# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 1420174'
_audit_update_record             
;
2015-10-10 deposited with the CCDC.
2015-10-15 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C53 H68 N12 Ni2 O8,8(H2 O),C3 H7 N O'
_chemical_formula_sum            'C56 H91 N13 Ni2 O17'
_chemical_formula_weight         1335.83

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'
Ni Ni 0.3393 1.1124 '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'

_space_group_crystal_system      tetragonal
_space_group_IT_number           117
_space_group_name_H-M_alt        'P -4 b 2'
_space_group_name_Hall           'P -4 -2ab'

_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'
'y, -x, -z'
'-x, -y, z'
'-y, x, -z'
'-x+1/2, y+1/2, z'
'y+1/2, x+1/2, -z'
'x+1/2, -y+1/2, z'
'-y+1/2, -x+1/2, -z'

_cell_length_a                   16.7806(6)
_cell_length_b                   16.7806(6)
_cell_length_c                   12.2501(13)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3449.5(4)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    1918
_cell_measurement_theta_min      3.18
_cell_measurement_theta_max      23.52

_exptl_crystal_description       block
_exptl_crystal_colour            purple
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_F_000             1420
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.290
_exptl_crystal_size_mid          0.270
_exptl_crystal_size_min          0.200
_exptl_absorpt_coefficient_mu    0.617
_shelx_estimated_absorpt_T_min   0.841
_shelx_estimated_absorpt_T_max   0.886
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6699
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_process_details   'SADABS (Bruker, 2000)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            7913
_diffrn_reflns_av_unetI/netI     0.0599
_diffrn_reflns_av_R_equivalents  0.0475
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         3.183
_diffrn_reflns_theta_max         25.395
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measured_fraction_theta_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.894
_diffrn_reflns_point_group_measured_fraction_full 0.900
_reflns_number_total             2850
_reflns_number_gt                2014
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.652
_reflns_Friedel_fraction_max     0.789
_reflns_Friedel_fraction_full    0.796

_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       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Diamond 3.2'
_computing_publication_material  'Diamond 3.2'
_refine_special_details          SQUEEZE
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0487P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_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 
;
 Flack x determined using 629 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.035(13)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         2850
_refine_ls_number_parameters     170
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0700
_refine_ls_R_factor_gt           0.0438
_refine_ls_wR_factor_ref         0.0988
_refine_ls_wR_factor_gt          0.0901
_refine_ls_goodness_of_fit_ref   0.983
_refine_ls_restrained_S_all      0.983
_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_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
Ni1 Ni 0.69405(3) 0.80595(3) 1.0000 0.0483(3) Uani 1 2 d S T P . .
O1 O 0.63314(19) 0.74348(18) 0.8725(3) 0.0524(9) Uani 1 1 d . . . . .
O2 O 0.5778(3) 0.8318(2) 0.7595(4) 0.0920(16) Uani 1 1 d . . . . .
N1 N 0.7113(3) 0.6942(2) 1.0739(4) 0.0605(13) Uani 1 1 d . . . . .
N2 N 0.5854(3) 0.6872(3) 1.1488(4) 0.0711(14) Uani 1 1 d . . . . .
N3 N 0.6735(2) 0.9101(2) 0.9179(4) 0.0535(11) Uani 1 1 d . . . . .
H3A H 0.6491 0.8948 0.8465 0.064 Uiso 1 1 d R U . . .
C1 C 0.5000 0.5000 0.5000 0.0352(18) Uani 1 4 d S T P . .
C2 C 0.5239(2) 0.5702(2) 0.5749(4) 0.0349(10) Uani 1 1 d . . . . .
C3 C 0.5016(3) 0.6481(3) 0.5534(4) 0.0480(12) Uani 1 1 d . . . . .
H3 H 0.4707 0.6596 0.4903 0.058 Uiso 1 1 calc R U . . .
C4 C 0.5699(3) 0.5568(3) 0.6681(3) 0.0381(11) Uani 1 1 d . . . . .
H4 H 0.5857 0.5038 0.6848 0.046 Uiso 1 1 calc R U . . .
C5 C 0.5929(3) 0.6162(3) 0.7356(4) 0.0448(12) Uani 1 1 d . . . . .
H5 H 0.6247 0.6045 0.7977 0.054 Uiso 1 1 calc R U . . .
C6 C 0.5697(3) 0.6954(3) 0.7143(4) 0.0446(12) Uani 1 1 d . . . . .
C7 C 0.5237(3) 0.7090(3) 0.6226(4) 0.0573(15) Uani 1 1 d . . . . .
H7 H 0.5069 0.7619 0.6068 0.069 Uiso 1 1 calc R U . . .
C8 C 0.5957(3) 0.7620(3) 0.7865(5) 0.0536(14) Uani 1 1 d . . . . .
C9 C 0.6401(4) 0.7048(4) 1.2417(6) 0.082(2) Uani 1 1 d . . . . .
H9A H 0.6318 0.6664 1.3019 0.098 Uiso 1 1 calc R U . . .
H9B H 0.6310 0.7594 1.2697 0.098 Uiso 1 1 calc R U . . .
C10 C 0.7241(4) 0.6968(3) 1.1947(5) 0.0718(17) Uani 1 1 d . . . . .
H10A H 0.7575 0.7430 1.2154 0.086 Uiso 1 1 calc R U . . .
H10B H 0.7500 0.6474 1.2207 0.086 Uiso 1 1 calc R U . . .
C11 C 0.7767(3) 0.6593(3) 1.0116(6) 0.0756(18) Uani 1 1 d . . . . .
H11A H 0.7561 0.6377 0.9418 0.091 Uiso 1 1 calc R U . . .
H11B H 0.8006 0.6148 1.0534 0.091 Uiso 1 1 calc R U . . .
C12 C 0.6102(3) 0.9510(3) 0.9810(5) 0.0535(14) Uani 1 1 d . . . . .
H12A H 0.5839 0.9916 0.9347 0.064 Uiso 1 1 calc R U . . .
H12B H 0.6338 0.9782 1.0450 0.064 Uiso 1 1 calc R U . . .
C13 C 0.7442(3) 0.9593(3) 0.8905(5) 0.0668(17) Uani 1 1 d . . . . .
H13A H 0.7288 0.9985 0.8339 0.080 Uiso 1 1 calc R U . . .
H13B H 0.7603 0.9895 0.9563 0.080 Uiso 1 1 calc R U . . .
C14 C 0.6347(3) 0.6488(3) 1.0699(5) 0.0682(17) Uani 1 1 d . . . . .
H14A H 0.6105 0.6517 0.9963 0.082 Uiso 1 1 calc R U . . .
H14B H 0.6432 0.5921 1.0892 0.082 Uiso 1 1 calc R U . . .


