# 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_ddb
_database_code_depnum_ccdc_archive 'CCDC 1544252'
_audit_update_record             
;
2017-08-29 deposited with the CCDC.
2017-09-06 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         ?
_chemical_formula_sum            'C44 H42 N4 Ni3 O16'
_chemical_formula_weight         1058.94

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'
Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           165
_space_group_name_H-M_alt        'P -3 c 1'
_space_group_name_Hall           '-P 3 2"c'

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

_cell_length_a                   19.403(2)
_cell_length_b                   19.403(2)
_cell_length_c                   21.606(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     7044(2)
_cell_formula_units_Z            6
_cell_measurement_temperature    273(2)
_cell_measurement_reflns_used    5065
_cell_measurement_theta_min      2.24
_cell_measurement_theta_max      23.25

_exptl_crystal_description       block
_exptl_crystal_colour            green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.498
_exptl_crystal_F_000             3276
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.140
_exptl_absorpt_coefficient_mu    1.264
_shelx_estimated_absorpt_T_min   0.786
_shelx_estimated_absorpt_T_max   0.843
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      273(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            33281
_diffrn_reflns_av_unetI/netI     0.0363
_diffrn_reflns_av_R_equivalents  0.0644
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         2.301
_diffrn_reflns_theta_max         25.049
_diffrn_reflns_theta_full        25.049
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measured_fraction_theta_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_point_group_measured_fraction_full 0.989
_reflns_number_total             4123
_reflns_number_gt                3076
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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    'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_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)+(0.0130P)²+82.1032P] 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_number_reflns         4123
_refine_ls_number_parameters     322
_refine_ls_number_restraints     30
_refine_ls_R_factor_all          0.0955
_refine_ls_R_factor_gt           0.0709
_refine_ls_wR_factor_ref         0.1619
_refine_ls_wR_factor_gt          0.1544
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_restrained_S_all      1.028
_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 0.93589(5) 0.16357(5) 0.42095(4) 0.0320(2) Uani 1 1 d . . . A 1
Ni2 Ni 1.3333 0.6667 0.33690(6) 0.0221(3) Uani 1 3 d S TU P A 1
Ni3 Ni 1.0000 0.0000 0.2500 0.0261(4) Uani 1 6 d S T P A 1
O1 O 0.9753(3) 0.1503(3) 0.3355(2) 0.0404(11) Uani 1 1 d . . . A 1
O2 O 1.0680(4) 0.1213(4) 0.3095(3) 0.0781(19) Uani 1 1 d . . . A 1
O3 O 1.0466(3) 0.1949(3) 0.4578(2) 0.0438(12) Uani 1 1 d . . . A 1
O4 O 1.1695(3) 0.2720(3) 0.4909(2) 0.0421(12) Uani 1 1 d . . . A 1
