# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# 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. 
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data_lb170722wy_0m
_database_code_depnum_ccdc_archive 'CCDC 1999020'
_audit_update_record             
;
2020-04-24 deposited with the CCDC.	2020-06-25 downloaded from the CCDC.
;
_audit_creation_date             2019-10-28
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '1(O36 V15), 1(Cl1), 6(C9 H14 N)'
_chemical_formula_sum            'C54 H84 Cl N6 O36 V15'
_chemical_formula_weight         2192.90
_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'
Cl Cl 0.1484 0.1585 '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'

_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           194
_space_group_name_H-M_alt        'P 63/m m c'
_space_group_name_Hall           '-P 6c 2c'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'-x, -y, z+1/2'
'y, -x+y, z+1/2'
'x-y, x, z+1/2'
'y, x, -z'
'x-y, -y, -z'
'-x, -x+y, -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'
'x, y, -z-1/2'
'-y, x-y, -z-1/2'
'-x+y, -x, -z-1/2'
'-y, -x, z'
'-x+y, y, z'
'x, x-y, z'
'y, x, z-1/2'
'x-y, -y, z-1/2'
'-x, -x+y, z-1/2'

_cell_length_a                   14.1100(6)
_cell_length_b                   14.110
_cell_length_c                   22.0265(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     3797.8(4)
_cell_formula_units_Z            1.99992
_cell_measurement_reflns_used    8535
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.764
_cell_measurement_theta_min      2.490
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    1.877
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.5867
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1209 before and 0.0510 after correction.
The Ratio of minimum to maximum transmission is 0.7867.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.918
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2200
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.18
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0840
_diffrn_reflns_av_unetI/netI     0.0383
_diffrn_reflns_Laue_measured_fraction_full 0.968
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            40116
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.194
_diffrn_reflns_theta_min         2.887
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.968
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1076
_reflns_number_total             1922
_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       'SAINT V8.38A (?, 2016)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         1.048
_refine_diff_density_min         -0.600
_refine_diff_density_rms         0.160
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.166
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     135
_refine_ls_number_reflns         1922
_refine_ls_number_restraints     195
_refine_ls_R_factor_all          0.1653
_refine_ls_R_factor_gt           0.1049
_refine_ls_restrained_S_all      1.116
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2842
_refine_ls_wR_factor_ref         0.3361
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N00D-C7
 2.5 with sigma of 0.02
 C8-C6
 2.5 with sigma of 0.02
 C8-C7
 1.48 with sigma of 0.005
 N00D-C6 = C7-C6 = C8-C7 = C8-C9
 1.48 with sigma of 0.01
 C7-C9
 2.5 with sigma of 0.02
 C8-C9
 1.48 with sigma of 0.005
 C8-O6
 2.5 with sigma of 0.02
 C1-C6 \\sim C6-C5
 with sigma of 0.01
3. Restrained planarity
 C6, N00D, C5, C1
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C7 \\sim C1 \\sim C2 \\sim N00D \\sim C3 \\sim C5 \\sim C6 \\sim C4 \\sim C8
\\sim C9: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(N00D)
\\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq,
Uanis(C4) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(O0AA) = Uanis(O2)
5. Rigid body (RIGU) restrains
 C7, C1, C2, N00D, C3, C5, C6, C4, C8, C9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Others
 Sof(O2)=1-FVAR(1)
 Sof(O0AA)=FVAR(1)
 Fixed Sof: C1(0.5) H1(0.5) C2(0.5) H2(0.5) C3(0.5) H3(0.5) C4(0.5) H4(0.5)
 C5(0.5) H5(0.5) N00D(0.5) C8(0.5) H8A(0.5) H8B(0.5) C6(0.5) H6A(0.5) H6B(0.5)
 C7(0.5) H7A(0.5) H7B(0.5) C9(0.5) H9A(0.5) H8C(0.5) H9B(0.5)
7.a Riding coordinates:
 C9(H9A,H8C,H9B)
7.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C6(H6A,H6B), C7(H7A,H7B)
7.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5)
7.d Fitted hexagon refined as free rotating group:
 C1(C2,C3,C4,C5,N00D)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_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
V1 V 0.58301(6) 0.16602(11) 0.62572(7) 0.0570(6) Uani 1 2 d S T P . .
V2 V 0.53154(9) 0.06307(18) 0.750000 0.0686(8) Uani 1 4 d S T P A .
V3 V 0.79399(7) 0.20601(7) 0.67396(9) 0.0738(7) Uani 1 2 d S T P A .
Cl1 Cl 0.666667 0.333333 0.750000 0.0561(11) Uani 1 12 d S T P . .
O1 O 0.7303(3) 0.2697(3) 0.6121(2) 0.0595(13) Uani 1 2 d S T P A .
O2 O 0.6429(4) 0.1074(3) 0.68412(19) 0.0532(11) Uani 0.855(5) 1 d . . . A 2
O3 O 0.5419(3) 0.0838(6) 0.5687(3) 0.0802(19) Uani 1 2 d S T P A .
