# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.
# This journal is © The Royal Society of Chemistry 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_alsd158b_abs
_database_code_depnum_ccdc_archive 'CCDC 2291474'
loop_
_audit_author_name
_audit_author_address
'Brendan Abrahams'
;University of Melbourne
Australia
;
_audit_update_record             
;
2023-08-29 deposited with the CCDC.	2023-10-15 downloaded from the CCDC.
;
_audit_creation_date             2023-08-18
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_shelx_SHELXL_version_number     2018/3
loop_
_audit_author_email
''
''
''
''
''
''
''
_chemical_name_common            ?
_chemical_name_systematic        CuTCNQ
_chemical_formula_moiety         'C12 H4 Cu N4'
_chemical_formula_sum            'C12 H4 Cu N4'
_chemical_formula_weight         267.73
_chemical_melting_point          ?
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'
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'

_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      tetragonal
_space_group_IT_number           136
_space_group_name_H-M_alt        'P 42/m n m'
_space_group_name_Hall           '-P 4n 2n'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-y+1/2, x+1/2, z+1/2'
'y+1/2, -x+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'y, x, -z'
'-y, -x, -z'
'-x, -y, -z'
'x, y, -z'
'y-1/2, -x-1/2, -z-1/2'
'-y-1/2, x-1/2, -z-1/2'
'x-1/2, -y-1/2, z-1/2'
'-x-1/2, y-1/2, z-1/2'
'-y, -x, z'
'y, x, z'

_cell_length_a                   11.2444(6)
_cell_length_b                   11.2444(6)
_cell_length_c                   3.8703(15)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     489.3(2)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    337
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      71.9070
_cell_measurement_theta_min      5.5410
_shelx_estimated_absorpt_T_max   0.980
_shelx_estimated_absorpt_T_min   0.811
_exptl_absorpt_coefficient_mu    2.960
_exptl_absorpt_correction_T_max  0.981
_exptl_absorpt_correction_T_min  0.909
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.36a (Rigaku Oxford Diffraction, 2018)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear dark blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.817
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             266
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
1 -1 -2 0.0346
0 -7 1 0.0036
-7 -1 0 0.0036
7 1 0 0.0036
0 7 -1 0.0036
-1 1 2 0.0346

_exptl_crystal_size_max          0.074
_exptl_crystal_size_mid          0.008
_exptl_crystal_size_min          0.007
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0428
_diffrn_reflns_av_unetI/netI     0.0218
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       4
_diffrn_reflns_limit_l_min       -4
_diffrn_reflns_number            1459
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.791
_diffrn_reflns_theta_min         5.564
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -22.00   3.00   0.50   12.00    --   48.05 -18.00 -34.00   50
  2  ω    -18.00  28.00   0.50   12.00    --   48.05 -19.00-150.00   92
  3  ω     39.00  99.00   0.50   45.00    --  107.75 -77.00 -60.00  120
  4  ω     39.00  66.00   0.50   45.00    --  107.75 -61.00  30.00   54
  5  ω     41.00  66.00   0.50   45.00    --  107.75 -61.00  60.00   50
  6  ω     95.00 120.00   0.50   45.00    --  107.75-142.00  99.00   50
  7  ω    133.00 172.00   0.50   45.00    --  107.75  30.00   0.00   78
  8  ω    109.00 169.00   0.50   45.00    --  107.75 108.00 -94.00  120
  9  ω    102.00 128.00   0.50   45.00    --  107.75  30.00   0.00   52
 10  ω     54.00  86.00   0.50   45.00    --  107.75 -77.00-180.00   64
 11  ω    -68.00 -19.00   0.50   45.00    --  -86.25 108.00 -94.00   98
 12  ω   -119.00 -73.00   0.50   12.00    --  -48.05-125.00-150.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                194
_reflns_number_total             295
_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 1.171.40.36a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.36a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.36a (Rigaku OD, 2018)'
_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    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.185
_refine_diff_density_rms         0.059
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_matrix_type           full
_refine_ls_number_parameters     42
_refine_ls_number_reflns         295
_refine_ls_number_restraints     7
_refine_ls_R_factor_all          0.0882
_refine_ls_R_factor_gt           0.0633
_refine_ls_restrained_S_all      1.069
_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)+(0.1065P)²+0.4967P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1806
_refine_ls_wR_factor_ref         0.1996
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C4-H4
 0.95 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N1 \\sim C1: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
4. Others
 Fixed Sof: Cu1(0.125) N1(0.5) C2(0.25) C3(0.25) C4(0.5) H4(0.5)
;
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     dual
_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 0.500000 1.000000 0.750000 0.1114(16) Uani 0.5 4 d S T P . .
N1 N 0.4218(4) 0.8593(4) 0.569(6) 0.086(4) Uani 0.5 1 d . U P . .
C1 C 0.3869(4) 0.7654(4) 0.500000 0.084(3) Uani 1 2 d S TU P . .
C2 C 0.3495(5) 0.6505(5) 0.381(2) 0.044(3) Uani 0.5 2 d S T P A .
C3 C 0.4237(5) 0.5763(5) 0.197(4) 0.080(5) Uani 0.5 2 d S T P . .
C4 C 0.5408(6) 0.6127(5) 0.106(3) 0.066(6) Uani 0.5 1 d D . P A -1
H4 H 0.573(7) 0.688(4) 0.163(18) 0.079 Uiso 0.5 1 d D U P B -1


