data_md2
# end Validation Reply Form
_audit_creation_date               2019-05-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number       '2017/1'
_audit_contact_author_address      ?
_audit_contact_author_email        ?
_audit_contact_author_name         ''
_audit_contact_author_phone        ?
_publ_contact_author_id_orcid      ?
_publ_section_references
;
Dolomanov, O.V., Bourhis, L.J., Gildea, R.J, Howard, J.A.K. & Puschmann, H.
 (2009), J. Appl. Cryst. 42, 339-341.

Sheldrick, G.M. (2008). Acta Cryst. A64, 112-122.

Sheldrick, G.M. (2015). Acta Cryst. A71, 3-8.
;
_chemical_name_common              ?
_chemical_name_systematic          ?
_chemical_formula_moiety           'C32 H28 N4 S3, C2 H6 O S'
_chemical_formula_sum              'C34 H34 N4 O S4'
_chemical_formula_weight           642.89
_chemical_melting_point            ?
loop_
  _atom_type_symbol
  _atom_type_description
  _atom_type_scat_dispersion_real
  _atom_type_scat_dispersion_imag
  _atom_type_scat_source
 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system        'monoclinic'
_space_group_IT_number             14
_space_group_name_H-M_alt          'P 1 21/n 1'
_space_group_name_Hall             '-P 2yn'
loop_
  _space_group_symop_operation_xyz
 'x, y, z'
 '-x+1/2, y+1/2, -z+1/2'
 '-x, -y, -z'
 'x-1/2, -y-1/2, z-1/2'

_cell_length_a                     13.222(2)
_cell_length_b                     9.2365(14)
_cell_length_c                     25.947(4)
_cell_angle_alpha                  90
_cell_angle_beta                   96.211(5)
_cell_angle_gamma                  90
_cell_volume                       3150.2(8)
_cell_formula_units_Z              4
_cell_measurement_reflns_used      9981
_cell_measurement_temperature      100.0
_cell_measurement_theta_max        22.992
_cell_measurement_theta_min        2.687
_shelx_estimated_absorpt_T_max     0.993
_shelx_estimated_absorpt_T_min     0.928
_exptl_absorpt_coefficient_mu      0.337
_exptl_absorpt_correction_T_max    0.7449
_exptl_absorpt_correction_T_min    0.6594
_exptl_absorpt_correction_type     multi-scan
_exptl_absorpt_process_details    
 'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1423 before and 0.0616 after correction. The Ratio of minimum to maximum transmission is 0.8852. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details     ?
_exptl_crystal_colour              yellow
_exptl_crystal_colour_primary      yellow
_exptl_crystal_density_diffrn      1.356
_exptl_crystal_density_meas        ?
_exptl_crystal_density_method      ?
_exptl_crystal_description         needle
_exptl_crystal_F_000               1352
_exptl_crystal_size_max            0.226
_exptl_crystal_size_mid            0.104
_exptl_crystal_size_min            0.02
_exptl_transmission_factor_max     ?
_exptl_transmission_factor_min     ?
_diffrn_reflns_av_R_equivalents    0.0775
_diffrn_reflns_av_unetI/netI       0.0532
_diffrn_reflns_Laue_measured_fraction_full  0.996
_diffrn_reflns_Laue_measured_fraction_max  0.996
_diffrn_reflns_limit_h_max         14
_diffrn_reflns_limit_h_min         -14
_diffrn_reflns_limit_k_max         10
_diffrn_reflns_limit_k_min         -10
_diffrn_reflns_limit_l_max         28
_diffrn_reflns_limit_l_min         -28
_diffrn_reflns_number              28082
_diffrn_reflns_point_group_measured_fraction_full  0.996
_diffrn_reflns_point_group_measured_fraction_max  0.996
_diffrn_reflns_theta_full          23.053
_diffrn_reflns_theta_max           23.053
_diffrn_reflns_theta_min           2.342
_diffrn_ambient_temperature        100.0
_diffrn_detector_area_resol_mean   ?
_diffrn_measured_fraction_theta_full  0.996
_diffrn_measured_fraction_theta_max  0.996
_diffrn_measurement_device_type    'Bruker APEX-II CCD'
_diffrn_measurement_method         'φ and ω scans'
_diffrn_radiation_type             MoK\a
_diffrn_radiation_wavelength       0.71073
_diffrn_source                     ?
_diffrn_special_details            ?
_diffrn_standards_number           0
_reflns_Friedel_coverage           0.000
_reflns_Friedel_fraction_full      .
_reflns_Friedel_fraction_max       .
_reflns_number_gt                  3205
_reflns_number_total               4393
_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.
