# Electronic Supplementary Material (ESI) for New Journal of Chemistry.
# This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2020

####################################################################### 
# 
# 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_thnTSC
_database_code_depnum_ccdc_archive 'CCDC 1986236'
loop_
_audit_author_name
_audit_author_address
'Nora Veronika May'
;Research Centre for Natural Sciences, Hungarian Academy of Sciences
Hungary
;
_audit_update_record             
;
2020-02-25 deposited with the CCDC.	2020-07-01 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            
"2-((1-hydroxy-5,6,7,8-tetrahydronaphthalen-2-yl)methylene)hydrazine-1-carbothioamide '"
_chemical_melting_point          ?
_chemical_formula_moiety         'C12 H15 N3 O S'
_chemical_formula_sum            'C12 H15 N3 O S'
_chemical_formula_weight         249.33

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      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                   8.8483(7)
_cell_length_b                   10.5831(7)
_cell_length_c                   13.2516(10)
_cell_angle_alpha                90
_cell_angle_beta                 102.518(7)
_cell_angle_gamma                90
_cell_volume                     1211.41(16)
_cell_formula_units_Z            4
_cell_measurement_temperature    162(2)
_cell_measurement_reflns_used    8791
_cell_measurement_theta_min      3.415
_cell_measurement_theta_max      68.350

_exptl_crystal_description       prism
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.367
_exptl_crystal_F_000             528
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_exptl_absorpt_coefficient_mu    2.272
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_max  0.960
_exptl_absorpt_correction_T_min  0.912
_exptl_absorpt_process_details   
;
  NUMABS, Numerical Absorption correction Program (T.Higashi, 2011)
;
_diffrn_ambient_temperature      162(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'Sealed Tube'
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_detector       RX
_diffrn_measurement_device       RAXIS-RAPID
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measurement_method       dtprofit.ref
_diffrn_reflns_number            10216
_diffrn_reflns_av_unetI/netI     0.0425
_diffrn_reflns_av_R_equivalents  0.0420
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         5.400
_diffrn_reflns_theta_max         68.206
_diffrn_reflns_theta_full        67.679
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measured_fraction_theta_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_point_group_measured_fraction_full 0.990
_reflns_number_total             2196
_reflns_number_gt                1878
_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       'RAPID-AUTO (Rigaku Corp., Tokyo, Japan, 2015)'
_computing_cell_refinement       'RAPID-AUTO (Rigaku Corp., Tokyo, Japan, 2015)'
_computing_data_reduction        'RAPID-AUTO (Rigaku Corp., Tokyo, Japan, 2015)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'MERCURY (Macrae et al., 2006)'
_computing_publication_material  'Spek, A.L. (2003). J.Appl.Cryst. 36,7-13.'
_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)+(0.0372P)²+1.2143P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     difmap
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2196
_refine_ls_number_parameters     173
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0557
_refine_ls_R_factor_gt           0.0452
_refine_ls_wR_factor_ref         0.1079
_refine_ls_wR_factor_gt          0.1034
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_restrained_S_all      1.059
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
S1 S 0.68954(7) -0.04140(5) 0.13257(5) 0.0317(2) Uani 1 1 d . . . . .
O1 O 0.49134(17) 0.52642(14) 0.17760(12) 0.0261(4) Uani 1 1 d . . . . .
H1O H 0.5245 0.4489 0.1770 0.039 Uiso 1 1 d R U . . .
N1 N 0.4965(2) 0.29351(17) 0.09240(14) 0.0239(4) Uani 1 1 d . . . . .
N2 N 0.5355(2) 0.16907(16) 0.08196(15) 0.0255(5) Uani 1 1 d . . . . .
H2N H 0.4801 0.1241 0.0333 0.031 Uiso 1 1 d R U . . .
N3 N 0.7446(2) 0.18480(17) 0.21750(14) 0.0274(5) Uani 1 1 d . . . . .
H3A H 0.7244 0.2638 0.2222 0.033 Uiso 1 1 calc R U . . .
H3B H 0.8225 0.1517 0.2593 0.033 Uiso 1 1 calc R U . . .
C1 C 0.3648(3) 0.5471(2) 0.09973(17) 0.0216(5) Uani 1 1 d . . . . .
