# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_1ni_sq
_database_code_depnum_ccdc_archive 'CCDC 1552248'
_audit_update_record             
;
2017-10-01 deposited with the CCDC.
2017-10-04 downloaded from the CCDC.
;
_audit_creation_date             2017-10-01
_audit_creation_method           
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '0.33(C126 H114 Co3 N18 Ni6 O60), 4(H2 O)'
_chemical_formula_sum            'C42 H46 Co N6 Ni2 O24'
_chemical_formula_weight         1195.20
_chemical_absolute_configuration ?
_chemical_melting_point          ?
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'
Co Co 0.3494 0.9721 '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'

_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.
;
_space_group_crystal_system      hexagonal
_space_group_IT_number           180
_space_group_name_H-M_alt        'P 62 2 2'
_space_group_name_Hall           'P 62 2c (0 0 1)'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'x-y, x, z+1/3'
'-y, x-y, z+2/3'
'-x, -y, z'
'-x+y, -x, z+1/3'
'y, -x+y, z+2/3'
'x-y, -y, -z'
'-x, -x+y, -z+1/3'
'y, x, -z+2/3'
'-y, -x, -z+2/3'
'-x+y, y, -z'
'x, x-y, -z+1/3'

_cell_length_a                   27.857(2)
_cell_length_b                   27.857(2)
_cell_length_c                   10.0365(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     6745.2(11)
_cell_formula_units_Z            3
_cell_measurement_reflns_used    1197
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      18.5710
_cell_measurement_theta_min      3.6610
_shelx_estimated_absorpt_T_max   0.926
_shelx_estimated_absorpt_T_min   0.881
_exptl_absorpt_coefficient_mu    0.648
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75483
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    0.883
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             1845
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1768
_diffrn_reflns_av_unetI/netI     0.0854
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            67475
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_min         3.018
_diffrn_ambient_temperature      173.15
_diffrn_detector_area_resol_mean 15.9853
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       'ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'Enhance (Mo) X-ray Source'
_reflns_Friedel_coverage         0.720
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3255
_reflns_number_total             4121
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
;
_computing_data_collection       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
;
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_refine_diff_density_max         0.274
_refine_diff_density_min         -0.334
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details 
;
 Flack x determined using 963 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.019(13)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.944
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     173
_refine_ls_number_reflns         4121
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.0712
_refine_ls_R_factor_gt           0.0543
_refine_ls_restrained_S_all      1.261
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0488P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0995
_refine_ls_wR_factor_ref         0.1054
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All H(H) groups, All H(H,H) groups, All C(H) groups
2. Restrained distances
 O1W-H1WA = O4-H4
 0.82 with sigma of 0.02
 O1W-H1WB = O6-H6A
 0.82 with sigma of 0.02
 O5-H5A = O5-H5B
 0.82 with sigma of 0.02
 O1W-H1WA = O4-H4
 1.39 with sigma of 0.02
 O1W-H1WB = O6-H6A
 1.39 with sigma of 0.02
 O5-H5A = O5-H5B
 1.39 with sigma of 0.02
3.a Everything fixed:
 H1WA, H1WB, H5A, H5B, H6A(H4)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C6(H6), C7(H7), C9(H9), C10(H10)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
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
C1 C 0.6633(3) 0.0000 0.0000 0.066(3) Uani 1 2 d S T P . .
H1 H 0.6974 0.0000 0.0000 0.079 Uiso 1 2 calc RS T P . .
C2 C 0.6551(2) 0.0335(2) 0.0886(5) 0.0546(16) Uani 1 1 d . . . . .
H2 H 0.6833 0.0562 0.1504 0.065 Uiso 1 1 calc R . . . .
C3 C 0.60538(19) 0.03359(19) 0.0857(4) 0.0298(11) Uani 1 1 d . . . . .
C4 C 0.58903(19) 0.06737(18) 0.1682(5) 0.0273(10) Uani 1 1 d . . . . .
C5 C 0.5161(2) 0.0862(2) 0.2025(4) 0.0332(12) Uani 1 1 d . . . . .
C6 C 0.5123(2) 0.1282(2) 0.1404(4) 0.0393(13) Uani 1 1 d . . . . .
H6 H 0.5239 0.1370 0.0504 0.047 Uiso 1 1 calc R . . . .
C7 C 0.4922(3) 0.1576(2) 0.2058(5) 0.0500(16) Uani 1 1 d . . . . .
H7 H 0.4902 0.1863 0.1598 0.060 Uiso 1 1 calc R . . . .
C8 C 0.4745(2) 0.14654(19) 0.3382(5) 0.0393(13) Uani 1 1 d . . . . .
C9 C 0.4778(2) 0.1047(2) 0.4011(5) 0.0451(14) Uani 1 1 d . . . . .
H9 H 0.4663 0.0965 0.4914 0.054 Uiso 1 1 calc R . . . .
C10 C 0.4976(2) 0.0737(2) 0.3366(5) 0.0449(13) Uani 1 1 d . . . . .
H10 H 0.4987 0.0444 0.3820 0.054 Uiso 1 1 calc R . . . .
C11 C 0.4576(3) 0.1822(2) 0.4099(5) 0.0568(17) Uani 1 1 d . . . . .
Co1 Co 0.5000 0.0000 0.0000 0.0236(3) Uani 1 4 d S T P . .
N1 N 0.56712(18) 0.0000 0.0000 0.0267(12) Uani 1 2 d S T P . .
N2 N 0.53829(16) 0.05651(14) 0.1377(3) 0.0266(9) Uani 1 1 d . . . . .
Ni1 Ni 0.42950(5) 0.21475(2) 0.6667 0.0449(3) Uani 1 2 d S T P . .
O1 O 0.62089(14) 0.10148(15) 0.2517(3) 0.0450(10) Uani 1 1 d . . . . .
O2 O 0.4720(2) 0.22916(19) 0.3608(4) 0.0905(16) Uani 1 1 d . . . . .
O1W O 0.5709(2) 0.3728(2) 0.7027(5) 0.1006(17) Uani 1 1 d D . . . .
O3 O 0.43255(17) 0.16510(14) 0.5192(4) 0.0556(11) Uani 1 1 d . . . . .
O4 O 0.5163(2) 0.25814(11) 0.6667 0.0710(17) Uani 1 2 d DS T P . .
O5 O 0.42825(17) 0.26836(15) 0.5308(3) 0.0551(11) Uani 1 1 d D . . . .
O6 O 0.3421(3) 0.17105(13) 0.6667 0.0842(19) Uani 1 2 d DS T P . .
H1WA H 0.5734 0.3632 0.5966 0.020 Uiso 1 1 d D . . . .
H1WB H 0.5454 0.3922 0.6837 0.256 Uiso 1 1 d D . . . .
H5A H 0.3957 0.2551 0.5030 0.308 Uiso 1 1 d D . . . .
H5B H 0.4520 0.2817 0.4756 0.308 Uiso 1 1 d D . . . .
H6A H 0.3161 0.1323 0.7229 0.123 Uiso 1 1 d D . . . .
H4 H 0.5455 0.3002 0.6965 0.148 Uiso 1 1 d D . . . .


