 110.22(16) . . . no H31A N3A H32A 117(2) . . . no C3A N3A H32A 118.7(18) . . . no C3A N3A H31A 119.2(15) . . . no C2B N1B C6B 111.48(15) . . . no C6B N1B H11B 107.2(12) . . . no C2B N1B H12B 108.7(13) . . . no H11B N1B H12B 109.7(18) . . . no C6B N1B H12B 109.9(11) . . . no C2B N1B H11B 109.9(13) . . . no C2A C1A C11A 121.28(17) . . . no C2A C1A C6A 119.57(18) . . . no C6A C1A C11A 119.13(15) . . . no C1A C2A C3A 120.86(18) . . . no N3A C3A C2A 120.87(19) . . . no C2A C3A C4A 118.60(17) . . . no N3A C3A C4A 120.49(19) . . . no C3A C4A C5A 120.44(18) . . . no C4A C5A C6A 120.80(19) . . . no C1A C6A C5A 119.68(17) . . . no O12A C11A C1A 120.03(15) . . . no O11A C11A C1A 117.74(16) . . . no O11A C11A O12A 122.24(17) . . . no C3A C2A H2A 120.00 . . . no C1A C2A H2A 120.00 . . . no C5A C4A H4A 120.00 . . . no C3A C4A H4A 120.00 . . . no C6A C5A H5A 120.00 . . . no C4A C5A H5A 120.00 . . . no C1A C6A H6A 120.00 . . . no C5A C6A H6A 120.00 . . . no N1B C2B C3B 109.66(16) . . . no O4B C3B C2B 111.30(16) . . . no O4B C5B C6B 110.63(16) . . . no N1B C6B C5B 109.21(15) . . . no N1B C2B H21B 110.00 . . . no N1B C2B H22B 110.00 . . . no C3B C2B H21B 110.00 . . . no C3B C2B H22B 110.00 . . . no H21B C2B H22B 108.00 . . . no O4B C3B H31B 109.00 . . . no O4B C3B H32B 109.00 . . . no C2B C3B H31B 109.00 . . . no C2B C3B H32B 109.00 . . . no H31B C3B H32B 108.00 . . . no O4B C5B H51B 110.00 . . . no O4B C5B H52B 109.00 . . . no C6B C5B H51B 110.00 . . . no C6B C5B H52B 109.00 . . . no H51B C5B H52B 108.00 . . . no N1B C6B H61B 110.00 . . . no N1B C6B H62B 110.00 . . . no C5B C6B H61B 110.00 . . . no C5B C6B H62B 110.00 . . . no H61B C6B H62B 108.00 . . . no 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 C3B O4B C5B C6B -61.89(19) . . . . no C5B O4B C3B C2B 61.0(2) . . . . no C2B N1B C6B C5B -54.4(2) . . . . no C6B N1B C2B C3B 53.4(2) . . . . no C11A C1A C6A C5A 177.28(19) . . . . no C2A C1A C11A O12A -10.1(3) . . . . no C6A C1A C11A O11A -8.0(3) . . . . no C2A C1A C11A O11A 170.50(19) . . . . no C6A C1A C2A C3A 2.3(3) . . . . no C11A C1A C2A C3A -176.21(19) . . . . no C2A C1A C6A C5A -1.3(3) . . . . no C6A C1A C11A O12A 171.36(19) . . . . no C1A C2A C3A N3A -178.8(2) . . . . no C1A C2A C3A C4A -1.2(3) . . . . no C2A C3A C4A C5A -1.0(3) . . . . no N3A C3A C4A C5A 176.6(2) . . . . no C3A C4A C5A C6A 2.0(3) . . . . no C4A C5A C6A C1A -0.9(3) . . . . no N1B C2B C3B O4B -56.2(2) . . . . no O4B C5B C6B N1B 58.2(2) . . . . no 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 _geom_hbond_publ_flag # #D H A D - H H...A D...A D - H...A symm(A) # N1B H11B O11A 0.922(19) 1.79(2) 2.678(2) 161.7(18) 4_455 yes N1B H11B O12A 0.922(19) 2.509(18) 3.259(2) 138.8(16) 4_455 yes N1B H12B O12A 0.941(19) 1.715(19) 2.649(2) 171.2(17) . yes N3A H31A O4B 0.88(2) 2.28(2) 3.136(3) 165(2) 4_454 yes N3A H32A O12A 0.89(2) 2.18(2) 3.050(3) 167(3) 4_455 yes C5B H51B O11A 0.99 2.38 3.365(2) 175 3_655 yes # END

