# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_ReOMorph
_database_code_depnum_ccdc_archive 'CCDC 1547255'
_audit_update_record             
;
2017-05-01 deposited with the CCDC.
2017-06-22 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        
;
[(Z)-11-carboxy-1-morpholino-6,9-dioxo-3-phenyl-1-
thioxo-2,4,7,10-tetraazaundec-2-ene-4,7,10-triido]oxidorhenium(V)}
monohydrate
;
_chemical_name_common            JC301
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H20 N5 O6 Re S, O1 H2'
_chemical_formula_sum            'C18 H22 N5 O7 Re S'
_chemical_formula_weight         638.67

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0030 0.0020 '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 0.0060 0.0030 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0110 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Re Re -1.0180 7.2310 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1250 0.1230 '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                   10.313(1)
_cell_length_b                   10.470(1)
_cell_length_c                   19.742(2)
_cell_angle_alpha                90
_cell_angle_beta                 93.17(1)
_cell_angle_gamma                90
_cell_volume                     2128.4(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    11068
_cell_measurement_theta_min      3.39
_cell_measurement_theta_max      29.61

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.993
_exptl_crystal_F_000             1248
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.06
_exptl_absorpt_coefficient_mu    5.859
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   integration
_exptl_absorpt_correction_T_min  .4795
_exptl_absorpt_correction_T_max  .6524
_exptl_absorpt_process_details   'STOE XRED'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      200(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focussed sealed tube'
_diffrn_measurement_device_type  'STOE IPDS T2'
_diffrn_measurement_method       'rotation method'
_diffrn_detector_area_resol_mean 6.67
_diffrn_reflns_number            16371
_diffrn_reflns_av_unetI/netI     0.0768
_diffrn_reflns_av_R_equivalents  0.0591
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         3.394
_diffrn_reflns_theta_max         29.264
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             5731
_reflns_number_gt                3856
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .



_computing_data_collection       'STOE X-AREA'
_computing_cell_refinement       'STOE X-AREA'
_computing_data_reduction        'STOE X-RED'
_computing_structure_solution    SHELXS
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    ORTEP
_computing_publication_material  WINGX
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0412P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         5731
_refine_ls_number_parameters     305
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0789
_refine_ls_R_factor_gt           0.0432
_refine_ls_wR_factor_ref         0.0881
_refine_ls_wR_factor_gt          0.0803
_refine_ls_goodness_of_fit_ref   0.951
_refine_ls_restrained_S_all      0.951
_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
Re1A Re 0.24026(2) 0.09566(2) 0.05565(2) 0.02290(7) Uani 0.95 1 d . . P A 1
Re1B Re 0.3495(7) 0.0333(8) 0.0576(4) 0.059(2) Uani 0.05 1 d . . P A 2
O10 O 0.1094(5) 0.1882(5) 0.0528(2) 0.0372(11) Uani 1 1 d . . . . .
S1 S 0.18317(17) -0.11514(14) 0.06334(8) 0.0331(4) Uani 1 1 d . . . . .
C2 C 0.1786(6) -0.1822(6) -0.0191(3) 0.0289(13) Uani 1 1 d . . . . .
N3 N 0.1732(5) -0.1158(5) -0.0767(3) 0.0299(11) Uani 1 1 d . . . . .
C4 C 0.2191(6) 0.0011(6) -0.0850(3) 0.0280(13) Uani 1 1 d . . . . .
N5 N 0.2908(5) 0.0700(5) -0.0403(3) 0.0293(12) Uani 1 1 d . . . . .
C6 C 0.3816(7) 0.1678(6) -0.0643(3) 0.0331(15) Uani 1 1 d . . . . .
H6A H 0.333882 0.230681 -0.091860 0.040 Uiso 1 1 calc R U . . .
H6B H 0.444863 0.127777 -0.092054 0.040 Uiso 1 1 calc R U . . .
C7 C 0.4494(6) 0.2317(7) -0.0044(3) 0.0330(14) Uani 1 1 d . . . . .
N8 N 0.4020(5) 0.1966(5) 0.0561(3) 0.0301(12) Uani 1 1 d . . . . .
C9 C 0.4617(7) 0.2412(7) 0.1198(3) 0.0384(17) Uani 1 1 d . . . . .
H9A H 0.449073 0.332528 0.124386 0.046 Uiso 1 1 calc R U . . .
H9B H 0.554262 0.223864 0.121854 0.046 Uiso 1 1 calc R U . . .
C10 C 0.3981(6) 0.1711(6) 0.1756(3) 0.0311(14) Uani 1 1 d . . . . .
N11 N 0.3041(5) 0.0871(5) 0.1542(2) 0.0273(10) Uani 1 1 d . . . . .
C12 C 0.2485(7) 0.0118(6) 0.2076(3) 0.0320(14) Uani 1 1 d . . . . .
H12A H 0.163483 -0.017813 0.190944 0.038 Uiso 1 1 calc R U . . .
H12B H 0.235894 0.067580 0.245882 0.038 Uiso 1 1 calc R U . . .
C13 C 0.3269(7) -0.1029(7) 0.2327(3) 0.0353(14) Uani 1 1 d . . . . .
O14 O 0.4439(5) -0.1109(5) 0.2108(3) 0.0456(12) Uani 1 1 d . . . . .
H14 H 0.478720 -0.176640 0.225271 0.068 Uiso 1 1 calc R U . . .
O15 O 0.2835(6) -0.1780(6) 0.2723(3) 0.0626(17) Uani 1 1 d . . . . .
N21 N 0.1688(5) -0.3072(5) -0.0237(3) 0.0284(11) Uani 1 1 d . . . . .
C22 C 0.1571(7) -0.3928(6) 0.0347(3) 0.0361(14) Uani 1 1 d . . . . .
H22A H 0.066096 -0.410849 0.040530 0.043 Uiso 1 1 calc R U . . .
H22B H 0.192437 -0.351189 0.075539 0.043 Uiso 1 1 calc R U . . .
C23 C 0.2299(7) -0.5182(6) 0.0240(4) 0.0376(16) Uani 1 1 d . . . . .
H23A H 0.322453 -0.501164 0.025330 0.045 Uiso 1 1 calc R U . . .
H23B H 0.213529 -0.576368 0.060818 0.045 Uiso 1 1 calc R U . . .
O24 O 0.1919(5) -0.5766(4) -0.0381(2) 0.0410(12) Uani 1 1 d . . . . .
C25 C 0.2223(8) -0.4933(7) -0.0922(4) 0.0436(18) Uani 1 1 d . . . . .
H25A H 0.201901 -0.535336 -0.135293 0.052 Uiso 1 1 calc R U . . .
H25B H 0.314619 -0.474694 -0.089243 0.052 Uiso 1 1 calc R U . . .
C26 C 0.1471(7) -0.3704(6) -0.0895(3) 0.0368(16) Uani 1 1 d . . . . .
H26A H 0.173352 -0.313758 -0.125063 0.044 Uiso 1 1 calc R U . . .
H26B H 0.055209 -0.388210 -0.097450 0.044 Uiso 1 1 calc R U . . .
C41 C 0.1831(7) 0.0579(6) -0.1528(3) 0.0331(15) Uani 1 1 d . . . . .
C42 C 0.1148(7) 0.1740(7) -0.1541(4) 0.0406(17) Uani 1 1 d . . . . .
H42 H 0.098222 0.215697 -0.113901 0.049 Uiso 1 1 calc R U . . .
C43 C 0.0716(8) 0.2265(9) -0.2171(5) 0.056(2) Uani 1 1 d . . . . .
H43 H 0.021948 0.300668 -0.218768 0.067 Uiso 1 1 calc R U . . .
C44 C 0.1032(10) 0.1680(10) -0.2753(5) 0.065(3) Uani 1 1 d . . . . .
H44 H 0.077135 0.204294 -0.316843 0.078 Uiso 1 1 calc R U . . .
C45 C 0.1730(12) 0.0556(9) -0.2740(4) 0.073(3) Uani 1 1 d . . . . .
H45 H 0.194691 0.017796 -0.314440 0.087 Uiso 1 1 calc R U . . .
C46 C 0.2113(9) -0.0014(8) -0.2124(4) 0.049(2) Uani 1 1 d . . . . .
H46 H 0.255488 -0.078883 -0.211581 0.058 Uiso 1 1 calc R U . . .
O101 O 0.4302(5) 0.1896(5) 0.2369(2) 0.0431(12) Uani 1 1 d . . . . .
O71 O 0.5380(5) 0.3087(5) -0.0107(3) 0.0497(13) Uani 1 1 d . . . . .
O50 O 0.5653(9) 0.0653(7) 0.3565(4) 0.081(2) Uani 1 1 d D . . . .
H51 H 0.548(11) 0.119(7) 0.387(3) 0.101 Uiso 1 1 d D U . . .
H52 H 0.543(11) 0.104(8) 0.320(2) 0.100 Uiso 1 1 d D 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
Re1A O10 1.660(5) . ?
Re1A N8 1.974(5) . ?
Re1A N5 2.010(5) . ?
Re1A N11 2.022(4) . ?
Re1A S1 2.2915(15) . ?
Re1B N8 1.794(10) . ?
Re1B N5 2.030(9) . ?
Re1B N11 2.066(10) . ?
Re1B S1 2.322(9) . ?
S1 C2 1.770(6) . ?
C2 N21 1.316(8) . ?
C2 N3 1.331(8) . ?
N3 C4 1.326(8) . ?
C4 N5 1.333(7) . ?
C4 C41 1.492(9) . ?
N5 C6 1.482(8) . ?
C6 C7 1.498(9) . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?
C7 O71 1.230(7) . ?
C7 N8 1.367(8) . ?
N8 C9 1.447(8) . ?
C9 C10 1.504(10) . ?
C9 H9A 0.9700 . ?
C9 H9B 0.9700 . ?
C10 O101 1.253(7) . ?
C10 N11 1.358(8) . ?
N11 C12 1.458(8) . ?
C12 C13 1.516(9) . ?
C12 H12A 0.9700 . ?
C12 H12B 0.9700 . ?
C13 O15 1.212(8) . ?
C13 O14 1.307(8) . ?
O14 H14 0.8200 . ?
N21 C26 1.464(8) . ?
N21 C22 1.470(8) . ?
C22 C23 1.532(9) . ?
C22 H22A 0.9700 . ?
C22 H22B 0.9700 . ?
C23 O24 1.407(8) . ?
C23 H23A 0.9700 . ?
C23 H23B 0.9700 . ?
O24 C25 1.427(8) . ?
C25 C26 1.505(10) . ?
C25 H25A 0.9700 . ?
C25 H25B 0.9700 . ?
C26 H26A 0.9700 . ?
C26 H26B 0.9700 . ?
C41 C46 1.375(10) . ?
C41 C42 1.405(10) . ?
C42 C43 1.409(10) . ?
C42 H42 0.9300 . ?
C43 C44 1.358(14) . ?
C43 H43 0.9300 . ?
C44 C45 1.379(14) . ?
C44 H44 0.9300 . ?
C45 C46 1.392(11) . ?
C45 H45 0.9300 . ?
C46 H46 0.9300 . ?
O50 H51 0.853(10) . ?
O50 H52 0.852(10) . ?