;
_reflns_threshold_expression       'I > 2σ(I)'
_computing_cell_refinement         'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection         ?
_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    'XL (Sheldrick, 2008)'
_computing_structure_solution      'XT (Sheldrick, 2015)'
_refine_diff_density_max           0.469
_refine_diff_density_min           -0.524
_refine_diff_density_rms           0.073
_refine_ls_extinction_coef         .
_refine_ls_extinction_method       none
_refine_ls_goodness_of_fit_ref     1.080
_refine_ls_hydrogen_treatment      constr
_refine_ls_matrix_type             full
_refine_ls_number_parameters       392
_refine_ls_number_reflns           4393
_refine_ls_number_restraints       6
_refine_ls_R_factor_all            0.0895
_refine_ls_R_factor_gt             0.0581
_refine_ls_restrained_S_all        1.082
_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/[σ²(Fo²)+(0.0339P)²+8.8912P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme        calc
_refine_ls_wR_factor_gt            0.1186
_refine_ls_wR_factor_ref           0.1334
_refine_special_details            ?
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 S2A-C30 \\sim S2-C32
 with sigma of 0.02
 C31-C30 \\sim C32-C31A
 with sigma of 0.02
 S2-C31 \\sim S2A-C31A
 with sigma of 0.02
 C22-C21A \\sim C21-C20
 with sigma of 0.02
 S3A-C20 \\sim S3-C22
 with sigma of 0.02
 S3A-C21A \\sim S3-C21
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(S2) = Uanis(S2A)
Uanis(C31) = Uanis(C31A)
Uanis(S2) = Uanis(C31) = Uanis(S2A) = Uanis(C31A)
Uanis(S3) = Uanis(S3A)
Uanis(C21) = Uanis(C21A)
Uanis(S3) = Uanis(C21) = Uanis(S3A) = Uanis(C21A)
4. Others
 Sof(H30A)=Sof(H32A)=Sof(S2A)=Sof(C31A)=Sof(H31A)=1-FVAR(1)
 Sof(S2)=Sof(H30)=Sof(C31)=Sof(H31)=Sof(H32)=FVAR(1)
 Sof(H20A)=Sof(H22A)=Sof(S3A)=Sof(C21A)=Sof(H21A)=1-FVAR(2)
 Sof(S3)=Sof(H20)=Sof(C21)=Sof(H21)=Sof(H22)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B)
5.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12), C14(H14), C15(H15),
 C17(H17), C18(H18), C20(H20), C20(H20A), C21(H21), C22(H22), C22(H22A),
 C24(H24), C25(H25), C27(H27), C28(H28), C30(H30), C30(H30A), C31(H31),
 C32(H32), C32(H32A), C31A(H31A), C21A(H21A)
5.c Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C34(H34A,H34B,H34C)
;
_atom_sites_solution_hydrogens     geom
_atom_sites_solution_primary       dual
_atom_sites_solution_secondary     ?
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
 S1 S -0.02182(9) 0.70886(13) 0.72540(4) 0.0317(3) Uani 1 1 d . . . . .
 S2 S 0.95456(16) 0.9534(3) 0.43276(10) 0.0376(5) Uani 0.627(3) 1 d D . P A 1
 S3 S 0.0212(3) 0.8401(4) 0.12144(15) 0.0335(5) Uani 0.567(4) 1 d D . P B 1
 N1 N -0.0888(3) 0.7376(4) 0.62500(13) 0.0269(9) Uani 1 1 d . . . . .
 N2 N 0.0604(3) 0.6052(4) 0.64530(13) 0.0261(9) Uani 1 1 d . . . . .
 H2 H 0.090079 0.537578 0.665477 0.031 Uiso 1 1 calc R . . . .
 N3 N 0.0925(3) 0.6333(4) 0.59721(12) 0.0234(9) Uani 1 1 d . . . . .
 N4 N 0.3470(2) 0.7305(4) 0.40330(12) 0.0208(8) Uani 1 1 d . . . . .
 C1 C -0.0179(3) 0.6840(5) 0.66082(16) 0.0246(11) Uani 1 1 d . . . . .
 C2 C -0.1701(3) 0.8343(5) 0.63954(18) 0.0339(12) Uani 1 1 d . . . . .
 H2A H -0.141593 0.926111 0.654492 0.041 Uiso 1 1 calc R . . . .
 H2B H -0.210451 0.787059 0.664791 0.041 Uiso 1 1 calc R . . . .
 C3 C -0.2334(4) 0.8599(5) 0.58862(17) 0.0351(12) Uani 1 1 d . . . . .