_iucr_refine_instructions_details ; TITL gs15gs28 MORPHMABA in Pna2(1) CELL 0.71073 9.3899 16.6789 7.4463 90.000 90.000 90.000 ZERR 4.00 0.0004 0.0007 0.0003 0.000 0.000 0.000 LATT -1 SYMM - X, - Y, 1/2 + Z SYMM 1/2 - X, 1/2 + Y, 1/2 + Z SYMM 1/2 + X, 1/2 - Y, Z SFAC C H N O UNIT 44 64 8 12 MERG 2 FMAP 2 PLAN 10 BOND $H ACTA 52 DFIX 0.90 N1B H11B N1B H12B DFIX 0.90 N3A H31A N3A H32A L.S. 10 TEMP -73.00 WGHT 0.031000 0.174600 FVAR 9.18489 O12A 4 0.691483 0.220470 0.523181 11.00000 0.02946 0.03148 = 0.04147 -0.01288 -0.00441 0.00173 O4B 4 0.461770 0.411974 0.990615 11.00000 0.03862 0.03922 = 0.03205 -0.00837 0.00035 0.00003 O11A 4 0.825269 0.118948 0.438640 11.00000 0.03128 0.04099 = 0.04988 -0.01596 -0.01386 0.01147 N1B 3 0.508352 0.319646 0.677588 11.00000 0.02645 0.03191 = 0.02989 -0.00753 -0.00566 0.00582 H11B 2 0.431724 0.333693 0.607354 11.00000 -1.20000 H12B 2 0.565835 0.282495 0.616368 11.00000 -1.20000 C6A 1 0.624553 0.063505 0.196391 11.00000 0.02813 0.02933 = 0.02978 -0.00393 0.00115 0.00066 AFIX 43 H6A 2 0.718094 0.041998 0.189890 11.00000 -1.20000 AFIX 0 N3A 3 0.213857 0.159099 0.216290 11.00000 0.03264 0.06069 = 0.08504 -0.03989 -0.02401 0.01282 H31A 2 0.143094 0.132112 0.169043 11.00000 -1.20000 H32A 2 0.191779 0.193779 0.303203 11.00000 -1.20000 C11A 1 0.710783 0.157430 0.433108 11.00000 0.02515 0.02282 = 0.02492 0.00084 0.00183 -0.00112 C1A 1 0.594934 0.126518 0.312607 11.00000 0.02588 0.02155 = 0.02435 0.00373 -0.00016 -0.00156 C2A 1 0.458487 0.158473 0.318070 11.00000 0.02967 0.02371 = 0.03107 -0.00566 -0.00548 0.00068 AFIX 43 H2A 2 0.439115 0.202863 0.394189 11.00000 -1.20000 AFIX 0 C2B 1 0.457572 0.282166 0.846584 11.00000 0.03939 0.03193 = 0.03830 -0.00120 0.00049 -0.00199 AFIX 23 H21B 2 0.539841 0.261998 0.916391 11.00000 -1.20000 H22B 2 0.394830 0.236159 0.818351 11.00000 -1.20000 AFIX 0 C3B 1 0.377058 0.342858 0.955700 11.00000 0.03661 0.04292 = 0.03955 -0.00436 0.00814 -0.00518 AFIX 23 H31B 2 0.289953 0.358973 0.890061 11.00000 -1.20000 H32B 2 0.347574 0.318374 1.070966 11.00000 -1.20000 AFIX 0 C6B 1 0.590204 0.393959 0.713423 11.00000 0.03072 0.03384 = 0.03196 -0.00159 -0.00014 -0.00354 AFIX 23 H61B 2 0.615257 0.420344 0.598596 11.00000 -1.20000 H62B 2 0.679574 0.380704 0.777408 11.00000 -1.20000 AFIX 0 C5B 1 0.501367 0.449629 0.826152 11.00000 0.03799 0.02997 = 0.03632 -0.00446 -0.00036 0.00136 AFIX 23 H51B 2 0.556157 0.498999 0.852114 11.00000 -1.20000 H52B 2 0.414626 0.465033 0.758911 11.00000 -1.20000 AFIX 0 C4A 1 0.380915 0.062294 0.100305 11.00000 0.03563 0.03661 = 0.03587 -0.00675 -0.01264 -0.00258 AFIX 43 H4A 2 0.307709 0.039046 0.029289 11.00000 -1.20000 AFIX 0 C3A 1 0.349523 0.126283 0.213332 11.00000 0.03156 0.02958 = 0.03496 -0.00325 -0.00833 0.00071 C5A 1 0.517621 0.032368 0.090644 11.00000 0.04235 0.03325 = 0.03622 -0.01359 -0.00192 0.00206 AFIX 43 H5A 2 0.538302 -0.010236 0.010084 11.00000 -1.20000 HKLF 4