O4 O 0.4662(5) -0.0677(9) 0.750000 0.105(4) Uani 1 4 d S T P . .
O6 O 0.8224(4) 0.1776(4) 0.750000 0.084(3) Uani 1 4 d DS T P . .
O5 O 0.8455(3) 0.1545(3) 0.6305(4) 0.102(3) Uani 1 2 d S T P . .
C1 C 0.6835(18) -0.0911(16) 0.6037(10) 0.246(8) Uani 0.5 1 d D U . B -1
H1 H 0.728462 -0.021013 0.618839 0.295 Uiso 0.5 1 calc R . . B -1
C2 C 0.630(2) -0.105(2) 0.5487(10) 0.236(8) Uani 0.5 1 d G U . B -1
H2 H 0.638639 -0.044768 0.527040 0.283 Uiso 0.5 1 calc R . . B -1
C3 C 0.5624(17) -0.210(3) 0.5260(9) 0.235(8) Uani 0.5 1 d G U . B -1
H3 H 0.526438 -0.219607 0.489174 0.282 Uiso 0.5 1 calc R . . B -1
C4 C 0.549(2) -0.301(2) 0.5583(11) 0.235(8) Uani 0.5 1 d G U . B -1
H4 H 0.504058 -0.370691 0.543107 0.282 Uiso 0.5 1 calc R . . B -1
C5 C 0.603(2) -0.2864(16) 0.6133(11) 0.242(8) Uani 0.5 1 d DG U . B -1
H5 H 0.593880 -0.346938 0.634907 0.291 Uiso 0.5 1 calc R . . B -1
N00D N 0.6701(15) -0.1816(15) 0.6360(8) 0.254(7) Uani 0.5 1 d DG U . B -1
C8 C 0.809(2) -0.0050(16) 0.7639(13) 0.274(10) Uani 0.5 1 d D U . B -1
H8A H 0.754303 0.016118 0.755504 0.329 Uiso 0.5 1 calc R . . B -1
H8B H 0.780541 -0.058480 0.796397 0.329 Uiso 0.5 1 calc R . . B -1
C6 C 0.727(2) -0.167(2) 0.6946(10) 0.260(8) Uani 0.5 1 d D U . B -1
H6A H 0.673704 -0.186047 0.726772 0.312 Uiso 0.5 1 calc R . . B -1
H6B H 0.752365 -0.219511 0.696115 0.312 Uiso 0.5 1 calc R . . B -1
C7 C 0.8214(18) -0.058(2) 0.7090(11) 0.264(9) Uani 0.5 1 d D U . B -1
H7A H 0.834733 -0.010305 0.674491 0.317 Uiso 0.5 1 calc R . . B -1
H7B H 0.885666 -0.065645 0.714067 0.317 Uiso 0.5 1 calc R . . B -1
C9 C 0.910(3) 0.093(3) 0.7856(14) 0.286(13) Uani 0.5 1 d D U . B -1
H9A H 0.972454 0.146967 0.763969 0.429 Uiso 0.5 1 d R . . B -1
H8C H 0.916264 0.028977 0.791849 0.429 Uiso 0.5 1 d R . . B -1
H9B H 0.904584 0.121657 0.824129 0.429 Uiso 0.5 1 d R . . B -1
O0AA O 0.6368(15) 0.0474(14) 0.750000 0.0532(11) Uani 0.291(11) 2 d S T P A 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
V1 V2 3.0127(18) . ?
V1 V3 2.9376(15) . ?
V1 V3 2.9375(15) 3_665 ?
V1 O1 1.874(2) 3_665 ?
V1 O1 1.874(2) . ?
V1 O2 1.938(4) 20_655 ?
V1 O2 1.938(4) . ?
V1 O3 1.608(6) . ?
V2 O2 1.996(5) 16_557 ?
V2 O2 1.996(5) 20_655 ?
V2 O2 1.996(5) . ?
V2 O2 1.996(5) 11_656 ?
V2 O4 1.598(12) . ?
V2 O0AA 1.607(18) 20_655 ?
V2 O0AA 1.607(18) . ?
V3 O1 2.067(7) . ?
V3 O2 1.888(5) . ?
V3 O2 1.888(5) 19_665 ?
V3 O6 1.813(4) . ?
V3 O5 1.581(7) . ?
C1 C2 1.3900 . ?
C1 N00D 1.3900 . ?
C2 C3 1.3900 . ?
C3 C4 1.3900 . ?
C4 C5 1.3900 . ?
C5 N00D 1.3900 . ?
N00D C6 1.481(10) . ?
C8 C7 1.481(5) . ?
C8 C9 1.480(5) . ?
C6 C7 1.477(10) . ?

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
V3 V1 V2 74.98(4) 3_665 . ?
V3 V1 V2 74.98(4) . . ?
V3 V1 V3 133.07(8) 3_665 . ?
O1 V1 V2 115.31(18) 3_665 . ?
O1 V1 V2 115.31(18) . . ?