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
O10 Re1A N8 111.9(2) . . ?
O10 Re1A N5 107.4(2) . . ?
N8 Re1A N5 79.2(2) . . ?
O10 Re1A N11 106.2(2) . . ?
N8 Re1A N11 77.8(2) . . ?
N5 Re1A N11 144.4(2) . . ?
O10 Re1A S1 110.69(17) . . ?
N8 Re1A S1 137.33(17) . . ?
N5 Re1A S1 90.86(14) . . ?
N11 Re1A S1 87.98(15) . . ?
N8 Re1B N5 83.0(4) . . ?
N8 Re1B N11 80.8(4) . . ?
N5 Re1B N11 139.1(4) . . ?
N8 Re1B S1 149.6(4) . . ?
N5 Re1B S1 89.5(3) . . ?
N11 Re1B S1 86.1(3) . . ?
C2 S1 Re1A 108.3(2) . . ?
C2 S1 Re1B 101.7(3) . . ?
N21 C2 N3 117.4(6) . . ?
N21 C2 S1 117.1(5) . . ?
N3 C2 S1 125.2(5) . . ?
C4 N3 C2 126.1(5) . . ?
N3 C4 N5 127.3(6) . . ?
N3 C4 C41 114.0(5) . . ?
N5 C4 C41 118.7(5) . . ?
C4 N5 C6 119.9(5) . . ?
C4 N5 Re1A 122.2(4) . . ?
C6 N5 Re1A 114.3(4) . . ?
C4 N5 Re1B 130.8(5) . . ?
C6 N5 Re1B 106.0(4) . . ?
N5 C6 C7 109.3(5) . . ?
N5 C6 H6A 109.8 . . ?
C7 C6 H6A 109.8 . . ?
N5 C6 H6B 109.8 . . ?
C7 C6 H6B 109.8 . . ?
H6A C6 H6B 108.3 . . ?
O71 C7 N8 124.6(6) . . ?
O71 C7 C6 122.0(6) . . ?
N8 C7 C6 113.4(5) . . ?
C7 N8 C9 121.2(5) . . ?
C7 N8 Re1B 113.2(5) . . ?
C9 N8 Re1B 114.0(5) . . ?
C7 N8 Re1A 118.9(4) . . ?
C9 N8 Re1A 119.7(4) . . ?
N8 C9 C10 107.3(5) . . ?
N8 C9 H9A 110.3 . . ?
C10 C9 H9A 110.3 . . ?
N8 C9 H9B 110.3 . . ?
C10 C9 H9B 110.3 . . ?
H9A C9 H9B 108.5 . . ?
O101 C10 N11 123.2(6) . . ?
O101 C10 C9 122.0(6) . . ?
N11 C10 C9 114.9(5) . . ?
C10 N11 C12 115.3(5) . . ?
C10 N11 Re1A 117.4(4) . . ?
C12 N11 Re1A 126.8(4) . . ?
C10 N11 Re1B 105.6(5) . . ?
C12 N11 Re1B 129.6(5) . . ?
N11 C12 C13 116.2(6) . . ?
N11 C12 H12A 108.2 . . ?
C13 C12 H12A 108.2 . . ?
N11 C12 H12B 108.2 . . ?
C13 C12 H12B 108.2 . . ?
H12A C12 H12B 107.4 . . ?
O15 C13 O14 123.6(7) . . ?
O15 C13 C12 121.1(6) . . ?
O14 C13 C12 115.3(6) . . ?
C13 O14 H14 109.5 . . ?
C2 N21 C26 121.2(5) . . ?
C2 N21 C22 124.2(5) . . ?
C26 N21 C22 113.9(5) . . ?
N21 C22 C23 110.6(6) . . ?
N21 C22 H22A 109.5 . . ?
C23 C22 H22A 109.5 . . ?
N21 C22 H22B 109.5 . . ?
C23 C22 H22B 109.5 . . ?
H22A C22 H22B 108.1 . . ?
O24 C23 C22 112.2(6) . . ?
O24 C23 H23A 109.2 . . ?
C22 C23 H23A 109.2 . . ?
O24 C23 H23B 109.2 . . ?
C22 C23 H23B 109.2 . . ?
H23A C23 H23B 107.9 . . ?
C23 O24 C25 109.0(5) . . ?
O24 C25 C26 111.1(6) . . ?
O24 C25 H25A 109.4 . . ?
C26 C25 H25A 109.4 . . ?
O24 C25 H25B 109.4 . . ?
C26 C25 H25B 109.4 . . ?
H25A C25 H25B 108.0 . . ?
N21 C26 C25 111.4(5) . . ?
N21 C26 H26A 109.3 . . ?
C25 C26 H26A 109.3 . . ?
N21 C26 H26B 109.3 . . ?
C25 C26 H26B 109.3 . . ?
H26A C26 H26B 108.0 . . ?
C46 C41 C42 120.3(7) . . ?
C46 C41 C4 122.2(6) . . ?
C42 C41 C4 117.4(6) . . ?
C41 C42 C43 119.2(8) . . ?
C41 C42 H42 120.4 . . ?
C43 C42 H42 120.4 . . ?
C44 C43 C42 119.5(9) . . ?
C44 C43 H43 120.3 . . ?
C42 C43 H43 120.3 . . ?
C43 C44 C45 121.2(8) . . ?
C43 C44 H44 119.4 . . ?
C45 C44 H44 119.4 . . ?
C44 C45 C46 120.4(9) . . ?
C44 C45 H45 119.8 . . ?
C46 C45 H45 119.8 . . ?
C41 C46 C45 119.4(8) . . ?
C41 C46 H46 120.3 . . ?
C45 C46 H46 120.3 . . ?
H51 O50 H52 104(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
O50 H52 O101 0.852(10) 2.15(4) 2.974(8) 163(11) .
O14 H14 O101 0.82 1.82 2.639(7) 173.2 2_645
O50 H51 O71 0.853(10) 2.16(4) 2.962(9) 157(8) 4_566