REM gs15gs28 MORPHMABA in Pna2(1) REM R1 = 0.0379 for 1764 Fo > 4sig(Fo) and 0.0459 for all 2005 data REM 157 parameters refined using 5 restraints

END

WGHT 0.0305 0.1507 REM Highest difference peak 0.159, deepest hole -0.196, 1-sigma level 0.037 Q1 1 0.2181 0.1212 0.2946 11.00000 0.05 0.16 Q2 1 0.6268 0.2567 0.5177 11.00000 0.05 0.13 Q3 1 0.6576 0.1516 0.3334 11.00000 0.05 0.13 Q4 1 0.5801 0.2088 0.7266 11.00000 0.05 0.13 Q5 1 0.4446 0.2209 0.3210 11.00000 0.05 0.13 Q6 1 0.6765 0.3162 0.9668 11.00000 0.05 0.12 Q7 1 0.5888 0.2196 0.5746 11.00000 0.05 0.12 Q8 1 0.8645 0.1247 0.2694 11.00000 0.05 0.12 Q9 1 0.5020 -0.0897 0.1535 11.00000 0.05 0.12 Q10 1 0.3608 0.0845 0.1810 11.00000 0.05 0.12 # END of data ; ------Compound (3): MORPHPABA: gs15gs30 Reference: Smith, G.: J. Chem. Cryst., 2016. CCDC xxxxxx ------data_(3)

_audit_creation_method SHELXL-97 _chemical_name_systematic ; tetrahydro-2H-1,4-oxazin-4-ium 4-aminobenzoate ; _chemical_name_common 'morpholinium 4-aminobenzoate' _chemical_melting_point ? _chemical_formula_moiety 'C7 H6 N O2, C4 H10 N O' _chemical_formula_sum 'C11 H16 N2 O3' _chemical_formula_weight 224.26 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_Hall 'C -2yc' _symmetry_space_group_name_H-M 'C c' loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 x,-y,1/2+z 3 1/2+x,1/2+y,z 4 1/2+x,1/2-y,1/2+z

_cell_length_a 5.9233(6) _cell_length_b 18.048(2) _cell_length_c 10.5478(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.376(10) _cell_angle_gamma 90.00 _cell_volume 1127.6(2) _cell_formula_units_Z 4 _cell_measurement_temperature 200(1) _cell_measurement_reflns_used 720 _cell_measurement_theta_min 3.62 _cell_measurement_theta_max 27.03

_exptl_crystal_description 'plate' _exptl_crystal_colour 'colourless' _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.321 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 480 _exptl_absorpt_coefficient_mu 0.097 _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min 0.840 _exptl_absorpt_correction_T_max 0.980 _exptl_absorpt_process_details 'CrysAlis PRO'

_exptl_special_details ; ? ;

