# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2022

####################################################################### 
# 
# 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_khc019R
_audit_block_doi                 10.5517/cc113n2w
_database_code_depnum_ccdc_archive 'CCDC 956817'
loop_
_citation_id
_citation_doi
_citation_year
1 10.1021/cg501324r 2015
_audit_update_record             
;
2013-08-21 deposited with the CCDC.	2022-02-14 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C44 H30 N6 Zn'
_chemical_formula_weight         708.11

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'
Zn Zn -1.5491 0.6778 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Trigonal
_symmetry_space_group_name_H-M   R-3

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'

_cell_length_a                   32.9136(15)
_cell_length_b                   32.9136(15)
_cell_length_c                   9.2886(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     8714.3(7)
_cell_formula_units_Z            9
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       needle
_exptl_crystal_colour            'dark brown'
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.214
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             3294
_exptl_absorpt_coefficient_mu    1.167
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.986
_exptl_absorpt_correction_T_max  0.989
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'D8 Venture'
_diffrn_measurement_method       'phi and omega sacns'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            32296
_diffrn_reflns_av_R_equivalents  0.0529
_diffrn_reflns_av_sigmaI/netI    0.0302
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.68
_diffrn_reflns_theta_max         78.95
_reflns_number_total             4118
_reflns_number_gt                3347
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'D8 Venture'
_computing_cell_refinement       'D8 Venture'
_computing_data_reduction        'D8 Venture'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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 > 2sigma(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     
'calc w=1/[σ²(Fo²)+(0.0326P)²+15.8850P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         4118
_refine_ls_number_parameters     233
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0489
_refine_ls_R_factor_gt           0.0343
_refine_ls_wR_factor_ref         0.0820
_refine_ls_wR_factor_gt          0.0759
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_restrained_S_all      1.039
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Zn1 Zn 0.5000 0.0000 0.0000 0.01362(9) Uani 1 2 d S . .
N1 N 0.49917(5) 0.05897(5) 0.07195(14) 0.0143(3) Uani 1 1 d . . .
N2 N 0.53442(5) 0.00111(5) 0.18889(14) 0.0148(3) Uani 1 1 d . . .
N3 N 0.57569(5) 0.04345(5) -0.09110(15) 0.0177(3) Uani 1 1 d . . .
C1 C 0.47470(6) 0.07750(6) 0.00794(17) 0.0157(3) Uani 1 1 d . . .
C2 C 0.47737(6) 0.11489(6) 0.09648(18) 0.0198(4) Uani 1 1 d . . .
H2 H 0.4639 0.1339 0.0756 0.024 Uiso 1 1 calc R . .
C3 C 0.50266(6) 0.11773(6) 0.21459(19) 0.0196(4) Uani 1 1 d . . .
H3 H 0.5102 0.1390 0.2925 0.023 Uiso 1 1 calc R . .
C4 C 0.51608(6) 0.08215(6) 0.19993(17) 0.0156(3) Uani 1 1 d . . .
C5 C 0.54092(6) 0.07198(6) 0.30359(17) 0.0160(3) Uani 1 1 d . . .
C6 C 0.55049(6) 0.03478(6) 0.29424(17) 0.0163(3) Uani 1 1 d . . .
C7 C 0.58156(6) 0.02828(6) 0.38907(19) 0.0208(4) Uani 1 1 d . . .
H7 H 0.5970 0.0465 0.4718 0.025 Uiso 1 1 calc R . .
C8 C 0.58459(6) -0.00850(6) 0.33815(19) 0.0215(4) Uani 1 1 d . . .
H8 H 0.6027 -0.0210 0.3780 0.026 Uiso 1 1 calc R . .
C9 C 0.55515(6) -0.02542(6) 0.21138(17) 0.0165(3) Uani 1 1 d . . .
C10 C 0.55051(6) -0.06185(6) 0.12199(18) 0.0163(3) Uani 1 1 d . . .
C11 C 0.55902(6) 0.10334(6) 0.43211(18) 0.0171(3) Uani 1 1 d . . .
C12 C 0.54334(6) 0.08565(6) 0.57014(18) 0.0200(4) Uani 1 1 d . . .
H12 H 0.5214 0.0532 0.5826 0.024 Uiso 1 1 calc R . .
C13 C 0.55945(6) 0.11495(7) 0.68951(19) 0.0243(4) Uani 1 1 d . . .
H13 H 0.5480 0.1023 0.7824 0.029 Uiso 1 1 calc R . .
C14 C 0.59193(7) 0.16243(7) 0.6758(2) 0.0268(4) Uani 1 1 d . . .
C15 C 0.60774(7) 0.17987(7) 0.5385(2) 0.0282(4) Uani 1 1 d . . .
H15 H 0.6300 0.2122 0.5267 0.034 Uiso 1 1 calc R . .
C16 C 0.59164(6) 0.15103(6) 0.4184(2) 0.0233(4) Uani 1 1 d . . .
H16 H 0.6030 0.1639 0.3256 0.028 Uiso 1 1 calc R . .
C17 C 0.61014(9) 0.19324(8) 0.8080(2) 0.0412(5) Uani 1 1 d . . .
H17A H 0.5853 0.1822 0.8807 0.062 Uiso 1 1 calc R . .
H17B H 0.6200 0.2257 0.7818 0.062 Uiso 1 1 calc R . .
H17C H 0.6370 0.1918 0.8472 0.062 Uiso 1 1 calc R . .
C18 C 0.67065(6) 0.09046(6) -0.16719(18) 0.0170(3) Uani 1 1 d . . .
C19 C 0.65432(6) 0.10648(6) -0.05539(19) 0.0210(4) Uani 1 1 d . . .
H19 H 0.6753 0.1338 -0.0027 0.025 Uiso 1 1 calc R . .
C20 C 0.60706(6) 0.08214(6) -0.02191(19) 0.0206(4) Uani 1 1 d . . .
H20 H 0.5963 0.0936 0.0545 0.025 Uiso 1 1 calc R . .
C21 C 0.59153(6) 0.02784(6) -0.19755(18) 0.0201(4) Uani 1 1 d . . .
H21 H 0.5698 0.0002 -0.2473 0.024 Uiso 1 1 calc R . .
C22 C 0.63818(6) 0.05002(6) -0.23881(18) 0.0203(4) Uani 1 1 d . . .
H22 H 0.6479 0.0377 -0.3154 0.024 Uiso 1 1 calc R . .