O5 O 1.2832(4) 0.5452(3) 0.3864(3) 0.0613(15) Uani 1 1 d . U . A 1
O6 O 1.2742(4) 0.5470(4) 0.2855(3) 0.0775(18) Uani 1 1 d . U . A 1
C1 C 1.0455(4) 0.1688(5) 0.3277(3) 0.0418(17) Uani 1 1 d . . . A 1
C2 C 1.1165(4) 0.2506(4) 0.4512(3) 0.0340(15) Uani 1 1 d . . . A 1
C3 C 1.2582(5) 0.5077(5) 0.3354(4) 0.0500(19) Uani 1 1 d . . . A 1
C4 C 1.1080(4) 0.2557(5) 0.3338(3) 0.0397(17) Uani 1 1 d . . . A 1
C5 C 1.1392(4) 0.2959(4) 0.3901(3) 0.0354(15) Uani 1 1 d . . . A 1
C6 C 1.1906(4) 0.3763(4) 0.3902(3) 0.0410(16) Uani 1 1 d . . . A 1
H6A H 1.2122 0.4020 0.4275 0.049 Uiso 1 1 calc R U . A 1
C7 C 1.2114(4) 0.4209(4) 0.3354(3) 0.0409(16) Uani 1 1 d . . . A 1
C8 C 1.1836(5) 0.3795(5) 0.2802(3) 0.051(2) Uani 1 1 d . . . A 1
H8A H 1.1997 0.4074 0.2431 0.061 Uiso 1 1 calc R U . A 1
C9 C 1.1336(4) 0.2995(5) 0.2787(3) 0.0443(18) Uani 1 1 d . . . A 1
H9A H 1.1162 0.2737 0.2409 0.053 Uiso 1 1 calc R U . A 1
N1 N 0.8221(3) 0.1215(3) 0.3868(3) 0.0388(14) Uani 1 1 d . . . A 1
N2 N 0.3129(3) 0.0296(3) 0.4101(3) 0.0358(13) Uani 1 1 d . . . A 1
C10 C 0.6996(5) 0.1226(5) 0.3898(4) 0.053(2) Uani 1 1 d . . . A 1
H10A H 0.6718 0.1478 0.4020 0.063 Uiso 1 1 calc R U . A 1
C11 C 0.7784(4) 0.1545(5) 0.4058(4) 0.0469(19) Uani 1 1 d . . . A 1
H11A H 0.8024 0.2000 0.4303 0.056 Uiso 1 1 calc R U . A 1
C12 C 0.7863(4) 0.0564(4) 0.3524(3) 0.0409(17) Uani 1 1 d . . . A 1
H12A H 0.8155 0.0332 0.3389 0.049 Uiso 1 1 calc R U . A 1
C13 C 0.7071(4) 0.0217(4) 0.3360(3) 0.0437(18) Uani 1 1 d . . . A 1
H13A H 0.6846 -0.0235 0.3111 0.052 Uiso 1 1 calc R U . A 1
C14 C 0.6614(4) 0.0525(5) 0.3554(4) 0.050(2) Uani 1 1 d . . . A 1
C15 C 0.5727(5) 0.0114(6) 0.3435(4) 0.061(2) Uani 1 1 d . . . A 1
H15A H 0.5610 -0.0143 0.3033 0.073 Uiso 1 1 calc R U . A 1
H15B H 0.5554 0.0504 0.3433 0.073 Uiso 1 1 calc R U . A 1
C16 C 0.5279(4) -0.0504(5) 0.3933(4) 0.0495(19) Uani 1 1 d . . . A 1
H16A H 0.5368 -0.0235 0.4329 0.059 Uiso 1 1 calc R U . A 1
H16B H 0.5494 -0.0859 0.3960 0.059 Uiso 1 1 calc R U . A 1
C17 C 0.4372(4) -0.1004(5) 0.3817(4) 0.050(2) Uani 1 1 d . . . A 1
H17A H 0.4280 -0.1209 0.3397 0.060 Uiso 1 1 calc R U . A 1
H17B H 0.4143 -0.1455 0.4097 0.060 Uiso 1 1 calc R U . A 1
C18 C 0.3963(4) -0.0520(4) 0.3909(3) 0.0399(17) Uani 1 1 d . . . A 1
C19 C 0.3785(5) -0.0166(5) 0.3430(3) 0.0489(19) Uani 1 1 d . . . A 1
H19A H 0.3945 -0.0193 0.3030 0.059 Uiso 1 1 calc R U . A 1
C20 C 0.3373(4) 0.0227(5) 0.3539(3) 0.0430(17) Uani 1 1 d . . . A 1
H20A H 0.3259 0.0456 0.3205 0.052 Uiso 1 1 calc R U . A 1
C21 C 0.3324(4) -0.0024(4) 0.4577(3) 0.0413(17) Uani 1 1 d . . . A 1
H21A H 0.3177 0.0031 0.4975 0.050 Uiso 1 1 calc R U . A 1
C22 C 0.3729(4) -0.0426(5) 0.4494(4) 0.0457(18) Uani 1 1 d . . . A 1
H22A H 0.3849 -0.0639 0.4835 0.055 Uiso 1 1 calc R U . A 1
O1W O 0.9156(3) 0.0480(3) 0.4341(2) 0.0563(15) Uani 1 1 d . . . A 1
H1WC H 0.8938 0.0124 0.4064 0.068 Uiso 1 1 d R U . A 1
H1WD H 0.8845 0.0353 0.4650 0.068 Uiso 1 1 d R U . A 1
O2W O 1.2575(12) 0.5452(10) 0.5099(6) 0.115(6) Uani 0.5 1 d . U P B 2
O3W O 1.1821(18) 0.5723(19) 0.1991(14) 0.094(9) Uani 0.25 1 d . U P C 2
O4W O 1.3847(16) 0.562(2) 0.5607(14) 0.103(11) Uani 0.25 1 d . . P D 1


