# Supplementary Material (ESI) for Dalton Transactions
# This journal is (c) The Royal Society of Chemistry 2010


data_global
_journal_name_full               'Dalton Trans.'

_journal_coden_Cambridge         0222

_publ_contact_author_name        'Chand, Dillip'
_publ_contact_author_email       dillip@iitm.ac.in,

_publ_section_title              
;
Conformation of N,N'-bis(3-pyridylformyl)piperazine and spontaneous
formation of a saturated quadruple stranded metallohelicate
;
_publ_author_name                'Dillip Chand'

# Attachment '- helicateRevised.txt'

#===========================================================================
data_tetra
_database_code_depnum_ccdc_archive 'CCDC 745870'
#TrackingRef '- helicateRevised.txt'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C64 H96 N20 O48 Pd2'
_chemical_formula_weight         2126.41

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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pd Pd -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Tetragonal
_symmetry_space_group_name_H-M   P4/n

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

_cell_length_a                   17.0336(7)
_cell_length_b                   17.0336(7)
_cell_length_c                   17.5784(9)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     5100.3(4)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       blocks
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.22
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.385
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2192
_exptl_absorpt_coefficient_mu    0.450
_exptl_absorpt_correction_type   Multi-Scan
_exptl_absorpt_correction_T_min  0.871
_exptl_absorpt_correction_T_max  0.908
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(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  ?
_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            60629
_diffrn_reflns_av_R_equivalents  0.1112
_diffrn_reflns_av_sigmaI/netI    0.0897
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.05
_diffrn_reflns_theta_max         28.35
_reflns_number_total             6354
_reflns_number_gt                3006
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
The hydrogen atoms of the water molecules could neither be added
at calculated positions nor be located from FMAP.
The very large ellipsoids for O9 and O13 could be explained by a disorder
on the position.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.1303P)^2^+19.5464P] where P=(Fo^2^+2Fc^2^)/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     SHELXL
_refine_ls_extinction_coef       0.0043(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_number_reflns         6354
_refine_ls_number_parameters     296
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1870
_refine_ls_R_factor_gt           0.0844
_refine_ls_wR_factor_ref         0.2345
_refine_ls_wR_factor_gt          0.2131
_refine_ls_goodness_of_fit_ref   0.998
_refine_ls_restrained_S_all      0.998
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.015

