# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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. 
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data_Zn(BrTAP)(py)
_database_code_depnum_ccdc_archive 'CCDC 1855204'
_audit_update_record             
;
2018-07-11 deposited with the CCDC.
2018-10-09 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C81 H45 Br4 N5 Zn'
_chemical_formula_weight         1473.23

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           79
_space_group_name_H-M_alt        'I 4'
_space_group_name_Hall           'I 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.
;
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-y, x, z'
'y, -x, z'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-y+1/2, x+1/2, z+1/2'
'y+1/2, -x+1/2, z+1/2'

_cell_length_a                   14.8911(18)
_cell_length_b                   14.8911(18)
_cell_length_c                   14.4517(16)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3204.6(9)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    26163
_cell_measurement_theta_min      3.37
_cell_measurement_theta_max      25.65

_exptl_crystal_description       platelet
_exptl_crystal_colour            'dark purple'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.527
_exptl_crystal_F_000             1472
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.08
_exptl_absorpt_coefficient_mu    2.928
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.572
_exptl_absorpt_correction_T_max  0.791
_exptl_absorpt_process_details   'SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_special_details           'crystal-to-detector distance 33 mm'
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Nonius Kappa-CCD area-detector diffractometer'
_diffrn_measurement_method       
'two φ and three ω scans with 2° steps (268 frames)'
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_diffrn_standards_decay_%        0
_diffrn_reflns_number            26163
_diffrn_reflns_av_unetI/netI     0.0709
_diffrn_reflns_av_R_equivalents  0.0961
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         3.368
_diffrn_reflns_theta_max         25.650
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measured_fraction_theta_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_point_group_measured_fraction_full 0.994
_reflns_number_total             3036
_reflns_number_gt                2372
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.920
_reflns_Friedel_fraction_max     0.995
_reflns_Friedel_fraction_full    0.995

_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       'COLLECT (Nonius, 1998)'
_computing_cell_refinement       'HKL2000 (Otwinowski & Minor, 1997)'
_computing_data_reduction        'HKL2000 (Otwinowski & Minor, 1997)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2015)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2008)'
_computing_publication_material  
'SHELXTL (Sheldrick, 2008); PLATON (Spek, 2003)'

