# Electronic Supplementary Material (ESI) for New Journal of Chemistry.
# This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2022

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_shelx
_database_code_depnum_ccdc_archive 'CCDC 2089708'
loop_
_audit_author_name
_audit_author_address
'Oscar Enrique Piro'
;Universidad Nacional de La Plata
Argentina
;
_audit_update_record             
;
2021-09-13 deposited with the CCDC.	2022-01-24 downloaded from the CCDC.
;
_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
(6R,12S)-4,10-dimethoxy-13-(thiophen-2-ylmethyl)-6,12-dihydro-6,12-epiminodibenzo[b,f][1,5]dioxocine
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C21 H19 N O4 S'
_chemical_formula_weight         381.43
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
_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.
;
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   9.2740(6)
_cell_length_b                   9.9087(7)
_cell_length_c                   11.3130(6)
_cell_angle_alpha                99.480(5)
_cell_angle_beta                 102.576(5)
_cell_angle_gamma                112.887(7)
_cell_volume                     898.10(11)
_cell_formula_units_Z            2
_cell_measurement_temperature    297(2)
_cell_measurement_reflns_used    2824
_cell_measurement_theta_min      4.1639
_cell_measurement_theta_max      73.2469
_exptl_crystal_description       fragment
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.410
_exptl_crystal_F_000             400
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.409
_exptl_crystal_size_mid          0.140
_exptl_crystal_size_min          0.121
_exptl_absorpt_coefficient_mu    1.839
_shelx_estimated_absorpt_T_min   0.520
_shelx_estimated_absorpt_T_max   0.808
_exptl_absorpt_correction_T_min  0.94982
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      297(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_source         'Enhance (Cu) X-ray Source'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_detector_area_resol_mean 16.0604
_diffrn_reflns_number            7377
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_av_R_equivalents  0.0303
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         4.167
_diffrn_reflns_theta_max         73.405
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3552
_reflns_number_gt                2969
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .
_reflns_special_details          
;
Reflections were merged by SHELXL according to the crystal
class for the calculation of statistics and refinement. 
_reflns_Friedel_fraction is defined as the number of unique
Friedel pairs measured divided by the number that would be
possible theoretically, ignoring centric projections and
systematic absences.
;
_computing_data_collection       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'ORTEP for Windows (Farrugia, 2012)'
_computing_publication_material  'SHELXL-2014/7 (Sheldrick, 2014)'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1496P)²+0.1581P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_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         3552
_refine_ls_number_parameters     246
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0794
_refine_ls_R_factor_gt           0.0681
_refine_ls_wR_factor_ref         0.2206
_refine_ls_wR_factor_gt          0.1981
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_restrained_S_all      1.092
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
# start Validation Reply Form
_vrf_PLAT230_shelx               
;
PROBLEM: Hirshfeld Test Diff for    C32      --C33      .       12.5 s.u.  
RESPONSE: This is due to rotational disorder of thiophen ring around the
linking C1-C31 bond which despite many attemps could not be properly modeled.  
;
# end Validation Reply Form 
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
C1 C 0.2513(3) 0.6235(3) -0.2398(2) 0.0345(5) Uani 1 1 d . . . . .
H1 H 0.1678 0.6557 -0.2250 0.041 Uiso 1 1 calc R U . . .
C11 C 0.2499(3) 0.3704(3) -0.2371(2) 0.0341(5) Uani 1 1 d . . . . .
C12 C 0.1703(3) 0.2099(3) -0.2687(2) 0.0392(5) Uani 1 1 d . . . . .
C13 C 0.0142(4) 0.1331(3) -0.3555(3) 0.0499(6) Uani 1 1 d . . . . .
H13 H -0.0388 0.0271 -0.3788 0.060 Uiso 1 1 calc R U . . .
C14 C -0.0634(3) 0.2138(4) -0.4080(3) 0.0547(7) Uani 1 1 d . . . . .
H14 H -0.1677 0.1611 -0.4669 0.066 Uiso 1 1 calc R U . . .
C15 C 0.0115(3) 0.3702(3) -0.3742(2) 0.0467(6) Uani 1 1 d . . . . .
