# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_ha004
_database_code_depnum_ccdc_archive 'CCDC 1908640'
loop_
_audit_author_name
_audit_author_address
'Eric C. Hosten'
;Nelson Mandela University
South Africa
;
_audit_update_record             
;
2019-09-05 deposited with the CCDC.	2019-10-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H14 N4 O3 V, 2(C2 H6 O S)'
_chemical_formula_sum            'C22 H26 N4 O5 S2 V'
_chemical_formula_weight         541.53

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'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_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+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   15.8192(9)
_cell_length_b                   10.5686(6)
_cell_length_c                   14.8615(8)
_cell_angle_alpha                90
_cell_angle_beta                 94.964(2)
_cell_angle_gamma                90
_cell_volume                     2475.3(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    9974
_cell_measurement_theta_min      2.32
_cell_measurement_theta_max      28.29

_exptl_crystal_description       platelet
_exptl_crystal_colour            'dark blue green'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.453
_exptl_crystal_F_000             1124
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.612
_exptl_crystal_size_mid          0.498
_exptl_crystal_size_min          0.186
_exptl_absorpt_coefficient_mu    0.610
_shelx_estimated_absorpt_T_min   0.707
_shelx_estimated_absorpt_T_max   0.895
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.9125
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   'SADABS V2008/1 (Bruker AXS)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      200(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 8.3333
_diffrn_reflns_number            43888
_diffrn_reflns_av_unetI/netI     0.0172
_diffrn_reflns_av_R_equivalents  0.0240
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         2.320
_diffrn_reflns_theta_max         28.335
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             6170
_reflns_number_gt                5249
_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       'Bruker Instrument Service v2011.4.0.0'
_computing_cell_refinement       'APEX2 v2011.4-1 (Bruker AXS)'
_computing_data_reduction        'SAINT V7.68A (Bruker AXS, 2009)'
_computing_structure_solution    'SHELXT-2018/2 (Sheldrick, 2015)'
_computing_structure_refinement  
'SHELXL-2018/3 (Sheldrick, 2015) and ShelXle (Hübschle, 2011)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 2012)'
_computing_publication_material  
'PLATON (Spek, 2009) and MERCURY (Macrae, 2008)'

_refine_special_details          
;
Carbon and nitrogen bound H atoms were placed in calculated positions and were
included in the refinement in the riding model approximation, with U(H)
set to 1.2 Ueq(C/N). The H atoms of the disordered methyl group were
also placed in calculated positions but with Uiso(H) set to 1.5
Ueq(C).

The solvent DMSO are disordered neccesitating the use of the EADP constraint for
the methyl carbons.

Two reflections with large differences between their observed and calculated
intensities were omitted. This is due to obstruction by the beam stop.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0435P)²+1.9176P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         6170
_refine_ls_number_parameters     345
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0459
_refine_ls_R_factor_gt           0.0370
_refine_ls_wR_factor_ref         0.1028
_refine_ls_wR_factor_gt          0.0966
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_restrained_S_all      1.075
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_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
V1 V 0.14520(2) 0.44109(3) 0.41162(2) 0.01954(8) Uani 1 1 d . . . . .
O1 O 0.08217(8) 0.32164(12) 0.39845(8) 0.0276(3) Uani 1 1 d . . . . .
O2 O 0.20627(8) 0.46152(12) 0.30687(8) 0.0258(3) Uani 1 1 d . . . . .
O3 O 0.13828(8) 0.52576(12) 0.52370(8) 0.0268(3) Uani 1 1 d . . . . .
O4 O 0.44533(11) 0.21639(16) 0.73298(11) 0.0485(4) Uani 1 1 d . . . . .
O5 O 0.57225(14) 0.2161(4) 0.5078(2) 0.1235(12) Uani 1 1 d . . . . .
N21 N 0.07184(9) 0.58974(14) 0.35988(9) 0.0225(3) Uani 1 1 d . . . . .
N22 N -0.00376(9) 0.70559(14) 0.26072(10) 0.0251(3) Uani 1 1 d . . . . .
H22 H -0.024044 0.738148 0.208783 0.030 Uiso 1 1 calc R U . . .
N31 N 0.25659(9) 0.36619(14) 0.47143(9) 0.0236(3) Uani 1 1 d . . . . .
N32 N 0.35426(9) 0.29559(15) 0.57276(10) 0.0274(3) Uani 1 1 d . . . . .
H32 H 0.382440 0.280073 0.625273 0.033 Uiso 1 1 calc R U . . .
C21 C 0.10257(10) 0.56153(15) 0.20038(11) 0.0220(3) Uani 1 1 d . . . . .
C22 C 0.17542(10) 0.48691(16) 0.22251(11) 0.0223(3) Uani 1 1 d . . . . .
C23 C 0.21826(12) 0.43640(17) 0.15144(12) 0.0280(4) Uani 1 1 d . . . . .
H23 H 0.268787 0.389026 0.165034 0.034 Uiso 1 1 calc R U . . .
C24 C 0.18808(13) 0.45451(19) 0.06215(12) 0.0337(4) Uani 1 1 d . . . . .
H24 H 0.216728 0.416891 0.015319 0.040 Uiso 1 1 calc R U . . .
C25 C 0.11619(13) 0.5274(2) 0.04074(12) 0.0353(4) Uani 1 1 d . . . . .
H25 H 0.095917 0.540517 -0.020597 0.042 Uiso 1 1 calc R U . . .
C26 C 0.07420(12) 0.58069(18) 0.10929(12) 0.0291(4) Uani 1 1 d . . . . .
H26 H 0.025303 0.631201 0.094440 0.035 Uiso 1 1 calc R U . . .
C27 C 0.05746(10) 0.61686(15) 0.27203(11) 0.0212(3) Uani 1 1 d . . . . .
C28 C 0.01781(11) 0.66514(17) 0.40486(11) 0.0261(3) Uani 1 1 d . . . . .
H28 H 0.014286 0.666452 0.468347 0.031 Uiso 1 1 calc R U . . .
C29 C -0.02910(11) 0.73656(17) 0.34409(12) 0.0282(4) Uani 1 1 d . . . . .
H29 H -0.071340 0.796462 0.356488 0.034 Uiso 1 1 calc R U . . .
C31 C 0.23700(11) 0.42046(16) 0.63083(11) 0.0242(3) Uani 1 1 d . . . . .
C32 C 0.16730(11) 0.49991(16) 0.60795(11) 0.0236(3) Uani 1 1 d . . . . .
C33 C 0.12731(12) 0.55827(18) 0.67811(12) 0.0307(4) Uani 1 1 d . . . . .
H33 H 0.080381 0.612868 0.663672 0.037 Uiso 1 1 calc R U . . .
C34 C 0.15496(15) 0.5376(2) 0.76715(13) 0.0406(5) Uani 1 1 d . . . . .
H34 H 0.127015 0.577849 0.813462 0.049 Uiso 1 1 calc R U . . .
C35 C 0.22331(16) 0.4586(2) 0.78972(13) 0.0474(6) Uani 1 1 d . . . . .
H35 H 0.241986 0.443897 0.851317 0.057 Uiso 1 1 calc R U . . .
C36 C 0.26425(14) 0.4010(2) 0.72203(12) 0.0371(4) Uani 1 1 d . . . . .
H36 H 0.311537 0.347580 0.737603 0.044 Uiso 1 1 calc R U . . .
C37 C 0.28112(10) 0.36169(15) 0.55984(11) 0.0224(3) Uani 1 1 d . . . . .
C38 C 0.31706(11) 0.30099(18) 0.42809(12) 0.0294(4) Uani 1 1 d . . . . .
H38 H 0.316363 0.289217 0.364653 0.035 Uiso 1 1 calc R U . . .
C39 C 0.37726(12) 0.25667(19) 0.49007(13) 0.0328(4) Uani 1 1 d . . . . .
H39 H 0.425819 0.208243 0.478775 0.039 Uiso 1 1 calc R U . . .
S41 S 0.50553(5) 0.10789(8) 0.74859(5) 0.0579(3) Uani 0.901(2) 1 d . . P A 1
S51 S 0.66086(7) 0.17688(10) 0.51053(10) 0.0612(4) Uani 0.598(2) 1 d . . P B 1
C41 C 0.4887(3) 0.0069(4) 0.6552(3) 0.0732(11) Uani 0.901(2) 1 d . . P A 1
H41A H 0.527118 -0.065712 0.662973 0.110 Uiso 0.901(2) 1 calc R U P A 1
H41B H 0.429774 -0.022922 0.650336 0.110 Uiso 0.901(2) 1 calc R U P A 1
H41C H 0.499619 0.052874 0.600162 0.110 Uiso 0.901(2) 1 calc R U P A 1
C42 C 0.4582(4) 0.0068(5) 0.8270(4) 0.130(3) Uani 0.901(2) 1 d . . P A 1
H42A H 0.494729 -0.066970 0.840284 0.195 Uiso 0.901(2) 1 calc R U P A 1
H42B H 0.451539 0.053385 0.882916 0.195 Uiso 0.901(2) 1 calc R U P A 1
H42C H 0.402463 -0.021440 0.800576 0.195 Uiso 0.901(2) 1 calc R U P A 1
C51 C 0.698(3) 0.255(3) 0.414(2) 0.098(6) Uani 0.598(2) 1 d . . P B 1
H51A H 0.757865 0.234088 0.409915 0.146 Uiso 0.598(2) 1 calc R U P B 1
H51B H 0.664535 0.226291 0.359252 0.146 Uiso 0.598(2) 1 calc R U P B 1
H51C H 0.691694 0.346513 0.420549 0.146 Uiso 0.598(2) 1 calc R U P B 1
C52 C 0.721(3) 0.271(3) 0.594(3) 0.120(6) Uani 0.598(2) 1 d . . P B 1
H52A H 0.781284 0.246101 0.596437 0.180 Uiso 0.598(2) 1 calc R U P B 1
H52B H 0.716186 0.360792 0.577111 0.180 Uiso 0.598(2) 1 calc R U P B 1
H52C H 0.700005 0.258176 0.652925 0.180 Uiso 0.598(2) 1 calc R U P B 1
S42 S 0.4458(4) 0.0604(7) 0.7229(7) 0.071(3) Uani 0.099(2) 1 d . . P A 2
S52 S 0.64927(16) 0.3085(2) 0.4930(2) 0.1010(11) Uani 0.402(2) 1 d . . P B 2
C43 C 0.541(3) 0.036(4) 0.671(4) 0.11(2) Uani 0.099(2) 1 d . . P A 2
H43A H 0.549287 -0.054419 0.660963 0.169 Uiso 0.099(2) 1 calc R U P A 2
H43B H 0.538000 0.080729 0.612855 0.169 Uiso 0.099(2) 1 calc R U P A 2
H43C H 0.589170 0.069208 0.710219 0.169 Uiso 0.099(2) 1 calc R U P A 2
C44 C 0.514(4) 0.054(5) 0.840(4) 0.130(3) Uani 0.099(2) 1 d . . P A 2
H44A H 0.526461 -0.034031 0.855736 0.195 Uiso 0.099(2) 1 calc R U P A 2
H44B H 0.566655 0.100905 0.835543 0.195 Uiso 0.099(2) 1 calc R U P A 2
H44C H 0.481538 0.092783 0.886142 0.195 Uiso 0.099(2) 1 calc R U P A 2
C53 C 0.692(4) 0.238(5) 0.392(4) 0.098(6) Uani 0.402(2) 1 d . . P B 2
H53A H 0.740887 0.287834 0.376224 0.146 Uiso 0.402(2) 1 calc R U P B 2
H53B H 0.710066 0.150929 0.405771 0.146 Uiso 0.402(2) 1 calc R U P B 2
H53C H 0.648069 0.238423 0.341735 0.146 Uiso 0.402(2) 1 calc R U P B 2
C54 C 0.720(4) 0.252(5) 0.574(4) 0.120(6) Uani 0.402(2) 1 d . . P B 2
H54A H 0.772999 0.300404 0.574368 0.180 Uiso 0.402(2) 1 calc R U P B 2
H54B H 0.697096 0.260744 0.633113 0.180 Uiso 0.402(2) 1 calc R U P B 2
H54C H 0.731274 0.162809 0.562562 0.180 Uiso 0.402(2) 1 calc R U 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
V1 O1 1.6101(12) . ?
V1 O3 1.9024(12) . ?
V1 O2 1.9140(12) . ?
V1 N31 2.0617(14) . ?
V1 N21 2.0619(14) . ?
O2 C22 1.3326(19) . ?
O3 C32 1.3242(19) . ?
O4 S41 1.4958(16) . ?
O4 S42 1.655(8) . ?
O5 S51 1.459(3) . ?
O5 S52 1.592(4) . ?
N21 C27 1.337(2) . ?
N21 C28 1.383(2) . ?
N22 C27 1.348(2) . ?
N22 C29 1.374(2) . ?
N22 H22 0.8800 . ?
N31 C37 1.338(2) . ?
N31 C38 1.383(2) . ?
N32 C37 1.351(2) . ?
N32 C39 1.375(2) . ?
N32 H32 0.8800 . ?
C21 C26 1.404(2) . ?
C21 C22 1.412(2) . ?
C21 C27 1.455(2) . ?
C22 C23 1.408(2) . ?
C23 C24 1.384(3) . ?
C23 H23 0.9500 . ?
C24 C25 1.387(3) . ?
C24 H24 0.9500 . ?
C25 C26 1.383(3) . ?
C25 H25 0.9500 . ?
C26 H26 0.9500 . ?
C28 C29 1.349(2) . ?
C28 H28 0.9500 . ?
C29 H29 0.9500 . ?
C31 C36 1.401(2) . ?
C31 C32 1.404(2) . ?
C31 C37 1.454(2) . ?
C32 C33 1.408(2) . ?
C33 C34 1.375(3) . ?
C33 H33 0.9500 . ?
C34 C35 1.385(3) . ?
C34 H34 0.9500 . ?
C35 C36 1.383(3) . ?
C35 H35 0.9500 . ?
C36 H36 0.9500 . ?
C38 C39 1.350(3) . ?
C38 H38 0.9500 . ?
C39 H39 0.9500 . ?
S41 C41 1.753(4) . ?
S41 C42 1.792(5) . ?
S51 C51 1.79(4) . ?
S51 C52 1.80(3) . ?
C41 H41A 0.9800 . ?
C41 H41B 0.9800 . ?
C41 H41C 0.9800 . ?
C42 H42A 0.9800 . ?
C42 H42B 0.9800 . ?
C42 H42C 0.9800 . ?
C51 H51A 0.9800 . ?
C51 H51B 0.9800 . ?
C51 H51C 0.9800 . ?
C52 H52A 0.9800 . ?
C52 H52B 0.9800 . ?
C52 H52C 0.9800 . ?
S42 C43 1.77(3) . ?
S42 C44 1.96(7) . ?
S52 C54 1.68(6) . ?
S52 C53 1.85(6) . ?
C43 H43A 0.9800 . ?
C43 H43B 0.9800 . ?
C43 H43C 0.9800 . ?
C44 H44A 0.9800 . ?
C44 H44B 0.9800 . ?
C44 H44C 0.9800 . ?
C53 H53A 0.9800 . ?
C53 H53B 0.9800 . ?
C53 H53C 0.9800 . ?
C54 H54A 0.9800 . ?
C54 H54B 0.9800 . ?
C54 H54C 0.9800 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 V1 O3 113.16(6) . . ?
O1 V1 O2 109.90(6) . . ?
O3 V1 O2 136.93(6) . . ?
O1 V1 N31 104.39(6) . . ?
O3 V1 N31 85.12(5) . . ?
O2 V1 N31 85.49(5) . . ?
O1 V1 N21 103.26(6) . . ?
O3 V1 N21 83.97(5) . . ?
O2 V1 N21 85.31(5) . . ?
N31 V1 N21 152.35(6) . . ?
C22 O2 V1 128.20(10) . . ?
C32 O3 V1 133.58(11) . . ?
C27 N21 C28 106.77(14) . . ?
C27 N21 V1 124.77(11) . . ?
C28 N21 V1 127.62(11) . . ?
C27 N22 C29 108.40(14) . . ?
C27 N22 H22 125.8 . . ?
C29 N22 H22 125.8 . . ?
C37 N31 C38 106.63(14) . . ?
C37 N31 V1 126.97(11) . . ?
C38 N31 V1 126.19(11) . . ?
C37 N32 C39 108.50(14) . . ?
C37 N32 H32 125.7 . . ?
C39 N32 H32 125.7 . . ?
C26 C21 C22 119.46(15) . . ?
C26 C21 C27 120.79(15) . . ?
C22 C21 C27 119.75(14) . . ?
O2 C22 C23 117.93(15) . . ?
O2 C22 C21 123.83(14) . . ?
C23 C22 C21 118.24(15) . . ?
C24 C23 C22 121.21(17) . . ?
C24 C23 H23 119.4 . . ?
C22 C23 H23 119.4 . . ?
C23 C24 C25 120.30(17) . . ?
C23 C24 H24 119.8 . . ?
C25 C24 H24 119.8 . . ?
C26 C25 C24 119.57(17) . . ?
C26 C25 H25 120.2 . . ?
C24 C25 H25 120.2 . . ?
C25 C26 C21 121.18(17) . . ?
C25 C26 H26 119.4 . . ?
C21 C26 H26 119.4 . . ?
N21 C27 N22 109.31(14) . . ?
N21 C27 C21 125.16(15) . . ?
N22 C27 C21 125.51(15) . . ?
C29 C28 N21 109.03(15) . . ?
C29 C28 H28 125.5 . . ?
N21 C28 H28 125.5 . . ?
C28 C29 N22 106.49(15) . . ?
C28 C29 H29 126.8 . . ?
N22 C29 H29 126.8 . . ?
C36 C31 C32 119.42(16) . . ?
C36 C31 C37 120.83(16) . . ?
C32 C31 C37 119.73(15) . . ?
O3 C32 C31 123.59(15) . . ?
O3 C32 C33 117.94(15) . . ?
C31 C32 C33 118.45(15) . . ?
C34 C33 C32 121.16(18) . . ?
C34 C33 H33 119.4 . . ?
C32 C33 H33 119.4 . . ?
C33 C34 C35 120.38(18) . . ?
C33 C34 H34 119.8 . . ?
C35 C34 H34 119.8 . . ?
C36 C35 C34 119.60(18) . . ?
C36 C35 H35 120.2 . . ?
C34 C35 H35 120.2 . . ?
C35 C36 C31 120.99(18) . . ?
C35 C36 H36 119.5 . . ?
C31 C36 H36 119.5 . . ?
N31 C37 N32 109.26(14) . . ?
N31 C37 C31 125.50(15) . . ?
N32 C37 C31 125.23(15) . . ?
C39 C38 N31 109.31(15) . . ?
C39 C38 H38 125.3 . . ?
N31 C38 H38 125.3 . . ?
C38 C39 N32 106.29(16) . . ?
C38 C39 H39 126.9 . . ?
N32 C39 H39 126.9 . . ?
O4 S41 C41 107.02(15) . . ?
O4 S41 C42 105.18(18) . . ?
C41 S41 C42 96.2(3) . . ?
O5 S51 C51 103.1(13) . . ?
O5 S51 C52 108.4(16) . . ?
C51 S51 C52 95.9(19) . . ?
S41 C41 H41A 109.5 . . ?
S41 C41 H41B 109.5 . . ?
H41A C41 H41B 109.5 . . ?
S41 C41 H41C 109.5 . . ?
H41A C41 H41C 109.5 . . ?
H41B C41 H41C 109.5 . . ?
S41 C42 H42A 109.5 . . ?
S41 C42 H42B 109.5 . . ?
H42A C42 H42B 109.5 . . ?
S41 C42 H42C 109.5 . . ?
H42A C42 H42C 109.5 . . ?
H42B C42 H42C 109.5 . . ?
S51 C51 H51A 109.5 . . ?
S51 C51 H51B 109.5 . . ?
H51A C51 H51B 109.5 . . ?
S51 C51 H51C 109.5 . . ?
H51A C51 H51C 109.5 . . ?
H51B C51 H51C 109.5 . . ?
S51 C52 H52A 109.5 . . ?
S51 C52 H52B 109.5 . . ?
H52A C52 H52B 109.5 . . ?
S51 C52 H52C 109.5 . . ?
H52A C52 H52C 109.5 . . ?
H52B C52 H52C 109.5 . . ?
O4 S42 C43 101.2(14) . . ?
O4 S42 C44 87.7(17) . . ?
C43 S42 C44 88(3) . . ?
O5 S52 C54 99(2) . . ?
O5 S52 C53 101.8(17) . . ?
C54 S52 C53 100(3) . . ?
S42 C43 H43A 109.5 . . ?
S42 C43 H43B 109.5 . . ?
H43A C43 H43B 109.5 . . ?
S42 C43 H43C 109.5 . . ?
H43A C43 H43C 109.5 . . ?
H43B C43 H43C 109.5 . . ?
S42 C44 H44A 109.5 . . ?
S42 C44 H44B 109.5 . . ?
H44A C44 H44B 109.5 . . ?
S42 C44 H44C 109.5 . . ?
H44A C44 H44C 109.5 . . ?
H44B C44 H44C 109.5 . . ?
S52 C53 H53A 109.5 . . ?
S52 C53 H53B 109.5 . . ?
H53A C53 H53B 109.5 . . ?
S52 C53 H53C 109.5 . . ?
H53A C53 H53C 109.5 . . ?
H53B C53 H53C 109.5 . . ?
S52 C54 H54A 109.5 . . ?
S52 C54 H54B 109.5 . . ?
H54A C54 H54B 109.5 . . ?
S52 C54 H54C 109.5 . . ?
H54A C54 H54C 109.5 . . ?
H54B C54 H54C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
V1 O2 C22 C23 -147.71(13) . . . . ?
V1 O2 C22 C21 32.4(2) . . . . ?
C26 C21 C22 O2 -178.76(16) . . . . ?
C27 C21 C22 O2 0.8(2) . . . . ?
C26 C21 C22 C23 1.4(2) . . . . ?
C27 C21 C22 C23 -179.06(15) . . . . ?
O2 C22 C23 C24 177.41(17) . . . . ?
C21 C22 C23 C24 -2.7(3) . . . . ?
C22 C23 C24 C25 2.4(3) . . . . ?
C23 C24 C25 C26 -0.7(3) . . . . ?
C24 C25 C26 C21 -0.6(3) . . . . ?
C22 C21 C26 C25 0.2(3) . . . . ?
C27 C21 C26 C25 -179.31(17) . . . . ?
C28 N21 C27 N22 -0.37(18) . . . . ?
V1 N21 C27 N22 169.80(11) . . . . ?
C28 N21 C27 C21 178.10(16) . . . . ?
V1 N21 C27 C21 -11.7(2) . . . . ?
C29 N22 C27 N21 0.24(19) . . . . ?
C29 N22 C27 C21 -178.23(16) . . . . ?
C26 C21 C27 N21 169.87(16) . . . . ?
C22 C21 C27 N21 -9.7(3) . . . . ?
C26 C21 C27 N22 -11.9(3) . . . . ?
C22 C21 C27 N22 168.54(16) . . . . ?
C27 N21 C28 C29 0.4(2) . . . . ?
V1 N21 C28 C29 -169.44(12) . . . . ?
N21 C28 C29 N22 -0.2(2) . . . . ?
C27 N22 C29 C28 0.0(2) . . . . ?
V1 O3 C32 C31 23.4(3) . . . . ?
V1 O3 C32 C33 -158.43(14) . . . . ?
C36 C31 C32 O3 178.57(18) . . . . ?
C37 C31 C32 O3 -0.1(3) . . . . ?
C36 C31 C32 C33 0.4(3) . . . . ?
C37 C31 C32 C33 -178.27(16) . . . . ?
O3 C32 C33 C34 -178.84(19) . . . . ?
C31 C32 C33 C34 -0.6(3) . . . . ?
C32 C33 C34 C35 0.1(3) . . . . ?
C33 C34 C35 C36 0.5(4) . . . . ?
C34 C35 C36 C31 -0.7(4) . . . . ?
C32 C31 C36 C35 0.3(3) . . . . ?
C37 C31 C36 C35 178.9(2) . . . . ?
C38 N31 C37 N32 -0.31(19) . . . . ?
V1 N31 C37 N32 174.62(11) . . . . ?
C38 N31 C37 C31 178.68(16) . . . . ?
V1 N31 C37 C31 -6.4(2) . . . . ?
C39 N32 C37 N31 0.0(2) . . . . ?
C39 N32 C37 C31 -178.96(17) . . . . ?
C36 C31 C37 N31 174.58(18) . . . . ?
C32 C31 C37 N31 -6.8(3) . . . . ?
C36 C31 C37 N32 -6.6(3) . . . . ?
C32 C31 C37 N32 172.04(16) . . . . ?
C37 N31 C38 C39 0.5(2) . . . . ?
V1 N31 C38 C39 -174.50(13) . . . . ?
N31 C38 C39 N32 -0.5(2) . . . . ?
C37 N32 C39 C38 0.3(2) . . . . ?