_diffrn_ambient_temperature 200(1) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Enhance (Mo) X-ray source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Oxford Diffraction Gemini-S CCD-detector diffractometer' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 16.077 _diffrn_standards_number 0 _diffrn_standards_interval_count . _diffrn_standards_interval_time . _diffrn_standards_decay_% ? _diffrn_reflns_number 2512 _diffrn_reflns_av_R_equivalents 0.0179 _diffrn_reflns_av_sigmaI/netI 0.0389 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.62 _diffrn_reflns_theta_max 29.11 _diffrn_measured_fraction_theta_max 0.854 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.998 _reflns_number_total 1808 _reflns_number_gt 1547 _reflns_threshold_expression 'I>2\s(I)'

_computing_data_collection 'CrysAlis PRO (Agilent, 2014)' _computing_cell_refinement 'CrysAlis PRO' _computing_data_reduction 'CrysAlis PRO' _computing_structure_solution 'SIR92 (Altomare et al, 1993)' _computing_structure_refinement 'SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012)' _computing_molecular_graphics 'PLATON (Spek, 2009)' _computing_publication_material 'PLATON'

_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^)+(0.0699P)^2^+1.9288P] 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 mixed _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 3(3) _refine_ls_number_reflns 1808 _refine_ls_number_parameters 157 _refine_ls_number_restraints 6 _refine_ls_R_factor_all 0.0739 _refine_ls_R_factor_gt 0.0636 _refine_ls_wR_factor_ref 0.1606 _refine_ls_wR_factor_gt 0.1507 _refine_ls_goodness_of_fit_ref 1.042 _refine_ls_restrained_S_all 1.040 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 0.482 _refine_diff_density_min -0.331 _refine_diff_density_rms 0.056 loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags

