# Electronic Supplementary Material (ESI) for ChemComm.
# 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. 
# 
#######################################################################

data_matrm13
_database_code_depnum_ccdc_archive 'CCDC 2001476'
loop_
_audit_author_name
_audit_author_address
'William Brennessel'
;University of Rochester
United States of America
;
_audit_update_record             
;
2020-05-06 deposited with the CCDC.	2020-06-26 downloaded from the CCDC.
;

_vrf_PLAT605_matrm13             
;
PROBLEM: _G Largest Solvent Accessible VOID in the Structure .. 101 A**3 
RESPONSE: Reflection contributions from highly disordered solvent,
located at a crystallographic -3 position, were fixed and added to
the calculated structure factors using the SQUEEZE routine of
program Platon (Spek, 2015), which determined there to be four
instances of 17 electrons in 101 \%A^3^ requiring this treatment.
Because the exact identity and amount of solvent were unknown, no
solvent was included in the atom list or molecular formula. Thus
all calculated quantities that derive from the molecular formula
(e.g., F(000), density, molecular weight, etc.) are known to be
incorrect.
;

_vrf_PLAT869_matrm13             
;
PROBLEM: _G ALERTS Related to the Use of SQUEEZE Suppressed! 
RESPONSE: See above.
;

_audit_creation_date             2018-06-13
_audit_creation_method           
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C24 H60 O18 V6'
_chemical_formula_sum            'C24 H60 O18 V6'
_chemical_formula_weight         942.36
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C96 H240 O72 V24 '
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
V V 0.0687 2.1097 '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      cubic
_space_group_IT_number           205
_space_group_name_H-M_alt        'P a -3'
_space_group_name_Hall           '-P 2ac 2ab 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'
'z, x, y'
'z+1/2, -x+1/2, -y'
'-z+1/2, -x, y+1/2'
'-z, x+1/2, -y+1/2'
'y, z, x'
'-y, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x'
'-y+1/2, -z, x+1/2'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x, -y-1/2, z-1/2'
'-x-1/2, y-1/2, z'
'-z, -x, -y'
'-z-1/2, x-1/2, y'
'z-1/2, x, -y-1/2'
'z, -x-1/2, y-1/2'
'-y, -z, -x'
'y, -z-1/2, x-1/2'
'-y-1/2, z-1/2, x'
'y-1/2, z, -x-1/2'

_cell_length_a                   16.36790(10)
_cell_length_b                   16.36790(10)
_cell_length_c                   16.36790(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4385.09(8)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    11788
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      77.3670
_cell_measurement_theta_min      4.6750
_shelx_estimated_absorpt_T_max   0.301
_shelx_estimated_absorpt_T_min   0.250
_exptl_absorpt_coefficient_mu    10.825
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52381
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.427
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1944
_exptl_crystal_size_max          0.177
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.146
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_av_unetI/netI     0.0173
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            17780
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.601
_diffrn_reflns_theta_min         4.679
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω   -121.00 -41.00   0.50    0.34    --  -49.87 -42.00 109.00  160
  2  ω    -65.00 -12.00   0.50    1.37    --  -84.25  42.00 -98.00  106
  3  ω     34.00  85.00   0.50    1.37    --  105.75 -42.00 109.00  102
  4  ω   -121.00 -70.00   0.50    0.34    --  -49.87-125.00 -90.00  102
  5  ω     33.00  82.00   0.50    1.37    --  105.75 -15.00 150.00   98
  6  ω     34.00 109.00   0.50    1.37    --  105.75 -94.00-150.00  150
  7  ω    114.00 173.00   0.50    1.37    --  105.75  30.00 120.00  118
  8  ω     45.00  77.00   0.50    1.37    --  105.75 -15.00   0.00   64
  9  ω     48.00  73.00   0.50    1.37    --  105.75 -45.00-150.00   50
 10  ω     34.00  71.00   0.50    1.37    --  105.75 -30.00 -30.00   74
 11  ω     36.00  71.00   0.50    1.37    --  105.75 -30.00  60.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0795655000
_diffrn_orient_matrix_UB_12      0.0498470000
_diffrn_orient_matrix_UB_13      -0.0064993000
_diffrn_orient_matrix_UB_21      -0.0105463000
_diffrn_orient_matrix_UB_22      0.0046581000
_diffrn_orient_matrix_UB_23      -0.0933911000
_diffrn_orient_matrix_UB_31      -0.0491286000
_diffrn_orient_matrix_UB_32      0.0797463000
_diffrn_orient_matrix_UB_33      0.0095324000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1482
_reflns_number_total             1567
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_refine_diff_density_max         0.209
_refine_diff_density_min         -0.614
_refine_diff_density_rms         0.065
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     75
_refine_ls_number_reflns         1567
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0306
_refine_ls_R_factor_gt           0.0293
_refine_ls_restrained_S_all      1.071
_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)+(0.0509P)²+2.1606P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0797
_refine_ls_wR_factor_ref         0.0807
_refine_special_details          
;
Reflection contributions from highly disordered solvent, located
at a crystallographic -3 position, were fixed and added to the
calculated structure factors using the SQUEEZE routine of
program Platon (Spek, 2015), which determined there to be four
instances of 17 electrons in 101 Å³ requiring this treatment.
Because the exact identity and amount of solvent were unknown, no
solvent was included in the atom list or molecular formula. Thus
all calculated quantities that derive from the molecular formula
(e.g., F(000), density, molecular weight, etc.) are known to be
incorrect.
;
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B)
2.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
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 0.59284(2) 0.56175(2) 0.34473(2) 0.01705(13) Uani 1 1 d . . . . .
O1 O 0.63933(9) 0.59246(8) 0.26544(8) 0.0325(3) Uani 1 1 d . . . . .
O2 O 0.55944(7) 0.66467(7) 0.40032(7) 0.0191(3) Uani 1 1 d . . . . .
O3 O 0.66061(7) 0.52755(7) 0.43873(7) 0.0205(3) Uani 1 1 d . . . . .
C1 C 0.60244(11) 0.74114(10) 0.39477(11) 0.0262(4) Uani 1 1 d . . . . .
H1A H 0.659465 0.732132 0.408136 0.031 Uiso 1 1 calc R . . . .
H1B H 0.580190 0.778649 0.434896 0.031 Uiso 1 1 calc R . . . .
C2 C 0.59707(13) 0.77986(13) 0.31155(13) 0.0347(5) Uani 1 1 d . . . . .
H2A H 0.626943 0.830332 0.311513 0.052 Uiso 1 1 calc GR . . . .
H2B H 0.540870 0.790394 0.298482 0.052 Uiso 1 1 calc GR . . . .
H2C H 0.619965 0.743555 0.271584 0.052 Uiso 1 1 calc GR . . . .
C3 C 0.70003(10) 0.57987(10) 0.49705(10) 0.0209(3) Uani 1 1 d . . . . .
H3A H 0.705728 0.551232 0.548623 0.025 Uiso 1 1 calc R . . . .
H3B H 0.666578 0.627904 0.506307 0.025 Uiso 1 1 calc R . . . .
C4 C 0.78285(13) 0.60558(16) 0.46700(14) 0.0424(5) Uani 1 1 d . . . . .
H4A H 0.806472 0.643596 0.504907 0.064 Uiso 1 1 calc GR . . . .
H4B H 0.777536 0.631096 0.414465 0.064 Uiso 1 1 calc GR . . . .
H4C H 0.817485 0.558460 0.462437 0.064 Uiso 1 1 calc GR . . . .