O1 V1 V3 44.39(19) . . ?
O1 V1 V3 44.39(19) 3_665 3_665 ?
O1 V1 V3 127.25(19) . 3_665 ?
O1 V1 V3 127.25(19) 3_665 . ?
O1 V1 O1 92.0(4) . 3_665 ?
O1 V1 O2 83.6(2) 3_665 20_655 ?
O1 V1 O2 145.5(2) 3_665 . ?
O1 V1 O2 83.6(2) . . ?
O1 V1 O2 145.5(2) . 20_655 ?
O2 V1 V2 40.74(14) . . ?
O2 V1 V2 40.74(14) 20_655 . ?
O2 V1 V3 39.21(14) . . ?
O2 V1 V3 114.68(15) 20_655 . ?
O2 V1 O2 81.1(3) 20_655 . ?
O3 V1 V2 116.6(3) . . ?
O3 V1 V3 112.73(5) . . ?
O3 V1 V3 112.73(5) . 3_665 ?
O3 V1 O1 107.3(3) . 3_665 ?
O3 V1 O1 107.3(3) . . ?
O3 V1 O2 106.7(2) . 20_655 ?
O3 V1 O2 106.7(2) . . ?
V1 V2 V1 130.64(9) . 16_557 ?
O2 V2 V1 39.31(12) . . ?
O2 V2 V1 123.18(14) 20_655 16_557 ?
O2 V2 V1 123.18(14) 16_557 . ?
O2 V2 V1 123.18(14) 11_656 . ?
O2 V2 V1 39.31(12) 11_656 16_557 ?
O2 V2 V1 39.31(12) 16_557 16_557 ?
O2 V2 V1 123.18(14) . 16_557 ?
O2 V2 V1 39.31(12) 20_655 . ?
O2 V2 O2 93.3(2) 16_557 . ?
O4 V2 V1 114.68(5) . . ?
O4 V2 V1 114.68(5) . 16_557 ?
O4 V2 O2 105.73(13) . 16_557 ?
O4 V2 O2 105.73(13) . 11_656 ?
O4 V2 O2 105.73(13) . . ?
O4 V2 O2 105.73(13) . 20_655 ?
O4 V2 O0AA 83.2(6) . . ?
O4 V2 O0AA 83.2(6) . 20_655 ?
O0AA V2 V1 92.9(3) . . ?
O0AA V2 V1 92.9(3) 20_655 . ?
O0AA V2 V1 92.9(3) 20_655 16_557 ?
O0AA V2 V1 92.9(3) . 16_557 ?
O0AA V2 O2 131.2(2) . 11_656 ?
O0AA V2 O2 53.6(3) 20_655 20_655 ?
O0AA V2 O2 131.2(2) 20_655 16_557 ?
O0AA V2 O2 53.6(3) 20_655 11_656 ?
O0AA V2 O2 53.6(3) . 16_557 ?
O0AA V2 O2 131.2(2) . 20_655 ?
O0AA V2 O0AA 166.3(12) . 20_655 ?
V1 V3 V1 74.13(7) 2_655 . ?
O1 V3 V1 39.34(6) . 2_655 ?
O1 V3 V1 39.34(6) . . ?
O2 V3 V1 40.46(13) . . ?
O2 V3 V1 111.35(14) 19_665 . ?
O2 V3 O1 79.80(14) . . ?
O2 V3 O1 79.80(14) 19_665 . ?
O2 V3 O2 137.9(3) 19_665 . ?
O6 V3 V1 127.34(19) . 2_655 ?
O6 V3 V1 127.34(19) . . ?
O6 V3 O1 153.7(3) . . ?
O6 V3 O2 91.17(18) . 19_665 ?
O6 V3 O2 91.17(18) . . ?
O5 V3 V1 110.3(3) . . ?
O5 V3 V1 110.3(3) . 2_655 ?
O5 V3 O1 101.6(4) . . ?
O5 V3 O2 109.99(14) . 19_665 ?
O5 V3 O2 109.99(14) . . ?
O5 V3 O6 104.7(4) . . ?
V1 O1 V1 141.8(4) . 2_655 ?
V1 O1 V3 96.3(2) . . ?
V1 O1 V3 96.3(2) 2_655 . ?
V1 O2 V2 100.0(2) . . ?
V3 O2 V1 100.3(2) . . ?
V3 O2 V2 137.6(2) . . ?
V3 O6 V3 135.0(6) . 16_557 ?
C2 C1 N00D 120.0 . . ?
C1 C2 C3 120.0 . . ?
C2 C3 C4 120.0 . . ?
C5 C4 C3 120.0 . . ?
C4 C5 N00D 120.0 . . ?
C1 N00D C6 120.2(4) . . ?
C5 N00D C1 120.0 . . ?
C5 N00D C6 119.8(4) . . ?
C9 C8 C7 115.6(14) . . ?
C7 C6 N00D 118.4(15) . . ?
C6 C7 C8 115.3(15) . . ?

_olex2_submission_special_instructions 'No special instructions were received'