_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
Ni1 N3 2.046(4) 8_667 ?
Ni1 N3 2.046(4) . ?
Ni1 N1 2.102(4) 8_667 ?
Ni1 N1 2.102(4) . ?
Ni1 O1 2.141(3) . ?
Ni1 O1 2.141(3) 8_667 ?
O1 C8 1.265(6) . ?
O2 C8 1.254(6) . ?
N1 C11 1.459(7) . ?
N1 C10 1.495(8) . ?
N1 C14 1.496(7) . ?
N2 C14 1.425(8) . ?
N2 C13 1.455(7) 8_667 ?
N2 C9 1.492(7) . ?
N3 C12 1.482(6) . ?
N3 C13 1.484(6) . ?
N3 H3A 1.0000 . ?
C1 C2 1.546(4) . ?
C1 C2 1.546(4) 4_656 ?
C1 C2 1.546(4) 3_665 ?
C1 C2 1.546(4) 2_566 ?
C2 C3 1.385(6) . ?
C2 C4 1.396(6) . ?
C3 C7 1.380(6) . ?
C3 H3 0.9500 . ?
C4 C5 1.350(6) . ?
C4 H4 0.9500 . ?
C5 C6 1.408(6) . ?
C5 H5 0.9500 . ?
C6 C7 1.383(7) . ?
C6 C8 1.491(6) . ?
C7 H7 0.9500 . ?
C9 C10 1.528(9) . ?
C9 H9A 0.9900 . ?
C9 H9B 0.9900 . ?
C10 H10A 0.9900 . ?
C10 H10B 0.9900 . ?
C11 C11 1.547(12) 8_667 ?
C11 H11A 0.9900 . ?
C11 H11B 0.9900 . ?
C12 C12 1.524(9) 8_667 ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C13 N2 1.455(7) 8_667 ?
C13 H13A 0.9900 . ?
C13 H13B 0.9900 . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?