_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 O1 2.063(5) . ?
Ni1 O4 2.069(5) 9_546 ?
Ni1 N1 2.070(6) . ?
Ni1 O3 2.077(5) . ?
Ni1 N2 2.084(6) 2_655 ?
Ni1 O1W 2.093(5) . ?
Ni2 O6 2.297(6) 3_775 ?
Ni2 O6 2.297(6) 2_755 ?
Ni2 O6 2.297(6) . ?
Ni2 O5 2.313(5) . ?
Ni2 O5 2.313(5) 3_775 ?
Ni2 O5 2.313(6) 2_755 ?
Ni3 O2 2.413(7) . ?
O1 C1 1.234(8) . ?
O2 C1 1.265(9) . ?
O3 C2 1.250(8) . ?
O4 C2 1.240(8) . ?
O4 Ni1 2.069(5) 8_666 ?
O5 C3 1.276(9) . ?
O6 C3 1.265(9) . ?
C1 C4 1.512(11) . ?
C2 C5 1.523(9) . ?
C3 C7 1.459(11) . ?
C4 C9 1.403(10) . ?
C4 C5 1.408(9) . ?
C5 C6 1.369(10) . ?
C6 C7 1.401(9) . ?
C6 H6A 0.9300 . ?
C7 C8 1.388(10) . ?
C8 C9 1.358(11) . ?
C8 H8A 0.9300 . ?
C9 H9A 0.9300 . ?
N1 C12 1.324(9) . ?
N1 C11 1.356(9) . ?
N2 C20 1.334(9) . ?
N2 C21 1.348(9) . ?
N2 Ni1 2.084(6) 3_665 ?
C10 C11 1.376(10) . ?
C10 C14 1.394(11) . ?
C10 H10A 0.9300 . ?
C11 H11A 0.9300 . ?
C12 C13 1.381(10) . ?
C12 H12A 0.9300 . ?
C13 C14 1.360(11) . ?
C13 H13A 0.9300 . ?
C14 C15 1.512(10) . ?
C15 C16 1.519(11) . ?
C15 H15A 0.9700 . ?
C15 H15B 0.9700 . ?
C16 C17 1.547(10) . ?
C16 H16A 0.9700 . ?
C16 H16B 0.9700 . ?
C17 C18 1.515(10) . ?
C17 H17A 0.9700 . ?
C17 H17B 0.9700 . ?
C18 C19 1.379(10) . ?
C18 C22 1.386(10) . ?
C19 C20 1.373(10) . ?
C19 H19A 0.9300 . ?
C20 H20A 0.9300 . ?
C21 C22 1.369(10) . ?
C21 H21A 0.9300 . ?
C22 H22A 0.9300 . ?
O1W H1WC 0.8500 . ?
O1W H1WD 0.8500 . ?