_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
Zn1 N1 2.0656(13) 10_655 ?
Zn1 N1 2.0657(13) . ?
Zn1 N2 2.0788(13) . ?
Zn1 N2 2.0788(13) 10_655 ?
Zn1 N3 2.3247(14) . ?
Zn1 N3 2.3247(14) 10_655 ?
N1 C1 1.366(2) . ?
N1 C4 1.371(2) . ?
N2 C9 1.367(2) . ?
N2 C6 1.371(2) . ?
N3 C21 1.335(2) . ?
N3 C20 1.336(2) . ?
C1 C10 1.408(2) 10_655 ?
C1 C2 1.446(2) . ?
C2 C3 1.352(2) . ?
C2 H2 0.9500 . ?
C3 C4 1.450(2) . ?
C3 H3 0.9500 . ?
C4 C5 1.408(2) . ?
C5 C6 1.411(2) . ?
C5 C11 1.494(2) . ?
C6 C7 1.444(2) . ?
C7 C8 1.349(2) . ?
C7 H7 0.9500 . ?
C8 C9 1.448(2) . ?
C8 H8 0.9500 . ?
C9 C10 1.403(2) . ?
C10 C1 1.408(2) 10_655 ?
C10 C18 1.492(2) 5_545 ?
C11 C16 1.396(2) . ?
C11 C12 1.396(2) . ?
C12 C13 1.389(2) . ?
C12 H12 0.9500 . ?
C13 C14 1.390(3) . ?
C13 H13 0.9500 . ?
C14 C15 1.388(3) . ?
C14 C17 1.512(3) . ?
C15 C16 1.387(3) . ?
C15 H15 0.9500 . ?
C16 H16 0.9500 . ?
C17 H17A 0.9800 . ?
C17 H17B 0.9800 . ?
C17 H17C 0.9800 . ?
C18 C19 1.389(2) . ?
C18 C22 1.391(2) . ?
C18 C10 1.492(2) 9_654 ?
C19 C20 1.383(2) . ?
C19 H19 0.9500 . ?
C20 H20 0.9500 . ?
C21 C22 1.384(2) . ?
C21 H21 0.9500 . ?
C22 H22 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
N1 Zn1 N1 179.997(1) 10_655 . ?
N1 Zn1 N2 91.52(5) 10_655 . ?
N1 Zn1 N2 88.48(5) . . ?
N1 Zn1 N2 88.48(5) 10_655 10_655 ?
N1 Zn1 N2 91.52(5) . 10_655 ?
N2 Zn1 N2 179.996(1) . 10_655 ?
N1 Zn1 N3 86.95(5) 10_655 . ?
N1 Zn1 N3 93.05(5) . . ?
N2 Zn1 N3 83.66(5) . . ?
N2 Zn1 N3 96.34(5) 10_655 . ?
N1 Zn1 N3 93.05(5) 10_655 10_655 ?
N1 Zn1 N3 86.95(5) . 10_655 ?
N2 Zn1 N3 96.34(5) . 10_655 ?
N2 Zn1 N3 83.66(5) 10_655 10_655 ?
N3 Zn1 N3 180.0 . 10_655 ?
C1 N1 C4 107.15(13) . . ?
C1 N1 Zn1 124.51(11) . . ?
C4 N1 Zn1 127.65(11) . . ?
C9 N2 C6 107.05(13) . . ?
C9 N2 Zn1 124.02(11) . . ?
C6 N2 Zn1 127.12(11) . . ?
C21 N3 C20 117.30(14) . . ?
C21 N3 Zn1 122.51(11) . . ?
C20 N3 Zn1 119.40(11) . . ?
N1 C1 C10 125.52(15) . 10_655 ?
N1 C1 C2 109.52(14) . . ?
C10 C1 C2 124.93(15) 10_655 . ?