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
N3 Ni1 N3 87.3(2) 8_667 . ?
N3 Ni1 N1 175.54(17) 8_667 8_667 ?
N3 Ni1 N1 93.25(18) . 8_667 ?
N3 Ni1 N1 93.25(18) 8_667 . ?
N3 Ni1 N1 175.55(16) . . ?
N1 Ni1 N1 86.5(3) 8_667 . ?
N3 Ni1 O1 91.90(14) 8_667 . ?
N3 Ni1 O1 88.82(14) . . ?
N1 Ni1 O1 92.53(15) 8_667 . ?
N1 Ni1 O1 86.75(14) . . ?
N3 Ni1 O1 88.82(14) 8_667 8_667 ?
N3 Ni1 O1 91.90(14) . 8_667 ?
N1 Ni1 O1 86.75(14) 8_667 8_667 ?
N1 Ni1 O1 92.53(15) . 8_667 ?
O1 Ni1 O1 179.01(18) . 8_667 ?
C8 O1 Ni1 136.4(3) . . ?
C11 N1 C10 115.0(4) . . ?
C11 N1 C14 115.1(4) . . ?
C10 N1 C14 99.8(5) . . ?
C11 N1 Ni1 103.7(4) . . ?
C10 N1 Ni1 114.8(3) . . ?
C14 N1 Ni1 108.8(3) . . ?
C14 N2 C13 115.6(5) . 8_667 ?
C14 N2 C9 104.5(5) . . ?
C13 N2 C9 114.3(5) 8_667 . ?
C12 N3 C13 115.8(4) . . ?
C12 N3 Ni1 105.1(3) . . ?
C13 N3 Ni1 116.8(3) . . ?
C12 N3 H3A 106.4 . . ?
C13 N3 H3A 105.8 . . ?
Ni1 N3 H3A 106.2 . . ?
C2 C1 C2 110.65(16) . 4_656 ?
C2 C1 C2 107.1(3) . 3_665 ?
C2 C1 C2 110.65(16) 4_656 3_665 ?
C2 C1 C2 110.65(16) . 2_566 ?
C2 C1 C2 107.1(3) 4_656 2_566 ?
C2 C1 C2 110.65(16) 3_665 2_566 ?
C3 C2 C4 117.2(4) . . ?
C3 C2 C1 122.3(4) . . ?
C4 C2 C1 120.5(3) . . ?
C7 C3 C2 120.6(4) . . ?
C7 C3 H3 119.7 . . ?
C2 C3 H3 119.7 . . ?
C5 C4 C2 122.7(4) . . ?
C5 C4 H4 118.7 . . ?
C2 C4 H4 118.7 . . ?
C4 C5 C6 120.3(4) . . ?
C4 C5 H5 119.9 . . ?
C6 C5 H5 119.9 . . ?
C7 C6 C5 117.5(4) . . ?
C7 C6 C8 121.4(4) . . ?
C5 C6 C8 121.1(4) . . ?
C3 C7 C6 121.8(4) . . ?
C3 C7 H7 119.1 . . ?
C6 C7 H7 119.1 . . ?
O2 C8 O1 124.6(5) . . ?
O2 C8 C6 118.3(5) . . ?
O1 C8 C6 117.1(4) . . ?
N2 C9 C10 105.2(5) . . ?
N2 C9 H9A 110.7 . . ?
C10 C9 H9A 110.7 . . ?
N2 C9 H9B 110.7 . . ?
C10 C9 H9B 110.7 . . ?
H9A C9 H9B 108.8 . . ?
N1 C10 C9 104.1(5) . . ?
N1 C10 H10A 110.9 . . ?
C9 C10 H10A 110.9 . . ?
N1 C10 H10B 110.9 . . ?
C9 C10 H10B 110.9 . . ?
H10A C10 H10B 109.0 . . ?
N1 C11 C11 109.8(4) . 8_667 ?
N1 C11 H11A 109.7 . . ?
C11 C11 H11A 109.7 8_667 . ?
N1 C11 H11B 109.7 . . ?
C11 C11 H11B 109.7 8_667 . ?
H11A C11 H11B 108.2 . . ?
N3 C12 C12 109.3(3) . 8_667 ?
N3 C12 H12A 109.8 . . ?
C12 C12 H12A 109.8 8_667 . ?
N3 C12 H12B 109.8 . . ?
C12 C12 H12B 109.8 8_667 . ?
H12A C12 H12B 108.3 . . ?
N2 C13 N3 114.9(4) 8_667 . ?
N2 C13 H13A 108.5 8_667 . ?
N3 C13 H13A 108.5 . . ?
N2 C13 H13B 108.5 8_667 . ?
N3 C13 H13B 108.5 . . ?
H13A C13 H13B 107.5 . . ?
N2 C14 N1 104.3(4) . . ?
N2 C14 H14A 110.9 . . ?
N1 C14 H14A 110.9 . . ?
N2 C14 H14B 110.9 . . ?
N1 C14 H14B 110.9 . . ?
H14A C14 H14B 108.9 . . ?