_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
C1 H1 0.9500 . ?
C1 C2 1.388(7) 7 ?
C1 C2 1.388(7) . ?
C2 H2 0.9500 . ?
C2 C3 1.387(7) . ?
C3 C4 1.486(6) . ?
C3 N1 1.324(5) . ?
C4 N2 1.325(5) . ?
C4 O1 1.245(5) . ?
C5 C6 1.376(6) . ?
C5 C10 1.420(6) . ?
C5 N2 1.414(6) . ?
C6 H6 0.9500 . ?
C6 C7 1.368(6) . ?
C7 H7 0.9500 . ?
C7 C8 1.397(7) . ?
C8 C9 1.369(7) . ?
C8 C11 1.481(7) . ?
C9 H9 0.9500 . ?
C9 C10 1.395(7) . ?
C10 H10 0.9500 . ?
C11 O2 1.262(6) . ?
C11 O3 1.258(6) . ?
Co1 N1 1.870(5) 4_655 ?
Co1 N1 1.870(5) . ?
Co1 N2 1.961(3) 7 ?
Co1 N2 1.961(3) . ?
Co1 N2 1.961(3) 11_655 ?
Co1 N2 1.961(3) 4_655 ?
N1 C3 1.325(5) 7 ?
Ni1 O3 2.056(3) 12_556 ?
Ni1 O3 2.056(3) . ?
Ni1 O4 2.093(6) . ?
Ni1 O5 2.035(3) . ?
Ni1 O5 2.035(3) 12_556 ?
Ni1 O6 2.109(6) . ?
O1W H1WA 1.1091 . ?
O1W H1WB 1.1042 . ?
O4 H4 1.0814 . ?
O5 H5A 0.8376 . ?
O5 H5B 0.7991 . ?
O6 H6A 1.1076 . ?