_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 Cu1 1.9351(8) 10_556 ?
Cu1 N1 1.942(10) 2_675 ?
Cu1 N1 1.942(10) 11_577 ?
Cu1 N1 1.942(10) . ?
Cu1 N1 1.942(10) 12_767 ?
N1 N1 0.53(5) 10_556 ?
N1 C1 1.157(9) . ?
C1 C2 1.435(6) . ?
C1 C2 1.435(6) 10_556 ?
C2 C2 0.918(18) 10_556 ?
C2 C3 1.379(13) . ?
C2 C3 2.013(15) 10_556 ?
C3 C3 1.53(3) 10 ?
C3 C3 1.53(3) 8_665 ?
C3 C4 1.810(14) 10 ?
C3 C4 1.423(8) . ?
C4 H4 0.95(2) . ?

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
Cu1 Cu1 N1 68.8(6) 10_556 . ?
Cu1 Cu1 N1 111.2(6) 10_556 12_767 ?
Cu1 Cu1 N1 68.8(6) 10_556 2_675 ?
Cu1 Cu1 N1 111.2(6) 10_556 11_577 ?
N1 Cu1 N1 97.5(5) . 11_577 ?
N1 Cu1 N1 137.7(13) 12_767 11_577 ?
N1 Cu1 N1 137.7(13) . 2_675 ?
N1 Cu1 N1 97.5(4) 2_675 11_577 ?
N1 Cu1 N1 97.5(5) 2_675 12_767 ?
N1 Cu1 N1 97.5(4) . 12_767 ?
Cu1 N1 Cu1 0.0 3_654 9_676 ?
Cu1 N1 Cu1 55.45(18) . 10_556 ?
Cu1 N1 Cu1 0.0 10_556 9_676 ?
Cu1 N1 Cu1 0.0 10_556 3_654 ?
Cu1 N1 Cu1 55.45(18) . 3_654 ?
Cu1 N1 Cu1 55.45(18) . 9_676 ?
N1 N1 Cu1 55.7(5) 10_556 9_676 ?
N1 N1 Cu1 55.7(5) 10_556 3_654 ?
N1 N1 Cu1 55.7(5) 10_556 10_556 ?
N1 N1 Cu1 111.2(6) 10_556 . ?
N1 N1 C1 76.7(11) 10_556 . ?
C1 N1 Cu1 131.7(16) . 9_676 ?
C1 N1 Cu1 131.7(16) . 3_654 ?
C1 N1 Cu1 168.6(13) . . ?
C1 N1 Cu1 131.7(16) . 10_556 ?
N1 C1 N1 27(2) . 10_556 ?
N1 C1 C2 147.9(12) 10_556 . ?
N1 C1 C2 174.2(11) 10_556 10_556 ?
N1 C1 C2 174.2(11) . . ?
N1 C1 C2 147.9(12) . 10_556 ?
C2 C1 C2 37.3(7) . 10_556 ?
C1 C2 C1 115.2(6) 15_665 . ?
C1 C2 C3 89.6(4) 15_665 10_556 ?
C1 C2 C3 89.6(4) . 10_556 ?
C2 C2 C1 71.3(4) 10_556 15_665 ?
C2 C2 C1 71.3(4) 10_556 . ?
C2 C2 C3 121.1(7) 10_556 . ?
C2 C2 C3 35.9(4) 10_556 10_556 ?
C3 C2 C1 122.2(3) . . ?
C3 C2 C1 122.2(3) . 15_665 ?
C3 C2 C3 85.2(10) . 10_556 ?
C2 C3 C2 23.0(6) . 10_556 ?
C2 C3 C3 121.1(7) . 8_665 ?
C2 C3 C3 121.1(7) . 10 ?
C2 C3 C4 129.7(5) . 10 ?
C2 C3 C4 120.9(5) . . ?
C3 C3 C2 144.1(4) 8_665 10_556 ?
C3 C3 C2 144.1(4) 10 10_556 ?
C3 C3 C3 0.0(5) 10 8_665 ?
C3 C3 C4 49.6(5) 10 10 ?
C3 C3 C4 49.6(5) 8_665 10 ?
C4 C3 C2 137.1(3) 10 10_556 ?
C4 C3 C2 117.8(7) . 10_556 ?
C4 C3 C3 75.6(7) . 8_665 ?
C4 C3 C3 75.6(7) . 10 ?
C4 C3 C4 26.0(8) . 10 ?
C3 C4 H4 123(5) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Cu1 N1 C1 N1 -135(6) . . . 10_556 ?
Cu1 N1 C1 N1 -9.6(6) 3_654 . . 10_556 ?
Cu1 N1 C1 N1 -9.6(6) 10_556 . . 10_556 ?
Cu1 N1 C1 N1 -9.6(6) 9_676 . . 10_556 ?
Cu1 N1 C1 C2 41(7) . . . 10_556 ?
Cu1 N1 C1 C2 166.1(9) 9_676 . . 10_556 ?
