Development of sterically hindered siloxide-functionalized polyoxotungstates for the complexation of 5d-metals.
Auvray, Thomas; Nachtigall, Olaf; Brennessel, William W.; Jones, William D.; Matson, Ellen M.; Dalton transactions (Cambridge, England : 2003) 50 (2021) 4300–4310; doi:10.1039/d1dt00256b

data_7706756
_publ_section_title
;
 Development of sterically hindered siloxide-functionalized
 polyoxotungstates for the complexation of 5d-metals.
;
_journal_issue                   12
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              4300
_journal_page_last               4310
_journal_paper_doi               10.1039/d1dt00256b
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety
'C36 H72 Hf2 O78 P2 Si6 W18, 4(H2 O), 3.402(C4 H8 O), 6(C24 H52 N)'
_chemical_formula_sum            'C193.59 H419.17 Hf2 N6 O85.39 P2 Si6 W18'
_chemical_formula_weight         8094.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-12-23
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2021-01-25 deposited with the CCDC.	2021-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.6830(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   25.2799(3)
_cell_length_b                   25.7240(3)
_cell_length_c                   21.8787(3)
_cell_measurement_reflns_used    56089
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.1960
_cell_measurement_theta_min      2.7050
_cell_volume                     14025.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (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 0.999
_diffrn_measured_fraction_theta_max 0.985
_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    -70.00  22.00   0.50    0.35    --  -49.62  78.00 112.00  184
  2  \w     29.00 122.00   0.50    0.35    --   49.62  78.00 112.00  186
  3  \w    100.00 127.00   0.50    1.39    --  105.75  30.00  90.00   54
  4  \w     98.00 178.00   0.50    1.39    --  105.75  30.00  30.00  160
  5  \w    148.00 173.00   0.50    1.39    --  105.75  30.00  90.00   50
  6  \w     98.00 164.00   0.50    1.39    --  105.75  15.00  90.00  132
  7  \w    100.00 173.00   0.50    1.39    --  105.75  30.00  90.00  146
  8  \w     92.00 178.00   0.50    1.39    --  105.75 125.00  60.00  172
  9  \w     85.00 178.00   0.50    1.39    --  105.75  78.00 112.00  186
 10  \w     85.00 178.00   0.50    1.39    --  105.75  77.00  60.00  186
 11  \w     92.00 178.00   0.50    1.39    --  105.75  61.00  30.00  172
 12  \w     34.00 127.00   0.50    1.39    --  105.75 -78.00 -12.00  186
 13  \w     34.00  87.00   0.50    1.39    --  105.75 -61.00   0.00  106
 14  \w     34.00  87.00   0.50    1.39    --  105.75 -61.00  30.00  106
 15  \w     34.00  87.00   0.50    1.39    --  105.75 -61.00  60.00  106
 16  \w     34.00 109.00   0.50    1.39    --  105.75 -94.00 -30.00  150
 17  \w     34.00  87.00   0.50    1.39    --  105.75 -61.00-180.00  106
 18  \w     34.00  87.00   0.50    1.39    --  105.75 -61.00-120.00  106
 19  \w     37.00  87.00   0.50    1.39    --  105.75 -61.00-150.00  100
 20  \w    -21.00  71.00   0.50    0.35    --   49.62 -78.00 -12.00  184
 21  \w     34.00  87.00   0.50    1.39    --  105.75 -61.00  90.00  106
 22  \w     40.00  74.00   0.50    1.39    --  105.75 -61.00 150.00   68
 23  \w    -23.00   5.00   0.50    0.35    --   49.62 -19.00-180.00   56
 24  \w   -121.00 -29.00   0.50    0.35    --  -49.62 -78.00 -12.00  184
 25  \w   -121.00 -70.00   0.50    0.35    --  -49.62-125.00 120.00  102
 26  \w   -121.00 -70.00   0.50    0.35    --  -49.62-125.00-120.00  102
;
_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      0.0461385000
_diffrn_orient_matrix_UB_12      -0.0322065000
_diffrn_orient_matrix_UB_13      -0.0185751000
_diffrn_orient_matrix_UB_21      -0.0410105000
_diffrn_orient_matrix_UB_22      -0.0391541000
_diffrn_orient_matrix_UB_23      -0.0336609000
_diffrn_orient_matrix_UB_31      -0.0036670000
_diffrn_orient_matrix_UB_32      0.0318824000
_diffrn_orient_matrix_UB_33      -0.0601836000
_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  0.0839
_diffrn_reflns_av_unetI/netI     0.0460
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            175802
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.827
_diffrn_reflns_theta_min         2.674
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    15.482
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.26782
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.917
_exptl_crystal_description       block
_exptl_crystal_F_000             7792
_exptl_crystal_size_max          0.253
_exptl_crystal_size_mid          0.186
_exptl_crystal_size_min          0.12
_refine_diff_density_max         2.082
_refine_diff_density_min         -1.853
_refine_diff_density_rms         0.229
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1559
_refine_ls_number_reflns         29494
_refine_ls_number_restraints     1307
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0718
_refine_ls_R_factor_gt           0.0645
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1150P)^2^+74.1997P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1808
_refine_ls_wR_factor_ref         0.1882
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25500
_reflns_number_total             29494
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt00256b2.cif
_cod_data_source_block           matta03
_cod_depositor_comments
'Adding full bibliography for 7706755--7706757.cif.'