_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 O1 1.5861(13) . ?
V1 O2 1.9928(11) 17_666 ?
V1 O2 1.9912(12) . ?
V1 O3 1.9726(12) 21_666 ?
V1 O3 1.9777(12) . ?
O2 C1 1.4387(19) . ?
O3 C3 1.4356(19) . ?
C1 H1A 0.9700 . ?
C1 H1B 0.9700 . ?
C1 C2 1.505(3) . ?
C2 H2A 0.9600 . ?
C2 H2B 0.9600 . ?
C2 H2C 0.9600 . ?
C3 H3A 0.9700 . ?
C3 H3B 0.9700 . ?
C3 C4 1.502(3) . ?
C4 H4A 0.9600 . ?
C4 H4B 0.9600 . ?
C4 H4C 0.9600 . ?

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 V1 O2 103.74(6) . . ?
O1 V1 O2 103.03(6) . 17_666 ?
O1 V1 O3 116.37(7) . 21_666 ?
O1 V1 O3 117.21(7) . . ?
O2 V1 O2 153.23(6) . 17_666 ?
O3 V1 O2 92.79(5) 21_666 17_666 ?
O3 V1 O2 92.17(5) . . ?
O3 V1 O2 75.48(5) 21_666 . ?
O3 V1 O2 75.34(5) . 17_666 ?
O3 V1 O3 126.42(7) 21_666 . ?
V1 O2 V1 103.51(5) . 21_666 ?
C1 O2 V1 123.89(10) . 21_666 ?
C1 O2 V1 124.94(10) . . ?
V1 O3 V1 104.76(5) 17_666 . ?
C3 O3 V1 126.91(10) . . ?
C3 O3 V1 128.20(10) . 17_666 ?
O2 C1 H1A 108.9 . . ?
O2 C1 H1B 108.9 . . ?
O2 C1 C2 113.27(15) . . ?
H1A C1 H1B 107.7 . . ?
C2 C1 H1A 108.9 . . ?
C2 C1 H1B 108.9 . . ?
C1 C2 H2A 109.5 . . ?
C1 C2 H2B 109.5 . . ?
C1 C2 H2C 109.5 . . ?
H2A C2 H2B 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
O3 C3 H3A 109.5 . . ?
O3 C3 H3B 109.5 . . ?
O3 C3 C4 110.79(14) . . ?
H3A C3 H3B 108.1 . . ?
C4 C3 H3A 109.5 . . ?
C4 C3 H3B 109.5 . . ?
C3 C4 H4A 109.5 . . ?
C3 C4 H4B 109.5 . . ?
C3 C4 H4C 109.5 . . ?
H4A C4 H4B 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
V1 O2 C1 C2 69.19(19) . . . . ?
V1 O2 C1 C2 -75.18(18) 21_666 . . . ?
V1 O3 C3 C4 97.74(17) 17_666 . . . ?
V1 O3 C3 C4 -86.85(18) . . . . ?

_olex2_submission_original_sample_id matrm13
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.496
_oxdiff_exptl_absorpt_empirical_full_min 0.713