_refine_diff_density_max         1.236
_refine_diff_density_min         -2.188
_refine_diff_density_rms         0.181

####################################################################### 
# 
# 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_TcOMorph
_database_code_depnum_ccdc_archive 'CCDC 1547254'
_audit_update_record             
;
2017-05-01 deposited with the CCDC.
2017-06-22 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        
'[(Z)-11-carboxy-1-morpholino-6,9-dioxo-3-phenyl-1-thioxo-2,4,7,10-tetraazaundec-2-ene-4,7,10-triido]oxidotechnetium(V)}monohydrate'
_chemical_name_common            JC419
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H20 N5 O6 S Tc, H2 O'
_chemical_formula_sum            'C18 H22 N5 O7 S Tc'
_chemical_formula_weight         550.47

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0030 0.0020 '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 0.0060 0.0030 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0110 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1250 0.1230 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Tc Tc -1.4390 0.7590 '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                   10.291(1)
_cell_length_b                   10.494(2)
_cell_length_c                   19.742(2)
_cell_angle_alpha                90
_cell_angle_beta                 92.84(1)
_cell_angle_gamma                90
_cell_volume                     2129.4(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    7104
_cell_measurement_theta_min      3.40
_cell_measurement_theta_max      27.66

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.717
_exptl_crystal_F_000             1120
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.10
_exptl_absorpt_coefficient_mu    0.826
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      200(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'STOE IPDS T2'
_diffrn_measurement_method       'rotation method'
_diffrn_detector_area_resol_mean 6.67
_diffrn_reflns_number            16677
_diffrn_reflns_av_unetI/netI     0.1235
_diffrn_reflns_av_R_equivalents  0.0894
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_theta_min         3.400
_diffrn_reflns_theta_max         29.321
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             5730
_reflns_number_gt                2911
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .



_computing_data_collection       'STOE X-AREA'
_computing_cell_refinement       'STOE X-AREA'
_computing_data_reduction        'STOE X-RED'
_computing_structure_solution    SHELXS
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    ORTEP
_computing_publication_material  WINGX
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0635P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_extinction_coef       0.0074(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         5730
_refine_ls_number_parameters     306
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.1228
_refine_ls_R_factor_gt           0.0527
_refine_ls_wR_factor_ref         0.1295
_refine_ls_wR_factor_gt          0.1080
_refine_ls_goodness_of_fit_ref   0.825
_refine_ls_restrained_S_all      0.825
_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
TcA Tc 0.74146(4) 0.09607(4) 1.05645(2) 0.03073(14) Uani 0.92 1 d . . P A 1
TcB Tc 0.8484(8) 0.0289(9) 1.0580(6) 0.092(3) Uani 0.08 1 d . . P A 2
O10 O 0.6102(4) 0.1847(3) 1.0542(2) 0.0508(10) Uani 1 1 d . . . . .
S1 S 0.69219(15) -0.11659(12) 1.06467(7) 0.0447(3) Uani 1 1 d . . . . .
C2 C 0.6811(5) -0.1806(5) 0.9829(3) 0.0372(11) Uani 1 1 d . . . . .
N3 N 0.6736(4) -0.1158(4) 0.9245(2) 0.0386(9) Uani 1 1 d . . . . .
C4 C 0.7192(5) 0.0000(5) 0.9158(3) 0.0351(11) Uani 1 1 d . . . . .
N5 N 0.7917(4) 0.0699(4) 0.9604(2) 0.0388(10) Uani 1 1 d . . . . .
C6 C 0.8790(5) 0.1696(5) 0.9358(3) 0.0450(13) Uani 1 1 d . . . . .
H6A H 0.829004 0.232034 0.909295 0.054 Uiso 1 1 calc R U . . .
H6B H 0.942389 0.131881 0.907063 0.054 Uiso 1 1 calc R U . . .
C7 C 0.9470(5) 0.2329(5) 0.9956(3) 0.0429(12) Uani 1 1 d . . . . .
N8 N 0.9023(4) 0.1973(4) 1.0555(2) 0.0394(10) Uani 1 1 d . . . . .
C9 C 0.9616(5) 0.2414(5) 1.1200(3) 0.0451(13) Uani 1 1 d . . . . .
H9A H 0.947779 0.332279 1.124976 0.054 Uiso 1 1 calc R U . . .
H9B H 1.054552 0.225469 1.121596 0.054 Uiso 1 1 calc R U . . .
C10 C 0.9004(5) 0.1710(5) 1.1759(3) 0.0393(12) Uani 1 1 d . . . . .
N11 N 0.8061(4) 0.0863(4) 1.1548(2) 0.0366(9) Uani 1 1 d . . . . .
C12 C 0.7492(5) 0.0118(5) 1.2080(3) 0.0387(12) Uani 1 1 d . . . . .
H12A H 0.664474 -0.018039 1.190988 0.046 Uiso 1 1 calc R U . . .
H12B H 0.735187 0.067966 1.245924 0.046 Uiso 1 1 calc R U . . .
C13 C 0.8262(5) -0.1016(5) 1.2340(3) 0.0429(11) Uani 1 1 d . . . . .
O14 O 0.9435(4) -0.1119(4) 1.2117(2) 0.0539(10) Uani 1 1 d . . . . .
H14 H 0.976641 -0.178678 1.225469 0.081 Uiso 1 1 calc R U . . .
O15 O 0.7821(5) -0.1748(4) 1.2733(2) 0.0684(13) Uani 1 1 d . . . . .
N20 N 0.6691(4) -0.3071(4) 0.9780(2) 0.0382(10) Uani 1 1 d . . . . .
C61 C 0.6416(6) -0.3693(5) 0.9125(3) 0.0438(13) Uani 1 1 d . . . . .
H61A H 0.664978 -0.312600 0.876270 0.053 Uiso 1 1 calc R U . . .
H61B H 0.549215 -0.387118 0.906826 0.053 Uiso 1 1 calc R U . . .
C62 C 0.7174(6) -0.4922(5) 0.9082(3) 0.0517(14) Uani 1 1 d . . . . .
H62A H 0.695459 -0.533698 0.865215 0.062 Uiso 1 1 calc R U . . .
H62B H 0.809822 -0.473682 0.910165 0.062 Uiso 1 1 calc R U . . .
O63 O 0.6884(4) -0.5756(3) 0.96253(19) 0.0503(9) Uani 1 1 d . . . . .
C64 C 0.7302(6) -0.5160(5) 1.0241(3) 0.0462(13) Uani 1 1 d . . . . .
H64A H 0.822886 -0.499789 1.023550 0.055 Uiso 1 1 calc R U . . .
H64B H 0.715658 -0.573553 1.061410 0.055 Uiso 1 1 calc R U . . .
C65 C 0.6601(5) -0.3916(5) 1.0359(3) 0.0432(12) Uani 1 1 d . . . . .
H65A H 0.569313 -0.408751 1.043516 0.052 Uiso 1 1 calc R U . . .
H65B H 0.698255 -0.350486 1.076173 0.052 Uiso 1 1 calc R U . . .
C31 C 0.6843(5) 0.0556(5) 0.8475(3) 0.0406(12) Uani 1 1 d . . . . .
C32 C 0.7135(7) -0.0028(6) 0.7886(3) 0.0617(17) Uani 1 1 d . . . . .
H32 H 0.757132 -0.080474 0.789837 0.074 Uiso 1 1 calc R U . . .
C33 C 0.6782(9) 0.0534(8) 0.7266(4) 0.082(2) Uani 1 1 d . . . . .
H33 H 0.702422 0.016124 0.686423 0.098 Uiso 1 1 calc R U . . .
C34 C 0.6077(8) 0.1635(8) 0.7252(4) 0.075(2) Uani 1 1 d . . . . .
H34 H 0.582330 0.199758 0.683673 0.090 Uiso 1 1 calc R U . . .
C35 C 0.5737(6) 0.2214(7) 0.7836(4) 0.0653(19) Uani 1 1 d . . . . .
H35 H 0.523926 0.295417 0.781838 0.078 Uiso 1 1 calc R U . . .
C36 C 0.6141(5) 0.1690(5) 0.8454(3) 0.0492(14) Uani 1 1 d . . . . .
H36 H 0.594326 0.209430 0.885540 0.059 Uiso 1 1 calc R U . . .
O71 O 1.0358(4) 0.3109(4) 0.9882(2) 0.0603(11) Uani 1 1 d . . . . .
O101 O 0.9319(4) 0.1893(4) 1.23696(19) 0.0511(10) Uani 1 1 d . . . . .
O50 O 0.9397(7) 0.5659(5) 0.1431(3) 0.0944(18) Uani 1 1 d D . . . .
H51 H 0.945(14) 0.625(7) 0.114(4) 0.200 Uiso 1 1 d D U . . .
H52 H 0.956(13) 0.599(10) 0.182(2) 0.200 Uiso 1 1 d D 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
TcA O10 1.639(4) . ?
TcA N8 1.968(4) . ?
TcA N5 2.009(4) . ?
TcA N11 2.023(4) . ?
TcA S1 2.2961(14) . ?
TcB N8 1.854(11) . ?
TcB N5 2.032(11) . ?
TcB N11 2.070(11) . ?
TcB S1 2.225(11) . ?
S1 C2 1.748(5) . ?
C2 N3 1.337(6) . ?
C2 N20 1.336(6) . ?
N3 C4 1.318(6) . ?
C4 N5 1.343(6) . ?
C4 C31 1.496(7) . ?
N5 C6 1.477(6) . ?
C6 C7 1.498(7) . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?
C7 O71 1.240(6) . ?
C7 N8 1.343(7) . ?
N8 C9 1.460(6) . ?
C9 C10 1.493(7) . ?
C9 H9A 0.9700 . ?
C9 H9B 0.9700 . ?
C10 O101 1.248(6) . ?
C10 N11 1.365(6) . ?
N11 C12 1.455(6) . ?
C12 C13 1.507(7) . ?
C12 H12A 0.9700 . ?
C12 H12B 0.9700 . ?
C13 O15 1.197(6) . ?
C13 O14 1.310(6) . ?
O14 H14 0.8200 . ?
N20 C65 1.454(6) . ?
N20 C61 1.462(7) . ?
C61 C62 1.512(8) . ?
C61 H61A 0.9700 . ?
C61 H61B 0.9700 . ?
C62 O63 1.427(7) . ?
C62 H62A 0.9700 . ?
C62 H62B 0.9700 . ?
O63 C64 1.414(6) . ?
C64 C65 1.515(7) . ?
C64 H64A 0.9700 . ?
C64 H64B 0.9700 . ?
C65 H65A 0.9700 . ?
C65 H65B 0.9700 . ?
C31 C32 1.361(8) . ?
C31 C36 1.391(8) . ?
C32 C33 1.390(9) . ?
C32 H32 0.9300 . ?
C33 C34 1.364(11) . ?
C33 H33 0.9300 . ?
C34 C35 1.363(10) . ?
C34 H34 0.9300 . ?
C35 C36 1.384(8) . ?
C35 H35 0.9300 . ?
C36 H36 0.9300 . ?
O50 H51 0.845(10) . ?
O50 H52 0.845(10) . ?