 H3A H -0.206909 0.942658 0.569908 0.042 Uiso 1 1 calc R . . . .
 H3B H -0.305288 0.878966 0.593849 0.042 Uiso 1 1 calc R . . . .
 C4 C -0.2234(3) 0.7195(5) 0.55925(18) 0.0314(11) Uani 1 1 d . . . . .
 H4A H -0.265863 0.642048 0.572147 0.038 Uiso 1 1 calc R . . . .
 H4B H -0.242439 0.732659 0.521588 0.038 Uiso 1 1 calc R . . . .
 C5 C -0.1120(3) 0.6862(5) 0.57093(16) 0.0278(11) Uani 1 1 d . . . . .
 H5A H -0.098896 0.581045 0.568236 0.033 Uiso 1 1 calc R . . . .
 H5B H -0.071204 0.738901 0.547161 0.033 Uiso 1 1 calc R . . . .
 C6 C 0.1790(3) 0.5813(4) 0.58925(15) 0.0217(10) Uani 1 1 d . . . . .
 H6 H 0.216110 0.522672 0.614774 0.026 Uiso 1 1 calc R . . . .
 C7 C 0.2203(3) 0.6132(4) 0.54034(15) 0.0199(10) Uani 1 1 d . . . . .
 C8 C 0.1652(3) 0.6954(5) 0.50165(15) 0.0231(10) Uani 1 1 d . . . . .
 H8 H 0.097922 0.725131 0.506092 0.028 Uiso 1 1 calc R . . . .
 C9 C 0.2070(3) 0.7339(4) 0.45722(15) 0.0218(10) Uani 1 1 d . . . . .
 H9 H 0.168519 0.790947 0.431676 0.026 Uiso 1 1 calc R . . . .
 C10 C 0.3049(3) 0.6900(5) 0.44932(15) 0.0192(10) Uani 1 1 d . . . . .
 C11 C 0.3587(3) 0.6042(5) 0.48665(15) 0.0220(10) Uani 1 1 d . . . . .
 H11 H 0.424692 0.570616 0.481346 0.026 Uiso 1 1 calc R . . . .
 C12 C 0.3170(3) 0.5669(4) 0.53177(15) 0.0221(10) Uani 1 1 d . . . . .
 H12 H 0.355150 0.508809 0.557102 0.027 Uiso 1 1 calc R . . . .
 C13 C 0.2817(3) 0.7408(4) 0.35615(15) 0.0170(10) Uani 1 1 d . . . . .
 C14 C 0.2060(3) 0.6387(4) 0.34367(15) 0.0187(10) Uani 1 1 d . . . . .
 H14 H 0.196884 0.561956 0.367109 0.022 Uiso 1 1 calc R . . . .
 C15 C 0.1437(3) 0.6477(4) 0.29746(15) 0.0179(9) Uani 1 1 d . . . . .
 H15 H 0.091397 0.577897 0.290103 0.021 Uiso 1 1 calc R . . . .
 C16 C 0.1556(3) 0.7563(4) 0.26134(15) 0.0156(9) Uani 1 1 d . . . . .
 C17 C 0.2303(3) 0.8590(4) 0.27478(15) 0.0198(10) Uani 1 1 d . . . . .
 H17 H 0.239343 0.935873 0.251390 0.024 Uiso 1 1 calc R . . . .
 C18 C 0.2925(3) 0.8526(4) 0.32150(15) 0.0200(10) Uani 1 1 d . . . . .
 H18 H 0.342566 0.925220 0.329720 0.024 Uiso 1 1 calc R . . . .
 C19 C 0.0936(3) 0.7579(4) 0.21031(16) 0.0192(10) Uani 1 1 d . . . . .
 C20 C 0.0246(3) 0.6488(5) 0.19129(16) 0.0245(10) Uani 1 1 d D . . . .
 H20 H 0.010543 0.563196 0.209496 0.029 Uiso 0.567(4) 1 calc R . P B 1
 H20A H 0.011452 0.565097 0.210750 0.029 Uiso 0.433(4) 1 calc R . P B 2
 C21 C -0.0330(12) 0.696(2) 0.1269(7) 0.0335(5) Uani 0.567(4) 1 d D . P B 1
 H21 H -0.081934 0.647056 0.103747 0.040 Uiso 0.567(4) 1 calc R . P B 1
 C22 C 0.0969(3) 0.8660(5) 0.17367(16) 0.0294(11) Uani 1 1 d D . . . .