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
N22 H22 O1 0.88 1.98 2.8515(18) 172 2 yes
N32 H32 O4 0.88 1.93 2.802(2) 170 . yes
C28 H28 O3 0.95 2.54 2.888(2) 102 . yes
C36 H36 O4 0.95 2.54 3.458(3) 164 . yes
C39 H39 O5 0.95 2.32 3.103(3) 139 . yes
C41 H41C O5 0.98 2.54 3.455(6) 155 . yes

_refine_diff_density_max         0.699
_refine_diff_density_min         -0.359
_refine_diff_density_rms         0.058

####################################################################### 
# 
# 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_ga314
_database_code_depnum_ccdc_archive 'CCDC 1908641'
loop_
_audit_author_name
_audit_author_address
'Eric C. Hosten'
;Nelson Mandela University
South Africa
;
_audit_update_record             
;
2019-09-05 deposited with the CCDC.	2019-10-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H15 N4 O4 V'
_chemical_formula_sum            'C18 H15 N4 O4 V'
_chemical_formula_weight         402.28

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'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'

_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+1/2, -y, z+1/2'
'x+1/2, -y+1/2, -z'
'-x, y+1/2, -z+1/2'

_cell_length_a                   7.2579(3)
_cell_length_b                   13.8117(5)
_cell_length_c                   16.2980(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1633.78(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    7346
_cell_measurement_theta_min      2.95
_cell_measurement_theta_max      28.28

_exptl_crystal_description       needle
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.635
_exptl_crystal_F_000             824
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.361
_exptl_crystal_size_mid          0.146
_exptl_crystal_size_min          0.121
_exptl_absorpt_coefficient_mu    0.643
_shelx_estimated_absorpt_T_min   0.801
_shelx_estimated_absorpt_T_max   0.926
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.9056
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   'SADABS V2008/1 (Bruker AXS)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      200(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 8.3333
_diffrn_reflns_number            15488
_diffrn_reflns_av_unetI/netI     0.0236
_diffrn_reflns_av_R_equivalents  0.0229
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_theta_min         1.933
_diffrn_reflns_theta_max         28.331
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             4064
_reflns_number_gt                3756
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.743
_reflns_Friedel_fraction_max     0.994
_reflns_Friedel_fraction_full    1.000

_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. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;

_computing_data_collection       'Bruker Instrument Service v2011.4.0.0'
_computing_cell_refinement       'APEX2 v2011.4-1 (Bruker AXS)'
_computing_data_reduction        'SAINT V7.68A (Bruker AXS, 2009)'
_computing_structure_solution    'SHELXT-2018/2 (Sheldrick, 2015)'
_computing_structure_refinement  
'SHELXL-2018/3 (Sheldrick, 2015) and ShelXle (Hübschle, 2011)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 2012)'
_computing_publication_material  
'PLATON (Spek, 2009) and MERCURY (Macrae, 2008)'

_refine_special_details          
;
Carbon and nirogen bound H atoms were placed in calculated positions and were
included in the refinement in the riding model approximation, with U(H)
set to 1.2 Ueq(C/N).