Cu1 N1 C1 C2 166.1(9) 10_556 . . 10_556 ?
Cu1 N1 C1 C2 166.1(9) 3_654 . . 10_556 ?
N1 N1 C1 C2 175.7(11) 10_556 . . 10_556 ?
N1 C1 C2 C1 -126.5(8) 10_556 . . 15_665 ?
N1 C1 C2 C2 175.6(11) 10_556 . . 10_556 ?
N1 C1 C2 C3 144.1(10) 10_556 . . 10_556 ?
N1 C1 C2 C3 60.0(16) 10_556 . . . ?
C1 C2 C3 C2 86.5(8) . . . 10_556 ?
C1 C2 C3 C2 -86.5(8) 15_665 . . 10_556 ?
C1 C2 C3 C3 -93.5(8) . . . 8_665 ?
C1 C2 C3 C3 -93.5(8) . . . 10 ?
C1 C2 C3 C3 93.5(8) 15_665 . . 10 ?
C1 C2 C3 C3 93.5(8) 15_665 . . 8_665 ?
C1 C2 C3 C4 -175.2(9) 15_665 . . . ?
C1 C2 C3 C4 -32.3(17) . . . 10 ?
C1 C2 C3 C4 154.7(8) 15_665 . . 10 ?
C1 C2 C3 C4 -2.2(18) . . . . ?
C2 C1 C2 C1 57.9(7) 10_556 . . 15_665 ?
C2 C1 C2 C3 -115.6(10) 10_556 . . . ?
C2 C1 C2 C3 -31.5(4) 10_556 . . 10_556 ?
C2 C2 C3 C3 180.000(6) 10_556 . . 8_665 ?
C2 C2 C3 C3 180.000(6) 10_556 . . 10 ?
C2 C2 C3 C4 -88.7(12) 10_556 . . . ?
C2 C2 C3 C4 -118.8(11) 10_556 . . 10 ?
C3 C2 C3 C2 0.000(11) 10_556 . . 10_556 ?
C3 C2 C3 C3 180.000(6) 10_556 . . 8_665 ?
C3 C2 C3 C3 180.000(6) 10_556 . . 10 ?
C3 C2 C3 C4 -118.8(11) 10_556 . . 10 ?
C3 C2 C3 C4 -88.7(12) 10_556 . . . ?

_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
;
_vrf_PLAT088_alsd158b_abs        
;
PROBLEM: Poor Data / Parameter Ratio ....................       7.02 Note  
RESPONSE: The data set collected on this crystal was not ideal but no 
better crystals could be identified. The model obtained from the data set
has revealed key aspects of the structure, namely the 
7,7,8,8-tetracyanoquinodimethane (TCNQ) anions form stacks that extend in 
the c-direction and Cu(I) centres are disordered over sites lying along 
the direction of this axis.
The crystal used was a very thin needle with a width less than 10 microns, 
and, as a result diffraction data failed to extend beyond a 2theta value 
of 135 degrees. A total of 1459 reflections were collected, of which only 
295 were unique. The considerable disorder in the structure resulted in 
the refinement of 42 parameters. This led to a relatively low reflection 
to parameter ratio.
;
_vrf_PLAT250_alsd158b_abs        
;
PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        7.5 Note  
RESPONSE:  Inspection of the thermal ellipsoids reveal the major axis of 
the thermal ellipsoids are close to parallel, indicating movement along 
the direction of the c-axis. This is consistent with considerable concerted 
thermal motion in the disordered structure along the stacking direction. 
;
