# Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 2023

####################################################################### 
# 
# 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_wtw_20230403_02
_database_code_depnum_ccdc_archive 'CCDC 2255172'
loop_
_audit_author_name
_audit_author_address
'Tingwei Wang'
;Beijing Institute of Technology
China
;
_audit_update_record             
;
2023-06-30 deposited with the CCDC.	2023-07-06 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT230_wtw_20230403_02     
;
PROBLEM: Hirshfeld Test Diff for    N3       --C4       .       11.8 s.u.
RESPONSE: Due to the relatively poor quality of our crystal, this error has occurred. Consultation with the tester revealed that this error cannot be eliminated through the refinement of single-crystal data. However, this does not affect our interpretation of the results.
;
# Added during the CSD deposition process: Friday 30 June 2023 03:25 AM
# end Validation Reply Form

_audit_creation_date             2023-04-04
_audit_creation_method           
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        wtw_20230403_02
_chemical_formula_moiety         'C4 H6 Cu0.5 N4 O, Cl O4'
_chemical_formula_sum            'C4 H6 Cl Cu0.50 N4 O5'
_chemical_formula_weight         257.35
_chemical_melting_point          ?
_chemical_oxdiff_usercomment     'C H '
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'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   7.1701(10)
_cell_length_b                   7.7300(11)
_cell_length_c                   8.4411(13)
_cell_angle_alpha                102.371(12)
_cell_angle_beta                 101.314(12)
_cell_angle_gamma                101.956(12)
_cell_volume                     432.67(11)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    2473
_cell_measurement_temperature    172.98(10)
_cell_measurement_theta_max      76.2790
_cell_measurement_theta_min      5.6750
_shelx_estimated_absorpt_T_max   0.617
_shelx_estimated_absorpt_T_min   0.617
_exptl_absorpt_coefficient_mu    5.339
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73558
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.55a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear light blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.975
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             259
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0460
_diffrn_reflns_av_unetI/netI     0.0520
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.923
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            4102
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.923
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.841
_diffrn_reflns_theta_min         5.544
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.98(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.923
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -60.00   0.00   0.50    0.05    --  -48.26  57.00 120.00  120
  2  ω     -5.00  21.00   0.50    0.05    --  -48.26  48.00   0.00   52
  3  ω    -52.00 -11.00   0.50    0.05    --  -48.26  48.00   0.00   82
  4  ω    -18.00  11.00   0.50    0.05    --   48.26 -48.00-147.00   58
  5  ω     15.00  54.00   0.50    0.05    --   48.26 -48.00-147.00   78
  6  ω    -20.00  20.00   0.50    0.05    --   48.26 -19.00  60.00   80
  7  ω     36.00  63.00   0.50    0.20    --  106.93 -99.00  30.00   54
  8  ω     37.00  77.00   0.50    0.20    --  106.93-131.00  92.39   80
  9  ω     81.00 116.00   0.50    0.20    --  106.93-131.00  92.39   70
 10  ω     60.00  86.00   0.50    0.20    --  106.93-125.00 120.00   52
 11  ω     41.00  97.00   0.50    0.20    --  106.93-125.00 -30.00  112
 12  ω     68.00 106.00   0.50    0.20    --  106.93 -99.00 -30.00   76
 13  ω     36.00  63.00   0.50    0.20    --  106.93 -57.00 -60.00   54
 14  ω     40.00  67.00   0.50    0.20    --  106.93 -57.00   0.00   54
 15  ω     36.00  67.00   0.50    0.20    --  106.93 -57.00  60.00   62
 16  ω     40.00 107.00   0.50    0.20    --  106.93 -77.00 120.00  134
 17  ω    123.00 150.00   0.50    0.20    --  106.93  38.00  60.00   54
