# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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_p16148a_mono
_database_code_depnum_ccdc_archive 'CCDC 1580495'
_audit_update_record             
;
2017-10-17 deposited with the CCDC.
2018-01-17 downloaded from the CCDC.
;
_audit_creation_date             2017-10-17
_audit_creation_method           
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'Cl O2.5 P0.5 V0.5, Na'
_chemical_formula_sum            'Cl Na O2.50 P0.50 V0.50'
_chemical_formula_weight         139.40
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C50 H50 V1 O3'
_chemical_oxdiff_usercomment     '@ 170 K Rm 564 F DMF/Et2O'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Cl Cl 0.1484 0.1585 '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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.1023 0.0942 '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           12
_space_group_name_H-M_alt        'I 1 2/m 1'
_space_group_name_Hall           '-I 2y'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z'
'-x+1/2, -y+1/2, -z+1/2'
'x+1/2, -y+1/2, z+1/2'

_cell_length_a                   7.3580(6)
_cell_length_b                   6.3903(6)
_cell_length_c                   15.2247(16)
_cell_angle_alpha                90
_cell_angle_beta                 90.318(9)
_cell_angle_gamma                90
_cell_volume                     715.85(12)
_cell_formula_units_Z            8
_cell_measurement_reflns_used    1708
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      26.0940
_cell_measurement_theta_min      4.1390
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    2.437
_exptl_absorpt_correction_T_max  0.953
_exptl_absorpt_correction_T_min  0.859
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.42b (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear pale green'
_exptl_crystal_density_diffrn    2.587
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             536
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-2 -6 -16 0.0421
2 6 16 0.0421
2 1 -21 0.0257
-2 -1 21 0.0257
-9 1 -10 0.0214
9 -1 10 0.0214

_exptl_crystal_size_max          0.164
_exptl_crystal_size_mid          0.068
_exptl_crystal_size_min          0.043
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-1.9998 -6.0000 -16.0000 0.4343 -0.8975 0.2077
1.9998 6.0000 16.0000 -0.4343 0.8975 -0.2077
2.0001 1.0000 -21.0000 0.2354 -0.3658 0.9031
-2.0001 -1.0000 21.0000 -0.2354 0.3658 -0.9031
-8.9999 1.0000 -10.0001 0.9892 0.0034 0.0806
8.9999 -1.0000 10.0001 -0.9892 -0.0034 -0.0806

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0568
_diffrn_reflns_av_unetI/netI     0.0336
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            5177
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.712
_diffrn_reflns_theta_max         24.712
_diffrn_reflns_theta_min         3.068
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1042
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -35.00  52.00   1.00   45.00    --  -16.31  57.00   0.00   87
  2  ω    -85.00   2.00   1.00   45.00    --  -16.31 -57.00-150.00   87
  3  ω    -25.00  24.00   1.00   45.00    --  -16.31 -99.00 120.00   49
  4  ω    -35.00  52.00   1.00   45.00    --  -16.31  57.00 120.00   87
  5  ω    -25.00  24.00   1.00   45.00    --  -16.31 -99.00-120.00   49
  6  ω    -25.00  59.00   1.00   45.00    --   18.03 -99.00  60.00   84
  7  ω    -35.00  52.00   1.00   45.00    --  -16.31  57.00-120.00   87
  8  ω    -85.00   2.00   1.00   45.00    --  -16.31 -57.00  90.00   87
  9  ω    -85.00   2.00   1.00   45.00    --  -16.31 -57.00 -30.00   87
 10  ω    -25.00  59.00   1.00   45.00    --   18.03 -99.00-120.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0877115000
_diffrn_orient_matrix_UB_12      0.0080071000
_diffrn_orient_matrix_UB_13      -0.0191828000
_diffrn_orient_matrix_UB_21      -0.0126744000
_diffrn_orient_matrix_UB_22      0.0981183000
_diffrn_orient_matrix_UB_23      0.0208833000
_diffrn_orient_matrix_UB_31      0.0378129000
_diffrn_orient_matrix_UB_32      0.0513470000
_diffrn_orient_matrix_UB_33      -0.0369601000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                566
_reflns_number_total             675
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.66
_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       'CrysAlisPro 1.171.38.42b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.42b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.42b (Rigaku OD, 2015)'
_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         1.529
_refine_diff_density_min         -1.720
_refine_diff_density_rms         0.282
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.126
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     51
_refine_ls_number_reflns         675
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1138
_refine_ls_R_factor_gt           0.0977
_refine_ls_restrained_S_all      1.126
_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)+(0.1246P)²+35.8176P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2447
_refine_ls_wR_factor_ref         0.2631
_refine_special_details          ?
_olex2_refinement_description    
;
1. Uiso/Uaniso restraints and constraints
Uanis(O2) = Uanis(P1)
Uanis(O3) = Uanis(O4)
;
_atom_sites_solution_hydrogens   .
_atom_sites_solution_primary     direct
_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 0.0686(3) 0.0000 0.31798(16) 0.0153(8) Uani 1 2 d S T P . .
P1 P 0.1307(5) 0.5000 0.3327(2) 0.0156(9) Uani 1 2 d S T P . .
O2 O 0.0228(9) 0.3089(11) 0.3087(4) 0.0156(9) Uani 1 1 d . . . . .
O1 O 0.2503(15) 0.0000 0.3753(7) 0.028(3) Uani 1 2 d S T P . .
O3 O 0.1527(14) 0.5000 0.4345(6) 0.0204(17) Uani 1 2 d S T P . .
O4 O 0.3250(14) 0.5000 0.3026(6) 0.0204(17) Uani 1 2 d S T P . .
Cl1 Cl -0.111(2) 0.0000 0.4226(11) 0.177(6) Uani 1 2 d S T P . .
Cl2 Cl -0.1886(18) 0.0000 0.2407(16) 0.217(10) Uani 1 2 d S T P . .
Na1 Na -0.4082(15) 0.263(3) 0.4232(8) 0.143(5) Uani 1 1 d . . . . .

