# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# 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_dp549
_database_code_depnum_ccdc_archive 'CCDC 1439952'
_audit_update_record             
;
2016-03-04 deposited with the CCDC.
2016-04-05 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C80 H52 N16 O4 Pd2'
_chemical_formula_weight         1514.18

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'
B B 0.0090 0.0039 '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'
F F 0.0727 0.0534 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pd Pd 0.1215 3.9337 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_H-M   'P 4/m'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-y, x, z'
'-x, -y, z'
'y, -x, z'
'-x, -y, -z'
'y, -x, -z'
'x, y, -z'
'-y, x, -z'

_cell_length_a                   11.3213(11)
_cell_length_b                   11.3213(11)
_cell_length_c                   34.953(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     4480.0(8)
_cell_formula_units_Z            2
_cell_measurement_temperature    100.(1)
_cell_measurement_reflns_used    2193
_cell_measurement_theta_min      4.0740
_cell_measurement_theta_max      70.2570

_exptl_crystal_description       block
_exptl_crystal_colour            orange
_exptl_crystal_size_max          0.2028
_exptl_crystal_size_mid          0.1121
_exptl_crystal_size_min          0.0485
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.122
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1536
_exptl_absorpt_coefficient_mu    3.643
_exptl_absorpt_correction_type   Gaussian
_exptl_absorpt_correction_T_min  0.56661
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;

_diffrn_ambient_temperature      100
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            34358
_diffrn_reflns_av_R_equivalents  0.1650
_diffrn_reflns_av_sigmaI/netI    0.1035
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_theta_min         3.79
_diffrn_reflns_theta_max         73.70
_reflns_number_total             4572
_reflns_number_gt                1770
_reflns_threshold_expression     >2σ(I)

_computing_data_collection       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_structure_solution    Superflip
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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 > 2σ(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)+(0.2000P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         4572
_refine_ls_number_parameters     237
_refine_ls_number_restraints     100
_refine_ls_R_factor_all          0.2259
_refine_ls_R_factor_gt           0.1445
_refine_ls_wR_factor_ref         0.4487
_refine_ls_wR_factor_gt          0.4099
_refine_ls_goodness_of_fit_ref   1.191
_refine_ls_restrained_S_all      1.192
_refine_ls_shift/su_max          0.000
_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
N2 N 0.3822(8) 0.3677(7) 0.3375(3) 0.085(3) Uani 1 1 d GU . .
C1 C 0.2894(10) 0.3527(11) 0.3120(3) 0.142(7) Uani 1 1 d GU . .
C2 C 0.2110(10) 0.2593(13) 0.3166(4) 0.150(7) Uani 1 1 d GU . .
H2 H 0.1475 0.2491 0.2992 0.180 Uiso 1 1 calc R . .
C3 C 0.2254(10) 0.1809(10) 0.3469(4) 0.141(7) Uani 1 1 d GU . .
H3 H 0.1719 0.1171 0.3501 0.169 Uiso 1 1 calc R . .
C4 C 0.3183(11) 0.1959(9) 0.3724(4) 0.119(5) Uani 1 1 d GU . .
C5 C 0.3967(8) 0.2892(8) 0.3678(3) 0.099(5) Uani 1 1 d GU . .
H5 H 0.4601 0.2995 0.3853 0.118 Uiso 1 1 calc R . .
C6 C 0.3380(16) 0.117(2) 0.4043(6) 0.119(6) Uani 1 1 d . . .
C7 C 0.3474(14) 0.0440(15) 0.4344(7) 0.108(6) Uani 1 1 d . . .
C8 C 0.3460(9) -0.0034(9) 0.4708(6) 0.087(5) Uani 1 1 d . . .
C9 C 0.3457(9) -0.1336(11) 0.4685(6) 0.094(5) Uani 1 1 d . . .
H9 H 0.3468 -0.1708 0.4441 0.113 Uiso 1 1 calc R . .
C10 C 0.3438(12) -0.2000(16) 0.5000 0.090(7) Uani 1 2 d S . .
C11 C 0.3399(12) -0.3306(11) 0.5000 0.060(4) Uani 1 2 d SDU . .
H11A H 0.3100 -0.3577 0.4749 0.072 Uiso 0.50 1 calc PR B .
H11B H 0.4214 -0.3610 0.5029 0.072 Uiso 0.50 1 calc PR . .
N5 N 0.1440(11) 0.1090(12) 0.1647(4) 0.155(7) Uani 1 1 d GU . .
C12 C 0.1561(13) 0.2048(14) 0.1892(4) 0.169(9) Uani 1 1 d GU . .
C13 C 0.2490(15) 0.2837(12) 0.1843(5) 0.184(10) Uani 1 1 d GU . .
H13 H 0.2573 0.3492 0.2011 0.220 Uiso 1 1 calc R . .
C14 C 0.3297(13) 0.2668(13) 0.1548(5) 0.167(9) Uani 1 1 d GU . .
H14 H 0.3932 0.3207 0.1515 0.200 Uiso 1 1 calc R . .
C15 C 0.3176(12) 0.1709(14) 0.1303(4) 0.139(7) Uani 1 1 d GU . .
C16 C 0.2247(12) 0.0920(11) 0.1352(4) 0.122(6) Uani 1 1 d GU . .
H16 H 0.2165 0.0265 0.1184 0.146 Uiso 1 1 calc R . .
C17 C 0.3822(17) 0.1641(15) 0.0927(9) 0.141(9) Uani 1 1 d . . .
C18 C 0.4430(13) 0.1570(14) 0.0682(6) 0.096(5) Uani 1 1 d . . .
C19 C 0.516(4) 0.1514(17) 0.0359(7) 0.184(16) Uani 1 1 d . . .
C20 C 0.6306(10) 0.1559(11) 0.0359(6) 0.086(5) Uani 1 1 d . . .
H20 H 0.6710 0.1608 0.0596 0.103 Uiso 1 1 calc R . .
C21 C 0.7009(14) 0.1537(12) 0.0000 0.103(9) Uani 1 2 d SD . .
C22 C 0.849(5) 0.139(5) 0.0000 0.31(4) Uani 1 2 d SDU . .
H22A H 0.8731 0.0571 0.0061 0.369 Uiso 0.50 1 calc PR A .
H22B H 0.8836 0.1624 -0.0249 0.369 Uiso 0.50 1 calc PR . .
N1 N 0.277(2) 0.423(2) 0.2849(10) 0.116(10) Uani 0.50 1 d P . .
H1A H 0.3268 0.4816 0.2819 0.139 Uiso 0.50 1 calc PR . .
H1B H 0.2182 0.4134 0.2687 0.139 Uiso 0.50 1 calc PR . .
N3 N 0.3486(14) 0.0503(13) 0.5000 0.082(5) Uani 1 2 d S . .
N4 N 0.065(4) 0.222(2) 0.2179(8) 0.134(12) Uani 0.50 1 d P . .
H4A H 0.0047 0.1725 0.2192 0.160 Uiso 0.50 1 calc PR . .
H4B H 0.0692 0.2815 0.2340 0.160 Uiso 0.50 1 calc PR . .
N6 N 0.4478(11) 0.1513(14) 0.0000 0.102(6) Uani 1 2 d S . .
O90 O 0.880(3) 0.217(3) 0.0288(10) 0.159(11) Uani 0.50 1 d PU A -1
H90 H 0.9271 0.2675 0.0201 0.238 Uiso 0.50 1 calc PRD A -1
O91 O 0.2789(19) -0.373(2) 0.5249(7) 0.111(6) Uani 0.50 1 d PDU B -1
H91 H 0.2074 -0.3602 0.5199 0.167 Uiso 0.50 1 calc PRD B -1
Pd1 Pd 0.5000 0.5000 0.33503(8) 0.0891(8) Uani 1 4 d S . .
Pd2 Pd 0.0000 0.0000 0.16605(7) 0.1019(9) Uani 1 4 d S . .