_refine_special_details          
;
 Structure solved by intrinsic phasing and subsequent difference Fourier
 synthesis. All non-hydrogen atoms were refined with anisotropic
 displacement parameters. The pyridine molecule is disordered over
 two positions related by the fourfold rotation axis and sharing the N and
 one C atom, which have been refined with occupancy parameters of 0.5.
 The H atoms were introduced at calculated positions and were treated
 as riding atoms with an isotropic displacement parameter equal to 1.2
 times that of the parent atom.
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0844P)²+1.1265P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.47(3)
_chemical_absolute_configuration unk
_refine_ls_number_reflns         3036
_refine_ls_number_parameters     218
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0851
_refine_ls_R_factor_gt           0.0643
_refine_ls_wR_factor_ref         0.1619
_refine_ls_wR_factor_gt          0.1541
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_restrained_S_all      1.084
_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_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
Zn1 Zn 0.5000 0.5000 0.55061(17) 0.0448(5) Uani 1 4 d S T P . .
Br1 Br 0.81392(7) 1.06758(6) 0.55326(13) 0.0713(4) Uani 1 1 d . . . . .
N1 N 0.6303(5) 0.5427(4) 0.5720(5) 0.0423(17) Uani 1 1 d . . . . .
N2 N 0.5000 0.5000 0.4011(11) 0.052(4) Uani 1 4 d S T P . .
C1 C 0.7055(6) 0.4911(6) 0.5687(6) 0.042(2) Uani 1 1 d . . . . .
C2 C 0.7835(6) 0.5469(7) 0.5671(8) 0.052(2) Uani 1 1 d . . . . .
H2 H 0.8440 0.5265 0.5658 0.062 Uiso 1 1 calc R U . . .
C3 C 0.7564(7) 0.6343(7) 0.5679(8) 0.053(3) Uani 1 1 d . . . . .
H3 H 0.7936 0.6862 0.5677 0.064 Uiso 1 1 calc R U . . .
C4 C 0.6586(6) 0.6319(6) 0.5691(6) 0.043(2) Uani 1 1 d . . . . .
C5 C 0.6044(6) 0.7064(5) 0.5682(8) 0.044(2) Uani 1 1 d . . . . .
C6 C 0.6493(6) 0.7983(6) 0.5645(8) 0.046(2) Uani 1 1 d . . . . .
C7 C 0.6535(7) 0.8509(7) 0.6429(8) 0.054(3) Uani 1 1 d . . . . .
C8 C 0.7000(8) 0.9367(8) 0.6410(10) 0.068(3) Uani 1 1 d . . . . .
C9 C 0.7425(6) 0.9615(5) 0.5565(11) 0.054(2) Uani 1 1 d . . . . .
C10 C 0.7370(7) 0.9111(7) 0.4763(8) 0.054(3) Uani 1 1 d . . . . .
C11 C 0.6867(7) 0.8272(6) 0.4784(7) 0.045(2) Uani 1 1 d . . . . .
C12 C 0.6813(6) 0.7763(8) 0.3955(8) 0.058(3) Uani 1 1 d . . . . .
H12 H 0.6495 0.7210 0.3963 0.070 Uiso 1 1 calc R U . . .
C13 C 0.7198(9) 0.8035(9) 0.3155(8) 0.072(3) Uani 1 1 d . . . . .
H13 H 0.7118 0.7692 0.2607 0.086 Uiso 1 1 calc R U . . .
C14 C 0.7718(9) 0.8828(10) 0.3135(8) 0.074(4) Uani 1 1 d . . . . .
H14 H 0.8018 0.8999 0.2583 0.088 Uiso 1 1 calc R U . . .
C15 C 0.7789(7) 0.9344(7) 0.3896(8) 0.061(3) Uani 1 1 d . . . . .
H15 H 0.8129 0.9882 0.3861 0.073 Uiso 1 1 calc R U . . .
C16 C 0.6113(8) 0.8262(8) 0.7258(9) 0.070(3) Uani 1 1 d . . . . .
H16 H 0.5794 0.7711 0.7290 0.084 Uiso 1 1 calc R U . . .
C17 C 0.6156(12) 0.8809(10) 0.8030(10) 0.094(5) Uani 1 1 d . . . . .
H17 H 0.5886 0.8620 0.8593 0.113 Uiso 1 1 calc R U . . .
C18 C 0.6586(14) 0.9623(13) 0.7986(12) 0.126(8) Uani 1 1 d . . . . .
H18 H 0.6574 1.0012 0.8507 0.151 Uiso 1 1 calc R U . . .
C19 C 0.7028(11) 0.9883(9) 0.7207(10) 0.099(5) Uani 1 1 d . . . . .
H19 H 0.7362 1.0426 0.7210 0.119 Uiso 1 1 calc R U . . .
C20 C 0.4272(13) 0.4727(12) 0.3535(14) 0.050(5) Uani 0.5 1 d . . P . .
H20 H 0.3744 0.4536 0.3862 0.060 Uiso 0.5 1 d R U P . .
C21 C 0.4282(17) 0.475(2) 0.2610(17) 0.088(9) Uani 0.5 1 d . . P . .
H21 H 0.3760 0.4542 0.2285 0.105 Uiso 0.5 1 d R U P . .
C22 C 0.5000 0.5000 0.2102(19) 0.090(8) Uani 1 4 d S T P . .
H22 H 0.5000 0.5000 0.1437 0.108 Uiso 1 4 d R U P . .