 H22 H 0.139990 0.948197 0.178782 0.035 Uiso 0.567(4) 1 calc R . P B 1
 H22A H 0.131176 0.956013 0.178989 0.035 Uiso 0.433(4) 1 calc R . P B 2
 C23 C 0.4524(3) 0.7656(4) 0.40466(15) 0.0196(10) Uani 1 1 d . . . . .
 C24 C 0.5066(3) 0.7300(4) 0.36309(15) 0.0211(10) Uani 1 1 d . . . . .
 H24 H 0.472751 0.683635 0.333404 0.025 Uiso 1 1 calc R . . . .
 C25 C 0.6086(3) 0.7616(5) 0.36482(15) 0.0207(10) Uani 1 1 d . . . . .
 H25 H 0.643814 0.737027 0.336001 0.025 Uiso 1 1 calc R . . . .
 C26 C 0.6616(3) 0.8283(4) 0.40758(15) 0.0189(10) Uani 1 1 d . . . . .
 C27 C 0.6063(3) 0.8654(4) 0.44857(16) 0.0229(10) Uani 1 1 d . . . . .
 H27 H 0.640073 0.912568 0.478097 0.028 Uiso 1 1 calc R . . . .
 C28 C 0.5037(3) 0.8353(4) 0.44730(15) 0.0222(10) Uani 1 1 d . . . . .
 H28 H 0.468039 0.862282 0.475682 0.027 Uiso 1 1 calc R . . . .
 C29 C 0.7724(3) 0.8556(5) 0.40959(16) 0.0258(11) Uani 1 1 d . . . . .
 C30 C 0.8379(3) 0.7843(5) 0.37802(17) 0.0272(11) Uani 1 1 d D . . . .
 H30 H 0.812486 0.715308 0.352723 0.033 Uiso 0.627(3) 1 calc R . P A 1
 H30A H 0.818364 0.711607 0.353020 0.033 Uiso 0.373(3) 1 calc R . P A 2
 C31 C 0.9389(10) 0.8186(13) 0.3853(4) 0.0376(5) Uani 0.627(3) 1 d D . P A 1
 H31 H 0.991172 0.776776 0.367720 0.045 Uiso 0.627(3) 1 calc R . P A 1
 C32 C 0.8258(3) 0.9562(5) 0.44164(17) 0.0352(12) Uani 1 1 d D . . . .
 H32 H 0.796240 1.018103 0.465141 0.042 Uiso 0.627(3) 1 calc R . P A 1
 H32A H 0.793351 1.007869 0.466920 0.042 Uiso 0.373(3) 1 calc R . P A 2
 S4 S 0.25975(9) 0.52918(12) 0.76114(4) 0.0290(3) Uani 1 1 d . . . . .
 O1 O 0.2091(2) 0.4596(3) 0.71269(11) 0.0386(8) Uani 1 1 d . . . . .
 C33 C 0.3856(4) 0.5631(6) 0.74778(19) 0.0424(13) Uani 1 1 d . . . . .
 H33A H 0.418654 0.471480 0.740555 0.064 Uiso 1 1 calc GR . . . .
 H33B H 0.423462 0.609930 0.777822 0.064 Uiso 1 1 calc GR . . . .
 H33C H 0.384657 0.626884 0.717535 0.064 Uiso 1 1 calc GR . . . .
 C34 C 0.2840(3) 0.3860(5) 0.80626(15) 0.0238(10) Uani 1 1 d . . . . .
 H34A H 0.219430 0.350106 0.816620 0.036 Uiso 1 1 calc GR . . . .
 H34B H 0.326689 0.421493 0.836879 0.036 Uiso 1 1 calc GR . . . .
 H34C H 0.319209 0.307325 0.790228 0.036 Uiso 1 1 calc GR . . . .
 S2A S 0.9561(4) 0.8505(5) 0.39231(19) 0.0376(5) Uani 0.373(3) 1 d D . P A 2
 C31A C 0.9223(13) 0.979(2) 0.4362(7) 0.0376(5) Uani 0.373(3) 1 d D . P A 2
 H31A H 0.965085 1.050714 0.453039 0.045 Uiso 0.373(3) 1 calc R . P A 2
 S3A S -0.0279(4) 0.6778(8) 0.1356(2) 0.0335(5) Uani 0.433(4) 1 d D . P B 2
 C21A C 0.0260(14) 0.808(2) 0.1145(9) 0.0335(5) Uani 0.433(4) 1 d D . P B 2
 H21A H 0.022857 0.846923 0.080448 0.040 Uiso 0.433(4) 1 calc R . P B 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
 S1 C1 1.697(4) . ?
 S2 C31 1.748(10) . ?
 S2 C32 1.743(5) . ?
 S3 C21 1.522(17) . ?
