# Supplementary Information (SI) for Chemical Communications.
# This journal is © The Royal Society of Chemistry 2025

####################################################################### 
# 
# 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_Cu4I4(Pip)2
_database_code_depnum_ccdc_archive 'CCDC 2394021'
loop_
_audit_author_name
_audit_author_address
'Bishnu P. Biswal'
;NISER Bhubaneswar
India
;
_audit_update_record             
;
2024-10-26 deposited with the CCDC.	2025-01-08 downloaded from the CCDC.
;
_audit_creation_date             2024-09-26
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_chemical_formula_moiety         'C2 H5 Cu I N'
_chemical_formula_sum            'C2 H5 Cu I N'
_chemical_formula_weight         233.52
_chemical_absolute_configuration unk
_chemical_oxdiff_formula         'C H N I Cu'
loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
_atom_type_scat_dispersion_source
I -0.19206 6.94430 20.14720 18.99490 7.51380 2.27350 4.34700 0.38140 27.76600
66.87760 4.07119989395
'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
H 0.00000 0.00000 0.49300 0.32291 0.14019 0.04081 10.51090 26.12570 3.14236
57.79970 0.0030380000826
'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
C 0.01920 0.00962 2.31000 1.02000 1.58860 0.86500 20.84390 10.20750 0.56870
51.65120 0.215599998832
'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
Cu -1.96878 0.60861 13.33800 7.16760 5.61580 1.67350 3.58280 0.24700 11.39660
64.81260 1.19099998474
'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
N 0.03256 0.01839 12.21260 3.13220 2.01250 1.16630 0.00570 9.89330 28.99750
0.58260 -11.5290002823
'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'

_space_group_crystal_system      hexagonal
_space_group_IT_number           180
_space_group_name_H-M_alt        'P 62 2 2'
_space_group_name_Hall           ' P 62 2 (x,y,z+1/3)'
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 x,y,z
2 x-y,x,z+1/3
3 y,-x+y,z+2/3
4 -y,x-y,z+2/3
5 -x+y,-x,z+1/3
6 x-y,-y,-z
7 -x,-x+y,-z+1/3
8 -x,-y,z
9 y,x,-z+2/3
10 -y,-x,-z+2/3
11 -x+y,y,-z
12 x,x-y,-z+1/3

_symmetry_Int_Tables_number      180
_cell_length_a                   17.5937(5)
_cell_length_b                   17.5937(5)
_cell_length_c                   7.3368(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     1966.76(10)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    7466
_cell_measurement_temperature    113(19)
_cell_measurement_theta_max      77.5420
_cell_measurement_theta_min      5.7740
_exptl_absorpt_coefficient_mu    40.597
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.02605
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colorless'
_exptl_crystal_density_diffrn    2.3658
_exptl_crystal_description       block
_exptl_crystal_F_000             1249.9958
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_diffrn_reflns_av_R_equivalents  0.0726
_diffrn_reflns_av_unetI/netI     0.0324
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       4
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            7796
_diffrn_reflns_theta_full        77.7445
_diffrn_reflns_theta_max         77.74
_diffrn_reflns_theta_min         5.03
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      113(19)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.9753
_diffrn_measured_fraction_theta_max 0.9753
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω   -104.00 -33.00   0.50    0.86    --  -38.50 150.00 119.00  142
  2  ω    -46.00 -17.00   0.50    0.86    --  -38.50 122.00 -42.00   58
  3  ω     40.00 116.00   0.50    0.86    --   49.56-150.00  74.00  152
  4  ω    102.00 160.00   0.50    3.47    --  107.46 150.00 119.00  116
  5  ω    103.00 158.00   0.50    3.47    --  107.46 122.00 -42.00  110
  6  ω    -41.00  27.00   0.50    0.86    --  -38.50  37.00-180.00  136
  7  ω     40.00 110.00   0.50    3.47    --  107.46 -30.00   0.00  140
  8  ω     43.00  96.00   0.50    3.47    --  107.46 -94.00  30.00  106
  9  ω     72.00 106.00   0.50    3.47    --  107.46 -94.00  60.00   68
 10  ω    127.00 164.00   0.50    3.47    --  107.46  77.00 -60.00   74
 11  ω     81.00 107.00   0.50    3.47    --  107.46-122.00-123.00   52
 12  ω    103.00 172.00   0.50    3.47    --  107.46  45.00 150.00  138
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0134627000
_diffrn_orient_matrix_UB_12      -0.0800225000
_diffrn_orient_matrix_UB_13      0.0030069000
_diffrn_orient_matrix_UB_21      -0.0997343000
_diffrn_orient_matrix_UB_22      -0.0613676000
_diffrn_orient_matrix_UB_23      0.0213661000
_diffrn_orient_matrix_UB_31      -0.0100457000
_diffrn_orient_matrix_UB_32      -0.0074741000
_diffrn_orient_matrix_UB_33      -0.2088422000
_diffrn_oxdiff_digest_frames     
;
012250d15385701d61bc02500d0e734c2b0002735b2
;
_diffrn_oxdiff_digest_hkl        
;
012ca85d6f6c17fe1cf3cc57e1dfa6dfc53926
;
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_reflns_Friedel_coverage         0.965
_reflns_limit_h_max              19
_reflns_limit_h_min              -18
_reflns_limit_k_max              11
_reflns_limit_k_min              -10
_reflns_limit_l_max              8
_reflns_limit_l_min              -8
_reflns_number_gt                1380
_reflns_number_total             1384
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_reflns_threshold_expression     I>=2u(I)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_refine_diff_density_max         2.2598
_refine_diff_density_min         -2.0084
_refine_diff_density_rms         0.4456
_refine_ls_abs_structure_details 
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   0.032(15)
_refine_ls_d_res_high            0.7889
_refine_ls_d_res_low             8.7968
_refine_ls_goodness_of_fit_ref   1.0015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    8
_refine_ls_number_parameters     46
_refine_ls_number_reflns         1384
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0551
_refine_ls_R_factor_gt           0.0539
_refine_ls_restrained_S_all      1.0015
_refine_ls_shift/su_max          0.0002
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1331P)²+34.7206P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1601
_refine_ls_wR_factor_ref         0.1631
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups
2.a Ternary CH refined with riding coordinates:
 N3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5a,H5b), C4(H4a,H4b)
;
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_refinement_flags_posn
I1 I 0.44893(4) 1.09600(4) 0.71131(9) 0.0084(3) Uani 1.000000 .
Cu2 Cu 0.41754(10) 0.93688(10) 0.6301(2) 0.0090(4) Uani 1.000000 .
N3 N 0.3186(6) 0.8454(6) 0.7878(14) 0.0100(18) Uani 1.000000 .
H3 H 0.3366(6) 0.8626(6) 0.9073(14) 0.012(2) Uiso 1.000000 R
C5 C 0.3092(7) 0.7579(7) 0.7716(17) 0.012(2) Uani 1.000000 .
H5a H 0.2934(7) 0.7375(7) 0.6441(17) 0.015(3) Uiso 1.000000 R
H5b H 0.3666(7) 0.7627(7) 0.7977(17) 0.015(3) Uiso 1.000000 R
C4 C 0.2315(7) 0.8385(7) 0.7744(18) 0.014(2) Uani 1.000000 .
H4a H 0.2377(7) 0.8958(7) 0.8082(18) 0.017(3) Uiso 1.000000 R
H4b H 0.2119(7) 0.8267(7) 0.6459(18) 0.017(3) Uiso 1.000000 R