Refined as a 2-component inversion twin.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0415P)²+0.4518P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.48(2)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         4064
_refine_ls_number_parameters     245
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0330
_refine_ls_R_factor_gt           0.0285
_refine_ls_wR_factor_ref         0.0763
_refine_ls_wR_factor_gt          0.0744
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_restrained_S_all      1.075
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_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
V1 V 0.77506(6) 0.16576(3) 0.32456(2) 0.01911(11) Uani 1 1 d . . . . .
O1 O 0.9647(3) 0.10568(13) 0.34342(13) 0.0309(5) Uani 1 1 d . . . . .
O2 O 0.6870(3) 0.11955(15) 0.24095(12) 0.0357(5) Uani 1 1 d . . . . .
O11 O 0.6032(3) 0.11082(12) 0.40373(12) 0.0227(4) Uani 1 1 d . . . . .
O21 O 0.7435(3) 0.27375(12) 0.40138(10) 0.0218(4) Uani 1 1 d . . . . .
N11 N 0.7706(3) 0.04777(15) 0.64141(13) 0.0228(4) Uani 1 1 d . . . . .
H11 H 0.775707 -0.009129 0.665600 0.027 Uiso 1 1 calc R U . . .
N12 N 0.7286(3) 0.15926(15) 0.55103(12) 0.0222(4) Uani 1 1 d . . . . .
H12 H 0.700820 0.188617 0.504737 0.027 Uiso 1 1 calc R U . . .
N21 N 0.9633(3) 0.41603(14) 0.19880(13) 0.0187(4) Uani 1 1 d . . . . .
H21 H 0.970915 0.478860 0.190482 0.022 Uiso 1 1 calc R U . . .
N22 N 0.8902(3) 0.27628(14) 0.25417(13) 0.0167(4) Uani 1 1 d . . . . .
C11 C 0.6525(4) -0.00917(18) 0.50580(16) 0.0203(5) Uani 1 1 d . . . . .
C12 C 0.6425(4) -0.10673(19) 0.52864(17) 0.0247(6) Uani 1 1 d . . . . .
H12A H 0.691257 -0.126407 0.580101 0.030 Uiso 1 1 calc R U . . .
C13 C 0.5636(4) -0.1745(2) 0.47795(18) 0.0299(6) Uani 1 1 d . . . . .
H13 H 0.557423 -0.240376 0.494595 0.036 Uiso 1 1 calc R U . . .
C14 C 0.4925(4) -0.14665(19) 0.40214(18) 0.0274(6) Uani 1 1 d . . . . .
H14 H 0.433348 -0.192975 0.368058 0.033 Uiso 1 1 calc R U . . .
C15 C 0.5081(4) -0.05148(19) 0.37645(16) 0.0236(5) Uani 1 1 d . . . . .
H15 H 0.462811 -0.033362 0.323965 0.028 Uiso 1 1 calc R U . . .
C16 C 0.5902(4) 0.01868(18) 0.42711(16) 0.0203(5) Uani 1 1 d . . . . .
C17 C 0.7174(4) 0.06347(18) 0.56381(15) 0.0201(5) Uani 1 1 d . . . . .
C18 C 0.8160(4) 0.13486(19) 0.67732(18) 0.0259(5) Uani 1 1 d . . . . .
H18 H 0.858110 0.143870 0.731988 0.031 Uiso 1 1 calc R U . . .
C19 C 0.7901(4) 0.20490(19) 0.62103(16) 0.0256(5) Uani 1 1 d . . . . .
H19 H 0.810215 0.272341 0.628165 0.031 Uiso 1 1 calc R U . . .
C21 C 0.7340(4) 0.36968(16) 0.39880(15) 0.0181(5) Uani 1 1 d . . . . .
C22 C 0.6694(4) 0.42088(19) 0.46741(16) 0.0223(5) Uani 1 1 d . . . . .
H22 H 0.637834 0.386726 0.516013 0.027 Uiso 1 1 calc R U . . .
C23 C 0.6512(4) 0.52041(19) 0.46503(17) 0.0252(6) Uani 1 1 d . . . . .
H23 H 0.609225 0.553964 0.512346 0.030 Uiso 1 1 calc R U . . .
C24 C 0.6935(4) 0.57197(18) 0.39453(18) 0.0269(6) Uani 1 1 d . . . . .
H24 H 0.675373 0.640051 0.392670 0.032 Uiso 1 1 calc R U . . .
C25 C 0.7620(3) 0.52367(16) 0.32719(17) 0.0218(5) Uani 1 1 d . . . . .
H25 H 0.792583 0.558901 0.279018 0.026 Uiso 1 1 calc R U . . .
C26 C 0.7873(3) 0.42274(15) 0.32900(15) 0.0168(4) Uani 1 1 d . . . . .
C27 C 0.8750(3) 0.37251(16) 0.26171(15) 0.0163(5) Uani 1 1 d . . . . .
C28 C 1.0392(3) 0.34529(18) 0.14994(15) 0.0209(5) Uani 1 1 d . . . . .
H28 H 1.110128 0.354767 0.101607 0.025 Uiso 1 1 calc R U . . .
C29 C 0.9931(3) 0.25987(17) 0.18424(16) 0.0203(5) Uani 1 1 d . . . . .
H29 H 1.026158 0.197968 0.163530 0.024 Uiso 1 1 calc R U . . .


_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
V1 O2 1.635(2) . ?
V1 O1 1.636(2) . ?
V1 O11 1.9484(19) . ?
V1 O21 1.9607(17) . ?
V1 N22 2.084(2) . ?
O11 C16 1.332(3) . ?
O21 C21 1.327(3) . ?
N11 C17 1.340(3) . ?
N11 C18 1.378(3) . ?
N11 H11 0.8800 . ?
N12 C17 1.342(3) . ?
N12 C19 1.378(3) . ?
N12 H12 0.8800 . ?
N21 C27 1.350(3) . ?
N21 C28 1.376(3) . ?
N21 H21 0.8800 . ?
N22 C27 1.339(3) . ?
N22 C29 1.381(3) . ?
C11 C12 1.400(3) . ?
C11 C16 1.413(4) . ?
C11 C17 1.457(3) . ?
C12 C13 1.374(4) . ?
C12 H12A 0.9500 . ?
C13 C14 1.393(4) . ?
C13 H13 0.9500 . ?
C14 C15 1.384(4) . ?
C14 H14 0.9500 . ?
C15 C16 1.406(4) . ?
C15 H15 0.9500 . ?
C18 C19 1.346(4) . ?
C18 H18 0.9500 . ?
C19 H19 0.9500 . ?
C21 C22 1.404(3) . ?
C21 C26 1.407(3) . ?
C22 C23 1.381(4) . ?
C22 H22 0.9500 . ?
C23 C24 1.386(4) . ?
C23 H23 0.9500 . ?
C24 C25 1.377(4) . ?
C24 H24 0.9500 . ?
C25 C26 1.406(3) . ?
C25 H25 0.9500 . ?
C26 C27 1.446(3) . ?
C28 C29 1.348(3) . ?
C28 H28 0.9500 . ?
C29 H29 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
O2 V1 O1 106.70(12) . . ?
O2 V1 O11 98.61(10) . . ?
O1 V1 O11 102.50(9) . . ?
O2 V1 O21 141.58(11) . . ?
O1 V1 O21 111.36(10) . . ?
O11 V1 O21 78.38(8) . . ?
O2 V1 N22 89.08(9) . . ?
O1 V1 N22 97.91(9) . . ?
O11 V1 N22 155.00(8) . . ?
O21 V1 N22 80.87(8) . . ?
C16 O11 V1 127.37(17) . . ?
C21 O21 V1 138.17(16) . . ?
C17 N11 C18 109.2(2) . . ?
C17 N11 H11 125.4 . . ?
C18 N11 H11 125.4 . . ?
C17 N12 C19 110.0(2) . . ?
C17 N12 H12 125.0 . . ?
C19 N12 H12 125.0 . . ?
C27 N21 C28 108.3(2) . . ?
C27 N21 H21 125.9 . . ?
C28 N21 H21 125.9 . . ?
C27 N22 C29 106.4(2) . . ?
C27 N22 V1 130.05(17) . . ?
C29 N22 V1 123.41(15) . . ?
C12 C11 C16 119.1(2) . . ?
C12 C11 C17 120.5(2) . . ?
C16 C11 C17 120.3(2) . . ?
C13 C12 C11 121.2(3) . . ?
C13 C12 H12A 119.4 . . ?
C11 C12 H12A 119.4 . . ?
C12 C13 C14 119.9(3) . . ?
C12 C13 H13 120.0 . . ?
C14 C13 H13 120.0 . . ?
C15 C14 C13 120.0(3) . . ?
C15 C14 H14 120.0 . . ?
C13 C14 H14 120.0 . . ?
C14 C15 C16 120.8(3) . . ?
C14 C15 H15 119.6 . . ?
C16 C15 H15 119.6 . . ?
O11 C16 C15 121.4(2) . . ?
O11 C16 C11 119.8(2) . . ?
C15 C16 C11 118.7(2) . . ?
N11 C17 N12 106.8(2) . . ?
N11 C17 C11 126.5(2) . . ?
N12 C17 C11 126.7(2) . . ?
C19 C18 N11 107.7(2) . . ?
C19 C18 H18 126.1 . . ?
N11 C18 H18 126.1 . . ?
C18 C19 N12 106.3(2) . . ?
C18 C19 H19 126.8 . . ?
N12 C19 H19 126.8 . . ?
O21 C21 C22 119.7(2) . . ?
O21 C21 C26 122.1(2) . . ?
C22 C21 C26 118.2(2) . . ?
C23 C22 C21 120.7(2) . . ?
C23 C22 H22 119.6 . . ?
C21 C22 H22 119.6 . . ?
C22 C23 C24 120.9(2) . . ?
C22 C23 H23 119.6 . . ?
C24 C23 H23 119.6 . . ?
C25 C24 C23 119.4(2) . . ?
C25 C24 H24 120.3 . . ?
C23 C24 H24 120.3 . . ?
C24 C25 C26 120.7(2) . . ?
C24 C25 H25 119.7 . . ?
C26 C25 H25 119.7 . . ?
C25 C26 C21 119.8(2) . . ?
C25 C26 C27 121.1(2) . . ?
C21 C26 C27 119.0(2) . . ?
N22 C27 N21 109.5(2) . . ?
N22 C27 C26 125.6(2) . . ?
N21 C27 C26 124.9(2) . . ?
C29 C28 N21 106.4(2) . . ?
C29 C28 H28 126.8 . . ?
N21 C28 H28 126.8 . . ?
C28 C29 N22 109.4(2) . . ?
C28 C29 H29 125.3 . . ?
N22 C29 H29 125.3 . . ?

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
C16 C11 C12 C13 -3.9(4) . . . . ?
C17 C11 C12 C13 173.0(3) . . . . ?
C11 C12 C13 C14 0.3(4) . . . . ?
C12 C13 C14 C15 2.6(4) . . . . ?
C13 C14 C15 C16 -1.9(4) . . . . ?
V1 O11 C16 C15 -75.9(3) . . . . ?
V1 O11 C16 C11 106.9(2) . . . . ?
C14 C15 C16 O11 -178.8(3) . . . . ?
C14 C15 C16 C11 -1.6(4) . . . . ?
C12 C11 C16 O11 -178.3(2) . . . . ?
C17 C11 C16 O11 4.8(4) . . . . ?
C12 C11 C16 C15 4.5(4) . . . . ?
C17 C11 C16 C15 -172.5(2) . . . . ?
C18 N11 C17 N12 -0.2(3) . . . . ?
C18 N11 C17 C11 -177.8(2) . . . . ?
C19 N12 C17 N11 0.2(3) . . . . ?
C19 N12 C17 C11 177.8(2) . . . . ?
C12 C11 C17 N11 -0.7(4) . . . . ?
C16 C11 C17 N11 176.2(3) . . . . ?
C12 C11 C17 N12 -177.8(3) . . . . ?
C16 C11 C17 N12 -0.9(4) . . . . ?
C17 N11 C18 C19 0.1(3) . . . . ?
N11 C18 C19 N12 0.0(3) . . . . ?
C17 N12 C19 C18 -0.2(3) . . . . ?
V1 O21 C21 C22 165.9(2) . . . . ?
V1 O21 C21 C26 -14.2(4) . . . . ?
O21 C21 C22 C23 -177.4(3) . . . . ?
C26 C21 C22 C23 2.8(4) . . . . ?
C21 C22 C23 C24 1.0(4) . . . . ?
C22 C23 C24 C25 -2.8(4) . . . . ?
C23 C24 C25 C26 0.8(4) . . . . ?
C24 C25 C26 C21 3.0(4) . . . . ?
C24 C25 C26 C27 -174.1(2) . . . . ?
O21 C21 C26 C25 175.4(2) . . . . ?
C22 C21 C26 C25 -4.7(4) . . . . ?
O21 C21 C26 C27 -7.4(4) . . . . ?
C22 C21 C26 C27 172.5(2) . . . . ?
C29 N22 C27 N21 0.5(3) . . . . ?
V1 N22 C27 N21 -175.78(16) . . . . ?
C29 N22 C27 C26 -176.2(2) . . . . ?
V1 N22 C27 C26 7.5(4) . . . . ?
C28 N21 C27 N22 -0.7(3) . . . . ?
C28 N21 C27 C26 176.0(2) . . . . ?
C25 C26 C27 N22 -173.5(2) . . . . ?
C21 C26 C27 N22 9.3(4) . . . . ?
C25 C26 C27 N21 10.3(4) . . . . ?
C21 C26 C27 N21 -166.9(2) . . . . ?
C27 N21 C28 C29 0.6(3) . . . . ?
N21 C28 C29 N22 -0.4(3) . . . . ?
C27 N22 C29 C28 -0.1(3) . . . . ?
V1 N22 C29 C28 176.51(17) . . . . ?