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
C2 C1 C2 C3 -17.7(4) 4_656 . . . ?
C2 C1 C2 C3 -138.4(5) 3_665 . . . ?
C2 C1 C2 C3 100.9(5) 2_566 . . . ?
C2 C1 C2 C4 162.5(4) 4_656 . . . ?
C2 C1 C2 C4 41.8(3) 3_665 . . . ?
C2 C1 C2 C4 -78.9(3) 2_566 . . . ?
C4 C2 C3 C7 -0.6(7) . . . . ?
C1 C2 C3 C7 179.6(4) . . . . ?
C3 C2 C4 C5 -0.3(7) . . . . ?
C1 C2 C4 C5 179.4(4) . . . . ?
C2 C4 C5 C6 0.8(7) . . . . ?
C4 C5 C6 C7 -0.3(7) . . . . ?
C4 C5 C6 C8 -178.8(4) . . . . ?
C2 C3 C7 C6 1.1(8) . . . . ?
C5 C6 C7 C3 -0.6(8) . . . . ?
C8 C6 C7 C3 177.9(5) . . . . ?
Ni1 O1 C8 O2 -8.0(9) . . . . ?
Ni1 O1 C8 C6 173.6(3) . . . . ?
C7 C6 C8 O2 -3.1(8) . . . . ?
C5 C6 C8 O2 175.3(5) . . . . ?
C7 C6 C8 O1 175.4(5) . . . . ?
C5 C6 C8 O1 -6.1(8) . . . . ?
C14 N2 C9 C10 16.6(6) . . . . ?
C13 N2 C9 C10 -110.8(6) 8_667 . . . ?
C11 N1 C10 C9 -159.3(4) . . . . ?
C14 N1 C10 C9 -35.6(5) . . . . ?
Ni1 N1 C10 C9 80.5(5) . . . . ?
N2 C9 C10 N1 12.8(6) . . . . ?
C10 N1 C11 C11 -84.6(7) . . . 8_667 ?
C14 N1 C11 C11 160.3(6) . . . 8_667 ?
Ni1 N1 C11 C11 41.6(6) . . . 8_667 ?
C13 N3 C12 C12 -170.5(5) . . . 8_667 ?
Ni1 N3 C12 C12 -40.0(6) . . . 8_667 ?
C12 N3 C13 N2 166.6(5) . . . 8_667 ?
Ni1 N3 C13 N2 42.1(6) . . . 8_667 ?
C13 N2 C14 N1 86.3(5) 8_667 . . . ?
C9 N2 C14 N1 -40.2(5) . . . . ?
C11 N1 C14 N2 171.3(4) . . . . ?
C10 N1 C14 N2 47.7(5) . . . . ?
Ni1 N1 C14 N2 -72.8(5) . . . . ?

_refine_diff_density_max         0.279
_refine_diff_density_min         -0.216
_refine_diff_density_rms         0.038
# SQUEEZE RESULTS (Version =  11015)
# 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 0.000 49 3 ' '
2 0.500 0.500 0.000 49 3 ' '
3 0.072 0.391 0.500 1035 300 ' '
_platon_squeeze_void_probe_radius 1.20
_platon_squeeze_details          ?
# start Validation Reply Form
_vrf_CHEMW03_1                   
;
PROBLEM: ALERT: The ratio of given/expected molecular weight as
RESPONSE: The difference is due to the crystallization solvent
molecules that were removed by using SQUEEZE.
;
# end Validation Reply Form
####################################################################### 
# 
# 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_2
_database_code_depnum_ccdc_archive 'CCDC 1420175'
_audit_update_record             
;
2015-10-10 deposited with the CCDC.
2015-10-15 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C57 H76 N12 Ni2 O8, 10(H2 O)'
_chemical_formula_sum            'C57 H96 N12 Ni2 O18'
_chemical_formula_weight         1354.87

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'
Ni Ni 0.3393 1.1124 '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'

_space_group_crystal_system      tetragonal
_space_group_IT_number           117
_space_group_name_H-M_alt        'P -4 b 2'
_space_group_name_Hall           'P -4 -2ab'