C2 C 0.3144(3) 0.4574(2) 0.02235(17) 0.0226(5) Uani 1 1 d . . . . .
C3 C 0.1877(3) 0.4893(2) -0.05693(18) 0.0283(5) Uani 1 1 d . . . . .
H3 H 0.1526 0.4319 -0.1099 0.034 Uiso 1 1 calc R U . . .
C4 C 0.1149(3) 0.6030(2) -0.05780(18) 0.0299(6) Uani 1 1 d . . . . .
H4 H 0.0334 0.6231 -0.1125 0.036 Uiso 1 1 calc R U . . .
C5 C 0.1614(3) 0.6898(2) 0.02251(19) 0.0281(5) Uani 1 1 d . . . . .
C6 C 0.0729(3) 0.8117(2) 0.0224(2) 0.0377(6) Uani 1 1 d . . . . .
H6A H -0.0270 0.7935 0.0382 0.045 Uiso 1 1 calc R U . A 1
H6B H 0.0545 0.8486 -0.0461 0.045 Uiso 1 1 calc R U . A 1
C7A C 0.1610(9) 0.9100(5) 0.1029(4) 0.0400(17) Uani 0.680(13) 1 d . . P B 1
H7A1 H 0.2449 0.9473 0.0766 0.048 Uiso 0.680(13) 1 calc R U P B 1
H7A2 H 0.0906 0.9770 0.1121 0.048 Uiso 0.680(13) 1 calc R U P B 1
C8A C 0.2260(7) 0.8478(6) 0.2062(5) 0.0380(15) Uani 0.680(13) 1 d . . P B 1
H8A1 H 0.2743 0.9108 0.2561 0.046 Uiso 0.680(13) 1 calc R U P B 1
H8A2 H 0.1434 0.8077 0.2321 0.046 Uiso 0.680(13) 1 calc R U P B 1
C7B C 0.0848(15) 0.8658(12) 0.1228(8) 0.036(3) Uani 0.320(13) 1 d . . P B 2
H7B1 H 0.0408 0.8098 0.1668 0.043 Uiso 0.320(13) 1 calc R U P B 2
H7B2 H 0.0315 0.9464 0.1181 0.043 Uiso 0.320(13) 1 calc R U P B 2
C8B C 0.2581(15) 0.8831(12) 0.1651(12) 0.038(3) Uani 0.320(13) 1 d . . P B 2
H8B1 H 0.2743 0.9347 0.2270 0.046 Uiso 0.320(13) 1 calc R U P B 2
H8B2 H 0.3027 0.9271 0.1144 0.046 Uiso 0.320(13) 1 calc R U P B 2
C9 C 0.3432(3) 0.7510(2) 0.1918(2) 0.0322(6) Uani 1 1 d . . . . .
H9A H 0.3723 0.7017 0.2547 0.039 Uiso 1 1 calc R U . B 1
H9B H 0.4352 0.7944 0.1814 0.039 Uiso 1 1 calc R U . B 1
C10 C 0.2883(3) 0.6621(2) 0.10225(18) 0.0243(5) Uani 1 1 d . . . . .
C11 C 0.3817(3) 0.3334(2) 0.02217(18) 0.0253(5) Uani 1 1 d . . . . .
H11 H 0.3399 0.2789 -0.0317 0.030 Uiso 1 1 calc R U . . .
C12 C 0.6558(3) 0.1141(2) 0.14571(17) 0.0232(5) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
S1 C12 1.689(2) . ?
O1 C1 1.366(3) . ?
O1 H1O 0.8724 . ?
N1 C11 1.291(3) . ?
N1 N2 1.376(2) . ?
N2 C12 1.340(3) . ?
N2 H2N 0.8639 . ?
N3 C12 1.326(3) . ?
N3 H3A 0.8600 . ?
N3 H3B 0.8600 . ?
C1 C10 1.396(3) . ?
C1 C2 1.398(3) . ?
C2 C3 1.402(3) . ?
C2 C11 1.441(3) . ?
C3 C4 1.363(3) . ?
C3 H3 0.9300 . ?
C4 C5 1.398(3) . ?
C4 H4 0.9300 . ?
C5 C10 1.396(3) . ?
C5 C6 1.509(3) . ?
C6 C7B 1.431(9) . ?
C6 C7A 1.571(6) . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?