C3 C2 C1 107.07(15) . . ?
C3 C2 H2 126.5 . . ?
C1 C2 H2 126.5 . . ?
C2 C3 C4 107.08(15) . . ?
C2 C3 H3 126.5 . . ?
C4 C3 H3 126.5 . . ?
N1 C4 C5 125.66(15) . . ?
N1 C4 C3 109.15(14) . . ?
C5 C4 C3 125.14(15) . . ?
C4 C5 C6 124.92(15) . . ?
C4 C5 C11 117.43(14) . . ?
C6 C5 C11 117.64(14) . . ?
N2 C6 C5 125.58(15) . . ?
N2 C6 C7 109.35(14) . . ?
C5 C6 C7 124.94(15) . . ?
C8 C7 C6 107.14(15) . . ?
C8 C7 H7 126.4 . . ?
C6 C7 H7 126.4 . . ?
C7 C8 C9 107.14(15) . . ?
C7 C8 H8 126.4 . . ?
C9 C8 H8 126.4 . . ?
N2 C9 C10 125.46(15) . . ?
N2 C9 C8 109.30(14) . . ?
C10 C9 C8 125.17(15) . . ?
C9 C10 C1 127.76(15) . 10_655 ?
C9 C10 C18 116.92(14) . 5_545 ?
C1 C10 C18 115.30(14) 10_655 5_545 ?
C16 C11 C12 117.99(16) . . ?
C16 C11 C5 121.39(15) . . ?
C12 C11 C5 120.62(15) . . ?
C13 C12 C11 120.70(17) . . ?
C13 C12 H12 119.7 . . ?
C11 C12 H12 119.7 . . ?
C12 C13 C14 121.31(17) . . ?
C12 C13 H13 119.3 . . ?
C14 C13 H13 119.3 . . ?
C15 C14 C13 117.87(17) . . ?
C15 C14 C17 121.84(19) . . ?
C13 C14 C17 120.26(19) . . ?
C16 C15 C14 121.36(17) . . ?
C16 C15 H15 119.3 . . ?
C14 C15 H15 119.3 . . ?
C15 C16 C11 120.77(17) . . ?
C15 C16 H16 119.6 . . ?
C11 C16 H16 119.6 . . ?
C14 C17 H17A 109.5 . . ?
C14 C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?
C14 C17 H17C 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
C19 C18 C22 117.58(15) . . ?
C19 C18 C10 121.40(15) . 9_654 ?
C22 C18 C10 121.01(15) . 9_654 ?
C20 C19 C18 119.02(16) . . ?
C20 C19 H19 120.5 . . ?
C18 C19 H19 120.5 . . ?
N3 C20 C19 123.59(16) . . ?
N3 C20 H20 118.2 . . ?
C19 C20 H20 118.2 . . ?
N3 C21 C22 123.08(16) . . ?
N3 C21 H21 118.5 . . ?
C22 C21 H21 118.5 . . ?
C21 C22 C18 119.43(16) . . ?
C21 C22 H22 120.3 . . ?
C18 C22 H22 120.3 . . ?

_diffrn_measured_fraction_theta_max 0.981
_diffrn_reflns_theta_full        78.95
_diffrn_measured_fraction_theta_full 0.981
_refine_diff_density_max         0.374
_refine_diff_density_min         -0.313
_refine_diff_density_rms         0.053