_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'
'y, -x, -z'
'-x, -y, z'
'-y, x, -z'
'-x+1/2, y+1/2, z'
'y+1/2, x+1/2, -z'
'x+1/2, -y+1/2, z'
'-y+1/2, -x+1/2, -z'

_cell_length_a                   17.173(5)
_cell_length_b                   17.173(5)
_cell_length_c                   11.406(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3364(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    4725
_cell_measurement_theta_min      2.37
_cell_measurement_theta_max      24.20

_exptl_crystal_description       block
_exptl_crystal_colour            purple
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.338
_exptl_crystal_F_000             1444
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.500
_exptl_crystal_size_mid          0.210
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    0.635
_shelx_estimated_absorpt_T_min   0.742
_shelx_estimated_absorpt_T_max   0.939
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6825
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_process_details   'SADABS (Bruker, 2000)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            22735
_diffrn_reflns_av_unetI/netI     0.0482
_diffrn_reflns_av_R_equivalents  0.0575
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         1.677
_diffrn_reflns_theta_max         28.451
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             4240
_reflns_number_gt                3223
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.823
_reflns_Friedel_fraction_max     0.996
_reflns_Friedel_fraction_full    1.000

_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       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Diamond 3.2'
_computing_publication_material  'Diamond 3.2'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0931P)²+0.6490P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_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 
;
 Flack x determined using 1189 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.025(8)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         4240
_refine_ls_number_parameters     202
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0775
_refine_ls_R_factor_gt           0.0546
_refine_ls_wR_factor_ref         0.1590
_refine_ls_wR_factor_gt          0.1452
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_restrained_S_all      1.064
_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
Ni1 Ni 0.81853(3) 0.68147(3) 0.0000 0.0326(3) Uani 1 2 d S T P . .
O1 O 0.7514(2) 0.6177(2) 0.1177(3) 0.0389(8) Uani 1 1 d . . . . .
O2 O 0.8300(2) 0.5424(2) 0.2258(4) 0.0449(10) Uani 1 1 d . . . . .
N1 N 0.7079(3) 0.5729(3) -0.1747(5) 0.0503(13) Uani 1 1 d . . . . .
N2 N 0.8418(3) 0.5822(2) -0.0936(4) 0.0329(9) Uani 1 1 d . . . . .
H2 H 0.8656 0.5987 -0.1697 0.039 Uiso 1 1 d R U . . .
N3 N 0.7149(3) 0.7055(3) -0.0973(5) 0.0458(12) Uani 1 1 d . . . . .
C1 C 0.5000 0.5000 0.5000 0.0272(16) Uani 1 4 d S T P . .
C2 C 0.5717(3) 0.5147(3) 0.4207(4) 0.0262(9) Uani 1 1 d . . . . .
C3 C 0.5625(3) 0.5630(3) 0.3233(4) 0.0321(10) Uani 1 1 d . . . . .