_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 2.066(7) 2_665 ?
Zn1 N1 2.066(7) 3_655 ?
Zn1 N1 2.066(7) 4_565 ?
Zn1 N1 2.066(7) . ?
Zn1 N2 2.160(16) . ?
Br1 C9 1.905(8) . ?
N1 C1 1.358(10) . ?
N1 C4 1.394(11) . ?
N2 C20 1.347(19) . ?
N2 C20 1.347(19) 3_655 ?
N2 C20 1.347(19) 2_665 ?
N2 C20 1.347(19) 4_565 ?
C1 C5 1.423(13) 4_565 ?
C1 C2 1.428(13) . ?
C2 C3 1.364(14) . ?
C2 H2 0.9500 . ?
C3 C4 1.457(13) . ?
C3 H3 0.9500 . ?
C4 C5 1.372(12) . ?
C5 C1 1.423(13) 3_655 ?
C5 C6 1.523(12) . ?
C6 C7 1.379(15) . ?
C6 C11 1.430(15) . ?
C7 C16 1.401(16) . ?
C7 C8 1.453(16) . ?
C8 C19 1.385(19) . ?
C8 C9 1.425(19) . ?
C9 C10 1.383(18) . ?
C10 C15 1.441(15) . ?
C10 C11 1.458(14) . ?
C11 C12 1.420(16) . ?
C12 C13 1.352(16) . ?
C12 H12 0.9500 . ?
C13 C14 1.41(2) . ?
C13 H13 0.9500 . ?
C14 C15 1.345(17) . ?
C14 H14 0.9500 . ?
C15 H15 0.9500 . ?
C16 C17 1.382(17) . ?
C16 H16 0.9500 . ?
C17 C18 1.37(2) . ?
C17 H17 0.9500 . ?
C18 C19 1.36(2) . ?
C18 H18 0.9500 . ?
C19 H19 0.9500 . ?
C20 C21 1.34(3) . ?
C20 C20 1.64(3) 4_565 ?
C20 C20 1.64(3) 3_655 ?
C20 H20 0.9602 . ?
C21 C22 1.35(3) . ?
C21 C21 1.60(3) 4_565 ?
C21 C21 1.60(3) 3_655 ?
C21 H21 0.9602 . ?
C22 C21 1.35(3) 2_665 ?
C22 C21 1.35(3) 4_565 ?
C22 C21 1.35(3) 3_655 ?
C22 H22 0.9603 . ?

