# Supplementary Information (SI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2025

####################################################################### 
# 
# 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_sp387_s2_150k
_database_code_depnum_ccdc_archive 'CCDC 2370279'
loop_
_audit_author_name
_audit_author_address
'Vladislav Komarov'
;Nikolaev Institute of Inorganic Chemistry
Russia
;
_audit_update_record             
;
2024-07-12 deposited with the CCDC.	2024-12-17 downloaded from the CCDC.
;
_audit_creation_date             2024-07-12
_audit_creation_method           
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'I5 O Se8 V4'
_chemical_formula_sum            'I5 O Se8 V4'
_chemical_formula_weight         1485.94
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
I I -0.4742 1.8119 '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'
Se Se -0.0929 2.2259 '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      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 1 2/c 1'
_space_group_name_Hall           '-C 2yc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'

_cell_length_a                   21.1319(13)
_cell_length_b                   5.8841(3)
_cell_length_c                   18.0933(9)
_cell_angle_alpha                90
_cell_angle_beta                 123.649(2)
_cell_angle_gamma                90
_cell_volume                     1872.81(18)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    3774
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      31.32
_cell_measurement_theta_min      2.32
_shelx_estimated_absorpt_T_max   0.904
_shelx_estimated_absorpt_T_min   0.299
_exptl_absorpt_coefficient_mu    25.707
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_correction_T_min  0.5179
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1089 before and 0.0521 after correction.
The Ratio of minimum to maximum transmission is 0.6940.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    5.270
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             2548
_exptl_crystal_preparation       ?
_exptl_crystal_size_max          0.062
_exptl_crystal_size_mid          0.005
_exptl_crystal_size_min          0.004
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0444
_diffrn_reflns_av_unetI/netI     0.0469
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            11066
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.503
_diffrn_reflns_theta_min         2.316
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 PIXEL
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON III area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture, PHOTON-III CMOS'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_radiation_monochromator  'Incoatec HELIOS multilayer mirrors'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'Incoatec IuS3.0 microfocus X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         .
_diffrn_measurement_details      
;
 Data collection was performed by Dr. V.Yu. Komarov in XRD Facility
 of NIIC SB RAS
;
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                2268
_reflns_number_total             2859
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_refine_diff_density_max         1.368
_refine_diff_density_min         -4.266
_refine_diff_density_rms         0.366
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     83
_refine_ls_number_reflns         2859
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0394
_refine_ls_restrained_S_all      1.059
_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)+(0.0445P)²+40.6730P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0971
_refine_ls_wR_factor_ref         0.1032
_refine_special_details          ?
_olex2_refinement_description    
;
;
_atom_sites_solution_hydrogens   .
_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
I1 I 0.34845(3) 0.31965(10) 0.48794(3) 0.01878(14) Uani 1 1 d . . . . .
I2 I 0.33208(3) 1.09207(10) 0.78999(4) 0.01921(14) Uani 1 1 d . . . . .
I3 I 0.5000 0.20463(14) 0.7500 0.02060(18) Uani 1 2 d S T P A 1
Se11 Se 0.52919(5) 0.86527(17) 0.93593(5) 0.0204(2) Uani 1 1 d . . . . .
Se12 Se 0.45420(5) 0.54182(17) 0.88276(5) 0.02003(19) Uani 1 1 d . . . . .
Se21 Se 0.33221(5) 0.86934(17) 0.59760(5) 0.0201(2) Uani 1 1 d . . . . .
Se22 Se 0.32721(5) 0.54453(17) 0.66644(5) 0.0202(2) Uani 1 1 d . . . . .
V1 V 0.43125(8) 0.5796(3) 0.63276(9) 0.0193(3) Uani 1 1 d . . . . .
V2 V 0.42435(8) 0.8312(3) 0.76794(9) 0.0190(3) Uani 1 1 d . . . . .
O1 O 0.5000 0.7027(14) 0.7500 0.0134(15) Uani 1 2 d S T P A .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
I1 0.0146(2) 0.0257(3) 0.0155(2) -0.0022(2) 0.00796(19) -0.0012(2)
I2 0.0152(2) 0.0242(3) 0.0214(3) 0.0004(2) 0.0121(2) 0.0013(2)
I3 0.0177(4) 0.0242(4) 0.0207(4) 0.000 0.0111(3) 0.000
Se11 0.0130(4) 0.0352(5) 0.0139(4) -0.0012(3) 0.0080(3) 0.0000(3)
Se12 0.0132(4) 0.0344(5) 0.0140(4) 0.0008(4) 0.0085(3) -0.0005(3)
Se21 0.0108(4) 0.0344(5) 0.0141(4) 0.0012(3) 0.0063(3) 0.0013(3)
Se22 0.0113(4) 0.0346(5) 0.0153(4) -0.0007(4) 0.0077(3) -0.0010(3)
V1 0.0108(6) 0.0348(9) 0.0131(6) -0.0044(6) 0.0072(5) -0.0029(6)
V2 0.0104(6) 0.0346(9) 0.0124(6) 0.0003(6) 0.0066(5) 0.0033(6)
O1 0.013(4) 0.016(4) 0.008(3) 0.000 0.004(3) 0.000