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
N11 H11 O2 0.88 1.98 2.840(3) 167 2_655 yes
N12 H12 O11 0.88 2.09 2.653(3) 121 . yes
N12 H12 O21 0.88 2.08 2.909(3) 157 . yes
N21 H21 O1 0.88 1.90 2.758(3) 166 4_755 yes

_refine_diff_density_max         0.492
_refine_diff_density_min         -0.240
_refine_diff_density_rms         0.051

####################################################################### 
# 
# 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_ha046
_database_code_depnum_ccdc_archive 'CCDC 1908642'
loop_
_audit_author_name
_audit_author_address
'Eric C. Hosten'
;Nelson Mandela University
South Africa
;
_audit_update_record             
;
2019-09-06 deposited with the CCDC.	2019-10-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H12 Br2 N4 O3 V, 2(C2 H6 O S)'
_chemical_formula_sum            'C22 H24 Br2 N4 O5 S2 V'
_chemical_formula_weight         699.33

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'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 '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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'

_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+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   15.3157(7)
_cell_length_b                   15.8806(8)
_cell_length_c                   22.1939(13)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5398.1(5)
_cell_formula_units_Z            8
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    9955
_cell_measurement_theta_min      2.24
_cell_measurement_theta_max      27.65

_exptl_crystal_description       blocks
_exptl_crystal_colour            'dark blue green'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.721
_exptl_crystal_F_000             2792
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.486
_exptl_crystal_size_mid          0.296
_exptl_crystal_size_min          0.142
_exptl_absorpt_coefficient_mu    3.523
_shelx_estimated_absorpt_T_min   0.279
_shelx_estimated_absorpt_T_max   0.635
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.6424
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   'SADABS V2008/1 (Bruker AXS)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      200(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 8.3333
_diffrn_reflns_number            56689
_diffrn_reflns_av_unetI/netI     0.0528
_diffrn_reflns_av_R_equivalents  0.0349
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_theta_min         1.577
_diffrn_reflns_theta_max         28.301
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             13338
_reflns_number_gt                10145
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.819
_reflns_Friedel_fraction_max     0.988
_reflns_Friedel_fraction_full    0.993

_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       'Bruker Instrument Service v2011.4.0.0'
_computing_cell_refinement       'APEX2 v2011.4-1 (Bruker AXS)'
_computing_data_reduction        'SAINT V7.68A (Bruker AXS, 2009)'
_computing_structure_solution    'SHELXT-2018/2 (Sheldrick, 2015)'
_computing_structure_refinement  
'SHELXL-2018/3 (Sheldrick, 2015) and ShelXle (Hübschle, 2011)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 2012)'
_computing_publication_material  
'PLATON (Spek, 2009) and MERCURY (Macrae, 2008)'

_refine_special_details          
;
Carbon-bound H atoms were placed in calculated positions and were included in
the refinement in the riding model approximation, with U(H) set to 1.2
Ueq(C).

Where possible the H atoms of the methyl groups were allowed to rotate with a
fixed angle around the C---C bonds to best fit the experimental electron density
(HFIX 137 in the SHELX program suite (Sheldrick, 2015)), with Uiso(H)
set to 1.5Ueq(C), otherwise the H atoms were placed in calculated
positions.

The nitrogen-bound H atoms were located on a difference Fourier map and refined
freely.