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
C2 C1 H1 120.0 7 . ?
C2 C1 H1 120.0 . . ?
C2 C1 C2 120.0(7) 7 . ?
C1 C2 H2 120.4 . . ?
C1 C2 C3 119.1(5) . . ?
C3 C2 H2 120.4 . . ?
C2 C3 C4 127.7(4) . . ?
N1 C3 C2 117.7(5) . . ?
N1 C3 C4 114.6(4) . . ?
N2 C4 C3 110.9(4) . . ?
O1 C4 C3 122.1(4) . . ?
O1 C4 N2 127.0(4) . . ?
C6 C5 C10 117.7(4) . . ?
C6 C5 N2 122.1(4) . . ?
N2 C5 C10 120.3(4) . . ?
C5 C6 H6 119.3 . . ?
C7 C6 C5 121.3(4) . . ?
C7 C6 H6 119.3 . . ?
C6 C7 H7 119.0 . . ?
C6 C7 C8 122.0(4) . . ?
C8 C7 H7 119.0 . . ?
C7 C8 C11 120.7(4) . . ?
C9 C8 C7 117.3(5) . . ?
C9 C8 C11 121.8(5) . . ?
C8 C9 H9 119.0 . . ?
C8 C9 C10 121.9(5) . . ?
C10 C9 H9 119.0 . . ?
C5 C10 H10 120.1 . . ?
C9 C10 C5 119.7(5) . . ?
C9 C10 H10 120.1 . . ?
O2 C11 C8 117.5(5) . . ?
O3 C11 C8 118.2(5) . . ?
O3 C11 O2 124.2(5) . . ?
N1 Co1 N1 180.0 4_655 . ?
N1 Co1 N2 81.80(11) 4_655 4_655 ?
N1 Co1 N2 98.20(11) 4_655 . ?
N1 Co1 N2 98.20(11) 4_655 7 ?
N1 Co1 N2 98.20(11) . 4_655 ?
N1 Co1 N2 81.80(11) . 7 ?
N1 Co1 N2 81.80(11) . . ?
N1 Co1 N2 81.80(11) 4_655 11_655 ?
N1 Co1 N2 98.20(11) . 11_655 ?
N2 Co1 N2 163.6(2) 11_655 4_655 ?
N2 Co1 N2 90.41(19) 4_655 . ?
N2 Co1 N2 91.92(19) 11_655 . ?
N2 Co1 N2 90.41(19) 7 11_655 ?
N2 Co1 N2 91.92(19) 7 4_655 ?
N2 Co1 N2 163.6(2) 7 . ?
C3 N1 C3 126.3(6) . 7 ?
C3 N1 Co1 116.8(3) 7 . ?
C3 N1 Co1 116.8(3) . . ?
C4 N2 C5 119.2(4) . . ?
C4 N2 Co1 115.9(3) . . ?
C5 N2 Co1 124.9(3) . . ?
O3 Ni1 O3 175.9(2) . 12_556 ?
O3 Ni1 O4 87.95(12) 12_556 . ?
O3 Ni1 O4 87.95(12) . . ?
O3 Ni1 O6 92.05(12) 12_556 . ?
O3 Ni1 O6 92.05(12) . . ?
O4 Ni1 O6 180.00(7) . . ?
O5 Ni1 O3 91.89(13) . . ?
O5 Ni1 O3 88.17(13) 12_556 . ?
O5 Ni1 O3 88.17(13) . 12_556 ?
O5 Ni1 O3 91.89(13) 12_556 12_556 ?
O5 Ni1 O4 90.85(12) 12_556 . ?
O5 Ni1 O4 90.85(12) . . ?
O5 Ni1 O5 178.3(2) . 12_556 ?
O5 Ni1 O6 89.15(12) 12_556 . ?
O5 Ni1 O6 89.15(12) . . ?
H1WA O1W H1WB 94.9 . . ?
C11 O3 Ni1 125.1(3) . . ?
Ni1 O4 H4 130.6 . . ?
Ni1 O5 H5A 108.1 . . ?
Ni1 O5 H5B 119.4 . . ?
H5A O5 H5B 115.9 . . ?
Ni1 O6 H6A 124.4 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C2 H2 O5 0.95 2.55 3.260(6) 131.8 3_654
O1W H1WB O1 1.10 1.93 2.863(6) 140.1 5_665
O5 H5B O1 0.80 2.65 2.728(5) 86.7 5_665
O5 H5B O2 0.80 2.14 2.632(5) 119.6 .
O4 H4 O1W 1.08 1.78 2.791(6) 153.8 .

_olex2_submission_special_instructions 'No special instructions were received'