C7A C8A 1.516(10) . ?
C7A H7A1 0.9700 . ?
C7A H7A2 0.9700 . ?
C8A C9 1.499(5) . ?
C8A H8A1 0.9700 . ?
C8A H8A2 0.9700 . ?
C7B C8B 1.52(2) . ?
C7B H7B1 0.9700 . ?
C7B H7B2 0.9700 . ?
C8B C9 1.591(11) . ?
C8B H8B1 0.9700 . ?
C8B H8B2 0.9700 . ?
C9 C10 1.510(3) . ?
C9 H9A 0.9700 . ?
C9 H9B 0.9700 . ?
C11 H11 0.9300 . ?

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
C1 O1 H1O 111.5 . . ?
C11 N1 N2 114.58(18) . . ?
C12 N2 N1 122.29(18) . . ?
C12 N2 H2N 118.5 . . ?
N1 N2 H2N 119.2 . . ?
C12 N3 H3A 120.0 . . ?
C12 N3 H3B 120.0 . . ?
H3A N3 H3B 120.0 . . ?
O1 C1 C10 116.34(19) . . ?
O1 C1 C2 121.64(19) . . ?
C10 C1 C2 122.0(2) . . ?
C1 C2 C3 117.5(2) . . ?
C1 C2 C11 123.6(2) . . ?
C3 C2 C11 118.8(2) . . ?
C4 C3 C2 121.2(2) . . ?
C4 C3 H3 119.4 . . ?
C2 C3 H3 119.4 . . ?
C3 C4 C5 120.8(2) . . ?
C3 C4 H4 119.6 . . ?
C5 C4 H4 119.6 . . ?
C10 C5 C4 119.6(2) . . ?
C10 C5 C6 120.8(2) . . ?
C4 C5 C6 119.6(2) . . ?
C7B C6 C5 114.1(4) . . ?
C5 C6 C7A 112.6(2) . . ?
C5 C6 H6A 109.1 . . ?
C7A C6 H6A 109.1 . . ?
C5 C6 H6B 109.1 . . ?
C7A C6 H6B 109.1 . . ?
H6A C6 H6B 107.8 . . ?
C8A C7A C6 111.2(5) . . ?
C8A C7A H7A1 109.4 . . ?
C6 C7A H7A1 109.4 . . ?
C8A C7A H7A2 109.4 . . ?
C6 C7A H7A2 109.4 . . ?
H7A1 C7A H7A2 108.0 . . ?
C9 C8A C7A 108.6(6) . . ?
C9 C8A H8A1 110.0 . . ?
C7A C8A H8A1 110.0 . . ?
C9 C8A H8A2 110.0 . . ?
C7A C8A H8A2 110.0 . . ?
H8A1 C8A H8A2 108.4 . . ?
C6 C7B C8B 104.8(12) . . ?
C6 C7B H7B1 110.8 . . ?
C8B C7B H7B1 110.8 . . ?
C6 C7B H7B2 110.8 . . ?
C8B C7B H7B2 110.8 . . ?
H7B1 C7B H7B2 108.9 . . ?
C7B C8B C9 111.5(11) . . ?
C7B C8B H8B1 109.3 . . ?
C9 C8B H8B1 109.3 . . ?
C7B C8B H8B2 109.3 . . ?
C9 C8B H8B2 109.3 . . ?
H8B1 C8B H8B2 108.0 . . ?
C8A C9 C10 114.4(3) . . ?
C10 C9 C8B 108.5(5) . . ?
C8A C9 H9A 108.7 . . ?
C10 C9 H9A 108.7 . . ?
C8A C9 H9B 108.7 . . ?
C10 C9 H9B 108.7 . . ?
H9A C9 H9B 107.6 . . ?
C1 C10 C5 118.6(2) . . ?
C1 C10 C9 119.2(2) . . ?
C5 C10 C9 122.2(2) . . ?
N1 C11 C2 123.9(2) . . ?
N1 C11 H11 118.1 . . ?
C2 C11 H11 118.1 . . ?
N3 C12 N2 118.3(2) . . ?
N3 C12 S1 122.22(17) . . ?
N2 C12 S1 119.48(17) . . ?

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
C11 N1 N2 C12 177.2(2) . . . . ?
O1 C1 C2 C3 -177.2(2) . . . . ?