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
V1 0.0082(12) 0.0109(13) 0.0268(14) 0.000 0.0052(9) 0.000
P1 0.0152(17) 0.0108(17) 0.0209(17) 0.000 0.0053(13) 0.000
O2 0.0152(17) 0.0108(17) 0.0209(17) 0.000 0.0053(13) 0.000
O1 0.026(6) 0.028(6) 0.030(6) 0.000 -0.003(5) 0.000
O3 0.028(4) 0.024(4) 0.009(3) 0.000 0.004(3) 0.000
O4 0.028(4) 0.024(4) 0.009(3) 0.000 0.004(3) 0.000
Cl1 0.193(14) 0.125(10) 0.214(14) 0.000 0.111(12) 0.000
Cl2 0.101(9) 0.115(11) 0.43(3) 0.000 -0.082(13) 0.000
Na1 0.088(6) 0.223(17) 0.119(8) -0.003(9) -0.001(6) 0.026(8)

_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 O2 2.008(7) 6 ?
V1 O2 2.008(7) . ?
V1 O1 1.592(11) . ?
V1 O4 1.999(9) 7 ?
V1 Cl1 2.073(13) . ?
V1 Cl2 2.223(14) . ?
P1 O2 1.500(7) 6_565 ?
P1 O2 1.501(7) . ?
P1 O3 1.558(10) . ?
P1 O4 1.504(11) . ?
O4 V1 1.999(9) 7 ?
Na1 Cl2 3.01(3) 7_455 ?
Na1 Na1 3.36(3) 6 ?

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
O2 V1 O2 159.1(4) 6 . ?
O2 V1 Cl1 87.0(2) . . ?
O2 V1 Cl1 87.0(2) 6 . ?
O2 V1 Cl2 79.7(2) 6 . ?
O2 V1 Cl2 79.7(2) . . ?
O1 V1 O2 100.3(2) . 6 ?
O1 V1 O2 100.3(2) . . ?
O1 V1 O4 99.9(5) . 7 ?
O1 V1 Cl1 96.6(7) . . ?
O1 V1 Cl2 178.8(7) . . ?
O4 V1 O2 90.1(2) 7 6 ?
O4 V1 O2 90.1(2) 7 . ?
O4 V1 Cl1 163.6(6) 7 . ?
O4 V1 Cl2 81.4(7) 7 . ?
Cl1 V1 Cl2 82.2(9) . . ?
O2 P1 O2 108.9(6) 6_565 . ?
O2 P1 O3 107.1(3) . . ?
O2 P1 O3 107.1(3) 6_565 . ?
O2 P1 O4 115.3(3) 6_565 . ?
O2 P1 O4 115.3(3) . . ?
O4 P1 O3 102.1(6) . . ?
P1 O2 V1 134.0(4) . . ?
P1 O4 V1 131.1(6) . 7 ?
Cl2 Na1 Na1 120.3(4) 7_455 6 ?

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
O2 P1 O2 V1 179.52(18) 6_565 . . . ?
O2 P1 O4 V1 64.2(4) . . . 7 ?
O2 P1 O4 V1 -64.2(4) 6_565 . . 7 ?
O3 P1 O2 V1 -64.9(7) . . . . ?
O3 P1 O4 V1 180.000(1) . . . 7 ?
O4 P1 O2 V1 48.0(7) . . . . ?

