Site-selective halogenation of mixed-valent vanadium oxide clusters.
Maiola, Michela L.; Petel, Brittney E.; Brennessel, William W.; Matson, Ellen M.; Dalton transactions (Cambridge, England : 2003) 49 (2020) 16184–16192; doi:10.1039/d0dt01077d

data_7704070
_publ_section_title
;
 Site-selective halogenation of mixed-valent vanadium oxide clusters.
;
_journal_issue                   45
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              16184
_journal_page_last               16192
_journal_paper_doi               10.1039/d0dt01077d
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         'C4 H10 Cl5 O8 W3, C24 H60 Cl O18 V6'
_chemical_formula_sum            'C28 H70 Cl6 O26 V6 W3'
_chemical_formula_weight         1892.73
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-02-29
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2020-03-12 deposited with the CCDC.	2020-04-13 downloaded from the CCDC.
;
_cell_angle_alpha                81.532(2)
_cell_angle_beta                 87.046(3)
_cell_angle_gamma                83.092(3)
_cell_formula_units_Z            2
_cell_length_a                   10.7819(4)
_cell_length_b                   15.5823(4)
_cell_length_c                   16.9994(5)
_cell_measurement_reflns_used    15382
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.2920
_cell_measurement_theta_min      2.6730
_cell_volume                     2802.71(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.959
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     -5.00  22.00   0.50    1.76    --  -49.75  19.00-120.00   54
  2  \w    -34.00  22.00   0.50    1.76    --  -49.75  38.00 -60.00  112
  3  \w     -5.00  21.00   0.50    1.76    --  -49.75  19.00  30.00   52
  4  \w    -40.00 -13.00   0.50    7.02    --  -84.25  45.00 -90.00   54
  5  \w    -83.00  -8.00   0.50    1.76    --  -49.75 115.00  49.00  150
  6  \w    -42.00 -15.00   0.50    7.02    --  -84.25  45.00  60.00   54
  7  \w    -72.00 -47.00   0.50    7.02    --  -84.25 115.00  49.00   50
  8  \w   -117.00 -84.00   0.50    1.76    --  -49.75 170.00-167.00   66
  9  \w     84.00 114.00   0.50    1.76    --   49.75 170.00-167.00   60
 10  \w     85.00 110.00   0.50    7.02    --  105.75 170.00-167.00   50
 11  \w    133.00 166.00   0.50    7.02    --  105.75 125.00 -30.00   66
 12  \w    115.00 140.00   0.50    7.02    --  105.75 115.00  49.00   50
 13  \w     96.00 130.00   0.50    7.02    --  105.75 125.00 -30.00   68
 14  \w     97.00 177.00   0.50    7.02    --  105.75  45.00  60.00  160
 15  \w    116.00 170.00   0.50    7.02    --  105.75  15.00 -60.00  108
 16  \w    102.00 152.00   0.50    7.02    --  105.75  30.00-150.00  100
 17  \w    109.00 135.00   0.50    7.02    --  105.75  61.00-180.00   52
 18  \w    105.00 178.00   0.50    7.02    --  105.75  45.00 -30.00  146
 19  \w     98.00 174.00   0.50    7.02    --  105.75  15.00  60.00  152
 20  \w     91.00 119.00   0.50    7.02    --  105.75 -77.00 120.00   56
 21  \w     90.00 116.00   0.50    7.02    --  105.75 -84.00 143.90   52
 22  \w     75.00 105.00   0.50    7.02    --  105.75 -94.00 150.00   60
 23  \w     79.00 106.00   0.50    7.02    --  105.75 -96.00 100.45   54
 24  \w     65.00  90.00   0.50    1.76    --   49.75-170.00 177.00   50
 25  \w     68.00 102.00   0.50    7.02    --  105.75-170.00 177.00   68
 26  \w     51.00  77.00   0.50    7.02    --  105.75 -77.00 120.00   52
 27  \w     42.00  67.00   0.50    7.02    --  105.75 -94.00 150.00   50
 28  \w     39.00  73.00   0.50    7.02    --  105.75 -61.00 120.00   68
 29  \w     36.00  68.00   0.50    7.02    --  105.75 -94.00  90.00   64
 30  \w     38.00  63.00   0.50    7.02    --  105.75 -61.00  30.00   50
 31  \w     52.00  94.00   0.50    7.02    --  105.75 -77.00   0.00   84
 32  \w     75.00 104.00   0.50    7.02    --  105.75 -94.00 -60.00   58