C10 C1 C2 C3 3.3(3) . . . . ?
O1 C1 C2 C11 5.2(4) . . . . ?
C10 C1 C2 C11 -174.3(2) . . . . ?
C1 C2 C3 C4 -0.9(4) . . . . ?
C11 C2 C3 C4 176.8(2) . . . . ?
C2 C3 C4 C5 -2.2(4) . . . . ?
C3 C4 C5 C10 2.9(4) . . . . ?
C3 C4 C5 C6 -176.5(2) . . . . ?
C10 C5 C6 C7B -24.5(8) . . . . ?
C4 C5 C6 C7B 155.0(8) . . . . ?
C10 C5 C6 C7A 13.4(5) . . . . ?
C4 C5 C6 C7A -167.1(4) . . . . ?
C5 C6 C7A C8A -45.3(7) . . . . ?
C6 C7A C8A C9 63.2(8) . . . . ?
C5 C6 C7B C8B 56.9(14) . . . . ?
C6 C7B C8B C9 -70.3(17) . . . . ?
C7A C8A C9 C10 -49.1(8) . . . . ?
C7B C8B C9 C10 46.6(15) . . . . ?
O1 C1 C10 C5 177.9(2) . . . . ?
C2 C1 C10 C5 -2.6(3) . . . . ?
O1 C1 C10 C9 -3.4(3) . . . . ?
C2 C1 C10 C9 176.2(2) . . . . ?
C4 C5 C10 C1 -0.6(4) . . . . ?
C6 C5 C10 C1 178.9(2) . . . . ?
C4 C5 C10 C9 -179.3(2) . . . . ?
C6 C5 C10 C9 0.2(4) . . . . ?
C8A C9 C10 C1 -160.5(4) . . . . ?
C8B C9 C10 C1 169.6(7) . . . . ?
C8A C9 C10 C5 18.3(5) . . . . ?
C8B C9 C10 C5 -11.7(8) . . . . ?
N2 N1 C11 C2 175.3(2) . . . . ?
C1 C2 C11 N1 -1.1(4) . . . . ?
C3 C2 C11 N1 -178.6(2) . . . . ?
N1 N2 C12 N3 -3.8(3) . . . . ?
N1 N2 C12 S1 176.17(17) . . . . ?

_refine_diff_density_max         0.320
_refine_diff_density_min         -0.202
_refine_diff_density_rms         0.052


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: acetone'
####################################################################### 
# 
# 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_[Cu(thn-TSCH-1)(Cl)]
_database_code_depnum_ccdc_archive 'CCDC 1986237'
loop_
_audit_author_name
_audit_author_address
'Nora Veronika May'
;Research Centre for Natural Sciences, Hungarian Academy of Sciences
Hungary
;
_audit_update_record             
;
2020-04-28 deposited with the CCDC.	2020-07-01 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_RINTA01_[Cu(thn-TSCH-1)(Cl)] 
;
PROBLEM: The value of Rint is greater than 0.18
RESPONSE: Small size and platelet shape crystal prevented the collection of high resolution data which resulted in a higher Rint and final R1 and wR2 values.
