# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_SKD13_a
_database_code_depnum_ccdc_archive 'CCDC 1839257'
loop_
_audit_author_name
_audit_author_address
'Sathish Kumar Kurapati'
;University of Hyderabad
India
;
_audit_update_record             
;
2019-02-17 deposited with the CCDC.	2019-05-06 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/1
_shelx_SHELXL_version_number     2018/1
_chemical_name_systematic        'Compound 1'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C H0 N6 Na6 O73 V15'
_chemical_formula_sum            'C H0 N6 Na6 O73 V15'
_chemical_formula_weight         2166.11

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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Na Na 0.0362 0.0249 '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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      hexagonal
_space_group_IT_number           190
_space_group_name_H-M_alt        'P -6 2 c'
_space_group_name_Hall           'P -6c -2c'

_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, 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                   12.9910(6)
_cell_length_b                   12.9910(6)
_cell_length_c                   23.1099(12)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     3377.6(4)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9250
_cell_measurement_theta_min      2.14
_cell_measurement_theta_max      35.21

_exptl_crystal_description       block
_exptl_crystal_colour            black
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    2.130
_exptl_crystal_F_000             2086
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_exptl_absorpt_coefficient_mu    2.143
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.635
_exptl_absorpt_correction_T_max  0.773
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(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       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            79029
_diffrn_reflns_av_unetI/netI     0.0209
_diffrn_reflns_av_R_equivalents  0.0532
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_theta_min         2.527
_diffrn_reflns_theta_max         35.266
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 0.994
_reflns_number_total             5165
_reflns_number_gt                4927
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.809
_reflns_Friedel_fraction_max     0.997
_reflns_Friedel_fraction_full    0.997

_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 APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2018/1 (Sheldrick, 2018)'
_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)+(0.0416P)²+3.2475P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   None
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 2140 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.018(6)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         5165
_refine_ls_number_parameters     163
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0313
_refine_ls_R_factor_gt           0.0285
_refine_ls_wR_factor_ref         0.0788
_refine_ls_wR_factor_gt          0.0769
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_restrained_S_all      1.085
_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
V2 V -0.01375(3) -0.16956(3) 0.62993(2) 0.00704(7) Uani 1 1 d . . . . .
V3 V 0.22617(4) -0.02012(4) 0.67903(2) 0.00995(8) Uani 1 1 d . . . . .
V1 V -0.02619(5) -0.26293(5) 0.750000 0.00746(9) Uani 1 2 d S T P . .
Na1 Na -0.333333 -0.666667 0.68030(8) 0.0146(3) Uani 1 3 d S T P . .
Na3 Na 0.333333 -0.333333 0.54267(8) 0.0138(3) Uani 1 3 d S T P . .
Na2 Na 0.333333 -0.333333 0.68147(8) 0.0166(4) Uani 1 3 d S T P . .
O7 O 0.2874(2) -0.0232(2) 0.750000 0.0090(4) Uani 1 2 d S T P . .
O8 O 0.28949(16) 0.15091(16) 0.68204(7) 0.0105(3) Uani 1 1 d . . . . .
O1 O -0.0696(3) -0.1122(3) 0.750000 0.0219(6) Uani 1 2 d S T P . .
O3 O 0.08810(15) -0.17415(15) 0.68932(7) 0.0090(3) Uani 1 1 d . . . . .
O10 O -0.2364(2) -0.4987(2) 0.62038(9) 0.0187(4) Uani 1 1 d . . . . .
O16 O 0.000000 0.000000 0.500000 0.045(2) Uani 1 6 d S T P . .
O12 O 0.22637(18) -0.28654(19) 0.61255(9) 0.0185(4) Uani 1 1 d . . . . .
O2 O -0.0306(2) -0.3911(2) 0.750000 0.0135(4) Uani 1 2 d S T P . .
O5 O 0.11775(17) -0.00932(15) 0.62317(8) 0.0116(3) Uani 1 1 d . . . . .
O6 O 0.31323(17) -0.03854(18) 0.63477(8) 0.0139(3) Uani 1 1 d . . . . .
O11 O 0.1718(3) -0.4348(3) 0.750000 0.0194(5) Uani 1 2 d S T P . .