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 88.72(6) 2_665 3_655 ?
N1 Zn1 N1 88.72(6) 2_665 4_565 ?
N1 Zn1 N1 162.8(4) 3_655 4_565 ?
N1 Zn1 N1 162.8(4) 2_665 . ?
N1 Zn1 N1 88.72(6) 3_655 . ?
N1 Zn1 N1 88.72(6) 4_565 . ?
N1 Zn1 N2 98.6(2) 2_665 . ?
N1 Zn1 N2 98.6(2) 3_655 . ?
N1 Zn1 N2 98.6(2) 4_565 . ?
N1 Zn1 N2 98.6(2) . . ?
C1 N1 C4 106.8(7) . . ?
C1 N1 Zn1 126.5(6) . . ?
C4 N1 Zn1 124.9(6) . . ?
C20 N2 C20 74.8(10) . 3_655 ?
C20 N2 C20 118(2) . 2_665 ?
C20 N2 C20 74.8(10) 3_655 2_665 ?
C20 N2 C20 74.8(10) . 4_565 ?
C20 N2 C20 118(2) 3_655 4_565 ?
C20 N2 C20 74.8(10) 2_665 4_565 ?
C20 N2 Zn1 120.8(11) . . ?
C20 N2 Zn1 120.8(11) 3_655 . ?
C20 N2 Zn1 120.8(11) 2_665 . ?
C20 N2 Zn1 120.8(11) 4_565 . ?
N1 C1 C5 125.0(8) . 4_565 ?
N1 C1 C2 110.0(8) . . ?
C5 C1 C2 124.9(8) 4_565 . ?
C3 C2 C1 108.3(9) . . ?
C3 C2 H2 125.9 . . ?
C1 C2 H2 125.9 . . ?
C2 C3 C4 105.8(8) . . ?
C2 C3 H3 127.1 . . ?
C4 C3 H3 127.1 . . ?
C5 C4 N1 126.4(8) . . ?
C5 C4 C3 124.6(8) . . ?
N1 C4 C3 109.0(8) . . ?
C4 C5 C1 125.4(7) . 3_655 ?
C4 C5 C6 118.0(8) . . ?
C1 C5 C6 116.6(7) 3_655 . ?
C7 C6 C11 121.7(8) . . ?
C7 C6 C5 120.1(10) . . ?
C11 C6 C5 118.1(9) . . ?
C6 C7 C16 122.2(10) . . ?
C6 C7 C8 120.4(10) . . ?
C16 C7 C8 117.4(10) . . ?
C19 C8 C9 123.7(11) . . ?
C19 C8 C7 119.1(12) . . ?
C9 C8 C7 117.1(11) . . ?
C10 C9 C8 123.4(8) . . ?
C10 C9 Br1 117.6(9) . . ?
C8 C9 Br1 119.0(10) . . ?
C9 C10 C15 124.9(10) . . ?
C9 C10 C11 118.6(9) . . ?
C15 C10 C11 116.5(10) . . ?
C12 C11 C6 123.5(9) . . ?
C12 C11 C10 118.0(10) . . ?
C6 C11 C10 118.5(9) . . ?
C13 C12 C11 122.5(11) . . ?
C13 C12 H12 118.7 . . ?
C11 C12 H12 118.7 . . ?
C12 C13 C14 120.0(11) . . ?
C12 C13 H13 120.0 . . ?
C14 C13 H13 120.0 . . ?
C15 C14 C13 120.2(11) . . ?
C15 C14 H14 119.9 . . ?
C13 C14 H14 119.9 . . ?
C14 C15 C10 122.6(11) . . ?
C14 C15 H15 118.7 . . ?
C10 C15 H15 118.7 . . ?
C17 C16 C7 121.0(11) . . ?
C17 C16 H16 119.5 . . ?
C7 C16 H16 119.5 . . ?
C18 C17 C16 120.3(13) . . ?
C18 C17 H17 119.9 . . ?
C16 C17 H17 119.9 . . ?
C19 C18 C17 121.0(13) . . ?
C19 C18 H18 119.5 . . ?
C17 C18 H18 119.5 . . ?
C18 C19 C8 121.1(13) . . ?
C18 C19 H19 119.5 . . ?
C8 C19 H19 119.5 . . ?
C21 C20 N2 119.6(18) . . ?
C21 C20 C20 88.3(15) . 4_565 ?
N2 C20 C20 52.6(5) . 4_565 ?
C21 C20 C20 90.1(15) . 3_655 ?
N2 C20 C20 52.6(5) . 3_655 ?
C20 C20 C20 90.002(8) 4_565 3_655 ?
C21 C20 H20 120.6 . . ?
N2 C20 H20 119.7 . . ?
C20 C20 H20 127.4 4_565 . ?
C20 C20 H20 128.6 3_655 . ?
C20 C21 C22 124(2) . . ?
C20 C21 C21 91.7(14) . 4_565 ?
C22 C21 C21 53.6(7) . 4_565 ?
C20 C21 C21 89.8(16) . 3_655 ?
C22 C21 C21 53.6(7) . 3_655 ?
C21 C21 C21 90.000(10) 4_565 3_655 ?
C20 C21 H21 118.0 . . ?
C22 C21 H21 117.7 . . ?
C21 C21 H21 130.4 4_565 . ?
C21 C21 H21 125.8 3_655 . ?
C21 C22 C21 114(3) . 2_665 ?
C21 C22 C21 72.8(13) . 4_565 ?
C21 C22 C21 72.8(13) 2_665 4_565 ?
C21 C22 C21 72.8(14) . 3_655 ?
C21 C22 C21 72.8(14) 2_665 3_655 ?
C21 C22 C21 114(3) 4_565 3_655 ?
C21 C22 H22 123.0 . . ?
C21 C22 H22 123.0 2_665 . ?
C21 C22 H22 123.0 4_565 . ?
C21 C22 H22 123.0 3_655 . ?

_refine_diff_density_max         1.268
_refine_diff_density_min         -0.439
_refine_diff_density_rms         0.085

_shelxl_version_number           2014-3