_geom_special_details            
;
 All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell s.u.'s are taken
 into account individually in the estimation of s.u.'s in distances, angles
 and torsion angles; correlations between s.u.'s in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell s.u.'s is used for estimating s.u.'s 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
N2 C1 1.3900 . ?
N2 C5 1.3900 . ?
N2 Pd1 2.008(7) . ?
C1 N1 1.24(3) . ?
C1 C2 1.3900 . ?
C2 C3 1.3900 . ?
C3 C4 1.3900 . ?
C4 C5 1.3900 . ?
C4 C6 1.45(3) . ?
C6 C7 1.34(3) . ?
C7 C8 1.38(3) . ?
C8 N3 1.189(18) . ?
C8 C9 1.477(16) . ?
C9 C10 1.333(19) . ?
C10 C9 1.333(19) 7_556 ?
C10 C11 1.48(2) . ?
C11 O91 1.21(2) 7_556 ?
C11 O91 1.21(2) . ?
N5 C12 1.3900 . ?
N5 C16 1.3900 . ?
N5 Pd2 2.045(9) . ?
C12 C13 1.3900 . ?
C12 N4 1.46(4) . ?
C13 C14 1.3900 . ?
C14 C15 1.3900 . ?
C15 C16 1.3900 . ?
C15 C17 1.51(3) . ?
C17 C18 1.10(3) . ?
C18 C19 1.40(4) . ?
C19 C20 1.29(4) . ?
C19 N6 1.48(2) . ?
C20 C21 1.485(19) . ?
C21 C20 1.485(19) 7 ?
C21 C22 1.68(6) . ?
C22 O90 1.38(3) . ?
C22 O90 1.38(3) 7 ?
N3 C8 1.189(18) 7_556 ?
N6 C19 1.48(2) 7 ?
Pd1 N2 2.008(8) 3_665 ?
Pd1 N2 2.008(7) 4_565 ?
Pd1 N2 2.008(7) 2_655 ?
Pd2 N5 2.045(9) 3 ?
Pd2 N5 2.045(9) 4 ?
Pd2 N5 2.045(9) 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
C1 N2 C5 120.0 . . ?
C1 N2 Pd1 124.4(6) . . ?
C5 N2 Pd1 115.6(6) . . ?
N1 C1 N2 119.9(14) . . ?
N1 C1 C2 120.1(14) . . ?
N2 C1 C2 120.0 . . ?
C3 C2 C1 120.0 . . ?
C2 C3 C4 120.0 . . ?
C3 C4 C5 120.0 . . ?
C3 C4 C6 122.4(10) . . ?
C5 C4 C6 117.6(10) . . ?
C4 C5 N2 120.0 . . ?
C7 C6 C4 175.6(18) . . ?
C6 C7 C8 164.0(18) . . ?
N3 C8 C7 126.3(11) . . ?
N3 C8 C9 123.8(19) . . ?
C7 C8 C9 109.8(18) . . ?
C10 C9 C8 121.2(18) . . ?
C9 C10 C9 111.3(18) . 7_556 ?
C9 C10 C11 124.3(9) . . ?
C9 C10 C11 124.3(9) 7_556 . ?
O91 C11 O91 92(3) 7_556 . ?
O91 C11 C10 114.4(14) 7_556 . ?
O91 C11 C10 114.4(14) . . ?
C12 N5 C16 120.0 . . ?
C12 N5 Pd2 122.3(7) . . ?
C16 N5 Pd2 117.3(7) . . ?
N5 C12 C13 120.0 . . ?
N5 C12 N4 117.3(16) . . ?
C13 C12 N4 122.6(16) . . ?
C14 C13 C12 120.0 . . ?
C13 C14 C15 120.0 . . ?
C16 C15 C14 120.0 . . ?
C16 C15 C17 116.3(11) . . ?
C14 C15 C17 122.0(11) . . ?
C15 C16 N5 120.0 . . ?
C18 C17 C15 170(3) . . ?
C17 C18 C19 177(2) . . ?
C20 C19 C18 126.2(19) . . ?
C20 C19 N6 122(3) . . ?
C18 C19 N6 112(3) . . ?
C19 C20 C21 122.3(19) . . ?
C20 C21 C20 115.2(14) . 7 ?
C20 C21 C22 122.3(7) . . ?
C20 C21 C22 122.3(7) 7 . ?
O90 C22 O90 93(4) . 7 ?
O90 C22 C21 101(4) . . ?
O90 C22 C21 101(4) 7 . ?
C8 N3 C8 118.4(19) 7_556 . ?
C19 N6 C19 116(3) . 7 ?
N2 Pd1 N2 175.0(7) 3_665 . ?
N2 Pd1 N2 89.9 3_665 4_565 ?
N2 Pd1 N2 89.9 . 4_565 ?
N2 Pd1 N2 89.9 3_665 2_655 ?
N2 Pd1 N2 89.9 . 2_655 ?
N2 Pd1 N2 175.0(7) 4_565 2_655 ?
N5 Pd2 N5 177.3(7) 3 . ?
N5 Pd2 N5 90.0 3 4 ?
N5 Pd2 N5 90.0 . 4 ?
N5 Pd2 N5 90.0 3 2 ?
N5 Pd2 N5 90.0 . 2 ?
N5 Pd2 N5 177.3(7) 4 2 ?