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
O10 TcA N8 112.70(18) . . ?
O10 TcA N5 107.56(19) . . ?
N8 TcA N5 79.00(17) . . ?
O10 TcA N11 106.67(19) . . ?
N8 TcA N11 78.44(17) . . ?
N5 TcA N11 144.19(17) . . ?
O10 TcA S1 111.65(14) . . ?
N8 TcA S1 135.59(13) . . ?
N5 TcA S1 90.10(12) . . ?
N11 TcA S1 86.91(12) . . ?
N8 TcB N5 81.1(4) . . ?
N8 TcB N11 79.9(4) . . ?
N5 TcB N11 138.6(4) . . ?
N8 TcB S1 150.9(4) . . ?
N5 TcB S1 91.6(4) . . ?
N11 TcB S1 87.7(4) . . ?
C2 S1 TcB 102.9(3) . . ?
C2 S1 TcA 108.23(17) . . ?
N3 C2 N20 116.2(5) . . ?
N3 C2 S1 126.8(4) . . ?
N20 C2 S1 116.8(4) . . ?
C4 N3 C2 125.2(4) . . ?
N3 C4 N5 127.4(5) . . ?
N3 C4 C31 114.0(4) . . ?
N5 C4 C31 118.6(4) . . ?
C4 N5 C6 119.9(4) . . ?
C4 N5 TcA 122.2(3) . . ?
C6 N5 TcA 113.7(3) . . ?
C4 N5 TcB 129.1(4) . . ?
C6 N5 TcB 108.1(4) . . ?
N5 C6 C7 108.9(4) . . ?
N5 C6 H6A 109.9 . . ?
C7 C6 H6A 109.9 . . ?
N5 C6 H6B 109.9 . . ?
C7 C6 H6B 109.9 . . ?
H6A C6 H6B 108.3 . . ?
O71 C7 N8 125.0(5) . . ?
O71 C7 C6 121.2(5) . . ?
N8 C7 C6 113.8(4) . . ?
C7 N8 C9 122.2(4) . . ?
C7 N8 TcB 113.9(5) . . ?
C9 N8 TcB 113.1(4) . . ?
C7 N8 TcA 118.9(3) . . ?
C9 N8 TcA 118.6(3) . . ?
N8 C9 C10 108.3(4) . . ?
N8 C9 H9A 110.0 . . ?
C10 C9 H9A 110.0 . . ?
N8 C9 H9B 110.0 . . ?
C10 C9 H9B 110.0 . . ?
H9A C9 H9B 108.4 . . ?
O101 C10 N11 122.8(5) . . ?
O101 C10 C9 122.6(4) . . ?
N11 C10 C9 114.6(4) . . ?
C10 N11 C12 115.8(4) . . ?
C10 N11 TcA 117.0(3) . . ?
C12 N11 TcA 126.5(3) . . ?
C10 N11 TcB 107.0(4) . . ?
C12 N11 TcB 128.3(4) . . ?
N11 C12 C13 116.6(4) . . ?
N11 C12 H12A 108.2 . . ?
C13 C12 H12A 108.2 . . ?
N11 C12 H12B 108.2 . . ?
C13 C12 H12B 108.2 . . ?
H12A C12 H12B 107.3 . . ?
O15 C13 O14 123.4(5) . . ?
O15 C13 C12 121.2(5) . . ?
O14 C13 C12 115.3(5) . . ?
C13 O14 H14 109.5 . . ?
C2 N20 C65 123.9(4) . . ?
C2 N20 C61 121.3(4) . . ?
C65 N20 C61 114.0(4) . . ?
N20 C61 C62 110.6(4) . . ?
N20 C61 H61A 109.5 . . ?
C62 C61 H61A 109.5 . . ?
N20 C61 H61B 109.5 . . ?
C62 C61 H61B 109.5 . . ?
H61A C61 H61B 108.1 . . ?
O63 C62 C61 110.7(5) . . ?
O63 C62 H62A 109.5 . . ?
C61 C62 H62A 109.5 . . ?
O63 C62 H62B 109.5 . . ?
C61 C62 H62B 109.5 . . ?
H62A C62 H62B 108.1 . . ?
C64 O63 C62 108.0(4) . . ?
O63 C64 C65 112.8(4) . . ?
O63 C64 H64A 109.0 . . ?
C65 C64 H64A 109.0 . . ?
O63 C64 H64B 109.0 . . ?
C65 C64 H64B 109.0 . . ?
H64A C64 H64B 107.8 . . ?
N20 C65 C64 110.7(4) . . ?
N20 C65 H65A 109.5 . . ?
C64 C65 H65A 109.5 . . ?
N20 C65 H65B 109.5 . . ?
C64 C65 H65B 109.5 . . ?
H65A C65 H65B 108.1 . . ?
C32 C31 C36 119.8(5) . . ?
C32 C31 C4 122.7(5) . . ?
C36 C31 C4 117.4(5) . . ?
C31 C32 C33 120.1(7) . . ?
C31 C32 H32 120.0 . . ?
C33 C32 H32 120.0 . . ?
C34 C33 C32 119.5(7) . . ?
C34 C33 H33 120.2 . . ?
C32 C33 H33 120.2 . . ?
C33 C34 C35 121.3(6) . . ?
C33 C34 H34 119.4 . . ?
C35 C34 H34 119.4 . . ?
C34 C35 C36 119.3(7) . . ?
C34 C35 H35 120.3 . . ?
C36 C35 H35 120.3 . . ?
C35 C36 C31 119.9(6) . . ?
C35 C36 H36 120.1 . . ?
C31 C36 H36 120.1 . . ?
H51 O50 H52 106(3) . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O50 H51 O71 0.845(10) 2.15(5) 2.920(7) 151(10) 3_766
O50 H52 O101 0.845(10) 2.15(5) 2.953(6) 158(13) 2_756
O14 H14 O101 0.82 1.81 2.626(5) 171.1 2_747