_cod_database_code               7706756
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.258
_shelx_estimated_absorpt_t_min   0.111
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 N2-C43 = N2-C49 = N2-C55 = N2-C61
 1.51 with sigma of 0.03
 C43-C44 = C44-C45 = C45-C46 = C46-C47 = C47-C48
 1.53 with sigma of 0.03
 C49-C50 = C50-C51 = C51-C52 = C52-C53 = C53-C54
 1.53 with sigma of 0.03
 C55-C56 = C56-C57 = C57-C58 = C58-C59 = C59-C60
 1.53 with sigma of 0.03
 C61-C62 = C62-C63 = C63-C64 = C64-C65 = C65-C66
 1.53 with sigma of 0.03
 N3-C67 = N3-C73 = N3-C79 = N3-C85
 1.51 with sigma of 0.03
 C67-C68 = C68-C69 = C69-C70 = C70-C71 = C71-C72
 1.53 with sigma of 0.03
 C73-C74 = C74-C75 = C75-C76 = C76-C77 = C77-C78
 1.53 with sigma of 0.03
 C79-C80 = C80-C81 = C81-C82 = C82-C83 = C83-C84
 1.53 with sigma of 0.03
 C85-C86 = C86-C87 = C87-C88 = C88-C89 = C89-C90
 1.53 with sigma of 0.03
 C43-C49 \\sim C43-C55 \\sim C43-C61 \\sim C49-C55 \\sim C49-C61 \\sim C55-C61
 with sigma of 0.01
 C43-C45 \\sim C44-C46 \\sim C45-C47 \\sim C46-C48 \\sim C49-C51 \\sim C50-C52
\\sim C51-C53 \\sim C52-C54
 \\sim C55-C57 \\sim C56-C58 \\sim C57-C59 \\sim C58-C60 \\sim C61-C63 \\sim
C62-C64 \\sim C63-C65 \\sim C64-C66
 with sigma of 0.06
 C67-C73 \\sim C67-C79 \\sim C67-C85 \\sim C73-C79 \\sim C73-C85 \\sim C79-C85
 with sigma of 0.01
 Si2-C7 \\sim Si2-C7' \\sim Si2-C7"
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 1.2A
N2 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim
C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim
C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim
C66: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C46 \\sim C47 \\sim C48: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
N3 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim
C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim
C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89 \\sim
C90: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
O43 \\sim O43' \\sim O43": within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
Uanis(C69) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 N2, C43, C44, C45, C46, C47, C48, C49, C50, C51, C52, C53, C54, C55, C56, C57,
  C58, C59, C60, C61, C62, C63, C64, C65, C66
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N3, C67, C68, C69, C70, C71, C72, C73, C74, C75, C76, C77, C78, C79, C80, C81,
  C82, C83, C84, C85, C86, C87, C88, C89, C90
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7, C8, C9, C10, C11, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7', C8', C9', C10', C11', C12'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7", C8", C9", C10", C11", C12"
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O42, C95, C96, C97, C98
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{O42, C98, C97, C96, C95} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O42, C95, C96, C97, C98}
{N2, C49, C50, C51, C52, C53, C54} sigma for 1-2: 0.01, 1-3: 0.04
{N2, C61, C62, C63, C64, C65, C66} sigma for 1-2: 0.01, 1-3: 0.04
{N2, C55, C56, C57, C58, C59, C60} sigma for 1-2: 0.01, 1-3: 0.04
as in
{N2, C43, C44, C45, C46, C47, C48}
{N3, C79, C80, C81, C82, C83, C84} sigma for 1-2: 0.02, 1-3: 0.04
{N3, C85, C86, C87, C88, C89, C90} sigma for 1-2: 0.02, 1-3: 0.04
{N3, C73, C74, C75, C76, C77, C78} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N3, C67, C68, C69, C70, C71, C72}
{C7, C12, C11, C10, C9, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C7, C8, C9, C10, C11, C12}
{C7, C8, C9, C10, C11, C12} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C7', C8', C9', C10', C11', C12'}
{C7, C8, C9, C10, C11, C12} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C7", C8", C9", C10", C11", C12"}