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
Pd1 Pd 0.2500 0.2500 1.10172(6) 0.0475(4) Uani 1 4 d S . .
Pd2 Pd 0.2500 0.2500 0.56446(6) 0.0521(4) Uani 1 4 d S . .
O1 O 0.4144(5) 0.5171(6) 0.7380(4) 0.130(3) Uani 1 1 d . . .
O2 O 0.0581(5) 0.4932(7) 0.9223(5) 0.140(4) Uani 1 1 d . . .
O3 O 0.2500 0.2500 0.8949(9) 0.144(7) Uani 1 4 d S . .
O4 O 0.2500 0.2500 0.7653(12) 0.199(11) Uani 1 4 d S . .
O5 O 0.2500 0.2500 0.3945(8) 0.121(6) Uani 1 4 d S . .
O6 O 0.2500 0.2500 0.2738(7) 0.117(5) Uani 1 4 d S . .
O7 O 0.5433(6) 0.4985(8) 0.6511(6) 0.171(4) Uani 1 1 d . . .
O8 O 0.1330(7) 0.5216(10) 0.5665(8) 0.198(6) Uani 1 1 d . . .
O9 O 0.218(2) 0.590(6) 0.321(4) 1.08(9) Uani 1 1 d . . .
O10 O 0.3245(9) 0.4883(13) 0.2643(11) 0.274(9) Uani 1 1 d . . .
O11 O 0.1925(17) 0.652(2) 0.577(2) 0.47(2) Uani 1 1 d . . .
O12 O 0.5258(10) 0.6404(11) 0.5835(10) 0.235(7) Uani 1 1 d . . .
O13 O 0.1498(15) 0.7201(19) 0.946(2) 0.44(2) Uani 1 1 d . . .
O14 O 0.0126(7) 0.6599(6) 0.9028(8) 0.168(4) Uani 1 1 d . . .
N1 N 0.2882(4) 0.3625(4) 0.5683(3) 0.0567(15) Uani 1 1 d . . .
N2 N 0.1976(3) 0.3559(3) 1.0970(3) 0.0504(14) Uani 1 1 d . . .
N3 N 0.1817(5) 0.4919(7) 0.8882(5) 0.113(3) Uani 1 1 d . . .
N4 N 0.2920(5) 0.5052(6) 0.7719(5) 0.105(3) Uani 1 1 d . . .
N5 N 0.2500 0.2500 0.8303(8) 0.059(3) Uani 1 4 d S . .
N6 N 0.2500 0.2500 0.3343(11) 0.169(12) Uani 1 4 d S . .
C1 C 0.3027(5) 0.4045(5) 0.5053(4) 0.069(2) Uani 1 1 d . . .
H1 H 0.2935 0.3824 0.4578 0.083 Uiso 1 1 calc R . .
C2 C 0.3307(6) 0.4791(6) 0.5102(5) 0.086(3) Uani 1 1 d . . .
H2 H 0.3399 0.5076 0.4660 0.104 Uiso 1 1 calc R . .
C3 C 0.3455(6) 0.5127(6) 0.5795(6) 0.085(3) Uani 1 1 d . . .
H3 H 0.3672 0.5627 0.5826 0.102 Uiso 1 1 calc R . .
C4 C 0.3278(5) 0.4715(5) 0.6442(4) 0.065(2) Uani 1 1 d . . .
C5 C 0.3001(4) 0.3955(5) 0.6371(4) 0.0619(19) Uani 1 1 d . . .
H5 H 0.2895 0.3665 0.6807 0.074 Uiso 1 1 calc R . .
C6 C 0.3469(6) 0.5007(6) 0.7231(6) 0.086(3) Uani 1 1 d . . .
C7 C 0.3119(8) 0.5248(12) 0.8505(7) 0.150(7) Uani 1 1 d . . .
H7A H 0.3669 0.5131 0.8595 0.180 Uiso 1 1 calc R . .
H7B H 0.3043 0.5807 0.8585 0.180 Uiso 1 1 calc R . .
C8 C 0.2669(8) 0.4839(11) 0.9009(7) 0.151(7) Uani 1 1 d . . .
H8A H 0.2791 0.5018 0.9519 0.181 Uiso 1 1 calc R . .
H8B H 0.2808 0.4288 0.8978 0.181 Uiso 1 1 calc R . .
C9 C 0.1601(8) 0.5030(18) 0.8063(9) 0.238(14) Uani 1 1 d . . .
H9A H 0.1154 0.4694 0.7960 0.286 Uiso 1 1 calc R . .
H9B H 0.1422 0.5568 0.8005 0.286 Uiso 1 1 calc R . .
C10 C 0.2065(7) 0.4915(13) 0.7584(8) 0.167(8) Uani 1 1 d . . .
H10A H 0.1915 0.5234 0.7151 0.200 Uiso 1 1 calc R . .
H10B H 0.2007 0.4371 0.7430 0.200 Uiso 1 1 calc R . .
C11 C 0.1261(6) 0.4839(6) 0.9379(6) 0.083(3) Uani 1 1 d . . .
C12 C 0.1472(4) 0.4576(5) 1.0170(5) 0.0612(19) Uani 1 1 d . . .
C13 C 0.1822(4) 0.3870(4) 1.0276(4) 0.0564(18) Uani 1 1 d . . .
H13 H 0.1965 0.3582 0.9848 0.068 Uiso 1 1 calc R . .
C14 C 0.1777(5) 0.3982(5) 1.1583(4) 0.066(2) Uani 1 1 d . . .
H14 H 0.1892 0.3787 1.2065 0.080 Uiso 1 1 calc R . .
C15 C 0.1409(6) 0.4693(6) 1.1517(6) 0.086(3) Uani 1 1 d . . .
H15 H 0.1262 0.4971 1.1949 0.103 Uiso 1 1 calc R . .
C16 C 0.1259(6) 0.4992(6) 1.0804(6) 0.081(3) Uani 1 1 d . . .
H16 H 0.1014 0.5477 1.0752 0.097 Uiso 1 1 calc R . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Pd1 0.0522(5) 0.0522(5) 0.0383(6) 0.000 0.000 0.000
Pd2 0.0589(5) 0.0589(5) 0.0384(6) 0.000 0.000 0.000
O1 0.094(5) 0.203(9) 0.093(5) -0.043(6) -0.003(4) -0.057(6)
O2 0.079(5) 0.245(12) 0.097(6) 0.056(6) 0.006(4) 0.048(6)
O3 0.185(13) 0.185(13) 0.063(11) 0.000 0.000 0.000
O4 0.260(19) 0.260(19) 0.077(14) 0.000 0.000 0.000
O5 0.157(10) 0.157(10) 0.049(8) 0.000 0.000 0.000
O6 0.155(9) 0.155(9) 0.041(8) 0.000 0.000 0.000
O7 0.136(8) 0.243(13) 0.135(9) -0.006(8) 0.029(6) -0.001(8)
O8 0.143(10) 0.267(16) 0.183(12) 0.019(10) -0.013(8) 0.033(10)
O9 0.24(3) 2.0(2) 1.00(12) -1.00(14) -0.11(5) 0.22(7)
O10 0.194(14) 0.37(2) 0.257(19) -0.111(18) -0.030(13) 0.002(14)
O11 0.31(3) 0.37(4) 0.72(7) -0.05(4) -0.07(3) 0.03(3)
O12 0.242(17) 0.227(16) 0.235(17) 0.059(13) 0.048(13) -0.018(13)
O13 0.25(2) 0.44(4) 0.64(6) -0.19(4) -0.03(3) -0.07(2)
O14 0.144(9) 0.120(8) 0.240(14) -0.006(8) -0.009(8) 0.024(6)
N1 0.065(4) 0.063(4) 0.042(3) 0.000(3) 0.000(3) 0.001(3)
N2 0.053(3) 0.053(3) 0.045(3) -0.004(2) 0.002(2) -0.002(3)
N3 0.077(6) 0.187(10) 0.075(5) 0.054(6) -0.006(4) -0.010(6)
N4 0.073(5) 0.171(9) 0.069(5) -0.045(6) -0.006(4) -0.012(5)
N5 0.065(5) 0.065(5) 0.046(7) 0.000 0.000 0.000
N6 0.24(2) 0.24(2) 0.030(10) 0.000 0.000 0.000
C1 0.089(6) 0.075(6) 0.043(4) 0.009(4) 0.006(4) -0.008(4)
C2 0.123(8) 0.075(6) 0.061(5) 0.017(5) 0.019(5) -0.015(6)
C3 0.106(8) 0.065(6) 0.084(7) 0.008(5) 0.008(6) -0.017(5)
C4 0.076(5) 0.069(5) 0.052(4) -0.006(4) 0.001(4) -0.012(4)
C5 0.062(5) 0.073(5) 0.050(4) -0.001(4) 0.000(3) -0.006(4)
C6 0.086(7) 0.101(7) 0.070(6) -0.028(5) -0.005(5) -0.028(6)
C7 0.101(9) 0.27(2) 0.075(8) -0.062(10) -0.011(7) -0.029(11)
C8 0.098(9) 0.28(2) 0.077(8) 0.068(10) -0.047(7) -0.061(11)
C9 0.077(9) 0.55(4) 0.092(10) 0.138(17) -0.011(8) -0.011(16)
C10 0.072(8) 0.34(2) 0.086(9) -0.075(12) -0.010(6) 0.023(11)
C11 0.063(6) 0.104(8) 0.081(6) 0.021(5) -0.006(5) 0.022(5)
C12 0.055(4) 0.064(5) 0.065(5) 0.000(4) 0.003(4) 0.013(4)
C13 0.059(4) 0.063(5) 0.047(4) -0.002(3) 0.004(3) 0.009(4)
C14 0.077(5) 0.072(5) 0.050(4) -0.009(4) 0.007(4) 0.010(4)
C15 0.101(7) 0.084(7) 0.074(6) -0.030(5) 0.011(5) 0.020(6)
C16 0.081(6) 0.063(5) 0.098(7) -0.007(5) 0.008(5) 0.023(5)