_diffrn_measured_fraction_theta_max 0.988
_diffrn_reflns_theta_full        73.70
_diffrn_measured_fraction_theta_full 0.988
_refine_diff_density_max         0.774
_refine_diff_density_min         -0.693
_refine_diff_density_rms         0.118

# SQUEEZE RESULTS
# Note: Data are Listed for all Voids in the P1 Unit Cell
# i.e. Centre of Gravity, Solvent Accessible Volume,
# Recovered number of Electrons in the Void and
# Details about the Squeezed Material
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 0.000 0.000 0.077 18 10 'One water (H2O) molecule '
2 0.000 0.500 0.253 127 43 'One tetrafluoroborate (BF4) anion '
3 0.000 0.000 0.500 246 110
'Two tetrafluoroborate (2 x BF4) anions and one acetonitrile (CH3CN) molecule '
4 0.000 0.500 0.747 127 43 'One tetrafluoroborate (BF4) anion '
5 0.000 0.000 0.923 18 10 ' One water (H2O) molecule'
6 0.500 0.000 0.253 127 43 'One tetrafluoroborate (BF4) anion '
7 0.500 0.000 0.747 127 43 'One tetrafluoroborate (BF4) anion '
8 0.500 0.500 0.000 249 136
'Two tetrafluoroborate (2 x BF4) anions, two acetonitrile (2 x CH3CN) molecules and one water (H2O) molecule '
9 0.500 0.500 0.432 23 11 'One water (H2O) molecule '
10 0.500 0.500 0.568 23 11 ' One water (H2O) molecule'
_platon_squeeze_void_probe_radius 1.20
_platon_squeeze_details          ?