 S3 C22 1.613(6) . ?
 N1 C1 1.342(5) . ?
 N1 C2 1.477(5) . ?
 N1 C5 1.481(5) . ?
 N2 H2 0.8800 . ?
 N2 N3 1.385(4) . ?
 N2 C1 1.361(5) . ?
 N3 C6 1.278(5) . ?
 N4 C10 1.421(5) . ?
 N4 C13 1.422(5) . ?
 N4 C23 1.428(5) . ?
 C2 H2A 0.9900 . ?
 C2 H2B 0.9900 . ?
 C2 C3 1.505(6) . ?
 C3 H3A 0.9900 . ?
 C3 H3B 0.9900 . ?
 C3 C4 1.517(6) . ?
 C4 H4A 0.9900 . ?
 C4 H4B 0.9900 . ?
 C4 C5 1.503(6) . ?
 C5 H5A 0.9900 . ?
 C5 H5B 0.9900 . ?
 C6 H6 0.9500 . ?
 C6 C7 1.465(5) . ?
 C7 C8 1.399(6) . ?
 C7 C12 1.388(6) . ?
 C8 H8 0.9500 . ?
 C8 C9 1.378(5) . ?
 C9 H9 0.9500 . ?
 C9 C10 1.393(6) . ?
 C10 C11 1.387(6) . ?
 C11 H11 0.9500 . ?
 C11 C12 1.391(6) . ?
 C12 H12 0.9500 . ?
 C13 C14 1.388(5) . ?
 C13 C18 1.387(5) . ?
 C14 H14 0.9500 . ?
 C14 C15 1.381(5) . ?
 C15 H15 0.9500 . ?
 C15 C16 1.393(5) . ?
 C16 C17 1.387(5) . ?
 C16 C19 1.480(6) . ?
 C17 H17 0.9500 . ?
 C17 C18 1.390(5) . ?
 C18 H18 0.9500 . ?
 C19 C20 1.412(6) . ?
 C19 C22 1.382(6) . ?
 C20 H20 0.9500 . ?
 C20 H20A 0.9500 . ?
 C20 C21 1.814(15) . ?
 C20 S3A 1.557(6) . ?
 C21 H21 0.9500 . ?
 C22 H22 0.9500 . ?
 C22 H22A 0.9500 . ?
 C22 C21A 1.791(18) . ?
 C23 C24 1.397(5) . ?
 C23 C28 1.391(6) . ?
 C24 H24 0.9500 . ?
 C24 C25 1.376(6) . ?
 C25 H25 0.9500 . ?
 C25 C26 1.391(6) . ?
 C26 C27 1.397(6) . ?
 C26 C29 1.481(6) . ?
 C27 H27 0.9500 . ?
 C27 C28 1.381(6) . ?
 C28 H28 0.9500 . ?
 C29 C30 1.417(6) . ?
 C29 C32 1.389(6) . ?
 C30 H30 0.9500 . ?
 C30 H30A 0.9500 . ?
 C30 C31 1.366(13) . ?
 C30 S2A 1.681(6) . ?
 C31 H31 0.9500 . ?
 C32 H32 0.9500 . ?
 C32 H32A 0.9500 . ?
 C32 C31A 1.315(17) . ?
 S4 O1 1.503(3) . ?
 S4 C33 1.764(5) . ?
 S4 C34 1.772(4) . ?
 C33 H33A 0.9800 . ?
 C33 H33B 0.9800 . ?
 C33 H33C 0.9800 . ?
 C34 H34A 0.9800 . ?
 C34 H34B 0.9800 . ?
 C34 H34C 0.9800 . ?
 S2A C31A 1.734(15) . ?
 C31A H31A 0.9500 . ?
 S3A C21A 1.532(19) . ?
 C21A H21A 0.9500 . ?

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
 C32 S2 C31 93.5(5) . . ?
 C21 S3 C22 107.9(8) . . ?
 C1 N1 C2 121.3(4) . . ?
 C1 N1 C5 126.5(4) . . ?
 C2 N1 C5 110.8(3) . . ?
 N3 N2 H2 120.6 . . ?
 C1 N2 H2 120.6 . . ?
 C1 N2 N3 118.9(4) . . ?
 C6 N3 N2 116.2(4) . . ?
 C10 N4 C13 119.0(3) . . ?
 C10 N4 C23 120.6(3) . . ?
 C13 N4 C23 120.4(3) . . ?
 N1 C1 S1 122.7(3) . . ?
 N1 C1 N2 119.3(4) . . ?
 N2 C1 S1 118.0(3) . . ?