_refine_diff_density_max         0.819
_refine_diff_density_min         -0.956
_refine_diff_density_rms         0.114

####################################################################### 
# 
# 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_TcOEt
_database_code_depnum_ccdc_archive 'CCDC 1547253'
_audit_update_record             
;
2017-05-01 deposited with the CCDC.
2017-06-22 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
'[(Z)-11-carboxy-1-diethylamino-6,9-dioxo-3-phenyl-1-thioxo-2,4,7,10-tetraazaundec-2-ene-4,7,10-triido]oxidotechnetium(V)}monohydrate; Acetone'
_chemical_name_common            JC455
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H22 N5 O5 S Tc, O1 C3 H6, O1 H2'
_chemical_formula_sum            'C21 H30 N5 O7 S Tc'
_chemical_formula_weight         594.57

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0030 0.0020 '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 0.0060 0.0030 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0110 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1250 0.1230 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Tc Tc -1.4390 0.7590 '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/n'
_space_group_name_Hall           '-P 2yn'

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

_cell_length_a                   14.654(1)
_cell_length_b                   9.687(1)
_cell_length_c                   17.806(1)
_cell_angle_alpha                90
_cell_angle_beta                 94.15(1)
_cell_angle_gamma                90
_cell_volume                     2521.0(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    13647
_cell_measurement_theta_min      3.47
_cell_measurement_theta_max      29.53

_exptl_crystal_description       needle
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.567
_exptl_crystal_F_000             1224
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.03
_exptl_absorpt_coefficient_mu    0.704
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      200(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method'
_diffrn_detector_area_resol_mean 6.67
_diffrn_reflns_number            21066
_diffrn_reflns_av_unetI/netI     0.0618
_diffrn_reflns_av_R_equivalents  0.0532
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         3.342
_diffrn_reflns_theta_max         29.307
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             6798
_reflns_number_gt                4750
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .



_computing_data_collection       'STOE X-AREA'
_computing_cell_refinement       'STOE X-AREA'
_computing_data_reduction        'STOE X-RED'
_computing_structure_solution    'SHELXS-86 (Sheldrick, 1986)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ORTEP-3
_computing_publication_material  WinGX