 18  ω     93.00 169.00   0.50    0.20    --  106.93  57.00  60.00  152
 19  ω     99.00 138.00   0.50    0.20    --  106.93  48.00   0.00   78
 20  ω    146.00 178.00   0.50    0.20    --  106.93  48.00   0.00   64
 21  ω     38.00 121.00   0.50    0.05    --   48.26  48.00   0.00  166
 22  ω   -126.00-100.00   0.50    0.20    -- -104.00 145.00-146.78   52
 23  ω   -105.00 -32.00   0.50    0.20    -- -104.00 125.00-150.00  146
 24  ω   -106.00 -80.00   0.50    0.20    -- -104.00 125.00  90.00   52
 25  ω   -109.00 -84.00   0.50    0.20    -- -104.00 118.00 139.18   50
 26  ω    -57.00 -32.00   0.50    0.20    -- -104.00 118.00 139.18   50
 27  ω    -57.00 -32.00   0.50    0.20    -- -104.00 125.00  90.00   50
 28  ω    -61.00 -35.00   0.50    0.20    -- -104.00  57.00 -90.00   52
 29  ω    -61.00 -33.00   0.50    0.20    -- -104.00  57.00-150.00   56
 30  ω    -64.00 -39.00   0.50    0.20    -- -104.00  57.00-180.00   50
 31  ω   -169.00-144.00   0.50    0.20    -- -104.00 -48.00-147.00   50
 32  ω   -164.00 -95.00   0.50    0.20    -- -104.00 -57.00-180.00  138
 33  ω   -128.00-102.00   0.50    0.20    -- -104.00 -48.00-147.00   52
 34  ω   -119.00 -58.00   0.50    0.05    --  -48.26 -48.00-147.00  122
 35  ω   -175.00-101.00   0.50    0.20    -- -104.00 -57.00 -30.00  148
 36  ω   -119.00 -93.00   0.50    0.05    --  -48.26-125.00 150.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0837577000
_diffrn_orient_matrix_UB_12      0.1612654000
_diffrn_orient_matrix_UB_13      -0.0312825000
_diffrn_orient_matrix_UB_21      -0.1423826000
_diffrn_orient_matrix_UB_22      -0.0397181000
_diffrn_orient_matrix_UB_23      0.1105171000
_diffrn_orient_matrix_UB_31      0.1555946000
_diffrn_orient_matrix_UB_32      0.1306473000
_diffrn_orient_matrix_UB_33      0.1551800000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1449
_reflns_number_total             1703
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    ?
_refine_diff_density_max         1.303
_refine_diff_density_min         -0.995
_refine_diff_density_rms         0.163
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.114
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     133
_refine_ls_number_reflns         1703
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.0705
_refine_ls_R_factor_gt           0.0604
_refine_ls_restrained_S_all      1.117
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1381P)²+0.3037P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1823
_refine_ls_wR_factor_ref         0.1959
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All N(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(N3) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
3.a Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B)
3.b Aromatic/amide H refined with riding coordinates:
 C4(H4), N2(H2), C1(H1), N3(H3)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.000000 0.500000 0.500000 0.0228(3) Uani 1 2 d S . P . .
Cl1 Cl 0.14432(13) 0.10065(13) 0.32439(11) 0.0257(3) Uani 1 1 d . . . . .
O1 O 0.0897(4) 0.5286(4) 0.7412(3) 0.0262(7) Uani 1 1 d . . . . .
O2 O 0.1870(6) 0.2652(5) 0.4589(4) 0.0511(10) Uani 1 1 d . . . . .
C4 C 0.5661(5) 0.7483(5) 1.2223(4) 0.0172(7) Uani 1 1 d . U . . .
H4 H 0.680585 0.810914 1.310337 0.021 Uiso 1 1 calc R U . . .
N2 N 0.3586(5) 0.7134(5) 0.7080(4) 0.0252(7) Uani 1 1 d . . . . .
H2 H 0.479404 0.784223 0.749088 0.030 Uiso 1 1 calc R U . . .
O3 O 0.2042(6) 0.1486(7) 0.1856(5) 0.0556(11) Uani 1 1 d . . . . .
N1 N 0.2573(5) 0.6811(5) 0.5371(4) 0.0226(7) Uani 1 1 d . . . . .
H1A H 0.328637 0.635547 0.468088 0.027 Uiso 1 1 calc R U . . .
H1B H 0.237558 0.787379 0.515811 0.027 Uiso 1 1 calc R U . . .
N4 N 0.4120(5) 0.6226(5) 1.2401(4) 0.0273(8) Uani 1 1 d . . . . .
O5 O 0.2605(9) -0.0104(7) 0.3864(6) 0.0656(13) Uani 1 1 d . . . . .
C2 C 0.3586(6) 0.6619(6) 0.9796(5) 0.0244(8) Uani 1 1 d . . . . .
O4 O -0.0600(6) 0.0194(7) 0.2806(5) 0.0661(14) Uani 1 1 d . . . . .
C1 C 0.2857(6) 0.5724(6) 1.0904(5) 0.0269(9) Uani 1 1 d . . . . .
H1 H 0.160947 0.486143 1.062223 0.032 Uiso 1 1 calc R U . . .