_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
Pd1 N2 2.014(6) 3 ?
Pd1 N2 2.014(6) . ?
Pd1 N2 2.014(6) 2 ?
Pd1 N2 2.014(6) 4 ?
Pd2 N1 2.024(6) 3 ?
Pd2 N1 2.024(6) . ?
Pd2 N1 2.024(6) 2 ?
Pd2 N1 2.024(6) 4 ?
O1 C6 1.212(11) . ?
O2 C11 1.201(11) . ?
O3 N5 1.137(18) . ?
O4 N5 1.14(2) . ?
O5 N6 1.06(2) . ?
O6 N6 1.06(2) . ?
N1 C1 1.342(9) . ?
N1 C5 1.349(9) . ?
N2 C14 1.339(9) . ?
N2 C13 1.355(9) . ?
N3 C11 1.296(12) . ?
N3 C9 1.498(15) . ?
N3 C8 1.474(15) . ?
N4 C6 1.272(12) . ?
N4 C7 1.460(13) . ?
N4 C10 1.494(15) . ?
C1 C2 1.361(12) . ?
C2 C3 1.369(13) . ?
C3 C4 1.371(12) . ?
C4 C5 1.384(11) . ?
C4 C6 1.509(12) . ?
C7 C8 1.363(18) . ?
C9 C10 1.170(18) . ?
C11 C12 1.505(12) . ?
C12 C13 1.356(10) . ?
C12 C16 1.369(12) . ?
C14 C15 1.369(13) . ?
C15 C16 1.378(13) . ?

