A thirty-year old mystery solved: identification of a new heptatungstate from non-aqueous solutions.
Shiels, Dominic; Pascual-Borràs, Magda; Waddell, Paul G.; Wills, Corinne; Poblet, Josep-Maria; Errington, R. John; Chemical communications (Cambridge, England) 59 (2023) 7919–7922; doi:10.1039/d3cc02061d

data_1569248
_publ_section_title
;
 A thirty-year old mystery solved: identification of a new heptatungstate
 from non-aqueous solutions.
;
_journal_issue                   51
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7919
_journal_page_last               7922
_journal_paper_doi               10.1039/d3cc02061d
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety         'O24 W7, 2(C2 H6 O S), 1.707(O), 5(C10 H16 N)'
_chemical_formula_sum            'C54 H92 N5 O27.71 S2 W7'
_chemical_formula_weight         2605.71
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.12.01 svn.r5f60950 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-04-27 deposited with the CCDC.	2023-05-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.2090(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.7639(3)
_cell_length_b                   10.4977(2)
_cell_length_c                   29.5824(4)
_cell_measurement_reflns_used    29071
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      76.7480
_cell_measurement_theta_min      2.2040
_cell_volume                     7284.69(19)
_computing_cell_refinement       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.922
_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    -89.00 -21.00   0.50    1.50    --  -92.01  71.00 -54.00  136
  2  \w    -72.00  21.00   0.50    1.50    --  -49.76  71.00 -54.00  186
  3  \w    -48.00 -18.00   0.50    1.50    --  -92.01  45.00 150.00   60
  4  \w     39.00  96.00   0.50    1.50    --  108.00 -95.00  30.00  114
  5  \w   -120.00 -78.00   0.50    1.50    --  -49.76-125.00-120.00   84
  6  \w   -168.00 -75.00   0.50    1.50    --  -92.01 -45.00-120.00  186
  7  \w   -153.00 -68.00   0.50    1.50    --  -92.01 -71.00 174.00  170
  8  \w    -93.00 -27.00   0.50    1.50    --  -49.76 -71.00 174.00  132
  9  \w     66.00 105.00   0.50    1.50    --  108.00 -77.00 -90.00   78
 10  \w     42.00  67.00   0.50    1.50    --  108.00 -61.00-150.00   50
 11  \w     23.00  71.00   0.50    1.50    --   96.11 -61.00 -30.00   96
 12  \w     18.00  43.00   0.50    1.50    --   96.11 -45.00-150.00   50
 13  \w     19.00  45.00   0.50    1.50    --   96.11 -45.00  30.00   52
 14  \w     19.00  50.00   0.50    1.50    --   96.11 -45.00-180.00   62
 15  \w     23.00  60.00   0.50    1.50    --   96.11 -61.00 120.00   74
 16  \w     39.00  64.00   0.50    1.50    --  108.00 -71.00 174.00   50
 17  \w     34.00  86.00   0.50    1.50    --   96.11 -71.00 174.00  104
 18  \w    -17.00  50.00   0.50    1.50    --   48.76 -71.00 174.00  134
 19  \w    111.00 137.00   0.50    1.50    --   96.11  71.00 -54.00   52
 20  \w    144.00 169.00   0.50    1.50    --  108.00  71.00 -54.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0598722000
_diffrn_orient_matrix_UB_12      0.0582695000
_diffrn_orient_matrix_UB_13      -0.0130172000
_diffrn_orient_matrix_UB_21      0.0148074000
_diffrn_orient_matrix_UB_22      0.1017115000
_diffrn_orient_matrix_UB_23      0.0376387000
_diffrn_orient_matrix_UB_31      0.0225622000
_diffrn_orient_matrix_UB_32      0.0883158000
_diffrn_orient_matrix_UB_33      -0.0345998000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0434
_diffrn_reflns_av_unetI/netI     0.0433
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.922
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            49180
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.922
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.391
_diffrn_reflns_theta_min         2.219
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    21.044
_exptl_absorpt_correction_T_max  0.709
_exptl_absorpt_correction_T_min  0.421
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.73a (Rigaku Oxford Diffraction, 2022)
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_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.376
_exptl_crystal_description       block
_exptl_crystal_F_000             4891
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.151
_refine_diff_density_min         -2.735
_refine_diff_density_rms         0.195
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     922
_refine_ls_number_reflns         14433
_refine_ls_number_restraints     960
_refine_ls_restrained_S_all      0.985
_refine_ls_R_factor_all          0.0492
_refine_ls_R_factor_gt           0.0370
_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^)+(0.0408P)^2^+58.1946P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0889
_refine_ls_wR_factor_ref         0.0974
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11853
_reflns_number_total             14433
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc02061d2.cif
_cod_data_source_block           rje220110_fa
_cod_depositor_comments
'Adding full bibliography for 1569248--1569249.cif.'
_cod_database_code               1569248
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H81 N5 W7 O24'
_shelx_estimated_absorpt_t_max   0.678
_shelx_estimated_absorpt_t_min   0.321
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
2. Restrained distances
 S1A-O26A \\sim S1B-O26B
 with sigma of 0.02
 C54A-C53A \\sim C53B-C54B
 with sigma of 0.04
 S1A-C54A \\sim S1B-C53B
 with sigma of 0.02
 S1A-C53A \\sim S1B-C54B
 with sigma of 0.02
 O26A-C54A \\sim O26B-C53B
 with sigma of 0.04
 O26A-C53A \\sim O26B-C54B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
S1A \\sim O26A \\sim C53A \\sim C54A \\sim S1B \\sim O26B \\sim C53B \\sim
C54B: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within
2A
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: O28(0.70717) S1A(0.72599) O26A(0.72599) C53A(0.72599)
 H53A(0.72599) H53B(0.72599) H53C(0.72599) C54A(0.72599) H54A(0.72599)
 H54B(0.72599) H54C(0.72599) S1B(0.27401) O26B(0.27401) C53B(0.27401)
 H53D(0.27401) H53E(0.27401) H53F(0.27401) C54B(0.27401) H54D(0.27401)
 H54E(0.27401) H54F(0.27401)
6.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C14(H14A,H14B), C24(H24A,H24B), C34(H34A,H34B), C44(H44A,H44B)
6.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C36(H36),
  C37(H37), C38(H38), C39(H39), C40(H40), C46(H46), C47(H47), C48(H48),
 C49(H49), C50(H50)
6.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C),
 C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C53A(H53A,H53B,H53C), C54A(H54A,H54B,
 H54C), C53B(H53D,H53E,H53F), C54B(H54D,H54E,H54F)
;
_shelx_res_checksum              22542
_shelx_hkl_checksum              80957
_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 1.404
_oxdiff_exptl_absorpt_empirical_full_min 0.595