 33  \w     85.00 111.00   0.50    7.02    --  105.75-125.00 -90.00   52
 34  \w     71.00 105.00   0.50    7.02    --  105.75 -94.00 -90.00   68
 35  \w     50.00  76.00   0.50    7.02    --  105.75-115.00 -39.00   52
 36  \w     35.00 106.00   0.50    7.02    --  105.75 -97.00  17.60  142
 37  \w     38.00 106.00   0.50    7.02    --  105.75 -94.00  60.00  136
 38  \w     40.00  67.00   0.50    7.02    --  105.75 -94.00 -60.00   54
 39  \w     43.00 107.00   0.50    7.02    --  105.75-106.00 -89.29  128
 40  \w     43.00  78.00   0.50    7.02    --  105.75 -61.00-180.00   70
 41  \w     34.00 105.00   0.50    7.02    --  105.75 -94.00-180.00  142
 42  \w     36.00  67.00   0.50    7.02    --  105.75-125.00 -90.00   62
 43  \w     36.00  94.00   0.50    7.02    --  105.75-125.00 -60.00  116
 44  \w     34.00  59.00   0.50    1.76    --   49.75-115.00 -39.00   50
 45  \w     35.00  61.00   0.50    7.02    --  105.75 -61.00 -30.00   52
 46  \w     34.00 106.00   0.50    7.02    --  105.75 -94.00 -30.00  144
 47  \w     38.00  64.00   0.50    7.02    --  105.75-125.00  60.00   52
 48  \w     42.00 102.00   0.50    7.02    --  105.75 -94.00 120.00  120
 49  \w     35.00  72.00   0.50    7.02    --  105.75 -96.00 100.45   74
 50  \w     98.00 152.00   0.50    7.02    --  105.75  15.00 150.00  108
 51  \w     98.00 178.00   0.50    7.02    --  105.75  30.00 150.00  160
 52  \w     34.00  74.00   0.50    7.02    --  105.75 -61.00 -90.00   80
 53  \w    -88.00 -47.00   0.50    1.76    --  -49.75-170.00 177.00   82
 54  \w   -121.00 -33.00   0.50    1.76    --  -49.75 -77.00   0.00  176
 55  \w   -114.00 -89.00   0.50    7.02    --  -84.25-115.00 -39.00   50
 56  \w   -121.00 -73.00   0.50    1.76    --  -49.75-125.00  30.00   96
 57  \w   -119.00 -74.00   0.50    1.76    --  -49.75-125.00   0.00   90
 58  \w   -114.00 -89.00   0.50    7.02    --  -84.25-170.00 177.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0288948000
_diffrn_orient_matrix_UB_12      -0.0045274000
_diffrn_orient_matrix_UB_13      0.0901209000
_diffrn_orient_matrix_UB_21      0.1108951000
_diffrn_orient_matrix_UB_22      0.0517055000
_diffrn_orient_matrix_UB_23      0.0075608000
_diffrn_orient_matrix_UB_31      -0.0872217000
_diffrn_orient_matrix_UB_32      0.0861911000
_diffrn_orient_matrix_UB_33      -0.0150276000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1213
_diffrn_reflns_av_unetI/netI     0.0851
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            48081
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         79.864
_diffrn_reflns_theta_min         2.629
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    22.322
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68548
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.71a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.243
_exptl_crystal_description       block
_exptl_crystal_F_000             1816
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.054
_exptl_crystal_size_min          0.035
_refine_diff_density_max         3.821
_refine_diff_density_min         -3.025
_refine_diff_density_rms         0.282
_refine_ls_extinction_coef       0.00034(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     736
_refine_ls_number_reflns         11712
_refine_ls_number_restraints     238
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.1280
_refine_ls_R_factor_gt           0.1002
_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/[\s^2^(Fo^2^)+(0.1901P)^2^+12.3525P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2861
_refine_ls_wR_factor_ref         0.3201
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8069
_reflns_number_total             11712
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt01077d2.cif
_cod_data_source_block           matbp48
_cod_depositor_comments
'Adding full bibliography for 7704070--7704072.cif.'