 N1 C2 H2A 111.2 . . ?
 N1 C2 H2B 111.2 . . ?
 N1 C2 C3 102.8(4) . . ?
 H2A C2 H2B 109.1 . . ?
 C3 C2 H2A 111.2 . . ?
 C3 C2 H2B 111.2 . . ?
 C2 C3 H3A 111.0 . . ?
 C2 C3 H3B 111.0 . . ?
 C2 C3 C4 103.7(4) . . ?
 H3A C3 H3B 109.0 . . ?
 C4 C3 H3A 111.0 . . ?
 C4 C3 H3B 111.0 . . ?
 C3 C4 H4A 111.3 . . ?
 C3 C4 H4B 111.3 . . ?
 H4A C4 H4B 109.2 . . ?
 C5 C4 C3 102.2(4) . . ?
 C5 C4 H4A 111.3 . . ?
 C5 C4 H4B 111.3 . . ?
 N1 C5 C4 102.9(3) . . ?
 N1 C5 H5A 111.2 . . ?
 N1 C5 H5B 111.2 . . ?
 C4 C5 H5A 111.2 . . ?
 C4 C5 H5B 111.2 . . ?
 H5A C5 H5B 109.1 . . ?
 N3 C6 H6 120.4 . . ?
 N3 C6 C7 119.3(4) . . ?
 C7 C6 H6 120.4 . . ?
 C8 C7 C6 121.1(4) . . ?
 C12 C7 C6 120.9(4) . . ?
 C12 C7 C8 118.0(4) . . ?
 C7 C8 H8 119.5 . . ?
 C9 C8 C7 121.0(4) . . ?
 C9 C8 H8 119.5 . . ?
 C8 C9 H9 119.6 . . ?
 C8 C9 C10 120.7(4) . . ?
 C10 C9 H9 119.6 . . ?
 C9 C10 N4 120.1(4) . . ?
 C11 C10 N4 121.3(4) . . ?
 C11 C10 C9 118.6(4) . . ?
 C10 C11 H11 119.7 . . ?
 C10 C11 C12 120.6(4) . . ?
 C12 C11 H11 119.7 . . ?
 C7 C12 C11 121.0(4) . . ?
 C7 C12 H12 119.5 . . ?
 C11 C12 H12 119.5 . . ?
 C14 C13 N4 120.7(4) . . ?
 C18 C13 N4 120.8(4) . . ?
 C18 C13 C14 118.5(4) . . ?
 C13 C14 H14 119.7 . . ?
 C15 C14 C13 120.6(4) . . ?
 C15 C14 H14 119.7 . . ?
 C14 C15 H15 119.1 . . ?
 C14 C15 C16 121.8(4) . . ?
 C16 C15 H15 119.1 . . ?
 C15 C16 C19 121.2(4) . . ?
 C17 C16 C15 116.9(4) . . ?
 C17 C16 C19 121.9(4) . . ?
 C16 C17 H17 119.0 . . ?
 C16 C17 C18 121.9(4) . . ?
 C18 C17 H17 119.0 . . ?
 C13 C18 C17 120.3(4) . . ?
 C13 C18 H18 119.9 . . ?
 C17 C18 H18 119.9 . . ?
 C20 C19 C16 125.4(4) . . ?
 C22 C19 C16 124.5(4) . . ?
 C22 C19 C20 110.0(4) . . ?
 C19 C20 H20 125.1 . . ?
 C19 C20 H20A 122.9 . . ?
 C19 C20 C21 109.9(7) . . ?
 C19 C20 S3A 114.1(4) . . ?
 C21 C20 H20 125.1 . . ?
 S3A C20 H20A 122.9 . . ?
 S3 C21 C20 98.1(12) . . ?
 S3 C21 H21 130.9 . . ?
 C20 C21 H21 130.9 . . ?
 S3 C22 H22 123.0 . . ?
 C19 C22 S3 114.1(4) . . ?
 C19 C22 H22 123.0 . . ?
 C19 C22 H22A 125.6 . . ?
 C19 C22 C21A 108.8(9) . . ?
 C21A C22 H22A 125.6 . . ?
 C24 C23 N4 120.6(4) . . ?
 C28 C23 N4 121.0(4) . . ?
 C28 C23 C24 118.4(4) . . ?
 C23 C24 H24 119.7 . . ?
 C25 C24 C23 120.5(4) . . ?
 C25 C24 H24 119.7 . . ?
 C24 C25 H25 119.1 . . ?
 C24 C25 C26 121.8(4) . . ?
 C26 C25 H25 119.1 . . ?
 C25 C26 C27 117.1(4) . . ?