O14 O -0.0072(2) -0.4621(2) 0.63092(11) 0.0237(4) Uani 1 1 d . . . . .
O4 O -0.01320(17) -0.23703(16) 0.57089(8) 0.0139(3) Uani 1 1 d . . . . .
O9 O -0.1808(3) -0.6358(3) 0.750000 0.0182(5) Uani 1 2 d S T P . .
O13 O 0.1708(2) -0.4803(2) 0.48527(11) 0.0236(4) Uani 1 1 d . . . . .
O15 O 0.000000 -0.4098(2) 0.500000 0.0223(6) Uani 1 2 d S T P . .
N1 N 0.2140(3) -0.0588(2) 0.51259(11) 0.0217(4) Uani 1 1 d . . . . .
C1 C 0.000000 0.000000 0.750000 0.0121(9) Uani 1 6 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
V2 O4 1.6236(18) . ?
V2 O5 1.9067(18) 3 ?
V2 O3 1.9280(17) . ?
V2 O5 1.9287(18) . ?
V2 O8 1.9952(18) 3 ?
V2 V3 2.9530(6) . ?
V2 V3 2.9550(6) 3 ?
V2 V1 3.0002(4) . ?
V3 O6 1.6290(19) . ?
V3 O7 1.8318(11) . ?
V3 O3 1.9206(17) . ?
V3 O8 1.9469(19) . ?
V3 O5 1.9665(19) . ?
V1 O2 1.637(3) . ?
V1 O3 1.9464(17) 4_556 ?
V1 O3 1.9465(17) . ?
V1 O8 2.0527(18) 3 ?
V1 O8 2.0527(18) 6_556 ?
V1 O1 2.293(3) . ?
Na1 O10 2.349(2) 3_545 ?
Na1 O10 2.349(2) . ?
Na1 O10 2.349(2) 2_445 ?
Na1 O9 2.426(3) . ?
Na1 O9 2.426(3) 3_545 ?
Na1 O9 2.426(3) 2_445 ?
Na1 Na1 3.221(4) 4_556 ?
Na3 O12 2.399(2) . ?
Na3 O12 2.399(2) 3_655 ?
Na3 O12 2.399(2) 2_545 ?
Na3 O13 2.415(3) 3_655 ?
Na3 O13 2.415(3) . ?
Na3 O13 2.415(3) 2_545 ?
Na3 Na2 3.208(3) . ?
Na2 O12 2.384(3) . ?
Na2 O12 2.384(3) 3_655 ?
Na2 O12 2.384(3) 2_545 ?
Na2 O11 2.426(3) 3_655 ?
Na2 O11 2.426(3) . ?
Na2 O11 2.426(3) 2_545 ?
Na2 Na2 3.167(4) 4_556 ?
O1 C1 1.275(3) . ?
N1 N1 1.446(5) 8_556 ?

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
O4 V2 O5 109.53(9) . 3 ?
O4 V2 O3 113.15(9) . . ?
O5 V2 O3 137.08(8) 3 . ?
O4 V2 O5 105.90(9) . . ?
O5 V2 O5 92.06(11) 3 . ?
O3 V2 O5 80.78(8) . . ?
O4 V2 O8 107.87(9) . 3 ?
O5 V2 O8 81.69(8) 3 3 ?
O3 V2 O8 81.29(7) . 3 ?
O5 V2 O8 145.81(8) . 3 ?
O4 V2 V3 112.94(7) . . ?
O5 V2 V3 123.15(6) 3 . ?
O3 V2 V3 39.80(5) . . ?
O5 V2 V3 41.18(6) . . ?
O8 V2 V3 117.39(5) 3 . ?
O4 V2 V3 117.92(7) . 3 ?
O5 V2 V3 41.03(6) 3 3 ?
O3 V2 V3 110.55(5) . 3 ?
O5 V2 V3 122.91(6) . 3 ?
O8 V2 V3 40.83(5) 3 3 ?
V3 V2 V3 128.88(2) . 3 ?
O4 V2 V1 124.95(7) . . ?
O5 V2 V1 108.87(6) 3 . ?
O3 V2 V1 39.48(5) . . ?
O5 V2 V1 110.54(6) . . ?
O8 V2 V1 42.91(5) 3 . ?
V3 V2 V1 74.706(15) . . ?