_shelx_res_file                  
;
    p16148a_mono.res created by SHELXL-2014/7

TITL p16148a_mono_a.res in I2/m
REM Old TITL P16148a_mono in I2 #5
REM SHELXT solution in I2/m
REM R1 0.216, Rweak 0.026, Alpha 0.050, Orientation as input
REM Formula found by SHELXT: C2 O7 V2
CELL 0.71073 7.357966 6.390337 15.224692 90 90.318 90
ZERR 8 0.000647 0.000572 0.001622 0 0.0086 0
LATT 2
SYMM -X,+Y,-Z
SFAC Cl Na O P V
UNIT 8 8 20 4 4
EQIV $1 -1-X,+Y,1-Z
EQIV $2 -0.5-X,-1.5+Y,0.5-Z
EQIV $3 -0.5-X,0.5-Y,0.5-Z
EQIV $4 +X,-Y,+Z
EQIV $5 -1-X,1-Y,1-Z
EQIV $6 +X,1-Y,+Z
EQIV $7 -0.5-X,-0.5-Y,0.5-Z
EQIV $8 -0.5-X,-0.5+Y,0.5-Z
EADP O2 P1
EADP O3 O4

L.S. 4
PLAN  20
FREE Cl2 Na1_$7
FREE Cl2 Na1_$8
FREE Cl2 Na1_$2
FREE Cl2 Na1_$3
FREE Na1 Na1_$6
FREE Na1 Na1_$1
FREE Na1 Na1_$5
FREE Cl1 Na1_$4
FREE Cl1 Na1
BOND $H
LIST 6
MORE -1
CONF
fmap 2
acta 52
REM <olex2.extras>
REM <HklSrc "%.\\P16148a_mono.hkl">
REM </olex2.extras>

WGHT    0.124600   35.817596
FVAR       0.50241
V1    5    0.068594    0.000000    0.317983    10.50000    0.00824    0.01091 =
         0.02677    0.00000    0.00516    0.00000
P1    4    0.130691    0.500000    0.332704    10.50000    0.01523    0.01081 =
         0.02086    0.00000    0.00525    0.00000
O2    3    0.022825    0.308932    0.308660    11.00000    0.01523    0.01081 =
         0.02086    0.00000    0.00525    0.00000
O1    3    0.250262    0.000000    0.375286    10.50000    0.02650    0.02787 =
         0.02998    0.00000   -0.00294    0.00000
O3    3    0.152714    0.500000    0.434512    10.50000    0.02820    0.02387 =
         0.00923    0.00000    0.00427    0.00000
O4    3    0.325007    0.500000    0.302575    10.50000    0.02820    0.02387 =
         0.00923    0.00000    0.00427    0.00000
CL1   1   -0.110515    0.000000    0.422635    10.50000    0.19283    0.12469 =
         0.21397    0.00000    0.11061    0.00000
CL2   1   -0.188574    0.000000    0.240656    10.50000    0.10065    0.11541 =
         0.43490    0.00000   -0.08172    0.00000
NA1   2   -0.408229    0.262706    0.423243    11.00000    0.08762    0.22257 =
         0.11921   -0.00316   -0.00114    0.02639
HKLF 4

REM  p16148a_mono_a.res in I2/m
REM R1 =  0.0977 for     566 Fo > 4sig(Fo)  and  0.1138 for all     675 data
REM     51 parameters refined using      0 restraints

END

WGHT      0.1246     35.8060

REM Highest difference peak  1.529,  deepest hole -1.720,  1-sigma level  0.282
Q1    1   0.0710  0.5000  0.4262  10.50000  0.05    1.53
Q2    1  -0.4077  0.5000  0.4560  10.50000  0.05    1.30
Q3    1   0.0140  0.2959  0.3522  11.00000  0.05    1.07
Q4    1   0.3268  0.5000  0.2749  10.50000  0.05    0.86
Q5    1  -0.1946  0.0000  0.2613  10.50000  0.05    0.83
Q6    1   0.0409  0.3471  0.2701  11.00000  0.05    0.82
Q7    1   0.2133  0.5000  0.4365  10.50000  0.05    0.79
Q8    1  -0.3351  0.0000  0.2109  10.50000  0.05    0.78
Q9    1   0.3102  0.5000  0.3290  10.50000  0.05    0.67
Q10   1  -0.0764  0.3103  0.2784  11.00000  0.05    0.64
Q11   1   0.0432  0.0000  0.3880  10.50000  0.05    0.55
Q12   1  -0.2285  0.0801  0.4626  11.00000  0.05    0.45
Q13   1  -0.1046  0.5000  0.4192  10.50000  0.05    0.42
Q14   1   0.0580  0.5000  0.5156  10.50000  0.05    0.42
Q15   1  -0.0725  0.4356  0.4113  11.00000  0.05    0.40
Q16   1  -0.1289  0.0000  0.5187  10.50000  0.05    0.39
Q17   1  -0.2938  0.0000  0.1278  10.50000  0.05    0.39
Q18   1   0.1251  0.2751  0.3003  11.00000  0.05    0.38
Q19   1  -0.5187  0.2727  0.4860  11.00000  0.05    0.37
Q20   1  -0.2580  0.2585  0.4243  11.00000  0.05    0.36
;
_shelx_res_checksum              28503
_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 1.459
_oxdiff_exptl_absorpt_empirical_full_min 0.686
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