 C25 C26 C29 120.9(4) . . ?
 C27 C26 C29 121.9(4) . . ?
 C26 C27 H27 119.1 . . ?
 C28 C27 C26 121.7(4) . . ?
 C28 C27 H27 119.1 . . ?
 C23 C28 H28 119.8 . . ?
 C27 C28 C23 120.4(4) . . ?
 C27 C28 H28 119.8 . . ?
 C30 C29 C26 124.4(4) . . ?
 C32 C29 C26 124.9(4) . . ?
 C32 C29 C30 110.7(4) . . ?
 C29 C30 H30 121.2 . . ?
 C29 C30 H30A 125.8 . . ?
 C29 C30 S2A 108.4(4) . . ?
 C31 C30 C29 117.6(7) . . ?
 C31 C30 H30 121.2 . . ?
 S2A C30 H30A 125.8 . . ?
 S2 C31 H31 126.2 . . ?
 C30 C31 S2 107.6(9) . . ?
 C30 C31 H31 126.2 . . ?
 S2 C32 H32 124.7 . . ?
 C29 C32 S2 110.6(4) . . ?
 C29 C32 H32 124.7 . . ?
 C29 C32 H32A 120.7 . . ?
 C31A C32 C29 118.5(9) . . ?
 C31A C32 H32A 120.7 . . ?
 O1 S4 C33 104.8(2) . . ?
 O1 S4 C34 105.4(2) . . ?
 C33 S4 C34 98.9(2) . . ?
 S4 C33 H33A 109.5 . . ?
 S4 C33 H33B 109.5 . . ?
 S4 C33 H33C 109.5 . . ?
 H33A C33 H33B 109.5 . . ?
 H33A C33 H33C 109.5 . . ?
 H33B C33 H33C 109.5 . . ?
 S4 C34 H34A 109.5 . . ?
 S4 C34 H34B 109.5 . . ?
 S4 C34 H34C 109.5 . . ?
 H34A C34 H34B 109.5 . . ?
 H34A C34 H34C 109.5 . . ?
 H34B C34 H34C 109.5 . . ?
 C30 S2A C31A 95.3(9) . . ?
 C32 C31A S2A 106.6(14) . . ?
 C32 C31A H31A 126.7 . . ?
 S2A C31A H31A 126.7 . . ?
 C21A S3A C20 106.7(11) . . ?
 C22 C21A H21A 130.7 . . ?
 S3A C21A C22 98.6(15) . . ?
 S3A C21A H21A 130.7 . . ?

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
 N2 H2 O1 0.88 2.02 2.827(5) 152.0 . yes

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
 N1 C2 C3 C4 32.0(4) . . . . ?
 N2 N3 C6 C7 -176.8(3) . . . . ?
 N3 N2 C1 S1 -151.9(3) . . . . ?
 N3 N2 C1 N1 28.7(6) . . . . ?
 N3 C6 C7 C8 -2.1(6) . . . . ?
 N3 C6 C7 C12 175.6(4) . . . . ?
 N4 C10 C11 C12 179.2(4) . . . . ?
 N4 C13 C14 C15 -179.0(3) . . . . ?
 N4 C13 C18 C17 178.0(3) . . . . ?
 N4 C23 C24 C25 -178.8(4) . . . . ?
 N4 C23 C28 C27 178.4(4) . . . . ?
 C1 N1 C2 C3 -177.1(4) . . . . ?
 C1 N1 C5 C4 150.1(4) . . . . ?
 C1 N2 N3 C6 164.7(4) . . . . ?
 C2 N1 C1 S1 6.0(6) . . . . ?
 C2 N1 C1 N2 -174.6(4) . . . . ?
 C2 N1 C5 C4 -16.3(5) . . . . ?
 C2 C3 C4 C5 -42.6(4) . . . . ?
 C3 C4 C5 N1 35.4(4) . . . . ?
 C5 N1 C1 S1 -159.0(3) . . . . ?
 C5 N1 C1 N2 20.4(6) . . . . ?
 C5 N1 C2 C3 -9.9(5) . . . . ?
 C6 C7 C8 C9 175.4(4) . . . . ?
 C6 C7 C12 C11 -176.2(4) . . . . ?
 C7 C8 C9 C10 0.9(6) . . . . ?
 C8 C7 C12 C11 1.6(6) . . . . ?
 C8 C9 C10 N4 180.0(4) . . . . ?
 C8 C9 C10 C11 1.3(6) . . . . ?
 C9 C10 C11 C12 -2.1(6) . . . . ?
 C10 N4 C13 C14 -40.9(5) . . . . ?