H15 H -0.0432 0.4226 -0.4088 0.056 Uiso 1 1 calc R U . . .
C16 C 0.1703(3) 0.4510(3) -0.2878(2) 0.0365(5) Uani 1 1 d . . . . .
C17 C 0.1829(5) -0.0164(3) -0.2322(3) 0.0584(7) Uani 1 1 d . . . . .
H17A H 0.0770 -0.0494 -0.2191 0.088 Uiso 1 1 calc R U . . .
H17B H 0.2509 -0.0468 -0.1766 0.088 Uiso 1 1 calc R U . . .
H17C H 0.1695 -0.0620 -0.3180 0.088 Uiso 1 1 calc R U . . .
O1 O 0.4048(2) 0.44076(18) -0.15211(16) 0.0368(4) Uani 1 1 d . . . . .
O11 O 0.2591(3) 0.1459(2) -0.2066(2) 0.0484(5) Uani 1 1 d . . . . .
C2 C 0.4870(3) 0.6051(2) -0.1382(2) 0.0348(5) Uani 1 1 d . . . . .
H2 H 0.5847 0.6515 -0.0636 0.042 Uiso 1 1 calc R U . . .
C21 C 0.4562(3) 0.6812(3) -0.3382(2) 0.0370(5) Uani 1 1 d . . . . .
C22 C 0.5125(3) 0.7212(3) -0.4395(2) 0.0441(6) Uani 1 1 d . . . . .
C23 C 0.6522(4) 0.7069(3) -0.4526(3) 0.0530(7) Uani 1 1 d . . . . .
H23 H 0.6908 0.7323 -0.5190 0.064 Uiso 1 1 calc R U . . .
C24 C 0.7343(4) 0.6549(4) -0.3673(3) 0.0541(7) Uani 1 1 d . . . . .
H24 H 0.8262 0.6441 -0.3781 0.065 Uiso 1 1 calc R U . . .
C25 C 0.6811(3) 0.6190(3) -0.2666(3) 0.0452(6) Uani 1 1 d . . . . .
H25 H 0.7376 0.5852 -0.2095 0.054 Uiso 1 1 calc R U . . .
C26 C 0.5416(3) 0.6339(2) -0.2512(2) 0.0367(5) Uani 1 1 d . . . . .
C27 C 0.4717(7) 0.8111(5) -0.6195(4) 0.0773(11) Uani 1 1 d . . . . .
H27A H 0.5817 0.8921 -0.5888 0.116 Uiso 1 1 calc R U . . .
H27B H 0.3986 0.8452 -0.6649 0.116 Uiso 1 1 calc R U . . .
H27C H 0.4694 0.7250 -0.6747 0.116 Uiso 1 1 calc R U . . .
O2 O 0.3166(2) 0.6940(2) -0.32992(16) 0.0396(4) Uani 1 1 d . . . . .
O21 O 0.4207(3) 0.7681(3) -0.5161(2) 0.0596(6) Uani 1 1 d . . . . .
C3 C 0.3252(3) 0.6557(3) -0.0114(2) 0.0399(5) Uani 1 1 d . . . . .
H3A H 0.4182 0.6782 0.0605 0.048 Uiso 1 1 calc R U . . .
H3B H 0.2477 0.5497 -0.0289 0.048 Uiso 1 1 calc R U . . .
C31 C 0.2443(3) 0.7548(3) 0.0211(2) 0.0367(5) Uani 1 1 d . . . . .
C32 C 0.0641(3) 0.7022(2) -0.0068(2) 0.0359(5) Uani 1 1 d . . . . .
H32 H -0.0190 0.6046 -0.0487 0.043 Uiso 1 1 calc R U . . .
C33 C 0.0455(4) 0.8384(4) 0.0464(3) 0.0570(7) Uani 1 1 d . . . . .
H33 H -0.0572 0.8356 0.0412 0.068 Uiso 1 1 calc R U . . .
C34 C 0.1855(5) 0.9665(3) 0.1026(3) 0.0576(7) Uani 1 1 d . . . . .
H34 H 0.1891 1.0591 0.1402 0.069 Uiso 1 1 calc R U . . .