_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
I1 V1 2.6808(16) . ?
I2 V2 2.6793(16) . ?
I3 V1 2.8395(18) . ?
I3 V1 2.8395(18) 2_656 ?
I3 V2 2.8396(18) 1_545 ?
I3 V2 2.8396(17) 2_646 ?
Se11 Se12 2.3172(14) . ?
Se11 V1 2.4940(18) 2_656 ?
Se11 V2 2.5931(16) . ?
Se12 V1 2.5963(16) 2_656 ?
Se12 V2 2.4822(18) . ?
Se21 Se22 2.3154(14) . ?
Se21 V1 2.4933(18) . ?
Se21 V2 2.5866(16) . ?
Se22 V1 2.5946(16) . ?
Se22 V2 2.5009(18) . ?
V1 Se11 2.4940(18) 2_656 ?
V1 Se12 2.5963(16) 2_656 ?
V1 V2 2.942(2) 2_656 ?
V1 V2 2.931(2) . ?
V1 O1 1.929(3) . ?
V2 I3 2.8396(17) 1_565 ?
V2 V1 2.942(2) 2_656 ?
V2 O1 1.951(3) . ?
O1 V1 1.929(3) 2_656 ?
O1 V2 1.951(3) 2_656 ?

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
V1 I3 V1 78.02(6) . 2_656 ?
V1 I3 V2 126.81(4) 2_656 2_646 ?
V1 I3 V2 126.81(4) . 1_545 ?
V1 I3 V2 127.10(4) 2_656 1_545 ?
V1 I3 V2 127.10(4) . 2_646 ?
V2 I3 V2 78.62(6) 1_545 2_646 ?
Se12 Se11 V1 65.20(5) . 2_656 ?
Se12 Se11 V2 60.42(5) . . ?
V1 Se11 V2 70.63(5) 2_656 . ?
Se11 Se12 V1 60.69(5) . 2_656 ?
Se11 Se12 V2 65.30(5) . . ?
V2 Se12 V1 70.76(5) . 2_656 ?
Se22 Se21 V1 65.19(5) . . ?
Se22 Se21 V2 61.05(5) . . ?
V1 Se21 V2 70.45(5) . . ?
Se21 Se22 V1 60.72(5) . . ?
Se21 Se22 V2 64.83(5) . . ?
V2 Se22 V1 70.20(5) . . ?
I1 V1 I3 94.22(5) . . ?
I1 V1 V2 142.80(6) . . ?
I1 V1 V2 141.12(6) . 2_656 ?
I3 V1 V2 90.61(5) . . ?
I3 V1 V2 90.38(5) . 2_656 ?
Se11 V1 I1 96.60(5) 2_656 . ?
Se11 V1 I3 136.21(6) 2_656 . ?
Se11 V1 Se12 54.11(4) 2_656 2_656 ?
Se11 V1 Se22 137.07(7) 2_656 . ?
Se11 V1 V2 56.26(5) 2_656 2_656 ?
Se11 V1 V2 105.12(7) 2_656 . ?
Se12 V1 I1 89.32(5) 2_656 . ?
Se12 V1 I3 83.83(5) 2_656 . ?
Se12 V1 V2 127.88(6) 2_656 . ?
Se12 V1 V2 52.81(4) 2_656 2_656 ?
Se21 V1 I1 98.03(5) . . ?