V3 V2 V1 72.696(15) 3 . ?
O6 V3 O7 102.61(10) . . ?
O6 V3 O3 106.26(9) . . ?
O7 V3 O3 93.21(9) . . ?
O6 V3 O8 105.19(9) . . ?
O7 V3 O8 92.99(10) . . ?
O3 V3 O8 145.71(8) . . ?
O6 V3 O5 99.96(9) . . ?
O7 V3 O5 157.43(9) . . ?
O3 V3 O5 80.01(7) . . ?
O8 V3 O5 81.44(7) . . ?
O6 V3 V2 104.14(7) . . ?
O7 V3 V2 131.05(8) . . ?
O3 V3 V2 39.98(5) . . ?
O8 V3 V2 117.96(6) . . ?
O5 V3 V2 40.23(5) . . ?
O6 V3 V2 109.40(7) . 2 ?
O7 V3 V2 129.72(8) . 2 ?
O3 V3 V2 112.92(6) . 2 ?
O8 V3 V2 42.07(5) . 2 ?
O5 V3 V2 39.53(5) . 2 ?
V2 V3 V2 76.814(19) . 2 ?
O2 V1 O3 103.35(8) . 4_556 ?
O2 V1 O3 103.35(8) . . ?
O3 V1 O3 92.18(10) 4_556 . ?
O2 V1 O8 99.73(8) . 3 ?
O3 V1 O8 156.71(8) 4_556 3 ?
O3 V1 O8 79.40(7) . 3 ?
O2 V1 O8 99.73(8) . 6_556 ?
O3 V1 O8 79.41(7) 4_556 6_556 ?
O3 V1 O8 156.71(8) . 6_556 ?
O8 V1 O8 99.83(10) 3 6_556 ?
O2 V1 O1 165.98(13) . . ?
O3 V1 O1 86.24(8) 4_556 . ?
O3 V1 O1 86.24(8) . . ?
O8 V1 O1 71.67(7) 3 . ?
O8 V1 O1 71.67(7) 6_556 . ?
O2 V1 V2 112.249(12) . . ?
O3 V1 V2 123.76(6) 4_556 . ?
O3 V1 V2 39.03(5) . . ?
O8 V1 V2 41.44(5) 3 . ?
O8 V1 V2 131.73(5) 6_556 . ?
O1 V1 V2 68.973(16) . . ?
O2 V1 V2 112.248(12) . 4_556 ?
O3 V1 V2 39.03(5) 4_556 4_556 ?
O3 V1 V2 123.77(5) . 4_556 ?
O8 V1 V2 131.73(5) 3 4_556 ?
O8 V1 V2 41.44(5) 6_556 4_556 ?
O1 V1 V2 68.974(16) . 4_556 ?
V2 V1 V2 135.30(2) . 4_556 ?
O10 Na1 O10 88.77(9) 3_545 . ?
O10 Na1 O10 88.77(9) 3_545 2_445 ?
O10 Na1 O10 88.77(9) . 2_445 ?
O10 Na1 O9 88.44(8) 3_545 . ?
O10 Na1 O9 102.92(8) . . ?
O10 Na1 O9 167.91(9) 2_445 . ?
O10 Na1 O9 102.92(8) 3_545 3_545 ?
O10 Na1 O9 167.91(9) . 3_545 ?
O10 Na1 O9 88.44(8) 2_445 3_545 ?
O9 Na1 O9 80.73(9) . 3_545 ?
O10 Na1 O9 167.91(9) 3_545 2_445 ?
O10 Na1 O9 88.44(8) . 2_445 ?
O10 Na1 O9 102.92(8) 2_445 2_445 ?
O9 Na1 O9 80.73(9) . 2_445 ?
O9 Na1 O9 80.73(9) 3_545 2_445 ?
O10 Na1 Na1 126.13(7) 3_545 4_556 ?
O10 Na1 Na1 126.13(7) . 4_556 ?
O10 Na1 Na1 126.13(7) 2_445 4_556 ?
O9 Na1 Na1 48.40(6) . 4_556 ?
O9 Na1 Na1 48.40(6) 3_545 4_556 ?
O9 Na1 Na1 48.40(6) 2_445 4_556 ?