H3 H 0.5125 0.5838 0.3061 0.038 Uiso 1 1 calc R U . . .
C4 C 0.6234(3) 0.5808(3) 0.2526(4) 0.0317(10) Uani 1 1 d . . . . .
H4 H 0.6161 0.6146 0.1875 0.038 Uiso 1 1 calc R U . . .
C5 C 0.6973(3) 0.5495(3) 0.2755(5) 0.0307(10) Uani 1 1 d . . . . .
C6 C 0.7055(3) 0.5004(3) 0.3705(4) 0.0314(10) Uani 1 1 d . . . . .
H6 H 0.7550 0.4780 0.3864 0.038 Uiso 1 1 calc R U . . .
C7 C 0.6441(3) 0.4832(3) 0.4419(4) 0.0300(10) Uani 1 1 d . . . . .
H7 H 0.6514 0.4493 0.5069 0.036 Uiso 1 1 calc R U . . .
C8 C 0.7653(3) 0.5708(3) 0.2004(5) 0.0367(11) Uani 1 1 d . . . . .
C9 C 0.6775(3) 0.7637(4) -0.0215(7) 0.0553(19) Uani 1 1 d . . . . .
H9A H 0.6532 0.7373 0.0464 0.066 Uiso 1 1 calc R U . . .
H9B H 0.6360 0.7907 -0.0658 0.066 Uiso 1 1 calc R U . . .
C10 C 0.7208(4) 0.7362(4) -0.2190(6) 0.0525(16) Uani 1 1 d . . . . .
H10A H 0.7529 0.7840 -0.2183 0.063 Uiso 1 1 calc R U . . .
H10B H 0.6680 0.7506 -0.2466 0.063 Uiso 1 1 calc R U . . .
C11 C 0.7566(4) 0.6779(3) -0.3063(6) 0.0498(15) Uani 1 1 d . . . . .
H11A H 0.7503 0.6981 -0.3870 0.060 Uiso 1 1 calc R U . . .
H11B H 0.8130 0.6728 -0.2904 0.060 Uiso 1 1 calc R U . . .
C12 C 0.7189(4) 0.5992(4) -0.2978(6) 0.0554(17) Uani 1 1 d . . . . .
H12A H 0.6676 0.6009 -0.3373 0.067 Uiso 1 1 calc R U . . .
H12B H 0.7516 0.5607 -0.3397 0.067 Uiso 1 1 calc R U . . .
C13 C 0.7729(3) 0.5327(3) -0.1221(5) 0.0406(12) Uani 1 1 d . . . . .
H13A H 0.7898 0.4909 -0.1762 0.049 Uiso 1 1 calc R U . . .
H13B H 0.7547 0.5075 -0.0491 0.049 Uiso 1 1 calc R U . . .
C14 C 0.6701(3) 0.6308(4) -0.1053(6) 0.0481(15) Uani 1 1 d . . . . .
H14A H 0.6620 0.6101 -0.0253 0.058 Uiso 1 1 calc R U . . .
H14B H 0.6182 0.6418 -0.1394 0.058 Uiso 1 1 calc R U . . .
C15 C 0.9020(3) 0.5404(3) -0.0272(4) 0.0311(11) Uani 1 1 d . . . . .
H15A H 0.9301 0.5044 -0.0801 0.037 Uiso 1 1 calc R U . . .
H15B H 0.8772 0.5092 0.0355 0.037 Uiso 1 1 calc R U . . .
O1W O 0.9330(6) 0.5502(4) 0.6173(6) 0.137(3) Uani 1 1 d . . . . .
O2W O 0.6034(6) 0.9037(6) 0.7124(9) 0.161(3) Uani 1 1 d . . . . .
O3W O 0.6637(6) 0.8363(6) 0.5000 0.278(14) Uani 1 2 d S T 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
Ni1 N2 2.050(4) 8_665 ?
Ni1 N2 2.050(4) . ?
Ni1 O1 2.082(3) 8_665 ?
Ni1 O1 2.082(3) . ?
Ni1 N3 2.137(5) 8_665 ?
Ni1 N3 2.137(5) . ?
O1 C8 1.263(6) . ?
O2 C8 1.248(6) . ?
N1 C14 1.427(9) . ?
N1 C13 1.443(7) . ?
N1 C12 1.487(8) . ?
N2 C15 1.469(6) . ?
N2 C13 1.493(6) . ?
N2 H2 1.0000 . ?
N3 C9 1.468(9) . ?
N3 C10 1.488(8) . ?
N3 C14 1.499(8) . ?
C1 C2 1.549(5) . ?
C1 C2 1.549(5) 3_665 ?
C1 C2 1.549(5) 4_656 ?
C1 C2 1.549(5) 2_566 ?
C2 C7 1.377(7) . ?
C2 C3 1.396(7) . ?
C3 C4 1.357(7) . ?
C3 H3 0.9500 . ?
C4 C5 1.402(7) . ?
C4 H4 0.9500 . ?
C5 C6 1.380(7) . ?
C5 C8 1.494(7) . ?
C6 C7 1.365(7) . ?
C6 H6 0.9500 . ?
C7 H7 0.9500 . ?
C9 C9 1.510(14) 8_665 ?
C9 H9A 0.9900 . ?
C9 H9B 0.9900 . ?
C10 C11 1.540(9) . ?
C10 H10A 0.9900 . ?
C10 H10B 0.9900 . ?
C11 C12 1.501(8) . ?
C11 H11A 0.9900 . ?
C11 H11B 0.9900 . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C13 H13A 0.9900 . ?
C13 H13B 0.9900 . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 C15 1.530(9) 8_665 ?
C15 H15A 0.9900 . ?
C15 H15B 0.9900 . ?