_atom_site_disorder_assembly _atom_site_disorder_group

O11A O Uani 0.7012(5) 0.41476(14) 0.0560(2) 1.000 0.0358(8) d . . . O12A O Uani 0.5384(5) 0.41591(15) 0.2466(3) 1.000 0.0403(9) d . . . N4A N Uani 1.2657(7) 0.1552(3) 0.3133(4) 1.000 0.0579(16) d D . . C1A C Uani 0.8250(6) 0.32631(18) 0.2052(3) 1.000 0.0269(9) d . . . C2A C Uani 0.7875(6) 0.2853(2) 0.3158(3) 1.000 0.0308(10) d . . . C3A C Uani 0.9292(6) 0.2288(2) 0.3511(3) 1.000 0.0321(10) d . . . C4A C Uani 1.1212(7) 0.2119(2) 0.2782(4) 1.000 0.0383(12) d . . . C5A C Uani 1.1626(8) 0.2536(3) 0.1697(4) 1.000 0.0489(16) d . . . C6A C Uani 1.0160(7) 0.3085(2) 0.1338(4) 1.000 0.0399(12) d . . . C11A C Uani 0.6775(6) 0.38999(19) 0.1686(3) 1.000 0.0294(11) d . . . O4B O Uani 0.0370(8) 0.3980(3) 0.5406(6) 1.000 0.091(2) d . . . N1B N Uani 0.4350(6) 0.4775(2) 0.4790(3) 1.000 0.0412(11) d D . . C2B C Uani 0.2162(9) 0.5129(3) 0.4616(7) 1.000 0.070(2) d . . . C3B C Uani 0.0347(11) 0.4497(4) 0.4428(9) 1.000 0.096(3) d . . . C5B C Uani 0.2417(10) 0.3617(3) 0.5431(6) 1.000 0.070(2) d . . . C6B C Uani 0.4310(11) 0.4154(3) 0.5750(5) 1.000 0.0622(19) d . . . H2A H Uiso 0.66130 0.29680 0.36730 1.000 0.0370 c R . . H3A H Uiso 0.89790 0.20090 0.42520 1.000 0.0380 c R . . H5A H Uiso 1.29300 0.24390 0.12040 1.000 0.0590 c R . . H6A H Uiso 1.04480 0.33540 0.05820 1.000 0.0480 c R . . H41A H Uiso 1.256(14) 0.134(4) 0.389(4) 1.000 0.1160 d D . . H42A H Uiso 1.404(6) 0.159(5) 0.280(7) 1.000 0.1160 d D . . H11B H Uiso 0.491(13) 0.460(4) 0.406(4) 1.000 0.1160 d D . . H12B H Uiso 0.523(11) 0.516(3) 0.493(8) 1.000 0.1160 d D . . H21B H Uiso 0.21880 0.54570 0.38630 1.000 0.0840 c R . . H22B H Uiso 0.17890 0.54330 0.53680 1.000 0.0840 c R . . H31B H Uiso -0.11720 0.47250 0.43720 1.000 0.1160 c R . . H32B H Uiso 0.06360 0.42400 0.36160 1.000 0.1160 c R . . H51B H Uiso 0.27000 0.33880 0.45950 1.000 0.0840 c R . . H52B H Uiso 0.23770 0.32170 0.60740 1.000 0.0840 c R . . H61B H Uiso 0.40790 0.43610 0.66090 1.000 0.0750 c R . . H62B H Uiso 0.57740 0.38900 0.57460 1.000 0.0750 c 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 O11A 0.0470(16) 0.0320(13) 0.0283(12) 0.0017(11) 0.0019(11) 0.0127(14) O12A 0.0448(16) 0.0449(16) 0.0312(14) -0.0053(12) 0.0087(12) 0.0152(15) N4A 0.060(3) 0.070(3) 0.044(2) 0.032(2) 0.0187(19) 0.035(2) C1A 0.0326(17) 0.0222(16) 0.0260(15) 0.0004(13) 0.0040(13) 0.0013(16) C2A 0.0356(19) 0.0347(19) 0.0221(16) -0.0025(14) 0.0079(15) 0.0032(17) C3A 0.044(2) 0.0332(19) 0.0191(15) 0.0057(14) 0.0064(15) 0.0025(18) C4A 0.042(2) 0.040(2) 0.033(2) 0.0092(16) 0.0029(17) 0.009(2) C5A 0.048(3) 0.057(3) 0.042(2) 0.021(2) 0.022(2) 0.024(2) C6A 0.049(2) 0.039(2) 0.032(2) 0.0119(17) 0.0146(18) 0.015(2) C11A 0.034(2) 0.0263(17) 0.0279(18) -0.0072(15) 0.0011(15) 0.0015(16) O4B 0.060(3) 0.062(3) 0.152(5) -0.025(3) 0.041(3) -0.022(2) N1B 0.041(2) 0.043(2) 0.0398(18) -0.0139(15) 0.0142(15) -0.0191(18) C2B 0.046(3) 0.055(3) 0.109(5) -0.037(3) 0.013(3) 0.001(3) C3B 0.049(3) 0.080(5) 0.159(8) -0.047(5) -0.024(4) 0.026(4) C5B 0.071(4) 0.056(3) 0.084(4) -0.025(3) 0.040(3) -0.024(3) C6B 0.079(4) 0.057(3) 0.051(3) -0.005(2) 0.021(3) -0.033(3)