Se21 V1 I3 137.02(6) . . ?
Se21 V1 Se11 82.98(6) . 2_656 ?
Se21 V1 Se12 137.06(7) . 2_656 ?
Se21 V1 Se22 54.10(4) . . ?
Se21 V1 V2 104.58(7) . 2_656 ?
Se21 V1 V2 56.26(5) . . ?
Se22 V1 I1 90.29(5) . . ?
Se22 V1 I3 84.96(5) . . ?
Se22 V1 Se12 168.72(8) . 2_656 ?
Se22 V1 V2 128.59(6) . 2_656 ?
Se22 V1 V2 53.40(4) . . ?
V2 V1 V2 75.55(6) . 2_656 ?
O1 V1 I1 167.2(2) . . ?
O1 V1 I3 73.1(2) . . ?
O1 V1 Se11 92.22(18) . 2_656 ?
O1 V1 Se12 88.39(6) . 2_656 ?
O1 V1 Se21 92.18(18) . . ?
O1 V1 Se22 89.51(6) . . ?
O1 V1 V2 40.98(9) . 2_656 ?
O1 V1 V2 41.23(9) . . ?
I2 V2 I3 94.36(5) . 1_565 ?
I2 V2 V1 142.23(6) . . ?
I2 V2 V1 142.32(6) . 2_656 ?
I3 V2 V1 90.23(5) 1_565 . ?
I3 V2 V1 90.01(5) 1_565 2_656 ?
Se11 V2 I2 90.05(5) . . ?
Se11 V2 I3 84.54(5) . 1_565 ?
Se11 V2 V1 53.11(4) . 2_656 ?
Se11 V2 V1 127.73(6) . . ?
Se12 V2 I2 97.86(5) . . ?
Se12 V2 I3 136.75(6) . 1_565 ?
Se12 V2 Se11 54.28(4) . . ?
Se12 V2 Se21 136.99(7) . . ?
Se12 V2 Se22 82.90(6) . . ?
Se12 V2 V1 104.17(7) . . ?
Se12 V2 V1 56.43(5) . 2_656 ?
Se21 V2 I2 89.90(5) . . ?
Se21 V2 I3 84.06(5) . 1_565 ?
Se21 V2 Se11 168.55(8) . . ?
Se21 V2 V1 127.77(6) . 2_656 ?
Se21 V2 V1 53.28(4) . . ?
Se22 V2 I2 97.29(5) . . ?
Se22 V2 I3 136.30(6) . 1_565 ?
Se22 V2 Se11 137.17(7) . . ?
Se22 V2 Se21 54.11(4) . . ?
Se22 V2 V1 105.10(7) . 2_656 ?
Se22 V2 V1 56.40(5) . . ?
V1 V2 V1 74.99(6) . 2_656 ?
O1 V2 I2 167.8(2) . . ?
O1 V2 I3 73.5(2) . 1_565 ?
O1 V2 Se11 88.76(6) . . ?
O1 V2 Se12 91.24(18) . . ?
O1 V2 Se21 88.89(6) . . ?
O1 V2 Se22 91.79(18) . . ?
O1 V2 V1 40.40(9) . 2_656 ?
O1 V2 V1 40.65(9) . . ?
V1 O1 V1 135.9(5) . 2_656 ?
V1 O1 V2 98.12(6) 2_656 2_656 ?
V1 O1 V2 98.62(6) 2_656 . ?
V1 O1 V2 98.12(6) . . ?
V1 O1 V2 98.62(6) . 2_656 ?
V2 O1 V2 134.4(4) . 2_656 ?