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 Ni1 N2 87.0(2) 8_665 . ?
N2 Ni1 O1 90.37(16) 8_665 8_665 ?
N2 Ni1 O1 91.26(16) . 8_665 ?
N2 Ni1 O1 91.27(16) 8_665 . ?
N2 Ni1 O1 90.37(16) . . ?
O1 Ni1 O1 177.8(2) 8_665 . ?
N2 Ni1 N3 93.01(19) 8_665 8_665 ?
N2 Ni1 N3 179.8(2) . 8_665 ?
O1 Ni1 N3 88.58(16) 8_665 8_665 ?
O1 Ni1 N3 89.79(16) . 8_665 ?
N2 Ni1 N3 179.8(2) 8_665 . ?
N2 Ni1 N3 93.01(19) . . ?
O1 Ni1 N3 89.79(16) 8_665 . ?
O1 Ni1 N3 88.58(17) . . ?
N3 Ni1 N3 87.0(3) 8_665 . ?
C8 O1 Ni1 135.4(3) . . ?
C14 N1 C13 117.1(5) . . ?
C14 N1 C12 111.8(5) . . ?
C13 N1 C12 116.0(5) . . ?
C15 N2 C13 113.1(4) . . ?
C15 N2 Ni1 106.0(3) . . ?
C13 N2 Ni1 115.6(4) . . ?
C15 N2 H2 107.3 . . ?
C13 N2 H2 107.2 . . ?
Ni1 N2 H2 107.3 . . ?
C9 N3 C10 109.8(5) . . ?
C9 N3 C14 113.2(5) . . ?
C10 N3 C14 106.3(5) . . ?
C9 N3 Ni1 100.9(4) . . ?
C10 N3 Ni1 119.8(4) . . ?
C14 N3 Ni1 107.1(3) . . ?
C2 C1 C2 108.5(3) . 3_665 ?
C2 C1 C2 109.96(17) . 4_656 ?
C2 C1 C2 109.96(17) 3_665 4_656 ?
C2 C1 C2 109.96(17) . 2_566 ?
C2 C1 C2 109.96(17) 3_665 2_566 ?
C2 C1 C2 108.5(3) 4_656 2_566 ?
C7 C2 C3 118.4(4) . . ?
C7 C2 C1 123.5(4) . . ?
C3 C2 C1 118.1(4) . . ?
C4 C3 C2 121.3(4) . . ?
C4 C3 H3 119.4 . . ?
C2 C3 H3 119.4 . . ?
C3 C4 C5 120.0(5) . . ?
C3 C4 H4 120.0 . . ?
C5 C4 H4 120.0 . . ?
C6 C5 C4 118.3(4) . . ?
C6 C5 C8 121.3(4) . . ?
C4 C5 C8 120.4(5) . . ?
C7 C6 C5 121.4(5) . . ?
C7 C6 H6 119.3 . . ?
C5 C6 H6 119.3 . . ?
C6 C7 C2 120.5(5) . . ?
C6 C7 H7 119.7 . . ?
C2 C7 H7 119.7 . . ?
O2 C8 O1 126.3(5) . . ?
O2 C8 C5 117.9(5) . . ?
O1 C8 C5 115.8(5) . . ?
N3 C9 C9 110.7(4) . 8_665 ?
N3 C9 H9A 109.5 . . ?
C9 C9 H9A 109.5 8_665 . ?
N3 C9 H9B 109.5 . . ?
C9 C9 H9B 109.5 8_665 . ?
H9A C9 H9B 108.1 . . ?
N3 C10 C11 113.6(5) . . ?
N3 C10 H10A 108.8 . . ?
C11 C10 H10A 108.8 . . ?
N3 C10 H10B 108.8 . . ?
C11 C10 H10B 108.8 . . ?
H10A C10 H10B 107.7 . . ?
C12 C11 C10 111.8(6) . . ?
C12 C11 H11A 109.3 . . ?
C10 C11 H11A 109.3 . . ?
C12 C11 H11B 109.3 . . ?
C10 C11 H11B 109.3 . . ?
H11A C11 H11B 107.9 . . ?
N1 C12 C11 112.9(6) . . ?
N1 C12 H12A 109.0 . . ?
C11 C12 H12A 109.0 . . ?
N1 C12 H12B 109.0 . . ?
C11 C12 H12B 109.0 . . ?
H12A C12 H12B 107.8 . . ?
N1 C13 N2 115.5(4) . . ?
N1 C13 H13A 108.4 . . ?
N2 C13 H13A 108.4 . . ?
N1 C13 H13B 108.4 . . ?
N2 C13 H13B 108.4 . . ?
H13A C13 H13B 107.5 . . ?
N1 C14 N3 113.3(5) . . ?
N1 C14 H14A 108.9 . . ?
N3 C14 H14A 108.9 . . ?
N1 C14 H14B 108.9 . . ?
N3 C14 H14B 108.9 . . ?
H14A C14 H14B 107.7 . . ?
N2 C15 C15 110.4(3) . 8_665 ?
N2 C15 H15A 109.6 . . ?
C15 C15 H15A 109.6 8_665 . ?
N2 C15 H15B 109.6 . . ?
C15 C15 H15B 109.6 8_665 . ?
H15A C15 H15B 108.1 . . ?