_geom_special_details ; Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag O11A C11A 1.278(4) . . no O12A C11A 1.258(5) . . no O4B C5B 1.378(8) . . no O4B C3B 1.391(10) . . no N4A C4A 1.383(6) . . no N4A H42A 0.90(4) . . no N4A H41A 0.89(5) . . no N1B C6B 1.511(6) . . no N1B C2B 1.456(6) . . no N1B H11B 0.90(5) . . no N1B H12B 0.88(6) . . no C1A C6A 1.401(5) . . no C1A C2A 1.401(5) . . no C1A C11A 1.493(5) . . no C2A C3A 1.371(5) . . no C3A C4A 1.410(5) . . no C4A C5A 1.393(6) . . no C5A C6A 1.369(6) . . no C2A H2A 0.9500 . . no C3A H3A 0.9500 . . no C5A H5A 0.9500 . . no C6A H6A 0.9500 . . no C2B C3B 1.579(9) . . no C5B C6B 1.518(8) . . no C2B H21B 0.9900 . . no C2B H22B 0.9900 . . no C3B H31B 0.9900 . . no C3B H32B 0.9900 . . no C5B H51B 0.9900 . . no C5B H52B 0.9900 . . no C6B H61B 0.9900 . . no C6B H62B 0.9900 . . no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C3B O4B C5B 109.7(5) . . . no H41A N4A H42A 117(7) . . . no C4A N4A H42A 114(5) . . . no C4A N4A H41A 121(5) . . . no C2B N1B C6B 113.1(4) . . . no C6B N1B H11B 109(4) . . . no C2B N1B H12B 102(4) . . . no H11B N1B H12B 102(7) . . . no C6B N1B H12B 119(5) . . . no C2B N1B H11B 112(4) . . . no C2A C1A C11A 121.8(3) . . . no C2A C1A C6A 117.4(3) . . . no C6A C1A C11A 120.7(3) . . . no C1A C2A C3A 121.3(3) . . . no C2A C3A C4A 120.5(3) . . . no N4A C4A C3A 120.9(4) . . . no N4A C4A C5A 120.5(4) . . . no C3A C4A C5A 118.6(4) . . . no C4A C5A C6A 120.2(4) . . . no C1A C6A C5A 122.0(4) . . . no O12A C11A C1A 120.1(3) . . . no O11A C11A C1A 116.2(3) . . . no O11A C11A O12A 123.7(3) . . . no C3A C2A H2A 119.00 . . . no C1A C2A H2A 119.00 . . . no C4A C3A H3A 120.00 . . . no C2A C3A H3A 120.00 . . . no C6A C5A H5A 120.00 . . . no C4A C5A H5A 120.00 . . . no C1A C6A H6A 119.00 . . . no C5A C6A H6A 119.00 . . . no N1B C2B C3B 107.7(4) . . . no O4B C3B C2B 112.8(6) . . . no O4B C5B C6B 110.4(5) . . . no N1B C6B C5B 109.9(4) . . . no N1B C2B H21B 110.00 . . . no N1B C2B H22B 110.00 . . . no C3B C2B H21B 110.00 . . . no C3B C2B H22B 110.00 . . . no H21B C2B H22B 108.00 . . . no O4B C3B H31B 109.00 . . . no O4B C3B H32B 109.00 . . . no C2B C3B H31B 109.00 . . . no C2B C3B H32B 109.00 . . . no H31B C3B H32B 108.00 . . . no O4B C5B H51B 110.00 . . . no O4B C5B H52B 110.00 . . . no C6B C5B H51B 110.00 . . . no C6B C5B H52B 110.00 . . . no H51B C5B H52B 108.00 . . . no N1B C6B H61B 110.00 . . . no N1B C6B H62B 110.00 . . . no C5B C6B H61B 110.00 . . . no C5B C6B H62B 110.00 . . . no H61B C6B H62B 108.00 . . . no 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 C3B O4B C5B C6B 64.6(7) . . . . no C5B O4B C3B C2B -63.4(7) . . . . no C2B N1B C6B C5B 51.7(6) . . . . no C6B N1B C2B C3B -48.2(7) . . . . no C11A C1A C6A C5A 175.6(4) . . . . no C2A C1A C11A O12A 11.6(5) . . . . no C6A C1A C11A O11A 16.4(5) . . . . no C2A C1A C11A O11A -167.8(3) . . . . no C6A C1A C2A C3A -1.5(5) . . . . no C11A C1A C2A C3A -177.4(3) . . . . no C2A C1A C6A C5A -0.3(6) . . . . no C6A C1A C11A O12A -164.1(3) . . . . no C1A C2A C3A C4A 1.8(5) . . . . no C2A C3A C4A N4A 179.7(4) . . . . no C2A C3A C4A C5A -0.3(6) . . . . no C3A C4A C5A C6A -1.6(6) . . . . no N4A C4A C5A C6A 178.4(4) . . . . no C4A C5A C6A C1A 1.9(7) . . . . no N1B C2B C3B O4B 54.5(8) . . . . no O4B C5B C6B N1B -58.0(6) . . . . no 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 _geom_hbond_publ_flag # #D H A D - H H...A D...A D - H...A symm(A) # N1B H11B O12A 0.90(5) 1.88(5) 2.764(4) 167(7) . yes N1B H12B O11A 0.88(6) 1.76(6) 2.629(4) 167(8) 2_565 yes N4A H41A O11A 0.89(5) 2.00(5) 2.882(5) 174(8) 4_555 yes # END

