p<i>K</i><sub>a</sub> of alcohols dictates their reactivity with reduced uranium-substituted thiomolybdate clusters.
Patra, Kamaless; Brennessel, William W.; Matson, Ellen M.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 966–976; doi:10.1039/d4dt02803a

data_7717552
_publ_section_title
;
 p<i>K</i><sub>a</sub> of alcohols dictates their reactivity with reduced
 uranium-substituted thiomolybdate clusters.
;
_journal_issue                   3
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              966
_journal_page_last               976
_journal_paper_doi               10.1039/d4dt02803a
_journal_volume                  54
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C52 H70 Mo3 O2 S4 U, C6 D6'
_chemical_formula_sum            'C58 H70 D6 Mo3 O2 S4 U'
_chemical_formula_weight         1465.31
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-10-04 deposited with the CCDC.	2024-11-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.99181(6)
_cell_length_b                   20.28569(11)
_cell_length_c                   24.73170(15)
_cell_measurement_reflns_used    39275
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      79.5680
_cell_measurement_theta_min      2.8210
_cell_volume                     5514.59(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(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 0.990
_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   -118.00 -68.00   0.50    1.00    --  -47.06-133.00-131.00  100
  2  \w     52.00 116.00   0.50    1.00    --   47.06-159.00 -23.00  128
  3  \w    -92.00 -21.00   0.50    4.00    --  -91.75 133.00 -63.00  142
  4  \w   -166.00 -75.00   0.50    4.00    --  -91.75 -10.00 -88.00  182
  5  \w     42.00 121.00   0.50    4.00    --  113.25-137.00  50.00  158
  6  \w     97.00 178.00   0.50    4.00    --  113.25  10.00  85.00  162
  7  \w     45.00 110.00   0.50    4.00    --  113.25-118.00 129.00  130
  8  \w     -9.00  28.00   0.50    1.00    --  -47.06  19.00-150.00   74
  9  \w     -9.00  28.00   0.50    1.00    --  -47.06  19.00 120.00   74
 10  \w     -9.00  28.00   0.50    1.00    --  -47.06  19.00 150.00   74
 11  \w     -9.00  28.00   0.50    1.00    --  -47.06  19.00  90.00   74
 12  \w    -31.00  26.00   0.50    1.00    --  -47.06  38.00-120.00  114
 13  \w     42.00  83.00   0.50    4.00    --  113.25 -61.00 -60.00   82
 14  \w     42.00  83.00   0.50    4.00    --  113.25 -61.00  60.00   82
 15  \w     42.00  83.00   0.50    4.00    --  113.25 -61.00  30.00   82
 16  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00-180.00  128
 17  \w     42.00  83.00   0.50    4.00    --  113.25 -61.00-180.00   82
 18  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00 120.00  128
 19  \w     97.00 178.00   0.50    4.00    --  113.25  61.00 -90.00  162
 20  \w     42.00  83.00   0.50    4.00    --  113.25 -61.00 120.00   82
 21  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00-150.00  128
 22  \w    101.00 178.00   0.50    4.00    --  113.25  45.00   0.00  154
 23  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00 150.00  128
 24  \w    100.00 178.00   0.50    4.00    --  113.25  15.00-180.00  156
 25  \w     42.00  83.00   0.50    4.00    --  113.25 -61.00 -90.00   82
 26  \w    101.00 178.00   0.50    4.00    --  113.25  45.00-120.00  154
 27  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00-120.00  128
 28  \w     42.00  83.00   0.50    4.00    --  113.25 -61.00   0.00   82
 29  \w     25.00 120.00   0.50    1.00    --   47.06  77.00 -30.00  190
 30  \w     32.00 114.00   0.50    1.00    --   47.06  57.00-150.00  164
 31  \w     25.00 120.00   0.50    1.00    --   47.06  77.00  90.00  190
;
_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      -0.0189599000
_diffrn_orient_matrix_UB_12      0.0746235000
_diffrn_orient_matrix_UB_13      0.0079036000
_diffrn_orient_matrix_UB_21      0.0003713000
_diffrn_orient_matrix_UB_22      -0.0096488000