_shelx_res_file                  
;
    sp387_s2_150k.res created by SHELXL-2014/7

TITL sp387_s2_150k_a.res in C2/c
REM Old TITL sp387_s2_150K in C2/c
REM SHELXT solution in C2/c
REM R1 0.089, Rweak 0.002, Alpha 0.010, Orientation as input
REM Formula found by SHELXT: O V4 Se8 I5
CELL 0.71073 21.1319 5.8841 18.0933 90 123.649 90
ZERR 4 0.0013 0.0003 0.0009 0 0.002 0
LATT 7
SYMM -X,+Y,0.5-Z
SFAC I O Se V
UNIT 20 4 32 16

L.S. 10
PLAN  5
SIZE 0.004 0.005 0.062
TEMP -123(2)
CONF
list 4
MORE -1
fmap -2 53
acta
SHEL 17 0.7
REM <olex2.extras>
REM <HklSrc "%.\\sp387_s2_150K.hkl">
REM </olex2.extras>

WGHT    0.044500   40.672997
FVAR       0.09047
I1    1    0.348452    0.319645    0.487938    11.00000    0.01455    0.02573 =
         0.01548   -0.00217    0.00796   -0.00118
I2    1    0.332082    1.092065    0.789993    11.00000    0.01516    0.02419 =
         0.02145    0.00039    0.01213    0.00128
PART 1
I3    1    0.500000    0.204627    0.750000    10.50000    0.01767    0.02422 =
         0.02069    0.00000    0.01112    0.00000
PART 0
SE11  3    0.529191    0.865265    0.935930    11.00000    0.01304    0.03517 =
         0.01394   -0.00119    0.00803   -0.00001
SE12  3    0.454202    0.541818    0.882765    11.00000    0.01321    0.03445 =
         0.01399    0.00082    0.00850   -0.00046
SE21  3    0.332209    0.869345    0.597598    11.00000    0.01081    0.03441 =
         0.01412    0.00118    0.00627    0.00126
SE22  3    0.327215    0.544534    0.666441    11.00000    0.01135    0.03457 =
         0.01532   -0.00070    0.00770   -0.00105
V1    4    0.431253    0.579595    0.632764    11.00000    0.01083    0.03476 =
         0.01315   -0.00444    0.00721   -0.00292
V2    4    0.424352    0.831224    0.767943    11.00000    0.01036    0.03463 =
         0.01241    0.00030    0.00656    0.00331
O1    2    0.500000    0.702722    0.750000    10.50000    0.01292    0.01605 =
         0.00835    0.00000    0.00400    0.00000
HKLF 4

REM  sp387_s2_150k_a.res in C2/c
REM R1 =  0.0394 for    2268 Fo > 4sig(Fo)  and  0.0542 for all    2859 data
REM     83 parameters refined using      0 restraints

END

WGHT      0.0445     40.7285

REM Highest difference peak  1.368,  deepest hole -4.266,  1-sigma level  0.366
Q1    1   0.4784  0.0906  0.7821  11.00000  0.05    1.37
Q2    1   0.3484  0.4148  0.4768  11.00000  0.05    1.34
Q3    1   0.3472  0.2095  0.4924  11.00000  0.05   -1.30
Q4    1   0.4605  0.4849  0.8195  11.00000  0.05    1.30
Q5    1   0.3400  0.3213  0.4248  11.00000  0.05    1.25
;
_shelx_res_checksum              15043
_olex2_submission_special_instructions 'No special instructions were received'

# start Validation Reply Form
_vrf_PLAT972_sp387_s2_150k       
;
PROBLEM: Check Calcd Resid. Dens.  0.69Ang From I3             -3.85 eA-3  
RESPONSE: 
 There may be a complex occupancy of the I3 position (e.g. I/vacancy with
 occupansies of 0.87/0.13 or I/Se of 64/36) or systematic deviations in
 the hklFo data.
 The artefact is discussed the dedicated article.
;
# end Validation Reply Form