_iucr_refine_instructions_details ; TITL gs15gs30 MORPHPABA in Cc CELL 0.71073 5.9233 18.0480 10.5478 90.000 90.376 90.000 ZERR 4.00 0.0006 0.0024 0.0010 0.000 0.010 0.000 LATT -7 SYMM X, - Y, 1/2 + Z SFAC C H N O UNIT 44 64 8 12 MERG 2 DFIX 0.90 0.02 N1B H11B N1B H12B DFIX 0.90 0.02 N4A H41A N4A H42A FMAP 2 PLAN 10 ACTA 50 BOND $H L.S. 10 TEMP -73.00 WGHT 0.069900 1.928800 FVAR 7.55570 O11A 4 0.701160 0.414762 0.055993 11.00000 0.04703 0.03199 = 0.02829 0.00167 0.00194 0.01267 O12A 4 0.538438 0.415905 0.246587 11.00000 0.04483 0.04494 = 0.03122 -0.00530 0.00873 0.01520 N1B 3 0.434972 0.477501 0.479048 11.00000 0.04059 0.04327 = 0.03983 -0.01392 0.01420 -0.01912 N4A 3 1.265707 0.155184 0.313257 11.00000 0.06001 0.07049 = 0.04426 0.03192 0.01869 0.03535 C1A 1 0.825027 0.326315 0.205194 11.00000 0.03263 0.02219 = 0.02596 0.00045 0.00404 0.00126 C11A 1 0.677525 0.389991 0.168581 11.00000 0.03434 0.02628 = 0.02786 -0.00725 0.00111 0.00148 C3A 1 0.929204 0.228846 0.351076 11.00000 0.04382 0.03324 = 0.01912 0.00567 0.00643 0.00255 AFIX 43 H3A 2 0.897908 0.200894 0.425228 11.00000 -1.20000 AFIX 0 C4A 1 1.121234 0.211914 0.278192 11.00000 0.04191 0.04019 = 0.03266 0.00924 0.00295 0.00942 C2A 1 0.787486 0.285278 0.315775 11.00000 0.03564 0.03468 = 0.02213 -0.00247 0.00790 0.00323 AFIX 43 H2A 2 0.661303 0.296804 0.367292 11.00000 -1.20000 AFIX 0 C6A 1 1.016037 0.308510 0.133829 11.00000 0.04949 0.03900 = 0.03225 0.01193 0.01461 0.01490 AFIX 43 H6A 2 1.044832 0.335365 0.058180 11.00000 -1.20000 AFIX 0 C5A 1 1.162592 0.253584 0.169721 11.00000 0.04850 0.05695 = 0.04158 0.02063 0.02214 0.02449 AFIX 43 H5A 2 1.292951 0.243880 0.120428 11.00000 -1.20000 AFIX 0 O4B 4 0.036992 0.398028 0.540584 11.00000 0.06036 0.06233 = 0.15168 -0.02465 0.04100 -0.02165 C2B 1 0.216188 0.512922 0.461590 11.00000 0.04616 0.05521 = 0.10866 -0.03685 0.01336 0.00117 AFIX 23 H21B 2 0.218847 0.545678 0.386328 11.00000 -1.20000 H22B 2 0.178874 0.543266 0.536782 11.00000 -1.20000 AFIX 0 C6B 1 0.430971 0.415423 0.575010 11.00000 0.07950 0.05674 = 0.05144 -0.00506 0.02065 -0.03345 AFIX 23 H61B 2 0.407872 0.436079 0.660901 11.00000 -1.20000 H62B 2 0.577413 0.388989 0.574582 11.00000 -1.20000 AFIX 0 C5B 1 0.241749 0.361698 0.543149 11.00000 0.07072 0.05627 = 0.08388 -0.02493 0.04034 -0.02375 AFIX 23 H51B 2 0.270036 0.338804 0.459453 11.00000 -1.20000 H52B 2 0.237748 0.321723 0.607365 11.00000 -1.20000 AFIX 0 C3B 1 0.034710 0.449746 0.442770 11.00000 0.04922 0.07980 = 0.15946 -0.04681 -0.02387 0.02586 AFIX 23 H31B 2 -0.117159 0.472468 0.437248 11.00000 -1.20000 H32B 2 0.063628 0.424023 0.361584 11.00000 -1.20000 AFIX 0 H11B 2 0.491377 0.459884 0.405858 11.00000 -1.20000 H12B 2 0.523067 0.516290 0.492939 11.00000 -1.20000 H41A 2 1.255969 0.134399 0.389298 11.00000 -1.20000 H42A 2 1.404145 0.159130 0.280037 11.00000 -1.20000 HKLF 4