S S 0.35450(10) 0.94226(9) 0.09814(8) 0.0581(3) Uani 1 1 d . . . . .
N N 0.3830(2) 0.6774(2) -0.12168(18) 0.0343(4) Uani 1 1 d . . . . .


_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
C1 O2 1.438(3) . ?
C1 N 1.453(3) . ?
C1 C16 1.516(3) . ?
C11 O1 1.369(3) . ?
C11 C16 1.392(3) . ?
C11 C12 1.409(3) . ?
C12 O11 1.370(3) . ?
C12 C13 1.384(4) . ?
C13 C14 1.388(5) . ?
C14 C15 1.371(4) . ?
C15 C16 1.402(3) . ?
C17 O11 1.429(3) . ?
O1 C2 1.468(3) . ?
C2 N 1.432(3) . ?
C2 C26 1.503(3) . ?
C21 O2 1.370(3) . ?
C21 C26 1.385(3) . ?
C21 C22 1.412(3) . ?
C22 O21 1.345(4) . ?
C22 C23 1.393(4) . ?
C23 C24 1.387(5) . ?
C24 C25 1.382(4) . ?
C25 C26 1.402(3) . ?
C27 O21 1.422(4) . ?
C3 N 1.476(3) . ?
C3 C31 1.496(3) . ?
C31 C32 1.484(3) . ?
C31 S 1.690(2) . ?
C32 C33 1.474(4) . ?
C33 C34 1.340(5) . ?
C34 S 1.685(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
O2 C1 N 108.88(18) . . ?
O2 C1 C16 111.82(18) . . ?
N C1 C16 111.34(18) . . ?
O1 C11 C16 122.6(2) . . ?
O1 C11 C12 116.7(2) . . ?
C16 C11 C12 120.7(2) . . ?
O11 C12 C13 126.6(2) . . ?
O11 C12 C11 114.5(2) . . ?
C13 C12 C11 118.9(2) . . ?
C12 C13 C14 120.2(3) . . ?
C15 C14 C13 121.0(2) . . ?
C14 C15 C16 120.1(3) . . ?
C11 C16 C15 119.0(2) . . ?
C11 C16 C1 119.2(2) . . ?
C15 C16 C1 121.6(2) . . ?
C11 O1 C2 112.83(16) . . ?
C12 O11 C17 117.1(2) . . ?
N C2 O1 112.19(18) . . ?
N C2 C26 109.10(18) . . ?
O1 C2 C26 110.54(18) . . ?
O2 C21 C26 122.5(2) . . ?
O2 C21 C22 116.9(2) . . ?
C26 C21 C22 120.6(2) . . ?
O21 C22 C23 126.4(2) . . ?
O21 C22 C21 114.9(2) . . ?
C23 C22 C21 118.6(3) . . ?
C24 C23 C22 120.5(3) . . ?
C25 C24 C23 120.8(3) . . ?
C24 C25 C26 119.6(3) . . ?
C21 C26 C25 119.9(2) . . ?
C21 C26 C2 119.3(2) . . ?
C25 C26 C2 120.8(2) . . ?
C21 O2 C1 112.59(17) . . ?
C22 O21 C27 117.6(3) . . ?
N C3 C31 112.61(18) . . ?
C32 C31 C3 125.2(2) . . ?
C32 C31 S 112.92(17) . . ?
C3 C31 S 121.91(19) . . ?
C33 C32 C31 105.0(2) . . ?
C34 C33 C32 115.9(3) . . ?
C33 C34 S 112.9(2) . . ?
C34 S C31 93.26(14) . . ?
C2 N C1 107.56(18) . . ?
C2 N C3 112.45(18) . . ?
C1 N C3 114.02(19) . . ?

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 C11 C12 O11 1.5(3) . . . . ?
C16 C11 C12 O11 -176.4(2) . . . . ?
O1 C11 C12 C13 -179.2(2) . . . . ?
C16 C11 C12 C13 2.9(3) . . . . ?
O11 C12 C13 C14 177.7(3) . . . . ?
C11 C12 C13 C14 -1.5(4) . . . . ?