_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0352P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         6798
_refine_ls_number_parameters     329
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0604
_refine_ls_R_factor_gt           0.0332
_refine_ls_wR_factor_ref         0.0701
_refine_ls_wR_factor_gt          0.0649
_refine_ls_goodness_of_fit_ref   0.864
_refine_ls_restrained_S_all      0.864
_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
Tc1 Tc 0.57743(2) 0.20822(2) 0.45715(2) 0.02098(5) Uani 1 1 d . . . . .
O10 O 0.55446(13) 0.05079(18) 0.42690(10) 0.0348(4) Uani 1 1 d . . . . .
S1 S 0.65677(4) 0.32717(6) 0.37046(3) 0.02683(13) Uani 1 1 d . . . . .
C2 C 0.77232(16) 0.2812(2) 0.38840(12) 0.0250(5) Uani 1 1 d . . . . .
N3 N 0.81375(14) 0.2660(2) 0.45677(11) 0.0274(4) Uani 1 1 d . . . . .
C4 C 0.77544(16) 0.2466(2) 0.52113(13) 0.0231(5) Uani 1 1 d . . . . .
N5 N 0.69231(13) 0.1970(2) 0.52947(10) 0.0243(4) Uani 1 1 d . . . . .
C6 C 0.66746(17) 0.1531(3) 0.60462(13) 0.0280(5) Uani 1 1 d . . . . .
H6A H 0.7130 0.1855 0.6428 0.034 Uiso 1 1 calc R U . . .
H6B H 0.6654 0.0531 0.6071 0.034 Uiso 1 1 calc R U . . .
C7 C 0.57527(15) 0.2119(3) 0.61898(12) 0.0248(4) Uani 1 1 d . . . . .
N8 N 0.52665(13) 0.2474(2) 0.55458(10) 0.0233(4) Uani 1 1 d . . . . .
C9 C 0.43693(15) 0.3111(3) 0.55586(13) 0.0267(5) Uani 1 1 d . . . . .
H9A H 0.4382 0.3835 0.5936 0.032 Uiso 1 1 calc R U . . .
H9B H 0.3918 0.2429 0.5680 0.032 Uiso 1 1 calc R U . . .
C10 C 0.41294(17) 0.3706(3) 0.47897(14) 0.0273(5) Uani 1 1 d . . . . .
N11 N 0.47113(13) 0.3320(2) 0.42576(11) 0.0249(4) Uani 1 1 d . . . . .
C12 C 0.44440(17) 0.3861(3) 0.35065(13) 0.0295(5) Uani 1 1 d . . . . .
H12A H 0.4911 0.3616 0.3171 0.035 Uiso 1 1 calc R U . . .
H12B H 0.4421 0.4861 0.3533 0.035 Uiso 1 1 calc R U . . .
C13 C 0.35306(17) 0.3338(2) 0.31733(13) 0.0251(5) Uani 1 1 d . . . . .
O14 O 0.32322(12) 0.22091(19) 0.34742(10) 0.0328(4) Uani 1 1 d . . . . .
H14 H 0.2731 0.2006 0.3269 0.049 Uiso 1 1 calc R U . . .
O15 O 0.31264(13) 0.39243(19) 0.26441(10) 0.0345(4) Uani 1 1 d . . . . .
N20 N 0.82386(14) 0.2728(2) 0.32985(11) 0.0285(4) Uani 1 1 d . . . . .
C61 C 0.92228(18) 0.2399(3) 0.34142(15) 0.0397(7) Uani 1 1 d . . . . .
H61A H 0.9461 0.2758 0.3898 0.048 Uiso 1 1 calc R U . . .
H61B H 0.9549 0.2846 0.3026 0.048 Uiso 1 1 calc R U . . .
C62 C 0.9388(2) 0.0870(4) 0.3390(2) 0.0675(11) Uani 1 1 d . . . . .
H62A H 0.9087 0.0430 0.3787 0.101 Uiso 1 1 calc R U . . .
H62B H 1.0033 0.0691 0.3454 0.101 Uiso 1 1 calc R U . . .
H62C H 0.9148 0.0511 0.2913 0.101 Uiso 1 1 calc R U . . .
C64 C 0.8042(3) 0.4478(4) 0.2293(2) 0.0572(9) Uani 1 1 d . . . . .
H64A H 0.7766 0.5079 0.2640 0.086 Uiso 1 1 calc R U . . .
H64B H 0.7766 0.4633 0.1794 0.086 Uiso 1 1 calc R U . . .
H64C H 0.8686 0.4665 0.2302 0.086 Uiso 1 1 calc R U . . .
C65 C 0.78950(17) 0.2996(3) 0.25152(12) 0.0309(5) Uani 1 1 d . . . . .
H65A H 0.7247 0.2785 0.2457 0.037 Uiso 1 1 calc R U . . .
H65B H 0.8207 0.2393 0.2182 0.037 Uiso 1 1 calc R U . . .
C31 C 0.83868(15) 0.2849(3) 0.58786(12) 0.0251(4) Uani 1 1 d . . . . .
C32 C 0.92459(18) 0.2261(3) 0.59970(15) 0.0381(6) Uani 1 1 d . . . . .
H32 H 0.9424 0.1566 0.5678 0.046 Uiso 1 1 calc R U . . .
C33 C 0.98412(19) 0.2700(4) 0.65880(17) 0.0478(8) Uani 1 1 d . . . . .
H33 H 1.0412 0.2285 0.6674 0.057 Uiso 1 1 calc R U . . .
C34 C 0.9586(2) 0.3757(3) 0.70506(16) 0.0451(7) Uani 1 1 d . . . . .
H34 H 0.9989 0.4059 0.7444 0.054 Uiso 1 1 calc R U . . .
C35 C 0.8740(2) 0.4361(3) 0.69313(16) 0.0397(7) Uani 1 1 d . . . . .
H35 H 0.8575 0.5080 0.7239 0.048 Uiso 1 1 calc R U . . .
C36 C 0.81334(19) 0.3899(3) 0.63527(14) 0.0333(6) Uani 1 1 d . . . . .
H36 H 0.7555 0.4293 0.6281 0.040 Uiso 1 1 calc R U . . .
O71 O 0.54765(12) 0.2247(2) 0.68260(9) 0.0328(4) Uani 1 1 d . . . . .
O101 O 0.34661(13) 0.4463(2) 0.46575(11) 0.0401(5) Uani 1 1 d . . . . .
O50 O 0.83701(14) 0.8522(2) 0.70551(11) 0.0366(4) Uani 1 1 d D . . . .
H50A H 0.833(3) 0.932(2) 0.722(2) 0.086(15) Uiso 1 1 d D . . . .
H50B H 0.863(2) 0.797(3) 0.7370(16) 0.062(11) Uiso 1 1 d D . . . .
O90 O 0.7067(2) 0.2264(5) 0.09930(15) 0.1137(14) Uani 1 1 d . . . . .
C91 C 0.6726(2) 0.2372(4) 0.03785(18) 0.0597(10) Uani 1 1 d . . . . .
C92 C 0.6830(6) 0.3610(7) -0.0070(3) 0.154(3) Uani 1 1 d . . . . .
H91A H 0.6239 0.4006 -0.0200 0.230 Uiso 1 1 calc R U . . .
H92B H 0.7116 0.3375 -0.0521 0.230 Uiso 1 1 calc R U . . .
H92C H 0.7204 0.4265 0.0216 0.230 Uiso 1 1 calc R U . . .
C93 C 0.6181(4) 0.1232(6) 0.0027(3) 0.116(2) Uani 1 1 d . . . . .
H93A H 0.6246 0.0427 0.0341 0.174 Uiso 1 1 calc R U . . .
H93B H 0.6394 0.1030 -0.0458 0.174 Uiso 1 1 calc R U . . .
H93C H 0.5549 0.1498 -0.0030 0.174 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
Tc1 O10 1.6440(17) . ?
Tc1 N8 1.9734(19) . ?
Tc1 N11 2.013(2) . ?
Tc1 N5 2.0470(19) . ?
Tc1 S1 2.3069(6) . ?
S1 C2 1.758(2) . ?
C2 N3 1.329(3) . ?
C2 N20 1.333(3) . ?
N3 C4 1.325(3) . ?
C4 N5 1.328(3) . ?
C4 C31 1.500(3) . ?
N5 C6 1.475(3) . ?
C6 C7 1.505(3) . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?
C7 O71 1.236(3) . ?
C7 N8 1.350(3) . ?
N8 C9 1.454(3) . ?
C9 C10 1.503(3) . ?
C9 H9A 0.9700 . ?
C9 H9B 0.9700 . ?
C10 O101 1.227(3) . ?
C10 N11 1.372(3) . ?
N11 C12 1.463(3) . ?
C12 C13 1.512(3) . ?
C12 H12A 0.9700 . ?
C12 H12B 0.9700 . ?
C13 O15 1.217(3) . ?
C13 O14 1.307(3) . ?
O14 H14 0.8200 . ?
N20 C65 1.471(3) . ?
N20 C61 1.477(3) . ?
C61 C62 1.502(5) . ?
C61 H61A 0.9700 . ?
C61 H61B 0.9700 . ?
C62 H62A 0.9600 . ?
C62 H62B 0.9600 . ?
C62 H62C 0.9600 . ?
C64 C65 1.509(4) . ?
C64 H64A 0.9600 . ?
C64 H64B 0.9600 . ?
C64 H64C 0.9600 . ?
C65 H65A 0.9700 . ?
C65 H65B 0.9700 . ?
C31 C32 1.384(3) . ?
C31 C36 1.389(4) . ?
C32 C33 1.384(4) . ?
C32 H32 0.9300 . ?
C33 C34 1.382(5) . ?
C33 H33 0.9300 . ?
C34 C35 1.373(4) . ?
C34 H34 0.9300 . ?
C35 C36 1.385(4) . ?
C35 H35 0.9300 . ?
C36 H36 0.9300 . ?
O50 H50A 0.831(18) . ?
O50 H50B 0.842(18) . ?
O90 C91 1.174(4) . ?
C91 C92 1.454(7) . ?
C91 C93 1.475(6) . ?
C92 H91A 0.9600 . ?
C92 H92B 0.9600 . ?
C92 H92C 0.9600 . ?
C93 H93A 0.9600 . ?
C93 H93B 0.9600 . ?
C93 H93C 0.9600 . ?