Three DMSO solvent molecules are disordered necessitating the use of various
constraints and restraints: EXYZ, EADP and SADI.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0387P)²+6.3758P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 3855 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(3)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         13338
_refine_ls_number_parameters     656
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0700
_refine_ls_R_factor_gt           0.0418
_refine_ls_wR_factor_ref         0.1028
_refine_ls_wR_factor_gt          0.0898
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_restrained_S_all      1.029
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_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
Br1 Br 0.24889(5) 0.62420(5) 0.59151(4) 0.0585(2) Uani 1 1 d . . . . .
Br2 Br 0.92411(6) 0.31333(6) 0.16281(5) 0.0761(3) Uani 1 1 d . . . . .
Br3 Br 0.00645(5) 0.62784(5) 0.45714(4) 0.0614(2) Uani 1 1 d . . . . .
Br4 Br 0.69697(4) 0.34656(4) 0.03619(3) 0.04148(16) Uani 1 1 d . . . . .
V1 V 0.60374(6) 0.45342(6) 0.39137(4) 0.0267(2) Uani 1 1 d . . . . .
V2 V 0.34830(6) 0.48494(6) 0.24992(4) 0.02417(19) Uani 1 1 d . . . . .
S6 S 1.04697(13) 0.57962(19) 0.23347(10) 0.0738(7) Uani 1 1 d . . . . .
O1 O 0.6576(3) 0.3982(3) 0.43875(18) 0.0366(10) Uani 1 1 d . . . . .
O2 O 0.2950(3) 0.5405(3) 0.20273(19) 0.0359(9) Uani 1 1 d . . . . .
O5 O 0.2069(3) 0.3502(4) 0.5065(3) 0.0634(15) Uani 1 1 d . . . . .
O6 O 0.9515(3) 0.5967(3) 0.2227(2) 0.0485(12) Uani 1 1 d . . . . .
O7 O -0.0133(4) 0.3431(5) 0.3926(4) 0.106(3) Uani 1 1 d . . . . .
O11 O 0.5583(3) 0.5501(3) 0.43258(19) 0.0351(9) Uani 1 1 d . . . . .
O21 O 0.6103(3) 0.3969(3) 0.31507(17) 0.0319(9) Uani 1 1 d . . . . .
O31 O 0.3379(2) 0.5344(2) 0.32837(17) 0.0304(9) Uani 1 1 d . . . . .
O41 O 0.4020(2) 0.3888(2) 0.21282(18) 0.0316(9) Uani 1 1 d . . . . .
N11 N 0.4788(3) 0.4055(3) 0.3961(2) 0.0276(10) Uani 1 1 d . . . . .
N12 N 0.3481(3) 0.3762(3) 0.4299(2) 0.0296(10) Uani 1 1 d . . . . .
N21 N 0.6961(3) 0.5350(3) 0.3561(2) 0.0279(10) Uani 1 1 d . . . . .
N22 N 0.8087(3) 0.5799(3) 0.3031(2) 0.0363(12) Uani 1 1 d . . . . .
N31 N 0.2516(3) 0.4023(3) 0.2781(2) 0.0272(10) Uani 1 1 d . . . . .
N32 N 0.1333(3) 0.3584(3) 0.3230(2) 0.0385(13) Uani 1 1 d . . . . .
N41 N 0.4698(3) 0.5408(3) 0.2453(2) 0.0276(10) Uani 1 1 d . . . . .
N42 N 0.5938(3) 0.5818(3) 0.2052(2) 0.0332(11) Uani 1 1 d . . . . .
C11 C 0.4190(4) 0.5040(3) 0.4727(2) 0.0287(12) Uani 1 1 d . . . . .
C12 C 0.4903(4) 0.5603(3) 0.4693(3) 0.0295(12) Uani 1 1 d . . . . .
C13 C 0.4885(4) 0.6319(4) 0.5056(3) 0.0347(13) Uani 1 1 d . . . . .
H13 H 0.537146 0.668983 0.505252 0.042 Uiso 1 1 calc R U . . .
C14 C 0.4184(4) 0.6506(4) 0.5420(3) 0.0364(13) Uani 1 1 d . . . . .
H14 H 0.418393 0.700520 0.565541 0.044 Uiso 1 1 calc R U . . .
C15 C 0.3480(4) 0.5963(4) 0.5441(3) 0.0351(13) Uani 1 1 d . . . . .
C16 C 0.3479(4) 0.5233(4) 0.5107(3) 0.0330(13) Uani 1 1 d . . . . .
H16 H 0.299784 0.485787 0.513231 0.040 Uiso 1 1 calc R U . . .
C17 C 0.4166(4) 0.4297(3) 0.4343(2) 0.0268(12) Uani 1 1 d . . . . .
C18 C 0.4467(4) 0.3353(4) 0.3669(3) 0.0344(13) Uani 1 1 d . . . . .
H18 H 0.476729 0.304897 0.336442 0.041 Uiso 1 1 calc R U . . .
C19 C 0.3676(4) 0.3162(4) 0.3876(3) 0.0331(13) Uani 1 1 d . . . . .
H19 H 0.331826 0.270309 0.375456 0.040 Uiso 1 1 calc R U . . .
C21 C 0.7529(4) 0.4370(4) 0.2773(2) 0.0314(12) Uani 1 1 d . . . . .
C22 C 0.6807(4) 0.3824(4) 0.2814(2) 0.0297(12) Uani 1 1 d . . . . .
C23 C 0.6840(4) 0.3074(4) 0.2479(3) 0.0369(14) Uani 1 1 d . . . . .
H23 H 0.635775 0.269782 0.249574 0.044 Uiso 1 1 calc R U . . .
C24 C 0.7547(5) 0.2869(4) 0.2129(3) 0.0432(16) Uani 1 1 d . . . . .
H24 H 0.755591 0.235589 0.190817 0.052 Uiso 1 1 calc R U . . .
C25 C 0.8242(4) 0.3416(5) 0.2101(3) 0.0449(16) Uani 1 1 d . . . . .
C26 C 0.8245(4) 0.4171(4) 0.2415(3) 0.0403(15) Uani 1 1 d . . . . .
H26 H 0.872722 0.454493 0.238573 0.048 Uiso 1 1 calc R U . . .
C27 C 0.7520(4) 0.5159(4) 0.3113(3) 0.0311(12) Uani 1 1 d . . . . .
C28 C 0.7201(4) 0.6146(4) 0.3763(3) 0.0333(13) Uani 1 1 d . . . . .
H28 H 0.692350 0.644660 0.407992 0.040 Uiso 1 1 calc R U . . .
C29 C 0.7888(4) 0.6424(4) 0.3442(3) 0.0382(14) Uani 1 1 d . . . . .
H29 H 0.817868 0.694825 0.348844 0.046 Uiso 1 1 calc R U . . .
C31 C 0.1897(4) 0.4981(3) 0.3548(2) 0.0284(12) Uani 1 1 d . . . . .
C32 C 0.2649(3) 0.5493(4) 0.3583(2) 0.0269(11) Uani 1 1 d . . . . .
C33 C 0.2610(4) 0.6210(4) 0.3957(3) 0.0324(12) Uani 1 1 d . . . . .
H33 H 0.311519 0.655272 0.399979 0.039 Uiso 1 1 calc R U . . .
C34 C 0.1862(4) 0.6428(4) 0.4261(3) 0.0385(14) Uani 1 1 d . . . . .
H34 H 0.185224 0.690907 0.451561 0.046 Uiso 1 1 calc R U . . .
C35 C 0.1129(4) 0.5940(4) 0.4193(3) 0.0354(14) Uani 1 1 d . . . . .
C36 C 0.1137(4) 0.5213(4) 0.3857(3) 0.0316(12) Uani 1 1 d . . . . .
H36 H 0.063006 0.487061 0.383390 0.038 Uiso 1 1 calc R U . . .
C37 C 0.1921(4) 0.4219(3) 0.3196(3) 0.0280(12) Uani 1 1 d . . . . .
C38 C 0.2298(4) 0.3242(3) 0.2553(3) 0.0328(13) Uani 1 1 d . . . . .
H38 H 0.261124 0.294629 0.225065 0.039 Uiso 1 1 calc R U . . .
C39 C 0.1566(4) 0.2968(4) 0.2831(3) 0.0409(15) Uani 1 1 d . . . . .
H39 H 0.127148 0.244968 0.276214 0.049 Uiso 1 1 calc R U . . .
C41 C 0.5358(3) 0.4447(4) 0.1700(3) 0.0271(12) Uani 1 1 d . . . . .
C42 C 0.4704(3) 0.3819(3) 0.1765(2) 0.0244(11) Uani 1 1 d . . . . .
C43 C 0.4791(4) 0.3080(4) 0.1430(3) 0.0284(12) Uani 1 1 d . . . . .
H43 H 0.437080 0.264529 0.148091 0.034 Uiso 1 1 calc R U . . .
C44 C 0.5468(4) 0.2959(4) 0.1027(3) 0.0315(13) Uani 1 1 d . . . . .
H44 H 0.551383 0.244765 0.080651 0.038 Uiso 1 1 calc R U . . .
C45 C 0.6079(3) 0.3591(4) 0.0949(2) 0.0280(12) Uani 1 1 d . . . . .
C46 C 0.6028(3) 0.4325(4) 0.1284(3) 0.0277(12) Uani 1 1 d . . . . .
H46 H 0.645670 0.475059 0.123017 0.033 Uiso 1 1 calc R U . . .
C47 C 0.5331(3) 0.5209(4) 0.2059(2) 0.0250(11) Uani 1 1 d . . . . .
C48 C 0.4930(4) 0.6179(4) 0.2704(3) 0.0317(13) Uani 1 1 d . . . . .
H48 H 0.460579 0.647500 0.300109 0.038 Uiso 1 1 calc R U . . .
C49 C 0.5690(4) 0.6440(4) 0.2458(3) 0.0375(14) Uani 1 1 d . . . . .
H49 H 0.599468 0.694636 0.254552 0.045 Uiso 1 1 calc R U . . .
C61 C 1.0801(6) 0.5021(8) 0.1867(8) 0.149(7) Uani 1 1 d . . . . .
H61A H 1.142168 0.490560 0.193457 0.224 Uiso 1 1 calc R U . . .
H61B H 1.046088 0.450987 0.194662 0.224 Uiso 1 1 calc R U . . .
H61C H 1.071178 0.519671 0.144819 0.224 Uiso 1 1 calc R U . . .
C62 C 1.1033(7) 0.6581(8) 0.2001(11) 0.214(12) Uani 1 1 d . . . . .
H62A H 1.166018 0.649170 0.206134 0.321 Uiso 1 1 calc R U . . .
H62B H 1.090430 0.658646 0.156813 0.321 Uiso 1 1 calc R U . . .
H62C H 1.086242 0.712161 0.217844 0.321 Uiso 1 1 calc R U . . .
H12 H 0.307(4) 0.385(3) 0.453(3) 0.016(13) Uiso 1 1 d . . . . .
H22 H 0.855(4) 0.588(4) 0.278(3) 0.037(18) Uiso 1 1 d . . . . .
H32 H 0.087(4) 0.357(4) 0.345(3) 0.024(15) Uiso 1 1 d . . . . .
H42 H 0.642(5) 0.592(4) 0.184(3) 0.043(19) Uiso 1 1 d . . . . .
S81 S 0.78565(11) 0.60074(13) 0.08155(10) 0.0381(6) Uani 0.817(4) 1 d D . P A 1
O81 O 0.7445(4) 0.6140(4) 0.1425(3) 0.0534(10) Uani 0.817(4) 1 d D . P A 1
C81 C 0.8552(5) 0.5139(5) 0.0889(4) 0.0534(10) Uani 0.817(4) 1 d . . P A 1
H81A H 0.883704 0.502676 0.050258 0.080 Uiso 0.817(4) 1 calc R U P A 1
H81B H 0.899550 0.526005 0.119549 0.080 Uiso 0.817(4) 1 calc R U P A 1
H81C H 0.821146 0.464545 0.101163 0.080 Uiso 0.817(4) 1 calc R U P A 1
C82 C 0.8673(5) 0.6797(5) 0.0772(4) 0.0534(10) Uani 0.817(4) 1 d . . P A 1
H82A H 0.897653 0.675530 0.038454 0.080 Uiso 0.817(4) 1 calc R U P A 1
H82B H 0.840145 0.735376 0.080771 0.080 Uiso 0.817(4) 1 calc R U P A 1
H82C H 0.909352 0.671935 0.110061 0.080 Uiso 0.817(4) 1 calc R U P A 1
S82 S 0.8092(7) 0.6088(7) 0.1240(6) 0.0534(10) Uani 0.183(4) 1 d D . P A 2
O82 O 0.7147(13) 0.6154(18) 0.1103(14) 0.0534(10) Uani 0.183(4) 1 d D . P A 2
C83 C 0.8552(5) 0.5139(5) 0.0889(4) 0.0534(10) Uani 0.183(4) 1 d . . P A 2
H83A H 0.917567 0.510226 0.098303 0.080 Uiso 0.183(4) 1 calc R U P A 2
H83B H 0.825151 0.464035 0.104612 0.080 Uiso 0.183(4) 1 calc R U P A 2
H83C H 0.847262 0.516959 0.045177 0.080 Uiso 0.183(4) 1 calc R U P A 2
C84 C 0.8673(5) 0.6797(5) 0.0772(4) 0.0534(10) Uani 0.183(4) 1 d . . P A 2
H84A H 0.929916 0.675747 0.086003 0.080 Uiso 0.183(4) 1 calc R U P A 2
H84B H 0.857025 0.665395 0.034872 0.080 Uiso 0.183(4) 1 calc R U P A 2
H84C H 0.847214 0.737319 0.084923 0.080 Uiso 0.183(4) 1 calc R U P A 2
S51 S 0.12193(12) 0.33807(14) 0.53852(9) 0.0462(6) Uani 0.885(5) 1 d . . P B 1
C51 C 0.0855(7) 0.4411(6) 0.5568(4) 0.0746(18) Uani 0.885(5) 1 d . . P B 1
H51A H 0.029589 0.437630 0.578064 0.112 Uiso 0.885(5) 1 calc R U P B 1
H51B H 0.128778 0.468674 0.582615 0.112 Uiso 0.885(5) 1 calc R U P B 1
H51C H 0.078091 0.473772 0.519665 0.112 Uiso 0.885(5) 1 calc R U P B 1
C52 C 0.1469(7) 0.3049(6) 0.6119(4) 0.0746(18) Uani 0.885(5) 1 d . . P B 1
H52A H 0.092632 0.296153 0.634470 0.112 Uiso 0.885(5) 1 calc R U P B 1
H52B H 0.179638 0.251912 0.610132 0.112 Uiso 0.885(5) 1 calc R U P B 1
H52C H 0.182212 0.347915 0.631982 0.112 Uiso 0.885(5) 1 calc R U P B 1
S52 S 0.1895(16) 0.3834(13) 0.5634(10) 0.0746(18) Uani 0.115(5) 1 d . . P B 2
C53 C 0.0855(7) 0.4411(6) 0.5568(4) 0.0746(18) Uani 0.115(5) 1 d . . P B 2
H53A H 0.070319 0.465781 0.595836 0.112 Uiso 0.115(5) 1 calc R U P B 2
H53B H 0.091609 0.485929 0.526729 0.112 Uiso 0.115(5) 1 calc R U P B 2
H53C H 0.039337 0.402146 0.544173 0.112 Uiso 0.115(5) 1 calc R U P B 2
C54 C 0.1469(7) 0.3049(6) 0.6119(4) 0.0746(18) Uani 0.115(5) 1 d . . P B 2
H54A H 0.135112 0.329377 0.651563 0.112 Uiso 0.115(5) 1 calc R U P B 2
H54B H 0.092477 0.282624 0.594866 0.112 Uiso 0.115(5) 1 calc R U P B 2
H54C H 0.189375 0.259095 0.615952 0.112 Uiso 0.115(5) 1 calc R U P B 2
S71 S -0.11003(15) 0.34646(16) 0.40482(11) 0.0582(7) Uani 0.872(5) 1 d . . P C
1
C71 C -0.1232(6) 0.2807(6) 0.4684(5) 0.0767(19) Uani 0.872(5) 1 d . . P C 1
H71A H -0.184991 0.278997 0.479864 0.115 Uiso 0.872(5) 1 calc R U P C 1
H71B H -0.103198 0.223712 0.458685 0.115 Uiso 0.872(5) 1 calc R U P C 1
H71C H -0.088739 0.303002 0.502055 0.115 Uiso 0.872(5) 1 calc R U P C 1
C72 C -0.1325(5) 0.4417(6) 0.4391(5) 0.0767(19) Uani 0.872(5) 1 d . . P C 1
H72A H -0.195211 0.445471 0.447491 0.115 Uiso 0.872(5) 1 calc R U P C 1
H72B H -0.099800 0.445787 0.476888 0.115 Uiso 0.872(5) 1 calc R U P C 1
H72C H -0.115330 0.487794 0.412227 0.115 Uiso 0.872(5) 1 calc R U P C 1
S72 S -0.0537(12) 0.3655(13) 0.4459(10) 0.0767(19) Uani 0.128(5) 1 d . . P C 2
C73 C -0.1232(6) 0.2807(6) 0.4684(5) 0.0767(19) Uani 0.128(5) 1 d . . P C 2
H73A H -0.152558 0.295427 0.506243 0.115 Uiso 0.128(5) 1 calc R U P C 2
H73B H -0.167001 0.270517 0.437088 0.115 Uiso 0.128(5) 1 calc R U P C 2
H73C H -0.088173 0.229747 0.474359 0.115 Uiso 0.128(5) 1 calc R U P C 2
C74 C -0.1325(5) 0.4417(6) 0.4391(5) 0.0767(19) Uani 0.128(5) 1 d . . P C 2
H74A H -0.157627 0.453648 0.478761 0.115 Uiso 0.128(5) 1 calc R U P C 2
H74B H -0.106409 0.493107 0.422610 0.115 Uiso 0.128(5) 1 calc R U P C 2
H74C H -0.178565 0.421774 0.411899 0.115 Uiso 0.128(5) 1 calc R U P C 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
Br1 C15 1.900(6) . ?
Br2 C25 1.908(6) . ?
Br3 C35 1.911(5) . ?
Br4 C45 1.898(5) . ?
V1 O1 1.599(4) . ?
V1 O11 1.918(4) . ?
V1 O21 1.919(4) . ?
V1 N11 2.062(4) . ?
V1 N21 2.072(5) . ?
V2 O2 1.594(4) . ?
V2 O31 1.917(4) . ?
V2 O41 1.920(4) . ?
V2 N41 2.063(4) . ?
V2 N31 2.075(4) . ?
S6 O6 1.506(5) . ?
S6 C62 1.688(15) . ?
S6 C61 1.689(11) . ?
O5 S52 1.40(2) . ?
O5 S51 1.495(5) . ?
O7 S72 1.38(2) . ?
O7 S71 1.508(6) . ?
O11 C12 1.332(7) . ?
O21 C22 1.331(7) . ?
O31 C32 1.321(6) . ?
O41 C42 1.325(6) . ?
N11 C17 1.332(7) . ?
N11 C18 1.380(7) . ?
N12 C17 1.354(7) . ?
N12 C19 1.371(8) . ?
N12 H12 0.82(6) . ?
N21 C27 1.347(7) . ?
N21 C28 1.391(7) . ?
N22 C27 1.349(8) . ?
N22 C29 1.382(8) . ?
N22 H22 0.92(7) . ?
N31 C37 1.333(7) . ?
N31 C38 1.380(7) . ?
N32 C37 1.354(7) . ?
N32 C39 1.369(8) . ?
N32 H32 0.85(6) . ?
N41 C47 1.344(7) . ?
N41 C48 1.391(7) . ?
N42 C47 1.342(7) . ?
N42 C49 1.388(8) . ?
N42 H42 0.89(7) . ?
C11 C16 1.411(8) . ?
C11 C12 1.413(8) . ?
C11 C17 1.456(8) . ?
C12 C13 1.395(8) . ?
C13 C14 1.375(9) . ?
C13 H13 0.9500 . ?
C14 C15 1.380(9) . ?
C14 H14 0.9500 . ?
C15 C16 1.376(8) . ?
C16 H16 0.9500 . ?
C18 C19 1.330(8) . ?
C18 H18 0.9500 . ?
C19 H19 0.9500 . ?
C21 C26 1.391(8) . ?
C21 C22 1.408(8) . ?
C21 C27 1.462(8) . ?
C22 C23 1.405(8) . ?
C23 C24 1.373(9) . ?
C23 H23 0.9500 . ?
C24 C25 1.376(10) . ?
C24 H24 0.9500 . ?
C25 C26 1.387(9) . ?
C26 H26 0.9500 . ?
C28 C29 1.345(9) . ?
C28 H28 0.9500 . ?
C29 H29 0.9500 . ?
C31 C36 1.399(8) . ?
C31 C32 1.412(8) . ?
C31 C37 1.441(8) . ?
C32 C33 1.411(8) . ?
C33 C34 1.374(8) . ?
C33 H33 0.9500 . ?
C34 C35 1.372(9) . ?
C34 H34 0.9500 . ?
C35 C36 1.374(9) . ?
C36 H36 0.9500 . ?
C38 C39 1.352(8) . ?
C38 H38 0.9500 . ?
C39 H39 0.9500 . ?
C41 C46 1.394(7) . ?
C41 C42 1.421(8) . ?
C41 C47 1.450(8) . ?