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
N2 Pd1 N2 89.903(14) 3 . ?
N2 Pd1 N2 89.903(14) 3 2 ?
N2 Pd1 N2 175.3(3) . 2 ?
N2 Pd1 N2 175.3(3) 3 4 ?
N2 Pd1 N2 89.903(15) . 4 ?
N2 Pd1 N2 89.903(14) 2 4 ?
N1 Pd2 N1 89.935(11) 3 . ?
N1 Pd2 N1 89.935(12) 3 2 ?
N1 Pd2 N1 176.2(3) . 2 ?
N1 Pd2 N1 176.2(3) 3 4 ?
N1 Pd2 N1 89.935(12) . 4 ?
N1 Pd2 N1 89.935(11) 2 4 ?
C1 N1 C5 119.4(7) . . ?
C1 N1 Pd2 122.4(5) . . ?
C5 N1 Pd2 118.2(5) . . ?
C14 N2 C13 117.7(6) . . ?
C14 N2 Pd1 124.1(5) . . ?
C13 N2 Pd1 118.2(5) . . ?
C11 N3 C9 118.8(9) . . ?
C11 N3 C8 127.4(9) . . ?
C9 N3 C8 113.5(9) . . ?
C6 N4 C7 118.7(9) . . ?
C6 N4 C10 126.9(9) . . ?
C7 N4 C10 114.4(9) . . ?
O4 N5 O3 180.000(9) . . ?
O6 N6 O5 180.000(4) . . ?
N1 C1 C2 120.7(8) . . ?
C1 C2 C3 120.8(8) . . ?
C4 C3 C2 118.9(9) . . ?
C3 C4 C5 118.7(8) . . ?
C3 C4 C6 123.1(8) . . ?
C5 C4 C6 117.8(8) . . ?
N1 C5 C4 121.5(7) . . ?
O1 C6 N4 122.6(9) . . ?
O1 C6 C4 118.6(9) . . ?
N4 C6 C4 118.8(9) . . ?
C8 C7 N4 111.5(12) . . ?
C7 C8 N3 114.1(11) . . ?
C10 C9 N3 120.2(14) . . ?
C9 C10 N4 121.1(13) . . ?
O2 C11 N3 122.5(9) . . ?
O2 C11 C12 118.7(9) . . ?
N3 C11 C12 118.7(8) . . ?
C13 C12 C16 117.7(8) . . ?
C13 C12 C11 119.7(7) . . ?
C16 C12 C11 122.3(8) . . ?
C12 C13 N2 123.7(7) . . ?
N2 C14 C15 121.6(8) . . ?
C14 C15 C16 119.3(8) . . ?
C12 C16 C15 120.0(8) . . ?

_diffrn_measured_fraction_theta_max 0.995
_diffrn_reflns_theta_full        28.35
_diffrn_measured_fraction_theta_full 0.995
_refine_diff_density_max         1.155
_refine_diff_density_min         -0.870
_refine_diff_density_rms         0.141