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
O10 Tc1 N8 112.65(8) . . ?
O10 Tc1 N11 109.01(9) . . ?
N8 Tc1 N11 78.23(8) . . ?
O10 Tc1 N5 107.23(9) . . ?
N8 Tc1 N5 78.61(8) . . ?
N11 Tc1 N5 142.29(8) . . ?
O10 Tc1 S1 110.20(7) . . ?
N8 Tc1 S1 137.10(6) . . ?
N11 Tc1 S1 86.21(6) . . ?
N5 Tc1 S1 90.93(5) . . ?
C2 S1 Tc1 106.10(8) . . ?
N3 C2 N20 117.5(2) . . ?
N3 C2 S1 124.40(17) . . ?
N20 C2 S1 117.79(17) . . ?
C4 N3 C2 127.9(2) . . ?
N3 C4 N5 126.7(2) . . ?
N3 C4 C31 111.9(2) . . ?
N5 C4 C31 121.35(19) . . ?
C4 N5 C6 119.65(19) . . ?
C4 N5 Tc1 129.02(15) . . ?
C6 N5 Tc1 109.91(14) . . ?
N5 C6 C7 109.18(18) . . ?
N5 C6 H6A 109.8 . . ?
C7 C6 H6A 109.8 . . ?
N5 C6 H6B 109.8 . . ?
C7 C6 H6B 109.8 . . ?
H6A C6 H6B 108.3 . . ?
O71 C7 N8 124.4(2) . . ?
O71 C7 C6 123.4(2) . . ?
N8 C7 C6 112.16(19) . . ?
C7 N8 C9 121.12(19) . . ?
C7 N8 Tc1 119.23(15) . . ?
C9 N8 Tc1 119.63(14) . . ?
N8 C9 C10 107.47(18) . . ?
N8 C9 H9A 110.2 . . ?
C10 C9 H9A 110.2 . . ?
N8 C9 H9B 110.2 . . ?
C10 C9 H9B 110.2 . . ?
H9A C9 H9B 108.5 . . ?
O101 C10 N11 123.6(2) . . ?
O101 C10 C9 122.2(2) . . ?
N11 C10 C9 114.1(2) . . ?
C10 N11 C12 113.3(2) . . ?
C10 N11 Tc1 118.53(16) . . ?
C12 N11 Tc1 128.16(16) . . ?
N11 C12 C13 114.2(2) . . ?
N11 C12 H12A 108.7 . . ?
C13 C12 H12A 108.7 . . ?
N11 C12 H12B 108.7 . . ?
C13 C12 H12B 108.7 . . ?
H12A C12 H12B 107.6 . . ?
O15 C13 O14 123.3(2) . . ?
O15 C13 C12 121.0(2) . . ?
O14 C13 C12 115.6(2) . . ?
C13 O14 H14 109.5 . . ?
C2 N20 C65 123.8(2) . . ?
C2 N20 C61 120.5(2) . . ?
C65 N20 C61 115.72(19) . . ?
N20 C61 C62 111.5(3) . . ?
N20 C61 H61A 109.3 . . ?
C62 C61 H61A 109.3 . . ?
N20 C61 H61B 109.3 . . ?
C62 C61 H61B 109.3 . . ?
H61A C61 H61B 108.0 . . ?
C61 C62 H62A 109.5 . . ?
C61 C62 H62B 109.5 . . ?
H62A C62 H62B 109.5 . . ?
C61 C62 H62C 109.5 . . ?
H62A C62 H62C 109.5 . . ?
H62B C62 H62C 109.5 . . ?
C65 C64 H64A 109.5 . . ?
C65 C64 H64B 109.5 . . ?
H64A C64 H64B 109.5 . . ?
C65 C64 H64C 109.5 . . ?
H64A C64 H64C 109.5 . . ?
H64B C64 H64C 109.5 . . ?
N20 C65 C64 111.8(2) . . ?
N20 C65 H65A 109.3 . . ?
C64 C65 H65A 109.3 . . ?
N20 C65 H65B 109.3 . . ?
C64 C65 H65B 109.3 . . ?
H65A C65 H65B 107.9 . . ?
C32 C31 C36 119.3(2) . . ?
C32 C31 C4 121.5(2) . . ?
C36 C31 C4 119.0(2) . . ?
C31 C32 C33 120.4(3) . . ?
C31 C32 H32 119.8 . . ?
C33 C32 H32 119.8 . . ?
C34 C33 C32 119.9(3) . . ?
C34 C33 H33 120.1 . . ?
C32 C33 H33 120.1 . . ?
C35 C34 C33 120.2(3) . . ?
C35 C34 H34 119.9 . . ?
C33 C34 H34 119.9 . . ?
C34 C35 C36 120.1(3) . . ?
C34 C35 H35 120.0 . . ?
C36 C35 H35 120.0 . . ?
C35 C36 C31 120.2(3) . . ?
C35 C36 H36 119.9 . . ?
C31 C36 H36 119.9 . . ?
H50A O50 H50B 114(3) . . ?
O90 C91 C92 122.0(5) . . ?
O90 C91 C93 120.6(5) . . ?
C92 C91 C93 117.3(5) . . ?
C91 C92 H91A 109.5 . . ?
C91 C92 H92B 109.5 . . ?
H91A C92 H92B 109.5 . . ?
C91 C92 H92C 109.5 . . ?
H91A C92 H92C 109.5 . . ?
H92B C92 H92C 109.5 . . ?
C91 C93 H93A 109.5 . . ?
C91 C93 H93B 109.5 . . ?
H93A C93 H93B 109.5 . . ?
C91 C93 H93C 109.5 . . ?
H93A C93 H93C 109.5 . . ?
H93B C93 H93C 109.5 . . ?

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
O50 H50A O15 0.831(18) 1.894(19) 2.720(3) 173(4) 4_676
O50 H50B O71 0.842(18) 2.00(2) 2.804(3) 160(3) 2_656
O14 H14 O50 0.82 1.75 2.566(3) 172.5 3_666

_refine_diff_density_max         0.484
_refine_diff_density_min         -0.757
_refine_diff_density_rms         0.077

_shelxl_version_number           2013-4