C42 C43 1.396(8) . ?
C43 C44 1.384(8) . ?
C43 H43 0.9500 . ?
C44 C45 1.383(8) . ?
C44 H44 0.9500 . ?
C45 C46 1.384(8) . ?
C46 H46 0.9500 . ?
C48 C49 1.351(8) . ?
C48 H48 0.9500 . ?
C49 H49 0.9500 . ?
C61 H61A 0.9800 . ?
C61 H61B 0.9800 . ?
C61 H61C 0.9800 . ?
C62 H62A 0.9800 . ?
C62 H62B 0.9800 . ?
C62 H62C 0.9800 . ?
S81 O81 1.507(6) . ?
S81 C81 1.749(8) . ?
S81 C82 1.774(7) . ?
C81 H81A 0.9800 . ?
C81 H81B 0.9800 . ?
C81 H81C 0.9800 . ?
C82 H82A 0.9800 . ?
C82 H82B 0.9800 . ?
C82 H82C 0.9800 . ?
S82 O82 1.48(2) . ?
S82 C84 1.773(13) . ?
S82 C83 1.835(13) . ?
C83 H83A 0.9800 . ?
C83 H83B 0.9800 . ?
C83 H83C 0.9800 . ?
C84 H84A 0.9800 . ?
C84 H84B 0.9800 . ?
C84 H84C 0.9800 . ?
S51 C52 1.753(9) . ?
S51 C51 1.775(9) . ?
C51 H51A 0.9800 . ?
C51 H51B 0.9800 . ?
C51 H51C 0.9800 . ?
C52 H52A 0.9800 . ?
C52 H52B 0.9800 . ?
C52 H52C 0.9800 . ?
S52 C54 1.77(2) . ?
S52 C53 1.84(2) . ?
C53 H53A 0.9800 . ?
C53 H53B 0.9800 . ?
C53 H53C 0.9800 . ?
C54 H54A 0.9800 . ?
C54 H54B 0.9800 . ?
C54 H54C 0.9800 . ?
S71 C72 1.727(10) . ?
S71 C71 1.768(9) . ?
C71 H71A 0.9800 . ?
C71 H71B 0.9800 . ?
C71 H71C 0.9800 . ?
C72 H72A 0.9800 . ?
C72 H72B 0.9800 . ?
C72 H72C 0.9800 . ?
S72 C74 1.72(2) . ?
S72 C73 1.79(2) . ?
C73 H73A 0.9800 . ?
C73 H73B 0.9800 . ?
C73 H73C 0.9800 . ?
C74 H74A 0.9800 . ?
C74 H74B 0.9800 . ?
C74 H74C 0.9800 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 V1 O11 108.2(2) . . ?
O1 V1 O21 107.3(2) . . ?
O11 V1 O21 144.50(19) . . ?
O1 V1 N11 104.0(2) . . ?
O11 V1 N11 86.25(17) . . ?
O21 V1 N11 85.46(17) . . ?
O1 V1 N21 103.9(2) . . ?
O11 V1 N21 85.84(17) . . ?
O21 V1 N21 85.57(17) . . ?
N11 V1 N21 152.06(19) . . ?
O2 V2 O31 109.1(2) . . ?
O2 V2 O41 112.2(2) . . ?
O31 V2 O41 138.69(18) . . ?
O2 V2 N41 101.0(2) . . ?
O31 V2 N41 86.76(17) . . ?
O41 V2 N41 86.23(17) . . ?
O2 V2 N31 100.5(2) . . ?
O31 V2 N31 85.77(17) . . ?
O41 V2 N31 86.13(17) . . ?
N41 V2 N31 158.47(19) . . ?
O6 S6 C62 107.0(6) . . ?
O6 S6 C61 109.0(4) . . ?
C62 S6 C61 96.6(7) . . ?
C12 O11 V1 132.2(4) . . ?
C22 O21 V1 128.2(3) . . ?
C32 O31 V2 126.9(3) . . ?
C42 O41 V2 131.7(4) . . ?
C17 N11 C18 106.1(5) . . ?
C17 N11 V1 126.1(4) . . ?
C18 N11 V1 127.3(4) . . ?
C17 N12 C19 108.5(5) . . ?
C17 N12 H12 116(4) . . ?
C19 N12 H12 135(4) . . ?
C27 N21 C28 106.0(5) . . ?
C27 N21 V1 124.9(4) . . ?
C28 N21 V1 128.8(4) . . ?
C27 N22 C29 108.1(5) . . ?
C27 N22 H22 134(4) . . ?
C29 N22 H22 118(4) . . ?
C37 N31 C38 107.3(5) . . ?
C37 N31 V2 123.3(4) . . ?
C38 N31 V2 129.1(4) . . ?
C37 N32 C39 108.8(5) . . ?
C37 N32 H32 127(4) . . ?
C39 N32 H32 124(4) . . ?
C47 N41 C48 106.4(4) . . ?
C47 N41 V2 125.6(4) . . ?
C48 N41 V2 126.1(4) . . ?
C47 N42 C49 108.4(5) . . ?
C47 N42 H42 135(4) . . ?
C49 N42 H42 117(4) . . ?
C16 C11 C12 119.4(5) . . ?
C16 C11 C17 120.5(5) . . ?
C12 C11 C17 120.0(5) . . ?
O11 C12 C13 117.9(5) . . ?
O11 C12 C11 124.1(5) . . ?
C13 C12 C11 118.0(5) . . ?
C14 C13 C12 122.0(6) . . ?
C14 C13 H13 119.0 . . ?
C12 C13 H13 119.0 . . ?
C13 C14 C15 119.6(6) . . ?
C13 C14 H14 120.2 . . ?
C15 C14 H14 120.2 . . ?
C16 C15 C14 120.6(6) . . ?
C16 C15 Br1 119.6(5) . . ?
C14 C15 Br1 119.8(4) . . ?
C15 C16 C11 120.3(6) . . ?
C15 C16 H16 119.9 . . ?
C11 C16 H16 119.9 . . ?
N11 C17 N12 109.1(5) . . ?
N11 C17 C11 126.1(5) . . ?
N12 C17 C11 124.8(5) . . ?
C19 C18 N11 110.3(5) . . ?
C19 C18 H18 124.8 . . ?
N11 C18 H18 124.8 . . ?
C18 C19 N12 106.0(5) . . ?
C18 C19 H19 127.0 . . ?
N12 C19 H19 127.0 . . ?
C26 C21 C22 121.1(6) . . ?
C26 C21 C27 119.8(5) . . ?
C22 C21 C27 119.1(5) . . ?
O21 C22 C23 118.2(5) . . ?
O21 C22 C21 124.5(5) . . ?
C23 C22 C21 117.4(5) . . ?
C24 C23 C22 121.9(6) . . ?
C24 C23 H23 119.0 . . ?
C22 C23 H23 119.0 . . ?
C23 C24 C25 119.1(6) . . ?
C23 C24 H24 120.4 . . ?
C25 C24 H24 120.4 . . ?
C24 C25 C26 121.7(6) . . ?
C24 C25 Br2 119.8(5) . . ?
C26 C25 Br2 118.5(5) . . ?
C25 C26 C21 118.8(6) . . ?
C25 C26 H26 120.6 . . ?
C21 C26 H26 120.6 . . ?
N21 C27 N22 109.8(5) . . ?
N21 C27 C21 125.4(5) . . ?
N22 C27 C21 124.8(5) . . ?
C29 C28 N21 109.5(5) . . ?
C29 C28 H28 125.3 . . ?
N21 C28 H28 125.3 . . ?
C28 C29 N22 106.7(5) . . ?
C28 C29 H29 126.7 . . ?
N22 C29 H29 126.7 . . ?
C36 C31 C32 120.0(5) . . ?
C36 C31 C37 120.5(5) . . ?
C32 C31 C37 119.5(5) . . ?
O31 C32 C33 118.4(5) . . ?
O31 C32 C31 124.0(5) . . ?
C33 C32 C31 117.5(5) . . ?
C34 C33 C32 121.8(6) . . ?
C34 C33 H33 119.1 . . ?
C32 C33 H33 119.1 . . ?
C35 C34 C33 119.1(6) . . ?
C35 C34 H34 120.5 . . ?
C33 C34 H34 120.5 . . ?
C34 C35 C36 121.8(5) . . ?
C34 C35 Br3 119.4(4) . . ?
C36 C35 Br3 118.8(5) . . ?
C35 C36 C31 119.7(5) . . ?
C35 C36 H36 120.2 . . ?
C31 C36 H36 120.2 . . ?
N31 C37 N32 108.7(5) . . ?
N31 C37 C31 126.0(5) . . ?
N32 C37 C31 125.3(5) . . ?
C39 C38 N31 108.9(5) . . ?
C39 C38 H38 125.5 . . ?
N31 C38 H38 125.5 . . ?
C38 C39 N32 106.3(5) . . ?
C38 C39 H39 126.9 . . ?
N32 C39 H39 126.9 . . ?
C46 C41 C42 119.3(5) . . ?
C46 C41 C47 120.1(5) . . ?
C42 C41 C47 120.6(5) . . ?
O41 C42 C43 117.9(5) . . ?
O41 C42 C41 124.1(5) . . ?
C43 C42 C41 117.9(5) . . ?
C44 C43 C42 122.2(5) . . ?
C44 C43 H43 118.9 . . ?
C42 C43 H43 118.9 . . ?
C45 C44 C43 119.1(5) . . ?
C45 C44 H44 120.5 . . ?
C43 C44 H44 120.5 . . ?
C44 C45 C46 120.5(5) . . ?
C44 C45 Br4 119.7(4) . . ?
C46 C45 Br4 119.8(4) . . ?
C45 C46 C41 120.9(5) . . ?
C45 C46 H46 119.5 . . ?
C41 C46 H46 119.5 . . ?
N42 C47 N41 109.7(5) . . ?
N42 C47 C41 125.2(5) . . ?
N41 C47 C41 125.1(5) . . ?
C49 C48 N41 109.2(5) . . ?
C49 C48 H48 125.4 . . ?
N41 C48 H48 125.4 . . ?
C48 C49 N42 106.2(5) . . ?
C48 C49 H49 126.9 . . ?
N42 C49 H49 126.9 . . ?
S6 C61 H61A 109.5 . . ?
S6 C61 H61B 109.5 . . ?
H61A C61 H61B 109.5 . . ?
S6 C61 H61C 109.5 . . ?
H61A C61 H61C 109.5 . . ?
H61B C61 H61C 109.5 . . ?
S6 C62 H62A 109.5 . . ?
S6 C62 H62B 109.5 . . ?
H62A C62 H62B 109.5 . . ?
S6 C62 H62C 109.5 . . ?
H62A C62 H62C 109.5 . . ?
H62B C62 H62C 109.5 . . ?
O81 S81 C81 106.3(4) . . ?
O81 S81 C82 104.2(4) . . ?
C81 S81 C82 97.6(3) . . ?
S81 C81 H81A 109.5 . . ?
S81 C81 H81B 109.5 . . ?
H81A C81 H81B 109.5 . . ?
S81 C81 H81C 109.5 . . ?
H81A C81 H81C 109.5 . . ?
H81B C81 H81C 109.5 . . ?
S81 C82 H82A 109.5 . . ?
S81 C82 H82B 109.5 . . ?
H82A C82 H82B 109.5 . . ?
S81 C82 H82C 109.5 . . ?
H82A C82 H82C 109.5 . . ?
H82B C82 H82C 109.5 . . ?
O82 S82 C84 108.9(14) . . ?
O82 S82 C83 110.2(14) . . ?
C84 S82 C83 94.6(6) . . ?
S82 C83 H83A 109.5 . . ?
S82 C83 H83B 109.5 . . ?
H83A C83 H83B 109.5 . . ?
S82 C83 H83C 109.5 . . ?
H83A C83 H83C 109.5 . . ?
H83B C83 H83C 109.5 . . ?
S82 C84 H84A 109.5 . . ?
S82 C84 H84B 109.5 . . ?
H84A C84 H84B 109.5 . . ?
S82 C84 H84C 109.5 . . ?
H84A C84 H84C 109.5 . . ?
H84B C84 H84C 109.5 . . ?
O5 S51 C52 106.9(4) . . ?
O5 S51 C51 105.3(4) . . ?
C52 S51 C51 97.7(4) . . ?
S51 C51 H51A 109.5 . . ?
S51 C51 H51B 109.5 . . ?
H51A C51 H51B 109.5 . . ?
S51 C51 H51C 109.5 . . ?
H51A C51 H51C 109.5 . . ?
H51B C51 H51C 109.5 . . ?
S51 C52 H52A 109.5 . . ?
S51 C52 H52B 109.5 . . ?
H52A C52 H52B 109.5 . . ?
S51 C52 H52C 109.5 . . ?
H52A C52 H52C 109.5 . . ?
H52B C52 H52C 109.5 . . ?
O5 S52 C54 110.7(14) . . ?
O5 S52 C53 106.3(15) . . ?
C54 S52 C53 94.6(11) . . ?
S52 C53 H53A 109.5 . . ?
S52 C53 H53B 109.5 . . ?
H53A C53 H53B 109.5 . . ?
S52 C53 H53C 109.5 . . ?
H53A C53 H53C 109.5 . . ?
H53B C53 H53C 109.5 . . ?
S52 C54 H54A 109.5 . . ?
S52 C54 H54B 109.5 . . ?
H54A C54 H54B 109.5 . . ?
S52 C54 H54C 109.5 . . ?
H54A C54 H54C 109.5 . . ?
H54B C54 H54C 109.5 . . ?
O7 S71 C72 107.8(5) . . ?
O7 S71 C71 103.6(4) . . ?
C72 S71 C71 98.2(5) . . ?
S71 C71 H71A 109.5 . . ?
S71 C71 H71B 109.5 . . ?
H71A C71 H71B 109.5 . . ?
S71 C71 H71C 109.5 . . ?
H71A C71 H71C 109.5 . . ?
H71B C71 H71C 109.5 . . ?
S71 C72 H72A 109.5 . . ?
S71 C72 H72B 109.5 . . ?
H72A C72 H72B 109.5 . . ?
S71 C72 H72C 109.5 . . ?
H72A C72 H72C 109.5 . . ?
H72B C72 H72C 109.5 . . ?
O7 S72 C74 114.9(14) . . ?
O7 S72 C73 108.2(14) . . ?
C74 S72 C73 97.8(9) . . ?
S72 C73 H73A 109.5 . . ?
S72 C73 H73B 109.5 . . ?
H73A C73 H73B 109.5 . . ?
S72 C73 H73C 109.5 . . ?
H73A C73 H73C 109.5 . . ?
H73B C73 H73C 109.5 . . ?
S72 C74 H74A 109.5 . . ?
S72 C74 H74B 109.5 . . ?
H74A C74 H74B 109.5 . . ?
S72 C74 H74C 109.5 . . ?
H74A C74 H74C 109.5 . . ?
H74B C74 H74C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
V1 O11 C12 C13 161.7(4) . . . . ?
V1 O11 C12 C11 -19.7(8) . . . . ?
C16 C11 C12 O11 -176.4(5) . . . . ?
C17 C11 C12 O11 -0.4(8) . . . . ?
C16 C11 C12 C13 2.2(8) . . . . ?
C17 C11 C12 C13 178.1(5) . . . . ?
O11 C12 C13 C14 175.7(5) . . . . ?
C11 C12 C13 C14 -3.0(9) . . . . ?
C12 C13 C14 C15 1.5(9) . . . . ?
C13 C14 C15 C16 0.8(9) . . . . ?
C13 C14 C15 Br1 -177.3(5) . . . . ?
C14 C15 C16 C11 -1.6(9) . . . . ?
Br1 C15 C16 C11 176.6(4) . . . . ?
C12 C11 C16 C15 0.0(8) . . . . ?
C17 C11 C16 C15 -175.9(5) . . . . ?
C18 N11 C17 N12 0.6(6) . . . . ?
V1 N11 C17 N12 -171.3(4) . . . . ?
C18 N11 C17 C11 -176.4(5) . . . . ?
V1 N11 C17 C11 11.7(8) . . . . ?
C19 N12 C17 N11 0.1(6) . . . . ?
C19 N12 C17 C11 177.2(5) . . . . ?
C16 C11 C17 N11 179.0(5) . . . . ?
C12 C11 C17 N11 3.1(8) . . . . ?
C16 C11 C17 N12 2.4(8) . . . . ?
C12 C11 C17 N12 -173.5(5) . . . . ?
C17 N11 C18 C19 -1.1(7) . . . . ?
V1 N11 C18 C19 170.7(4) . . . . ?
N11 C18 C19 N12 1.1(7) . . . . ?
C17 N12 C19 C18 -0.8(7) . . . . ?
V1 O21 C22 C23 145.9(4) . . . . ?
V1 O21 C22 C21 -33.8(8) . . . . ?
C26 C21 C22 O21 179.4(6) . . . . ?
C27 C21 C22 O21 -0.5(8) . . . . ?
C26 C21 C22 C23 -0.2(8) . . . . ?
C27 C21 C22 C23 179.8(5) . . . . ?
O21 C22 C23 C24 -178.9(6) . . . . ?
C21 C22 C23 C24 0.8(9) . . . . ?
C22 C23 C24 C25 -0.5(10) . . . . ?
C23 C24 C25 C26 -0.4(11) . . . . ?
C23 C24 C25 Br2 178.8(5) . . . . ?
C24 C25 C26 C21 0.9(11) . . . . ?
Br2 C25 C26 C21 -178.3(5) . . . . ?
C22 C21 C26 C25 -0.6(9) . . . . ?
C27 C21 C26 C25 179.4(6) . . . . ?
C28 N21 C27 N22 -0.2(6) . . . . ?
V1 N21 C27 N22 -174.1(4) . . . . ?
C28 N21 C27 C21 178.5(5) . . . . ?
V1 N21 C27 C21 4.7(8) . . . . ?
C29 N22 C27 N21 0.2(7) . . . . ?
C29 N22 C27 C21 -178.6(5) . . . . ?
C26 C21 C27 N21 -166.1(6) . . . . ?
C22 C21 C27 N21 13.9(9) . . . . ?
C26 C21 C27 N22 12.5(9) . . . . ?
C22 C21 C27 N22 -167.6(6) . . . . ?
C27 N21 C28 C29 0.2(6) . . . . ?
V1 N21 C28 C29 173.7(4) . . . . ?
N21 C28 C29 N22 -0.1(7) . . . . ?
C27 N22 C29 C28 0.0(7) . . . . ?
V2 O31 C32 C33 -146.0(4) . . . . ?
V2 O31 C32 C31 33.3(8) . . . . ?
C36 C31 C32 O31 -176.6(5) . . . . ?
C37 C31 C32 O31 3.8(8) . . . . ?
C36 C31 C32 C33 2.7(8) . . . . ?
C37 C31 C32 C33 -176.9(5) . . . . ?
O31 C32 C33 C34 177.0(5) . . . . ?
C31 C32 C33 C34 -2.3(8) . . . . ?
C32 C33 C34 C35 -0.9(9) . . . . ?
C33 C34 C35 C36 3.9(10) . . . . ?
C33 C34 C35 Br3 -175.9(5) . . . . ?
C34 C35 C36 C31 -3.4(9) . . . . ?
Br3 C35 C36 C31 176.4(4) . . . . ?
C32 C31 C36 C35 0.0(9) . . . . ?
C37 C31 C36 C35 179.6(5) . . . . ?
C38 N31 C37 N32 -0.5(6) . . . . ?
V2 N31 C37 N32 173.5(4) . . . . ?
C38 N31 C37 C31 -180.0(5) . . . . ?
V2 N31 C37 C31 -6.0(8) . . . . ?
C39 N32 C37 N31 0.5(7) . . . . ?
C39 N32 C37 C31 -180.0(6) . . . . ?
C36 C31 C37 N31 164.0(6) . . . . ?
C32 C31 C37 N31 -16.4(9) . . . . ?
C36 C31 C37 N32 -15.4(9) . . . . ?
C32 C31 C37 N32 164.2(6) . . . . ?
C37 N31 C38 C39 0.3(7) . . . . ?
V2 N31 C38 C39 -173.3(4) . . . . ?
N31 C38 C39 N32 0.1(7) . . . . ?
C37 N32 C39 C38 -0.4(8) . . . . ?
V2 O41 C42 C43 -161.7(4) . . . . ?
V2 O41 C42 C41 18.9(8) . . . . ?
C46 C41 C42 O41 -177.1(5) . . . . ?
C47 C41 C42 O41 2.8(8) . . . . ?
C46 C41 C42 C43 3.5(8) . . . . ?
C47 C41 C42 C43 -176.6(5) . . . . ?
O41 C42 C43 C44 178.2(5) . . . . ?
C41 C42 C43 C44 -2.4(8) . . . . ?
C42 C43 C44 C45 -0.4(8) . . . . ?
C43 C44 C45 C46 2.0(8) . . . . ?
C43 C44 C45 Br4 -176.0(4) . . . . ?
C44 C45 C46 C41 -0.9(8) . . . . ?
Br4 C45 C46 C41 177.2(4) . . . . ?
C42 C41 C46 C45 -1.9(8) . . . . ?
C47 C41 C46 C45 178.1(5) . . . . ?
C49 N42 C47 N41 0.0(7) . . . . ?
C49 N42 C47 C41 -179.6(5) . . . . ?
C48 N41 C47 N42 -0.3(6) . . . . ?
V2 N41 C47 N42 164.7(4) . . . . ?
C48 N41 C47 C41 179.3(5) . . . . ?
V2 N41 C47 C41 -15.7(8) . . . . ?
C46 C41 C47 N42 -3.4(8) . . . . ?
C42 C41 C47 N42 176.6(5) . . . . ?
C46 C41 C47 N41 177.0(5) . . . . ?
C42 C41 C47 N41 -2.9(8) . . . . ?
C47 N41 C48 C49 0.5(7) . . . . ?
V2 N41 C48 C49 -164.4(4) . . . . ?
N41 C48 C49 N42 -0.5(7) . . . . ?
C47 N42 C49 C48 0.3(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
N12 H12 O5 0.82(6) 2.02(6) 2.782(7) 154(5) . yes
N22 H22 O6 0.92(7) 1.92(7) 2.836(7) 176(6) . yes
N32 H32 O7 0.85(6) 1.89(6) 2.735(7) 175(6) . yes
N42 H42 O81 0.89(7) 1.85(7) 2.743(7) 178(7) . yes
N42 H42 O82 0.89(7) 2.01(8) 2.86(3) 157(6) . yes
C16 H16 S52 0.95 2.60 3.49(2) 158 . yes
C16 H16 O5 0.95 2.59 3.498(8) 161 . yes
C18 H18 O21 0.95 2.56 2.927(7) 103 . yes
C19 H19 O82 0.95 2.58 3.43(3) 149 3_645 yes
C26 H26 O6 0.95 2.59 3.478(8) 157 . yes
C36 H36 O7 0.95 2.58 3.438(9) 151 . yes
C46 H46 O82 0.95 2.48 3.40(3) 161 . yes
C52 H52C O2 0.98 2.39 3.301(11) 154 2_565 yes
C61 H61A O2 0.98 2.48 3.367(10) 150 1_655 yes
C72 H72A O1 0.98 2.38 3.288(9) 153 1_455 yes