O12 Na3 O12 79.63(9) . 3_655 ?
O12 Na3 O12 79.63(9) . 2_545 ?
O12 Na3 O12 79.63(9) 3_655 2_545 ?
O12 Na3 O13 87.37(8) . 3_655 ?
O12 Na3 O13 100.48(8) 3_655 3_655 ?
O12 Na3 O13 166.78(9) 2_545 3_655 ?
O12 Na3 O13 100.48(8) . . ?
O12 Na3 O13 166.78(9) 3_655 . ?
O12 Na3 O13 87.37(8) 2_545 . ?
O13 Na3 O13 92.72(10) 3_655 . ?
O12 Na3 O13 166.78(9) . 2_545 ?
O12 Na3 O13 87.37(8) 3_655 2_545 ?
O12 Na3 O13 100.48(8) 2_545 2_545 ?
O13 Na3 O13 92.72(10) 3_655 2_545 ?
O13 Na3 O13 92.72(10) . 2_545 ?
O12 Na3 Na2 47.68(6) . . ?
O12 Na3 Na2 47.68(6) 3_655 . ?
O12 Na3 Na2 47.68(6) 2_545 . ?
O13 Na3 Na2 123.32(7) 3_655 . ?
O13 Na3 Na2 123.32(7) . . ?
O13 Na3 Na2 123.32(7) 2_545 . ?
O12 Na2 O12 80.23(9) . 3_655 ?
O12 Na2 O12 80.23(9) . 2_545 ?
O12 Na2 O12 80.23(9) 3_655 2_545 ?
O12 Na2 O11 101.08(8) . 3_655 ?
O12 Na2 O11 96.80(8) 3_655 3_655 ?
O12 Na2 O11 176.54(9) 2_545 3_655 ?
O12 Na2 O11 96.80(8) . . ?
O12 Na2 O11 176.55(9) 3_655 . ?
O12 Na2 O11 101.08(8) 2_545 . ?
O11 Na2 O11 81.98(9) 3_655 . ?
O12 Na2 O11 176.54(9) . 2_545 ?
O12 Na2 O11 101.08(8) 3_655 2_545 ?
O12 Na2 O11 96.80(8) 2_545 2_545 ?
O11 Na2 O11 81.98(9) 3_655 2_545 ?
O11 Na2 O11 81.98(9) . 2_545 ?
O12 Na2 Na2 131.93(6) . 4_556 ?
O12 Na2 Na2 131.93(6) 3_655 4_556 ?
O12 Na2 Na2 131.93(6) 2_545 4_556 ?
O11 Na2 Na2 49.24(6) 3_655 4_556 ?
O11 Na2 Na2 49.24(6) . 4_556 ?
O11 Na2 Na2 49.24(6) 2_545 4_556 ?
O12 Na2 Na3 48.07(6) . . ?
O12 Na2 Na3 48.07(6) 3_655 . ?
O12 Na2 Na3 48.07(6) 2_545 . ?
O11 Na2 Na3 130.76(6) 3_655 . ?
O11 Na2 Na3 130.76(6) . . ?
O11 Na2 Na3 130.76(6) 2_545 . ?
Na2 Na2 Na3 180.0 4_556 . ?
V3 O7 V3 127.12(14) 4_556 . ?
V3 O8 V2 97.10(8) . 2 ?
V3 O8 V1 123.88(9) . 2 ?
V2 O8 V1 95.65(8) 2 2 ?
C1 O1 V1 129.80(19) . . ?
V3 O3 V2 100.22(8) . . ?
V3 O3 V1 138.15(9) . . ?
V2 O3 V1 101.49(8) . . ?
Na2 O12 Na3 84.25(8) . . ?
V2 O5 V2 146.26(11) 2 . ?
V2 O5 V3 99.44(8) 2 . ?
V2 O5 V3 98.59(8) . . ?
Na2 O11 Na2 81.52(12) 4_556 . ?
Na1 O9 Na1 83.19(12) . 4_556 ?
O1 C1 O1 120.000(1) 3 . ?
O1 C1 O1 120.002(1) 3 2 ?
O1 C1 O1 120.0 . 2 ?

_refine_diff_density_max         2.384
_refine_diff_density_min         -0.705
_refine_diff_density_rms         0.130