N3 N 0.5402(6) 0.7741(6) 1.0703(5) 0.0349(9) Uani 1 1 d . U . . .
H3 H 0.622782 0.848225 1.034414 0.042 Uiso 1 1 calc R U . . .
C3 C 0.2614(5) 0.6310(5) 0.8028(4) 0.0215(8) 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
Cu1 O1 1.960(2) . ?
Cu1 O1 1.960(2) 2_566 ?
Cu1 N1 1.994(3) 2_566 ?
Cu1 N1 1.994(3) . ?
Cl1 O2 1.444(4) . ?
Cl1 O3 1.418(4) . ?
Cl1 O5 1.423(4) . ?
Cl1 O4 1.409(4) . ?
O1 C3 1.258(5) . ?
C4 H4 0.9500 . ?
C4 N4 1.368(5) . ?
C4 N3 1.324(5) . ?
N2 H2 0.8800 . ?
N2 N1 1.425(4) . ?
N2 C3 1.337(5) . ?
N1 H1A 0.9100 . ?
N1 H1B 0.9100 . ?
N4 C1 1.328(5) . ?
C2 C1 1.395(6) . ?
C2 N3 1.375(6) . ?
C2 C3 1.462(5) . ?
C1 H1 0.9500 . ?
N3 H3 0.8800 . ?

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 O1 180.0 . 2_566 ?
O1 Cu1 N1 96.75(12) 2_566 . ?
O1 Cu1 N1 83.25(12) . . ?
O1 Cu1 N1 96.75(12) . 2_566 ?
O1 Cu1 N1 83.25(12) 2_566 2_566 ?
N1 Cu1 N1 180.00(13) 2_566 . ?
O3 Cl1 O2 108.8(3) . . ?
O3 Cl1 O5 109.4(3) . . ?
O5 Cl1 O2 105.8(3) . . ?
O4 Cl1 O2 108.3(3) . . ?
O4 Cl1 O3 110.3(3) . . ?
O4 Cl1 O5 114.0(3) . . ?
C3 O1 Cu1 112.3(2) . . ?
N4 C4 H4 123.3 . . ?
N3 C4 H4 123.3 . . ?
N3 C4 N4 113.4(3) . . ?
N1 N2 H2 121.6 . . ?
C3 N2 H2 121.6 . . ?
C3 N2 N1 116.8(3) . . ?
Cu1 N1 H1A 110.4 . . ?
Cu1 N1 H1B 110.4 . . ?
N2 N1 Cu1 106.7(2) . . ?
N2 N1 H1A 110.4 . . ?
N2 N1 H1B 110.4 . . ?
H1A N1 H1B 108.6 . . ?
C1 N4 C4 103.3(3) . . ?
C1 C2 C3 125.7(4) . . ?
N3 C2 C1 105.3(3) . . ?
N3 C2 C3 129.0(4) . . ?
N4 C1 C2 111.7(4) . . ?
N4 C1 H1 124.2 . . ?
C2 C1 H1 124.2 . . ?
C4 N3 C2 106.3(4) . . ?
C4 N3 H3 126.9 . . ?
C2 N3 H3 126.9 . . ?
O1 C3 N2 120.6(3) . . ?
O1 C3 C2 120.6(3) . . ?
N2 C3 C2 118.7(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
Cu1 O1 C3 N2 3.0(5) . . . . ?
Cu1 O1 C3 C2 -176.9(3) . . . . ?
C4 N4 C1 C2 0.8(5) . . . . ?
N1 N2 C3 O1 0.8(6) . . . . ?
N1 N2 C3 C2 -179.3(3) . . . . ?
N4 C4 N3 C2 0.6(5) . . . . ?
C1 C2 N3 C4 0.0(5) . . . . ?
C1 C2 C3 O1 6.7(7) . . . . ?
C1 C2 C3 N2 -173.2(4) . . . . ?
N3 C4 N4 C1 -0.8(5) . . . . ?
N3 C2 C1 N4 -0.5(5) . . . . ?
N3 C2 C3 O1 -176.9(4) . . . . ?
N3 C2 C3 N2 3.2(7) . . . . ?
C3 N2 N1 Cu1 -4.1(4) . . . . ?
C3 C2 C1 N4 176.6(4) . . . . ?
C3 C2 N3 C4 -177.0(4) . . . . ?

_olex2_submission_original_sample_id wtw_20230403_02
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.600
_oxdiff_exptl_absorpt_empirical_full_min 0.448