_diffrn_orient_matrix_UB_23      0.0617700000
_diffrn_orient_matrix_UB_31      0.1389054000
_diffrn_orient_matrix_UB_32      0.0101999000
_diffrn_orient_matrix_UB_33      0.0008782000
_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  0.0481
_diffrn_reflns_av_unetI/netI     0.0330
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            63887
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.235
_diffrn_reflns_theta_min         2.817
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    15.345
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48802
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.101a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.765
_exptl_crystal_description       needle
_exptl_crystal_F_000             2888
_exptl_crystal_size_max          0.138
_exptl_crystal_size_mid          0.038
_exptl_crystal_size_min          0.015
_refine_diff_density_max         1.454
_refine_diff_density_min         -0.874
_refine_diff_density_rms         0.120
_refine_ls_abs_structure_details
;
 Flack x determined using 4830 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0237(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     734
_refine_ls_number_reflns         11807
_refine_ls_number_restraints     332
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0264
_refine_ls_R_factor_gt           0.0249
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+19.6747P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0541
_refine_ls_wR_factor_ref         0.0547
_reflns_Friedel_coverage         0.795
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.968
_reflns_number_gt                11423
_reflns_number_total             11807
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02803a2.cif
_cod_data_source_block           matkp19
_cod_depositor_comments
'Adding full bibliography for 7717551--7717554.cif.'
_cod_database_code               7717552
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.802
_shelx_estimated_absorpt_t_min   0.226
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. 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
Uanis(C48) \\sim Ueq, Uanis(C52') \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
3. Rigid body (RIGU) restrains
 C47, C48', C49', C50', C51', C52'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{C53, C58, C57, C56, C55, C54} sigma for 1-2: 0.02, 1-3: 0.04
{C54, C55, C56, C57, C58, C53} sigma for 1-2: 0.02, 1-3: 0.04
{C53A, C54A, C55A, C56A, C57A, C58A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C53, C54, C55, C56, C57, C58}
{C47, C52, C51, C50, C49, C48} sigma for 1-2: 0.02, 1-3: 0.04
{C47, C48', C49', C50', C51', C52'} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C47, C48, C49, C50, C51, C52}
5. Others
 Sof(C48')=Sof(H48')=Sof(C49')=Sof(H49')=Sof(C50')=Sof(H50')=Sof(C51')=
 Sof(H51')=Sof(C52')=Sof(H52')=1-FVAR(1)
 Sof(C48)=Sof(H48)=Sof(C49)=Sof(H49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=
 Sof(C52)=Sof(H52)=FVAR(1)
 Sof(C53A)=Sof(D53A)=Sof(C54A)=Sof(D54A)=Sof(C55A)=Sof(D55A)=Sof(C56A)=
 Sof(D56A)=Sof(C57A)=Sof(D57A)=Sof(C58A)=Sof(D58A)=1-FVAR(2)
 Sof(C53)=Sof(D53)=Sof(C54)=Sof(D54)=Sof(C55)=Sof(D55)=Sof(C56)=Sof(D56)=
 Sof(C57)=Sof(D57)=Sof(C58)=Sof(D58)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C48(H48), C49(H49),
 C50(H50), C51(H51), C52(H52), C53(D53), C54(D54), C55(D55), C56(D56), C57(D57),
  C58(D58), C48'(H48'), C49'(H49'), C50'(H50'), C51'(H51'), C52'(H52'),
 C53A(D53A), C54A(D54A), C55A(D55A), C56A(D56A), C57A(D57A), C58A(D58A)
6.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C36(H36A,
 H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C),
 C40(H40A,H40B,H40C)
;
_shelx_res_checksum              19218
_shelx_hkl_checksum              14338
_olex2_submission_original_sample_id matkp19
_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 2.170
_oxdiff_exptl_absorpt_empirical_full_min 0.720