;
# Added during the CSD deposition process: Tuesday 28 April 2020 02:46 PM
# end Validation Reply Form


_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        
chloro-(2-((1-hydroxy-5,6,7,8-tetrahydronaphthalen-2-yl)methylene)hydrazine-1-carbothioamide)-copper(II)
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C12 H14 Cl Cu N3 O S'
_chemical_formula_sum            'C12 H14 Cl Cu N3 O S'
_chemical_formula_weight         347.31

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu -1.9646 0.5888 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_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'
'-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                   12.3620(7)
_cell_length_b                   9.1718(5)
_cell_length_c                   24.3156(13)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2756.9(3)
_cell_formula_units_Z            8
_cell_measurement_temperature    168(2)
_cell_measurement_reflns_used    21937
_cell_measurement_theta_min      3.575
_cell_measurement_theta_max      68.64

_exptl_crystal_description       platelet
_exptl_crystal_colour            blue
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'Not measured'
_exptl_crystal_density_diffrn    1.674
_exptl_crystal_F_000             1416
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.050
_exptl_absorpt_coefficient_mu    5.395
_shelx_estimated_absorpt_T_min   0.294
_shelx_estimated_absorpt_T_max   0.774
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.881749
_exptl_absorpt_correction_T_max  0.966832
_exptl_absorpt_process_details   
;
 T.Higashi, Numerical Absorption Correction, NUMABS, 2002
;
_diffrn_ambient_temperature      168(2)
_diffrn_radiation_wavelength     1.54187
_diffrn_radiation_type           CuK\a
_diffrn_source                   'Sealed Tube'
_diffrn_measurement_device_type  'Rigaku RAXIS-RAPID II'
_diffrn_radiation_detector       RX
_diffrn_measurement_method       dtprofit.ref
_diffrn_detector_area_resol_mean 10.0000
_diffrn_reflns_number            37412
_diffrn_reflns_av_unetI/netI     0.0987
_diffrn_reflns_av_R_equivalents  0.2023
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_theta_min         3.636
_diffrn_reflns_theta_max         68.244
_diffrn_reflns_theta_full        67.687
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             2513
_reflns_number_gt                1876
_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       'Crystal Clear V.1.4.1 (Rigaku/MSC, 2007)'
_computing_cell_refinement       'Crystal Clear V.1.4.1 (Rigaku/MSC, 2007)'
_computing_data_reduction        'Crystal Clear V.1.4.1 (Rigaku/MSC, 2007)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B)
2.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C3(H3), C4(H4), C11(H11)
2.c X=CH2 refined with riding coordinates:
 N3(H3A,H3B)
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0775P)²+24.3840P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     heavy
_atom_sites_solution_secondary   direct
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2513
_refine_ls_number_parameters     172
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1704
_refine_ls_R_factor_gt           0.1326
_refine_ls_wR_factor_ref         0.2774
_refine_ls_wR_factor_gt          0.2597
_refine_ls_goodness_of_fit_ref   1.260
_refine_ls_restrained_S_all      1.260
_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
Cl1 Cl 0.3714(2) 0.4484(4) 0.64218(11) 0.0485(8) Uani 1 1 d . . . . .
Cu1 Cu 0.53174(14) 0.49148(19) 0.68452(6) 0.0420(6) Uani 1 1 d . . . . .
S1 S 0.4833(3) 0.3500(3) 0.75678(11) 0.0455(8) Uani 1 1 d . . . . .
N1 N 0.6705(8) 0.5104(10) 0.7203(4) 0.039(2) Uani 1 1 d . . . . .
N2 N 0.6820(8) 0.4475(10) 0.7717(4) 0.047(3) Uani 1 1 d . . . . .
H2 H 0.743148 0.455948 0.789967 0.057 Uiso 1 1 calc R U . . .
N3 N 0.6113(9) 0.3170(12) 0.8434(4) 0.057(3) Uani 1 1 d . . . . .
H3A H 0.672981 0.329051 0.860852 0.068 Uiso 1 1 calc R U . . .
H3B H 0.558433 0.267766 0.858984 0.068 Uiso 1 1 calc R U . . .
O1 O 0.5677(6) 0.6349(8) 0.6313(3) 0.0408(19) Uani 1 1 d . . . . .
C1 C 0.6670(10) 0.6825(12) 0.6193(5) 0.040(3) Uani 1 1 d . . . . .
C2 C 0.7581(10) 0.6520(13) 0.6519(4) 0.040(3) Uani 1 1 d . . . . .
C3 C 0.8589(10) 0.7101(13) 0.6342(4) 0.043(3) Uani 1 1 d . . . . .
H3 H 0.922120 0.689507 0.655071 0.051 Uiso 1 1 calc R U . . .
C4 C 0.8677(10) 0.7956(13) 0.5877(4) 0.042(3) Uani 1 1 d . . . . .
H4 H 0.935854 0.834731 0.577351 0.050 Uiso 1 1 calc R U . . .
C5 C 0.7782(9) 0.8238(11) 0.5566(4) 0.032(2) Uani 1 1 d . . . . .
C6 C 0.7924(10) 0.9139(13) 0.5050(4) 0.043(3) Uani 1 1 d . . . . .
H6A H 0.825745 0.852156 0.476195 0.051 Uiso 1 1 calc R U . . .
H6B H 0.843032 0.994886 0.512880 0.051 Uiso 1 1 calc R U . . .