_cod_database_code               7704070
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.509
_shelx_estimated_absorpt_t_min   0.348
_diffrn_oxdiff_digest_frames
;
01b10cc4aa192927d798816e8a01a5e2140477678d1
;
_diffrn_oxdiff_digest_hkl
;
01c4099cce23a2957693149b2c97374e86b72f
;
_reflns_odcompleteness_completeness 99.22
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O14-C15 \\sim O14-C15'
 with sigma of 0.01
 C15-C16 \\sim C15'-C16'
 with sigma of 0.01
 O14-C16 \\sim O14-C16'
 with sigma of 0.02
 O10-C7 \\sim O10-C7'
 with sigma of 0.01
 C7-C8 \\sim C7'-C8'
 with sigma of 0.01
 O10-C8 \\sim O10-C8'
 with sigma of 0.02
 O17-C21 \\sim O17-C21'
 with sigma of 0.01
 C21-C22 \\sim C21'-C22'
 with sigma of 0.01
 O17-C22 \\sim O17-C22'
 with sigma of 0.02
 W1-Cl2 \\sim W1'-Cl2'
 with sigma of 0.01
 W1-O20 \\sim W1'-O20'
 with sigma of 0.01
 W1-O25 \\sim W1'-O25' \\sim O25-W3 \\sim O25'-W3
 with sigma of 0.01
 W2-O21 \\sim W2'-O21'
 with sigma of 0.01
 W2-O26 \\sim W2'-O26'
 with sigma of 0.01
 W2-O24 \\sim W2-O24' \\sim O24-W3 \\sim O24'-W3
 with sigma of 0.01
 W1-O23 \\sim W2-O23 \\sim W1'-O23' \\sim W2'-O23'
 with sigma of 0.01
 W1-Cl6 \\sim W2-Cl6 \\sim W3-Cl6 \\sim W1'-Cl6' \\sim W2'-Cl6' \\sim W3-Cl6'
 with sigma of 0.02
 C27-C28' \\sim C27-C28
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(W1) = Uanis(W1')
Uanis(W2) = Uanis(W2')
Uanis(O20) = Uanis(O20')
Uanis(O21) = Uanis(O21')
Uanis(O23) = Uanis(O23')
Uanis(O24) = Uanis(O24')
Uanis(O25) = Uanis(O25')
Uanis(Cl2) = Uanis(Cl2')
Uanis(Cl3) = Uanis(Cl3')
Uanis(Cl4) = Uanis(Cl4')
Uanis(Cl6) = Uanis(Cl6')
Uanis(O26) = Uanis(O26')
Uanis(C25) = Uanis(C25')
Uanis(C26) = Uanis(C26')
Uanis(C28') = Uanis(C28)
4. Rigid body (RIGU) restrains
 O10, C7, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O10, C7', C8'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O13, C13, C14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O14, C15, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O14, C15', C16'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O17, C21, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O17, C21', C22'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 W1, O20, O25
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 W1', O20', O25'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{O26, C25, C26} sigma for 1-2: 0.02, 1-3: 0.04
as
{O26', C25', C26'}
6. Others
 Sof(W1')=Sof(W2')=Sof(Cl2')=Sof(Cl3')=Sof(Cl4')=Sof(Cl6')=Sof(O20')=Sof(O21')=
 Sof(O23')=Sof(O24')=Sof(O25')=Sof(O26')=Sof(C25')=Sof(H25C)=Sof(H25D)=
 Sof(C26')=Sof(H26D)=Sof(H26E)=Sof(H26F)=1-FVAR(1)
 Sof(W1)=Sof(W2)=Sof(Cl2)=Sof(Cl3)=Sof(Cl4)=Sof(Cl6)=Sof(O20)=Sof(O21)=
 Sof(O23)=Sof(O24)=Sof(O25)=Sof(O26)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=
 Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(1)
 Sof(C7')=Sof(H7'A)=Sof(H7'B)=Sof(C8')=Sof(H8'A)=Sof(H8'B)=Sof(H8'C)=1-FVAR(2)
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(2)
 Sof(C15')=Sof(H15C)=Sof(H15D)=Sof(C16')=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(3)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(3)
 Sof(C21')=Sof(H21C)=Sof(H21D)=Sof(C22')=Sof(H22D)=Sof(H22E)=Sof(H22F)=1-FVAR(4)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=FVAR(4)
 Sof(H27C)=Sof(H27D)=Sof(C28')=Sof(H28D)=Sof(H28E)=Sof(H28F)=1-FVAR(5)
 Sof(H27A)=Sof(H27B)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(5)
7.a Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C27(H27C,H27D), C25(H25A,H25B), C25'(H25C,H25D), C1(H1A,H1B),
 C3(H3A,H3B), C5(H5A,H5B), C9(H9A,H9B), C11(H11A,H11B), C13(H13A,H13B),
 C17(H17A,H17B), C19(H19A,H19B), C23(H23A,H23B), C7(H7A,H7B), C15(H15A,H15B),
 C21(H21A,H21B), C7'(H7'A,H7'B), C15'(H15C,H15D), C21'(H21C,H21D)
7.b Me refined with riding coordinates:
 C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C26'(H26D,H26E,H26F), C28'(H28D,
 H28E,H28F), C8(H8A,H8B,H8C), C16(H16A,H16B,H16C), C22(H22A,H22B,H22C),
 C8'(H8'A,H8'B,H8'C), C16'(H16D,H16E,H16F), C22'(H22D,H22E,H22F)
7.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C10(H10A,H10B,H10C),
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C18(H18A,H18B,H18C), C20(H20A,H20B,
 H20C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              15167
_olex2_submission_original_sample_id matbp48
_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 3.617
_oxdiff_exptl_absorpt_empirical_full_min 0.232