_refine_diff_density_max         0.965
_refine_diff_density_min         -0.785
_refine_diff_density_rms         0.091

####################################################################### 
# 
# 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_ha145
_database_code_depnum_ccdc_archive 'CCDC 1908643'
loop_
_audit_author_name
_audit_author_address
'Eric C. Hosten'
;Nelson Mandela University
South Africa
;
_audit_update_record             
;
2019-04-08 deposited with the CCDC.	2019-10-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H12 N6 O7 V, C2 H6 O S'
_chemical_formula_sum            'C20 H18 N6 O8 S V'
_chemical_formula_weight         553.40

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'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_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+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   13.8817(5)
_cell_length_b                   13.0525(5)
_cell_length_c                   13.1235(5)
_cell_angle_alpha                90
_cell_angle_beta                 108.646(2)
_cell_angle_gamma                90
_cell_volume                     2253.05(15)
_cell_formula_units_Z            4
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    9934
_cell_measurement_theta_min      2.26
_cell_measurement_theta_max      28.23

_exptl_crystal_description       block
_exptl_crystal_colour            'dark blue green'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.631
_exptl_crystal_F_000             1132
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.281
_exptl_crystal_size_mid          0.241
_exptl_crystal_size_min          0.194
_exptl_absorpt_coefficient_mu    0.595
_shelx_estimated_absorpt_T_min   0.851
_shelx_estimated_absorpt_T_max   0.893
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.9166
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   'SADABS V2008/1 (Bruker AXS)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      200(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 8.3333
_diffrn_reflns_number            26442
_diffrn_reflns_av_unetI/netI     0.0218
_diffrn_reflns_av_R_equivalents  0.0242
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         1.548
_diffrn_reflns_theta_max         28.319
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             5606
_reflns_number_gt                4551
_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       'Bruker Instrument Service v2011.4.0.0'
_computing_cell_refinement       'APEX2 v2011.4-1 (Bruker AXS)'
_computing_data_reduction        'SAINT V7.68A (Bruker AXS, 2009)'
_computing_structure_solution    'SHELXT-2018/2 (Sheldrick, 2015)'
_computing_structure_refinement  
'SHELXL-2018/3 (Sheldrick, 2015) and ShelXle (Hübschle, 2011)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 2012)'
_computing_publication_material  
'PLATON (Spek, 2009) and MERCURY (Macrae, 2008)'

_refine_special_details          
;
Carbon-bound H atoms were placed in calculated positions and were included in
the refinement in the riding model approximation, with U(H) set to 1.2
Ueq(C). The H atoms of the disordered methyl groups were placed in
calculated positions with Uiso(H) set to 1.5Ueq(C).

The nitrogen-bound H atoms were located on a difference Fourier map and refined
freely. 