C7 C 0.6877(11) 0.9771(14) 0.4827(5) 0.048(3) Uani 1 1 d . . . . .
H7A H 0.661471 1.055325 0.507432 0.058 Uiso 1 1 calc R U . . .
H7B H 0.700169 1.019714 0.445880 0.058 Uiso 1 1 calc R U . . .
C8 C 0.6039(10) 0.8567(14) 0.4790(4) 0.049(3) Uani 1 1 d . . . . .
H8A H 0.631917 0.776402 0.455864 0.059 Uiso 1 1 calc R U . . .
H8B H 0.537221 0.894885 0.461673 0.059 Uiso 1 1 calc R U . . .
C9 C 0.5778(9) 0.7991(13) 0.5364(5) 0.043(3) Uani 1 1 d . . . . .
H9A H 0.530540 0.869876 0.555549 0.051 Uiso 1 1 calc R U . . .
H9B H 0.537490 0.706247 0.532971 0.051 Uiso 1 1 calc R U . . .
C10 C 0.6767(9) 0.7741(11) 0.5700(4) 0.033(3) Uani 1 1 d . . . . .
C11 C 0.7540(10) 0.5736(13) 0.7014(4) 0.038(3) Uani 1 1 d . . . . .
H11 H 0.818639 0.567453 0.722449 0.046 Uiso 1 1 calc R U . . .
C12 C 0.5979(10) 0.3731(12) 0.7935(5) 0.042(3) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cl1 Cu1 2.268(3) . ?
Cu1 O1 1.898(8) . ?
Cu1 N1 1.931(10) . ?
Cu1 S1 2.265(3) . ?
S1 C12 1.689(12) . ?
N1 C11 1.270(13) . ?
N1 N2 1.384(12) . ?
N2 C12 1.352(15) . ?
N2 H2 0.8800 . ?
N3 C12 1.328(14) . ?
N3 H3A 0.8800 . ?
N3 H3B 0.8800 . ?
O1 C1 1.335(13) . ?
C1 C2 1.405(15) . ?
C1 C10 1.470(15) . ?
C2 C11 1.404(14) . ?
C2 C3 1.421(15) . ?
C3 C4 1.381(15) . ?
C3 H3 0.9500 . ?
C4 C5 1.365(15) . ?
C4 H4 0.9500 . ?
C5 C10 1.374(15) . ?
C5 C6 1.512(14) . ?
C6 C7 1.518(16) . ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
C7 C8 1.517(17) . ?
C7 H7A 0.9900 . ?
C7 H7B 0.9900 . ?
C8 C9 1.526(15) . ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
C9 C10 1.488(15) . ?
C9 H9A 0.9900 . ?
C9 H9B 0.9900 . ?
C11 H11 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
O1 Cu1 N1 92.1(4) . . ?
O1 Cu1 S1 171.1(3) . . ?
N1 Cu1 S1 86.4(3) . . ?
O1 Cu1 Cl1 90.9(2) . . ?
N1 Cu1 Cl1 175.1(3) . . ?
S1 Cu1 Cl1 91.21(13) . . ?
C12 S1 Cu1 96.7(4) . . ?
C11 N1 N2 115.7(9) . . ?
C11 N1 Cu1 126.9(8) . . ?
N2 N1 Cu1 117.4(7) . . ?
C12 N2 N1 119.1(10) . . ?
C12 N2 H2 120.5 . . ?
N1 N2 H2 120.5 . . ?
C12 N3 H3A 120.0 . . ?
C12 N3 H3B 120.0 . . ?
H3A N3 H3B 120.0 . . ?
C1 O1 Cu1 126.2(7) . . ?
O1 C1 C2 123.3(10) . . ?
O1 C1 C10 116.1(10) . . ?
C2 C1 C10 120.6(11) . . ?
C11 C2 C1 123.8(11) . . ?
C11 C2 C3 118.8(11) . . ?
C1 C2 C3 117.3(10) . . ?
C4 C3 C2 121.9(11) . . ?
C4 C3 H3 119.0 . . ?
C2 C3 H3 119.0 . . ?
C5 C4 C3 119.9(11) . . ?
C5 C4 H4 120.0 . . ?
C3 C4 H4 120.0 . . ?
C4 C5 C10 123.0(10) . . ?
C4 C5 C6 118.0(10) . . ?