C12 C13 C14 C15 -0.7(5) . . . . ?
C13 C14 C15 C16 1.5(4) . . . . ?
O1 C11 C16 C15 -180.0(2) . . . . ?
C12 C11 C16 C15 -2.2(3) . . . . ?
O1 C11 C16 C1 -5.1(3) . . . . ?
C12 C11 C16 C1 172.7(2) . . . . ?
C14 C15 C16 C11 0.0(4) . . . . ?
C14 C15 C16 C1 -174.8(2) . . . . ?
O2 C1 C16 C11 106.4(2) . . . . ?
N C1 C16 C11 -15.7(3) . . . . ?
O2 C1 C16 C15 -78.9(3) . . . . ?
N C1 C16 C15 159.1(2) . . . . ?
C16 C11 O1 C2 -10.2(3) . . . . ?
C12 C11 O1 C2 171.95(19) . . . . ?
C13 C12 O11 C17 -0.9(4) . . . . ?
C11 C12 O11 C17 178.3(2) . . . . ?
C11 O1 C2 N 47.8(2) . . . . ?
C11 O1 C2 C26 -74.2(2) . . . . ?
O2 C21 C22 O21 0.2(3) . . . . ?
C26 C21 C22 O21 -178.8(2) . . . . ?
O2 C21 C22 C23 -178.8(2) . . . . ?
C26 C21 C22 C23 2.3(4) . . . . ?
O21 C22 C23 C24 -179.1(3) . . . . ?
C21 C22 C23 C24 -0.3(4) . . . . ?
C22 C23 C24 C25 -1.2(4) . . . . ?
C23 C24 C25 C26 0.6(4) . . . . ?
O2 C21 C26 C25 178.3(2) . . . . ?
C22 C21 C26 C25 -2.8(3) . . . . ?
O2 C21 C26 C2 -4.2(3) . . . . ?
C22 C21 C26 C2 174.7(2) . . . . ?
C24 C25 C26 C21 1.4(4) . . . . ?
C24 C25 C26 C2 -176.2(2) . . . . ?
N C2 C26 C21 -17.7(3) . . . . ?
O1 C2 C26 C21 106.1(2) . . . . ?
N C2 C26 C25 159.9(2) . . . . ?
O1 C2 C26 C25 -76.3(3) . . . . ?
C26 C21 O2 C1 -12.4(3) . . . . ?
C22 C21 O2 C1 168.6(2) . . . . ?
N C1 O2 C21 50.3(2) . . . . ?
C16 C1 O2 C21 -73.2(2) . . . . ?
C23 C22 O21 C27 -1.6(5) . . . . ?
C21 C22 O21 C27 179.6(3) . . . . ?
N C3 C31 C32 103.8(3) . . . . ?
N C3 C31 S -77.6(2) . . . . ?
C3 C31 C32 C33 178.2(2) . . . . ?
S C31 C32 C33 -0.6(3) . . . . ?
C31 C32 C33 C34 -0.1(4) . . . . ?
C32 C33 C34 S 0.7(4) . . . . ?
C33 C34 S C31 -0.8(3) . . . . ?
C32 C31 S C34 0.8(2) . . . . ?
C3 C31 S C34 -178.0(2) . . . . ?
O1 C2 N C1 -68.6(2) . . . . ?
C26 C2 N C1 54.2(2) . . . . ?
O1 C2 N C3 57.7(2) . . . . ?
C26 C2 N C3 -179.43(18) . . . . ?
O2 C1 N C2 -73.7(2) . . . . ?
C16 C1 N C2 50.0(2) . . . . ?
O2 C1 N C3 160.86(18) . . . . ?
C16 C1 N C3 -75.4(2) . . . . ?
C31 C3 N C2 169.0(2) . . . . ?
C31 C3 N C1 -68.2(3) . . . . ?

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
C27 H27B S 0.96 2.99 3.746(4) 136.2 1_554
C3 H3A O1 0.97 2.51 3.321(3) 140.5 2_665

_refine_diff_density_max         1.149
_refine_diff_density_min         -0.588
_refine_diff_density_rms         0.093


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Ethanol'