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
I1 Cu2 2.6365(18) . ?
I1 Cu2 2.6914(18) 6_676 ?
I1 Cu2 2.7510(18) 8_675 ?
Cu2 Cu2 2.710(3) 6_676 ?
Cu2 Cu2 2.628(3) 8_675 ?
Cu2 Cu2 2.618(3) 11_556 ?
Cu2 N3 2.040(9) . ?
N3 H3 0.9300 . ?
N3 C5 1.467(13) . ?
N3 C4 1.479(14) . ?
C5 C5 1.49(2) 10_666 ?
C5 H5a 0.9900 . ?
C5 H5b 0.9900 . ?
C4 C4 1.50(2) 10_666 ?
C4 H4a 0.9900 . ?
C4 H4b 0.9900 . ?

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
Cu2 Cu2 I1 106.37(3) 6_676 8_675 ?
Cu2 Cu2 I1 63.00(6) 8_675 . ?
Cu2 Cu2 I1 112.63(4) 11_556 . ?
Cu2 Cu2 I1 60.43(6) 6_676 . ?
Cu2 Cu2 I1 60.11(6) 11_556 8_675 ?
Cu2 Cu2 I1 58.43(6) 6_676 6_676 ?
Cu2 Cu2 I1 62.40(7) 11_556 6_676 ?
Cu2 Cu2 I1 58.65(6) 8_675 8_675 ?
Cu2 Cu2 I1 110.54(4) 8_675 6_676 ?
N3 Cu2 I1 101.1(3) . 8_675 ?
N3 Cu2 I1 104.8(3) . 6_676 ?
N3 Cu2 I1 110.7(3) . . ?
H3 N3 Cu2 105.1(3) . . ?
C5 N3 Cu2 112.7(7) . . ?
C5 N3 H3 105.1(7) . . ?
C4 N3 Cu2 117.8(7) . . ?
C4 N3 H3 105.1(7) . . ?
C4 N3 C5 109.9(9) . . ?
C5 C5 N3 114.3(8) 10_666 . ?
H5a C5 N3 108.7(7) . . ?
H5b C5 N3 108.7(6) . . ?
H5b C5 H5a 107.6 . . ?
C4 C4 N3 114.8(8) 10_666 . ?
H4a C4 N3 108.6(6) . . ?
H4b C4 N3 108.6(7) . . ?
H4b C4 H4a 107.5 . . ?

_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 18.692
_oxdiff_exptl_absorpt_empirical_full_min 0.456