C10 C5 C6 119.0(10) . . ?
C5 C6 C7 113.9(10) . . ?
C5 C6 H6A 108.8 . . ?
C7 C6 H6A 108.8 . . ?
C5 C6 H6B 108.8 . . ?
C7 C6 H6B 108.8 . . ?
H6A C6 H6B 107.7 . . ?
C8 C7 C6 109.0(10) . . ?
C8 C7 H7A 109.9 . . ?
C6 C7 H7A 109.9 . . ?
C8 C7 H7B 109.9 . . ?
C6 C7 H7B 109.9 . . ?
H7A C7 H7B 108.3 . . ?
C7 C8 C9 110.0(10) . . ?
C7 C8 H8A 109.7 . . ?
C9 C8 H8A 109.7 . . ?
C7 C8 H8B 109.7 . . ?
C9 C8 H8B 109.7 . . ?
H8A C8 H8B 108.2 . . ?
C10 C9 C8 112.4(10) . . ?
C10 C9 H9A 109.1 . . ?
C8 C9 H9A 109.1 . . ?
C10 C9 H9B 109.1 . . ?
C8 C9 H9B 109.1 . . ?
H9A C9 H9B 107.9 . . ?
C5 C10 C1 117.3(10) . . ?
C5 C10 C9 124.7(9) . . ?
C1 C10 C9 118.0(10) . . ?
N1 C11 C2 125.0(11) . . ?
N1 C11 H11 117.5 . . ?
C2 C11 H11 117.5 . . ?
N3 C12 N2 117.3(11) . . ?
N3 C12 S1 122.6(10) . . ?
N2 C12 S1 120.1(9) . . ?

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
C11 N1 N2 C12 -177.3(11) . . . . ?
Cu1 N1 N2 C12 2.0(13) . . . . ?
N1 Cu1 O1 C1 17.3(9) . . . . ?
Cl1 Cu1 O1 C1 -158.8(8) . . . . ?
Cu1 O1 C1 C2 -12.3(15) . . . . ?
Cu1 O1 C1 C10 169.3(7) . . . . ?
O1 C1 C2 C11 -2.7(18) . . . . ?
C10 C1 C2 C11 175.6(10) . . . . ?
O1 C1 C2 C3 -179.8(10) . . . . ?
C10 C1 C2 C3 -1.5(16) . . . . ?
C11 C2 C3 C4 -176.0(11) . . . . ?
C1 C2 C3 C4 1.2(17) . . . . ?
C2 C3 C4 C5 -1.4(17) . . . . ?
C3 C4 C5 C10 1.9(17) . . . . ?
C3 C4 C5 C6 -178.0(10) . . . . ?
C4 C5 C6 C7 -162.7(10) . . . . ?
C10 C5 C6 C7 17.4(14) . . . . ?
C5 C6 C7 C8 -49.7(13) . . . . ?
C6 C7 C8 C9 64.0(13) . . . . ?
C7 C8 C9 C10 -45.2(14) . . . . ?
C4 C5 C10 C1 -2.1(16) . . . . ?
C6 C5 C10 C1 177.8(9) . . . . ?
C4 C5 C10 C9 -178.2(11) . . . . ?
C6 C5 C10 C9 1.6(16) . . . . ?
O1 C1 C10 C5 -179.6(9) . . . . ?
C2 C1 C10 C5 1.9(15) . . . . ?
O1 C1 C10 C9 -3.2(14) . . . . ?
C2 C1 C10 C9 178.3(10) . . . . ?
C8 C9 C10 C5 12.7(16) . . . . ?
C8 C9 C10 C1 -163.4(10) . . . . ?
N2 N1 C11 C2 -175.8(11) . . . . ?
Cu1 N1 C11 C2 5.0(18) . . . . ?
C1 C2 C11 N1 6.6(19) . . . . ?
C3 C2 C11 N1 -176.4(11) . . . . ?
N1 N2 C12 N3 -178.6(10) . . . . ?
N1 N2 C12 S1 3.2(15) . . . . ?
Cu1 S1 C12 N3 176.4(10) . . . . ?
Cu1 S1 C12 N2 -5.6(10) . . . . ?

_refine_diff_density_max         0.982
_refine_diff_density_min         -0.487
_refine_diff_density_rms         0.150