 C10 N4 C13 C18 139.3(4) . . . . ?
 C10 N4 C23 C24 145.1(4) . . . . ?
 C10 N4 C23 C28 -34.6(6) . . . . ?
 C10 C11 C12 C7 0.6(6) . . . . ?
 C12 C7 C8 C9 -2.4(6) . . . . ?
 C13 N4 C10 C9 -34.6(6) . . . . ?
 C13 N4 C10 C11 144.0(4) . . . . ?
 C13 N4 C23 C24 -37.2(6) . . . . ?
 C13 N4 C23 C28 143.1(4) . . . . ?
 C13 C14 C15 C16 1.5(6) . . . . ?
 C14 C13 C18 C17 -1.8(6) . . . . ?
 C14 C15 C16 C17 -2.5(6) . . . . ?
 C14 C15 C16 C19 175.2(4) . . . . ?
 C15 C16 C17 C18 1.5(6) . . . . ?
 C15 C16 C19 C20 -5.4(6) . . . . ?
 C15 C16 C19 C22 176.3(4) . . . . ?
 C16 C17 C18 C13 0.6(6) . . . . ?
 C16 C19 C20 C21 -179.5(7) . . . . ?
 C16 C19 C20 S3A -178.4(4) . . . . ?
 C16 C19 C22 S3 180.0(3) . . . . ?
 C16 C19 C22 C21A 170.4(7) . . . . ?
 C17 C16 C19 C20 172.2(4) . . . . ?
 C17 C16 C19 C22 -6.1(6) . . . . ?
 C18 C13 C14 C15 0.8(6) . . . . ?
 C19 C16 C17 C18 -176.2(4) . . . . ?
 C19 C20 C21 S3 0.1(11) . . . . ?
 C19 C20 S3A C21A 9.2(9) . . . . ?
 C19 C22 C21A S3A 12.9(11) . . . . ?
 C20 C19 C22 S3 1.4(5) . . . . ?
 C20 C19 C22 C21A -8.1(8) . . . . ?
 C20 S3A C21A C22 -11.8(10) . . . . ?
 C21 S3 C22 C19 -1.3(9) . . . . ?
 C22 S3 C21 C20 0.6(10) . . . . ?
 C22 C19 C20 C21 -0.9(8) . . . . ?
 C22 C19 C20 S3A 0.1(5) . . . . ?
 C23 N4 C10 C9 143.1(4) . . . . ?
 C23 N4 C10 C11 -38.3(6) . . . . ?
 C23 N4 C13 C14 141.4(4) . . . . ?
 C23 N4 C13 C18 -38.4(5) . . . . ?
 C23 C24 C25 C26 0.5(6) . . . . ?
 C24 C23 C28 C27 -1.3(6) . . . . ?
 C24 C25 C26 C27 -1.4(6) . . . . ?
 C24 C25 C26 C29 177.3(4) . . . . ?
 C25 C26 C27 C28 1.0(6) . . . . ?
 C25 C26 C29 C30 -18.6(6) . . . . ?
 C25 C26 C29 C32 159.8(4) . . . . ?
 C26 C27 C28 C23 0.3(6) . . . . ?
 C26 C29 C30 C31 -178.4(7) . . . . ?
 C26 C29 C30 S2A 178.9(4) . . . . ?
 C26 C29 C32 S2 179.3(3) . . . . ?
 C26 C29 C32 C31A -174.0(10) . . . . ?
 C27 C26 C29 C30 160.1(4) . . . . ?
 C27 C26 C29 C32 -21.5(6) . . . . ?
 C28 C23 C24 C25 0.9(6) . . . . ?
 C29 C26 C27 C28 -177.7(4) . . . . ?
 C29 C30 C31 S2 -2.3(9) . . . . ?
 C29 C30 S2A C31A -3.4(8) . . . . ?
 C29 C32 C31A S2A -6.9(15) . . . . ?
 C30 C29 C32 S2 -2.0(5) . . . . ?
 C30 C29 C32 C31A 4.6(11) . . . . ?
 C30 S2A C31A C32 5.8(12) . . . . ?
 C31 S2 C32 C29 0.7(5) . . . . ?
 C32 S2 C31 C30 0.9(7) . . . . ?
 C32 C29 C30 C31 3.0(8) . . . . ?
 C32 C29 C30 S2A 0.3(5) . . . . ?

_olex2_submission_special_instructions  'No special instructions were received'
# start Validation Reply Form
_vrf_THETM01_md2
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.575
RESPONSE: No reflections were found above 50 degrees 2-theta and
the final least squares refinement was restrainted to that value.
;