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
C2 C1 C2 C7 -137.4(5) 3_665 . . . ?
C2 C1 C2 C7 102.3(5) 4_656 . . . ?
C2 C1 C2 C7 -17.1(4) 2_566 . . . ?
C2 C1 C2 C3 43.3(3) 3_665 . . . ?
C2 C1 C2 C3 -77.0(3) 4_656 . . . ?
C2 C1 C2 C3 163.6(4) 2_566 . . . ?
C7 C2 C3 C4 -1.9(7) . . . . ?
C1 C2 C3 C4 177.4(4) . . . . ?
C2 C3 C4 C5 1.1(7) . . . . ?
C3 C4 C5 C6 0.4(7) . . . . ?
C3 C4 C5 C8 -178.1(5) . . . . ?
C4 C5 C6 C7 -1.0(7) . . . . ?
C8 C5 C6 C7 177.4(5) . . . . ?
C5 C6 C7 C2 0.2(7) . . . . ?
C3 C2 C7 C6 1.3(7) . . . . ?
C1 C2 C7 C6 -178.0(4) . . . . ?
Ni1 O1 C8 O2 -9.0(9) . . . . ?
Ni1 O1 C8 C5 169.6(3) . . . . ?
C6 C5 C8 O2 0.4(8) . . . . ?
C4 C5 C8 O2 178.8(5) . . . . ?
C6 C5 C8 O1 -178.3(5) . . . . ?
C4 C5 C8 O1 0.1(7) . . . . ?
C10 N3 C9 C9 -83.6(7) . . . 8_665 ?
C14 N3 C9 C9 157.9(6) . . . 8_665 ?
Ni1 N3 C9 C9 43.8(7) . . . 8_665 ?
C9 N3 C10 C11 -177.9(5) . . . . ?
C14 N3 C10 C11 -55.1(6) . . . . ?
Ni1 N3 C10 C11 66.2(6) . . . . ?
N3 C10 C11 C12 49.2(7) . . . . ?
C14 N1 C12 C11 50.9(7) . . . . ?
C13 N1 C12 C11 -86.9(7) . . . . ?
C10 C11 C12 N1 -44.6(7) . . . . ?
C14 N1 C13 N2 -63.9(6) . . . . ?
C12 N1 C13 N2 71.6(7) . . . . ?
C15 N2 C13 N1 172.8(5) . . . . ?
Ni1 N2 C13 N1 50.4(6) . . . . ?
C13 N1 C14 N3 76.3(6) . . . . ?
C12 N1 C14 N3 -61.0(6) . . . . ?
C9 N3 C14 N1 -177.4(5) . . . . ?
C10 N3 C14 N1 62.1(6) . . . . ?
Ni1 N3 C14 N1 -67.0(6) . . . . ?
C13 N2 C15 C15 -164.8(5) . . . 8_665 ?
Ni1 N2 C15 C15 -37.2(5) . . . 8_665 ?

_refine_diff_density_max         0.877
_refine_diff_density_min         -0.430
_refine_diff_density_rms         0.082
# start Validation Reply Form
_vrf_PLAT043_2                   
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PROBLEM: Calculated and Reported Mol. Weight Differ by ..      20.19 Check 
RESPONSE: The differnce is due to the hydrogen atoms on isolated water 
molecules that cannot be found from E-map during the refinement.
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_vrf_PLAT306_2                   
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PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?) .......        O1W Check 
RESPONSE: The hydrogen atoms on isolated water were not added.
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_vrf_PLAT430_2                   
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PROBLEM: Short Inter D...A Contact  O1W    ..  O1W     ..       2.71 Ang.  
RESPONSE: The hydrogen bonding should be present between the two atoms.
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_vrf_PLAT987_2                   
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PROBLEM: The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check
RESPONSE: The Flack value is 0.025(8), suggesting the presence of a 
small degree of disorder.
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# end Validation Reply Form