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
O1 Ni1 O4 175.5(2) . 9_546 ?
O1 Ni1 N1 91.2(2) . . ?
O4 Ni1 N1 90.4(2) 9_546 . ?
O1 Ni1 O3 89.21(19) . . ?
O4 Ni1 O3 88.8(2) 9_546 . ?
N1 Ni1 O3 174.6(2) . . ?
O1 Ni1 N2 96.1(2) . 2_655 ?
O4 Ni1 N2 88.0(2) 9_546 2_655 ?
N1 Ni1 N2 94.8(2) . 2_655 ?
O3 Ni1 N2 90.5(2) . 2_655 ?
O1 Ni1 O1W 82.6(2) . . ?
O4 Ni1 O1W 93.1(2) 9_546 . ?
N1 Ni1 O1W 92.0(2) . . ?
O3 Ni1 O1W 82.7(2) . . ?
N2 Ni1 O1W 173.1(2) 2_655 . ?
O6 Ni2 O6 98.62(19) 3_775 2_755 ?
O6 Ni2 O6 98.62(19) 3_775 . ?
O6 Ni2 O6 98.62(19) 2_755 . ?
O6 Ni2 O5 132.3(2) 3_775 . ?
O6 Ni2 O5 123.2(2) 2_755 . ?
O6 Ni2 O5 56.7(2) . . ?
O6 Ni2 O5 56.7(2) 3_775 3_775 ?
O6 Ni2 O5 132.3(2) 2_755 3_775 ?
O6 Ni2 O5 123.2(2) . 3_775 ?
O5 Ni2 O5 100.32(19) . 3_775 ?
O6 Ni2 O5 123.2(2) 3_775 2_755 ?
O6 Ni2 O5 56.7(2) 2_755 2_755 ?
O6 Ni2 O5 132.3(2) . 2_755 ?
O5 Ni2 O5 100.32(19) . 2_755 ?
O5 Ni2 O5 100.32(19) 3_775 2_755 ?
C1 O1 Ni1 120.6(5) . . ?
C1 O2 Ni3 131.1(5) . . ?
C2 O3 Ni1 136.5(4) . . ?
C2 O4 Ni1 129.3(5) . 8_666 ?
C3 O5 Ni2 91.6(5) . . ?
C3 O6 Ni2 92.7(5) . . ?
O1 C1 O2 124.3(7) . . ?
O1 C1 C4 117.8(6) . . ?
O2 C1 C4 117.5(7) . . ?
O4 C2 O3 124.7(6) . . ?
O4 C2 C5 117.0(6) . . ?
O3 C2 C5 118.3(6) . . ?
O6 C3 O5 118.8(8) . . ?
O6 C3 C7 121.3(7) . . ?
O5 C3 C7 119.9(7) . . ?
C9 C4 C5 118.2(7) . . ?
C9 C4 C1 116.5(6) . . ?
C5 C4 C1 125.2(6) . . ?
C6 C5 C4 120.0(6) . . ?
C6 C5 C2 119.5(6) . . ?
C4 C5 C2 120.5(6) . . ?
C5 C6 C7 121.5(7) . . ?
C5 C6 H6A 119.2 . . ?
C7 C6 H6A 119.2 . . ?
C8 C7 C6 117.4(7) . . ?
C8 C7 C3 120.3(7) . . ?
C6 C7 C3 122.2(7) . . ?
C9 C8 C7 122.0(7) . . ?
C9 C8 H8A 119.0 . . ?
C7 C8 H8A 119.0 . . ?
C8 C9 C4 120.5(7) . . ?
C8 C9 H9A 119.8 . . ?
C4 C9 H9A 119.8 . . ?
C12 N1 C11 117.9(6) . . ?
C12 N1 Ni1 121.6(5) . . ?
C11 N1 Ni1 120.0(5) . . ?
C20 N2 C21 116.9(6) . . ?
C20 N2 Ni1 120.8(5) . 3_665 ?
C21 N2 Ni1 120.8(5) . 3_665 ?
C11 C10 C14 120.2(7) . . ?
C11 C10 H10A 119.9 . . ?
C14 C10 H10A 119.9 . . ?
N1 C11 C10 121.8(7) . . ?
N1 C11 H11A 119.1 . . ?
C10 C11 H11A 119.1 . . ?
N1 C12 C13 122.3(7) . . ?
N1 C12 H12A 118.9 . . ?
C13 C12 H12A 118.9 . . ?
C14 C13 C12 121.2(7) . . ?
C14 C13 H13A 119.4 . . ?
C12 C13 H13A 119.4 . . ?
C13 C14 C10 116.5(7) . . ?
C13 C14 C15 122.4(8) . . ?
C10 C14 C15 121.0(8) . . ?
C14 C15 C16 110.4(7) . . ?
C14 C15 H15A 109.6 . . ?
C16 C15 H15A 109.6 . . ?
C14 C15 H15B 109.6 . . ?
C16 C15 H15B 109.6 . . ?
H15A C15 H15B 108.1 . . ?
C15 C16 C17 113.7(7) . . ?
C15 C16 H16A 108.8 . . ?
C17 C16 H16A 108.8 . . ?
C15 C16 H16B 108.8 . . ?
C17 C16 H16B 108.8 . . ?
H16A C16 H16B 107.7 . . ?
C18 C17 C16 111.9(6) . . ?
C18 C17 H17A 109.2 . . ?
C16 C17 H17A 109.2 . . ?
C18 C17 H17B 109.2 . . ?
C16 C17 H17B 109.2 . . ?
H17A C17 H17B 107.9 . . ?
C19 C18 C22 115.9(7) . . ?
C19 C18 C17 123.4(7) . . ?
C22 C18 C17 120.7(7) . . ?
C20 C19 C18 120.7(7) . . ?
C20 C19 H19A 119.7 . . ?
C18 C19 H19A 119.7 . . ?
N2 C20 C19 123.0(7) . . ?
N2 C20 H20A 118.5 . . ?
C19 C20 H20A 118.5 . . ?
N2 C21 C22 122.4(7) . . ?
N2 C21 H21A 118.8 . . ?
C22 C21 H21A 118.8 . . ?
C21 C22 C18 120.9(7) . . ?
C21 C22 H22A 119.5 . . ?
C18 C22 H22A 119.5 . . ?
Ni1 O1W H1WC 121.6 . . ?
Ni1 O1W H1WD 98.2 . . ?
H1WC O1W H1WD 108.9 . . ?

_refine_diff_density_max         2.501
_refine_diff_density_min         -0.859
_refine_diff_density_rms         0.127

