# 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_isk244
_database_code_depnum_ccdc_archive 'CCDC 1499961'
_audit_update_record             
;
2016-08-18 deposited with the CCDC.
2016-09-19 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         'C36 H78 N6 O24 V6'
_chemical_formula_sum            'C36 H78 N6 O24 V6'
_chemical_formula_weight         1284.68

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'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_H-M_alt        'R -3 :H'
_space_group_name_Hall           '-R 3'

_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'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'

_cell_length_a                   13.6688(10)
_cell_length_b                   13.6688(10)
_cell_length_c                   25.0762(18)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     4057.4(7)
_cell_formula_units_Z            3
_cell_measurement_temperature    90(2)
_cell_measurement_reflns_used    6708
_cell_measurement_theta_min      2.37
_cell_measurement_theta_max      28.12

_exptl_crystal_description       irregular
_exptl_crystal_colour            blue
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.577
_exptl_crystal_F_000             1998
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.190
_exptl_crystal_size_mid          0.140
_exptl_crystal_size_min          0.120
_exptl_absorpt_coefficient_mu    1.077
_shelx_estimated_absorpt_T_min   0.822
_shelx_estimated_absorpt_T_max   0.882
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.802
_exptl_absorpt_correction_T_max  0.860
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2014)'
_exptl_absorpt_special_details   ?

_exptl_special_details           
; 
 Crystal orientation and preliminary unit cell constants were obtained from  
 reflections gathered from three sets of 20 frames each.  Refined cell 
 parameters were computed after data collection on the basis of the setting 
 angles of 950 reflections with a resolution limit of 0.75 Angstroms.
;

_diffrn_ambient_temperature      90(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '30s frames at 0.3 deg increments in ω'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            16882
_diffrn_reflns_av_unetI/netI     0.0174
_diffrn_reflns_av_R_equivalents  0.0274
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_theta_min         1.902
_diffrn_reflns_theta_max         28.254
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 1.000

_diffrn_special_details          
;
 A full sphere of data was collected by use of 0.3 degree omega increments 
 and 30s frame counting times.  To a limiting resolution of 0.75 A, the 
 average redundancy was 7.5 and R(sym) for the uncorrected data was 0.039.
;

_reflns_number_total             2242
_reflns_number_gt                1859
_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. 
  
 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. 
;

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT (Sheldrick 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 In addition to the primary species, the asymmetric unit contained
 a half-occupancy (by chemical analysis) acetonitrile molecule.This 
 species was multiply disordered along a line defined by x = 0.667, 
 y = 0.333. Attempted refinement with appropriate constraints and 
 restraints was unsuccessful. Hence the electron density of this 
 species was modeled by use of SQUEEZE (A. Spek, 2014).