The DMSO solvent molecule is disordered necessitating the use of various
constraints and restraints: EXYZ, EADP and SAME.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0638P)²+1.9658P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         5606
_refine_ls_number_parameters     343
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0584
_refine_ls_R_factor_gt           0.0447
_refine_ls_wR_factor_ref         0.1286
_refine_ls_wR_factor_gt          0.1199
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_restrained_S_all      1.080
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_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
V1 V 0.42744(3) 0.56855(3) 0.31062(3) 0.02700(12) Uani 1 1 d . . . . .
O3 O 0.39878(14) 0.58029(12) 0.18189(14) 0.0360(4) Uani 1 1 d . . . . .
O4 O 0.26920(18) 0.03593(15) 0.41841(19) 0.0548(6) Uani 1 1 d . . . . .
O11 O 0.57161(13) 0.57658(12) 0.37328(17) 0.0408(4) Uani 1 1 d . . . . .
O12 O 0.88550(14) 0.22312(14) 0.41485(16) 0.0428(4) Uani 1 1 d . . . . .
O13 O 0.98002(14) 0.35611(16) 0.42421(19) 0.0543(5) Uani 1 1 d . . . . .
O21 O 0.30495(12) 0.55326(12) 0.34624(14) 0.0326(4) Uani 1 1 d . . . . .
O22 O -0.00108(16) 0.90716(19) 0.3270(2) 0.0602(6) Uani 1 1 d . . . . .
O23 O -0.10076(15) 0.7764(2) 0.3065(2) 0.0667(7) Uani 1 1 d . . . . .
N11 N 0.44482(15) 0.41374(14) 0.34091(17) 0.0314(4) Uani 1 1 d . . . . .
N12 N 0.51051(16) 0.26000(15) 0.36634(17) 0.0322(4) Uani 1 1 d . . . . .
N13 N 0.89721(15) 0.31606(17) 0.41369(17) 0.0359(4) Uani 1 1 d . . . . .
N21 N 0.42778(13) 0.71804(14) 0.36198(15) 0.0272(4) Uani 1 1 d . . . . .
N22 N 0.37282(15) 0.86791(14) 0.39461(16) 0.0297(4) Uani 1 1 d . . . . .
N23 N -0.01644(16) 0.8145(2) 0.31982(18) 0.0469(6) Uani 1 1 d . . . . .
C111 C 0.53134(17) 0.36037(16) 0.36228(18) 0.0285(4) Uani 1 1 d . . . . .
C112 C 0.36755(19) 0.34334(18) 0.3299(2) 0.0364(5) Uani 1 1 d . . . . .
H112 H 0.297580 0.359456 0.314318 0.044 Uiso 1 1 calc R U . . .
C113 C 0.40771(19) 0.24782(18) 0.3449(2) 0.0361(5) Uani 1 1 d . . . . .
H113 H 0.372010 0.185137 0.341412 0.043 Uiso 1 1 calc R U . . .
C121 C 0.63174(16) 0.40296(16) 0.37642(18) 0.0272(4) Uani 1 1 d . . . . .
C122 C 0.64570(17) 0.51118(17) 0.3806(2) 0.0334(5) Uani 1 1 d . . . . .
C123 C 0.74324(19) 0.55064(19) 0.3936(2) 0.0423(6) Uani 1 1 d . . . . .
H123 H 0.752798 0.622770 0.395581 0.051 Uiso 1 1 calc R U . . .
C124 C 0.82498(19) 0.4877(2) 0.4034(2) 0.0397(6) Uani 1 1 d . . . . .
H124 H 0.890419 0.515567 0.412497 0.048 Uiso 1 1 calc R U . . .
C125 C 0.80986(17) 0.38246(18) 0.39977(19) 0.0311(5) Uani 1 1 d . . . . .
C126 C 0.71568(17) 0.33994(17) 0.38652(17) 0.0286(4) Uani 1 1 d . . . . .
H126 H 0.707839 0.267593 0.384239 0.034 Uiso 1 1 calc R U . . .
C211 C 0.34659(16) 0.76909(16) 0.36933(17) 0.0258(4) Uani 1 1 d . . . . .
C212 C 0.50683(17) 0.78744(17) 0.38231(19) 0.0302(5) Uani 1 1 d . . . . .
H212 H 0.573813 0.772474 0.382346 0.036 Uiso 1 1 calc R U . . .
C213 C 0.47318(18) 0.88017(17) 0.40215(19) 0.0322(5) Uani 1 1 d . . . . .
H213 H 0.511479 0.941798 0.418185 0.039 Uiso 1 1 calc R U . . .
C221 C 0.24629(16) 0.72581(16) 0.35200(17) 0.0259(4) Uani 1 1 d . . . . .
C222 C 0.23144(16) 0.61830(17) 0.34185(18) 0.0281(4) Uani 1 1 d . . . . .
C223 C 0.13358(19) 0.5782(2) 0.3275(2) 0.0354(5) Uani 1 1 d . . . . .
H223 H 0.123580 0.506165 0.323163 0.043 Uiso 1 1 calc R U . . .
C224 C 0.05265(18) 0.6414(2) 0.3197(2) 0.0383(5) Uani 1 1 d . . . . .
H224 H -0.013284 0.613834 0.308322 0.046 Uiso 1 1 calc R U . . .
C225 C 0.06868(17) 0.7462(2) 0.32871(19) 0.0356(5) Uani 1 1 d . . . . .
C226 C 0.16328(17) 0.78931(18) 0.34475(18) 0.0306(5) Uani 1 1 d . . . . .
H226 H 0.171854 0.861513 0.350801 0.037 Uiso 1 1 calc R U . . .
H12 H 0.548(2) 0.215(2) 0.372(3) 0.046(9) Uiso 1 1 d . . . . .
H22 H 0.336(2) 0.916(2) 0.404(3) 0.047(9) Uiso 1 1 d . . . . .
S4 S 0.24730(5) 0.08897(5) 0.50962(6) 0.0350(2) Uani 0.931(2) 1 d D . P A 1
C41 C 0.1700(2) 0.0061(2) 0.5559(3) 0.0503(7) Uani 0.931(2) 1 d D . P A 1
H41A H 0.153925 0.038373 0.615934 0.075 Uiso 0.931(2) 1 calc R U P A 1
H41B H 0.106819 -0.007688 0.497326 0.075 Uiso 0.931(2) 1 calc R U P A 1
H41C H 0.206143 -0.058410 0.580065 0.075 Uiso 0.931(2) 1 calc R U P A 1
C42 C 0.1569(3) 0.1834(3) 0.4499(3) 0.0723(11) Uani 0.931(2) 1 d D . P A 1
H42A H 0.139258 0.221244 0.505982 0.109 Uiso 0.931(2) 1 calc R U P A 1
H42B H 0.185279 0.230876 0.409069 0.109 Uiso 0.931(2) 1 calc R U P A 1
H42C H 0.095780 0.150974 0.401351 0.109 Uiso 0.931(2) 1 calc R U P A 1
S5 S 0.1725(8) 0.0719(7) 0.4216(8) 0.045(3) Uani 0.069(2) 1 d D . P A 2
C51 C 0.1700(2) 0.0061(2) 0.5559(3) 0.0503(7) Uani 0.069(2) 1 d D . P A 2
H51A H 0.106596 0.023964 0.569484 0.075 Uiso 0.069(2) 1 calc R U P A 2
H51B H 0.174002 -0.068409 0.549087 0.075 Uiso 0.069(2) 1 calc R U P A 2
H51C H 0.228002 0.030069 0.615807 0.075 Uiso 0.069(2) 1 calc R U P A 2
C52 C 0.1569(3) 0.1834(3) 0.4499(3) 0.0723(11) Uani 0.069(2) 1 d D . P A 2
H52A H 0.086335 0.193148 0.447894 0.109 Uiso 0.069(2) 1 calc R U P A 2
H52B H 0.202757 0.199058 0.522206 0.109 Uiso 0.069(2) 1 calc R U P A 2
H52C H 0.171724 0.229345 0.397713 0.109 Uiso 0.069(2) 1 calc R U P A 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
V1 O3 1.6144(18) . ?
V1 O11 1.9080(18) . ?
V1 O21 1.9126(16) . ?
V1 N11 2.0586(19) . ?
V1 N21 2.0638(18) . ?
O4 S5 1.435(10) . ?
O4 S4 1.496(2) . ?
O11 C122 1.316(3) . ?
O12 N13 1.225(3) . ?
O13 N13 1.230(3) . ?
O21 C222 1.314(3) . ?
O22 N23 1.226(3) . ?
O23 N23 1.232(3) . ?
N11 C111 1.338(3) . ?
N11 C112 1.384(3) . ?
N12 C111 1.346(3) . ?
N12 C113 1.373(3) . ?
N12 H12 0.77(3) . ?
N13 C125 1.454(3) . ?
N21 C211 1.339(3) . ?
N21 C212 1.381(3) . ?
N22 C211 1.352(3) . ?
N22 C213 1.374(3) . ?
N22 H22 0.84(3) . ?
N23 C225 1.455(3) . ?
C111 C121 1.456(3) . ?
C112 C113 1.354(3) . ?
C112 H112 0.9500 . ?
C113 H113 0.9500 . ?
C121 C126 1.398(3) . ?
C121 C122 1.424(3) . ?
C122 C123 1.407(3) . ?
C123 C124 1.373(3) . ?
C123 H123 0.9500 . ?
C124 C125 1.388(3) . ?
C124 H124 0.9500 . ?
C125 C126 1.379(3) . ?
C126 H126 0.9500 . ?
C211 C221 1.452(3) . ?
C212 C213 1.352(3) . ?
C212 H212 0.9500 . ?
C213 H213 0.9500 . ?
C221 C226 1.398(3) . ?
C221 C222 1.418(3) . ?
C222 C223 1.411(3) . ?
C223 C224 1.371(4) . ?
C223 H223 0.9500 . ?
C224 C225 1.385(4) . ?
C224 H224 0.9500 . ?
C225 C226 1.382(3) . ?
C226 H226 0.9500 . ?
S4 C42 1.755(3) . ?
S4 C41 1.763(3) . ?
C41 H41A 0.9800 . ?
C41 H41B 0.9800 . ?
C41 H41C 0.9800 . ?
C42 H42A 0.9800 . ?
C42 H42B 0.9800 . ?
C42 H42C 0.9800 . ?
S5 C52 1.535(9) . ?
S5 C51 1.971(10) . ?
C51 H51A 0.9800 . ?
C51 H51B 0.9800 . ?
C51 H51C 0.9800 . ?
C52 H52A 0.9800 . ?
C52 H52B 0.9800 . ?
C52 H52C 0.9800 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O3 V1 O11 108.62(9) . . ?
O3 V1 O21 108.96(9) . . ?
O11 V1 O21 142.41(9) . . ?
O3 V1 N11 105.65(8) . . ?
O11 V1 N11 85.91(7) . . ?
O21 V1 N11 84.77(7) . . ?
O3 V1 N21 103.06(8) . . ?
O11 V1 N21 85.11(7) . . ?
O21 V1 N21 85.89(7) . . ?
N11 V1 N21 151.29(8) . . ?
C122 O11 V1 133.10(15) . . ?
C222 O21 V1 131.32(14) . . ?
C111 N11 C112 106.85(19) . . ?
C111 N11 V1 126.39(15) . . ?
C112 N11 V1 126.32(16) . . ?
C111 N12 C113 109.1(2) . . ?
C111 N12 H12 127(2) . . ?
C113 N12 H12 124(2) . . ?
O12 N13 O13 122.9(2) . . ?
O12 N13 C125 118.9(2) . . ?
O13 N13 C125 118.2(2) . . ?
C211 N21 C212 107.14(18) . . ?
C211 N21 V1 125.44(15) . . ?
C212 N21 V1 127.00(14) . . ?
C211 N22 C213 108.42(18) . . ?
C211 N22 H22 128(2) . . ?
C213 N22 H22 124(2) . . ?
O22 N23 O23 122.9(2) . . ?
O22 N23 C225 118.8(2) . . ?
O23 N23 C225 118.3(3) . . ?
N11 C111 N12 109.0(2) . . ?
N11 C111 C121 125.89(19) . . ?
N12 C111 C121 125.1(2) . . ?
C113 C112 N11 109.1(2) . . ?
C113 C112 H112 125.5 . . ?
N11 C112 H112 125.5 . . ?
C112 C113 N12 106.0(2) . . ?
C112 C113 H113 127.0 . . ?
N12 C113 H113 127.0 . . ?
C126 C121 C122 118.7(2) . . ?
C126 C121 C111 121.5(2) . . ?
C122 C121 C111 119.76(19) . . ?
O11 C122 C123 118.1(2) . . ?
O11 C122 C121 123.1(2) . . ?
C123 C122 C121 118.8(2) . . ?
C124 C123 C122 121.8(2) . . ?
C124 C123 H123 119.1 . . ?
C122 C123 H123 119.1 . . ?
C123 C124 C125 118.5(2) . . ?
C123 C124 H124 120.7 . . ?
C125 C124 H124 120.7 . . ?
C126 C125 C124 122.0(2) . . ?
C126 C125 N13 119.7(2) . . ?
C124 C125 N13 118.3(2) . . ?
C125 C126 C121 120.2(2) . . ?
C125 C126 H126 119.9 . . ?
C121 C126 H126 119.9 . . ?
N21 C211 N22 108.99(19) . . ?
N21 C211 C221 125.61(19) . . ?
N22 C211 C221 125.39(19) . . ?
C213 C212 N21 108.8(2) . . ?
C213 C212 H212 125.6 . . ?
N21 C212 H212 125.6 . . ?
C212 C213 N22 106.7(2) . . ?
C212 C213 H213 126.7 . . ?
N22 C213 H213 126.7 . . ?
C226 C221 C222 119.2(2) . . ?
C226 C221 C211 120.6(2) . . ?
C222 C221 C211 120.20(19) . . ?
O21 C222 C223 117.9(2) . . ?
O21 C222 C221 123.2(2) . . ?
C223 C222 C221 118.9(2) . . ?
C224 C223 C222 121.2(2) . . ?
C224 C223 H223 119.4 . . ?
C222 C223 H223 119.4 . . ?
C223 C224 C225 118.9(2) . . ?
C223 C224 H224 120.6 . . ?
C225 C224 H224 120.6 . . ?
C226 C225 C224 122.3(2) . . ?
C226 C225 N23 118.1(2) . . ?
C224 C225 N23 119.6(2) . . ?
C225 C226 C221 119.5(2) . . ?
C225 C226 H226 120.3 . . ?
C221 C226 H226 120.3 . . ?
O4 S4 C42 105.50(15) . . ?
O4 S4 C41 107.07(14) . . ?
C42 S4 C41 99.08(18) . . ?
S4 C41 H41A 109.5 . . ?
S4 C41 H41B 109.5 . . ?
H41A C41 H41B 109.5 . . ?
S4 C41 H41C 109.5 . . ?
H41A C41 H41C 109.5 . . ?
H41B C41 H41C 109.5 . . ?
S4 C42 H42A 109.5 . . ?
S4 C42 H42B 109.5 . . ?
H42A C42 H42B 109.5 . . ?
S4 C42 H42C 109.5 . . ?
H42A C42 H42C 109.5 . . ?
H42B C42 H42C 109.5 . . ?
O4 S5 C52 121.5(7) . . ?
O4 S5 C51 99.7(5) . . ?
C52 S5 C51 98.8(5) . . ?
S5 C51 H51A 109.5 . . ?
S5 C51 H51B 109.5 . . ?
H51A C51 H51B 109.5 . . ?
S5 C51 H51C 109.5 . . ?
H51A C51 H51C 109.5 . . ?
H51B C51 H51C 109.5 . . ?
S5 C52 H52A 109.5 . . ?
S5 C52 H52B 109.5 . . ?
H52A C52 H52B 109.5 . . ?
S5 C52 H52C 109.5 . . ?
H52A C52 H52C 109.5 . . ?
H52B C52 H52C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C112 N11 C111 N12 -0.8(3) . . . . ?
V1 N11 C111 N12 -173.59(16) . . . . ?
C112 N11 C111 C121 177.8(2) . . . . ?
V1 N11 C111 C121 5.1(3) . . . . ?
C113 N12 C111 N11 1.2(3) . . . . ?
C113 N12 C111 C121 -177.4(2) . . . . ?
C111 N11 C112 C113 0.2(3) . . . . ?
V1 N11 C112 C113 172.91(18) . . . . ?
N11 C112 C113 N12 0.6(3) . . . . ?
C111 N12 C113 C112 -1.1(3) . . . . ?
N11 C111 C121 C126 -172.7(2) . . . . ?
N12 C111 C121 C126 5.8(4) . . . . ?
N11 C111 C121 C122 7.6(4) . . . . ?
N12 C111 C121 C122 -174.0(2) . . . . ?
V1 O11 C122 C123 155.6(2) . . . . ?
V1 O11 C122 C121 -24.6(4) . . . . ?
C126 C121 C122 O11 -179.1(2) . . . . ?
C111 C121 C122 O11 0.7(4) . . . . ?
C126 C121 C122 C123 0.7(4) . . . . ?
C111 C121 C122 C123 -179.6(2) . . . . ?
O11 C122 C123 C124 179.0(3) . . . . ?
C121 C122 C123 C124 -0.7(4) . . . . ?
C122 C123 C124 C125 0.3(4) . . . . ?
C123 C124 C125 C126 0.1(4) . . . . ?
C123 C124 C125 N13 -178.1(2) . . . . ?
O12 N13 C125 C126 -1.0(3) . . . . ?
O13 N13 C125 C126 179.3(2) . . . . ?
O12 N13 C125 C124 177.2(2) . . . . ?
O13 N13 C125 C124 -2.6(3) . . . . ?
C124 C125 C126 C121 -0.1(4) . . . . ?
N13 C125 C126 C121 178.0(2) . . . . ?
C122 C121 C126 C125 -0.3(3) . . . . ?
C111 C121 C126 C125 180.0(2) . . . . ?
C212 N21 C211 N22 -0.6(3) . . . . ?
V1 N21 C211 N22 -173.49(15) . . . . ?
C212 N21 C211 C221 178.9(2) . . . . ?
V1 N21 C211 C221 6.0(3) . . . . ?
C213 N22 C211 N21 0.8(3) . . . . ?
C213 N22 C211 C221 -178.7(2) . . . . ?
C211 N21 C212 C213 0.2(3) . . . . ?
V1 N21 C212 C213 172.92(16) . . . . ?
N21 C212 C213 N22 0.3(3) . . . . ?
C211 N22 C213 C212 -0.7(3) . . . . ?
N21 C211 C221 C226 -169.6(2) . . . . ?
N22 C211 C221 C226 9.7(3) . . . . ?
N21 C211 C221 C222 10.1(3) . . . . ?
N22 C211 C221 C222 -170.5(2) . . . . ?
V1 O21 C222 C223 152.85(18) . . . . ?
V1 O21 C222 C221 -27.9(3) . . . . ?
C226 C221 C222 O21 179.1(2) . . . . ?
C211 C221 C222 O21 -0.7(3) . . . . ?
C226 C221 C222 C223 -1.7(3) . . . . ?
C211 C221 C222 C223 178.6(2) . . . . ?
O21 C222 C223 C224 -178.5(2) . . . . ?
C221 C222 C223 C224 2.2(4) . . . . ?
C222 C223 C224 C225 -1.5(4) . . . . ?
C223 C224 C225 C226 0.3(4) . . . . ?
C223 C224 C225 N23 179.5(2) . . . . ?
O22 N23 C225 C226 -0.1(4) . . . . ?
O23 N23 C225 C226 -179.4(2) . . . . ?
O22 N23 C225 C224 -179.4(3) . . . . ?
O23 N23 C225 C224 1.4(4) . . . . ?
C224 C225 C226 C221 0.2(4) . . . . ?
N23 C225 C226 C221 -179.0(2) . . . . ?
C222 C221 C226 C225 0.5(3) . . . . ?
C211 C221 C226 C225 -179.7(2) . . . . ?

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
N12 H12 O3 0.77(3) 2.11(3) 2.828(3) 153(3) 2_645 yes
N22 H22 O4 0.84(3) 1.86(3) 2.695(3) 170(3) 1_565 yes
C41 H41A O22 0.98 2.57 3.383(4) 141 3_566 yes
C41 H41B O22 0.98 2.52 3.430(4) 155 1_545 yes
C41 H41C O12 0.98 2.51 3.144(4) 122 3_656 yes
C41 H41C O3 0.98 2.59 3.277(4) 127 4_566 yes
C112 H112 O21 0.95 2.56 2.903(3) 102 . yes
C212 H212 O11 0.95 2.56 2.909(3) 102 . yes
C223 H223 O22 0.95 2.51 3.178(3) 127 2_545 yes

_refine_diff_density_max         1.500
_refine_diff_density_min         -0.560
_refine_diff_density_rms         0.068