REM gs15gs30 MORPHPABA in Cc REM R1 = 0.0636 for 1549 Fo > 4sig(Fo) and 0.0739 for all 1808 data REM 157 parameters refined using 6 restraints

END

WGHT 0.0714 1.9171 REM Highest difference peak 0.482, deepest hole -0.331, 1-sigma level 0.056 Q1 1 0.0232 0.4742 0.3616 11.00000 0.05 0.48 Q2 1 -0.0566 0.4213 0.4612 11.00000 0.05 0.45 Q3 1 0.1637 0.3897 0.4983 11.00000 0.05 0.27 Q4 1 0.2069 0.5429 0.4157 11.00000 0.05 0.26 Q5 1 1.3534 0.1298 0.2592 11.00000 0.05 0.21 Q6 1 0.2820 0.4263 0.5573 11.00000 0.05 0.19 Q7 1 0.1983 0.3026 0.5584 11.00000 0.05 0.18 Q8 1 0.1397 0.4679 0.2783 11.00000 0.05 0.18 Q9 1 0.4383 0.4219 0.6434 11.00000 0.05 0.18 Q10 1 0.5724 0.2146 0.3889 11.00000 0.05 0.17 ; # END of data for (1)-(3).

(Type 2a) [such as is present in the structure of N-methylanilinium 3,5-dinitrobenzoate (Smith et al., 1998)], or the less common R^2^~4~(8) ring motif (Type 2b) (Fig. 1), found in the analogous morpholinium phenoxyacetates (Smith & Lynch, 2015).

Within the Type 1 structures, the ribbons comprise either the more common --(A--A--/--B--B-- sequences (Type 1a) or the --(A--B--/--B--A-- sequences (Type 1b). The less common 1b sub-type is found in the structure of morpholinium 2-chloro-4-nitrobenzoate (Ishida et al., 2001a) and in morpholinium (4-fluorphenoxy)acetate (Smith & Lynch, 2015), both of which having the (A--B sequence generated by a crystallographic 2~1~ screw operation.

The linear Type 1a chain structure is also found in the related anhydrous morpholinium salt of cinnamic acid (Smith, 2015) and two of the four morpholinium salts of phenoxyacetic acid analogues (Smith & Lynch, 2015). The fourth salt of this series, with (2,4-dichlorophenoxy)acetic acid, has the cyclic Type 2b structure. Of chemical interest is also the Type 2a structure of morpholinium morpholine-4-carboxylate (Brown & Gray, 1982; Von Dreele et al., 1983), a salt often readily formed in attempted preparations of morpholine salts and also by the reaction of morpholine with dry ice.

One structure among the few known anhydrous morpholine salts of the associatively-substituted benzoic acids which constitutes a variant of the described Type 1 and Type 2 sets is found in the 5-nitrosalicylate (Smith et al., 2005). In this structure, both the cations and anions lie respectively across and within crystallographic mirror planes and the primary association is a variant of the Type 2a sub-set but with an R^3^~4~(10) motif, involving three rather than four carboxyl O- atoms and giving an overall three-dimensional structure.