 Hydrogen atoms, with the exception of those on the acetonitrile 
 molecule were included at idealized positions and refined by use 
 of the riding model.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0700P)²+6.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2242
_refine_ls_number_parameters     109
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0485
_refine_ls_R_factor_gt           0.0381
_refine_ls_wR_factor_ref         0.1173
_refine_ls_wR_factor_gt          0.1089
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_restrained_S_all      1.048
_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
V1 V 0.24108(3) 0.22441(3) 0.50482(2) 0.02900(15) Uani 1 1 d . . . . .
O1 O 0.28526(13) 0.13657(12) 0.46044(6) 0.0324(3) Uani 1 1 d . . . . .
O2 O 0.09224(12) 0.17049(13) 0.45798(6) 0.0326(3) Uani 1 1 d . . . . .
O3 O 0.35322(13) 0.30512(14) 0.53976(7) 0.0377(4) Uani 1 1 d . . . . .
O4 O 0.50596(18) 0.55890(16) 0.38377(7) 0.0598(6) Uani 1 1 d . . . . .
H4C H 0.5582 0.5952 0.4057 0.078 Uiso 1 1 calc R U . . .
N1 N 0.30654(16) 0.33517(15) 0.43330(8) 0.0341(4) Uani 1 1 d . . . . .
C1 C 0.3969(2) 0.3113(2) 0.41508(10) 0.0393(5) Uani 1 1 d . . . . .
H1A H 0.4621 0.3472 0.4398 0.051 Uiso 1 1 calc R U . . .
H1B H 0.4233 0.3436 0.3791 0.051 Uiso 1 1 calc R U . . .
C2 C 0.3508(2) 0.1840(2) 0.41358(10) 0.0390(5) Uani 1 1 d . . . . .
H2A H 0.3034 0.1508 0.3815 0.051 Uiso 1 1 calc R U . . .
H2B H 0.4138 0.1679 0.4124 0.051 Uiso 1 1 calc R U . . .
C3 C 0.2174(2) 0.3025(2) 0.39156(9) 0.0398(5) Uani 1 1 d . . . . .
H3A H 0.2499 0.3039 0.3561 0.052 Uiso 1 1 calc R U . . .
H3B H 0.1912 0.3583 0.3912 0.052 Uiso 1 1 calc R U . . .
C4 C 0.1167(2) 0.1847(2) 0.40196(9) 0.0387(5) Uani 1 1 d . . . . .
H4A H 0.0499 0.1751 0.3821 0.050 Uiso 1 1 calc R U . . .
H4B H 0.1344 0.1266 0.3894 0.050 Uiso 1 1 calc R U . . .
C5 C 0.3529(2) 0.45582(19) 0.44933(10) 0.0372(5) Uani 1 1 d . . . . .
H5A H 0.4120 0.4746 0.4766 0.048 Uiso 1 1 calc R U . . .
H5B H 0.2914 0.4630 0.4664 0.048 Uiso 1 1 calc R U . . .
C6 C 0.4036(2) 0.5436(2) 0.40458(11) 0.0515(7) Uani 1 1 d . . . . .
H6A H 0.3479 0.5203 0.3752 0.067 Uiso 1 1 calc R U . . .
H6B H 0.4164 0.6169 0.4183 0.067 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
V1 O3 1.6258(16) . ?
V1 O1 1.9416(15) . ?
V1 O2 1.9659(15) 11_556 ?
V1 O1 2.0238(15) 12_556 ?
V1 O2 2.1361(15) . ?
V1 N1 2.2260(19) . ?
O1 C2 1.422(3) . ?
O1 V1 2.0239(15) 11_556 ?
O2 C4 1.434(3) . ?
O2 V1 1.9658(15) 12_556 ?
O4 C6 1.408(4) . ?
N1 C5 1.496(3) . ?
N1 C3 1.496(3) . ?
N1 C1 1.498(3) . ?
C1 C2 1.527(3) . ?
C3 C4 1.530(3) . ?
C5 C6 1.532(3) . ?

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
O3 V1 O1 104.44(8) . . ?
O3 V1 O2 104.54(8) . 11_556 ?
O1 V1 O2 77.88(6) . 11_556 ?
O3 V1 O1 93.41(7) . 12_556 ?
O1 V1 O1 162.13(8) . 12_556 ?
O2 V1 O1 97.08(6) 11_556 12_556 ?
O3 V1 O2 160.50(7) . . ?
O1 V1 O2 90.48(6) . . ?
O2 V1 O2 90.66(9) 11_556 . ?
O1 V1 O2 72.30(6) 12_556 . ?
O3 V1 N1 92.91(8) . . ?
O1 V1 N1 79.35(7) . . ?
O2 V1 N1 154.11(7) 11_556 . ?
O1 V1 N1 100.86(7) 12_556 . ?
O2 V1 N1 77.36(7) . . ?
C2 O1 V1 120.79(13) . . ?
C2 O1 V1 131.78(13) . 11_556 ?
V1 O1 V1 107.42(7) . 11_556 ?
C4 O2 V1 122.86(13) . 12_556 ?
C4 O2 V1 111.99(13) . . ?
V1 O2 V1 102.31(7) 12_556 . ?
C5 N1 C3 110.46(18) . . ?
C5 N1 C1 112.42(18) . . ?
C3 N1 C1 111.08(18) . . ?
C5 N1 V1 109.75(14) . . ?
C3 N1 V1 111.75(14) . . ?
C1 N1 V1 101.08(13) . . ?
N1 C1 C2 109.91(19) . . ?
O1 C2 C1 107.80(19) . . ?
N1 C3 C4 111.38(19) . . ?
O2 C4 C3 109.59(19) . . ?
N1 C5 C6 116.3(2) . . ?
O4 C6 C5 114.5(2) . . ?

_refine_diff_density_max         0.598
_refine_diff_density_min         -0.340
_refine_diff_density_rms         0.079