6. Others
 1*[Sof(C7)+Sof(H7)+Sof(C8)+Sof(H8A)+Sof(H8B)+Sof(C9)+Sof(H9A)+Sof(H9B)+
 Sof(C10)+Sof(H10A)+Sof(H10B)+Sof(C11)+Sof(H11A)+Sof(H11B)+Sof(C12)+Sof(H12A)+
 Sof(H12B)]+1*[Sof(C7')+Sof(H7')+Sof(C8')+Sof(H8'A)+Sof(H8'B)+Sof(C9')+
 Sof(H9'A)+Sof(H9'B)+Sof(C10')+Sof(H10C)+Sof(H10D)+Sof(C11')+Sof(H11C)+
 Sof(H11D)+Sof(C12')+Sof(H12C)+Sof(H12D)]+1*[Sof(C7")+Sof(H7")+Sof(C8")+
 Sof(H8"A)+Sof(H8"B)+Sof(C9")+Sof(H9"A)+Sof(H9"B)+Sof(C10")+Sof(H10E)+Sof(H10F)+
 Sof(C11")+Sof(H11E)+Sof(H11F)+Sof(C12")+Sof(H12E)+Sof(H12F)]=1 with esd of
 0.0001
 1*[Sof(O43)+Sof(H43C)+Sof(H43D)]+1*[Sof(O43')+Sof(H43E)+Sof(H43F)]+1*
 [Sof(O43")+Sof(H43G)+Sof(H43H)]=1 with esd of 0.0001
 Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=
 Sof(H10A)=Sof(H10B)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=
 FVAR(1)
 Sof(C7')=Sof(H7')=Sof(C8')=Sof(H8'A)=Sof(H8'B)=Sof(C9')=Sof(H9'A)=Sof(H9'B)=
 Sof(C10')=Sof(H10C)=Sof(H10D)=Sof(C11')=Sof(H11C)=Sof(H11D)=Sof(C12')=
 Sof(H12C)=Sof(H12D)=FVAR(2)
 Sof(C7")=Sof(H7")=Sof(C8")=Sof(H8"A)=Sof(H8"B)=Sof(C9")=Sof(H9"A)=Sof(H9"B)=
 Sof(C10")=Sof(H10E)=Sof(H10F)=Sof(C11")=Sof(H11E)=Sof(H11F)=Sof(C12")=
 Sof(H12E)=Sof(H12F)=FVAR(3)
 Sof(O42)=Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(C97)=
 Sof(H97A)=Sof(H97B)=Sof(C98)=Sof(H98A)=Sof(H98B)=FVAR(4)
 Sof(O43)=Sof(H43C)=Sof(H43D)=FVAR(5)
 Sof(O43')=Sof(H43E)=Sof(H43F)=FVAR(6)
 Sof(O43")=Sof(H43G)=Sof(H43H)=FVAR(7)
7.a Riding coordinates:
 O38(H38A,H38B), O39(H39), O40(H40C,H40D), O43(H43C,H43D), O43'(H43E,H43F),
 O43"(H43G,H43H)
7.b Ternary CH refined with riding coordinates:
 C1(H1), C13(H13), C7(H7), C7'(H7'), C7"(H7")
7.c Secondary CH2 refined with riding coordinates:
 C95(H95A,H95B), C96(H96A,H96B), C97(H97A,H97B), C98(H98A,H98B), C43(H43A,
 H43B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B),
 C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B), C70(H70A,H70B), C71(H71A,H71B),
  C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C14(H14A,
 H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B),
 C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B),
  C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,
 H29B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B),
 C35(H35A,H35B), C37(H37A,H37B), C38(H38C,H38D), C39(H39A,H39B), C40(H40A,H40B),
  C41(H41A,H41B), C91(H91A,H91B), C92(H92A,H92B), C93(H93A,H93B), C94(H94A,
 H94B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,
 H12B), C8'(H8'A,H8'B), C9'(H9'A,H9'B), C10'(H10C,H10D), C11'(H11C,H11D),
 C12'(H12C,H12D), C8"(H8"A,H8"B), C9"(H9"A,H9"B), C10"(H10E,H10F), C11"(H11E,
 H11F), C12"(H12E,H12F), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B),
 C52(H52A,H52B), C53(H53A,H53B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B),
  C58(H58A,H58B), C59(H59A,H59B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,
 H63B), C64(H64A,H64B), C65(H65A,H65B), C73(H73A,H73B), C74(H74A,H74B),
 C75(H75A,H75B), C76(H76A,H76B), C77(H77A,H77B), C79(H79A,H79B), C80(H80A,H80B),
  C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B), C85(H85A,H85B), C86(H86A,
 H86B), C87(H87A,H87B), C88(H88A,H88B), C89(H89A,H89B)
7.d Me refined with riding coordinates:
 C48(H48A,H48B,H48C), C72(H72A,H72B,H72C), C36(H36A,H36B,H36C), C54(H54A,H54B,
 H54C), C60(H60A,H60B,H60C), C66(H66A,H66B,H66C), C78(H78A,H78B,H78C), C84(H84A,
 H84B,H84C), C90(H90A,H90B,H90C)
7.e Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C30(H30A,H30B,H30C), C42(H42A,H42B,H42C)
;
_shelx_res_checksum              63950
_shelx_hkl_checksum              98579
_olex2_submission_original_sample_id matta03
_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 3.206
_oxdiff_exptl_absorpt_empirical_full_min 0.594